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1.
The phase diagram of the Al 2O 3–ZrO 2–Nd 2O 3 system was constructed in the temperature range 1250–2800 °C. The liquidus surface of the phase diagram reflects the preferentially eutectic interaction in the system. Two new ternary and one new binary eutectics were found. The minimum melting temperature is 1675 °C and it corresponds to the ternary eutectic Nd 2O 3·11Al 2O 3 + F-ZrO 2 + NdAlO 3. The solidus surface projection and the schematic of the alloy crystallization path confirm the preferentially congruent character of phase interaction in the ternary system. The polythermal sections present the complete phase diagram of the Al 2O 3–ZrO 2–Nd 2O 3 system. No ternary compounds or regions of remarkable solid solution were found in the components or binaries in this ternary system. 相似文献
2.
The system Al 2O 3–ZrO 2 was studied by differential thermal analysis in inert atmosphere and in vacuum. The eutectic was located at 1866°C and 40% mass of ZrO 2. Zirconia solid solution at the eutectic temperature is up to 1.1±0.3% mass of Al 2O 3. Enthalpy of melting of this eutectic is 1080±90 J/g. Pure ZrO 2 transforms from monoclinic to tetragonal at 1162±7°C, but the saturated solid solution of ZrO 2, with 0.7±0.2% mass Al 2O 3 at this temperature, transforms at 1085±5°C. Inverse transitions occur with hysteresis correspondingly at 1055±5 and 995±5°C. Enthalpy of transformation of pure ZrO 2 from monoclinic to tetragonal phase is 42±5 J/g (5.2±0.6 J/mol) but only 30±5 J/g for a ZrO 2 saturated solid solution. 相似文献
3.
CeO 2–ZrO 2–La 2O 3 (CZL) mixed oxides were prepared by citric acid sol–gel method. The as-received gel was calcined at 500, 700, 900 and 1050 °C to obtain the so-called C5, C7, C9 and CK, respectively. The C5, C7 and C9 powders were impregnated with H 2PtCl 6 and then calcined at 500 °C to prepare P5C5, P5C7 and P5C9, respectively. The impregnated CK powders were calcined at 500, 700 and 900 °C to prepare P5CK, P7CK and P9CK, respectively. The XRD and XPS analyses show that the surface distribution of Pt is evidently influenced by the structural and textural properties of the support. The CO adsorption followed by FTIR reveals that the dispersion and the chemisorption sites of Pt are reduced as the calcination temperature of CZL support increases. The chemisorption ability of the CK samples is even completely deactivated. The encapsulation mechanism, which has been applied to explain the so-called strong metal–support interaction (SMSI) after reductive treatment, is introduced here to demonstrate the abnormal observations though the samples were prepared in oxidative atmosphere. The HRTEM results also confirm this explanation. The effects of oxygen vacancies, the chemisorption sites on the Pt surface and Pt/Ce interfacial sites on the three-way catalytic activities are discussed. 相似文献
4.
This work aims at exploring the thermal ageing mechanism of Pt on ceria-based mixed oxides and the corresponding effect on the oxygen storage capacity (OSC) performance of the support material. Pt was supported on low-surface-area CeO 2–ZrO 2–La 2O 3 mixed oxides (CK) by impregnation method and subsequently calcined in static air at 500, 700 and 900 °C, respectively. The evolutions of textural, microstructural and redox properties of catalysts after the thermal treatments were identified by means of X-ray diffraction (XRD), Raman, X-ray photoelectron spectroscopy (XPS), temperature programmed reduction (TPR) and high-resolution transmission electron microscope (HRTEM). The results reveal that, besides the sintering of Pt, encapsulation of metal by the mixed oxides occurs at the calcination temperature of 700 °C and above. The burial of Pt crystallites by support particles is proposed as a potential mechanism for the encapsulation. Further, the HRTEM images show that the distortion of the mixed oxides lattice and other crystal defects are distributed at the metal/oxides interface, probably indicating the interdiffusion/interaction between the metal and mixed oxide. In this way, encapsulation of Pt is capable to promote the formation of Ce 3+ or oxygen vacancy on the surface and in the bulk of support. The OSC results show that the reducibility and oxygen release behavior of catalysts are related to both the metal dispersion and metal/oxides interface, and the latter seems to be more crucial for those supported on low-surface-area mixed oxides. Judging by the dynamic oxygen storage capacity (DOSC), oxygen storage capacity complete (OSCC) and oxygen releasing rate, the catalyst calcined at 700 °C shows the best OSC performance. This evident promotion of OSC performance is believed to benefit from the partial encapsulation of Pt species, which leads to the increment of Ce 3+ or oxygen vacancies both on the surface and in the bulk of oxides despite a loss of chemisorption sites on the surface of metal particles. 相似文献
5.
