Nanocrystalline BaAl2O4 powders prepared by aqueous combustion synthesis

In order to achieve BaAl₂O₄ formation via combustion synthesis, two types of recipes were designed: single fuel recipes (urea, glycine, β-alanine or hexamethylenetetramine) and innovative fuel mixture recipes (urea+glycine, urea+β-alanine and urea+hexamethylenetetramine respectively). No combustion reactions were noticed in the case of single fuel recipes based on urea or hexamethylenetetramine. The only crystalline phase present in the case of the powders obtained in such a way was unreacted Ba(NO₃)₂. Glycine and β-alanine generated smoldering reactions, leading to the formation of black powders, which consist of Ba(NO₃)₂, BaCO₃ and traces of BaAl₂O₄ (in the case of β-alanine). Fuel mixture recipes proved to be better than single fuel recipes, yielding BaAl₂O₄ as main crystalline phase. The specific surface area of the resulted powders ranges between 2.0 and 3.9 m²/g. The urea and glycine fuel mixture was the most efficient yielding BaAl₂O₄ with an average crystallite size of 60 nm.     

Influence of CuO on the formation and coexistence of 3CaO·SiO2 and 3CaO·3Al2O3·CaSO4 minerals

The influence of CuO on the formation and coexistence of 3CaO·SiO₂ and 3CaO·3Al₂O₃·CaSO₄ minerals in Portland cement containing 3CaO·3Al₂O₃·CaSO₄ mineral is reported in this paper. The results show that a suitable amount of CuO can lower the clinkering temperature and improve the burn-ability of clinkers. It can also promote the formation of 3CaO·SiO₂ and 3CaO·3Al₂O₃·CaSO₄ minerals and facilitate the coexistence of the two minerals in the clinkers. But adding 1% CuO to the raw material can cause the decomposition of 3CaO·3Al₂O₃·CaSO₄.     

Influence of MgO on the formation of Ca3SiO5 and 3CaO·3Al2O3·CaSO4 minerals in alite-sulphoaluminate cement

The influence of MgO on the formation of Ca₃SiO₅ and 3CaO·3Al₂O₃·CaSO₄ minerals in alite-sulphoaluminate cement is reported in this paper. The results show that adding a suitable amount of MgO can lower the clinkering temperature, promote the formation of Ca₃SiO₅ and 3CaO·3Al₂O₃·CaSO₄ minerals, and help in the coexistence of the two minerals in the clinker. MgO may obviously decrease the formation of Ca₃Al₂O₆, and increase the SiO₂ content incorporated into the interstitial phase.     

Densification ability of combustion-derived Al2O3 powders

Nanocrystalline Al₂O₃ powders containing different amounts of MgO (0.1–5.0 mol%) or added boehmite (AlOOH) have been synthesized by combustion synthesis from aluminium nitrate and magnesium nitrate, using urea or sucrose as fuels. The as synthesized alumina powders were deagglomerated, compacted by dry pressing and sintered at 1625 °C for 2 h. For comparison purposes, a commercial high purity α-Al₂O₃ powder (ACC) was also processed following the same route. The sintered materials were characterized for bulk density (BD), apparent porosity (AP), and water absorption (WA) capacity, microstructure using SEM, and XRD phase composition. In comparison to boehmite, the MgO had a considerable effect on the densification behaviour of combustion-synthesized powder.     

Large-scale fine structural alumina matrix ceramic guideway materials improved by diopside and Fe2O3

Diopside and Fe₂O₃ were introduced in alumina matrix ceramic materials. Large-scale fine structural alumina matrix ceramic guideway materials were fabricated by the technology of pressureless sintering, during which liquid phase sintering took place and new phases such as 3Al₂O₃·2SiO₂, CaO·Al₂O₃·2SiO₂ and CaO·6Al₂O₃ were produced by the chemical reactions taking place among alumina and the additives. The hardness, the fracture toughness and the bending strength of the guideway products were tested. The influences of diopside and Fe₂O₃ additions were studied by microstructural observations and mechanical properties evaluations. Meanwhile, the expected improvement of mechanical properties compared with pure alumina was indeed observed. The fracture mechanism and porosity of large-scale fine structural alumina matrix ceramic guideway materials were analyzed.     

