Pure Zirconium Research Articles

Critical Resolved Shear Stress and Work Hardening Determination in HCP Metals: Application to Zr Single Crystals

Obtaining precise parameters of deformation modes remains a significant challenge in materials science research. Critical resolved shear stresses (CRSS) and work hardening, particularly in hexagonal metals, are crucial parameters for constitutive laws in crystal plasticity. This paper presents a novel approach to determine CRSS and specific hardening matrix coefficients for commercially pure zirconium (α-Zr) at room temperature. In situ methods are employed to measure displacement fields using grids applied to the sample surface, while a comprehensive characterization of the activated deformation systems is performed via SEM and TEM. The CRSS for prismatic ⟨a⟩, pyramidal ⟨a⟩, and 101¯2 and 112¯1 twinning systems, as well as the self-hardening for prismatic slip and several work-hardening coefficients (for prismatic/prismatic and prismatic/pyramidal interactions), are reported in Zr single crystals. Finally, the results are compared with findings from the literature and atomistic simulations.

Bovine Mineral Grafting Affects the Hydrophilicity of Dental Implant Surfaces: An In Vitro Study.

Wettability is recognized as an important property of implant surfaces for ensuring improved biological responses. However, limited information exists on how bone grafting procedures including materials influence the hydrophilic behavior of implant surfaces. This in vitro study aimed to investigate the influence of two bovine grafting materials after hydration on the wettability of four different disk surfaces: commercially pure titanium (CP-Ti), titanium-zirconium dioxide (TiZrO2-Cerid®), zirconia (SDS®), and niobium. Wettability tests were performed on each of the four implant surfaces with a solution of 0.9% sodium chloride after mixture with W-boneTM (Group A) or Bio-Oss® (Group B) or 0.9% sodium chloride alone (Group C). In total, 360 contact angle measurements were completed with n = 30 per group. Statistical analysis was performed using a one-way analysis with variance (ANOVA) test with a significant mean difference at the 0.05 level. For pure titanium, Group A demonstrated increased hydrophilicity compared to Group B. Both TiZrO2 and zirconia showed significant differences for Groups A, B and C, exhibiting a decrease in hydrophilicity after the use of bovine grafting materials compared to titanium surfaces. Niobium remained consistently hydrophobic. In summary, this study revealed that bovine grafting materials may diminish the hydrophilicity of zirconia surfaces and exert varied effects on titanium and niobium. These findings contribute to the understanding of implant surface interactions with grafting materials, offering insights for optimizing biological responses in implantology.

An Integrated Solution to FIB-Induced Hydride Artifacts in Pure Zirconium.

The preparation method of transmission electron microscopy (TEM) samples for pure zirconium was successfully executed using a focused ion beam (FIB) system. These samples unveiled artifact hydrides induced during the FIB sample preparation process, which resulted from stress damage, ion implantation, and ion irradiation. An innovative solution was proposed to effectively reduce the effect of artifact hydrides for FIB-prepared samples of hydrogen-sensitive materials, such as zirconium alloys. This development lays the groundwork for further research on the micro/nanostructures of zirconium alloys after ion irradiation, thereby facilitating the study of corrosion mechanisms and the prediction of service life for nuclear fuel cladding materials. Furthermore, the solution proposed in this study is also applicable to TEM sample preparation using FIB for other hydrogen-sensitive materials such as titanium, magnesium, and palladium.

Drying kinetics and energy efficiency of Y2O3–CeO2 co-doped ZrO2 powder under microwave heating

Zirconia has important application prospects in the field of ceramics. However, during a high-temperature heating process, pure zirconia will undergo martensite transformation, which seriously affects its service performance. Metal oxides, such as Y2O3–CeO2 doping ZrO2, effectively improve the toughness and fire resistance of the material. Thus, the drying of Y2O3–CeO2 co-doped ZrO2 powder is an essential step before practical application. The study employs contemporary microwave drying techniques. The results of the experiment show that the average microwave drying rate increases with an increase in mass, water content, and microwave heating power. When the initial mass was 30 g, the initial moisture content was 12 %, microwave power was 720 W, and the drying rate was the fastest. We used four dynamic models: Modified Page, Quadratic, Wang and Singh, and Page to fit the experiment data. The best model was Modified Page, which describes the kinetic process most accurately. Fick's second law describes how, in the drying process, when microwave power is 720 W, initial mass is 15 g and initial water content is 8 %, the effective diffusion coefficient is 5.25 × 10−16 m2/s. Fourier Transforms of the infrared spectrum of the samples before and after drying were analyzed, the intensity of the O–H absorption peak located at 3442.03 cm/s, and O–H–O absorption peak located at 1594.48 cm/s. Both decreased significantly after drying. To discuss the relationship between the microwave power and the diffusion coefficient, the activating energy of microwave heating was 32.01 W/g. The experimental results show high heating efficiency and selective heating of the microwave method. This study provides a theoretical basis and research data for microwave drying of Y2O3/CeO2 co-doped ZrO2 powder in industry.

