High Zr Research Articles

Growth and characterization of high-quality Zr doped AlN epilayers

AlN stands out for its remarkable figures of merit for electronic and photonic devices, attributed to its ultrawide bandgap of ∼6.1 eV and an exceptionally high critical field of ∼15 MV/cm. More recently, zirconium (Zr) doped AlN (AlN:Zr) has also been identified as a promising material platform for the exploration of solid-state qubits for quantum information and technology, high performance piezoelectric acoustic wave resonators, and optically triggered ultrafast power switching devices facilitated by optically activating Zr related impurities. Despite the significant potential, the ability for producing AlN:Zr epitaxial structures has yet to be established. In this study, we have achieved AlN:Zr epilayers with a high Zr doping level [NZr] of up to 1020 cm−3 using industrial standard metal-organic chemical vapor deposition growth technique. High crystalline quality of AlN:Zr was confirmed by x-ray diffraction, revealing a narrow full width at half maximum of the (002) rocking curve at 216 arcsec for 1.8 μm thick epilayers deposited on sapphire at [NZr]=1020 cm−3. Zr doping was observed to slightly increase the c-lattice constant to 4.992 Å for AlN:Zr (at [NZr]=1020 cm−3) compared to 4.980 Å for undoped AlN. X-ray photoelectron spectroscopy measurement results verified the substitution of Zr at the Al site (ZrAl). The formation of (ZrAl–VN) complexes, which are predicted to possess all the desired properties required by quantum qubits, was confirmed through optical absorption studies. The realization of high-quality AlN:Zr epilayers significantly broadens the scope of technologically significant device applications for AlN.

Enhanced electrical reliability of Zr‐doped BaTiO3 nanoceramics: First‐principle calculations and experimental studies

AbstractWith the miniaturization of multilayer ceramic capacitors (MLCCs) and the increase of electric field on single‐layer dielectrics, it is essential for the development of nanograin high‐reliability dielectric materials. In this work, Zr‐doped BaTiO3‐based ceramics with an average grain size of 130–150 nm were prepared by a chemical coating method. The effects and intrinsic mechanisms of Zr concentration on microstructure, dielectric properties, and reliability were systematically investigated by theoretical calculations and experiments. Zr additives lower the migration barrier of the dopants, which consequently contributes to the formation of thick shell layers in the core‐shell structure and grain growth, affecting the temperature stability and DC bias characteristics of the dielectric constant. Owing to the large change rate of the Zr–O bond length, the introduction of Zr increases the migration barrier of oxygen vacancies. However, the decrease in the effective doping concentration of the shell part and the reduction in the number of grain boundaries of ceramics with high Zr content have a weakening effect on the inhibition of oxygen vacancy migration. An appropriate amount of Zr doping can adjust the dielectric properties and improve the reliability of BaTiO3‐based ceramics. This study provides a theoretical reference for the design of high‐quality MLCCs.

Remote sensing analysis and geodynamic setting of magmatic spessartine-almandine-bearing leucogranites, Um Addebaa area, southeastern Desert, Egypt: Bulk rock and mineral chemistry

This study aims to incorporate optical multispectral remote sensing, petrography, geochemical, and field investigations in producing mapping and surface abundance of garnet mineralization within Um Addebaa area, southeastern Desert of Egypt. Datasets of Landsat-8 OLI/TIRS, ASTER and Sentinel-2A (S2A) were handled and scaled enhanced to discriminate the units of lithologic rock and garnet mineralization. The spectral mapping techniques of constrained energy minimization (CEM) and matched filtering (MF) are used to detect the garnet-rich zones which confined to the leucogranites masses. These granites are spessartine-almandine-rich, certainly along the interaction with the ophiolitic mélange. Notably, they have high total alkalis, SiO2, and Al2O3, Rb, 104Ga/Al, Y, Zr, Pb, Rb/Sr, Al2O3/TiO2, and FeO/MgO, and strong Ti, Sr, and Ba depletion as well as low CaO/Na2O ratio (<0.3). These geochemical parameters reflecting calc-alkaline, and strongly peraluminous magma of S-type. They are derived by two episodes of partial melting clay-rich metapelite crustal rocks followed by extreme Fe-Ti oxides and feldspar fractionation. These leucogranites formed within extension tectonic regime during post-collisional episode, resulting raising of asthenosphere and partial melting of the crustal metasedimentary rocks. Garnet occurs as, aggregates and/or vein like-shape, subhedral to rounded grains, homogenous and rarely reveal weak zonation. It’s cracked and free of inclusions. It contains appreciated concentrations of FeO and MnO and minor amounts of CaO and MgO, dominantly spessartine-almandine end-member (Alm52-59Sps 31-36 Grs 8-12 Prp0.5-0.8 Adr0). Garnet chemical composition reflect it is magmatic origin with MnO- FeO-rich magma that is produced from in situ nucleation from strongly peraluminous magmas during post- collision setting.