Preparation of nanocrystalline Sr3Al2O6 powders via citric acid precursor

Sr₃Al₂O₆ was synthesized via citric acid precursor. The effects of the molar ratio of citric acid to total metal cations concentration (CA/M) on the formation of Sr₃Al₂O₆ were investigated. Increasing the CA/M promoted the formation of Sr₃Al₂O₆. Single-phase and well-crystallized Sr₃Al₂O₆ was obtained from the CA/M = 1, CA/M = 2 and CA/M = 4 precursor at temperature 1200 °C, 1100 °C and 900 °C, respectively. Differential thermal analysis and thermogravimetric (DTA/TG), X-ray diffractometry (XRD) and field emission scanning electron microscopy (FESEM) were used to characterize the precursors and the derived oxide powders. Sr₃Al₂O₆ nanoparticles with a diameter of about 50-70 nm were obtained.     

Pulsed electric current sintering of transparent Cr-doped Al2O3

Pulsed electric current sintering (PECS) was applied to obtain transparent ruby polycrystals. Al₂O₃-Cr₂O₃ powder mixture was prepared by drying an aqueous slurry consisting of Al₂O₃ and Cr(NO₃)₃ followed by PECS consolidation in vacuum at a sintering temperatures ranging from 1100 to 1300 °C with various heating rates between 2 and 100 °C/min and under an applied pressures from 40 to 100 MPa. Slow heating rate and high-pressure lead to highly densified and transparent Cr-doped Al₂O₃ polycrystals at sintering temperature of 1200 °C.     

Sintering of Al2O3-SiC composite from sol-gel method with MgO, TiO2 and Y2O3 addition

Al₂O₃-SiC composite ceramics were prepared by pressureless sintering with and without the addition of MgO, TiO₂ and Y₂O₃ as sintering aids. The effects of these compositional variables on final density and hardness were investigated. In the present article at first α-Al₂O₃ and β-SiC nano powders have been synthesized by sol-gel method separately by using AlCl₃, TEOS and saccharose as precursors. Pressureless sintering was carried out in nitrogen atmosphere at 1600 °C and 1630 °C. The addition of 5 vol.% SiC to Al₂O₃ hindered densification. In contrast, the addition of nano MgO and nano TiO₂ to Al₂O₃-5 vol.% SiC composites improved densification but Y₂O₃ did not have positive effect on sintering. Maximum density (97%) was achieved at 1630 °C. Vickers hardness was 17.7 GPa after sintering at 1630 °C. SEM revealed that the SiC particles were well distributed throughout the composite microstructures. The precursors and the resultant powders were characterized by XRD, STA and SEM.     

An efficient approach for direct synthesis of K0.5Na0.5NbO3 powders

Pure K_0.5Na_0.5NbO₃ powders were prepared at low temperatures by an efficient method using Na₂CO₃, K₂CO₃ and Nb₂O₅ as raw materials and urea as fuel. The phase evolution of the powders was investigated by X-ray diffractometer (XRD) and thermo gravimetric analysis-differential scanning calorimeter (TG-DSC). The phase composition and morphology of the powders were characterized by electron probe microanalysis (EPMA) and scanning electron microscope (SEM), respectively. The results reveal that single-phase K_0.5Na_0.5NbO₃ powder can be obtained at 550 °C by the method. The as-prepared powder is stoichimetric, fine and well-developed.     

Preparation and thermophysical properties of LaMgAl11O19–Yb3Al5O12 ceramic composites

LaMgAl₁₁O₁₉–Yb₃Al₅O₁₂ ceramic composites were prepared by pressureless sintering process at 1700 °C for 10 h in air. The microstructure and thermophysical properties of the composites were characterized by X-ray diffraction, scanning electron microscopy, high-temperature dilatometer and laser flash diffusivity measurements. LaMgAl₁₁O₁₉–Yb₃Al₅O₁₂ ceramic composites are composed of magnetoplumbite and garnet structures. LaMgAl₁₁O₁₉–Yb₃Al₅O₁₂ ceramic composites exhibit typical linear increase in thermal expansion with the increase of temperature. The measured thermal diffusivity gradually decreases with increasing temperature. Thermal conductivity of LaMgAl₁₁O₁₉–Yb₃Al₅O₁₂ ceramic composites is in the range of 2.6–3.9 W·m⁻¹·K⁻¹ from room temperature to 1200 °C.     

