Zirconia Phase Research Articles

Combined experimental and first principles look into (Ce, Mo) doped BiVO4

Here we investigated the effects of Ce and Mo doping on hydrothermally synthesized bismuth vanadate BiVO4 nanoparticles (NPs). The existence of monoclinic scheelite and tetragonal zircon phases of NPs was validated from Rietveld refinement of the powdered X-ray diffraction, room temperature Raman, and Fourier-transform infrared spectroscopy. The co-doping of Bi and V sites with respective Ce and Mo dopants in a mixed tetragonal zircon and monoclinic scheelite phases of BiVO4 lattice was corroborated from high-resolution transmission electron microscopy and X-ray photoelectron spectroscopy. The photoluminescence measurements revealed enhancement of photo-generated carrier recombination in (Ce, Mo) co-doped BiVO4 NPs which may have hampered its photocatalytic efficiency in degrading the methylene blue dye. The simulations based on Hubbard U corrected density functional theory (DFT+U) suggest that Mo and Ce co-doping introduced deep impurity states which may have facilitated the photo-generated carrier recombination detrimental to photocatalytic performance. The UV-vis diffuse reflectance measurements provided evidence for the presence of these defect states. In summary, this work may have presented a comprehensive experimental analysis of (Ce, Mo) doped BiVO4 supported by DFT simulations.

Color- and strength-graded zirconia: Strength, light transmission, and composition

Statement of problemNatural teeth are graded in terms of translucency and strength. Graded zirconia materials are now available with a higher yttria content on the top or in the enamel zone to increase surface translucency and a lower yttria content on the bottom or in the dentin zone to increase strength. Such materials could provide multiple advantages over uniform materials and reduce the need for porcelain veneering in anterior artificial crowns; however, studies on the properties of these materials are lacking. PurposeThe purpose of this in vitro study was to measure and compare the biaxial flexural strength, percentage light transmission, elemental content, and phase content of zones within and among color graded zirconia blocks and color- and strength-graded zirconia blocks. Material and methodsDisks of a color graded material (Katana STML) and a strength- and color-graded material (IPS e.max ZirCAD Prime) were fabricated (Zircom Furnace). Biaxial flexural strength was measured using a piston-on-3-ball test in a universal testing machine (n=10). Absolute light transmission was measured with a spectrophotometer. Elemental compositions were quantified for 3 zones in each of the 2 zirconia materials using X-ray fluorescence analysis. Zirconia phase fractions were quantified for 3 zones using X-ray diffraction analysis (XRD). Where appropriate, 2-way ANOVA, 1-way ANOVA, and Tukey multiple pairwise comparison testing were used to determine which of the 6 zones differed from one another (α=.05). ResultsThe color-graded zirconia exhibited gradients in light transmission and differences in phase content in the 3 zones measured. The color- and strength-graded zirconia exhibited gradients in light transmission, biaxial flexural strength, elemental composition, and phase content in the 3 zones measured. The bottom, dentin, or intaglio layer of a strength graded zirconia material was substantially stronger than all other zones of either material (P<.05). The top, enamel, zones of both materials possessed high light transmissibility (P<.05). The 2 materials differed with respect to biaxial strength (P<.001), light transmission (P<.02), elemental composition, and phase composition overall, as well as in most zone-by zone comparisons (P<.05). The performance and composition of the color graded material was consistent with it being a 5Y material throughout. The performance and composition of the color and strength graded material was consistent with it having a 3Y bottom zone and a 5Y top zone. ConclusionsA strength-graded and color-graded zirconia material offers potential advantages in both strength and translucency.

Enhanced hydrogen barrier performance of ZrH1.8 via yttria-zirconia composite film developed through the ECD-MAO technique

To address the inherent shortcomings of the direct micro-arc oxidation method, this study employed a combination of electroplating and micro-arc oxidation techniques. This approach successfully fabricated a hydrogen permeation barrier film on the surface of ZrH1.8, featuring a yttria-stabilized zirconia (YSZ) composite oxide. The prepared composite film layer underwent thorough evaluations, encompassing assessments of its microstructure, phase structure, adhesion strength, thickness, barrier properties, and hydrogen permeation performance. The findings indicated that the electroplated yttrium layer contributes to the stabilization of the tetragonal phase of zirconia (T-ZrO2) during the micro-arc oxidation process, thereby enhancing the discharge behavior of the film layer. By employing this treatment method, the content of T-ZrO2 in the film layer increased to 26.70%, and the film became denser with a thickness of 60.93 μm. Additionally, the adhesion strength between the film layer and the substrate significantly improved, reaching 75.95 N, with a hardness of 393.24 HV. Furthermore, the film layer exhibited an increased hydrogen release temperature of 680 °C, demonstrating excellent performance as a hydrogen permeation barrier.