Fluorous and Organic Extraction Systems: A Comparison from the Perspectives of Coordination Structures, Interfaces, and Bulk Extraction Phases.

Microscopic structures in liquid-liquid extraction, such as structuration between extractants or extracted complexes in bulk organic phases and at interfaces, can influence macroscopic phenomena, such as the distribution behavior of solutes, including extraction efficiency and selectivity. In this study, we correlated the macroscopic behavior of the Zr(IV) extraction from nitric acid solutions with microscopic structural information to understand at the molecular level the key factors contributing to the higher metal ion extraction performance in the fluorous extraction system as compared to the analogous organic extraction system. The fluorous and organic extraction systems consist of tris(4,4,5,5,6,6,7,7,7-nonafluoroheptyl) phosphate (TFP) in perfluorohexane and tri-n-heptyl phosphate (THP) in n-hexane, respectively. Extended X-ray absorption fine structure, neutron reflectometry (NR), and small-angle neutron scattering revealed the structural information around the central metal ion of the complex, at the interface, and in the bulk extraction phase, respectively. NR results showed that extractant molecules did not accumulate much at the interface in both extraction system. In the fluorous extraction system, extractant aggregates with a 1.46 nm radius of gyration (Rg) were formed after contact with nitric acid, and remained even after Zr(IV) extraction through the form of a 1:3 (Zr(IV):TFP) complex. In contrast, in the organic extraction system, only extractant dimers with Rg of 0.70 nm were formed and Zr(IV) is extracted through the form of a 1:2 (Zr(IV):THP) complex. We speculate that differences in the local coordination structure around the Zr(IV) ion and the structuration of the extractant molecules in the bulk extraction phase contribute to the high Zr(IV) extraction performance in the fluorous extraction system. In particular, the size of the aggregates hardly changed with increasing Zr(IV) concentration in the fluorous phase, which may be closely related to the absence of phase splitting in the fluorous extraction system.

Diverse magmatism along the northern margin of Tarim during the Ediacaran: Transition from Rodinian dispersing to Gondwana assemblage

The Ediacaran igneous rocks and sedimentary sequences play a key role for our understanding the transition from dispersing of the Rodinian continents to the assemblage of the Gondwana. On the other hand, some continental massifs at the marginal area of the Rodinia and Gondwana could preserve solid evidences for deciphering the geodynamic background from the break-up of Rodinia to the assemblage of Gondwana. In this contribution, we report field observations, petrography, ages and systematic geochemistry of the diverse Ediacaran igneous activities in the northern margin of the Tarim Block, which was favored as a marginal continental massif in the Rodinia configuration by most geologists. The Ediacaran igneous rocks along the northern margin of Tarim include the Baicheng and Yangxia granites, Tiemenguan syenite, Kurle mafic dykes and the basalt layers in the Zamoketi Formation (northeastern Tarim) and the Sugetbrak Formation (northwestern Tarim). Precise zircon UPb dating revealed that these distinct rocks were broadly coeval with crystallization/eruption ages of 630–600 Ma. Bulk-rock elemental and SrNd isotope compositions as well as zircon LuHf isotope compositions demonstrate that the Baicheng and Yangxia granites were derived from Neoarchean mafic lower crust and underwent intensive fractionation before their emplacements. The Tiemenguan syenites have potassic andesitic compositions, in combination with their pronounced enriched NdHf isotopes and extremely high Zr saturation temperatures (∼900 °C), we argue that their possible shoshonitic primary magmas were derived from previously metasomatized subcontinental lithospheric mantle source (amphibole-bearing) and then, coupling with assimilation and fractional crystallization (AFC) effects in magma chamber and/or en route to the emplacement space. This can account for their intriguing geochemical features. The ca. 615 Ma Zamoketi and Sugetbrak basalts and the slightly younger porphyrite dykes (ca. 580 Ma) cutting the Zamoketi basalt layer, show typical OIB-like geochemical signatures, they were most likely derived from a depleted asthenospheric mantle source with variable fractionation of olivine and pyroxene and negligible crustal contamination before eruption. On the whole, the geochemistry of the diverse Ediacaran igneous rocks unambiguously demonstrates that they were genetically related to an extensional environment. In combination with the significant passive continental features of the Ediacaran-Cambrian sedimentary sequences, we consider that these Ediacaran igneous rocks were the latest phase of igneous activity related to the dispersing of the Tarim at the margin of the Rodinia supercontinent.The dispersing of the Rodinian supra-continent was diachronic with the assemblage of the Gondwana. Late Tonian to Ediacaran dispersing of the Tarim from northern margin of Australia induced the opening of the Proto-Tethys Ocean. Then the initiation of the southward subduction of the Proto-Tethys Ocean at ca. 530 Ma (Fortunian) led to the Tarim assemblage to Gondwana at ca. 440 Ma.

