Hafnium Content Research Articles

Determination of Hafnium in Zirconium by Spectrophotometry

Zirconium and hafnium have opposite nuclear properties and are used very differently in the nuclear industry. However, hafnium is a common metal impurity in zirconium, and the chemical properties of the two are very similar except for nuclear properties, and it is difficult to separate and detect them. At present, the detection of hafnium content in zirconium is usually achieved by using an inductively coupled plasma (ICP) spectrometer, but ICP equipment is expensive, and the detection cost is high. Therefore, it is necessary to develop a simple and low-cost method for the determination of hafnium content in zirconium. Based on this, this paper takes the spectrophotometric method as a starting point. Through a series of experiments on the influence of pH and concentrations of the color-developing agent xylenol orange sodium salt on the absorbance of zirconium and hafnium ions, the appropriate variables are selected to detect the content of hafnium in zirconium. Finally, according to the measured absorbance and total ion concentration, by comparing the working curve of zirconium and hafnium ions, the content of hafnium in zirconium is calculated based on the lever principle.

Structural and luminescent properties of YSZ-YSH based ceramics depending on Zr/Hf ratio

Samples of crystalline cubic phased ceramics based on (Zr1-хHfх)0.82Y0.17Eu0.01O1.91 with different contents of hafnium (х = 0; 0.21; 0.50; 0.77; 1) were synthesized. The synthesis conditions were chosen to avoid the possible formation of a minor tetragonal phase. The average grain size was 2–5 microns. The structural parameters of ceramics, their band gap, luminescent and thermoluminescent properties were studied depending on the hafnium content. It was shown that single-phase sample with calculated formula ((Zr0.77Hf0.23)0.82Y0.17Eu0.1)O1.91 demonstrated the highest cathodoluminescent intensity upon excitation by electrons. It was found that thermoluminescent properties of ceramics with hafnium content of х = 0.50–0.77 range are prospective for application in thermodosimetry. The highest luminescence yield was observed in such samples.

Electron Beam Powder Bed Fusion of ATI C103TM Refractory Alloy

The study investigated the use of electron beam powder bed fusion (EB-PBF) to fabricate niobium ATI C103™ alloy articles for microstructural characterization and mechanical testing. The feedstock powder was consolidated into low-porosity articles, and both powder and sample chemistry were monitored. Oxygen uptake in the powder was limited to less than the ASTM B655/B655M (2018) specification limits for 7 uses. Manipulating vacuum chamber pressure showed stable hafnium content but decreasing titanium content with decreasing chamber pressure attributed to evaporation. AM samples were evaluated in the post-processed, as-fabricated, annealed, and hot isostatic pressing (HIP) condition with a maximum yield strength of 287 MPa, UTS of 375 MPa for the HIP, and maximum elongation of 32 pct for the annealed specimens, respectively. Mechanical properties are similar to typical wrought products, with a notable increase in yield strength after post-processing by HIP. The fracture behavior was driven by porosity in the as-fabricated specimens and grain boundary fracture after HIP.

Hot deformation behavior of NiTiHf alloy under compression: Effect of deformation heating on flow softening

High-temperature shape memory alloys are suitable materials for substituting hydraulic elements in the aerospace industry due to light weight and high reactive stresses developing during thermoelastic martensitic transformation and acceptable recoverable strain. These properties may be improved by plastic deformation; however, the plastic deformation of NiTiHf alloys along with structure investigation has yet to be studied systematically. Here, the hot deformation behavior of a NiTiHf alloy with hafnium content >20 at.% has been investigated, and the processing map has been elaborated according to the dynamic material model (DMM) based on the Prasad instability criterion. The deformation heating effect has been shown to affect the flow curves and accounts for profound softening during deformation due to quasi-adiabatic deformation mode at high strain rates. NiTiHf alloys have a much higher activation energy of plastic flow, and the instability region of plastic flow is much larger compared to binary NiTi alloys. Microstructural observations have revealed that in the instability regions, oxide bands and crack nucleation occur, whereas outside this region, such defects are not observed. Electron backscatter diffraction has demonstrated that at high temperatures and slow strain rates, discontinuous dynamic recrystallization occurs resulting in the necklace-type structure, while at high strain rates, this phenomenon has not been observed. Based on the obtained results, the preferable deformation conditions are established to be 850–1000 °C and 0.003–0.05 s−1.

