Pressure Temperature Conditions Research Articles

Analysis of the mechanism of the effect of N–H–O impurities on diamond growth under HPHT

In this work, diamond crystals were synthesized with N–H–O impurities by the temperature gradient method (TGM) under high pressure and high temperature (HPHT) conditions using FeNi alloy as the metal solvent (MS). The results indicated that the spontaneous nucleation rate and proportion, growth characteristics, surface growth texture, and the impurity concentration of diamond crystals changed drastically upon changing the impurity content in the system. Mutual diffusion between the MS and carbon source (CS) was also blocked, which seriously inhibited the growth rate of diamond crystals. X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) analyses corroborated that the zero-valent iron (Fe0) and nickel (Ni0) contents declined after N–H–O impurities were introduced. The newly formed graphite can be found in the MS, but the ferric carbide disappears. XPS also confirmed shifts in the binding energy of FeNi MS peaks, more iron oxide and nickel oxide were identified in MS, hindering the mass transfer process. CO and NO were absorbed on the surface of MS, which hindered the surface processes of diamond growth. The formation of intermediates (Fe3C) was impeded during diamond growth and blocked the spontaneous nucleation of diamond. All of these phenomena contributed to a poor growth rate and changed the surface growth process of diamond crystals.

Recycling of clay brick powder to improve the microstructure and mechanical properties of oil well cement pastes at high temperature and high pressure conditions

In oil well cementing involving high temperature and high pressure (HTHP), silica sources are usually incorporated into oil well cement to prevent its strength retrogression. This paper aims to use recycled clay brick powder (CBP), a silica-enriched material, as an alternative to the use of silica flour (SF) to inhibit the strength retrogression of the cement pastes after thermal cycling curing at 300 °C/13.0 MPa. Pure pastes (G), blended pastes with 40 wt% SF (40SF) and blended pastes with 40 wt% CBP (40CBP) were prepared to comparative analysis. The results showed that 40CBP and 40SF exhibited lower compressive strength and poorer pore structure than the G samples at 50 °C. However, the incorporation of CBP could effectively improve the compressive strength of the cement at 300 °C/13.0 MPa compared to that of the G paste. Mineralogical analysis indicated that xonotlite phases were the main crystalline phases in 40CBP and 40SF after thermal cycling curing. Compared to reinhardbraunsite in G samples, xonotlite could improve the pore structure and make the microstructure denser. In addition, there are some hibschite phases in 40CBP, which may make its compressive strength slightly lower than 40SF. Nevertheless, the environmental impact and cost analysis showed that the energy intensity and CO2 emissions of 40CBP were significantly lower than those of G and 40SF, and it had great cost advantages. This study is expected to provide some help in the rational recycling of CBP and reducing the CO2 emissions in cement production.

Flash-boiling effect on the droplet size distribution in low-pressure sprays formed at various ambient pressures and liquid temperatures — Experimental study and modelling

Flash-boiling injection occurs when a liquid is injected into an environment below its saturation pressure. It can be achieved either by reducing the ambient pressure or preheating the injected liquid. The goal of this work was to understand the influence of flash boiling on the droplet size distribution, depending on how it was achieved, and to model this influence in the function of the superheat parameters. For this purpose, systematic experimental tests were conducted, which covered a broad spectrum of fluid temperature and ambient pressure conditions. The tests showed that both liquid temperature and ambient pressure affect the droplet size distributions. Moreover, depending on the way of achieving flash boiling, the results were substantially different, even though the same superheating, expressed as the saturation to ambient pressure ratio, was maintained. Nevertheless, a similar and consistent pattern of droplet size reduction could be observed between the data series grouped by liquid temperature. Based on the experimental results, a model for simulating droplet size distribution at given superheat conditions was proposed. It takes into account the global trend of droplet size reduction observed for each fluid temperature. The model was found to simulate the droplet size probability density functions with satisfactory agreement under all performed experimental conditions.