Fracture strength of porcelain veneer on surface-treated zirconia.

In this study, we investigated the effects of surface treatment on the fracture strength of porcelain-veneered zirconia. Highly translucent 4 mol% yttria-stabilized zirconia disks (KATANA HT, Kuraray Noritake Dental) were divided into three surface-treatment groups: 1)as-sintered, 2) alumina sandblasted, and 3) ground. Crystallographic and surface-roughness analyses were conducted for each group. Veneering ceramics (Cerabien ZR, Kuraray Noritake Dental) were applied to the zirconia surfaces. The fracture strengths of the porcelain-veneered zirconia disks were measured using biaxial flexural-strength tests. Crystallographic analysis revealed that grinding and sandblasting increased the fractions of the monoclinic and rhombohedral zirconia phases. The ground specimens had a higher surface roughness than the sandblasted specimens. Weibull analysis showed no significant differences in biaxial flexural strength among the three groups. The results suggest that these surface treatments do not affect the fracture strength of porcelain-veneered zirconia.

Effects of multiple firings on the translucency, crystalline phase, and mechanical strength of highly translucent zirconia.

This study aimed to clarify the effects of multiple firings on the translucency, crystal structure, and mechanical strength of highly translucent zirconia. Four types of highly translucent zirconia (LAVA Esthetic, LAVA Plus, KATANA Zirconia STML, and KATANA Zirconia HTML) were fired three times at three different temperatures, and the translucency, crystal structure, and flexural strength were evaluated before and after firing. The translucency was statistically compared using repeated-measures analysis of variance; the zirconia phase composition was assessed using X-ray diffraction followed by Rietveld analysis; and the biaxial flexural strength was assessed using Weibull analysis. The translucency of LAVA Esthetic and KATANA Zirconia HTML decreased significantly after firing, and the crystal composition of LAVA Plus and KATANA Zirconia HTML changed after multiple firings, whereas multiple firings did not affect the biaxial flexural strength of any samples. Thus, multiple firings may affect the optical properties of highly translucent zirconia.

Zircon-to-reidite phase transition enhanced by minor radiation damage: Implications for hypervelocity impacts

Reidite, a high-pressure phase of zircon, is increasingly identified at terrestrial impact sites. Despite its growing recognition, the potential applications for estimating minimum impact pressure face impediments due to existing discrepancies in the condition of zircon-reidite transformation, controversial models governing the transformation mechanism, and unclear effects of pre-existing radiation damage on reidite formation. Here, we show enhanced reidite formation by synchrotron X-ray diffraction, Raman spectroscopy, and transmission electron microscopy analyses of zircon grains that have experienced different alpha-decay doses from U and Th impurities and subsequent pressurization in diamond anvil cells. Below ∼1 × 1018 α-decay events/g, the α-decay-induced isolated point defects in the still crystalline zircon facilitate the minor atomic readjustments required for reidite formation. However, above this dose, the loss of long-range periodicity in severely damaged or even metamict zircon inhibits the transformation. The enhanced reidite formation by minor radiation damage coincides with the more common occurrence of reidite at impact sites for which the precursor zircon has a relatively lower alpha-decay-event dose before the impact event. In addition, the detailed atomic-scale structures of twinned reidite provide unambiguous evidence for a characteristic internal stress-induced martensitic transition. These findings have important implications for interpreting the formation conditions of natural reidite due to the convergence of pressure from the static, shockwave, and natural reidite samples.