Synthesis and Characterization of Single Crystal Zircon-Hafnon Zr(1-x)Hf(x)SiO4 Solid Solutions and the Comparison with the Reaction Products of a TEOS-Based Hydrothermal Route.

Two synthesis routes of the zircon-hafnon solid solution series were carried out. The high-temperature route uses the growth of single crystals via a flux mixture that has been cooled down slowly from 1400 °C over 4 weeks. The reaction products were colorless and idiomorphic without byproducts. The hydrothermal tetraethoxysilane (TEOS)-based route represents the low-temperature method at 200 °C for approximately 7 days. The hydrothermal route yielded a white powder and scanning electron microscopy analysis thereof did not reveal any specific idiomorphic properties. However, the synthesis also featured some byproducts besides the zircon-hafnon solid solutions. Thermogravimetric analysis coupled with differential scanning calorimetry, and mass spectroscopy indicated, that hydrothermal reaction products feature the presence of organic residues originating from the starting materials. However, a specific dependency on the hafnium content could not be observed due to the data scatter. Infrared (IR) analysis revealed the presence of Zr/Hf-oxides. The structural characterization demonstrated that properties change constantly with the hafnium amount, however, gradual variations of some properties related to the composition of the solid solution series depend in part on the synthesis route, considering the c/a ratio and IR modes. Furthermore, analyses of the single crystals by Raman spectroscopy and μXRF suggested a nonequilibrated crystal growth based on the starting composition.

Изучение влияния содержания гафния и эрбия на формирование микроструктуры при литье алюминиевого сплава 1590 в медный кокиль

Introduction. High-magnesium aluminum alloys are widely used in the automotive, building and aerospace industries due to its low specific gravity and high strength. The characteristics of such alloys can be improved by small additions of scandium and zirconium. However, scandium is very expensive, so in new generation alloys its amount is tended to be reduced. In the recently developed 1590 aluminum alloy, this was achieved by addition of erbium and hafnium. The objective of the paper is to study the effect of erbium and hafnium concentrations on the modification of the cast structure in 1590 aluminum alloy at high solidification rates. Research Methods. The paper investigates the microstructure, chemical composition and size of intermetallic compounds in specimens from ten alloy 1590 modifications with different hafnium and erbium contents cast into a copper chill mold with a solidification rate of 10 °C/sec. The grain structure was studied using an optical microscope. The chemical composition and size of the intermetallic phases were studied using a Tescan Vega 3 scanning electron microscope. Results and discussion. It is established that as the amount of hafnium and erbium increases, the cast structure is modified. In general, grain refinement with the addition of hafnium and erbium can be explained by a higher degree of supercooling between the solid and liquid phases. At a hafnium content of 0.16 %, the dendritic structure begins to transform into an equiaxed grain structure. This transformation can be explained by the appearance of primary intermetallic compounds of the Al3Sc type in the liquid phase. Such intermetallic compounds are identified at a concentration of erbium and hafnium equal to 0.16 %. Moreover, in all alloys eutectic intermetallic compounds are identified that contained manganese and iron and had no effect on the cast structure. Comparison with previously obtained results on the grain size of specimens cast into a steel mold shows that with higher solidification rate, the structure modification in 1590 alloy is getting less efficient. This is explained by an increase in the concentration of transition elements in the solid solution, primarily scandium, necessary for the formation of primary intermetallic particles.

On the effect of hafnium loading and location in mesoporous silica on the activity of catalysts in oxidation of dibenzothiophene

Oxidation of thiophenes to sulfones (easily extracted from fuel) is of crucial importance in petrochemical and automotive industry. The rational design and synthesis of stable catalysts of this process still remains one of the biggest challenges. In this work, a series of HfSBA-15 mesoporous materials with different hafnium content (3, 5 or 10 wt.%) has been prepared and studied in the liquid phase oxidation of dibenzothiophene (DBT) with H2O2. The activity of HfSBA-15 samples prepared by one-pot method was compared to that of Hf/SBA-15 synthesized by impregnation and that of HfMCF type of silica. It has been shown that hafnium loading and its location in the silica structure (framework and/or extra-framework positions) affect the efficiency of DBT oxidation. Moreover, the reaction conditions (i.e. oxidation temperature, reaction time, oxidant/sulfur ratio and catalyst amount) were optimized to achieve maximum conversion of dibenzothiophene (99 %). The location of hafnium species in SBA-15 and MCF materials was influenced by the loading of the metal and the type of silica structure (determined by the preparation method). Hafnium located in the framework of SBA-15 promoted generation of a higher number of active Lewis acid sites (LAS) and higher activity in oxidation of dibenzothiophene compared to extra-framework HfO2 species anchored in HfMCF material. It indicates that the location (framework vs extra-framework) and formation of isolated Hf4+ species are decisive for high activity of hafnium-doped mesoporous molecular sieves. This finding opens up a pathway for the development of highly efficient, stable and relatively cheap solid acid catalyst for oxidation of thiophenes to sulfones.