Formation of LiNi0.5Co0.5VO4 nano-crystals by solvothermal reaction

LiNi_0.5Co_0.5VO₄ nano-crystals were solvothermally prepared using a mixture of LiOH·H₂O, Ni(NO₃)₂·6H₂O, Co(NO₃)₂·6H₂O and NH₄VO₃ in isopropanol at 150–200 °C followed by 300–600 °C calcination to form powders. TGA curves of the solvothermal products show weight losses due to evaporation and decomposition processes. The purified products seem to form at 500 °C and above. The products analyzed by XRD, selected area electron diffraction (SAED), energy dispersive X-ray (EDX) and atomic absorption spectrophotometer (AAS) correspond to LiNi_0.5Co_0.5VO₄. V–O stretching vibrations of VO₄ tetrahedrons analyzed using FTIR and Raman spectrometer are in the range of 620–900 cm⁻¹. A solvothermal reaction at 150 °C for 10 h followed by calcination at 600 °C for 6 h yields crystals with lattice parameter of 0.8252 ± 0.0008 nm. Transmission electron microscope (TEM) images clearly show that the solvothermal temperatures play a more important role in the size formation than the reaction times.     

NOx adsorption and diesel soot combustion over La2O3 supported catalysts containing K, Rh and Pt

In this work we report results of NOx adsorption and diesel soot combustion on a noble metal promoted K/La₂O₃ catalyst. The fresh-unpromoted solid is a complex mixture of hydroxide and carbonate compounds, but the addition of Rh favors the preferential formation of lanthanum oxycarbonate during the calcination step. K/La₂O₃ adsorbs NOx through the formation of La and K nitrate species when the solid is treated in NO + O₂ between 70 and 490 °C. Nitrates are stable in the same temperature range under helium flow. However, they become unstable at ca. 360 °C when either Rh and/or Pt are present, the effect of Rh being more pronounced. Nitrates decompose under different atmospheres: NO + O₂, He and H₂. The effect of Rh might be to form a thermally unstable complex (Rh–NO⁺) which takes part both in the formation of the nitrates when the catalyst is exposed to NOx and in the nitrates decomposition at higher temperatures. Regarding soot combustion, nitrates react with soot with a temperature of maximun reaction rate of ca. 370 °C, under tight contact conditions. This temperature is not affected by the presence of Rh, which indicates that the stability of nitrates has little effect on their reaction with soot.     

Influence of the Storage Material on the Storage of NOx at Low Temperatures

The NO _x storage performance at low temperature (100–200 °C) has been studied for model NO _x storage catalysts. The catalysts were prepared by sequentially depositing support, metal oxide and platinum on ceramic monoliths. The support material consisted of acidic aluminium silicate, alumina or basic aluminium magnesium oxide, and the added metal oxide was either ceria or barium oxide. The NO _x conversion was evaluated under net-oxidising conditions with transients between lean and rich gas composition and the NO _x storage performance was studied by isothermal adsorption of NO₂ followed by temperature programmed desorption of adsorbed species. The maximum in NO _x storage capacity was observed at 100 °C for all samples studied. The Pt/BaO/Al₂O₃ catalyst stored about twice the amount of NO _x compared with the Pt/Al₂O₃ and Pt/CeO₂/Al₂O₃ samples. The storage capacity increased with increasing basicity of the support material, i.e. Pt/Al₂O₃·SiO₂ < Pt/Al₂O₃ < Pt/Al₂O₃ · MgO. Water did not significantly affect the NO _x storage performance for Pt/Al₂O₃ or Pt/BaO/Al₂O₃.     

