Size driven thermodynamic crossovers in phase stability in zirconia and hafnia

Hafnia (HfO₂) and zirconia (ZrO₂) are of great interest in the quest for replacing silicon oxide in semiconductor field effect transistors because of their high permittivity. Both exhibit extensive polymorphism and understanding the energetics of their transitions is of major fundamental and practical importance. In this study, we present a systematic thermodynamic summary of the influence of particle size on thermodynamic phase stability in hafnia and zirconia using recently measured enthalpy data from the literature. The amorphous phase is found to be the most energetically stable above 165 and 363 m²/g of surface area for HfO₂ and ZrO₂, respectively. Below 16 and 20.3 m²/g of surface area, respectively, the monoclinic phase is the most energetically stable for HfO₂ and ZrO₂. At intermediate sizes there are closely balanced energetics among monoclinic, tetragonal, and cubic phases. The energy crossovers reflect decreasing surface enthalpy in the order monoclinic, tetragonal, cubic and amorphous for both hafnia and zirconia.     

Oxidation of o-Xylene to Phthalic Anhydride on Sb-V/ZrO2 Catalysts

Zirconia-supported and bulk-mixed vanadiumantimonium oxide catalysts were used for the oxidation of o-xylene to phthalic anhydride. X-ray diffraction, Raman spectroscopy and photoelectron spectroscopy were used for characterization. It was found that vanadium promotes the transition of tetragonal to monoclinic zirconia. The simultaneous presence of Sb and V on zirconia at low coverage led to a preferential interaction of individual V and Sb oxides with the zirconia surface rather than the formation of a binary Sb-V oxide, while at higher Sb-V contents the formation of SbVO₄ took place. Sb-V/ZrO₂ catalysts showed high activity for o-xylene conversion and better selectivity to phthalic anhydride as compared to V/ZrO₂ catalysts. However, their selectivity to phthalic anhydride was poor in comparison to a V/TiO₂ commercial catalyst. The improved selectivity of the Sb-containing catalysts is attributed to the blocking of non-effective surface sites of ZrO₂, the decrease of the total amount of acid sites and the formation of surface V-O-Sb-O-V structures.     

Methane Combustion and CO Oxidation on Zirconia-Supported La,Mn Oxides and LaMnO3 Perovskite

ZrO₂-supported La, Mn oxide catalysts with different La, Mn loading (0.7, 2, 4, 6, 12, and 16 wt% as LaMnO₃) were prepared by impregnation of tetragonal ZrO₂ with equimolar amounts of La and Mn citrate precursors and calcination at 1073 K. The catalysts were characterized by X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS), and BET specific surface area determination. The redox properties were tested by temperature-programmed reduction (TPR), and the catalytic tests were carried out for methane combustion at 650–1050 K and for CO oxidation at 350–800 K. XRD revealed the presence of tetragonal zirconia with traces of the monoclinic phase. LaMnO₃ perovskite was also detected for loading higher than 6%. XAS and TPR experiments suggested that at high loading small crystallites of LaMnO₃, not uniformly spread on the zirconia surface, were formed; while at low loading, La, Mn oxide species interacting with the support, and hard to be structurally defined, prevailed. The catalysis study indicated that the presence of a perovskite-like structure is necessary for the development of highly active sites. Dilute catalysts were in fact poorly active even when considering the activity per gram of La, Mn perovskite-like composition. For methane combustion and CO oxidation, similar trends of the activity as a function of the loading point to a similarity of the active sites for the two reactions on the examined catalytic system.     

TiO2–ZrO2 mixed oxide as a support for hydrotreating catalyst

Pure TiO₂, ZrO₂ and TiO₂–ZrO₂ mixed oxides are prepared by urea hydrolysis. Hydrotreating catalysts containing 12 wt% molybdenum are prepared using these oxides and characterized by BET surface area, pore volume, XRD and oxygen chemisorption. It is observed that oxides produced by the method of urea hydrolysis have higher surface area as compared to those available commercially. With increasing zirconia content in the mixed oxide, the surface area increases and a maximum value is obtained for a mixed oxide having Ti and Zr molar ratio of 65/35. XRD results indicate that mixed oxides are poorly crystalline in nature. Thiophene hydrodesulfurization, cyclohexene hydrogenation and tetrahydrofuran hydrodeoxygenation are taken as model reactions for evaluating catalytic activities. It is found that both O₂ uptake and catalytic activities increase with increasing zirconia content in mixed oxide and reach maximum values for the 12 wt% Mo/TiO₂–ZrO₂ (65/35) catalyst. With further increases in zirconia content, O₂ uptake and catalytic activities decrease and the lowest values are observed for the pure ZrO₂ supported catalyst.     

