Separation of hafnium and zirconium from ti- and fe-rich geological materials by extraction chromatography

This paper presents a new chemical separation method for Hf and Zr from rocks using extraction chromatographic resins prepared from inert polymeric supports and the liquid anionic exchangers tri-n-octylamine or trioctylmethylammonium chloride (Aliquat 336). The method was developed using basaltic and trachyandesitic rocks with high contents of Al, Fe, and Ti. A 100-mg rock sample was decomposed with HF-HNO(3)-HClO(4) and fumed with HClO(4). The residue of this process was dissolved in 10 M HCl and then loaded on the column (6 mm i.d. × 75 mm). The major elements (Al, Ca, Mg, Ti, etc.) were eluted with 10 mL of 10 M HCl, and then Hf, Zr, and Fe were eluted sequentially using 20 mL of 8 M HCl, 20 mL of 2 M HCl, and 5 mL of 1 M HNO(3). The removal efficiency of major elements (Al, Fe, Ca, Mg) was greater than 99% and that of Ti was greater than 95%. The recoveries of Hf and Zr were better than 90% and the Zr/Hf ratio decreased from the natural ratio of 45 in the rock sample to 0.3 in the Hf fraction. This method provides an alternative to the less straightforward procedures based on several stages of ion-exchange separation and might be used for sample preparation prior to (176)Hf/(177)Hf determinations by magnetic sector multicollection ICPMS.     

Ion-exchange separation of Zr and Hf microamounts in dilute HCl/HF solutions: A model system for chemical identification of Rf and study of its properties

A procedure was developed for selective separation of Group IV elements from Sr and Lu, followed by rapid separation of Zr and Hf by cation-exchange chromatography in dilute HCl/HF solutions. The possibility of using this procedure for chemical identification and determination of decay parameters of the new isotope ²⁶⁷Rf was demonstrated.     

Effect of TBP on Extraction of REE and TPE with 4d Element Salts of Dibutylphosphoric Acid

Extraction properties of 4d element (Ti, Zr, and Hf) salts of dibutylphosphoric acid (HDBP) are examined. In extraction of Eu from nitric acid solutions, the optimal [HDBP]/[M] ratio depends on the presence of TBP and a diluent in the extraction system and also on the HNO₃ concentration in solutions. With decane used as a diluent instead of xylene, the distribution coefficients of the extracted elements increase, and the extracting properties of the Zr and Hf salts become more similar. The extraction characteristics of these salts are similar over the entire examined range of HNO₃ concentrations. At the same time, the difference between the Zr and Hf salts in the extractive power applies to all the lanthanides. The extraction properties of the Ti salt strongly differ from those of the Zr and Hf salts. Thorough study of the behavior of the Ti salt is complicated by its limited solubility in organic solvents.     

Current Progress of Hf （Zr）-Based High-k Gate Dielectric Thin Films

With the continued downscaling of complementary metal-oxide-semiconductor field effect transistor dimensions, high-dielectric constant （high-k） gate materials, as alternatives to SiO2, have been extensively investigated. Hf （Zr）-based high-k gate dielectric thin films have been regarded as the most promising candidates for high-k gate dielectric according to the International Technology Roadmap for Semiconductor due to their excellent physical properties and performance. This paper reviews the recent progress on Hf （Zr）-based high-k gate dielectrics based on PVD （physical vapor deposition） process. This article begins with a survey of various methods developed for generating Hf （Zr）-based high-k gate dielectrics, and then mainly focuses on microstructure, synthesis, characterization, formation mechanisms of interfacial layer, and optical properties of Hf （Zr）-based high-k gate dielectrics. Finally, this review concludes with personal perspectives towards future research on Hf （Zr）-based high-k gate dielectrics.     