High-resolution chemofacies and pore system characterization of the Pennsylvanian Cline Shale, Midland Basin, Texas

The connections between the depositional environment, sediment chemistry, and pore structure of deep-water mudstones are still not completely understood. This study: 1) investigates the sediment chemistry and the depositional conditions of the Pennsylvanian Cline Shale chemofacies in the center of the Midland Basin, 2) characterizes the conditions favorable to organic matter accumulation of each mudstone chemofacies, and 3) examines the connection between the pore structure and the mudstones’ paleo-environmental and paleo-geochemical context and processes. This study uses X-ray fluorescence (XRF) and statistical methods (Isolation Forest, Principal Component Analysis, and K-means) to identify four chemofacies of 127 m of Cline Shale core from the Matthew 'D' 0906 well located in the Midland Basin depocenter in Glasscock County, Texas. In addition, petrographic and scanning electron microscopy and measurements by dual-energy computed tomography, X-ray diffraction, Rock-Eval pyrolysis, N2 isothermal adsorption tests, and mudrock reservoir properties were conducted on thin-sections, core slabs, and samples to understand the bulk geochemistry and petrophysical properties of the mudstones. Four chemofacies are identified: (1) Siliceous Mudstone with high Zr and low Ca and P, (2) Calcareous-argillaceous Mudstone I with high Ca and Zr, and low P, (3) Argillaceous Mudstone with high P and low Ca and Zr, and (4) Calcareous-argillaceous Mudstone II with high Ca and P, and low Zr. Based on elemental distribution, the first two and last two chemofacies are interpreted as low sea-level deposits and high sea-level deposits, respectively. Water stratification and P regeneration accounted for the highest total organic carbon (TOC) content, which resulted in the high porosity and pore volume of the low sea-level Siliceous Mudstone chemofacies, especially visible in the 8 nm–186 nm organic matter pores. Carbonate input hinders the development of the inorganic pore system, especially for organic lean Calcareous-argillaceous Mudstones. Nine sea-level cycles were observed in the cores and correlated to nine US mid-continent cycles attributed to the 405-kyr Milankovitch parameter (long orbital eccentricity) during the late Pennsylvanian. We hypothesize that late Pennsylvanian climate change, paced by orbital cycles, controlled the distribution and stacking pattern of mudstone chemofacies, which also controlled source rock quality and consequent pore system development.

Geochemistry and conditions of formation of Mesoarchean banded iron formations (BIF-1) from the Kostomuksha Greenstone belt, Karelian Craton

Three variably old groups of banded iron formation (BIF) are known in the Kostomuksha Greenstone belt (KGB) of the Karelian Craton. This paper deals with the earliest of them, Mesoarchean (2.87–2.81 Ga) – BIF-1. BIF-1 occurs among the komatiite-basalt unit of the KGB. BIF-1 consists mainly of quartz and magnetite, with varying amounts of amphibole, biotite, and garnet; they contain 48.3-58.6 SiO2 and 21.34–33.82 wt. %, Fe2O3T, suggesting that the rocks are BIF. BIF-1 of the KGB, as well as most Archean BIFs, contain high Fe2O3T, concentration, display a contrasting positive Eu anomaly, lost of Ce anomaly, the depletion of LREE relative to HREE. However, they stand out among other BIFs with high Al2O3, TiO2, MgO, K2O, Cr, Ni, Zr, Ba, Cu and Zn concentrations. BIF-1 was formed in a marine basin in an anoxic atmosphere due to hydrothermal fluids, the proportion of which varies from 20 to 80 %, and a terrigenous component derived mainly from basalts, komatiites, and dacites in host rocks. Mesoarchean BIF-1 of the KGB s was formed in a small rift within an oceanic volcanic plateau, the formation of which is associated with the influence of a mantle plume on the oceanic lithosphere.