Влияние гафния на высокомагниевые сплавы, легированные переходными металлами, при термической обработке

The purpose of the work is to study the influence of hafnium additives on the mechanical properties and thermal stability of particles at elevated temperature during heat treatment of aluminum alloys with a high magnesium content. Two modifications of 1570 alloy were chosen for the study: without hafnium content and with its addition of 0.5 % by weight. Both alloys were subjected to homogenizing annealing at a temperature of 440 °C with different exposure modes, which ranged from 2 to 100 h. Microhardness was studied for various heat treatment modes, and the fine microstructure was studied as well using transmission microscopy. As a result, it was possible to identify that during annealing at a short exposure time (2–8 h), the alloy with the hafnium addition has higher microhardness values exceeding those of 1570 alloy by an average of 20 HV units. This is associated with the fact that in 1570 alloy with hafnium additives, during heat treatment, the number of precipitated particles increases while their average size decreases compared to the base alloy. At the same time, in 1570 alloy without hafnium content, when annealed at a temperature of 440 °C, there is no increase in microhardness. This is caused by the fact that in 1570 alloy without hafnium content, when cooled after casting, discontinuous decomposition occurs, which resulted in the fact that most of the scandium precipitates from the supersaturated solid solution in the form of dispersoids. This phenomenon is not observed in the alloy with hafnium additives, which indicates its ability to stop discontinuous decomposition during cooling the ingot after casting.

Zircon Megacrysts from the Kawisigamuwa Carbonatite, Sri Lanka – A Potential Reference Material for In SituU‐Pb and Hf Isotope Measurement

We characterise zircon megacrysts from the Kawisigamuwa carbonatite as a new potential reference material for laser ablation‐inductively coupled plasma‐mass spectrometry U‐Pb and Hf isotope measurement. We studied ten 0.5–4 cm long, brown megacrysts that consist of oscillatory zoned (OZ) and nearly featureless cathodoluminescence‐bright recrystallised (RX) zircon domains. The zircons have low to moderate radiation damage (total α‐dose < 0.5 x 1018 events g‐1), tested by the measured FWHM of the ν3 (SiO4) Raman band < 5 cm‐1. An ID‐TIMS weighted mean 206Pb/238U age of 532.39 ± 0.66 Ma (2s uncertainty) was determined for OZ zircon domains of three grains. While hafnium content varies within and between crystals (6630–9960 μg g‐1) the in situ mean 176Hf/177Hf ratios of ten crystals overlap within uncertainty. We recommend a mean 176Hf/177Hf ratio of 0.282003 ± 0.000020 (2s) as preliminary working value for OZ domains. Two OZ megacrysts yield indistinguishable δ18OVSMOW of 12.1 ± 0.4‰ and 12.2 ± 0.4‰ (2s). Elevated Th/U (> 1.5), Zr/Hf (59–75) and low hafnium contents in OZ domains are similar to those of zircons from carbonatites of mantle origin, while high δ18O and low εHfi (‐15.8 to ‐17.1) indicate a crustal contribution. The zircons probably grew from crustal‐derived carbonate melts under high grade metamorphic conditions.

A phase 1 dose-escalation study of RiMO-301 with palliative radiation in advanced tumors.

