Dissolution-precipitation Process Research Articles

Repurposing Industrial and Agricultural Wastes as Sustainable Alternatives in Photovoltaic Cells and Dye Degradation

AbstractCombustion of coal at thermal power plants generates enormous amounts of coal fly ash (CFA). Proper disposal of CFA is an important issue today because environmental problems are considered a burning issue worldwide. On the other hand, groundnut shells (GNS), regarded as agricultural waste in general, litter landfills everywhere and create soil degradation. Since both CFA and GNS contain abundant silica, this work focuses on extracting amorphous silica from these materials through a total dissolution–precipitation process. The silica was extracted from it and used to prepare titanium oxide (TiO₂) hybrids. The GNSS were extracted from GNS, and the CFAS was extracted from the CFA. The methods used were based on sol–gel. These hybrids were further tested for the performance of their solar cells in dissolving dyes. The overall results of the obtained physical properties of CFAS and GNSS are similar to those of conventional silica. More importantly, TiO₂/GNSS and TiO₂/CFAS hybrids showed enhanced photocatalytic efficiency compared to the pure TiO₂. Therefore, it is evidence of repurposing CFA and GNS, which have high potential for use as sustainable applications in renewable energy and environmental remediation.

Hydrochemical characterization and health risk assessment of shallow groundwater in a northern coalfield of Anhui Province, China

In a global context, the hydrochemical characteristics of shallow groundwater in coalfields exhibit high degrees of diversity and complexity that are rooted in the intricate interplay of geological variations, diverse climatic conditions, and extensive human activities. The specific types and concentrations of ions, such as Ca2+, Cl−, and NO3−, show stark differences across geographical regions. Given the crucial roles of coalfields as energy suppliers, the potential environmental contamination risks posed by mining activities to groundwater cannot be overlooked as such pollution directly impacts human health and ecological safety. This study focuses on the Huainan coal mining area in northern Anhui Province (China), where shallow groundwater samples were systematically collected and analyzed to determine the hydrochemical characteristics and ascertain the water quality status. By integrating hydrogeochemical analysis techniques with inverse modeling methods, it was revealed that the groundwater in this region is predominantly HCO3-Ca type, exhibiting weak alkaline characteristics. The formation mechanisms are primarily governed by silicate rock weathering and mineral dissolution–precipitation processes, albeit with discernible influences from human activities. PHREEQC simulations were used to further confirm the precipitation tendencies of minerals like calcite, dolomite, and fluorite as well as the significant dissolution characteristics of halite. The inverse modeling pathway analysis reveals specific hydrochemical processes along different paths: paths I and IV are notably dominated by Ca2+ dissolution–precipitation and cation exchange–adsorption processes, whereas paths II and III are closely associated with the precipitation of calcium montmorillonite as well as dissolution of kaolinite, calcite, quartz, and mineral incongruents. Moreover, evaluations based on the entropy-weighted water quality index (EWQI) indicated overall positive trends of the groundwater quality indicators within the Huainan mining area, reflecting the effectiveness of regional water quality management efforts and providing a scientific basis for future water quality protection and improvement strategies. In summary, this study not only deepens our understanding of the groundwater chemistry in the Huainan coal mining area but also underscores the importance of scientifically assessing and managing groundwater resources to address the environmental challenges potentially arising from coal mining activities.

Preparation of ultrafine WC-V8C7-Cr3C2-co cemented carbides by spark plasma sintering in-situ synthesis of composite grain growth inhibitors

The growing high-precision manufacturing industry is increasing the demand for cemented carbide which has fine grain size and excellent machinability. In this research, ultrafine cemented carbide was successfully prepared by the method of in-situ synthesis using spark plasma sintering as densification method, V, Cr, WC and carbon black as raw materials. The formation mechanism of in-situ preparation of grain growth inhibitors (GGIs) and its influence on the properties of alloys were investigated. An excellent mechanical property (HV 2254 kgf/mm2, KIC 9.20 MPa·m1/2) and uniform microstructure of the alloys (0.8 wt% V8C7–0.8 wt% Cr3C2) prepared under 1350 °C, 6 min, 25 MPa were demonstrated by the results. The WC grain growth was significantly inhibited (about 200 nm). The in-situ synthesized GGIs significantly inhibited grain coarsening by interfering with the dissolution-precipitation process of WC during liquid-phase sintering. The combination of SPS and in-situ synthesized GGIs offers a novel approach to exploration of the preparation of high-performance ultrafine or nanocrystalline cemented carbides.