Improvement of coke resistance of Ni/Al2O3 catalyst in CH4/CO2 reforming by ZrO2 addition

This work investigates the improvement of Ni/Al₂O₃ catalyst stability by ZrO₂ addition for H₂ gas production from CH₄/CO₂ reforming reactions. The initial effect of Ni addition was followed by the effect of increasing operating temperature to 500–700 °C as well as the effect of ZrO₂ loading and the promoted catalyst preparation methods by using a feed gas mixture at a CH₄:CO₂ ratio of 1:1.25. The experimental results showed that a high reaction temperature of 700 °C was favored by an endothermic dry reforming reaction. In this reaction the deactivation of Ni/Al₂O₃ was mainly due to coke deposition. This deactivation was evidently inhibited by ZrO₂, as it enhances dissociation of CO₂ forming oxygen intermediates near the contact between ZrO₂ and nickel where the deposited coke is gasified afterwards. The texture of the catalyst or BET surface area was affected by the catalyst preparation method. The change of the catalyst texture resulted from the formation of ZrO₂–Al₂O₃ composite and the plugging of Al₂O₃ pore by ZrO₂. The 15% Ni/10% ZrO₂/Al₂O₃ co-impregnated catalyst showed a higher BET surface area and catalytic activity than the sequentially impregnated catalyst whereas coke inhibition capability of the promoted catalysts prepared by either method was comparable. Further study on long-term catalyst stability should be made.     

Study on the formation process of Al2O3-TiO2 composite powders

Fine particles of anatase were suspended in solutions of ammonium alum with Al₂O₃/TiO₂ molar ratios from 0.1:1 to 7:1. By spray drying the suspensions and calcining the spray-dried powders, Al₂O₃-TiO₂ composite particles were obtained. The results show that after the spray drying, coatings of ammomium alum are formed on the surface of the anatase particles, leading to composite precursor powders (CCPs) with larger particle sizes. Upon calcining the CCPs, ammomium alum pyrolyzes to amorphous Al₂O₃ and anatase transforms into rutile. Both are mainly responsible for the observed particle size reductions as well as the densification of each composite particle. The in-situ formed α-Al₂O₃ and rutile may have higher reactivities, forming aluminum titanate at 1150 °C, about 130 °C lower than the theoretical temperature for the formation of Al₂TiO₅ by solid reaction. The reaction between α-Al₂O₃ and rutile starts from the interface between the anatase and the alum coating and mainly takes place in the single particles formed by spray drying. The molar ratio of Al₂O₃ to TiO₂ influences the final crystalline phases in the composite powders, but not stoichiometrically.     

The solubility of selenate-AFt (3CaO·Al2O3·3CaSeO4·37.5H2O) and selenate-AFm (3CaO·Al2O3·CaSeO4·xH2O)

The Se(VI)-analogues of ettringite and monosulfate, selenate-AFt (3CaO·Al₂O₃·3CaSeO₄·37.5H₂O), and selenate-AFm (3CaO·Al₂O₃·CaSeO₄·xH₂O) were synthesised and characterised by bulk chemical analysis and X-ray diffraction. Their solubility products were determined from a series of batch and resuspension experiments conducted at 25 °C. For selenate-AFt suspensions, the pH varied between 11.37 and 11.61, and a solubility product, log K_so=61.29±0.60 (I=0 M), was determined for the reaction 3CaO·Al₂O₃·3CaSeO₄·37.5H₂O+12 H⁺⇔6Ca²⁺+2Al³⁺+3SeO₄²⁻+43.5H₂O. Selenate-AFm synthesis resulted in the uptake of Na, which was leached during equilibration and resuspension. For the pH range of 11.75 to 11.90, a solubility product, log K_so=73.40±0.22 (I=0 M), was determined for the reaction 3CaO·Al₂O₃·CaSeO₄·xH₂O+12 H⁺⇔4Ca²⁺+2Al³⁺+SeO₄²⁻+(x+6)H₂O. Thermodynamic modelling suggested that both selenate-AFt and selenate-AFm are stable in the cementitious matrix; and that in a cement limited in sulfate, selenate concentration may be limited by selenate-AFm to below the millimolar range above pH 12.     