2527 Background: Nanoscale metal−organic frameworks (MOFs) are a new class of organic−inorganic hybrid nanomaterials constructed from metal centers and organic ligands. Preclinical studies have shown that nanoscale MOFs can enhance the antitumor effects of ionizing radiation via a unique radiotherapy-radiodynamic therapy mode of action, and MOFs plus radiation can enhance the immunotherapeutic effects of immune checkpoint inhibitors. RiMO-301 is a hafnium-based MOF which enhances radiotherapy and checkpoint blockade immunotherapy without showing systemic toxicity in preclinical models. RiMO-301 is the first MOF to enter clinical trials on human patients. Methods: This is a multicenter, open-label, first-in-human dose-escalation phase I trial of RiMO-301 [NCT03444714]. The primary objective is to determine the maximum tolerated dose (MTD) of locally injected RiMO-301 with or without the PD-1 inhibitor pembrolizumab in patients treated with concurrent palliative doses of radiation (20 Gy in 5 fractions or 30 Gy in 10 fractions) using a 3+3 design. The MTD is defined as the dose associated with dose-limiting toxicity (DLT) in less than 33% of patients. The secondary objective is to evaluate antitumor response (objective response rate, ORR) using RECIST and itRECIST criteria. Results: A total of 25 patients were enrolled and treated with escalating doses of RiMO-301 (relative to tumor volumes). No protocol defined DLT was reported. The observed possibly treatment related adverse events included mild dermatitis radiation, mild dysgeusia, diarrhea, mild hypotension (30 days post treatment) and mild dizziness (30 days post treatment). One patient each experienced a Grade 2 alanine aminotransferase increase 45 days post treatment, a Grade 2 dry mouth, and a Grade 3 pain at the injection site. Nineteen patients were evaluable, with 13 and 6 patients, respectively, for RiMO-301 without and with pembrolizumab treatments. By itRECIST criteria, RiMO-301 without pembrolizumab demonstrated 38.5% (5/13) ORR (1 complete response and 4 partial responses) with 2 additional patients experiencing 20-30% tumor size reduction. RiMO-301 with pembrolizumab exhibited 66.7% (4/6) ORR with the 2 remaining patients showing 15-20% tumor size reduction. Preliminary pharmacokinetic analysis indicated that the hafnium concentrations in the systemic circulation were either below or barely above the level of detection. Conclusions: RiMO-301 with or without pembrolizumab was well tolerated and demonstrated promising signs of efficacy in patients with advanced tumors when treated with concurrent palliative radiotherapy. The results support the use of RiMO-301 as a potential radio-enhancer and will prompt further phase 2 studies in the development of RiMO-301 for patients undergoing radiotherapy. Clinical trial information: NCT03444714 .

Metasomatic alteration of zircon at lower crustal P-T conditions utilizing alkali- and F-bearing fluids: Trace element incorporation, depletion, and resetting the zircon geochronometer

Natural alteration of zircon takes place in melts or fluids either via dissolution coupled with overgrowth or via a coupled dissolution-reprecipitation process. The latter results in the zircon being partially or totally replaced by new, compositionally re-equilibrated zircon or a new mineral phase or both. In this study, fragments (50–300 μm) from a large, inclusion-free, clear, 520–530 Ma euhedral zircon with light radiation damage from a nepheline syenite pegmatite, Seiland Igneous Province, northern Norway, were experimentally reacted in 20 mg batches with 5 mg of ThO2 + ThSiO2 + SiO2 and a series of alkali-bearing fluids in sealed Pt capsules at 900 °C and 1000 MPa for 6–11 days in the piston cylinder press using a CaF2 setup with a cylindrical graphite oven. ThO2 + ThSiO2 + SiO2 was present at the end of the experiment. In experiments involving H2O, H2O + NaCl, H2O + KCl, and 2 N KOH, no reaction textures formed other than a slight dissolution of the zircon grain fragments. Experiments involving 2 N NaOH, Na2Si2O5 + H2O, and NaF + H2O resulted in zircon reaction textures with varying degrees of intensity, which took the form of partial replacement by compositionally modified zircon via a coupled dissolution-reprecipitation process. In the NaF + H2O experiment some overgrowth also occurred. Altered zircon is separated by sharp compositional boundaries from unaltered zircon. Secondary ion mass spectrometry (SIMS) and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) analysis indicates that, relative to the unaltered zircon, the altered zircon is strongly enriched in Th, and heavily to moderately depleted in U and (Y + REE). In all the experiments, 206Pb (3–5 ppm in unaltered zircon) is depleted in the altered zircon to below the SIMS detection limit and to at or below the LA-ICP-MS detection limit. Hafnium and Ti concentrations in the altered zircon retained the same approximate value (within error) as the original zircon. The results from these experiments demonstrate that zircon can be compositionally modified by alkali-bearing and alkali-F-bearing fluids via a coupled dissolution-reprecipitation process. Near to total loss of radiogenic Pb via such processes under high-grade conditions resets the internal zircon geochronometer. Although the end result is the same as with zircon overgrowth, i.e. the production of new generation zircon at the time of a metamorphic/metasomatic event, such replacement processes can explain incomplete isotopic ‘resetting’; inclusion production through unmixing of solid solutions in metastable zircon compositions; and ‘ghost’ textures that preserve initial growth features but with isotopic disturbance. Diagnostic replacement features produced in experiments, such as interface geometries between altered and unaltered zircon, provide markers of the mechanism and aid in zircon interpretation. A major implication from this study is that if zircon with low radiation damage can be metasomatically altered under high-grade conditions, this would have important consequences with respect to zircons presumed role as an impregnable container for mineral inclusions. Namely the mineral inclusions contained within zircon could also be altered, reset as a geochronometer, or even replaced by another mineral.

