Effect of chloride on sintering of Pt/Al2O3 catalysts

Reduced Pt/Al₂O₃ catalysts with different chloride contents were treated at different temperatures under oxygen flow. TPR and TPD studies of oxidized species show that at low Cl/Pt atomic ratio (1) PtO₂ is formed at low temperature (400–500 K) and is totally decomposed (900 K) yielding reduced metallic Pt and inducing metal sintering. At high Cl/Pt atomic ratio (6) formation of stable (up to 1000 K) platinum oxichloride avoids metal sintering.     

Effect of sintering on the catalytic functionalities of MOS2/Al2O3 catalysts

Effect of sintering on physico-chemical and catalytic properties of Mo, Co-Mo, Ni-Mosupported on -Al₂O₃ is reported. Such effects on hydrodesulfurization (HDS), hydrogenation (HYD) and hydrodeoxygenation (HDO) are investigated as a function of sintering temperature. The results indicated that HDS and HYD have different optimum calcination temperatures and these functionalities originate from different sites. The results are discussed in the light of molybdenum sulfide dispersion, promotional effects and phase transformations of active component, promoters and support.     

Effect of the addition of alkali metals on the metallic phase of Pt/Al2O3 catalysts

The effect of the addition of alkali metals to Pt/Al₂O₃ catalysts for dehydrogenation of paraffins was studied. Results can be interpreted in terms of different effects. Thus, the addition of alkali metals produces a poisoning of the acid sites of the alumina support and a modification of the characteristics of the metallic phase. The latter effect involves not only an increase of the Pt particles size, but also an electronic modification of the metallic phase. These two effects are more marked with alkali metals with higher ionic radius, such as K.     

氧化铝载体对镍/氧化铝催化剂性能的影响

氧化铝是化工催化行业广泛应用的催化剂载体。油脂加氢催化剂主要是以氧化铝为载体、镍为主要活性组分的催化剂。在制备镍/氧化铝催化剂的过程中,载体氧化铝使用的最佳条件：载体在共沉淀反应前加入,载体氧化铝比表面积为340.6 m2/g,载体氧化铝加入量为m（镍）∶m（氧化铝）=5∶4,反应的老化时间为45 min。在此条件下,制备的镍/氧化铝催化剂活性最高,应用效果最好。     

Flash sintering of 3YSZ/Al2O3-platelet composites

Preparation of 3YSZ/Al₂O₃-platelet composites always requires high temperature, long duration, and/or high pressure. Herein, 3YSZ/Al₂O₃-platelet composites are prepared at low temperature of 492°C-645°C in 30 seconds by flash sintering under the electric field of 300-800 V/cm. The influence of electric field and current limit on the densification and grain growth of composites is investigated. The onset temperature for flash sintering is determined by electric field, which is decreased with increasing the electric field. Under the constant electric field, the current limit has a great effect on the density and grain size of composite. The flash-sintered 3YSZ/Al₂O₃-platelet composites exhibit relatively high hardness and elastic modulus. Both Joule heating and defects generation are proposed to be responsible for the rapid densification in flash sintering. This work demonstrates the feasibility of employing the flash sintering to prepare ceramic composites with fine grain size.     

Microwave-assisted sintering of Al2O3-MWCNT nanocomposites

Alumina-MWCNT composite was densified by microwave sintering. CNTs were coated with boehmite nanoparticles to enhance their distribution in composite samples. Calcination temperature of composite powder was determined by TGA analysis (5 °C/min). Samples containing 0 and 1vol%CNT were produced by cold isostatic pressing at 180 MPa. Microwave sintering (1520 °C for 45 min) was conducted under the flow of argon. Phase analysis of the calcined composite powder showed complete transformation of boehmite into gamma-alumina. The relative densities were 99.3% and 98.1% for monolithic alumina and composite, respectively. CNT addition improved the fracture toughness of alumina by ~37%. SEM images showed that microwave sintering was successful. Also, coating CNTs improved their distribution in the alumina matrix.     