Solvent effect on synthesis of zirconia support for tungstated zirconia catalysts

Solvothermal reaction of zirconium n-butoxide (ZNB) in different solvent media, such as 1,3-pentanediol, 1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol resulted in the formation of zirconium dioxide (ZrO₂) nanostructure. Then, the 15%W/ZrO₂ (WZ) catalysts using different zirconia supports were prepared by impregnation method. The effects of solvent on preparation of zirconia on the catalytic performance of WZ catalysts in esterification of acetic acid and methanol at 60 °C were investigated. The experimental results showed that ZrO₂ particles prepared in 1,4-butanediol (ZrO₂-BG) have a spherical shape, while in other glycols the samples were irregularly-shaped particles. The reaction results of esterification illustrated that the W/ZrO₂-BG catalysts had high surface acidity and showed high acetic acid conversion. The W/ZrO₂-PeG catalysts (ZrO₂ particles prepared in 1,5-pentanediol, PeG) exhibited the lowest surface acidity among other samples due to strong interaction of proton species and the zirconia supports as proven by TGA. One of the possible reasons can be attributed to different amounts of carbon residue on the surface of catalysts.     

Biodiesel production from waste cooking oil over alkaline modified zirconia catalyst

Screening and catalytic activity of alkaline modified zirconia i.e. Mg/ZrO₂, Ca/ZrO₂, Sr/ZrO₂, and Ba/ZrO₂ as heterogeneous catalyst in biodiesel production from waste cooking oil (WCO) have been investigated. The catalysts were prepared via wet impregnation of alkaline nitrate salts supported on zirconia. Physico-chemical characteristics of the catalysts were analyzed by BET surface area, XRD, FESEM and CO₂–NH₃–TPD. Among the catalysts screened, Sr/ZrO₂ exhibited higher catalytic activities. Characterization results disclosed Sr/ZrO₂ catalyst possessed balanced basic and acid site concentrations with its pore volume, surface area as well as pore diameters suitable for biodiesel production. The balanced active sites facilitated simultaneous transesterification and esterification of WCO. A plausible mechanism has been suggested for the simultaneous reactions. The effects of operating process conditions such as methanol to oil molar ratio, reaction temperature and catalyst loading on biodiesel production in the presence of Sr/ZrO₂ were investigated. Methyl ester (ME) yield at 79.7% was produced over 2.7 wt.% catalyst loading (Sr/ZrO₂), 29:1 methanol to oil molar ratio, 169 min of reaction time and 115.5 °C temperature.     

Partial Oxidation of Ethanol to Hydrogen over Ni–Fe Catalysts

A study has been conducted to identify the influence of zirconia phase and copper to zirconia surface area on the activity of Cu/ZrO₂ catalysts for the synthesis of methanol from either CO/H₂ or CO₂/H₂. To determine the effects of zirconia phase, a pair of Cu/ZrO₂ catalysts was prepared on tetragonal (t-) and monoclinic (m-) zirconia. The zirconia surface area and the Cu dispersion were essentially identical for these two catalysts. At 548 K, 0.65 MPa, and H₂/CO_x= 3 (x = 1, 2), the catalyst prepared on m-ZrO₂ was 4.5 times more active for methanol synthesis from CO₂/H₂ than that prepared on t-ZrO₂, and 7.5 times more active when CO/H₂ was used as the feed. Increasing the surface area of m-ZrO₂ and the ratio of Cu to ZrO₂ surface areas further increased the methanol synthesis activity. In situ infrared spectroscopy and transient-response experiments indicate that the higher rate of methanol synthesis from CO₂/H₂ over Cu/m-ZrO₂ is due solely to the higher concentration of active intermediates. By contrast, the higher rate of methanol synthesis from CO/H₂ is due to both a higher concentration of surface intermediates and the more rapid dynamics of their transformation over Cu/ZrO₂.     