Seafloor spreading and the delivery of sulfur and metals to Earth’s oceans

Abstract Circulating fluids within Earth’s mid-ocean ridge system cool and alter the oceanic crust, contribute distinct chemistry to the ocean, and generate economically and geologically important metal-sulfide deposits at the seafloor. Yet, we have few constraints on the characteristics of these fluids at peak subseafloor pressure and temperature conditions or how the primary variable, seafloor spreading, affects these fluids’ delivery of metals and sulfur to seawater. Here, we develop a new, robust technique for estimating the peak endowment of heat and dissolved sulfur, iron, and copper in subseafloor hydrothermal fluids and determining their fate as these superheated fluids rise to the seafloor. Calculations using this technique indicate that >20%–70% of sulfur, iron, and copper dissolved at peak subseafloor conditions are lost during upflow due to cooling and concomitant decreases in sulfide mineral solubility. The interpretation of these estimates within the geologic context of vent fields allows us to demonstrate a strong inverse relationship between seafloor spreading rate and peak pressure-temperature conditions, subseafloor heat loss, and the magnitude of subseafloor sulfide mineralization. Our results demonstrate the extent to which the secular variation of Earth’s mid-ocean ridge system over geologic time has impacted sulfide deposition rates and hydrothermal fluxes of sulfur and metals to the ocean.

Collective motion in hcp-Fe at Earth’s inner core conditions

Earth's inner core is predominantly composed of solid iron (Fe) and displays intriguing properties such as strong shear softening and an ultrahigh Poisson's ratio. Insofar, physical mechanisms to explain these features coherently remain highly debated. Here, we have studied longitudinal and shear wave velocities of hcp-Fe (hexagonal close-packed iron) at relevant pressure-temperature conditions of the inner core using in situ shock experiments and machine learning molecular dynamics (MLMD) simulations. Our results demonstrate that the shear wave velocity of hcp-Fe along the Hugoniot in the premelting condition, defined as T/Tm (Tm: melting temperature of iron) above 0.96, is significantly reduced by ~30%, while Poisson's ratio jumps to approximately 0.44. MLMD simulations at 230 to 330 GPa indicate that collective motion with fast diffusive atomic migration occurs in premelting hcp-Fe primarily along [100] or [010] crystallographic direction, contributing to its elastic softening and enhanced Poisson's ratio. Our study reveals that hcp-Fe atoms can diffusively migrate to neighboring positions, forming open-loop and close-loop clusters in the inner core conditions. Hcp-Fe with collective motion at the inner core conditions is thus not an ideal solid previously believed. The premelting hcp-Fe with collective motion behaves like an extremely soft solid with an ultralow shear modulus and an ultrahigh Poisson's ratio that are consistent with seismic observations of the region. Our findings indicate that premelting hcp-Fe with fast diffusive motion represents the underlying physical mechanism to help explain the unique seismic and geodynamic features of the inner core.

Proterozoic Deep Carbon—Characterisation, Origin and the Role of Fluids during High-Grade Metamorphism of Graphite (Lofoten–Vesterålen Complex, Norway)

Graphite formation in the deep crust during granulite facies metamorphism is documented in the Proterozoic gneisses of the Lofoten–Vesterålen Complex, northern Norway. Graphite schist is hosted in banded gneisses dominated by orthopyroxene-bearing quartzofeldspathic gneiss, including marble, calcsilicate rocks and amphibolite. The schist has major graphite (<modality 39%), quartz, plagioclase, pyroxenes, biotite (Mg# = 0.67–0.91; Ti < 0.66 a.p.f.u.) and K-feldspar/perthite. Pyroxene is orthopyroxene (En69–74) and/or clinopyroxene (En33–53Fs1–14Wo44–53); graphite occurs in assemblage with metamorphic orthopyroxene. Phase diagram modelling (plagioclase + orthopyroxene (Mg#-ratio = 0.74) + biotite + quartz + rutile + ilmenite + graphite-assemblage) constrains pressure-temperature conditions of 810–835 °C and 0.73–0.77 GPa; Zr-in-rutile thermometry 726–854 °C. COH fluids stabilise graphite and orthopyroxene; the high Mg#-ratio of biotite and pyroxenes, and apatite Cl < 2 a.p.f.u., indicate the importance of fluids during metamorphism. Stable isotopic δ13Cgraphite in the graphite schist is −38 to −17‰; δ13Ccalcite of marbles +3‰ to +10‰. Samples with both graphite and calcite present give lighter values for δ13Ccalcite = −8.7‰ to −9.5‰ and heavier values for δ13Cgraphite = −11.5‰ to −8.9‰. δ18Ocalcite for marble shows lighter values, ranging from −15.4‰ to −7.5‰. We interpret the graphite origin as organic carbon accumulated in sediments, while isotopic exchange between graphite and calcite reflects metamorphic and hydrothermal re-equilibration.