Structure evolution and τf influence mechanism of Bi1–xHoxVO4 microwave dielectric ceramics for LTCC applications

Bi1–xHoxVO4 (0.1 ≤ x ≤ 0.9) ceramics were prepared via a solid-state reaction method, and all the ceramics could be well densified in the 920–980 °C range. The ceramics with 0.1 ≤ x < 0.4 were composed of both monoclinic scheelite (M) and tetragonal zircon (T) phases, and a single M phase could be obtained in the range of x ≥ 0.4. The measured εr decreased from 58.9 (x = 0.1) to 14.7 (x = 0.9), so do the calculated values (εr(C−M) = 34.3–12.1), and the main reason for εr > εr(C−M) was the rattling of Ho3+ in the dodecahedron. Two points with zero τf appeared in Bi1–xHoxVO4 (0 ≤ x ≤ 1) ceramics, and the best microwave dielectric properties with εr = 16.6, Q × f = 18,400 GHz (f = 10.69 GHz), and τf = +3.29 ppm/°C were obtained in the Bi0.2Ho0.8VO4 ceramic. The change in temperature coefficient of ionic polarizability (ταm) caused by the rattling effect of cations is the physical essence that affects τf. Therefore, the rattling effect can be used as an effective mechanism to regulate τf in low-εr materials. Furthermore, there was no chemical reaction between Bi1–xHoxVO4 and Ag electrode, which indicates potential applications in low-temperature co-fired ceramic (LTCC) technology.

Synthesis of zirconia nanoparticles by sol-gel. Influence of acidity-basicity on the stability transformation, particle, and crystallite size

Currently, zirconium oxide (ZrO2, also called zirconia) is used for restoration or as an implant in dentistry due to its properties and the aesthetics that can be achieved. In the present work, zirconia particles were obtained by the sol-gel method using acid or basic medium to study its influence on the nucleation and growth of the particle size and determine the crystallite size of the high-temperature phase. Also, to control the particle size and improve the solubility and dispersion of the colloidal particles resulting from the hydrolysis-condensation reactions, a mixture of alcohol of different chain lengths were used. The zirconia samples were heat treated at 400, 600, and 800 °C and up to 250 h of holding times to follow the growth of crystallite size of zirconia phases. The results showed tetragonal (ZrO2-t) and monoclinic (ZrO2-m) zirconia as predominant phases, regardless of the synthesis conditions and heat treatment used. The monoclinic phase is favored at elevated temperatures and prolonged holding times, while the tetragonal ones are favored at low temperatures. The holding time promotes the transformation from the tetragonal to the monoclinic phase in both media (acid and basic). However, this transformation is promoted by the basic catalyst, while the acid medium favors the stability of the tetragonal phase at 400 and 600 °C. The phase transformation, particle size, and crystallite size depend on the synthesis conditions and heat treatment used to obtain the zirconia particles.

Influence of 3D printed surface micro-structures on molding performance and dental bonding properties of zirconia

ObjectivesTo investigate the influence of the 3D printed micro-structured surfaces on the bond strength of zirconia to resin cement. MethodsZirconia specimens were divided into five groups based on manufacturing technique and surface preparation: (1) milled zirconia (M group); (2) milled zirconia airborne abraded (MA group); (3) printed zirconia (M group); (4) printed zirconia airborne abraded (PA group); and (5) printed zirconia with micro-structured surface (PM group). The surface morphology, cross-sectional morphology, and elemental composition were observed using a scanning electron microscope (SEM). Surface roughness was measured using a laser scanning confocal microscope (SLCM). Shear bond strength (SBS) was measured using a universal testing machine after bonding resin cement (n = 10). The failure modes of the bonded fracture interfaces were observed and counted using a stereomicroscope and a SEM. In addition, boundary dimensional accuracy (n = 10) and micro-structural dimensional accuracy (n = 20) of printed zirconia specimens with micro-structured surfaces were measured using digital calipers and Fiji software. The crystalline phase changes before and after surface treatment were investigated using X-ray diffractometry. Data was analysed using one-way ANOVA and Tukey HSD post-hoc tests (α = 0.05). ResultThe surface micro-structures of the PM group had regular morphology and no obvious defects. The surface roughness results showed that the PM group had higher Sa (42.21±1.38 um) and Ra (21.25±1.80 um) values than the other four groups (p < 0.001). The SBS test showed that the bond strength of the PM group reached 11.23 ± 0.66 MPa, which was 55.97% (p < 0.001) higher than that of the P group (7.20 ± 1.14 MPa). The boundary dimensional accuracy of the PM group was proficient (diameter: 99.63 ± 0.31%, thickness: 98.05 ± 1.12%), and the actual fabrication dimensions of the hexagonal micro-structures reached 77.45%-80.01% of the original design. The micro-structured surface did not affect the crystalline phase of zirconia. ConclusionsThe current study illustrates that 3D-printed microstructured surfaces effectively improve the bond strength of zirconia to resin cements. Clinical significanceWith the advantage of 3D printing, this study provides a new idea for improving the bonding properties of zirconia.