The hindering function of phosphate on the grain growth behavior of nanosized zirconia powders calcined at high temperatures

Nanosized zirconia was prepared by a hydrothermal method using ZrOCl₂·8H₂O and NaOH as raw materials. The obtained ZrO₂ powders were soaked in the phosphate solution with different concentrations. The as-prepared ZrO₂ powders and the powders treated with phosphate solution were calcined at different temperatures from 600 to 1000 °C. The samples were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM) and X-ray photoelectronic spectroscopy (XPS). The experimental results show that the untreated nanosized ZrO₂ grow and agglomerate to bulk when the ZrO₂ powders were calcined at high temperatures, while the ZrO₂ powders treated with phosphate solution grow slowly and remain nanosized crystal at the same calcination temperature. This phenomenon implied that phosphate treatment played an important role in inhibiting the crystal grain growth of ZrO₂. The possible inhibition mechanism could be explained to that P species on the surface of ZrO₂ can reduce the grain boundary mobility and prevent direct contact of ZrO₂ particles.     

Trimerization of isobutene over WOx/ZrO2 catalysts

Trimerization of isobutene to produce isobutene trimers has been investigated over WO_x/ZrO₂ catalysts that were obtained by wet-impregnation and successive calcination at high temperatures. Very stable isobutene conversion and high selectivity for trimers are attained over a WO_x/ZrO₂ catalyst obtained by calcination at 700 °C. From the XRD study it can be understood that tetragonal ZrO₂ is beneficial for stable performance; however, monoclinic ZrO₂ is not good for trimerization. Nitrogen adsorption and FTIR experiments suggest that amorphous WO_x/ZrO₂ is inefficient catalyst even though it has high surface area and high concentration of acid sites. The observed performance with the increased selectivity and stable conversion demonstrates that a WO_x/ZrO₂ having tetragonal zirconia, even with decreased porosity and acid sites, is one of the best catalysts to exhibit stable and high conversion, high selectivity for trimers and facile regeneration.     

Synthesis of the ZrO2–SiO2 microspheres as a mesoporous candidate material

A series of mesoporous ZrO₂?CSiO₂ microspheres with different amounts of silica were synthesized by a polymerization-induced colloid aggregation process, using zirconyl chloride and commercial SiO₂ colloids as the raw materials. The microspheres were characterized by scanning electron microscopy (SEM), N₂ adsorption?Cdesorption isotherms, X-ray powder diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR). According to the SEM results, the ZrO₂ and ZrO₂?CSiO₂ microspheres had spherical morphologies and the sizes of the ZrO₂?CSiO₂ microspheres increased with increasing SiO₂/ZrO₂ weight ratios. The XRD spectrum of the pure ZrO₂ microspheres contained characteristic peaks for a monoclinic crystalline zirconia structure. The XRD spectrum of the ZrO₂?CSiO₂ microspheres showed a tetragonal crystalline structure. The specific surface areas of the ZrO₂?CSiO₂ microspheres increased with increasing SiO₂/ZrO₂ weight ratios, and the pore volumes also increased. The average pore size of the ZrO₂?CSiO₂ microspheres was 3?C5?nm. The FT-IR spectrum of the ZrO₂?CSiO₂ microspheres confirmed the formation of Zr-O-Si bonds. The Zr-O-Si bonds make the metastable tetragonal zirconia stable at room temperature.     

A comparison of cesium-containing heteropolyacid and sulfated zirconia catalysts for isomerization of light alkanes