Temperature Dependent Thermal and Elastic Properties of High Entropy (Ti0.2Zr0.2Hf0.2Nb0.2Ta0.2)B2: Molecular Dynamics Simulation by Deep Learning Potential

High entropy diborides are new categories of ultra-high temperature ceramics,which are believed promising candidates for applications in hypersonic vehicles.However,knowledge on high temperature thermal and mechanical properties of high entropy diborides is still lacking unit now.In this work,variations of thermal and elastic properties of high entropy (Ti0.2Zr0.2Hf0.2Nb0.2Ta0.2)B2 with respect to temperature were predicted by molecular dynamics simulations.Firstly,a deep learning potential for Ti-Zr-Hf-Nb-Ta-B diboride system was fitted with its prediction error in energy and force respectively being 9.2 meV/atom and 208 meV/(A),in comparison with first-principles calculations.Then,temperature dependent lattice constants,anisotropic thermal expansions,anisotropic phonon thermal conductivities,and elastic properties of high entropy (Ti0.2Zr0.2Hf0.2Nb0.2Ta0.2)B2 from 0 ℃ to 2400 ℃ were evaluated,where the predicted room temperature values agree well with experimental measurements.In addition,intrinsic lattice distortions of (Ti0.2Zr0.2Hf0.2Nb0.2Ta0.2)B2 were analyzed by displacements of atoms from their ideal positions,which are in an order of 10-3 (A) and one order of magnitude smaller than those in (Ti0.2Zr0.2Hf0.2Nb0.2Ta0.2)C.It indicates that lattice distortions in (Ti0.2Zr0.2Hf0.2Nb0.2Ta0.2)B2 is not so severe as expected.With the new paradigm of machine learning potential,deep insight into high entropy materials can be achieved in the future,since the chemical and structural complexly in high entropy materials can be well handled by machine learning potential.     

Cation-exchange separation of Group V elements: Model experiments on isolation and chemical identification of Db

A cation-exchange procedure was developed for separating Nb from Ta, Pa from Ta, and Nb, Pa, and Ta from Zr, Hf, and lanthanides in dilute HC1/HF solutions. The stability of the fluoride complexes of Group IV and V elements decreases in the following order: Nb ～ Pa > Zr > Hf > Ta. This procedure can be used in experiments on synthesis of superheavy nuclei for isolation of Db from the reaction products and for its chemical identification.     

Structures and electronic properties of M2C2 @ C78 (M = Ti, Zr, Hf): a density functional theory study

A systematic DFT investigation has been conducted to explore the structures and electronic properties of the metal-carbide endofullerenes M2C2 @ C78 (M = Ti, Zr, Hf) at the PBE/DNP level of theory. The theoretical calculations predicted the following: (i) this series of endofullerenes have the valence states [M4+]2C2(2-) @ C78(6-) (ii) the structure of the [M2C2](6+) cluster encapsulated in the C78(6-) (D3h) cage varies with the increasing of the ionic radius of M4+, i.e., from a linear M-C [triple bond] C-M geometry for M = Ti, through a zigzag geometry for M = Hf to a side-on binding mode for M = Zr; (iii) M2C2 @ C78 (M = Zr, Hf) should display interesting intramolecular dynamic behavior at room temperature, i.e., the encapsulated C2(2-) moiety can rotate freely around the C3-axis of the C78(6-) (D3h) cage; (iv) the [Ti2C2]6+ in the lightest Ti2C2 @ C78 is far more fixed by adopting the linear Ti-C - C-Ti geometry; (v) the order for their ionization potentials is Ti2C2 @ C78 < Hf2C2 @ C78 < Zr2C2 @ C78, whereas their EAs follow the order: Ti2C2 @ C78 < Hf2C2 @ C78 approximately Zr2C2 @ C78. The predicted redox properties of these endofullerenes suggest that Zr2C2 @ C78 is synthetically as approachable as Hf2C2 @ C78.     

新型镍基高温合金化学成分分析技术研究

研究了新型镍基高温合金中Ｔａ、Ｚｒ和Ｈｆ的分析技术，并探讨了ＩＣＰ－原子发射光谱法中的某些影响因素及其校正。该分析方法用于合金样品分析取得了满意的效果。     

A Group of Cu（Zr）-based BMGs with Critical Diameter in the Range of 12 to 18 mm

A group of Cu（Zr）-based bulk metallic glasses （BMGs） with critical diameter （De） in the 12 to 18 mm range have been obtained using copper mould casting. In the Cu-Zr-Y-Al quaternary system, a new record of Dc=14 mm was established for Cu-based compositions, and 16 mm for compositions based on equi-atomic CuZr. Additional partial substitution of Hf for Zr further elevated the Dc to 18 mm at Cu42Zr43Hf1.5Y3.5Al10.     