Comparative study of aromatization selectivity during N‐heptane reforming on sintered Pt/Al2O3 and Pt‐Re/Al2O3 catalysts

BACKGROUND: The metal dispersed over a support can be present as small crystallites with sizes less than 5 nm. The smaller crystallites favour aromatization while larger crystallites favour cracking/hydrogenolysis. Sintering results in the agglomerization of smaller metal crystallites. Correlation of size with aromatization selectivity was investigated. RESULTS: The primary products of n‐heptane reforming on fresh Pt were methane, toluene, and benzene, while on fresh Pt‐Re, the only product was methane. Both catalysts exhibited enhanced aromatization selectivity at different oxygen sintering temperatures. The reaction products ranged from only toluene at 500 °C sintering temperature to methane at a sintering temperature of 650 °C with no reaction at 800 °C for the Pt/Al₂O₃ catalyst. On Pt‐Re/Al₂O₃ catalyst, methane was the sole product at a sintering temperature of 500 °C while only toluene was produced at a sintering temperature of 800 °C. CONCLUSION: This is the first time that sintering has been used to facilitate aromatization of supported Pt and Pt‐Re catalysts. A superior selectivity behaviour associated with bi‐metallic Pt catalysts is established. It was found that no reaction occurred on Pt catalyst after sintering at 800 °C whereas sintering Pt‐Re at 800 °C promoted aromatization solely to toluene. Copyright © 2008 Society of Chemical Industry     

Pt-Sn/Al2O3 sol-gel catalysts: Metallic phase characterization

Highly dispersed platinum was found in Pt-Sn/Al₂O₃ catalysts prepared by the sol-gel method, i.e., cogelation of aluminum tri-sec-butoxide and tetrabutyltin and subsequent impregnation with hexachloroplatinic acid. X-ray diffraction studies showed that the cell parameter of pure platinum is not modified in bimetallic Pt-Sn samples. Moreover, energy dispersive X-ray analysis studies (EDX) showed that platinum, but not tin, was detected in the catalysts where tin was incorporated by the sol-gel coprecipitation of tin and aluminum. Incorporation of tin into the alumina network is suggested.     

Comparison of hydrothermal corrosion behavior of SiC with Al2O3 and Al2O3 + Y2O3 sintering additives

Fully dense SiC bulks with Al₂O₃ and Al₂O₃ + Y₂O₃ sintering additives were prepared by spark plasma sintering and the effect of sintering additives on the hydrothermal corrosion behavior of SiC bulks was investigated in the static autoclave at 400°C/10.3 MPa. The SiC specimen with Al₂O₃ sintering additive exhibited a higher weight loss and followed a linear law. However, the SiC specimen with Al₂O₃ + Y₂O₃ additive exhibited a lower weight loss and followed a parabolic law, indicating that the corrosion kinetic and mechanism were different for these two SiC bulks. Further examination revealed that, a deposited layer was formed on the surface of SiC specimen with Al₂O₃ + Y₂O₃ sintering additive after corrosion, which can effectively protect the SiC specimen from further corrosion, and thereby improved the corrosion resistance of the SiC specimen with Al₂O₃ + Y₂O₃ sintering additive.     

Kinetics of acetone hydrogenation over Pt/Al2O3 catalysts

The hydrogenation of acetone to isopropanol has been studied in the vapour phase over Pt/Al₂O₃ catalysts. The rate law obtained at a total pressure of 1 atm and temperatures between 303 and 363 K is of the form V=kP⁰_aP^1/2_H exp (-44 kJ mol^?1 RT^?1). The kinetic results are consistent with a Langmuir-Hinshelwood hydrogenation mechanism involving a half hydrogenated species and a non-competitive chemisorption of acetone and hydrogen on the platinum surface. The specific activity (calculated per platinum surface atom) has been found to be scarcely dependent on the platinum particle size. It is suggested that the chemisorption sites are made of a very small ensemble of platinum atoms.     

Densification behaviors of Al2O3 ceramics during flash sintering

The densification behaviors of MgO-doped-Al₂O₃ ceramics in the flashing stage and the steady stage were investigated using the classic kinetic model. The results show that the most densification of MgO-doped Al₂O₃ was completed during the flashing stage. The densification mechanism transferred from particle rearrangement resulted from Columbic force among particles under the effect of electrical field in the flashing stage to the lattice diffusion in the steady stage. Therefore, the densification rate in the steady stage dramatically decreased. Additionally, the estimated densification activation energy in the steady stage of flash sintering is 396 kJ/mol, much lower than the activation densification of lattice diffusion measured from conventional sintering, likely due to the effect of electric field/current-induced point defects on the diffusion.     