A single-phase Nb25Ti35V5Zr35 refractory high-entropy alloy with excellent strength-ductility synergy

Refractory high entropy alloys (RHEAs) are promising candidates for high-temperature structural materials due to their excellent high-temperature performance. However, the room-temperature brittleness of most alloys results in poor plastic formability, thereby limiting their engineering applications. In this study, Nb25Ti35V5Zr35 alloy with cold-rollability was developed, and its phase stability, tensile mechanical properties, elastic properties, strengthening mechanism, and deformation mechanism were investigated by combining experiments, CALPHAD, DFT and molecular statics (MS) methods. The results demonstrate that Nb25Ti35V5Zr35 alloy possesses good phase stability, with both the as-cast and annealed states maintaining a single-phase BCC structure without undergoing phase transformation. The tensile yield strength of the alloy reaches its peak at 1152 MPa in the cold-rolled condition, while its annealed state exhibits an optimal balance of strength and plasticity, with a yield strength of 836 MPa and an elongation of 22.45 %, respectively. Solid solution strengthening is the primary source of its high strength, with V and Zr playing key roles in this strengthening mechanism. Dislocation slip plays a dominant role in plastic deformation. Additionally, compared to traditional BCC alloys, the significance of edge dislocations in the deformation process is notably enhanced, with the {112} plane serving as the preferred slip plane for dislocations. DFT results indicate that the alloy exhibits significant anisotropy in both Young's modulus and shear modulus. This work contributes to understanding the material properties of the Nb25Ti35V5Zr35 alloy and provides a reference for the design of new ductile RHEAs.

Anatomy and genesis of the world’s largest carbonate-hosted Zn-Pb deposit: New insights from ore characteristics, Zn-Pb-C-O isotopes, and trace element constraints of the Huoshaoyun deposit, Karakorum Range, Xinjiang

The Huoshaoyun deposit in the Karakorum area of NW China is the world’s largest zinc-lead carbonate ore deposit. Here we investigate the genesis of the mineralization based on multiproxy investigations. The deposit contains zinc-lead carbonate and sulfide minerals, with smithsonite (Smt), cerussite (Cer), and sulfides accounting for 85%, 10%, and 5% of the total lead and zinc resources, respectively. Three ore-forming stages, involving Smt, Cer, and sulfides ores were summarized. The Smt mineralization is characterized by veined, massive, and stratified Smt forming horizontal sedimentary layered ore and vertical feeder veins similar to the SEDEX-type deposits. The sulfide and Cer veins display typical hydrothermal characteristics and are superimposed on the massive Smt ores. The Smt ores show high Li, Be, Cr, Y, Ba, Nd, Yb, and Zr contents, whereas the Cer veins have extremely high Sr contents (up to 3814–9174 ppm) and low Zr contents (less than 0.01 ppm). Galena and sphalerite show higher Cd concentrations compared to Smt and Cer ores.The Smt ores differ with different spatial locations, with Smt ores formed at the vent have δ66Zn values of +0.15‰ to +0.21‰, the massive Smt formed close to the vent show a value of +0.13‰, and those formed away from the vent show a value of 0.05‰, all values being close to 0. The sulfides have δ66Zn values of −0.09‰ to +0.04‰. The C-O isotopes of Smt ores are similar to both altered and unaltered host limestone, suggesting that the limestone was a potential source for carbon and oxygen. Quartz with veined Smt shows magmatic signatures with δ18OVSMOW of +1.14‰ to +2.23‰, high Pb (115–401 ppm) and Zn concentrations (390–997 ppm), whereas quartz associated with sulfide has meteoric fluid signature with the lowest δ18OVSMOW (−14‰ to −10.7‰), low Pb (11.6–49.0 ppm) and Zn (18.1–72.8 ppm) concentrations. The temperature of equilibration computed based on oxygen isotope fractionation between Smt and coeval quartz indicate a dual source with that of quartz derived from an aqueous fluid, whereas the source for Smt might involve CO2 or HCO3−.We trace multiple metallogenic stages for this deposit including exhalation, hydrothermal deposition, and fault-controlled sulfide vein formation. The largest orebody (III-1) preserves a 16 Mt reserve of Zn and was formed by crust-mantle interaction at ca. 195 Ma in the early development of the Linjitang post-arc rift system. Fluid convection, zinc enrichment driven by granitic magma, volcanic activity, and karst alteration induced by acid rain in a lagoonal environment promoted ore enrichment.