Mechanical and structural properties of monatomic zirconium metallic glass under pressure variations and annealing processes: A molecular dynamics study

The aim of this study is to investigate how different pressure levels and annealing times affect the local atomic structure and mechanical properties of pure zirconium metallic glasses. Using molecular dynamics simulations with the embedded atom method, we explored how these changes influence the material's inherent characteristics. Analysis of the radial distribution function, coordination number, and Voronoi tessellation revealed a spectrum of structural arrangements in metallic glass formed across a pressure range of 0–70 GPa. Additionally, the glass transition temperature increased with increasing pressure, accompanied by reduced free volume. The annealing process, ranging from 0 to 5 ns on metallic glass synthesized under 0 GPa pressure, showed the coordination number's significance in achieving a glassy state. Regarding mechanical behavior, both elastic constants and moduli showed a progressive increase with rising pressure, while Young's modulus and hardness displayed enhanced values with longer annealing times.

Epitaxial Core/Shell Nanocrystals of (Europium-Doped) Zirconia and Hafnia.

A careful design of the nanocrystal architecture can strongly enhance the nanocrystal function. So far, this strategy has faced a synthetic bottleneck in the case of refractory oxides. Here we demonstrate the epitaxial growth of hafnia shells onto zirconia cores and pure zirconia shells onto europium-doped zirconia cores. The core/shell structures are fully crystalline. Upon shelling, the optical properties of the europium dopant are dramatically improved (featuring a more uniform coordination and a longer photoluminescence lifetime), indicating the suppression of nonradiative pathways. These results launch the stable zirconium and hafnium oxide hosts as alternatives for the established NaYF4 systems.

Comparative performance of fluorite-structured materials for nanosupercapacitor applications

Over the last fifteen years, ferroelectric (FE) and antiferroelectric (AFE) ultra-thin films based on fluorite-structured materials have drawn significant attention for a wide variety of applications requiring high integration density. AFE ZrO2, in particular, holds significant promise for nanosupercapacitors, owing to its potential for high energy storage density (ESD) and high efficiency (η). This work assesses the potential of high-performance Hf1−xZrxO2 thin films encapsulated by TiN electrodes that show linear dielectric (LD), FE, and AFE behavior. A wake-up effect is observed for AFE ZrO2, a phenomenon barely reported for pure zirconium oxide and AFE materials in general, correlated with the disappearance of the pinched hysteresis loop commonly observed for Zr-doped HfO2 thin films. ESD and η are compared for FE, AFE, and LD samples at the same electrical field (3.5 MV/cm). As expected, ESD is higher for the FE sample (95 J/cm3), but η is ridiculously small (≈55%) because of the opening of the FE hysteresis curve, inducing high loss. Conversely, LD samples exhibit the highest efficiency (nearly 100%), at the expense of a lower ESD. AFE ZrO2 thin film strikes a balance between FE and LD behavior, showing reduced losses compared to the FE sample but an ESD as high as 52 J/cm3 at 3.5 MV/cm. This value can be further increased up to 84 J/cm3 at a higher electrical field (4.0 MV/cm), with an η of 75%, among the highest values reported for fluorite-structured materials, offering promising perspectives for future optimization.