Protracted localization of metamorphism and deformation in a heterogeneous lower-crustal shear zone

Deformation of the continental crust is influenced by the pre-existing structural framework, fluid availability, strain rate, and pressure-temperature conditions. We investigate the evolution of a large (hundreds-of-meters wide) heterogeneous shear zone and associated brittle and ductile deformation structures (Lofoten, Norway) using structural analysis, mineral-chemical and microstructural observations, and U-Pb dating. The shear zone developed through a sequence of metamorphic stages: (1) migmatization and granulite-facies metamorphism, (2) eclogite-facies metamorphism, and (3) amphibolite-facies metamorphism. Stage (1) was related to magmatic activity at lower-crustal conditions prior to 1.7 Ga. Stage (2) likely occurred during the early phases of the collision between Baltica and Laurentia (Caledonian collision). Stage (3) was related to shortening during the main phase of the Caledonian collision (∼430–400 Ma) and was accompanied by hydration of the shear zone. We demonstrate how mechanical heterogeneities influence the deformation style from the centimeter to meter scale. Zones with a pre-existing fabric deformed by ductile shearing and folding, whereas homogeneous, dry rocks fractured. Fractures provided precursors for small-scale shear zones. These contrasting deformation styles occurred repeatedly. Consequently, pre-existing structures define the deformation style and serve as conduits for the channelization of fluids over extended periods of time.

Mechanical properties and microstructures of HPHT sintered polycrystalline diamond compacts reinforced with SiC whiskers

Polycrystalline diamond compact (PDC) cutters, the most widely used cutting tool in oil and gas drilling, often fail very quickly because of excessive wear and poor impact toughness in hard and complex formations. In this study, dense PDC samples doped with SiC whiskers (SiCw) were successfully synthesized under high pressure and high temperature (HPHT) conditions. The microstructures, elemental distributions, and phase compositions of the PDC samples were systematically investigated. The mechanical properties including the Vickers hardness, wear resistance, impact toughness and thermal stability, were tested. The introduction of SiCw reduced the Co content in the polycrystalline diamond layer. The testing results showed that the hardness of PDC doped with 0.5 wt% SiCw was 75.25 GPa, wear ratio was 145.6 × 104 and impact toughness reached 4020 J, which were 12.2%, 30.9%, and 142.2% higher than those of the control group (CG), respectively. The PDC-0.5 wt% SiCw had the lowest thermal expansion value, with a 57.5% reduction compared with the CG. In addition, the strengthening mechanism of SiCw was explored. SiCw partially replaced the weakening cobalt phase in the binder phase, thus improving the hardness, wear resistance, and thermal stability of the PDC. The introduction of SiCw inhibited the abnormal growth of WC at the interface of the cemented carbide substrate and changed the fracture mode from intergranular to transgranular, which were the main mechanisms responsible for the significant increase in the impact toughness of PDC.

Self-Catalyzed Hydrogenated Carbon Nano-Onions Facilitates Mild Synthesis of Transparent Nano-Polycrystalline Diamond.

Transparent nano-polycrystalline diamond (t-NPD) possesses superior mechanical properties compared to single and traditional polycrystalline diamonds. However, the harsh synthetic conditions significantly limit its synthesis and applications. In this study, a synthesis routine is presented for t-NPD under low pressure and low temperature conditions, 10 GPa, 1600 °C and 15 GPa, 1350 °C similar with the synthesis condition of organic precursor. Self-catalyzed hydrogenated carbon nano-onions (HCNOs) from the combustion of naphthalene enable synthesis under nearly industrial conditions, which are like organic precursor and much lower than that of graphite and other carbon allotropes. This is made possible thanks to the significant impact of hydrogen on the thermodynamics, as it chemically facilitates phase transition. Ubiquitous nanotwinned structures are observed throughout t-NPD due to the high concentration of puckered layers and stacking faults of HCNOs, which impart a Vickers hardness about 140 GPa. This high hardness and optical transparency can be attributed to the nanocrystalline grain size, thin intergranular films, absence of secondary phase and pore-free features. The facile and industrial-scale synthesis of the HCNOs precursor, and mild synthesis conditions make t-NPD suitable for a wide range of potential applications.

