Search Results (17)

Phenolic aerogel holds great promise for applications in thermal protection against ablation, and constructing inorganic–organic hybrid networks is an effective strategy to enhance its oxidation and ablation resistance. This study introduces a stepwise hybridization strategy for the preparation of SiO₂–ZrO₂–phenolic resin aerogels (SZPA). First, nano-silica sol and nanometer-scale zirconia were physically blended to form a uniformly dispersed mixture. Subsequently, the modified silica was incorporated into a phenolic resin solution to construct a three-dimensional hybrid silica–phenolic network framework. Nano-sized zirconia was then uniformly dispersed within the matrix as a physical reinforcing phase through high-shear dispersion. Finally, the SZPA with a hierarchical nanoporous structure was obtained via ambient-pressure drying. Owing to its unique hybrid network structure, the aerogel exhibits markedly improved properties: the thermal conductivity is as low as 0.0419–0.0431 W/(m·K) (a reduction of approximately 24%), and the specific surface area is as high as 190–232 m²/g (an increase of approximately 83%). Meanwhile, the inorganic network considerably enhances the residual mass at elevated temperatures, as well as the oxidation resistance and thermal stability of the matrix. Among the tested materials, the SZPA-4 exhibited outstanding thermal insulation capability at high temperatures; its back surface temperature reached only 74.4 °C after 600 s of exposure to a 1200 °C butane flame. This study provides a feasible route for the preparation of high-performance phenolic-based composite aerogels for aerospace thermal protection systems, thereby expanding their potential applications in extreme thermal environments. Full article

This study explores an innovative application of ultra-high-performance concrete (UHPC) by partially substituting cement with nano-zirconia (NZ) and micro-zirconia (MZ). A series of experiments were conducted to explore the influence of zirconia particle size (3860 nm and 320 nm) and varying replacement levels (0%, 0.5%, 1%, and 1.5%) on the workability, mechanical behavior, and microstructural characteristics of UHPC, utilizing the particle packing density model as a basis. Findings reveal that replacing 0.5% of the cement with MZ and NZ results in workability and mechanical performance comparable to the control mix. However, at 1.5 wt% MZ and 1.5 wt% NZ substitution levels, flowability declines by 22.01% and 24.71%, respectively, accompanied by a substantial increase in viscosity. The wet packing density of UHPC exhibits a linear rise with increasing zirconia content, with nano-sized particles exerting a more pronounced effect than their micro-sized counterparts. Specifically, at a 0.5% MZ replacement level, the 28-day compressive and flexural strengths show marginal improvements of 1.82% and 4.48%, respectively. The NZ1MZ0.5 mix achieves the highest 28-day compressive strength increase, reaching 9.45%, with an absolute gain of 11.92 MPa. Analyses using XRD, FTIR, and thermogravimetric analysis (TGA) demonstrate that zirconia incorporation has a negligible influence on the hydration process and does not alter the composition of hydration products in N-UHPC. Although zirconia effectively reduces porosity, excessive amounts (1.5%) increase pore size within the cement matrix, ultimately compromising mechanical properties. Based on these findings, the optimal NZ dosage for UHPC, when used in combination with MZ, is determined to be 0.5%. Full article

Dental zirconias have been broadly utilized in dentistry due to their high mechanical properties and biocompatibility. Although initially introduced in dentistry as an infrastructure material, the high rate of technical complications related to veneered porcelain has led to significant efforts to improve the optical properties of dental zirconias, allowing for its monolithic indication. Modifications in the composition, processing methods/parameters, and the increase in the yttrium content and cubic phase have been presented as viable options to improve zirconias’ translucency. However, concerns regarding the hydrothermal stability of partially stabilized zirconia and the trade-off observed between optical and mechanical properties resulting from the increased cubic content remain issues of concern. While the significant developments in polycrystalline ceramics have led to a wide diversity of zirconia materials with different compositions, properties, and clinical indications, the implementation of strong, esthetic, and sufficiently stable materials for long-span fixed dental prostheses has not been completely achieved. Alternatives, including advanced polycrystalline composites, functionally graded structures, and nanosized zirconia, have been proposed as promising pathways to obtain high-strength, hydrothermally stable biomaterials. Considering the evolution of zirconia ceramics in dentistry, this manuscript aims to present a critical perspective as well as an update to previous classifications of dental restorative ceramics, focusing on polycrystalline ceramics, their properties, indications, and performance. Full article