A mechanistic study of grain boundary behaviour during irradiation-induced growth in zirconium

Grain boundaries play a significant role during deformation and can exhibit both beneficial and adverse effects on deformation behaviour during irradiation. For instance, macroscopic irradiation growth is increased by the presence of a high density of grain boundaries. Grain boundaries can act as sinks for point defects and barriers to dislocation motion. Thus, a mechanistic assessment of the impact of grain boundaries is essential for better understanding irradiation-induced deformation. The interplay between irradiation-induced microstructure and mechanical properties has been an area of research for many decades, but many uncertainties remain. In the present work, the deformation fields adjacent to grain boundaries in pure zirconium are investigated by using high angular resolution electron backscatter diffraction (HR-EBSD) after a period of irradiation growth. It is observed that the extent of grain boundary deformation is associated with the crystallographic orientation difference between adjacent grains. High-angle grain boundaries function as a deformation constraint, whereas a significant grain boundary migration occurs at some low-angle grain boundaries, which likely act as an active diffusion path for the irradiation-induced point defects. In addition, the change in residual strain fields associated with the irradiation damage is quantified with respect to a non-irradiated reference. A net change in the state of residual elastic strain in the order of ∼10−3 has been estimated for ∼8 dpa proton irradiation. Furthermore, the origin of residual elastic strain and lattice misorientation concentration along (0002) traces are discussed.

Texture and Twinning Evolution of Cold-Rolled Industrial Pure Zirconium

Industrial pure zirconium plays an essential role as a structural material in the nuclear energy sector. Understanding the deformation mechanisms is crucial for effectively managing the plasticity and texture evolution of industrial pure zirconium. In the present study, the texture and microstructure evolution of industrial pure zirconium during the cold-rolling process have been characterized by XRD, EBSD, and TEM. The influences of various twins on texture evolution have also been simulated by the reaction stress model. The effects of slip and twinning on the deformation behavior and texture evolution have been discussed based on crystallographic and experimental considerations. Cold rolling yields a typical bimodal texture, resulting in the preferential <21-1-0>//RD orientation. The activation of the deformation mechanisms during cold rolling follows the sequential trend of slip, twinning, local slip. Experimental characterization and reaction stress simulation illustrate that T1 twins dominate in the early stage, whereas C2 twins develop at the later stage of the cold-rolling process. Twinning, especially the T1 twin, contributes to the formation of the {0001}<101-0> orientation.

Electride pure α-Zr: interstitial electrons induced type-II nodal line

Electrides have attracted significant attention in the fields of physics, materials science, and chemistry due to their distinctive electron properties characterized by weak nuclear binding. In this study, based on first-principles calculations and symmetry analysis, we report that the pure zirconium with alpha-phase (α-Zr) is expected to be the electrically neutral electride with topological nodal loop. Furthermore, the nodal loop located at the kz = 0 plane exhibits a clear drumhead-like surface state. The energy levels of the topological nodal loop can be regulated by applying uniaxial strain, resulting in the topological nodal loop being closer to the Fermi level. Remarkably, the work function of the electride Zr shows a significant anisotropy along the (001), (100), and (110) directions, particularly with a low work function of 3.14 eV along the (110) surface. Therefore, we predict that α-Zr provides a promising platform for future research on topological electrides.

Formation of pure zirconium islands inside c-component loops in high-burnup fuel cladding

High-burnup Zr-based nuclear fuel claddings exhibit accelerated irradiation growth, corrosion and hydrogen pick-up, all correlated with the emergence of c-component dislocation loops. We made use of sub-nm-resolution atom probe tomography to characterize the nanoscale chemistry of c-loops in fuel cladding from boiling water reactor operation. We found segregation of Fe, Ni and Sn to dislocation lines and depletion of Sn and O inside the loops, resulting in nearly pure Zr islands. We also observed nucleation of suboxide inside one c-loop, pointing to a possible mechanism of accelerated in-reactor corrosion. The Zr islands might also promote hydride precipitation and associated degradation.

Nanocrystalline Cubic Phase Scandium-Stabilized Zirconia Thin Films.

The cubic zirconia (ZrO2) is attractive for a broad range of applications. However, at room temperature, the cubic phase needs to be stabilized. The most studied stabilization method is the addition of the oxides of trivalent metals, such as Sc2O3. Another method is the stabilization of the cubic phase in nanostructures-nanopowders or nanocrystallites of pure zirconia. We studied the relationship between the size factor and the dopant concentration range for the formation and stabilization of the cubic phase in scandium-stabilized zirconia (ScSZ) films. The thin films of (ZrO2)1-x(Sc2O3)x, with x from 0 to 0.2, were deposited on room-temperature substrates by reactive direct current magnetron co-sputtering. The crystal structure of films with an average crystallite size of 85 Å was cubic at Sc2O3 content from 6.5 to 17.5 mol%, which is much broader than the range of 8-12 mol.% of the conventional deposition methods. The sputtering of ScSZ films on hot substrates resulted in a doubling of crystallite size and a decrease in the cubic phase range to 7.4-11 mol% of Sc2O3 content. This confirmed that the size of crystallites is one of the determining factors for expanding the concentration range for forming and stabilizing the cubic phase of ScSZ films.