Hybrid manufacturing and mechanical properties of architected interpenetrating phase metal-ceramic and metal-metal composites

A hybrid manufacturing process for the fabrication of architected metal-ceramic and metal-metal interpenetrating phase composites (IPCs) is elaborated and employed to assess the mechanical performance of novel, advanced composite materials. In particular, aluminum-based co-continuous composites, reinforced with triply periodic minimal surface (TPMS) steel and ceramic (zirconia) phases are engineered, combining 3D-printing and investment casting techniques. The hybrid process results in excellent wettability between the ceramic-Al and steel-Al phases, characterized through Scanning Electron Microscopy (SEM) and micro-CT scanning analysis. The arising IPCs yield mechanical properties that utterly differ from the performance of the base ceramic or steel TPMS reinforcement topologies, with the ceramic-Al composites to furnish a highly ductile response and steel-Al IPCs a remarkable post-elastic stiffening performance. Ceramic-based IPCs yield a specific energy absorption (SEA) that is more than 400 times higher than the one of single-phase ceramic metamaterials, while steel-based IPCs allow for SEA values in the order of 50 J/g, values which rank among the highest ever reported for architected IPCs. A broader Ashby-type classification is provided, while the efficiency of the IPC plastification process is associated with the obtained SEA values. Moreover, experimental results are complemented by finite element analysis insights in the effect of the interpenetrating phase design on the inner stresses developed. The hybrid manufacturing process and the co-continuous composites investigated open novel pathways in the engineering of next-generation multifunctional architected IPCs for base material combinations beyond the ones here considered.

Preparation of Solid Superacid SO42-/ZrO2 and SO42-/ZrO2-MxOy (M=Ce, Co, Mn, and Zn) and Its Application in Toluene Nitration.

The nitration reaction of aromatic compounds is one of the extensively studied chemical reactions that result in the manufacturing of various industrial products applied in pharmaceuticals, dyes, perfumes, and explosives. A series of modified sulfated zirconia (SZ) catalysts SO42-/ZrO2-MxOy (M=Ce, Co, Mn, Zn, and M/SZ) doped with different metal elements by a coprecipitation method were investigated in the toluene nitration reaction. Various characterization techniques (X-ray diffraction, Brunauer-Emmett-Teller, thermogravimetric analysis, X-ray photoelectron spectroscopy, and temperature-programmed desorption of ammonia) indicated that doping metal elements in SZ led to excellent catalytic properties, increasing the specific surface area of the catalyst and facilitating the formation of a stable tetragonal zirconia phase. Doping zinc and cobalt in SZ enhanced the acidity of the catalyst and formed stronger acidic sites, promoting the generation of nitronium ions and providing more active sites for the toluene nitration reaction. Additionally, it reduced the loss of sulfate ions in the catalytic system that helped in improving the stability of the catalyst. Under the same conditions, the catalytic activity of toluene nitration reaction demonstrated the following order: Zn/SZ > Ce/SZ > Co/SZ > Mn/SZ > SZ, with the zinc-doped SZ catalyst exhibiting the best catalytic performance, achieving a toluene conversion rate of 78.58% and a para/ortho nitrotoluene ratio of 0.67.

Influence of bioactive glass addition on the machinability, mechanical and biological response of Mg-PSZ-based biocomposites

The incorporation of bioactive glass (BG) into zirconia-based composite materials shows a feasible option to enhance the biological properties, reduce the sintering temperature, and resist the transformation of the tetragonal phase of zirconia. In this present work, the bioceramic composites, having the general formula [(100-x) (8 Mg-PSZ) – x (13–93 BG)] where x = 0 to 25 wt%, have been prepared and evaluated the effect of BG amounts on the machinability, mechanical and biological behavior of the composite material. The machining experiment is performed on an abrasive air jet machine (AAJM), and machinability is evaluated in the form of material removal rate (MRR), surface roughness (SR), and mechanics of material erosion (MME) at room temperature. The machinability results show that MRR decreases with enhancing the BG contents, and the SR follows the opposite trend of MRR. The MME indicates that the material is removed from the surface mainly due to the erosion crater and brittle fracture. Further, mechanical properties are evaluated, and it is found that the inclusion of BG frits and sintering temperature is substantially associated with the relative densities and the mechanical characteristics. Adding BG reinforcements increases the mechanical characteristics at lower sintering temperatures (1250 °C) while reducing the mechanical characteristics except hardness at higher sintering temperatures (1350 °C). Elastic modulus decreases with the addition of BG content up to 15 wt%; after that, it slightly increases up to 25 wt%. The in-vitro bioactivity and bio-degradation are tested in simulated body fluid (SBF), and both are increased by enhancing the BG contents up to 25 wt%. The in-vitro cell culture is performed on the MG-63 cell line. The biocompatibility increases with BG concentration (up to 25 wt%). Based on experimental results, it may be concluded that 8 Mg-PSZ/13-93BG bioceramic composites may be a potential choice for biomedical applications.