Influence of low concentration of SO2 for selective reduction of NO by C3H8 in lean-exhaust conditions on the activity of Ag/Al2O3 catalyst

The effect of SO₂ for the selective reduction of NO by C₃H₈ on Ag/Al₂O₃ was investigated in the presence of excess oxygen and water vapor. The NO_x conversion decreased permanently even in the presence of a low concentration of SO₂ (0.5–10 ppm) at <773 K. The increase in SO₂ concentration resulted in a large decrease in NO_x conversion at 773 K. However, when the reaction temperature was more than 823 K, the activity of Ag/Al₂O₃ remained constant even in the presence of 10 ppm of SO₂. The sulfate species formed on the used Ag/Al₂O₃ were characterized by a temperature programmed desorption method. The sulfated species formed on silver should mainly decrease the deNO_x activity on the Ag/Al₂O₃. The sulfated Ag/Al₂O₃ was appreciably regenerated by thermal treatment in the deNO_x feed at 873 K. The moderate activity remains at 773 K in the presence of 1 ppm SO₂ for long time by the heat treatment at every 20 h intervals.     

Precursor effects on ZrW2O8 formation kinetics

The synthesis of ZrW₂O₈ from different kinds of mixtures containing ZrO₂–WO₃, ZrO(NO₃)₂·2H₂O–WO₃, ZrCl₂O·8H₂O–WO₃, and ZrO₂–(NH₄)₁₀W₁₂O₄₁·5H₂O was investigated, and the kinetics was analyzed using JMA equation. It was found that ZrO(NO₃)₂·2H₂O, ZrCl₂O·8H₂O H₂O and (NH₄)₁₀W₁₂O₄₁·5H₂O that were used as inorganic precursors formed ZrO₂ and WO₃ after firing above 500 °C. The content of ZrW₂O₈ obtained by firing the mixtures is influenced by the kinds of precursors as well as mixing methods. The formation rate of ZrW₂O₈ depends on homogeneity related to mixing methods as well as the particle size of starting powders. Phase-pure ZrW₂O₈ is obtained from the ZrCl₂O·8H₂O–WO₃ mixtures at 1200 °C for 4 h, which is much shorter time than in the case of conventional ZrO₂–WO₃ mixtures. In the reaction kinetics of ZrO₂–WO₃ system, the Avrami exponent (n) is ∼0.5 above 1175 °C, indicating that the reaction is controlled by the diffusion-controlled reaction.     

Influence of the Type of Reducing Agent (H2, CO, C3H6 and C3H8) on the Reduction of Stored NOX in a Pt/BaO/Al2O3 Model Catalyst

In this investigation, a comparative study for a NO _X storage catalytic system was performed focusing on the parameters that affect the reduction by using different reductants (H₂, CO, C₃H₆ and C₃H₈) and different temperatures (350, 250 and 150 °C), for a Pt/BaO/Al₂O₃ catalyst. Transient experiments show that H₂ and CO are highly efficient reductants compared to C₃H₆ which is somewhat less efficient. H₂ shows a significant reduction effect at relatively low temperature (150 °C) but with a low storage capacity. We find that C₃H₈does not show any NO _X reduction ability for NO _X stored in Pt/BaO/Al₂O₃ at any of the temperatures. The formation of ammonia and nitrous oxide is also discussed.     

Matrix–filler interactions in polysilazane-derived ceramics with Al2O3 and ZrO2 fillers

Interactions between a poly(vinyl)silazane and Al₂O₃ or Y₂O₃-stabilised ZrO₂ fillers were studied during the fabrication of polysilazane-derived bulk ceramics in order to investigate the influence of oxide fillers on resulting properties. Specimens were produced by coating of the filler powders with the polysilazane, warm-pressing of the resulting composite powders, and pyrolytic conversion in flowing N₂ at various temperatures between 1000 °C and 1400 °C. Significant differences in densification were observed, depending on the filler used. Reactions between the polysilazane-derived matrix and Al₂O₃ or ZrO₂ at temperatures ≥1300 °C resulted in the formation of Si₅AlON₇ or ZrSiO₄, respectively. Reactivity in the polysilazane-derived component was a result of SiO₂ contamination caused primarily by adsorbed species on the filler particle surface. Knowledge of polysilazane/filler interface processes is found to be decisive for the prediction of properties such as shrinkage and porosity, which heavily influence performance of a material.