Laue microdiffraction on polycrystalline samples above 1500 K achieved with the QMAX-µLaue furnace.

X-ray Laue microdiffraction aims to characterize microstructural and mechanical fields in polycrystalline specimens at the sub-micrometre scale with a strain resolution of ∼10-4. Here, a new and unique Laue microdiffraction setup and alignment procedure is presented, allowing measurements at temperatures as high as 1500 K, with the objective to extend the technique for the study of crystalline phase transitions and associated strain-field evolution that occur at high temperatures. A method is provided to measure the real temperature encountered by the specimen, which can be critical for precise phase-transition studies, as well as a strategy to calibrate the setup geometry to account for the sample and furnace dilation using a standard α-alumina single crystal. A first application to phase transitions in a polycrystalline specimen of pure zirconia is provided as an illustrative example.

The pivotal role of oxygen vacancy and surface hydroxyl in the adsorption and activation of CO2 on ceria-zirconia mixed oxide

Ceria-zirconia mixed metal oxide along with pure ceria and zirconia were prepared by the co-precipitation method and characterized by N2-Physisorption, X-ray diffraction (XRD), H2-temperature programmed reduction (H2-TPR), CO-TPR with mass spectroscopy (CO-TPR/MS), oxygen storage capacity (OSC), CO and CO2-temperature programmed desorption with MS (TPD/MS), Raman spectroscopy, XPS, and diffuse reflectance infrared Fourier transform Spectroscopy (DRIFTS) techniques. Furthermore, Density Functional Theory (DFT) calculations were performed to acquire molecular insights into the role of oxygen vacancies and surface hydroxyl species in CO2 adsorption and subsequent activation. Our experimental and theoretical results corroborated the fact that the incorporation of zirconium ions into the ceria matrix enhanced the overall CO2 adsorption and activation by forming thermally stable surface species, which were eventually detected by DRIFTS. Additionally, DFT calculations revealed the oxygen vacancy mediated change in the electronic structure of ceria-zirconia mixed oxide, which had been argued to improve its catalytic activity. Furthermore, the oxygen vacancy formation energy (OVFE), oxygen storage capacity (OSC) and CO2 adsorption energies were correlated to augment the importance of these properties.

Electrochemical corrosion behavior of industrial pure zirconium in high Cl- containing solutions

The effects of different Cl- concentrations on the corrosion behavior of pure zirconium and its welded joint were studied by electrochemical test and numerical fitting, and the mechanism was discussed. The results showed that：In the solution containing Cl-, the potentiodynamic polarization curves of industrial pure zirconium base metal and its welded joint show certain passivation behavior, and with the increase of Cl- concentration, the corrosion tendency of the base metal and welded joint increases, the potentiodynamic polarization curves move to the lower right, the polarization resistance of the material decreases, the corrosion current density increases, and the corrosion resistance deteriorates. Compared with the base metal, the corrosion current of the welded joint is larger and the pitting potential is lower under the same Cl- concentration, and the difference in microstructure is the main reason for the poor corrosion resistance.

Investigation of electrical, corporeal, ocular, and aquaphobic properties of zirconia thin-films by varying substrate temperature for high voltage insulators

ABSTRACT The addition of ZrO2 nanoparticles to porcelain insulators and its influence on their electrical and corporeal characteristics are studied throughout a wide range of sintering temperatures. The DC magnetron sputtering with a 99.99% pure zirconium target is utilized to create zirconium oxide thin films on glass and silicon substrates in a 12-inch-diameter chamber. Different temperatures were used to sinter the produced samples (room temperature (RT) − 400°C) for 1 h with gas pressure of 15 mTorr for all depositions. Scanning electron microscopy (SEM) was used to characterize the microstructures of a subset of the samples. In order to assess the physical and microphysical changes brought on by an increase in substrate temperature, the phase composition of various nanocomposites samples was determined using X-ray diffraction (XRD). The breakdown strength, electrical resistivity, and dielectric constant were measured to assess the electrical attributes of the various samples. The obtained findings showed that the electrical and corporeal characteristics of samples sintered at RT were the best. In addition, the sample of nanocomposite porcelain sintered at room temperature has excellent insulating qualities, confirming the possibility of electro-technical porcelain manufacture (water contact angle = 103.5º), dielectric constant = 24.4, refractive index = 2.15, and bandgap = 5.33.