Lanthanide Contraction as a Design Factor for High‐Performance Half‐Heusler Thermoelectric Materials

Forming solid solutions, as an effective strategy to improve thermoelectric performance, has a dilemma that alloy scattering will reduce both the thermal conductivity and carrier mobility. Here, an intuitive way is proposed to decouple the opposite effects, that is, using lanthanide contraction as a design factor to select alloying atoms with large mass fluctuation but small radius difference from the host atoms. Typical half‐Heusler alloys, n‐type (Zr,Hf)NiSn and p‐type (Nb,Ta)FeSb solid solutions, are taken as paradigms to attest the validity of this design strategy, which exhibit greatly suppressed lattice thermal conductivity and maintained carrier mobility. Furthermore, by considering lanthanide contraction, n‐type (Zr,Hf)CoSb‐based alloys with high zT of ≈1.0 are developed. These results highlight the significance of lanthanide contraction as a design factor in enhancing the thermoelectric performance and reveal the practical potential of (Zr,Hf)CoSb‐based half‐Heusler compounds due to the matched n‐type and p‐type thermoelectric performance.     

The preparation of Ln2MX5 where Ln = rare earths,M = Zr and Hf,and X = S,Se

Compounds of the title formula were prepared by reactions of the elements in evacuated silica tubes in the presence of iodine. The compounds formed for the following combinations: When M = Zr or Hf and X = S, all rare earths except Eu and Yb. When M = Zr and X = Se, rare earths between La and Tb, except Eu. When M = Hf and X = Se, rare earths La and Ce. X-Ray powder patterns were indexed on the basis of orthorhombic cells analogous to that of U₃S₅. Electrical measurements show high-resistivity semiconduction for La₂ZrS₅ and Ce₂HfS₅ but lower resistivity for Sm₂HfS₅, perhaps indicative of the presence of some Sm⁺².     

Ab initio study of stacking faults and deformation mechanism in C15 Laves phases Cr2X (X = Nb,Zr, Hf)

Based on the synchroshear model, the formation of stacking fault and twinning fault in C15 Laves phases is modeled, then the generalized stacking fault energy curves and deformation mechanism in C15 Laves phases Cr₂X (X = Nb, Zr, Hf) alloys are investigated by ab initio calculations based on the density functional theory. The results demonstrate that the unstable stacking fault and twinning fault energies of C15 Laves phases Cr₂X (X = Nb, Zr, Hf) by the synchroshear are still large while the stable stacking fault and twinning fault energies are low, and the deformation modes by extended partial dislocation and twining are feasible in C15 Laves phases Cr₂X (X = Nb, Zr, Hf). Moreover, the Cr₂Nb has the largest deformation twinning tendency, followed by Cr₂Zr and Cr₂Hf. The evolution of electronic structure during the synchroshear process is further studied to unveil the intrinsic mechanism for the formation of stacking fault and twinning fault in C15 Laves phases Cr₂X (X = Nb, Zr, Hf).     

Evaluation of glass forming ability in binary and ternary metallic alloy systems – an application of thermodynamic phase diagram calculations

Abstract

The glass forming ability (GFA) of a wide range of binary and ternary alloy systems (Au–Si, Pd–Si, Ti–Be, Zr–Be, Hf–Be, Cu–Ti, Co–Zr, Ni–Zr, Cu–Zr, Ni–P, Pd–P, Ni–Pd–P, Cu–Pd–P, Co–Ti–Zr, Zr–Be–Hf, Ti–Be–Hf, Ti–Be–Zr) was calculated using a combined thermodynamic and kinetic approach. There is good agreement between the predicted glass forming ranges and those experimentally observed. By using this combined approach it has also proved possible to estimate critical cooling rates for phases not observed in the equilibrium phase diagram. A significant advantage of the approach is that, for multicomponent alloys, the melting temperatures and thermodynamic input parameters for the kinetic equations are derived using the constituent binary thermodynamic phase diagram calculations and, therefore, it has the potential to predict GFA in multicomponent systems using information from mainly binary systems.