The heteropolyacid H₃PW₁₂O₄₀ and its cesium salts Cs_xH_3-x PW₁₂O₄₀ (x = 1, 2, 2.5, 3) were synthesized, characterized and tested as catalysts for hydrocarbon reactions. All samples were characterized by a variety of techniques including elemental analysis, X-ray diffraction, dinitrogen adsorption, thermal gravimetric analysis and ammonia sorption. Results from these methods confirmed that pure cesium salts were prepared without significant contamination by amorphous oxide phases. Incorporation of cesium into the heteropolyacid decreased the acidic protons available for catalysis, increased the specific surface area, and increased the thermal stability. The heteropolyacids were tested as catalysts for butane skeletal isomerization, pentane skeletal isomerization and 1-butene double bond isomerization. For comparison, the activity of sulfated zirconia, a well-studied strong acid catalyst, was also evaluated for the three probe reactions. On a per gram basis, the Cs₂HPW₁₂O₄₀ sample was the most active heteropolyacid, presumably due to its high surface area. This sample was more active than sulfated zirconia for pentane skeletal isomerization and 1-butene double bond isomerization. However, sulfated zirconia was more effective for butane skeletal isomerization. Since the pentane and 1-butene reactions were monomolecular in nature, whereas butane isomerization was bimolecular, restrictions inside the micropores of the heteropolyacid may inhibit the formation of long chain intermediates. Interestingly, trace butenes were required to initiate butane isomerization reactions on sulfated zirconia, whereas heteropolyacids catalyzed the reaction in the absence of butenes. This revised version was published online in June 2006 with corrections to the Cover Date.     

Growth of nanolaminate structure of tetragonal zirconia by pulsed laser deposition

Alumina/zirconia (Al₂O₃/ZrO₂) multilayer thin films were deposited on Si (100) substrates at an optimized oxygen partial pressure of 3 Pa at room temperature by pulsed laser deposition. The Al₂O₃/ZrO₂ multilayers of 10:10, 5:10, 5:5, and 4:4 nm with 40 bilayers were deposited alternately in order to stabilize a high-temperature phase of zirconia at room temperature. All these films were characterized by X-ray diffraction (XRD), cross-sectional transmission electron microscopy (XTEM), and atomic force microscopy. The XRD studies of all the multilayer films showed only a tetragonal structure of zirconia and amorphous alumina. The high-temperature XRD studies of a typical 5:5-nm film indicated the formation of tetragonal zirconia at room temperature and high thermal stability. It was found that the critical layer thickness of zirconia is ≤10 nm, below which tetragonal zirconia is formed at room temperature. The XTEM studies on the as-deposited (Al₂O₃/ZrO₂) 5:10-nm multilayer film showed distinct formation of multilayers with sharp interface and consists of mainly tetragonal phase and amorphous alumina, whereas the annealed film (5:10 nm) showed the inter-diffusion of layers at the interface.     

Influence of oxygen and promoting effect of barium on the reduction of NOx by ethanol on Pd/ZrO2 catalyst

The NO reduction by ethanol over barium promoted Pd/ZrO₂ catalyst and the effect of the oxygen on the selectivity were studied. The catalysts were prepared by incipient wetness impregnation with 14.3% of Ba over zirconia and 1% of palladium. The specific surface areas were 58 and 47 m²/g and the dispersions of Pd were 37% and 30% for the Pd/ZrO₂ and Pd–Ba/ZrO₂ catalysts, respectively. The X-ray diffraction patterns indicate the presence of monoclinic zirconia phase on the support and BaCO₃, which is decomposed at 715 and 815 °C. Temperature programmed desorption profiles of NO on Pd/ZrO₂ and Pd–Ba/ZrO₂ catalyst showed a huge amount N₂ formation for the promoted Ba catalyst. Catalytic results showed high NO conversion even at low temperature, in accordance with the TPD results and an increasing selectivity to N₂ when compared with Pd/ZrO₂. The effect of O₂ in the NO_x reduction with ethanol provoked less NO dissociation and lower selectivity to methane.     

Characterization of rheological properties of colloidal zirconia

Dynamic viscosity of aqueous suspensions of nanosized zirconia (ZrO₂) have been studied for the low volume fraction range. The specific surface area of dry powder was determined from the BET method. The zeta potential of zirconia particles as a function of pH was measured by the microelectrophoretic method. The isoelectric point found in this way was 4.7. The particle density in aqueous suspensions was found by the dilution method. The dynamic viscosity of suspensions was measured by using a capillary viscometer that eliminated the sedimentation effects. Experimental data showed that for dilute zirconia suspension, the relative viscosity increased more rapidly with the volume fraction than that the Einstein formula predicts. This allowed one to calculate the specific hydrodynamic volume of particles in the suspensions and their apparent density. It was found that particles forming zirconia suspensions were composed of aggregates having porosity of 40–50%. The size of the primary particles forming these aggregates was 0.2 μm that agrees well with the BET specific surface data. The influence of an anionic polyelectrolyte:polysodium 4-styrenesulfonate (PSS) on zirconia suspension viscosity also was studied. First the PSS viscosity alone was measured as a function of its volume fraction for various ionic strength of the solutions. The data were interpreted in terms of the flexible rod model of the polyelectrolyte. Then, the viscosity of ZrO₂ in PSS solutions of fixed concentration was measured as a function of the concentration of zirconia. It was revealed that the viscosity of the mixtures was proportional to the product of the zirconia and polyelectrolyte viscosities taken separately.     