The promotive effects of cerium oxide on commercial three-way catalysts (TWCs) for purification of motor exhaust gases have been widely investigated in recent years. This work shows the cooperative effects of CeO 2–Pd on the kinetics of CO oxidation over Pd/CeO 2–ZrO 2. Under reducing-to-moderately oxidizing conditions, a zero-order O 2 pressure dependence is found which can be interpreted on the basis of a mechanism involving a reaction between CO adsorbed on Pd and surface oxygen from the support. The high oxygen-exchange capability of the CeO 2–ZrO 2 support, as determined from temperature-programmed reduction/oxygen uptake measurements is suggested as being responsible for such a catalytic behavior. 相似文献
6.
A suspension stabilizer-coating technique was employed to prepare x mol% Yb 2O 3 ( x = 1.0, 2.0, 3.0 and 4.0) and 1.0 mol% Y 2O 3 co-doped ZrO 2 powder. A systematic study was conducted on the sintering behaviour, phase assemblage, microstructural development and mechanical properties of Yb 2O 3 and Y 2O 3 co-doped zirconia ceramics. Fully dense ZrO 2 ceramics were obtained by means of pressureless sintering in air for 1 h at 1450 °C. The phase composition of the ceramics could be controlled by tuning the Yb 2O 3 content and the sintering parameters. Polycrystalline tetragonal ZrO 2 (TZP) and fully stabilised cubic ZrO 2 (FSZ) were achieved in the 1.0 mol% Y 2O 3 stabilised ceramic, co-doped with 1.0 mol% Yb 2O 3 and 4.0 mol% Yb 2O 3, respectively. The amount of stabilizer needed to form cubic ZrO 2 phase in the Yb 2O 3 and Y 2O 3 co-doped ZrO 2 ceramics was lower than that of single phase Y 2O 3-doped materials. The indentation fracture toughness could be tailored up to 8.5 MPa m 1/2 in combination with a hardness of 12 GPa by sintering a 1.0 mol% Yb 2O 3 and 1.0 mol% Y 2O 3 ceramic at 1450 °C for 1 h. 相似文献
7.
Mixed oxides of alumina and zirconia having a relative composition of 50, 80 and 100% Zr 2O were synthesized by means of sol–gel methods. The catalysts were sulfated with H 2SO 4 1N, and were loaded with 0.3% Pt metal using the incipient wetness technique. The characterization of the physicochemical properties was carried out using XRD, N 2-adsorption at 78 K, and SEM. The catalytic properties of the Al 2O 3–ZrO 2 series were studied by means of dehydration of 2-propanol at 180°C and isomerization of n-hexane at 250°C, 1 atm. The sulfated solids presented a high surface acidity and a limited crystallinity, together with high activity for alcohol dehydration (i.e. 2-propanol). On the other hand, the Al 2O 3–ZrO 2 solid solutions (i.e. those having a 20–80% composition) turned out to be the most active ones for the isomerization of n-hexane. 相似文献
8.