Effect of carbon content on the microstructure and mechanical properties of ultrafine WC-15Co cemented carbides using a Co-based solid solution binder phase

In this paper, a new method was proposed to improve the uniformity of the distribution of grain-growth inhibitors using a Co-based solid solution prepared with Co3O4, Cr2O3, and V2O5 as the raw materials through high-temperature hydrogen reduction. The effect of carbon content on the microstructure and mechanical properties of ultrafine WC-15Co cemented carbides using a Co-based solid solution binder phase were studied. The results demonstrated that the carbon content exerted a considerable influence on the composition of the binder phase, thereby affecting the morphology of the WC grains. With increasing the carbon content, Cr and V precipitated from the Co-based solid solution, adhering to the habit planes of WC or segregating at the WC-Co interface. This hindered the growth of WC grains, yielding an average particle size smaller than that of alloys containing 6.0wt.% carbon content. However, increased carbon content may enhance grain growth owing to the dissolution-precipitation process of WC grains during the liquid-phase sintering process. Thus, an alloy comprising 6.31wt.% carbon content and featuring trigonal prismatic-shaped WC grains with a mean particle size of 0.310 μm exhibited excellent comprehensive performance, characterized by a hardness, transverse rupture strength, and fracture toughness of 1579kg/mm2, 2581MPa, and 10.56MPa·m1/2, respectively.

Pre-planting amorphous carbon films based on Ir composite substrates for diamond nucleation

A tunable locally ordered amorphous carbon layer was pre-implanted on the iridium (Ir) composite substrate using a multi-excitation source plasma coating system. The nucleation interface was mainly studied by scanning electron microscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy. The results show that by designing and modulating the content and ordering of sp2/sp3 hybridized carbon bonds in the amorphous carbon on the surface of Ir thin films, an overall ordered diamond nucleation layer was obtained. When the pulse frequency of the carbon source was regulated to 9 Hz, the (100) diamond grains were uniformly aligned without the appearance of twins after 4 h of growth, and the nucleation density was 7.5 × 109 cm−2, which was subsequently expected to obtain single-crystal diamond by grain boundary annihilation. Based on the Ir-amorphous carbon pre-growth layer, it can accelerate the dissolution-precipitation process of carbon ions into the Ir film to form a supersaturated solid solution during the bias nucleation, and increase the nucleation sites, which is of great significance for improving the nucleation density of large-size single-crystal diamond heterogeneous epitaxy.

Robustly Boosting Thermoelectric Performance of N-Type PbSe via Lattice Plainification and Dynamic Doping.

Ideal thermoelectrics shall possess a high average ZT, which relies on high carrier mobility and appropriate carrier density at operating temperature. However, conventional doping usually results in a temperature-independent carrier concentration, making performance optimization over a wide temperature range be challenging. This work demonstrates the combination of lattice plainification and dynamic doping strategies is an effective route to boost the average ZT of N-type PbSe. Because Sn and Pb have similar ionic radii and electronegativity, this allows Sn to fill the intrinsic Pb vacancies and effectively improves the carrier mobility of PbSe to 1300 cm2 V-1 s-1. Furthermore, a trace amount of Cu is introduced into the Sn-filled PbSe to optimize the carrier concentration. The extra Cu is situated in the interstitial sides of the lattice, which undergoes a dissolution-precipitation process with temperature, leading to a strongly temperature-dependent carrier density in the material. This dynamic doping effectively improves the electrical transport properties and is also valid to suppress the lattice thermal conductivity. Ultimately, the resulting PbSn0.004Se+3‰Cu obtains a maximum ZT of ≈1.7 at 800 K and an average ZT of ≈1.0, with a 7.7% power generation efficiency in a single-arm device, showing significant potential for commercial application.