Grazing-incidence synchrotron radiation diffraction studies on irradiated Ce-doped and pristine Y-stabilized ZrO2 at the Rossendorf beamline.

In this work, Ce-doped yttria-stabilized zirconia (YSZ) and pure YSZ phases were subjected to irradiation with 14 MeV Au ions. Irradiation studies were performed to simulate long-term structural and microstructural damage due to self-irradiation in YSZ phases hosting alpha-active radioactive species. It was found that both the Ce-doped YSZ and the YSZ phases had a reasonable tolerance to irradiation at high ion fluences and the bulk crystallinity was well preserved. Nevertheless, local microstrain increased in all compounds under study after irradiation, with the Ce-doped phases being less affected than pure YSZ. Doping with cerium ions increased the microstructural stability of YSZ phases through a possible reduction in the mobility of oxygen atoms, which limits the formation of structural defects. Doping of YSZ with tetravalent actinide elements is expected to have a similar effect. Thus, YSZ phases are promising for the safe long-term storage of radioactive elements. Using synchrotron radiation diffraction, measurements of the thin irradiated layers of the Ce-YSZ and YSZ samples were performed in grazing incidence (GI) mode. A corresponding module for measurements in GI mode was developed at the Rossendorf Beamline and relevant technical details for sample alignment and data collection are also presented.

Layered ZrO2/SiO2 aerogel composite fibrous flexibility membrane for thermal insulation and sound absorption

AbstractAs promising candidates for widespread application, advanced ceramic fiber mats with robust mechanical properties are urgently needed. However, the brittleness, fatigue failure, and large density of ceramic fiber pose significant obstacles to its practical application. Herein, a novel SiO2 aerogel/ZrO2 composite nanofibrous membrane (SZCNFM) with excellent flexibility was prepared by introducing SiO2 aerogel nanoparticles into ZrO2 nanofiber via simple co‐electrospinning. The developed tetragonal zirconia phase without changing up to 1200°C endows SZCNFM material with excellent thermal stability. Furthermore, the as‐prepared membranes exhibit fatigue resistance ability which can maintain 98% of the original stress after 100 buckling cycle tests. The addition of mesoporous structure aerogel reduces the heat transfer of the nanofibrous membrane, giving its low thermal conductivity (30 mW/m/K) and low‐frequency sound absorption (noise reduction coefficient of 0.52). Combined with the high‐temperature resistance, low thermal conductivity and excellent sound‐absorption ability make it a promising material for heat insulation and acoustic absorption.

Effect of Frequency and Temperature on Dielectric and Transport Properties of CaO stabilized ZrO2@mullite composites

AbstractThis study concerns the synthesis and structure related electrical property analysis of CaO doped ZrO2@mullite composites. Two synthesis techniques (solid state reaction route and thermal plasma sintering) are used which results the formation of a composite consisting of mixed phase of orthorhombic mullite, tetragonal and monoclinic zirconia. The lattice parameters, residual strains, average crystallite size and cell volume of these CaO‐doped ZrO2@mullite composites are obtained from XRD analysis. Stabilization of t‐ZrO2 phase at room temperature is confirmed. Porous microstructure observed in SEM images results in low dielectric constant value of these composites. At room temperature and selected frequency of 1MHz, the dielectric constant and loss factor of 4.7 and 3.826 × 10−2 is observed for conventional CaO stabilized ZrO2@mullite composite and that of 3.8 and 2.19 × 10−2 is reported for plasma sintered CaO stabilized ZrO2@mullite composite. The impedance spectroscopic analysis demonstrates the negative temperature coefficient of resistance (NTCR) behavior and non‐Debye type relaxation behavior of both the CaO stabilized ZrO2@mullite composites. A negligible effect of electrode polarization is realized in these composites. The electronic band gap of conventional and plasma sintered CaO stabilized ZrO2@mullite composites is found to be around 3eV.