Enhanced surface area and thermal stability of mesoporous zirconia fibers modified by various oxides and the reinforcement mechanism

In the present work, four oxides (SiO₂, TiO₂, LaO_1.5, or CeO₂) were selected as additives to increase the surface areas and the pore wall stability of mesoporous zirconia (ZrO₂) fibers in virtue of enhancing the skeleton stability and hindering the grain growth. The preparation, characterization, and thermal evolution of mesoporous ZrO₂ fibers incorporated with different amounts of oxide additive and simultaneously combined with heat treatment via water vapour are presented. The effects of different oxide additives on the crystallization and phase transformation of mesoporous ZrO₂ fibers were investigated by X-ray diffraction. N₂ adsorption-desorption studies were conducted to investigate the changes in the porous structure of the ZrO₂ fibers heat-treated at different temperatures. Scanning electron microscopy confirmed the mesoporous structure of the ZrO₂ fibers. The oxide-added ZrO₂ fibers heat-treated in the presence of water vapour exhibited a mesoporous structure with increased surface areas and thermal stability. The related reinforcing mechanisms were proposed. It was deduced that water vapour promoted the removal of the soft template, leading to the formation of a mesoporous structure with a high surface area. Meanwhile, the increase in the surface areas of mesoporous ZrO₂ fibers with the incorporation of the oxide additive was mainly due to the enhanced thermal stability of the porous walls. The relationship between the mesoporous structure stability and the zirconia phase stability was fully discussed. This work provides a new route for enhancing the surface areas and structure thermal stability of mesoporous ZrO₂ fibers.     

Control of the textural properties of zirconium oxide

Several methods of preparation of pure and doped zirconia are compared, including aqueous precipitations, surfactant-aided syntheses, decomposition of salts, molten salt technique and kneading of wet hydrous zirconia with transition metal salts. The influence of the different preparation parameters on the textural properties of the solids is analysed, in order to design the optimal preparation technique leading to zirconia samples combining high surface areas and large pores required for use in catalytic processes. The best results have been obtained from the ageing of aqueous precipitates (surface area 267 m²/g, mean pore size 6 nm), from reactions in molten nitrate–carbonate mixtures (140 m²/g, 9 nm) and (Ni)Mo-doped molten salt preparations of ZrO₂ (270 m²/g, 3.5 nm). This opens a wide field of possible applications for Zr-based catalysts. This revised version was published online in June 2006 with corrections to the Cover Date.     

Effects of graphene oxide sheets-zirconia spheres nanohybrids on mechanical,thermal and tribological performances of epoxy composites

In this work, graphene oxide sheets-zirconia spheres (ZrO₂-rGO) nanohybrids were fabricated by Schiff base or Michael addition reaction. Their structure was characterized by FT-IR spectroscopy, UV–vis absorption spectra, Raman spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy and atomic force microscope in detail. The reaction process of PDA-capping on rGO and APTES treatment on ZrO₂ nanoparticles were verified and it was proved that the ZrO₂ nanoparticles were successfully adhered onto the wrinkled surface of the graphene oxide. As a new multifunctional nanofillers, the ZrO₂-rGO nanohybrids were introduced into epoxy matrix and the mechanical, thermal properties and tribological performances of the fabricated composites were also detailedly investigated. Compared with the neat EP composites, the tensile strength and elongation at break of 0.1?wt% ZrO₂-rGO/EP are improved by 33% and 40%, respectively. Besides, the propagation of decomposition reactions in the composites could be impeded by anchoring ZrO₂ nanoparticles on the lamellar skeleton of graphene oxide. Furthermore, the lubricating effect and strong interfacial interaction contributed by the ZrO₂-rGO nanohybrids result in efficient load transfer from the matrix to the hybrids, which enables the ZrO₂-rGO/EP composites to have a fairly high wear resistance performance. This novel and effective approach using ZrO₂-rGO nanohybrids as multifunctional nanofillers could be beneficial to promote the development of high performance composites.     