Rheology modification in a subduction channel due to eclogite facies metasomatism (Rocky Beach Metamorphic Mélange, Port Macquarie, Australia)

The rheological properties of the interface between the down-going and overriding plates in subduction zones provides insight into how plate convergence is accommodated and the controls on seismic and aseismic slip. This interface is known as the subduction channel and exhumed examples provide the only direct information on deformation mechanisms and the impact of metamorphism on rheology. The Rocky Beach Metamorphic Mélange in eastern Australia is one such exhumed subduction channel, composed of eclogite, blueschist and greenschist facies blocks within a mélange matrix. Previous phase equilibria modelling indicates that high pressure blocks were subducted to ca. 100 km depth and then retrogressed during return flow and exhumation. We found that the rheology of blocks is modified by metasomatism, consistent with studies on other subduction channels. However, through comparison of blocks from different metamorphic grades we found that the effect of metasomatism on rheology varied depending on the pressure and temperature conditions of metasomatism. While unmetasomatised eclogites behaved as rigid objects in the mélange matrix, rocks with mineral assemblages that equilibrated during eclogite facies metasomatism accumulated significant strain, forming isoclinal folds and refolded folds. Deformation of these blocks began at eclogite facies and continued during return flow and retrogression to blueschist facies. At blueschist facies, metasomatised blocks developed mm-scale isoclinal folds with shearing parallel to fold limbs forming rootless isoclinal folds. At the transition between blueschist and greenschist facies, pressure solution became important, preferentially focusing along layers of lawsonite, dissolving it from the rock. At greenschist facies, dissolution-precipitation processes caused significant mass loss, producing mm-spacing between pressure solution seams and cuspate folds, analogous to dewatering structures in sediments. In the Rocky Beach Metamorphic Mélange eclogite facies metasomatism reduces the competence of rigid blocks, reducing overall subduction channel heterogeneity during return flow. We suggest that subduction channels that experience widespread eclogite facies metasomatism may be less likely to generate seismic slip during return flow, since the proportion of rigid blocks and block strength are both reduced.

Densification and network structural changes in binary aluminosilicate glass via cold sintering process

Binary aluminosilicate glasses containing 20–50 wt% Al2O3 were successfully densified through a cold sintering process (CSP) using 1–10 M NaOH solutions. The investigation focused on densification and structural unit changes in the cold-sintered binary aluminosilicate glasses. Specifically, the binary aluminosilicate glass with 40 wt% Al2O3, cold-sintered at 180 °C using 1–10 M NaOH solutions, achieved a relative density of up to 90 % at 10 M NaOH. This was attributed to an enhanced dissolution-precipitation process facilitated by an increased concentration of the NaOH solution. In aluminosilicate glasses with 20–50 wt% Al2O3, the relative densities approached 90 % after CSP at 180 °C using a 10 M NaOH solution. Al(OH)3 formation in the cold-sintered glasses was confirmed, particularly at higher concentrations of NaOH solution (>10 M) and higher contents of Al2O3 (>40 wt%). Changes in Si structural units were observed during CSP, with Al-rich Si units becoming dominant as the concentration of the NaOH solution increased. The higher substitution of Si-O-Si bonds by Si-O-Al bonds led to the precipitation of Al(OH)3, as well as an increased Vickers hardness and biaxial flexural strength of the cold-sintered glasses. These findings demonstrate that the Al2O3 content and NaOH concentration play important roles in the densification and enhancement of the mechanical property in the cold-sintered alumina-rich binary aluminosilicate glasses and offer insights into the optimal conditions for obtaining desirable aluminosilicate materials through CSP.

The permeability evolution mechanism of ore-bearing strata during acid in-situ leaching of uranium: A case study of Bayanwula uranium mine in Inner Mongolia of China

Uranium mainly comes from ISL of sandstone-type uranium deposits in China. The change of porosity and permeability caused by blockage of ore-bearing strata is one of the most serious problems in acid ISL of uranium. In this paper, the groundwater tracer test was carried out before and 1 year after ISL to explore the pore and permeability evolution characteristics of the ore-bearing layer during ISL. The test results showed that the leaching solution migrated along two seepage channels and the water-bearing medium was isotropic. After 1 year of ISL, the flow rate of the leaching solution decreased obviously. However, the flow rate of the leaching solution in slower channel decreased more than that in the faster channel in all directions, which was caused by the more adequate chemical reactions between the leaching solution and the minerals of the ore-bearing layer and the more corresponding precipitation in the slower channel. In addition, the flow rate along the direction of groundwater flow decreased less than that in the direction of vertical groundwater flow. This was closely related to the transformation of aquifer medium by hydrodynamic field. Initial stage of ISL, the occurrence of plugging is closely related to the precipitation-dissolution process of iron and aluminum minerals under the change of pH, which is accompanied by the continuous precipitation of gypsum.