Phosphorus promoted WS2/Al2O3 catalysts studied by transmission electron microscopy

A series of WS₂/Al₂O₃ catalysts containing a varied amount of phosphorus (0.0,2.5 and 6.0 wt% P₂O₅), sulfided at two different temperatures (873 and 1073 K), were studied by means of high-resolution transmission electron microscopy (HRTEM). The stacking of (002) layers in the WS₂-2H crystallites of the rag structure increases with the addition of phosphorus, whereas its length is kept almost constant. At high sulfidation temperatures phosphorus shows a stabilizing effect on the catalysts by retarding the stacking growth of WS₂ crystallites. Additionally, an aluminum phosphate crystalline phase is identified in the phosphorus promoted catalysts.     

Microstructure and mechanical properties of Al2O3/ZrO2 composites by two-step sintering

Composites of Al₂O₃/ZrO₂ (containing 25, 50, and 75 vol% ZrO₂) were prepared by mixing Al₂O₃ and ZrO₂ suspensions. The microstructural control via two-step sintering (TSS) was the main objective of this work. For this purpose, different sintering curves were constructed, aiming to achieve the best temperature combination for the sintering steps that provides higher density and finer microstructure. The results were compared with single-step sintering (SSS). Furthermore, microhardness and fracture toughness were measured for the best TSS specimens under each composition. The results showed that the high densities were obtained, and the reduction of grain size was greater than 40% for two-step sintered specimens, compared to SSS ones. Consequently, microhardness values increased. However, fracture toughness values remained unchanged.     

Preparation of high-porosity Al2O3 ceramic foams via selective laser sintering of Al2O3 poly-hollow microspheres

In this paper, high-porosity Al₂O₃ ceramic foams called Al₂O₃ PHM ceramics were fabricated through selective laser sintering (SLS) via Al₂O₃ poly-hollow microspheres (Al₂O₃ PHMs). SLS parameters were optimized by an orthogonal experiment as to be laser power = 6 W, scanning speed = 1800 mm/s, and scanning space = 0.15 mm. The effect of sintering temperature on microstructure, shrinkage, porosity, phase composition, mechanical properties and pore size distribution of Al₂O₃ PHM ceramics were investigated. When sintering temperature increased, Al₂O₃ PHM ceramics contained only Al₂O₃ phase and were gradually densified. With the raise of sintering temperature, the porosity of Al₂O₃ PHM ceramics decreased gradually from 77.09% to 72.41%, but shrinkage in H direction and compressive strength of Al₂O₃ PHM ceramics increased from 6.63% and 0.18 MPa to 13.10% and 0.72 MPa, respectively. Sintering temperature had little effect on pore size distribution of Al₂O₃ PHM ceramics, which only declined from 24.2 to 21.4 μm with the increase of sintering temperature from 1600 to 1650 °C. This method can not only directly prepare ceramic foams with complex shapes, but also control properties of ceramic foams. It provides a simple preparation method for many kinds of ceramic foams with complex structure and high porosity by using PHMs with different composition.     

Studies on CrO x /La2O3/ZrO2 catalysts modified by Mg

Lanthana–zirconia supported chromium oxide and magnesium chromium mixed oxide catalysts were studied in the dehydrocyclization of n-octane and characterized by temperature-programmed desorption of NH₃, temperature-programmed reduction, XPS and DRIFTS. The Mg-free catalyst shows the highest activity, but suffers from rapid deactivation due to coke formation. The addition of Mg decreases the initial activity of the supported chromium oxide and retards its deactivation. The characterization results reveal that the deactivation retarding effect of Mg species not only consists in the deletion of strong acid sites but also in the decoration and/or dilution of Cr³⁺ oxide cluster, supposedly due to the formation of Mg–Cr surface compounds and, thus, in preventing the formation of coke.     

Low-temperature sintering of Al2O3 ceramics doped with 4CuO-TiO2-2Nb2O5 composite oxide sintering aid

Dense alumina ceramics doped with 5 wt% 4CuO-TiO₂-2Nb₂O₅ composite sintering aids were obtained at low sintering temperatures of 950∼975 °C. The ceramic sintered at optimal condition shows good microwave dielectric properties (ε_r = 12.7, Q × f = 7400 GHz), high thermal conductivity (18.4 W/m K) and high bending strength (320 MPa). TEM and EDS analysis revealed that amorphous Cu-Ti-Nb-O interfacial films with nanometer thickness formed at the grain boundaries, which could provide paths of mass transportation for densification. Al³⁺ ions may be involved in mass transportation through substitution by Ti³⁺ and Ti⁴⁺ ions near the grain boundary during the sintering process. The accumulation of copper ions at the trigeminal grain boundary was observed. The migration and reaction of copper ions in grain boundaries may also play an important role in promoting mass transportation and low-temperature densification of alumina ceramics.     