Hot subduction in the southern Paleo-Asian Ocean: Insights from clinopyroxene chemistry and Sr–Nd–Hf–Pb isotopes of Carboniferous volcanics in West Junggar

The chemical evolution and pressure–temperature conditions of subduction zone magmatism along ancient suture zones in orogenic belts can provide important information regarding plate convergence processes in paleo-oceans. Carboniferous magmatism in West Junggar is key to understanding the tectonothermal and subduction history of the Junggar Ocean, which was a branch of the Paleo-Asian Ocean, as well as the accretionary processes in the southwestern Central Asian Orogenic Belt (CAOB). We undertook a geochronological, mineralogical, geochemical, and Sr–Nd–Hf–Pb isotopic study of volcanic rocks from the Baikouquan area of West Junggar. We used these data to determine the petrogenesis, mantle source, and pressure–temperature conditions of these magmas, and further constrain the subduction and tectonic history of the Junggar Ocean. The studied volcanic rocks yielded zircon U–Pb ages of 342–337 Ma and are characterized by enrichments of large-ion lithophile elements (LILEs), and depletions in high-field-strength elements (HFSEs), indicative of an island arc affinity. The volcanic rocks have positive ƐNd(t) (5.83–7.04) and ƐHf(t) (13.47–15.74) values, 87Sr/86Sr(t) ratios of 0.704023–0.705658, and radiogenic 207Pb/204Pb(t) and 208Pb/204Pb(t) ratios at a given 206Pb/204Pb(t) ratio, indicative of a depleted mantle source contaminated by subduction-related materials. Geochemical modeling calculations indicate that ≤1% of a subduction component comprising fluid and sediment melt could have generated the source of the parental melts of the Baikouquan volcanic rocks. Clinopyroxene phenocrysts in the volcanic rocks are classified as high- and low-Ti clinopyroxene, and pressure–temperature calculations suggest the host rocks formed at high temperatures (∼1300 °C) and shallow to moderate depths (<2 GPa). The magma was probably generated by hot and hydrous melting in a mantle wedge in response to subduction of young, hot oceanic lithosphere. The present results, combined with published data, suggest that the Baikouquan volcanic rocks record a transition in tectonic setting from normal cold to anomalous hot subduction of young oceanic lithosphere close to a mid-ocean ridge. This indicates ridge subduction began shortly after 337 Ma. Our results provide new insights into the tectonomagmatic evolution during intra-oceanic subduction prior to ridge subduction.

Mantle metasomatism induced by water-fluxed melting of subducted continental crust at ultrahigh pressures

Abstract Mantle metasomatism under ultrahigh-pressure (UHP) conditions is widely recognized in orogenic peridotites and pyroxenites from UHP terranes. However, the processes by which the deeply subducted continental crust reacts with the mantle remain obscure. To investigate the metasomatic regime under UHP conditions, we conducted layered reaction experiments between gneiss and peridotite at 5 GPa and 800–1100 °C, with free water added in some of the experiments. At temperatures below the gneiss solidus, the major metasomatic agent is aqueous fluid, with the main reaction products being orthopyroxene + phlogopite + K-richterite. At temperatures above the gneiss solidus, hydrous melt becomes the major metasomatic agent, and the major reaction products vary from orthopyroxene + phlogopite to orthopyroxene + garnet with increasing degree of melting. The transformation from phlogopite to garnet occurred between 1000 °C and 1100 °C for runs without water added and between 800 °C and 900 °C for runs with water added. Pyroxenites in UHP terranes are mainly characterized by the metasomatic growth of orthopyroxene and garnet at 4–6 GPa and 750–1000 °C. Only experiments with water added reproduced the metasomatic assemblage at similar pressure-temperature conditions, indicating that mantle metasomatism in UHP terranes is probably mainly induced by water-fluxed melting of the continental crust under UHP conditions.