Effects of hafnium content on microstructures and properties of newly developed (Ti,Hf)(C,N) ceramics

In this study, novel (Ti,Hf)(C,N) ceramics with varying hafnium contents were fabricated via carbothermal reduction–nitridation and subsequent spark plasma sintering. The influence of Hf addition on the mechanical properties, wear properties, and corrosion resistance of the (Ti,Hf)(C,N) ceramics was systematically studied. The introduction of Hf promoted the sintering densification of the ceramics in the sintering process. The prepared (Ti,Hf)(C,N) ceramics exhibited excellent mechanical and wear properties owing to refinement and solution-strengthening mechanisms. The (Ti0.9,Hf0.1)(C0.5,N0.5) ceramic demonstrated higher Vickers hardness and fracture toughness, measuring 1997 HV5 and 4.28 MPa m1/2, respectively, compared to the pure Ti(C0.5,N0.5) ceramic which exhibited values of 1635 HV5 and 3.94 MPa MPa m1/2. The wear scar depth of the (Ti0.9,Hf0.1)(C0.5,N0.5) ceramic sample was 57.36% to that of the Ti(C0.5,N0.5) ceramic. Additionally, the addition of Hf improved the corrosion resistance of (Ti,Hf)(C,N) ceramics in a 0.5 M NaOH solution. The potential applications of (Ti,Hf)(C,N) ceramics include machining tools and wear-resistant parts.

Void swelling in additively manufactured 316L stainless steel with hafnium composition gradient under self-ion irradiation

Compositionally-graded austenitic 316L stainless steel (SS) samples with five different Hafnium (Hf) concentrations (up to 1 wt.%) were additively manufactured by directed energy deposition and then were irradiated using 5 MeV Fe2+ ions to 50 displacements per atom (dpa) at 500, 550, and 600 °C, respectively. A rastering beam was used to ensure homogenous irradiations for the large areas of ∼1.40 cm2. Composition-dependent void evolution was evaluated. Void size, void number density, and void swelling all tend to decrease with increasing Hf concentration at all three temperatures. When the nominal Hf concentration increases to 1 wt.% in the doped additively manufactured (AM) 316L SS, the void swelling is over an order of magnitude lower than that in pure AM 316L. Atom probe tomography results showed that about 0.14 wt.% Hf dissolved in the matrix at the 1 wt.%. Hf nominal concentration. The suppression of void swelling by Hf addition shows qualitative agreement with the numerical calculation based on the vacancy trapping mechanism, indicating that the oversized Hf reduces the steady state vacancy concentration, and hence the incubation period of swelling is extended, resulting in a dramatic difference in void swelling. Other factors including grain boundaries, dislocation and dislocation cells, Hf-rich particles, and delta ferrite are secondary to this mechanism. This work shows that additive manufacturing enabled microalloying is promising for developing void swelling resistant materials.

Influence of Hafnium Addition on the Microstructure, Microhardness and Corrosion Resistance of Ti20Ta20Nb20(ZrMo)20-xHfx (where x = 0, 5, 10, 15 and 20 at.%) High Entropy Alloys.

The presented work aimed to investigate the influence of the hafnium/(zirconium and molybdenum) ratio on the microstructure, microhardness and corrosion resistance of Ti20Ta20Nb20(ZrMo)20-xHfx (where x = 0, 5, 10, 15 and 20 at.%) high entropy alloys in an as-cast state produced from elemental powder and obtained via the vacuum arc melting technique. All studied alloys contained only biocompatible elements and were chosen based on the thermodynamical calculations of phase formation predictions after solidification. Thermodynamical calculations predicted the presence of multi-phase, body-centered cubic phases, which were confirmed using X-ray diffraction and scanning electron microscopy. Segregation of alloying elements was recorded using elemental distribution maps. A decrease in microhardness with an increase in hafnium content in the studied alloys was revealed (512-482 HV1). The electrochemical measurements showed that the studied alloys exhibited a high corrosion resistance in a simulated body fluid environment (breakdown potential 4.60-5.50 V vs. SCE).