Microwave hybrid and conventional sintering of Al2O3 and Al2O3/ZrO2 multilayers fabricated by aqueous tape casting

In this study, microwave hybrid sintering and conventional sintering of Al₂O₃- and Al₂O₃/ZrO₂-laminated structures fabricated via aqueous tape casting were investigated. A combination of process temperature control rings and thermocouples was used to measure the sample surface temperatures more accurately. Microwave hybrid sintering caused higher densification and resulted in higher hardness in Al₂O₃ and Al₂O₃/ZrO₂ than in their conventionally sintered counterparts. The flexural strength of microwave-hybrid-sintered Al₂O₃/ZrO₂ was 70.9% higher than that of the conventionally sintered composite, despite a lower sintering temperature. The fracture toughness of the microwave-hybrid-sintered Al₂O₃ increased remarkably by 107.8% despite a decrease in the relative density when only 3 wt.% t-ZrO₂ was added. The fracture toughness of the microwave-hybrid-sintered Al₂O₃/ZrO₂ was significantly higher (247.7%) than that of the conventionally sintered composite. A higher particle coordination and voids elimination due to the tape casting and the lamination processes, the microwave effect, the stress-induced martensitic phase transformation, and the grain refinement phenomenon are regarded as the main reasons for the mentioned outcomes.     

Laser sintering of Al2O3-based green ceramics prepared by different pre-sintering temperatures

Al₂O₃-based green ceramics are prepared by isostatic cold pressing technology. The prepared green ceramics are pre-sintered at the temperature from room temperature to 1100°C, and then Al₂O₃ ceramics are prepared by laser sintering. The effects of pre-sintering temperatures and laser parameters on mechanical properties and the sintering quality are analyzed. The results show that good crystallinity of Al₂O₃ particles is obtained at a higher pre-sintering temperature. The flexural strength and density of green ceramics increase with the temperature of heat treatment. The flexural strength decreases slightly at ∼200°C due to the paraffin binder disintegration. The pre-sintering temperature and laser processing parameters have a significant influence on the sintering quality. With the increase of laser power and laser frequency, dynamic grain growth occurs, and then grains are refined. The majority of plate-like grains are transformed into long cylindrical-like grains in the severe densification process. However, porous flocculation microstructures are generated on the samples pre-sintered at 1100°C after laser sintering, which is due to the material gasification in atmospheric environment during sintering by infrared laser. More uniform microstructure and better sintering quality of samples pre-sintered at 500°C can be achieved after laser sintering with a relatively narrower grain size distribution.     

Two-step pulsed electric current sintering of transparent Al2O3 ceramics

Abstract

Fully densified Al₂O₃ ceramics with fine grain size were obtained by pulsed electric current sintering through a two-step heating profile (referred to as TS-PECS). Highly transparent Al₂O₃ polycrystals with fine grain size (400 nm) were successfully fabricated by the TS-PECS process, namely, sintering at 1000°C for 1 h and followed at 1200°C for 20 min under uniaxial pressure of 100 MPa. Effects of the first step temperature and heating rate were discussed for bulk density, grain size and transparency. The temperature in the first step strongly affects densification and grain growth of Al₂O₃. On the other hand, heating rate, even of 100 K min^?1, in TS-PECS does not give significant influences on densification and grain growth of Al₂O₃. Inline transmittance at 640 nm in wavelength normalised to 1 mm in thickness is increased by decreasing heating rate even in TS-PECS.     

High performances of Pt-K/Al2O3 versus Pt-Ba/Al2O3 LNT catalysts in the simultaneous removal of NO x and soot

The potentiality of a Pt-K/Al₂O₃ catalyst in the simultaneous removal of particulate matter (soot) and NO _x is investigated in this work by means of Temperature Programmed Oxidation (TPO) experiments and Transient Response Method (TRM), and compared with Pt-Ba/Al₂O₃. The results point out the higher performances of K-based sample in the soot combustion as compared to the Ba-based catalyst, and similar behaviour in the NO _x -storage.