Thermodynamic analysis and experimental verification of interface reactions of iron aluminide/tetragonal zirconia composite

Abstract

This paper described the thermodynamic analysis and experimental verification of interface reactions between iron aluminide intermetallic and tetragonal zirconia. Thermodynamic analysis confirmed that chemical reactions between Fe–Al intermetallic and ZrO₂ (3 mol.–%Y₂O₃ stabilised zirconia) mainly depended on the Al content in Fe–Al intermetallic. For ZrO₂(3Y)/Fe₃Al composite, the interface reactions to form Al₂O₃ and ZrAl₂ would take place when Al content was >40 at-% in Fe–Al intermetallic, while no interface reaction occurred when using Fe₃Al as toughening phase. ZrO₂(3Y)/Fe₃Al composite was synthesised by hot press sintering to further verify the thermodynamic analysis of interface reactions between iron aluminide intermetallic and tetragonal zirconia. The phase composition, morphology and interface structure of ZrO₂(3Y)/Fe₃Al were investigated by X-ray diffraction, SEM and TEM. The results show that Fe₃Al was thermodynamic stable in ZrO₂(3Y) matrix, which was in good agreement with thermodynamically analysis.     

Highly translucent and strong ZrO2-SiO2 nanocrystalline glass ceramic prepared by sol-gel method and spark plasma sintering with fine 3D microstructure for dental restoration

Balance of better mechanical strength and good translucency for dental restorative materials is always a challenge. A translucent glass ceramic/ceramic with improved mechanical properties or a strong glass ceramic/ceramic with good translucency would therefore be interesting for dental application. Nanocrystalline glass ceramics (NCGC) attract a lot attention because of their superior optical and mechanical properties. This study aims to obtain ZrO₂-SiO₂ nanocrystalline glass-ceramic that possesses high mechanical strength as well as excellent translucency by controlling the content, size, and connection of nanocrystalline ZrO₂ in a ZrO₂-SiO₂ glass-ceramic material. Toward this end, well-homogenized nano-powders with three different compositions, 45%ZrO₂-55%SiO₂ (molar ratio, 45Zr), 55%ZrO₂-45%SiO₂ (55Zr), and 65%ZrO₂-35%SiO₂ (65Zr)_, were synthesized, followed by a fast sintering process. Highly-translucent nanocrystalline glass ceramics composed of tetragonal ZrO₂ were obtained. Samples with high zirconia content showed that the structure of the skeleton was predominately built by nano-sized ellipsoidal ZrO₂ particles bonded by grain boundaries, with amorphous SiO₂ filling the voids between the ZrO₂ particles. The achieved flexural strength measured by piston-on-three-ball test was as high as 1014 MPa. To our knowledge, this is one of the highest flexural strength values of glass ceramics ever reported, which is higher than transparent zirconia and alumina ceramics. The 3D structure of nanocrystalline zirconia in silica matrix did enhance the flexural strength of the NCGC. The results of this study suggest that the new ZrO₂-SiO₂ NCGC has great potential of using as dental restoration.     

Characterization and Catalytic Behavior of Potassium-Modified ZrO2 Base Catalysts

Potassium-modified ZrO₂ base catalysts were prepared by wet impregnation of hydrous zirconia and anhydrous zirconia with potassium compounds and calcined at 600 °C in air. The properties of the catalysts were characterized and compared. Catalytic activities were examined for the vapor-phase double-bond isomerization of 1-butene at 150 °C and the liquid-phase Michael addition of 2-methylcyclohexane-1,3-dione to methyl vinyl ketone at room temperature. The properties of the modified ZrO₂ i.e., basic site strength, were greatly affected by the ZrO₂ precursors and the potassium modifiers. High yields of 2-butene with relatively high cis/trans ratios were found. Leaching of the potassium-modified ZrO₂ makes the system less suitable for use in liquid-phase reactions.