Metal remobilization at the Nibao gold deposit in Youjiang basin, SW China: Implications from mineral texture, trace element and sulfur isotope compositions of sulfides and TiO2 polymorphs

Multistage mineralization overprinting is important for the formation of giant hydrothermal gold deposits. The Youjiang basin in SW China has undergone at least three major deformation phases in the Mesozoic, but their relationship with the large-scale gold accumulation in the region remains enigmatic. Here, we study the large Nibao gold deposit (reserve > 70 t Au) in the northern part of the basin, which has both fault-controlled and stratabound orebodies. We identified a pre-ore stage and syn-ore stage including four tectono-hydrothermal (T-H) substages (i.e., T-H stage 1, 2, 3 and 4) for the local mineralization at Nibao. The pre-ore stage is dominated by coarse-grained pyrite coexisting with TiO2 polymorphs in the Middle-Late Permian basaltic rocks. The T-H substage 1 is characterized in that the sedimentary pyrites are brecciated in bedding-parallel faults. Fluorination and silicification occur in the T-H substage 2, which is re-brecciated at the T-H substage 3 forming the highest gold grade ore in high-angle thrust fault. The T-H substage 4 presents as fault reactivation within minor calcite and pyrite deposition. Mineralogy and in-situ trace element analyses reveal that mineral dissolution and reprecipitation (incl. dolomite, auriferous pyrite and TiO2 polymorphs) is ubiquitous during the multistage tectono-hydrothermal process, and the continuous alteration overprinting may have promoted gold accumulation. This replacement process of different generations of auriferous pyrite is also recorded by their inherited sulfur isotopes, giving a narrow δ34S (−3.1 to + 2.1 ‰) range. Anatase is the main accessory phase of TiO2 polymorphs, as identified with LA-ICP-MS trace element and laser Raman spectroscopic analyses. Moreover, the anatase can been divided into two types (type-I and II) based on their texture, alteration and chemistry. The type-I anatase commonly occurring in the stratabound ore is characterized by higher Zr (mean 1,730 ppm), V (mean 1,412 ppm), and Cr (mean 110 ppm) contents than type-II that coexists with zoned pyrite in the fault-controlled ore (mean 26 ppm, 187 ppm, and 38 ppm, respectively). Additionally, W (mean 636 ppm) and Mg (10,021 ppm) in type-II are much higher than type-I ones (mean 135 ppm W and 476 Mg). These features show that the sedimentary-stage Zr-V-Cr-rich type-I anatase was dissolved via fluid metasomatism, and reprecipitated as the hydrothermal-stage W-Mg-rich and Zr-poor anatase, with gold gradually enriched. Besides, the anatase phase of TiO2 polymorphs also indicates that the Nibao gold deposit was formed under low pressure–temperature condition. Overall, we propose that the Nibao is a Carlin-type gold deposit, dominated by multistage tectono-hydrothermal events.

Early Cretaceous fayalite-, ferrosilite-, and biotite-bearing rhyolitic porphyries in the Baishuizhai area, South China: Formation by fractional crystallization in the shallow crust

Fayalite- and ferrosilite-bearing felsic igneous rocks are a distinctive category of A-type granitic magmas, and the origins of these rocks have proved controversial. In addition, the shallow-crust high-silica rhyolitic magmas responsible for such rocks are considered to have higher viscosities than their plutonic equivalents, which casts doubt on whether fractional crystallization could have occurred during the evolution of these high-silica melts. Here, we report a study of earliest Early Cretaceous (145–142 Ma) fayalite- and ferrosilite-bearing rhyolitic porphyries (FFBRPs) and closely associated biotite-bearing rhyolitic porphyries (BBRPs) from the Baishuizhai area, Guangzhou, Guangdong Province, South China. The Baishuizhai suite provides an excellent opportunity to establish the magmatic origins and evolutionary processes responsible for the FFBRPs. Rocks from the Baishuizhai suite have SiO2 contents of 73.2–77.7 wt%, Na2O + K2O contents of 7.83–9.42 wt%, and Fe2O3T contents of 1.52–2.97 wt%. They have A-type granite features including mineral assemblages (euhedral fayalite and ferrosilite in addition to anhedral amphibole and biotite) and geochemical characteristics [e.g., high 10,000 × Ga/Al values (3.7–4.7), high FeOT/MgO ratios (13.0–34.8), and high Zr (245–514 ppm) and Nb (56.4–96.5 ppm) contents]. The rocks have slightly enriched in situ plagioclase Sr [(87Sr/86Sr)i = 0.7070–0.7076] and whole-rock Nd [εNd(t) = −2.3 to −2.0] compositions and depleted zircon Hf isotopic compositions [εHf(t) = −0.9 to +7.0] relative to chondrite, as well as higher zircon δ18O values (6.3‰–7.8‰) and intermediate in situ plagioclase Pb isotopic compositions [(206Pb/204Pb)i = 18.368–18.727, (207Pb/204Pb)i = 15.488–15.673, and (208Pb/204Pb)i = 38.049–38.801] compared with depleted mantle. We infer that the primary magmas of this rock suite were formed by mixing of mantle-derived magmas with subordinate (20%–50%) metasedimentary-rock-derived magmas. Fayalite and ferrosilite in the FFBRPs were most likely crystallized from dry, hot, and reduced magma in a lower (<16.5 km depth) chamber. The lower magma gradually evolved during ascent to a water-enriched magma in an intermediate chamber at a shallow depth (3–4 km), forming the FFBRPs (elevation: 129–168 m). Finally, the residual melts migrated upward and resided in an upper (<3 km depth) chamber, forming the BBRPs (elevation: 196–824 m). According to the established temporal–spatial distribution of Early Cretaceous A-type granites and adakitic rocks in South China, we suggest that the Paleo-Pacific plate underwent diachronous rollback, starting during the earliest Early Cretaceous. This rollback enhanced the degree of crust–mantle interaction in the Guangzhou area.