MST/788     

Oxidation behaviors of(Hf0.25Zr0.25Ta0.25Nb0.25)C and(Hf0.25Zr0.25Ta0.25Nb0.25)C-SiC at 1300-1500℃

In this work,high-entropy ceramics(Hf_0.25 Zr_0.25Ta_0.25Nb_0.25)C(HZTNC) and HZTNC doped with 20 vol%SiC(HZTNC-SiC) were fabricated by spark plasma sintering.Their oxidation behavior was investigated over the temperature range of 1300-1500℃ for up to 60 min.Both HZTNC and HZTNC-SiC exhibited good oxidation resistance,and their weight change as a function of oxidation time obeyed a parabolic law.Through XRD,microstructure observation,and elemental mapping analysis of the oxide layers,it was found that the formation of Nb₂ Zr₆ O₁₇,Hf₆ Ta₂ O₁₇,and(Ta,Nb)₂ O₅ mixed-oxide layers effectively protected the matrix from further oxidation.Microcracks began to appear on the oxide layer of HZTNC at high temperatures after 60 min of oxidation.However,the addition of SiC in HZTNC suppressed these microcracks at high temperatures due to the active oxidation of SiC.Compared with the oxides formed on HZTNC,the additional formation of Hf(Zr)SiO₄ on HZTNC-SiC could further improve its oxidation resistance over HZTNC ceramics.     

Dust dispersal and Pb enrichment at the rare-metal Orlovka-Spokoinoe mining and ore processing site: insights from REE patterns and elemental ratios

Different geological, technogenic and environmental samples from the Orlovka-Spokoinoe Ta-Nb-Sn-W mining site and ore processing complex in Eastern Transbaikalia (Russia), were analysed for Pb, Y, Zr, Hf and rare earth elements (REE) to assess the effect of dust and metal dispersal on the environment within the Orlovka-Spokoinoe mining site. Potential source material analysed included ore-bearing and barren granites, host rocks, tailing pond sediments, and ore concentrates. Lichens and birch leaves were used as receptor samples. The REE enrichment relative to chondrite, the extent of the Eu anomalies, the enrichments of heavy REE (HREE), and Zr/Hf and Yb/Y ratios suggest that tailings, barren granites, and metasedimentary host rocks are the main sources of dust in the studied mining environment. In addition, calculated lead enrichment (relative to host rocks) suggests that the environment is polluted with Pb. Our results clearly demonstrate the potential of REE patterns and elemental ratios as a reliable technique to trace dust and metals sources and dispersal within a confined mining area offering a new tool for environmental assessment studies.     

Relationship between η phase formation and solidification rate in directionally solidified IN792 + Hf alloy

Abstract

The effect of solidification rate on the formation of η phase in a directionally solidified IN792 + Hf superalloy was studied. A Cr rich ‘precipitate free zone’ adjacent to the eutectic (γ + γ′) was noticed in the quenched directionally solidified microstructure of the alloy. The formation of the precipitate free zone was due to the solidification of eutectic (γ + γ′) which consumed a large amount of the γ′ forming elements and increased the ratio of (Ti + Hf + Ta + W)/Al in the residual liquid. The high ratio of (Ti + Hf + Ta + W)/Al in the final residual liquid induced the formation of η phase and hence η phase always appeared at the boundary between the eutectic regions and the dendrite core regions. The ratio of (Ti + Hf + Ta + W)/Al was decreased by the diffusion of elements between the residual liquid and the surrounding area. A lower solidification rate favoured the back diffusion and decreased the ratio of (Ti + Hf + Ta + W)/Al in the residual liquid, and hence reduced the formation of η phase.     

Electromagnetic wave absorbing properties of TMCs (TM=Ti,Zr, Hf,Nb and Ta) and high entropy (Ti0.2Zr0.2Hf0.2Nb0.2Ta0.2)C