Investigation of the effects of kiln roller waste addition on porcelain tile matte-opaque glazes

Ceramic tiles reach their final microstructures and acquire their technical properties by firing process after shaping, glazing, and drying processes. The firing process is carried out continuously in roller kilns. In roller kilns, tiles pass through firing zones at different firing temperatures such as preheating, firing, and cooling zones in which different types of rollers are used. deformations such as breakage and deterioration of roller smoothness occur in the kiln roller over time due to high temperature and tile mass. For these reasons, unused kiln rollers are separated into waste and replaced with new ones. In the present study, the purpose was to transform the kiln roller into a value-added product. For this purpose, the use of kiln roller wastes in glazed porcelain tile matte-opaque glaze was investigated. Ground kiln roller waste was used instead of alumina, quartz, and zircon in a standard matte-opaque glaze composition. The developed glazes were sintered at 1190 °C for 44 min. The thermal, optical, and physical properties of the glazes were examined and compared with the standard glaze recipe. The melting behaviors of the glazes were measured with a heating microscope, and the thermal expansion coefficients were measured with a dilatometer. The phases developed in the structure were determined by XRD analysis and scanning electron microscope (SEM). According to the results, the usage of roller waste instead of alumina and quartz decreased the crystal phase development in the glaze and the opacity, causing an increase in surface glossiness. When it was used instead of zircon, anorthite and crystal phase development increased and the surface brightness decreased, but the opacity decreased significantly due to the decline of zircon crystals. Considering all these thermal and optical properties, it was determined that the use of roller waste would be possible with some optimizations in the composition of matte-opaque glaze composition.

Wear behavior at high temperature of ZrO2–Y2O3 (YSZ) plasma-sprayed coatings

The wear behavior of two plasma-sprayed zirconia–yttria coatings was studied at high temperatures. Agglomerated and sintered, as well as fused and crushed zirconia–yttria feedstock powders were used to manufacture bimodal and monomodal coatings by atmospheric plasma spraying onto an INCONEL 718 substrate previously coated with a NiCrAlY bond coat. The structure of the coatings was analyzed by SEM on their cross section and surface. The samples were subjected to wear conditions by sliding contact through a ball-on-disk test up to 1000 °C, using an alumina ball 6 mm in diameter as the counterbody, on which a load of 5 N was applied. The samples were rotated during 20000 cycles, reaching a speed of 0.10 m·s−1 at the contact area with the counterbody. The porosity, phase, and mechanical properties were determined before and after wear tests. The results indicate that at 25 °C, both coatings have enough mechanical resistance to withstand the tribological conditions they were exposed to. Therefore, low wear rates were produced by ductile deformation. The tribological conditions became more aggressive as the thermal stresses increased with the test temperature, producing cracking, and detaching particles in the coatings tested at 500 and 750 °C. Consequently, high wear rates related to brittle deformation were obtained. However, the transformation of the amorphous phase to the t′-zirconia phase, produced at 1000 °C, increased the hardness of both coatings and, consequently, their wear resistance; thus, the predominant mechanism of damage was ductile deformation, with wear rates similar to those obtained when the coatings were tested at 25 °C.

Evaluation of Feasibility on Dental Zirconia-Accelerated Aging Test by Chemical Immersion Method.