Fatty alcohols are important products in the chemical industry, given that they are frequently used in the formulation of surfactants and lubricants. In this context, this work describes a catalytic heterogeneous approach for the production of 1-octadecanol (C₁₈OH) from ethyl stearate (ES) using nanosized Ru-supported on tungstated zirconia (W/Zr). The activity and selectivity of this series of catalysts have been studied during the hydrogenation of ES in a batch reactor at 175 °C and P_H2 = 40 bar. The so-prepared catalysts were characterized by a sort of characterization techniques (i.e., X-ray diffraction, H₂-TPR, etc.), confirming the high dispersion and higher reducibility of Ru nanoparticles on the W/Zr surface (primarily tetragonal zirconia) with respect to pure zirconia. Overall, the catalysts were significantly active. In addition, a strong synergistic effect was revealed between Ru and W species, according to catalytic data. Finally, the reaction sequence towards fatty alcohol has also been elucidated, pointing to the ester hydrogenolysis to the aldehyde and ulterior hydrogenation of the latter as the main route for fatty alcohol formation. Full article

(1) Background: Color changes, physical degradation, and fungal infections are challenges to the longevity of maxillofacial polydimethylsiloxane (PDMS) elastomers. This study aimed to evaluate color changes, physical properties, and antifungal properties of PDMS loaded with ZrO₂ and TiO₂ submicron- and nano-sized particles. (2) Methods: A 1% weight of 40 nm or 200 nm diameter ZrO₂ or TiO₂ nanoparticles was mixed into PDMS with 2% functional intrinsic yellow pigment and polymerized. Control materials contained 13% weight 200 nm silica. Samples were exposed to 3000 h of UVB radiation (200 µW/cm²) or darkness. Color parameters L*a*b* and ∆E_ab*, ultimate tensile strength, strain, elastic modulus, and Shore A hardness were measured. Candida albicans growth was measured using XTT and confocal microscopy, and data were analyzed with the Dunnett test (p < 0.01). (3) Results: TiO₂ 200 nm showed the least color change after 3000 h of UVB radiation, followed by TiO₂ 40 nm (p < 0.05). The silica-containing control group was superior in all physical property measurements due to higher additive content (p < 0.05). TiO₂-containing materials exhibited significantly lower C. albicans growth (p < 0.01) than those loaded with ZrO₂ or SiO₂. (4) Conclusions: TiO₂ nanoparticles of 40 nm and 200 nm, when added to pigmented PDMS at 1% weight, provided the best resistance to color change and significantly lowered C. albicans activity compared to silica- and zirconia-filled elastomers. Particle size differences rendered minor differences for most properties. The incorporation of low-level submicron- and nano-sized TiO₂ particles has the potential to improve color stability and antifungal activity in silicones designated for maxillofacial prostheses and may be extended to denture reline applications. Full article

In this study, we produced zirconia nanoparticles with a pure tetragonal phase, good dispersion, and an average particle size of approximately 7.3 nm using the modified hydrothermal method. Zirconium oxychloride (ZrOCl₂-8H₂O) was used as zirconium source, while propanetriol was used as an additive. The influence of propanetriol content, sonication time, hydrothermal temperature, and type of dispersant on the physical phase and dispersibility of zirconia nanoparticles was investigated. Monoclinic zirconia was found to completely transform into a tetragonal structure when the mass fraction of glycerol was increased to 5 wt%. With the increase in the mechanical stirring time under ultrasonic conditions, the size distribution range of the prepared particles became narrower and then wider, and the particle size became first smaller and then larger. Ultrasonic and mechanical stirring for 5 min had the best effect. When comparing the effects of different dispersants (PEG8000, PVP, and CTAB), it was found that the average particle size of zirconia nanoparticles prepared with 0.5 wt% PVP was the smallest. Furthermore, by adding different concentrations of pure tetragonal phase nanozirconia to 3Y-ZrO₂ as reinforcement additives, the bending strength of the prepared ceramics increased first and then decreased with increasing addition amounts. When the amount of addition was 1 wt% and the ceramic was calcined at 1600 °C, the flexural strength of the ceramic increased significantly, which was about 1.6 times that of the unadded ceramic. The results are expected to provide a reference for the reinforcement of high-purity zirconia ceramics. Full article