Electromagnetic wave (EMW) absorbing materials play a vital role in modern communication and information processing technologies to inhibit information leakage and prevent possible damages to environment and human bodies.Currently,most of EMW absorbing materials are either composites of two or more phases or in the form of nanosheets,nanowires or nanofibers in order to enhance the EMW absorption performance through dielectric loss,magnetic loss and dielectric/magnetic loss coupling.However,the combination of complex shapes/multi phases and nanosizes may compound the difficulties of materials processing,composition and interfaces control as well as performance maintenance during service.Thus,searching for single phase materials with good stability and superior EMW absorbing properties is appealing.To achieve this goal,the EMW absorbing properties of transition metal carbides TMCs (TM=Ti,Zr,Hf,Nb and Ta) and high entropy (Ti0.2Zr0.2Hf0.2Nb0.2Ta0.2)C which belong to ultrahigh temperature ceramics,were investigated in this work.Due to the good electrical conductivity and splitting ofd orbitals into lower energy t2g level and higher energy eg level in TMC6 octahedral arrangement,TMCs (TM=Ti,Zr,Hf,Nb and Ta) exhibit good EMW absorbing properties.Especially,HfC and TaC exhibit superior EMW absorbing properties.The minimum reflection loss (RLmin) value of HfC is -55.8 dB at 6.0 GHz with the thickness of 3.8 mm and the effective absorption bandwidth (EAB) is 6.0 GHz from 12.0 to 18.0 GHz at thickness of 1.9 mm;the RLmin value of TaC reaches-41.1 dB at 16.2 GHz with a thickness of 2.0 mm and the EAB is 6.1 GHz with a thickness of 2.2 mm.Intriguingly,the electromagnetic parameters,i.e.,complex permittivity and permeability are tunable by forming single phase solid solution or high entropy (Ti0.2Zr0.2Hf0.2Nb0.2Ta0.2)C.The RLmin value of high entropy (Ti0.2Zr0.2Hf0.2Nb0.2Ta0.2)C is -38.5 dB at 9.5 GHz with the thickness of 1.9 mm,and the EAB is 2.3 GHz (from 11.3 to 13.6 GHz) atthickness of 1.5 mm.The significance of this work is that it opens a new window to design single phase high performance EMW absorbing materials by dielectric/magnetic loss coupling through tuning the conductivity and crystal field splitting energy of d orbitals of transition metals in carbides,nitrides and possibly borides.     

Separation of trace level hafnium from tungsten: a step toward solving an astronomical puzzle

182Hf (T(1/2) = 9 x 10(6) y) is believed to be formed by pure r-process during a supernova explosion, and therefore, the search for minute traces of 182Hf in the earth's crust is of great interest. Only accelerator mass spectrometry (AMS) is well suited for detecting such low levels of 182Hf. But any attempt to measure 182Hf by AMS must ensure that the sample is free from its naturally occurring stable isobar 182W. A simple method for separation of tungsten and hafnium has been developed using radiometric simulation followed by checking the decontamination of tungsten from Hf in a synthetic sample by AMS. The separation studies were performed by a liquid-liquid extraction technique using tri-n-octylamine (TOA) as the organic reagent. It has been found that a very high separation factor (1.6 x 10(6)) can be achieved when 0.3 M TOA diluted in cyclohexane is used as the organic phase and 6 M HCl (in the presence of small amount of H2O2) is used as the aqueous phase.     

Photothermal‐Responsive Microporous Nanosheets Confined Ionic Liquid for Efficient CO2 Separation

2D materials hold promising potential for novel gas separation. However, a lack of in‐plane pores and the randomly stacked interplane channels of these membranes still hinder their separation performance. In this work, ferrocene based‐MOFs (Zr‐Fc MOF) nanosheets, which contain abundant of in‐plane micropores, are synthesized as porous supports to fabricate Zr‐Fc MOF supported ionic liquid membrane (Zr‐Fc‐SILM) for highly efficient CO₂ separation. The micropores of Zr‐Fc MOF nanosheets not only provide extra paths for CO₂ transportation, and thus increase its permeance up to 145.15 GPU, but also endow the Zr‐Fc‐SILM with high selectivity (216.9) of CO₂/N₂ through the nanoconfinement effect, which is almost ten times higher than common porous polymer SILM. Furthermore, based on the photothermal‐responsive properties of Zr‐Fc MOF, the performance is further enhanced (35%) by light irradiation through a photothermal heating process. This provides a brand new way to design light facilitating gas separation membranes.     

Thermochromatographic Determination of the Relative Volatility of Chlorides and Oxychlorides of Group IVb-VIb Elements

Thermochromatographic and gas-chromatographic experiments show that the recoil atoms of Group IV-VI elements (Zr, Hf, Nb, Ta, Mo, W) thermalized in inert gases (He, Ar) form in chloride systems both higher and lower chlorides and oxychlorides. The relative yields of these gaseous compounds depend on the experimental conditions.