Phase compositions and equilibria in the CaO–Al2O3–Fe2O3–SO3 system,for assemblages containing ye'elimite and ferrite Ca2(Al,Fe)O5

Phase equilibria in the CaO–Al₂O₃–Fe₂O₃–SO₃ system have been studied, mainly at 1325 °C. In particular the solid solution compositions of ye'elimite Ca₄(Al₆O₁₂)SO₄ and brownmillerite (C₂(A,F)) phases have been analysed and used to estimate the composition boundaries of these phases in their co-existence with liquid at 1325 °C. Sulfate and iron oxide facilitate the formation of a liquid phase, whose amount increases with overall Fe₂O₃ content. However, the solubility of sulfate in this liquid phase is very low and liquid formation tends to lead to the volatilisation of sulfate in unsealed samples.     

Hydration of Ca7ZrAl6O18 phase

The hydraulic properties of the Ca₇ZrAl₆O₁₈ (C₇A₃Z) phase as well as the hydration products and thermal decomposition mechanism of this hydrated phase were studied. Microcalorimetric analysis has shown that the C₇A₃Z phase reacts with water very quickly, especially in the first 2 h after the start of the experiment. Hydration of calcium zirconium aluminate proceeds with the formation of high refractory calcium zirconate (with melting point 2345 °C), apart from the hydrated, nearly amorphous material. According to the DTA–TG–EGA, FT-IR and SEM/EDS examinations it has been found that not only the hydrates CAH₁₀, C₂AH₈ and C₄AH₁₉ are present, but also C₃AH₆ (C = CaO, A = Al₂O₃, H = H₂O), the only hydrated calcium aluminate which is a thermodynamically stable phase above 40 °C. Unhydrated Ca₇ZrAl₆O₁₈ and CaZrO₃ phases have been found by XRD, but crystalline hydrates have not been detected.     

Formation of porous aggregations composed of Al2O3 platelets using potassium sulfate flux

Porous aggregations, with about 10 μm diameter, composed of Al₂O₃ platelet crystals were formed by heating a powder mixture consisting of Al₂(SO₄)₃+2K₂SO₄ (mol ratio) in an alumina crucible at temperatures 1000–1300°C for 3 h and removing the flux component with hot hydrochloric acid after heating. The specific surface area of the aggregations obtained by heating at 1000°C for 3 h was maximum and its value was 5·2 m² g⁻¹. Since the size of Al₂O₃ platelets increased and the number of Al₂O₃ platelets decreased, the specific surface area decreased to 0·7 m² g⁻¹ at 1100°C. When heated at 1300°C, the size of the Al₂O₃ platelets increased with increasing amount of K₂SO₄ in the starting powder mixture. ©     

Phase formation in Al2O3-C refractories with Al addition

Depending on the recipe and the firing conditions, several non-oxides can be formed in Al₂O₃-C refractories. In this paper, the effect of the purity of the recipe components on the phase formation in Al₂O₃-C refractories with Al addition was investigated. Two test series were sintered from 800 °C to 1600 °C under air embedded in coke breeze. One test series was with brown fused alumina, and the other was with tabular alumina. At temperatures of up to 1200 °C the phase formation was the same for both recipes. For temperatures greater than 1400 °C, the impurities of brown fused alumina enhanced the formation of a polytype, while Al₄O₄C and Al₂₈O₂₁C₆N₆ were formed in the other series. The findings explain the occurrence of several non-oxides in disequilibrium at the chosen temperatures. The occurrence of Al₄C₃ was of particular interest due to its low hydration resistance. It was formed at 1200 °C.     

Modification of the oxidation behaviour of Si3N4–TiB2 composites by PECVD alumina coatings

A nearly fully dense (>98%) electroconductive silicon nitride—35 vol.% titanium diboride composite was obtained by hot isostatic pressing (HIP) in presence of a low content of sintering aids (0.5 wt.% Y₂O₃ + 0.25 wt.% Al₂O₃). To improve the oxidation behaviour of this composite material, a 3-μm thick protective coating of aluminium oxide was deposited on cubic samples (4 mm × 4 mm × 4 mm) by microwave plasma-enhanced chemical vapor deposition (PECVD) using an oxygen plasma and an organometallic precursor (trimethylaluminium). SEM images demonstrated that the coating was homogeneously distributed on the external surface of the specimens.Non-isothermal and isothermal oxidation tests were carried out with a Setaram Microbalance under pure flowing oxygen (10 L/h) on both uncoated and coated Si₃N₄–TiB₂ samples. In the case of non-isothermal oxidation of a substrate without coating, the reaction started at 600 °C. Between 1100 and 1350 °C, a plateau was observed and above 1350 °C the weight gain increased significantly. In presence of an Al₂O₃ coating, the composite started to oxidize at higher temperature (1200 °C). Isothermal kinetics recorded for 24 h, at 1350 and 1400 °C, revealed that the presence of the Al₂O₃ coating improved drastically the oxidation resistance and changed the shape of the curves from globally parabolic to almost logarithmic. An explanation of this protective behaviour, based on the characterization by XRD, SEM and EDS of the reaction products, is proposed.     