Neoproterozoic slab window in the western Yangtze Block, South China: Evidence from adakitic granodiorites, gabbro-diorites and high-K granites in the Panxi arc belt

Neoproterozoic igneous rocks are widespread along the margins of the Yangtze Block and record key information on the tectonic evolution of the South China Craton. In this paper, we present a comprehensive study of zircon U-Pb ages, whole-rock geochemistry and Sr-Nd-Hf isotopes on the Neoproterozoic granodiorites, gabbro-diorites, and high-K granites in the western Yangtze Block. The granodiorites, gabbro-diorites and high-K granites were dated at 848 ± 5.3 Ma, 824 ± 5.1 Ma and 819 ± 1.5 Ma, respectively. The granodiorites have high Sr (567 ∼ 607 ppm) contents and Sr/Y (84.4 ∼ 88.0) ratios and low alkalis (Na2O + K2O = 4.3 ∼ 4.9 wt%) and Y (6.6 ∼ 7.1 ppm) and Yb (0.7 ∼ 0.9 ppm) contents, similar to typical adakitic rocks. They show low MgO (0.9 ∼ 1.3 wt%), Cr (15.2 ∼ 26.7 ppm) and Ni (3.6 ∼ 4.4 ppm) contents and positive εNd(t) (+1.7 to + 4.2) and εHf(t) (+3.0 to + 8.2) values. The parental magmas for granodiorites were generated by partial melting of thickened juvenile mafic lower crust. The gabbro-diorites are characterized by the enrichment in LREEs, significantly negative Nb, Ta and Ti anomalies, and positive εNd(t) (+2.2 to + 4.2) and εHf(t) (+5.8 to + 10.4) values. They are inferred to be derived from partial melting of lithospheric mantle modified by subduction-related fluids. The high-K granites display high Zr + Nb + Ce + Y (208 ∼ 366 ppm) and alkali (Na2O + K2O = 7.6 ∼ 8.4 wt%) contents, high 10000*Ga/Al (2.31 ∼ 2.64) ratios and zircon saturation temperatures, similar to A-type granites. We suggest that these granites were formed by the partial melting of felsic crustal materials under low pressure and high temperature conditions. The association of granodiorites, gabbro-diorites and high-K granites indicates Neoproterozoic oceanic slab subduction in the western Yangtze Block. We suggest that a subducting oceanic slab window can account for Neoproterozoic magmatism in the western Yangtze Block.

Clinopyroxene Compositions of E-MORB-Type Gabbro from Bingdaban Ophiolites in Central Tianshan, NW China: Insights into the Evolution of the Magmatic System and Geodynamic Setting

Clinopyroxene, one of the primary rock-forming minerals in mafic rocks, is the major host of lithophile elements in the mantle lithosphere and plays a crucial role in understanding mantle evolution and rock petrogenesis. Taking the Bingdaban ophiolite as an example, this study employed electron probe microanalysis and in situ trace element analysis to investigate the geochemistry of clinopyroxene in gabbros to determine the magma series and evolution, constrain the physicochemical conditions of the magmatic processes and explore the petrogenesis and tectonic setting. Representative gabbro samples were subjected to zircon U–Pb isotopic analysis, yielding an age of 424.3 ± 5.9 Ma. Geochemical investigations revealed that the Bingdaban gabbros exhibit tholeiitic composition, suggesting a genesis associated with enriched mid-ocean ridge basalt (E-MORB). Mineralogical analyses indicated that the clinopyroxene in the gabbros was Mg-rich, Fe-poor, and alkali-poor, representing a subalkaline series. The compositional end members of clinopyroxene were calculated as Wo38.9–48.0En30.9–48.1Fs10.4–24.4, indicating a predominance of diopside with a minor amount of augite. Temperature–pressure conditions imply that these rocks formed in a high-temperature, low-pressure, and shallow-source environment. Compositional estimates of the melt in equilibrium with clinopyroxene are consistent with the overall characteristics of the host rock, reflecting an E-MORB setting. The Bingdaban gabbro likely originated from an initially depleted mantle source that later received an input of enriched mantle material, indicating formation in either an initial oceanic or immature back-arc basin tectonic setting.