Effects of hafnium sources and hafnium content on the structures and properties of SiBNC–Hf ceramic precursors

AbstractThe synthesis of SiBNC–M (M is metal element) multinary ceramic precursors has mainly been through chemical modification of the SiBNC ceramic precursors with the introduction of the metal element/compound. This misses the simplicity, efficiency, and combined benefits of single reactor synthesis routes. We herein adopt a one‐pot method to synthesize SiBNC–Hf ceramic precursors (PBSHZ) from different Hf sources, and with varying Hf content. The starting materials include hafnium tetrachloride, hafnium dichloride, trichlorosilane, hexamethyldisilazane, and boron trichloride. Fourier transform infrared spectroscopy (FT‐IR), nuclear magnetic resonance (NMR), X‐ray photoelectron spectroscopy (XPS), and thermogravimetric analysis are employed to characterize the structures and properties of the PBSHZ. The results reveal the successful incorporation of Hf into the precursors. Compared to the hafnium tetrachloride source, the precursor synthesized from hafnium dichloride yields more ceramics and shows better solubility, due to fewer Hf–Cl bonds available for reaction. Meanwhile, there is a positive correlation between the rise in the Hf content of PBSHZ and the ceramic yield. However, the solubility and processability of the precursors decline, due to the multiplication of the cross‐linking degree in the molecular structure. Further FT‐IR, NMR, XPS, and thermogravimetry–mass spectrometry (TG–MS) analysis indicate a full polymer‐to‐ceramic transformation at 1000°C pyrolysis temperature. At this point, the SiBNC–Hf ceramics mainly consist of an Si–B–N skeleton, HfN, and free carbon.

Особенности люминесценции керамики на основе кубического (ZR-=SUB=-0.82-x-=/SUB=-HF-=SUB=-x-=/SUB=-Y-=SUB=-0.17-=/SUB=-Eu-=SUB=-0.01-=/SUB=-)O-=SUB=-1.91-=/SUB=-

The ceramics based on cubic (Zr0.82-xHfxY0.17Eu0.1)O1.91 with different contents of hafnium were studied. In the work, the elemental composition of the samples was obtained, the cathodoluminescence (CL) spectra and decay kinetics of europium luminescence were studied. The researched showed increase in the content of hafnium doesn’t affect the position and number of observed bands in the luminescence spectrum. The electric dipole and magnetic dipole radiative transitions ratio was estimated for all samples. It’s demonstrated that a decrease in the local symmetry of the europium ion associated with an increase in the hafnium content. It’s shown the 5D0-7F1 transition Eu3+ decay time doesn’t depend on the hafnium content, but varies significantly in different regions of the sample, which can be attributed to the influence of grain boundaries.

Effect of hafnium content on the microstructural evolution and stress rupture properties of K4750 nickel-based superalloy

The microstructural evolution of K4750 nickel-based superalloy with different hafnium (Hf) contents was investigated by thermodynamic calculations (TC) and experiments. According to TC, with the increases of Hf content from 0 wt% to 1.5 wt%, the redissolving temperature of MC carbide first decreased rapidly and then tended to be relatively stable, the precipitated temperature of M23C6 carbide decreased gradually, while the γ′ weight fraction increased first and then stabilized. Three alloys containing 0 wt%, 0.11 wt%, and 0.28 wt% Hf were then prepared to further study the evolution of the microstructure. The experimental results showed that the increase of Hf content changed the morphology of MC carbide from long strip to rodlike and blocky, which is caused by the decrease of Ti and Nb contents and the increase of Hf content in MC carbides. The addition of Hf also changed the morphology of M23C6 carbide from continuous to granular due to the different MC distribution at grain boundaries (GBs). In addition, a small amount of Hf segregated into the γ′ phase, reducing the Al and Nb contents of the γ′ phase, resulting in an increased γ/γ′ lattice mismatch. As the Hf content increased from 0 wt% to 0.11 wt% and 0.28 wt%, the mean stress rupture life at 750 °C and 430 MPa increased from 99.54 h to 105.73 h and 170.96 h, which was closely related to the evolution of MC, M23C6 and γ′ precipitates. Therefore, the relationship between microstructure and stress rupture properties was discussed in detail.