Over the years, advancement in ceramic-based dental restorative materials has led to the development of monolithic zirconia with increased translucency. The monolithic zirconia fabricated from nano-sized zirconia powders is shown to be superior in physical properties and more translucent for anterior dental restorations. Most in vitro studies on monolithic zirconia have focused mainly on the effect of surface treatment or the wear of the material, while the nanotoxicity of this material is yet to be explored. Hence, this research aimed to assess the biocompatibility of yttria-stabilized nanozirconia (3-YZP) on the three-dimensional oral mucosal models (3D-OMM). The 3D-OMMs were constructed using human gingival fibroblast (HGF) and immortalized human oral keratinocyte cell line (OKF6/TERT-2), co-cultured on an acellular dermal matrix. On day 12, the tissue models were exposed to 3-YZP (test) and inCoris TZI (IC) (reference material). The growth media were collected at 24 and 48 h of exposure to materials and assessed for IL-1β released. The 3D-OMMs were fixed with 10% formalin for the histopathological assessments. The concentration of the IL-1β was not statistically different between the two materials for 24 and 48 h of exposure (p = 0.892). Histologically, stratification of epithelial cells was formed without evidence of cytotoxic damage and the epithelial thickness measured was the same for all model tissues. The excellent biocompatibility of nanozirconia, as evidenced by the multiple endpoint analyses of the 3D-OMM, may indicate the potential of its clinical application as a restorative material. Full article

The development of active, selective, and stable multicrystalline catalytic coatings on the inner surface of microcapillary reactors addresses environmental problems of fine organic synthesis, in particular by reducing the large quantities of reagents and byproducts. Thin-film nanosized bimetallic catalysts based on mesoporous pure titania and doped with zirconia, ceria, and zinc oxide, for use in microreactors, were developed, and the regularities of their formation were studied. The efficiency of PdZn/Ti_xM_1−xO_2±y (M = Ce, Zr, Zn) in the hydrogenation of 2-methyl-3-butyn 2-ol was studied with an emphasis on the stability of the catalyst during the reaction. The catalytic parameters depend on the adsorption properties and activity of PdZn and Pd(0) active centers. Under reaction conditions, resistance to the decomposition of PdZn is a factor that affects the stability of the catalyst. The zinc-doped coating proved to be the most selective and stable in the reaction of selective hydrogenation of acetylenic alcohols in a microcapillary reactor. This coating retained a high selectivity of 98.2% during long-term testing up to 168 h. Modification of the morphology and electronic structure of the active component, by doping titania with Ce and Zr, is accompanied by a decrease in stability. Full article

The global trend in restrictions on pollutant emissions requires the use of catalytic converters in the automotive industry. Noble metals belonging to the platinum group metals (PGMs, platinum, palladium, and rhodium) are currently used for autocatalysts. However, recent efforts focus on the development of new catalytic converters that combine high activity and reduced cost, attracting the interest of the automotive industry. Among them, the partial substitution of PGMs by abundant non-PGMs (transition metals such as copper) seems to be a promising alternative. The PROMETHEUS catalyst (PROM100) is a polymetallic nanosized copper-based catalyst for automotives prepared by a wet impregnation method, using as a carrier an inorganic mixed oxide (CeO₂-ZrO₂) exhibiting elevated oxygen storage capacity. On the other hand, catalyst deactivation or ageing is defined as the process in which the structure and state of the catalyst change, leading to the loss of the catalyst’s active sites with a subsequent decrease in the catalyst’s performance, significantly affecting the emissions of the catalyst. The main scope of this research is to investigate in detail the effect of ageing on this low-cost, effective catalyst. To that end, a detailed characterization has been performed with a train of methods, such as SEM, Raman, XRD, XRF, BET and XPS, to both ceria–zirconia mixed inorganic oxide support (CZ-fresh and -aged) and to the copper-based catalyst (PROM100-fresh and -aged), revealing the impact of ageing on catalytic efficiency. It was found that ageing affects the Ce–Zr mixed oxide structure by initiating the formation of distinct ZrO₂ and CeO₂ structures monitored by Raman and XRD. In addition, it crucially affects the morphology of the sample by reducing the surface area by a factor of nearly two orders of magnitude and increasing particle size as indicated by BET and SEM due to sintering. Finally, the Pd concentration was found to be considerably reduced from the material’s surface as suggested by XPS data. The above-mentioned alterations observed after ageing increased the light-off temperatures by more than 175 °C, compared to the fresh sample, without affecting the overall efficiency of the catalyst for CO and CH₄ oxidation reactions. Metal particle and CeZr carrier sintering, washcoat loss as well as partial metal encapsulation by Cu and/or CeZrO₄ are identified as the main causes for the deactivation after hydrothermal ageing. Full article