Homogeneous-eutectic microstructure of Y 3Al 5O 12–Al 2O 3 system without coarse primary crystals was formed at an off-eutectic composition. This method utilizes a low migration rate in an amorphous phase. A mixture of Y 2O 3 and Al 2O 3 having the off-eutectic composition was melted and quenched rapidly to form an amorphous phase. A heat-treatment of the amorphous phase at 1000 °C and 1300 °C for 30 min formed Y 3Al 5O 12 and Al 2O 3 phases. SEM observation of this material, which was formed from the amorphous phase at 1300 °C for 30 min, showed homogeneous eutectic-like microstructure. The formation of the primary crystals (coarse Al 2O 3), which are always observed in the off-eutectic compositions by ordinary method, was completely suppressed. 相似文献
9.
The subsolidus region of the BaO–La 2O 3–V 2O 5 phase diagram has been redetermined. Previously reported binary phases of LaVO 4, La 8V 2O 17, La 3VO 7, BaLa 2O 4, Ba 3V 2O 8, Ba 2V 2O 7, Ba 3V 4O 13 and BaV 2O 6 have all been confirmed. The ternary phases Ba 2LaV 3O 11, Ba 3LaV 3O 12 and Ba 3La 40V 12O 93 have also been confirmed. The new phase “BaLa 10V 4O 26” has been synthesised for the first time and is reported here along with the amended phase diagram. The previously omitted phase of La 1.42V 0.58O 3.58 has also been included and reasons for this are cited. The diagram is shown for two temperatures (1000 and 600 °C) due to the low melting point of V 2O 5-rich compounds. 相似文献
10.
The introduction of trivalent cation — Y 3+ or La 3+ — into the lattice of CeO 2–ZrO 2 solid solutions allows to stabilise a cubic structure at low ceria content (30 mol%). The reducibility of the samples has been compared in the experiments of temperature-programmed reduction (TPR). The introduction of lanthanum cations decreases the amount of hydrogen consumed during TPR, while the introduction of yttrium ones increases this value. At the same time, the value of temperature of the maximum speed of reduction ( Tmax) is independent on the trivalent dopant. The reducibility of these solid solutions did not change during repeated red–ox treatments at temperature below 1220 K. It is connected with the high thermostability of all systems in this temperature interval. TPR up to 1470 K causes a significant shift of Tmax value to higher temperature and a slight decrease of hydrogen consumption in two to three cycles. It is suggested that this alterations are connected with the sharp decrease of the specific surface area of all samples and partially phase decomposition of CeO 2–ZrO 2 and Y 2O 3–CeO 2–ZrO 2 solid solutions. Raman characterisation of the oxygen sublattice of the fresh samples and of the samples after TPR has been carried out. 相似文献
11.
In order to assess the role of carbon with respect to the grain boundary chemistry of Si 3N 4-based ceramics model experiments were performed. Y 2O 3–SiO 2 glass systems with various amount of carbon (from 1 to 30 wt.%) were prepared by high-temperature treatment in a graphite furnace. High carbon activity of the furnace atmosphere was observed. EDX analysis proved the formation of SiC by the carbothermal reduction of SiO 2 either in the melt or in the solid state. The melting temperature of the Y 2O 3–SiO 2 system is strongly dependent on the amount of reduced SiO 2. XRD analysis of the products documented the presence of Y 2Si 2O 7, Y 2SiO 5 and Y 2O 3 crystalline phases in that order with an increasing amount of free C in the starting mixture. The reduction of Y 2O 3 was not confirmed. 相似文献
12.