Chloride binding behavior and mechanism of phosphoaluminate cement clinker and its hydration products

As one of potential materials for extending the lifetime of reinforced concrete serving in chloride-rich environments, phosphoaluminate cement (PAC) offers excellent chloride binding capacity and superior resistance to chloride penetration. The chloride binding behavior as well as binding routes and mechanisms of the clinker and its hydration products had not been clarified so far. This study revealed that the clinker would preferentially form Friedel's salts through a dissolution-precipitation route in NaCl solutions, thereby binding chloride. This dissolution-precipitation process led to an accumulation of Al3+ in solutions, which negatively affected the subsequent hydration reactivity of the clinker. In the hydration products, the calcium hydroaluminates, mainly as C2(A,P)H8 with minor C(A,P)H10, could bind chloride rapidly via an ion exchange mechanism. Through the ion-exchange route, the chemical binding of calcium hydroaluminates to chloride could be completed in less than 1 hour. In contrast, the unhydrated clinker exhibited a slow chloride binding behavior until 72 hours. All these would provide theoretical guidance for using PAC cementitious materials in reinforced concrete to enhance resistance to chloride attack.

Origin of discordant U[sbnd]Pb dates in non-metamict zircons in intrusives deformed at granulite facies: Grain scale processes, and relevance to Cambrian orogeny, Eastern Ghats Belt, India

Interpreting the origin of UPb discordance in zircons in intrusives that experience high-T metamorphic-deformation events is challenging. We investigate in depth the origin of UPb dates obtained from garnet-bearing border zone granitoids and a sheared ferrodiorite dyke bordering the Balangir anorthosite pluton, eastern India. The crustal domain is known for discordant ages resulting in disputes regarding the age of intrusion and multiple granulite facies events. We shed light on the origin of the discordant dates utilizing CL imaging, electron backscatter diffraction analysis, trace element mapping in zircons, and Ti-in-zircon thermometry.Zircons in the foliated border zone granitoids (BZG) comprise (a) embayed cores with varying Y, U and Hf oscillatory zones, and (b) well-faceted chemically-homogeneous mantles crystallographically continuous with the cores, which truncate the oscillatory zones. In the intensely sheared ferrodiorite, cauliflower-shaped zircons possess profuse micropores and micro-fractures. Ti-in-zircon temperatures (700–950 °C) overlap in the texturally-distinct zircons, but are somewhat lower in the mantles/cauliflower-shaped zircons relative to the oscillatory-zoned cores in BZGs.LA-ICP-MS dates of zircons in four samples constitute a near-unique discordia line with the upper and lower intercepts at ca. 980 Ma and 495 Ma. Interestingly, dates from the mantles are highly variable with no correlation between age decrease and distance to the cores. The lack of concordant dates at the two intercepts, and the increase in discordance away from the intercepts preclude episodic zircon growth, and suggests a single-stage granulite facies event (ca. 495 Ma) that modified the ∼980 Ma zircon xenocrysts entrained from protoliths into the intrusives. We propose the age discordance was caused by melt-mediated high-T interface coupled dissolution-precipitation processes at ∼495 Ma. Variable inheritance of isotopic signatures of ∼980 Ma zircon xenocrysts in the younger zircons contributed to discordance in UPb systematics; the effect of variable inheritance of ∼980 Ma isotope signatures is less pronounced in the cauliflower-shaped zircons from the HFSE enriched ferrodiorite residual melts from high degree of plagioclase fractionation.Our results are consistent with a distinct Cambrian (∼495 Ma) orogeny involving emplacement of anorthosite pluton and related intrusives and high-T granulite-facies deformation-metamorphism in the ∼980 Ma Eastern Ghats Province, and are a direct record of Cambrian collision between the Eastern Ghats Province and the Archean cratonic nucleus.