1.88 Ga granitoids at Sorsakoski, Central Finland: A-type magmatism within the Raahe-Ladoga suture zone

Four quartz monzonite – granite intrusions forming the Sorsakoski granite lithodeme, are found within the Raahe-Ladoga suture zone in Central Finland. The prevailing potassium feldspar megacrystic quartz monzonites and granites form a bimodal association with diorites and gabbros. The granitoids are mainly calc-alkaline, ferroan, per- to metaluminous, and have high Zr and REE contents. Dominant mafic minerals are biotite and hornblende, clinopyroxene and orthopyroxene are locally present. The mafic units display effects of fractionation of clinopyroxene. In our interpretation, these intrusions were emplaced during regional late stages of deformation and post-crystallisation deformation partitioned into major shear zones leaving bulk of the intrusions relatively undeformed. Based on one new (1876 ± 6 Ma) and one pre-existing (1882 ± 5 Ma) U-Pb zircon age determination, the crystallisation age of the granitoids can be assumed at ca. 1880 Ma. Based on mineralogy, petrography, geochemistry, bimodal nature of magmatism and age, we correlate these intrusions to the A-type rocks of the previously described Saarijärvi suite. This shows that the syn-orogenic A-type magmatism extended eastwards beyond the Central Finland Granitoid Complex.

Electrochemical behavior and passivation film characterization of TiZrHfNb multi-principal element alloys in NaCl-containing solution

In this work, the electrochemical behavior and passivation film characteristics of a TiZrHfNb multi-principal element alloy (MPEA) with an equal atomic ratio in Cl− solution were studied. The effect of constituent metals on the overall corrosion resistance of alloys focused on different aspects. Ti could reduce the point defect density of the passivation film, while Nb kept the passivation film stable at a high potential, Hf and Zr provided high resistance and charge transfer resistance to the passivation film, and hydroxides enhanced the repair ability of the passivation film. There was also a synergistic effect between the alloying elements.

Plastic quasicrystal-containing alloys prepared by annealing pseudo-high entropy Zr70–75(Al, Ni, Cu, Ag)25–30 glassy alloys

A glassy (G) phase was formed for Zr-rich Zr70–75(Al, Ni, Cu, Ag)25–30 (atomic percent, at.%) melt-spun alloy ribbons. These glassy alloys exhibit the glass transition, followed by a supercooled liquid region and then three-stage crystallization. The glass transition temperature and the onset temperature for the first-stage crystallization (Tx1) decrease from 630 to 668 K, respectively for the 70Zr alloy to 619 and 652 K, respectively for the 75Zr alloy. The first-stage exothermic peak is due to the precipitation of an icosahedral quasicrystal (IQ) phase. The IQ particle size decreases from 10 nm to 6 nm with increasing Zr content from 70 at.% to 74 at.%. The [G + IQ] phases change to Zr2Ni + Zr2(Cu, Ag) phases after the second exothermic peak and then Zr2Ni + Zr2(Cu, Ag) + Zr5Al3 phases after the third stage. It is noticed that the as-spun glassy alloy ribbons as well as the annealed [G + IQ] phase ribbons exhibit good bending plasticity. Furthermore, the 70Zr thicker ribbons also exhibit high tensile fracture strength of 1090–1187 MPa and plastic elongation of 0.17 %–0.42 %. The fracture mode is similar to that of ordinary bulk metallic glasses. The Vickers hardness (Hv) is 480 for 70Zr alloy and decreases to 436 for 75Zr alloy. The precipitation of IQ phase causes a significant increase in Hv to about 554. The formations of glassy alloys with high Zr contents of 70 at.%–75 at.% by melt spinning as well as the [G + IQ] phase alloys with good bending plasticity by annealing hold promise for the creation of a new type of engineering material, transcending mere academic novelty.