High surface area CeO 2–ZrO 2 mixed oxides were treated at 900–950°C either under wet air or under successive reducing and oxidizing atmospheres in order to study the evolution of the oxygen storage capacity (OSC) of these solids after different aging treatments. Several complementary methods were used to characterize the redox behavior: temperature programmed reduction (TPR) by H 2, TPO, magnetic susceptibility measurements to obtain the Ce 3+ content, FT-IR spectroscopy of adsorbed methanol and a method to compare the oxygen buffering capacity (OBC) of the oxides. All the results confirm that the mixed oxides exhibit better redox properties than pure ceria, particularly after aging. The enhancement in the OSC at moderate temperature has to be related to a deeper penetration of the reduction process from the surface into the under-layers. Redox cycling aging promotes the reduction at low temperature of all the mixed oxides, the improvement being much more important for low surface area aged samples. The magnitude of this effect does not depend on the BET surface areas which have similar values after cycling. This underlines the critical influence that the preparation and activation procedure have on the final OSC behaviors of the ceria–zirconia mixed oxides. 相似文献
13.
Co 3O 4–CeO 2 type mixed oxide catalyst compositions have been prepared by using co-precipitation method and, their catalytic activity towards diesel particulate matter (PM)/carbon oxidation has been evaluated under both loose and tight contact conditions. These catalysts show excellent catalytic activity for PM/carbon oxidation, despite their low surface area. The activation energy observed for non-catalyzed and catalyzed reactions are 163 kJ/mol and 140 kJ/mol, respectively, which also confirm the catalytic activity of catalyst for carbon/soot oxidation. The promotional effects of an optimum amount of cobalt oxide incorporation in ceria and presence of a small amount of potassium appears to be responsible for the excellent soot oxidation activity of this mixed oxide type material. The catalytic materials show good thermal stability, while their low cost will also add to their potential for practical applications. 相似文献
14.
Ni catalysts supported on various solid solutions of ZrO 2 with alkaline earth oxide and/or rare earth oxide were synthesized. The catalytic activities were compared for partial oxidation of methane and autothermal reforming of methane. For partial oxidation of methane, the Ni catalyst supported on a CaO–ZrO 2 solid solution showed a high activity. Incorporation of CaO in the ZrO 2 matrix was effective for increasing the reduction rate of the NiO particles and for decreasing the coke formation. On the other hand, the Ni particles supported on the CaO–CeO 2–ZrO 2 solid solution had a strong interaction with the support, and the Ni particles showed high activity and stability for autothermal reforming of methane. 相似文献
15.
Ni catalysts supported on γ-Al 2O 3, CeO 2 and CeO 2–Al 2O 3 systems were tested for catalytic CO 2 reforming of methane into synthesis gas. Ni/CeO 2–Al 2O 3 catalysts showed much better catalytic performance than either CeO 2- or γ-Al 2O 3-supported Ni catalysts. CeO 2 as a support for Ni catalysts produced a strong metal–support interaction (SMSI), which reduced the catalytic activity and carbon deposition. However, CeO 2 had positive effect on catalytic activity, stability, and carbon suppression when used as a promoter in Ni/γ-Al 2O 3 catalysts for this reaction. A weight loading of 1–5 wt% CeO 2 was found to be the optimum. Ni catalysts with CeO 2 promoters reduced the chemical interaction between nickel and support, resulting in an increase in reducibility and stronger dispersion of nickel. The stability and less coking on CeO 2-promoted catalysts are attributed to the oxidative properties of CeO 2. 相似文献
16.
Scanning electron microscopy (SEM), electron-probe microanalysis, energy- and wavelength-dispersive X-ray analysis and X-ray powder diffraction were used to investigate the subsolidus phase relations in the pseudo-ternary La 2O 3–TiO 2–Mn 2O 3 system in air (oxygen partial pressure pO2=0.21 atm) at 1275 °C. The addition of Mn 2O 3 to the starting La 2O 3:3TiO 2 mixture led to the formation of a La-deficient perovskite La 2/3TiO 3 compound. The oxides form two new compounds with the proposed compositions: (i) La 1.7Ti 13.0Mn 6.3O 38−x, with a davidite-like crystal structure, and (ii) La 49Ti 18Mn 13O 129. There were also several solid solutions existing over a wide range of concentrations. 相似文献
17.