Green color emitting pure cubic zirconia nano phosphor synthesized by solution combustion technique

Green color emitting pure cubic zirconia nano phosphor synthesized by solution combustion technique

Структура и свойства покрытий SiO2 – Cr2O3, полученных методом импульсного магнетронного распыления на керамической основе ZrO2

The technology for SiO2 – Cr2O3 coatings on a ceramic Y-TZP (ZrO2 stabilized by Y2O3) zirconia base has been proposed. The coating was produced in three stages: 1) formation of SiO2 adhesion layer by application of 5-amino-propyltriethoxysilane alcohol solution to the ceramic base surface followed by heat treatment at 450 ± 5 °C for 30 min. The next step was application of Cr at purity of 99.9 % by pulse magnetron sputtering; 3) diffusion oxidation of Cr, applied on the ceramic base, to Cr2O3 in the muffle furnace at 450 ± 5 °C for 30 min. Dependence of physical-mechanical characteristics of coating depending on preparatory and finishing operations (abrasive blasting, polishing) has been investigated. Samples with submicron coating with thickness of 150 ± 20 nm, having nanostructured lamellar structure, possessing open porosity value of 1.3 %, microhardness 2000 HV, roughness Ra 0.32 – 0.63, friction coefficient 0.175 and increased by 184 % wear resistance to abrasion loadings in comparison with pure zirconia ceramics were obtained.

Infrared Fingerprints of the CO2 Conversion into Methanol at Cu(s)/ZrO2(s): An Experimental and Theoretical Study

AbstractThe methanol economy is an attractive approach to tackle the current concerns over the depletion of natural resources and the global warming intrinsically associated with the use of fossil fuels. This can be achieved by hydrogenation of carbon dioxide to produce methanol, a liquid fuel with potential use in civil transportation. In this study, we aim to pinpoint the intermediates that are involved in the catalytic CO2 conversion into methanol on pure zirconia (ZrO2), Cu and Cu/ZrO2 systems. To accomplish this, we make use of infrared (IR) spectroscopy measurements and quantum chemical simulations within the hybrid density functional theory (DFT) framework. At 250 °C and p~30 bar, the main species formed on the partially hydroxylated ZrO2 is bidentate formate, whereas the co‐production of bicarbonate is relevant upon cooling to T=25 °C. On pure Cu, the IR fingerprints of methanol and carbon dioxide indicate their presence in the gas phase and surface environment, albeit formate/formic acid and methoxy species are also detected at these experimental conditions. The production of methanol on Cu/ZrO2 is mostly dependent on the Cu catalyst, but the higher amount of the methoxy intermediate can be correlated with the consumption of formate adsorbed on ZrO2 or at the Cu/ZrO2 interface. On the Cu/ZrO2 mixture, the reaction mechanism is likely to involve formate as the main intermediate, instead of CO which would result from the reverse water‐gas shift reaction. Ultimately, the higher activity shown by the Cu/ZrO2 mixture might be associated with the extra‐production of methoxy/methanol catalyzed by ZrO2 in the presence of Cu.

Optical and physical properties of zirconium dioxide reinforced poly(methyl methacrylate) nanocomposite films

AbstractThe objective of this study was to investigate the fundamental aspects of acrylic resin and zirconia nanoparticle interaction to analyze the optical properties and subsequent changes in refractive index with incremental loading of nanoparticles. Poly(methyl methacrylate) (PMMA) reinforced with zirconia nanoparticles were prepared by dip coating, spin coating and solvent casting techniques. An overall understanding of the polymer nanocomposite film has been achieved using the spectroscopic and morphological studies. The vital aspect of this whole study is to derive a simple yet an efficient nanocomposite film capable of imparting extraordinary optical properties. Within the limitations of this research a very crucial property of the material has been revealed. The RI as well as the optical transparency of the nanocomposite film has been steadily maintained with a significant increase of RI by the magnitude of 0.06 and ~100% light transmittance on incorporation of pure zirconia nanoparticles into PMMA matrix has been achieved. The best technique found was spin coating as it could yield thin films and better transparency and higher refractive index.