Opaline silica precipitations in the Permian Fengcheng Formation indicate hot spring environments in north Mahu Sag, NW China

The Permian Fengcheng Formation represents a series of deposits formed in an alkaline saline lake, characterized by high proportions of cherts, located in the Northwestern Junggar Basin in China. While discussions on silica-rich hot springs as sources of silica for brine and subsequent chert deposition have been extensively conducted for Quaternary and Mesozoic-Cenozoic alkaline saline lakes worldwide, investigations into Paleozoic alkaline saline lakes are scarce due to challenges associated with identifying evidences of hot spring environments. In this study, we present detailed SEM-EDS analyses and examine silica isotope compositions as well as oxygen isotope compositions to discuss hydrothermal-associated silica precipitation processes. Our findings suggest that migrating silica-rich hot springs along deep-rooted faults released silica into the brine, leading to chert deposition during cooling periods and induction of thermophilic microorganism degradation. Microorganism-associated siliceous precipitates primarily consist of opal-A spheres adhered by extracellular polymeric substances (EPS), while numerous microorganism spheres have undergone silicification. Opal-A spheres within these structures were partially transformed into well-crystallized quartz through multiple stages of dissolution-precipitation processes during prolonged burial history. Furthermore, our results indicate that deep-rooted fault-related hot springs can occur both in marginal and subaqueous areas within alkaline saline lakes, with chert formations observed in shallow-marginal saline lake settings as well as deeper regions. The findings of this study provide valuable insights into the paleoenvironmental conditions, which can be further explored in investigating the accumulation of organic matter in chert-rich successions formed within an alkaline saline lake.

Synergistic enhancement for room and high temperature properties of Ti(C, N)-based cermets by Re and (Cr, La)2(C, N) assistance

Heat resistance played a crucial role in evaluating matrix material to meet the rapid development of molding industry. For the traditional Ti(C, N)-based cermets, softening and heat stocking induced degradation of mechanical properties limited its constant application under high-temperature. Herein, a novel engineering strategy for synergistically improving both room and high temperature properties was proposed by using Rhenium (Re) as additive in a (Cr, La)2(C, N) modified Ti(C, N)-based cermets. Results indicated that Re could effectively adjust the dissolution-precipitation process by dispersing into binder phase, which brought out more even microstructure and enhanced mechanical properties at both room and elevated temperatures. Benefitting from dissolution strengthening and purification effect at the interface by La, the increased thermal conductivity and thermal shocking resistance could also be obtained. With the co-enhancement of mechanical and physical properties, this new strategy could anticipate with significant potential for consideration as matrix materials in manufacturing.

Accretion of the Lower Oceanic Crust at Fast-Spreading Ridges: Insights from Hess Deep (East Pacific Rise, IODP Expedition 345)

Abstract At mid-ocean ridges, melts that formed during adiabatic melting of a heterogeneous mantle migrate upwards and ultimately crystallize the oceanic crust. The lower crustal gabbros represent the first crystallization products of these melts and the processes involved in the accretion of the lowermost crust drive the chemical evolution of the magmas forming two thirds of Earth’s surface. At fast-spreading ridges, elevated melt supply leads to the formation of a ⁓6-km-thick layered oceanic crust. Here, we provide a detailed petrochemical characterization of the lower portion of the fast-spread oceanic crust drilled during IODP Expedition 345 at the East Pacific Rise (IODP Holes U1415), together with the processes involved in crustal accretion. The recovered gabbroic rocks are primitive in composition and range from troctolites to olivine gabbros, olivine gabbronorites and gabbros. Although textural evidence of dissolution-precipitation processes is widespread within this gabbroic section, only the most interstitial phases record chemical compositions driven by melt-mush interaction processes during closure of the magmatic system. Comparing mineral compositions from this lower crustal section with its slow-spreading counterparts, we propose that the impact of reactive processes on the chemical evolution of the parental melts is dampened in the lower gabbros from magmatically productive spreading centres. Oceanic accretion thereby seems driven by fractional crystallization in the lower gabbroic layers, followed by upward reactive percolation of melts towards shallower sections. Using the composition of clinopyroxene from these primitive, nearly unmodified gabbros, we estimate the parental melt trace element compositions of Hess Deep, showing that the primary melts of the East Pacific Rise are more depleted in incompatible trace elements compared to those formed at slower spreading rates, as a result of higher melting degrees of the underlying mantle.