In this paper, a strategy is described to develop high toughness yttria-stabilised tetragonal zirconia polycrystalline (Y-TZP) composites reinforced with hard TiB 2 particles. The experimental results revealed that fully dense Y-TZP composites with 30 vol.% TiB 2 can be obtained with a moderate hardness of 13 GPa, a high strength up to 1280 MPa and an excellent indentation toughness up to 10 MPa m 1/2 by hot pressing in vacuum at 1450 °C. The toughness of the composites can be tailored between 4 and 10 MPa m 1/2 by varying the yttria stabiliser content of the ZrO 2 matrix between 3 and 2 mol%. An optimum composite toughness was achieved for a ZrO 2 matrix with an overall yttria content of 2.5 mol%, obtained by mixing pure monoclinic and 3 mol% Y 2O 3 co-precipitated ZrO 2 starting powders. An important observation is that the thermal residual tensile stress in the ZrO 2 matrix due to the TiB 2 addition, needs to be taken into account when optimising the transformability of the ZrO 2 matrix in order to develop high toughness Y-TZP composites. 相似文献
18.
Plasma-sprayed stand-alone coatings of 7 wt.% Y 2O 3–ZrO 2 (YSZ), nominally 74 wt.% Al 2O 3–26 wt.% SiO 2 mullite, and a 46:54 volume ratio composite of YSZ to mullite were examined using X-ray diffraction, dilatometry, and compression creep. X-ray diffraction and dilatometer results showed that the as-sprayed predominantly amorphous mullite crystallized at 970 °C. Creep tests were conducted on all three coating types in the as-sprayed condition at stresses from 40 to 80 MPa and temperatures of 1000–1200 °C. The primary deformation mechanism in coatings made from all three materials was stress-assisted densification of the porous coating. While the creep behavior of YSZ/mullite composite specimens was between that of pure YSZ and pure mullite specimens for all combinations of temperature and stress tested, the creep response of the composite was more similar to that of pure mullite for all cases tested, consistent with mullite being the continuous phase in the composite. 相似文献
19.
In the present study, both t-phase zirconia and m-phase zirconia particles are incorporated into an alumina matrix. Dense Al 2O 3/(t-ZrO 2+m-ZrO 2) composites were prepared by sintering pressurelessly at 1600 °C. The microstructure of the composites are characterized, the elastic modulus, strength and toughness determined. Because the ZrO 2 inclusions are close to each other in the Al 2O 3 matrix, the yttrium ion originally in t-ZrO 2 particles can diffuse to nearby m-ZrO 2 particles during sintering, and the m-phase zirconia is thus stabilized after sintering. The strength of the Al 2O 3/(t-ZrO 2+m-ZrO 2) composites after surface grinding can reach values as high as 940 MPa, which is roughly three times that of Al 2O 3 alone. The strengthening effect is contributed by microstructural refinement together with the surface compressive stresses induced by grinding. The toughness of alumina is also enhanced by adding both t-phase and m-phase zirconia, which can reach values as high as two times that of Al 2O 3 alone. The toughening effect is attributed mainly to the zirconia t–m phase transformation. 相似文献
20.
Stable suspensions based on methylethylketone (MEK), n-butylamine and nitrocellulose were developed for the electrophoretic deposition (EPD) of Al 2O 3 and ZrO 2 powder. Deposits with a high green density, smooth surface and high deposition yield were obtained upon adding 10–15 vol.% n-butylamine in combination with 1 wt.% nitrocellulose. The influence of the reaction between MEK and n-butylamine, forming water and imines, on the electrophoretic deposition behaviour was investigated. Experimental results revealed that the zeta potential is not a straightforward indication of the stability of these suspensions, since the maximum absolute zeta potential did not correspond with a maximum suspension stability, due to the additional electrosteric stabilisation of the adsorbed charged nitrocellulose. 相似文献
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