Long-term environmental goals will motivate the automotive industry, component suppliers, and lubricating oil developers to reduce the friction of their tribosystems to improve overall efficiency and wear for increased component lifetime. Nanoscale ceramic particles have been shown to form a protective layer on components’ surface that reduces wear rate with its high hardness and chemical resistance. One such ceramic is yttria (Y₂O₃), which has an excellent anti-wear effect, but due to its rarity it would be extremely expensive to produce engine lubricant made from it. Therefore, part of the yttria is replaced by zirconia (ZrO₂) with similar physical properties. The study presents the result of the experimental tribological investigation of nanosized yttria–zirconia ceramic mixture as an engine lubricant additive. Yttria-stabilized zirconia (YSZ) nanoparticle was used as the basis for the ratio of the ceramic mixture, so that the weight ratio of yttria–zirconia in the resulting mixture was determined to be 11:69. After the evaluation of the ball-on-disc tribological measurements, it can be stated that the optimal concentration was 0.4 wt%, which reduced the wear diameter by 30% and the wear volume by 90% at the same coefficient of friction. High-resolution SEM analysis showed a significant amount of zirconia on the surface, but no yttria was found. Full article

A higher density of large-angle grain boundaries in palladium membranes promotes hydrogen diffusion whereas small-angle grain boundaries suppress it. In this paper, the microstructure formation in 10 µm thick palladium membranes is tuned to achieve a submicronic grain size above 100 nm with a high density of large-angle grain boundaries. Moreover, changes in the grain boundaries’ structure is investigated after exposure to hydrogen at 300 and 500 °C. To attain large-angle grain boundaries in Pd, the coating was performed on yttria-stabilized zirconia/porous Crofer 22 APU substrates (intended for use later in an ultracompact membrane reactor). Two techniques of plasma sprayings were used: suspension plasma spraying using liquid nano-sized powder suspension and vacuum plasma spraying using microsized powder as feedstock. By controlling the process parameters in these two techniques, membranes with a comparable density of large-angle grain boundaries could be developed despite the differences in the fabrication methods and feedstocks. Analyses showed that a randomly oriented submicronic structure could be attained with a very similar grain sizes between 100 and 500 nm which could enhance hydrogen permeation. Exposure to hydrogen for 72 h at high temperatures revealed that the samples maintained their large-angle grain boundaries despite the increase in average grain size to around 536 and 720 nm for vacuum plasma spraying and suspension plasma spraying, respectively. Full article

The present study was aimed at revealing the influence of the mechanical stress induced by water molecule adsorption on the composition of crystalline phases in the ZrO₂ + 3 mol% Y₂O₃-nanoparticles. Three basic methods were used to determine the phase transition: neutron diffraction, Raman microspectroscopic scanning, and X-ray diffraction. The fact of reversible phase-structural β → α transformation and the simultaneous presence of two polymorphic structural modifications (β is the phase of the tetragonal syngony and α of monoclinic syngony in nanosized particles (9 nm)) under normal physical conditions was established by these methods. An assumption was made regarding the connection of the physical mechanism of transformation of the extremely nonequilibrium surface of nanoparticles with electronic exchange of the material of the near-surface layer of nanoparticles with the adsorption layer through donor–acceptor interaction. The principal possibility of creating direct-acting hydroelectric converters based on nanoscale YSZ (Yttria-Stabilized Zirconia) systems due to the reversible character of the considered effect was shown. Full article