Fuel temperature and injection pressure influence on the cold start GDI sprays

Cold start in gasoline direct injection engines (GDI) is a critical issue that significantly impacts fuel consumption and emissions. Therefore, it is essential to investigate and improve the spray and air-fuel mixing processes during cold starts. This study employed a complimentary set of optical diagnostic techniques, including line-of-sight(extinction, Schlieren, and long-distance microscopy) and 3D computed tomography (CT), to characterize and understand the cold-start spray dynamics under various fuel temperature and injection pressure conditions. The experiments were conducted in a constant volume spray vessel and the fuel temperature was varied using a coolant circulator, with temperatures reaching as low as -7 °C to simulate cold-start conditions. The cold fuel exhibited longer liquid/vapor penetration lengths compared to hot fuel under low injection pressure conditions. This deterioration in spray characteristics was attributed to the attenuated fuel evaporation and reduced entrainment of ambient air. The 3D spray visualization obtained through the CT algorithm, particularly the cut plane images, revealed that plumes with low fuel temperatures had narrower individual plume widths, resulting in minimized plume-to-plume interaction. Microscopic imaging further confirmed this observation which showed separate plumes in the near-nozzle region for cold fuel conditions. Meanwhile, hot fuel under high injection pressure conditions exhibited complete plume collapsing, leading to a significant amount of liquid fuel remaining in the spray core. The liquid penetration reached 70 mm during the injection period, potentially can cause wall wetting on the piston top or cylinder wall. Based on the experimental findings, this study suggests the application of multiple injections with a moderate level of injection pressure for optimized engine performance and reduced emissions during cold starts.

Microstructures, geochemistry, and geochronology of mica fish: Review and advances

Shear zones are one of the most conspicuous structures in orogenic and rifting settings, accommodating high strain, rock displacement and influencing magma emplacement and fluid flow. Since shear zones may be simultaneously or sequentially affected by multiple processes involving mineral reactions, variations in pressure-temperature conditions, fluid-rock interaction, and diffusion, determining the timing of such structures has been one of the major challenges for modern geochronology. Although low- (up to lower greenschist facies) and high-temperature shear zones (above amphibolite facies) are well-dated through low- and high-closure temperature minerals, medium-temperature shear zones developed within the critical temperature window of ∼450–550 °C, in which conventional chronometers such as 40Ar/39Ar and Rb–Sr applied to mica fish may or may not record the timing of deformation for multiple reasons (e.g., grain size, cooling rate, mineral composition, fluid activity, deformation, neo- and recrystallization). Here, we review the current knowledge on the evolution of mica fish and the effect of deformation on its chemical and isotopic systems. We evaluate the effect on the widely deployed in situ 40Ar/39Ar technique. Furthermore, we demonstrate the potential to assess mica fish evolution applying high-spatial resolution microstructural and chemical mapping techniques such as electron backscatter diffraction (EBSD), time-of-flight secondary ion mass spectrometry (ToF–SIMS) and in situ Rb–Sr via triple quadrupole inductively coupled plasma mass spectrometry (TQ-ICP-MS) to a case study of medium-temperature mylonites from the well-characterized Taxaquara shear zone, SE Brazil. We show that mica fish display complex microstructures with variable strain intensity, commonly with low strain inner cores and high strain edges and along kink planes. Strain shadows in mica fish are commonly characterized by low-strain fine-grained muscovite, suggesting recrystallization coeval with ductile deformation. Despite being intensely deformed, muscovite fish Rb–Sr retain the protolith age (c. 600 Ma), whereas recrystallized fine-grained muscovite yields the timing of deformation (c. 550–540 Ma). Synthetic shear bands cross-cutting coarse-grained muscovite fish induce muscovite recrystallization consistent with their distinct chemistry, with recrystallized muscovite characterized by higher Fe–Mg and lower Na suggesting fluid-assisted recrystallization under lower temperature compared to the muscovite fish host. We propose that these shear bands across mica fish play an important role by accommodating grain size reduction and subsequent deformation, leading to the formation of smaller individual mica fish. Grain size reduction, likely enhanced by dynamic precipitation (i.e., coeval crystal-plastic deformation and dissolution-precipitation creep), appears as the key recrystallization mechanism that allows low strain muscovite in strain shadows and shear bands to record the timing of deformation in medium-temperature shear zones, consistent with qualitative Sr diffusion modelling.