Low-temperature aqueous synthesis and biocompatibility of manganese whitlockite

In this work, manganese whitlockite (Mn-WH, Ca18Mn2(HPO4)2(PO4)12) was successfully synthesized and comprehensively characterized. This material is a manganese-containing analog of the biomineral magnesium whitlockite (Mg-WH, Ca18Mg2(HPO4)2(PO4)12). The synthesis was performed via a low-temperature dissolution-precipitation process in aqueous medium under ambient pressure at 75 °C using dicalcium phosphate dehydrate and manganese acetate tetrahydrate as starting materials. The crystal structure of the synthesized powder was determined by powder X-ray diffraction, FTIR and Raman spectroscopies, demonstrating the presence of characteristic structural units. Morphological features and elemental distribution within the synthesized powder were studied by SEM/EDX analysis. XPS, EPR and magnetic studies confirmed the presence of Mn ions in a divalent state. Temperature-dependent magnetic measurements revealed a paramagnetic behavior of Mn-WH down to 5 K. In vitro cytotoxicity experiments were performed with MC3T3-E1 preosteoblastic cell line.

Development and investigation of salt based composite phase change material containing diatomite as skeleton substance by cold sintering technology for medium and high temperature thermal energy storage

This work concerns the development of a nitrate salt based form-stable composite phase change material by cold sintering technology with the employment of diatomite as skeleton substance. Such fabrication strategy has never before been reported in the literature and we demonstrate for the first time the feasibility of salt-diatomite composite production through a cold sintering process by means of sodium hydroxide solution as sintering additive. The microstructural characteristics and development mechanism, chemical and physical compatibility, mechanical strength, phase change behaviour, thermal and shape stability of the composite are investigated to reveal the structure formation and densification mechanism of salt and diatomite. The results show that the composite could be sintered at a temperature of 180 °C, far lower than that required in the traditional hot sintering approach. Due to the congruent solubility of the salt and diatomite in aqueous alkali, a rigid and dense structure induced by a so-called dissolution-precipitation process could be generated in the composite, which provides solution to accommodate the salt, endowing the composite with splendid capacity to maintain the structure stability and restrain the liquid leakage over the phase change process. An excellent chemical and physical compatibility has been achieved between the salt and other components, and over 60 wt% salt could be encapsulated in the composite by which a melting temperature around 278 °C and an energy storage density over 650 kJ/kg at a temperature range of 50–600 °C are attained. The results also reveal that the composite exhibits preeminent mechanical strength and excellent thermal cycling performance. For a given cycling temperature range of 50–500 °C, a stable macroscopic shape with a compressive strength over 210 MPa could be achieved in the composite even after 100 times of thermal cycles.

Phosphate uptake is an essential process for rapid bone mineralization during early diagenesis – evidence from bone alteration experiments

Bones and teeth are often the only fossil remains of vertebrates that are preserved over geological time in sedimentary rocks. They render valuable archives for geochemical proxies which are commonly used for paleo-reconstructions. However, the fossilization mechanisms of bone are not yet well understood. Crucial processes are the transformation of bioapatite into and the replacement of collagen by thermodynamically more stable apatite phases, such as fluorapatite. In the present study, aqueous alteration experiments on cortical bone samples were performed under simulated early diagenetic conditions in order to investigate whether and how an external phosphate (PO4) source affects post mortem bone mineralization. Additionally, abiotic oxygen isotope exchange mechanisms between bioapatite and aqueous solutions were assessed by using either 18O-enriched water or PO4 as a tracer. The presence of an external sedimentary 18O-labeled PO4 source led to a rapid formation of new fluorapatite crystallites at the sample’s margin that was highly enriched in 18O. Meanwhile, in the interior of the samples carbonate-poor hydroxylapatite formed through a dissolution-precipitation process without incorporating significant amounts of the 18O tracer. These two processes appear to act independently from each other. In samples exposed to 18O-labeled aqueous solutions lacking a PO4 source, no newly grown apatite crystallites were found, however in the interior of these samples, nano-crystalline carbonate-poor or -free hydroxylapatite precipitated. A comparatively low but uniform 18O-enrichment was measured from the sample’s margin towards its interior, which is assumed to have resulted from the adsorption of H218O onto crystallite surface sites and collagen. Overall, our results suggest that a fast incorporation of 18O-doped PO4 from the sediment source accelerated bone mineralization and consequently changed the oxygen isotope composition of the PO4 group in the bone mineral phase more rapidly and to a greater extent than in a diagenetic setting lacking additional external PO4. Dissolved PO4 from the taphonomic setting thus seems to be an important factor fostering bone fossilization and preservation as well as oxygen isotope alteration.