Iodine Uptake by Zr-/Hf-Based UiO-66 Materials: The Influence of Metal Substitution on Iodine Evolution.

Many works reported the encapsulation of iodine in metal-organic frameworks as well as the I2 → I3- chemical conversion. This transformation has been examined by adsorbing gaseous iodine on a series of UiO-66 materials and the different Hf/Zr metal ratios (0-100% Hf) were evaluated during the evolution of I2 into I3-. The influence of the hafnium content on the UiO-66 structure was highlighted by PXRD, SEM images, and gas sorption tests. The UiO-66(Hf) presented smaller lattice parameter (a = 20.7232 Å), higher crystallite size (0.18 ≤ Φ ≤ 3.33 μm), and smaller SSABET (818 m2·g-1) when compared to its parent UiO-66(Zr) ─ a = 20.7696 Å, 100 ≤ Φ ≤ 250 nm, and SSABET = 1262 m2·g-1. The effect of replacing Zr atoms by Hf in the physical properties of the UiO-66 was deeply evaluated by a spectroscopic study using UV-vis, FTIR, and Raman characterizations. In this case, the Hf presence reduced the band gap of the UiO-66, from 4.07 eV in UiO-66(Zr) to 3.98 eV in UiO-66(Hf). Furthermore, the UiO-66(Hf) showed a blue shift for several FTIR and Raman bands, indicating a stiffening on the implied interatomic bonds when comparing to UiO-66(Zr) spectra. Hafnium was found to clearly favor the capture of iodine [285 g·mol-1, against 230 g·mol-1 for UiO-66(Zr)] and the kinetic evolution of I2 into I3- after 16 h of I2 filtration. Three iodine species were typically identified by Raman spectroscopy and chemometric analysis. These species are as follows: "free" I2 (206 cm-1), "perturbed" I2 (173 cm-1), and I3- (115 and 141 cm-1). It was also verified, by FTIR spectroscopy, that the oxo and hydroxyl groups of the inorganic [M6O4(OH)4] (M = Zr, Hf) cluster were perturbed after the adsorption of I2 into UiO-66(Hf), which was ascribed to the higher acid character of Hf. Finally, with that in mind and considering that the EPR results discard the possibility of a redox phenomenon involving the tetravalent cations (Hf4+ or Zr4+), a mechanism was proposed for the conversion of I2 into I3- in UiO-66─based on an electron donor-acceptor complex between the aromatic ring of the BDC linker and the I2 molecule.

Effect of Hafnium content on structural evolution of SiHfOC ceramics at high temperatures

SiHfOC ceramics with different Hf contents were prepared by the sol-gel method using polymethylsilsesquioxane and HfOCl2·8H2O as the raw materials. The high-temperature structural evolution of the SiHfOC ceramics with different Hf contents was investigated under an inert atmosphere. The results showed that Hf existed in the free state in the SiHfOC precursors with Hf:Si atomic ratios of 0.05 and 0.1. When the Hf:Si ratio was increased to 0.2, Hf was bridged in the SiOC network to form Si–O–Hf bonds, which changed the pyrolysis behavior of the ceramics and improved the ceramic yield. Further, the formation of Si–O–Hf bonds promoted the uniform dispersion of HfO2 nanocrystals inside the ceramic, which further inhibited carbothermal reduction and increased the thermal stability of the SiHfOC ceramics.

Anomalous Behavior of Zirconium and Hafnium in Volcanic Fumarolic Fluids

AbstractThe Zirconium and Hafnium concentrations in worldwide fumaroles fed by magmatic fluids reveal that the Zr/Hf ratio is inversely related to the temperature of emission. Lower Zr/Hf ratio values below the chondritic signature are found in fluids having the highest temperature while super‐chondritic Zr/Hf ratio values are found in lower temperatures. Sub‐chondritic values of the Zr/Hf ratio may be related to larger volatility of Hf‐chloride gas species with respect to Zr‐Cl gas species, while super‐chondritic ratios may correspond to fluid‐rock processes resulting from cooling of uprising magmatic fluids. We propose that sub‐chondritic Zr/Hf ratio values in fumaroles associated with high temperature may be an appropriate marker of fast magmatic rising representing a new sensitive tool for volcanic risks strategies.