Laser-induced plasma and local temperature field for high-efficiency ammonia synthesis

The effective activation of chemically inert nitrogen under room temperature and normal pressure conditions has positive effects on the ammonia synthesis process. Herein, we propose a laser activated nitrogen to assist ammonia synthesis for the first time, which effectively activates nitrogen and facilitates the subsequent ammonia synthesis process. The nitrogen gas with a high bond dissociation enthalpy is ionized into nitrogen plasma on the local central region of catalyst tablet by pulsed laser, which can be controlled by the focused laser with high pulse energy but not be affected by the unfocus laser induced high temperature. Meanwhile, the ammonia synthesis is proceeded in the intermediate temperature annular region with Fe or iron nitride as catalyst, which is accelerated by pulsed laser produced nitrogen plasma. The laser-induced ammonia synthesis (LIAS) achieves the original ammonia yield of 70.8 μmol g−1 min−1 (28.32 μmol min−1) with a high hydrogen converting ratio of 9.5% by Fe as catalyst and a stable yield of 23.63 μmol g−1 min−1 (9.45 μmol min−1) with a hydrogen converting ratio of 3.2% by iron nitride as catalyst, which are 14.9 and 49.7 times than those of thermocatalysis using the same catalysts, respectively. As a precedent for laser-induced catalytic reactions, this work provides a perspective for nitrogen activation in the ammonia synthesis process.

The origin, nature and fluid characteristics of the hydrothermal veining crosscutting the Yzerfontein gabbro-diorite, Cape Granite Suite, South Africa

Abstract The mafic to felsic rocks at Yzerfontein form part of a composite 535 Ma post-orogenic pluton belonging to the Cape Granite Suite (CGS) of the Pan-African Saldania Belt of southwestern Africa. The pluton ranges from olivine gabbros (mostly at the northern end) to quartz monzonites, with monzonites the most abundant rock type. Minor felsic rocks in the form of quartz microsyenites and monzogranite occur more toward the southern end. The comparatively unaltered gabbro/monzonite has pyroxene δ18O values of 6.4‰, consistent with a mildly crustal-contaminated mantle-derived magma. Published εNd values of -1.9 to -0.3 similarly reflect crustal contamination of these mafic to intermediate rocks. The pluton is crosscut by extensive hydrothermal veining. Early quartz veining was followed by the precipitation of pyrite, calcite, tourmaline, jasper, epidote and a final stage involving the formation of barren quartz veins. The veins contain low-salinity (3 to 11 wt.% NaCl eq.), three phase (liquid + vapour ± opaques) fluid inclusions with total homogenisation temperatures of 125 to 320°C. The δ18O values of the quartz veins range from 9.8 to 14.7‰ and the fluid inclusion δD values range from -9 to -17‰. These ranges, together with the low salinities, are consistent with a meteoric origin for the vein fluids. Bulk-rock δ18O values range from 7.3 to 13.3‰ consistent with interaction of near surface fluids at temperatures of &amp;lt;300°C with the magmatic rocks. Open-space filling textures in quartz veins suggest vein formation in a hydrostatic regime. These, together with fluid inclusion isochores, suggest temperature-pressure conditions of no more than 170 to 300°C at ~0.5 kbar and no more than 1.6 kbar. The mineralised veins represent a shallow, poorly developed and possibly low-grade epithermal system. The mineralisation is likely related to drawdown of meteoric fluids during sub-solidus cooling of the dominantly intermediate pluton with little to no magmatic fluid influence. The mineralisation is poorly developed, possibly due to a lack of mixing between different fluid types. The various magmatic rocks, varying from mafic through dominantly intermediate to minor felsic, represents a minor mantle-derived mafic component of the Cape Granite Suite and likely related to the heat source that gave rise to voluminous crustal melting that generated the granitic magmas of the majority of the CGS.