A series of strontium titanates-vanadates (STVN) with nominal cation composition Sr_1-xTi_1-y-zV_yNi_zO_3-δ (x = 0–0.04, y = 0.20–0.40 and z = 0.02–0.12) were prepared by a solid-state reaction route in 10% H₂–N₂ atmosphere and characterized under reducing conditions as potential fuel electrode materials for solid oxide fuel cells. Detailed phase evolution studies using XRD and SEM/EDS demonstrated that firing at temperatures as high as 1200 °C is required to eliminate undesirable secondary phases. Under such conditions, nickel tends to segregate as a metallic phase and is unlikely to incorporate into the perovskite lattice. Ceramic samples sintered at 1500 °C exhibited temperature-activated electrical conductivity that showed a weak p(O₂) dependence and increased with vanadium content, reaching a maximum of ~17 S/cm at 1000 °C. STVN ceramics showed moderate thermal expansion coefficients (12.5–14.3 ppm/K at 25–1100 °C) compatible with that of yttria-stabilized zirconia (8YSZ). Porous STVN electrodes on 8YSZ solid electrolytes were fabricated at 1100 °C and studied using electrochemical impedance spectroscopy at 700–900 °C in an atmosphere of diluted humidified H₂ under zero DC conditions. As-prepared STVN electrodes demonstrated comparatively poor electrochemical performance, which was attributed to insufficient intrinsic electrocatalytic activity and agglomeration of metallic nickel during the high-temperature synthetic procedure. Incorporation of an oxygen-ion-conducting Ce_0.9Gd_0.1O_2-δ phase (20–30 wt.%) and nano-sized Ni as electrocatalyst (≥1 wt.%) into the porous electrode structure via infiltration resulted in a substantial improvement in electrochemical activity and reduction of electrode polarization resistance by 6–8 times at 900 °C and ≥ one order of magnitude at 800 °C. Full article

The enhancement of solid oxide cell (SOC) oxygen electrode performance through the generation of nanocomposite electrodes via infiltration using wet-chemistry processes has been widely studied in recent years. An efficient oxygen electrode consists of a porous backbone and an active catalyst, which should provide ionic conductivity, high catalytic activity and electronic conductivity. Inkjet printing is a versatile additive manufacturing technique, which can be used for reliable and homogeneous functionalization of SOC electrodes via infiltration for either small- or large-area devices. In this study, we implemented the utilization of an inkjet printer for the automatic functionalization of different gadolinium-doped ceria scaffolds, via infiltration with ethanol:water-based La_1−xSr_xCo_1−yFe_yO_3−δ (LSCF) ink. Scaffolds based on commercial and mesoporous Gd-doped ceria (CGO) powders were used to demonstrate the versatility of inkjet printing as an infiltration technique. Using yttrium-stabilized zirconia (YSZ) commercial electrolytes, symmetrical LSCF/LSCF–CGO/YSZ/LSCF–CGO/LSCF cells were fabricated via infiltration and characterized by SEM-EDX, XRD and EIS. Microstructural analysis demonstrated the feasibility and reproducibility of the process. Electrochemical characterization lead to an ASR value of ≈1.2 Ω cm² at 750 °C, in the case of nanosized rare earth-doped ceria scaffolds, with the electrode contributing ≈0.18 Ω cm². These results demonstrate the feasibility of inkjet printing as an infiltration technique for SOC fabrication. Full article

In this paper, the interface between yttria stabilized zirconia (Y_0.08Zr_0.92O₂, YSZ) electrolyte and Sr-doped lanthanum manganite (La_0.80Sr_0.20MnO₃, LSM) cathode for solid oxide fuel cells (SOFCs) is studied. For such a purpose, the combination of a suitable synthesis route for obtaining fine powders and simple aqueous colloidal shaping routes is proposed. The synthesis of nanosized particles of La_0.80Sr_0.20MnO₃ by a citrate route and their full characterization, including the colloidal stability and the densification and phase development determined by X-ray diffraction and electron microscopy at different temperatures, is reported. In a second step, YSZ tapes were obtained by aqueous tape casting and used as substrates for the preparation of LSM coatings by dip-coating using aqueous slurries. YSZ tapes were used either in the green state or after a pre-sintering treatment. Co-sintering at 1350 °C led to a sharp interface with excellent adhesion, also achieved when coating pre-sintered tapes. In both cases, the substrates are dense and the coatings are porous, with thicknesses of 85 and 60 μm for green and pre-sintered tapes, respectively. No diffusion of Zr and Y occurs at the LSM layer, but some diffusion of La and Mn towards the YSZ layer takes place. Full article