The Ophiolite-Hosted Cu-Zn VMS Deposits of Tuscany (Italy)

Several Jurassic, ophiolite-hosted Cu-Zn VMS deposits occur in Tuscany. They are hosted by tectonic units of oceanic affinity (Ligurian Units), such as the well-known deposits of nearby Liguria. Industrial production was small and definitively ceased in the 1960s. Locally, massive ore (chalcopyrite-bornite-chalcocite) with an exceptionally high grade was found. The Montecatini Val di Cecina mine exploited the largest “bonanza” and, for few decades in the 19th century, became one of the most profitable copper mines in Europe. This study provides an updated review of these deposits. Tuscan Cu-Zn VMSs mostly occur in proximity of the contact between the serpentinite-gabbro basement and the overlying basalts. Chalcopyrite-pyrite stockworks occur in serpentinite-gabbro cut by dolerite dykes, while the largest massive sulphide bodies are hosted by polymictic-monomictic breccias at the base of pillow basalts. Early chalcopyrite ores were mechanically–chemically reworked and upgraded to bornite-rich nodular ore embedded in a chlorite, calcic amphibole, Fe-rich serpentine, quartz, andradite, ilvaite, and xonotlite assemblage. This bornite-rich ore contains substantial amount of sphalerite and pyrite and ubiquitous grains of clausthalite, hessite, tellurium, and gold. They represent a prime example of the sub-seafloor portion of a hybrid mafic-ultramafic oceanic hydrothermal system formed in an OCC along the slow spreading ridge of the Jurassic Piedmont-Ligurian Ocean. The peculiar mineralogical–textural character of the bornite-rich ore was driven by an interface coupled dissolution–precipitation process mediated by fluids.

Effect of Spark Plasma Sintering Temperature on the Microstructure and Thermophysical Properties of High-Silicon–Aluminum Composites

Spark plasma sintering is a process of rapid, low-temperature, and high-density sintering. Moreover, traditional sintering methods can solve the problems of large grain sizes and low densities. The sintering temperature plays a crucial role in influencing the physical properties of high-silicon–aluminum (Si-Al) composites. This work investigated the impact of temperature on the microstructure, interface, and physical properties of high-Si-Al composites by spark plasma sintering. The results demonstrate that when the powder was processed by ball milling at a sintering temperature of 565 °C, the material exhibited the densest microstructure with minimal pore formation. The average size of the silicon phase is the smallest. The material’s thermal conductivity is 134.6 W/m·K, the thermal expansion coefficient is 8.55 × 10−6 K−1, the Brinell hardness is 219 HBW, the density is 2.415 g/cm3, and the density reaches 97.75%. An appropriate sintering temperature facilitates particle rearrangement and dissolution–precipitation processes, enhancing the material structure and performance.

Research on the mitigation of redeposition defects on the fused silica surface during wet etching process.

The laser-induced damage of ultraviolet fused silica optics is a critical factor that limits the performance enhancement of high-power laser facility. Currently, wet etching technology based on hydrofluoric acid (HF) can effectively eliminate absorbing impurities and subsurface defects, thereby significantly enhancing the damage resistance of fused silica optics. However, with an increase in the operating fluence, the redeposition defects generated during wet etching gradually become the primary bottleneck that restricts its performance improvement. The composition and morphology of redeposition defects were initially identified in this study, followed by an elucidation of their formation mechanism. A mitigation strategy was then proposed, which combines a reduction in the generation of precipitation with an acceleration of the precipitation dissolution process. Additionally, we systematically investigated the influence of various process parameters such as extrinsic impurity, etching depth, and megasonic excitation on the mitigation of deposition defects. Furthermore, a novel multiple-step dynamic etching method was developed. Through comprehensive characterization techniques, it has been confirmed that this new etching process not only effectively mitigate redeposition defects under low fluence conditions but also exhibits significant inhibition effects on high fluence precursors. Consequently, it significantly enhances the laser damage resistance performance of fused silica optics.