Numerical investigation of heat transfer and pressure drop characteristics on the hot fluid side of the plate-fin precooler under negative pressure conditions

Plate-fin heat exchangers are widely employed in aerospace and many other fields due to the advantage of high efficiency and low resistance. However, they usually operate at atmospheric or high-pressure conditions. In this study, The commercial CFD solver Fluent 16.0 was used to evaluate the overall performance of the plate-fin precooler whose hot fluid is nitrogen under negative pressure and high temperature conditions. The characteristics of the hot fluid flow field inside the precooler with and without fins were investigated. The effect of fin number on the heat transfer and pressure drop characteristics of the hot fluid side was analyzed. Furthermore, the comprehensive performance of the precooler under different pressure conditions was compared quantitatively. The results showed that under negative pressure conditions, the hot fluid flow field features inside the precooler without fins was regular, while that of the precooler with fins took on a “<” shaped flow features, indicating the evolving of thermal boundary layer. It was also found that the comprehensive performance of the precooler did not increase with an increase in the number of fins when the hot fluid was in a low-density and high-speed flow state. Moreover, pressure conditions did not affect the heat transfer performance of the precooler but had a significant impact on the pressure drop performance.

A wealth of P–T–t information from metasediments in the HP–UHP terrane of the Pohorje Mountains, Slovenia, elucidates the evolution of the Eastern Alps

AbstractContrasting views exist in regard of the evolution of metamorphic rocks in the southeastern Pohorje Mountains (Mts), located in the southeastern Eastern Alps. Major debated points are whether micaschists have experienced ultrahigh‐pressure metamorphism in the Late Cretaceous (Eo‐Alpine) and whether they were continuously exhumed or experienced a multiple subduction–exhumation process from that time on. Therefore, we studied micaschist sample 18Slo39 with two generations of garnet and phengitic muscovite from this area. Our detailed study of this rock included petrographic observations, chemical analyses of minerals with the electron microprobe, pseudosection modelling, conventional geothermometry, and monazite in‐situ U‐Th‐Pb dating using laser‐ablation inductively coupled plasma (ICP) mass spectrometry. The following results were obtained: The studied micaschist was subject to a peak pressure of 1.31 ± 0.14 GPa at 603 ± 26°C in Eo‐Alpine times: 90.62 ± 2.78 (2σ) Ma (Stage I). Contact metamorphism at pressure–temperature conditions of 0.66 ± 0.10 GPa and 577 ± 23°C was induced by the intrusion of the Pohorje pluton (Stage III). We determined an early Miocene age of 18.33 ± 0.43 (2σ) Ma for this intrusion. Based on this study and the previously reported data for a micaschist (16Slo12) taken in the vicinity of sample 18Slo39, a geodynamic model is proposed for the region of the Pohorje Mts considering Eo‐Alpine subduction of oceanic crust and European continental crust, of which the micaschist was part of. Another high‐pressure event in the Eocene (Stage II) was the result of intracontinental subduction because of transpression by the Periadriatic fault system that separates the Eastern Alps from the Southern Alps. This type of subduction gave rise to magma generation and ascent to form the Pohorje pluton, which caused contact metamorphism in its vicinity.

Monazite–xenotime thermometry: a review of best practices and an example from the Caledonides of northern Scotland

Abstract Monazite–xenotime thermometry is a potentially powerful technique for understanding the evolution of Earth systems. While a rich set of experimental and empirical datasets are available for monazite–xenotime equilibria, five different thermometric calibrations yield significantly different results, making this technique difficult to apply in practice. To clarify best practices for monazite–xenotime thermometry, a compilation of published compositional data for monazite and xenotime with independently determined pressure–temperature conditions is evaluated. For each existing thermometer, we examine how closely estimated temperatures match independent empirical temperatures and consider how best to calculate monazite end-members for each thermometer. Monazite–xenotime thermometry is applied to samples from the Northern Highlands Terrane of northern Scotland, which experienced amphibolite–upper greenschist facies metamorphism and penetrative deformation during the Scandian orogeny. Thermometry data in conjunction with U–Pb dating define relatively slow regional cooling across the Scandian thrust nappes. Thermometry data closely match quartz c -axis fabric-based deformation thermometry across the structurally lower nappes, suggesting that monazite and xenotime record the timing and temperature of penetrative deformation and shearing. The data suggest that ductile deformation in the hinterland nappes of the Scandian orogen in Scotland occurred as late as 415–410 Ma.