Mineralization of Zr-REE-Y in the Ngaoumbol iron formations, central Cameroon: Insights from petrography, mineral chemistry and whole rock geochemistry

The increasing importance of rare earth elements (REE) and critical metals in contemporary society has led us to investigate the mineral potential of the Ngaoumbol area, located within Cameroon's Central African Fold Belt (CAFB). In this study, we have conducted a comprehensive analysis that includes petrography, whole rock geochemistry, and mineral chemistry, along with the application of an outlook coefficient known as Koult, with the aim to evaluate the prospectivity of the Ngaoumbol iron formations as a potential source of REE-Y resources. This coefficient is defined as the ratio of the relative abundance of critical Rare Earth Elements to the relative abundance of excess REE. The iron formations in the Ngaoumbol area are fine-to medium-grained foliated rocks with alternating magnetite and actinolite bands and quartz bands, suggesting a sedimentary parentage. These rocks have an average REE-Y content of 1438.43 ppm and a Koult of 0.77, indicating their potential as raw sources for REE. Furthermore, the investigated samples exhibit high average Zr content (7748 ppm), suggesting that the rocks may host potentially economic Zr ore. The Zr-REE-Y mineralization in the Ngaoumbol area is hosted in detrital zircon, monazite and xenotime, probably deriving from the weathering of alkaline/subalkaline rocks surrounding the deposits. Our findings suggest that the Ngaoumbol area has promising REE and Zr resources. However, further exploration and evaluation are necessary to determine the extent and economic viability of these resources.

A strong and ductile biocompatible Ti40Zr25Nb25Ta5Mo5 high entropy alloy

A non-equiatomic high entropy alloy (HEA) Ti40Nb25Zr25Ta5Mo5 (at.%) was designed by replacing 5% Ta with 5% Mo in a precursor Ti40Nb25Zr25Ta10 HEA for improved mechanical properties and reduced density. The Ti40Nb25Zr25Ta5Mo5 HEA fabricated by copper mould casting exhibited a nearly equiaxed grain structure (grain size: 96 ± 16 μm), but within each equiaxed grain, dendritic structures are discernible in the backscattered electron imaging mode. These dendrites are enriched in Ta, Nb and Mo, while the inter-dendritic regions contain higher Zr and Ti. The as-cast HEA achieved tensile yield strength (σ0.2) of 976 ± 8 MPa and strain to fracture (εf) of 16.80 ± 1.86%, well above the minimum requirements of σ0.2 and εf for medical-grade titanium alloy Ti–6Al–4V (759 MPa and 10%). The formation of microscale and nanoscale shear bands and the presence of significant dislocations in the shear band boundary region played a key role in allowing this as-cast HEA to achieve the excellent combination of tensile strength and ductility. Furthermore, the HEA exhibited a lower wear rate, lower coefficient of friction and much higher corrosion resistance in Hank's solution (electrochemical assessments) than Ti–6Al–4V, making it a promising alternative biomedical alloy.

One-Step Synthesized Solid Acid Catalyst with High Zr Content for Efficient and Green PET Degradation in Supercritical CO2

One-Step Synthesized Solid Acid Catalyst with High Zr Content for Efficient and Green PET Degradation in Supercritical CO₂

Ultrapotassic plutons as a source of uranium of vein-type U-deposits (Moldanubian Zone, Bohemian Massif): insights from SIMS uraninite U–Pb dating and trace element geochemistry