The aim of this study was to investigate the low-temperature degradation (LTD) kinetics of tetragonal zirconia with 3 mol% yttria (3Y-TZP) dental ceramic using two degradation methods: hydrothermal degradation and immersed degradation. To study transformation kinetics, we prepared 3Y-TZP powders. We pressed these powders uniaxially into a stainless mold at 100 MPa. We then sintered the compacted bodies at intervals of 50 °C between 1300 °C and 1550 °C and immersed the specimens at various temperatures from 60 °C to 80 °C in 4% acetic acid or from 110 °C to 140 °C for the hydrothermal method. We used a scanning electron microscope (SEM) to confirm crystalline grain size and used X-ray diffraction to analyze the zirconia phase. As the sintering temperature increased, the calculated crystalline grain size also increased. We confirmed this change with the SEM image. The higher sintering temperatures were associated with more phase transformation. According to the Mehl-Avrami-Johnson equation, the activation energies achieved using the hydrothermal method were 101 kJ/mol, 95 kJ/mol, and 86 kJ/mol at sintering temperatures of 1450 °C, 1500 °C, and 1550 °C, respectively. In addition, the activation energies of the specimens immersed in 4% acetic acid were 60 kJ/mol, 55 kJ/mol, 48 kJ/mol, and 35 kJ/mol, with sintered temperatures of 1400 °C, 1450 °C, 1500 °C, and 1550 °C, respectively. The results showed that a lower sintering temperature would restrain the phase transformation of zirconia because of the smaller crystalline grain size. As a result, the rate of LTD decreased.

Nanoscale constraints on the nucleation and evolution of granular zircon from reidite in impactites at the Chicxulub impact structure

Zircon with granular texture from hypervelocity impact structures can be used to estimate the thermodynamic conditions of impact processes, including pressure and temperature, and in some cases the timing of impact events via U-Pb geochronology. However, two disparate formation models have been proposed to explain the occurrence of zircon neoblasts that preserve systematic orientation relations; one involves zircon-reidite phase transformations (FRIGN zircon), whereas the other features melting and thermal dissociation of zircon in the absence of reidite. Distinguishing between these models is hampered by the lack of observational constraints on the intermediate transformation steps at nanoscale, and what processes give rise to observed systematic orientation relations among zircon neoblasts. Here we report new analyses of reidite-bearing and granular zircons from peak ring core samples of the Chicxulub impact structure using nanoscale methods. We describe lamellar and lense-like reidite habits associated with reidite twins in shocked zircon from impact melt-bearing breccia, along with the first observation of nanoscale zircon granules forming locally within preserved reidite lamellae. The crystallographic orientation of the zircon nano-granules matches the orientations predicted by the FRIGN zircon model, confirming they formed directly by solid-state reversion of reidite to zircon, and represent the earliest stages of the formation of granular zircon. Minor occurrences of baddeleyite at the interface of reidite and neoblastic zircon domains suggest that the reversion of reidite to zircon can occur together with local ZrSiO4 dissociation driven either by the loss of SiO2, which creates excess zirconia, or by local thermal dissociation of reidite. Other partially- and fully-granular zircon grains from the same impact melt-bearing breccia also preserve systematic orientation relationships among zircon neoblasts, consistent with having transformed directly from reidite. The observation that zircon neoblasts maintain systematic orientations from nanoscale to microscale in granular zircon supports the idea that neoblast orientations are encoded at the nucleation stage via solid state phase transformation. Observations in this study provide direct evidence to explain the nature of systematic high-pressure phase transitions involving zircon and have implications for unraveling the pressure-temperature history of zircon phase transitions in large impacts on Earth or other planetary bodies.

Surface and interfacial microstructure evolution of isothermally oxidized thermal barrier coating system

Novel multilayer functionally graded thermal barrier coating (TBC) system consisting of a newly developed glass-ceramic based bond coating, glass-ceramic-25% yttria stabilized zirconia (YSZ) composite coating and 100% 8-YSZ top coating. Since TBC is a layered system property matching between each layer is a major concern. Therefore, thermal properties of the developed glass-ceramic coating and composite coating were studied in detail. The developed system was exposed to static oxidation at 1100 °C for 100 h. To assess the efficacy of the TBC system, XRD phase analysis and also mechanical properties like Young's modulus and nanohardness was performed at each layer for both before and after isothermal oxidation. From the surface and interfacial microstructure evolution it was observed that there was crack development at composite coating-top coating interface, which was due to zirconia phase transformation from tetragonal to monoclinic crystal structure, confirmed by the presence of monoclinic zirconia XRD diffraction peaks in XRD analysis. Additionally, Raman spectroscopy was also carried out on the isothermally oxidized specimen, which also pointed out the presence of monoclinic crystal structure. Even though developed TBC system failed to protect the nimonic alloy (AE435) substrate from thermal exposure at 1100 °C for 100 h the glass-ceramic/substrate had a good interfacial adhesion. Main advantage of using glass-ceramic coating is its ability to tune coating properties by changing the composition. Thus, future works are being carried out to alter the glass-ceramic composition to develop a potential TBC system.