The Bohemian Massif hosts significant hydrothermal U-deposits associated with shear zones in the high-grade metamorphic basement. But there is a lack of evidence of a genetic link between mineralization and U-fertile igneous rocks. This contribution provides constraints on the major U source of the vein-type U-deposits, the timing of ore formation and the metallogenetic model. The anomalous trace element signatures of the low-temperature hydrothermal deposits (high Zr, Y, Nb, Ti, ∑REE) and their close spatial relation with ultrapotassic rocks of the durbachite series point to a HFSE and REE enriched source rock. The durbachites have high U content (13.4–21.5 ppm) mainly stored in magmatic uraninite and other refractory minerals (e.g., thorite, zircon, allanite) that became metamict over a time interval sufficient to release U from their crystal structure, as suggested by the time gap between emplacement of the durbachites (EMP uraninite U–Pb age ~ 338 Ma) and hydrothermal activity (SIMS uranium ore U–Pb age ~ 270 Ma). Airborne radiometric data show highly variable Th/U ratios (1.5–6.0), likely reflecting a combination between (1) crystallization of magmatic uraninite, (2) hydrothermal alteration, and (3) leaching and mobilization of U along NW–SE-trending fault zones, manifested by elevated Th/U values in the radiometric map. The presence of rare magmatic uraninite in durbachites suggests almost complete uraninite dissolution; EMP imaging coupled with LA-ICP-MS analyses of refractory accessory phases revealed extensive mobilization of U together with HFSE and REE, providing direct evidence for metal leaching via fluid-driven alteration of radiation-damaged U-rich minerals. The large-scale HFSE and REE mobilization, demonstrated by the unusual trace element signatures of the U-deposits, was likely caused by low-temperature (270–300 °C), highly alkaline aqueous solutions containing F-, P-, and K-dominated complexing ligands. The first SIMS U–Pb age of 270.8 ± 7.5 Ma obtained so far for U-mineralization from the Bohemian Massif revealed a main Permian U mineralizing event, related to crustal extension, exhumation of the crystalline basement, and basin formation, as recorded by U–Pb apatite dates (280–290 Ma) and AFT thermal history models of the durbachites. The Permo-Carboniferous sedimentary cover probably represented a source of oxidized basinal brines infiltrating the basement-hosted durbachite plutons and triggering massive metal leaching. The interaction between basin-derived brines and durbachites resulted in significant modification of the chemical composition of the hydrothermal system (K and F release during biotite chloritization, P liberation through monazite alteration), leading to the formation of ore-bearing fluids responsible for the metallogenesis of the basement-hosted unconformity-related U-deposits in shear zones in the Bohemian Massif.

Dynamics-driven tailoring of Zr-embedded hierarchical ZSM-5 zeolites for enhanced catalytic performance from furfural to alkyl levulinate

The tandem reaction for generation of alkyl levulinate (AL) from bio-derived furfural (FUR) is environmental-friendly, in which the bifunctional catalyst with both metal active sites and acid sites are required. In this contribution, a MFI-type nanosponge zeolite with Zr-Al co-framework (Zr@NPZ) were one-pot hydrothermally synthesized using dual-template method. Series characterizations demonstrate that, highly dispersed Zr species embeds in the hierarchical zeolite framework and exhibits typical Lewis acids. Using isopropanol as solvent, Zr@NPZ catalyst gives isopropyl levulinate (IPL) yield up to 75.5 wt% at 180 °C after 2 h reaction from FUR, through sequenced transfer hydrogenation and hydrolysis, with production rates of 11.5 mmol g−1h−1. Moreover, although the enhanced acidities accelerate the conversion rates of FUR, the generation of β-angelica lactone (AGL) from 2-(isopropoxymethyl)furan (IPMF) and conversion of IPL to γ-valerolactone (GVL) are promoted, sacrificing the yield of IPL in the product. The synergism between high dispersed Zr species and moderate acid distribution lead to relative high yield of target IPL.

Achieving strength-ductility synergy in zirconium via ultra-dense twin-twin networks

Hierarchical nano-twinned structures have been proven to be an effective way in breaking the strength-ductility dilemma in face-centered cubic metals. However, it is challenging to introduce high-density of twinned structures in hexagonal-close packed (HCP) metals because deformation twinning are limited in fine-grained structures. Here, we propose an approach to introduce ultra-dense twin-twin networks in high purity HCP Zr with ultra-large grain size (>200 µm) via cryogenic biaxial-rolling. Tensile tests show that the yield strength and the elongation of the densely twinned Zr are increased by 76.5 % and 28.6 % compared with its coarse-grained counterparts, and reaches 360 MPa and 13.5 %, respectively. The strength of twinned Zr is enhanced by the synergy effect of grain refinement (from 241 µm to 1.2 µm) and the obstruction of dislocations by high-density intersecting twin boundaries (TBs). The ductility and strain-hardening ability are improved by the activation of massive prismatic 〈a〉 and pyramidal 〈c + a〉 dislocations. The three-dimensional TB networks are effective 〈c + a〉 dislocation sources which enhance the plasticity along 〈c〉 direction. Our work provides a new strategy to design ultra-dense twinned structures and sheds light on the twinning-induced plasticity in HCP metals.