Comparison between carbonization of wood charcoal with Al-triisopropoxide and alumina

A comparison was made between the catalytic carbonization of biomass carbon suspended in Al-triisopropoxide and in biomass carbon mixed with 40 μm sized Al₂O₃ particles. Both types of samples were plasma sintered during 5 min under an argon pressure of 50 MPa at temperatures up to 2200 °C. Plate-like catalytic graphitization develops by formation and dissociation of plate-like Al₄C₃. Plasma sintering under the proper CO partial pressure and heat treatment temperature is instrumental in forcing the Al₂O₃ to react with the carbon, forming first Al₄C₃ and subsequently graphite. The difference between Al-triisopropoxide and Al₂O₃ is a matter of intensity of the graphite reaction versus the size of the graphite patches.     

Catalytic conversion of CO,NO and SO2 on the supported sulfide catalyst: I. Catalytic reduction of SO2 by CO

Catalytic reduction of SO₂ to elemental sulfur by CO has been systematically investigated over γ-Al₂O₃-supported sulfide catalysts of transition metals including Co, Mo, Fe, CoMo and FeMo with different loadings of the metals. The sulfided CoMo/Al₂O₃ exhibited outstanding activity: a complete conversion of SO₂ was achieved at a temperature of 300°C. The reaction proceeds catalytically and consistently over time and most efficiently at a molar feed ratio CO/SO₂ = 2. A precursor CoMo/Al₂O₃ oxide which experienced sulfurization through the CO–SO₂ reaction yielded a working sulfide catalyst having a yet lower activity than the CoMo catalyst sulfided before reaction (pre-sulfiding). The catalytic activity of various metal sulfides decreased in order of 4% Co 16% Mo > 4% Fe15% Mo > 16% Mo ≥ 25% Mo > 14% Co ≥ 4% Co > 4% Fe. A DRIFT study showed that CO adsorbs exclusively on CoMo phase and that SO₂ predominantly on γ-Al₂O₃. It is suggested that the Co–Mo–S structure is more adequate than the other metal-sulfur structures for the formation of a carbonyl sulfide (COS) intermediate because of the proper strength of metal–sulfur bond, and catalytically works with γ-Al₂O₃ for the COS–SO₂ reaction.     

Studies on obtaining of aluminium ammonium calcium phosphates

Aluminium ammonium calcium phosphates were prepared with the use of AlCl₃, CaCO₃, H₃PO₄. The influence of the process parameters (pH 5 ± 3, the molar ratios of Ca²⁺:Al⁺³:PO₄^?3 in the substrates, respectively 0.31:0.62:1; 0.5:0.5:1; 0.72:0.36:1, temperature 40 ± 20 °C) on the phase composition and the product properties was determined. The process parameters that enable to obtain the material with expected physicochemical properties were determined based on the statistical evaluation of the experiments (fractional factorial design at three levels 3^(k?p)27). The phase composition of the obtained samples was studied with the use of XRD analysis. The specific surface area was calculated with the use of S_BET method and the particle size was determined by the laser scanning microscopy. The materials with the molar ratio of Al³⁺/NH₄⁺ and Al³⁺/Ca²⁺ in the range of 0.70–27.93 and 0.47–24.48, respectively, with an absorption oil number of 95–157 g/100 g paraffin oil, the S_BET within 25–118 m²/g, the pore volume within 0.14–0.74 cm³/g and the particle size in the range of 168–285 nm were obtained.     

In situ DRIFTS study of the effect of structure (CeO2–La2O3) and surface (Na) modifiers on the catalytic and surface behaviour of Pt/γ-Al2O3 catalyst under simulated exhaust conditions

The nature and relative populations of adsorbed species formed on the surface of un-promoted and sodium-promoted Pt catalysts supported either on bare Al₂O₃ or CeO₂/La₂O₃-modified Al₂O₃, were investigated by in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) under simulated automobile exhaust conditions (CO + NO + C₃H₆ + O₂) at the stoichiometric point. The DRIFT spectra indicate that interaction of the reaction mixture with the Pt/Al₂O₃ catalyst leads mainly to formation of formates and acetates on the support and carbonyl species on partially positively charged Pt atoms (Pt^δ+). Although enrichment of Al₂O₃ with lanthanide elements (CeO₂ and La₂O₃) does not significantly modify the carboxylate species formed on the support, it causes significant modification of the oxidation state of Pt, as indicated by the appearance of a substantial population of carbonyl species on reduced Pt sites (Pt⁰–CO). This modification of the Pt component is enhanced when Na-promotion is used, leading to formation of carbonyl species only on electron enriched Pt (i.e., fully reduced Pt⁰ sites) and to the formation of NCO on these Pt entities (2180 cm⁻¹). The latter are thought to result from enhanced NO dissociation at Na-modified Pt sites. These results correlate well with observed differences in the catalytic performance of the three different systems.     

Calcium Cl/OH-apatite,Cl/OH-apatite/Al2O3 and Ca3(PO4)2 fibre nonwovens: Potential ceramic components for osteosynthesis

Polycrystalline calcium phosphate ((Cl/OH)Ap = Ca₅(PO₄)₃(OH/Cl); TCP = Ca₃(PO₄)₂) fibres were prepared from aqueous solutions of calcium chloride and phosphoric acid using poly(ethylene oxide) (PEO) as spinning aid. Generation of nonwoven materials was accomplished via rotary jet spinning. Polycrystalline (Cl/OH)Ap fibres 10–25 μm in diameter were obtained with 37% ceramic yield by pyrolysis of the green fibres followed by sintering at 1150 °C in air. X-ray diffraction (XRD) analysis provided evidence for apatite formation starting at 650 °C while (Cl/OH)Ap ceramic fibres were obtained at 1100 °C via transformation through intermediate dicalcium dichloride hydrogen phosphate (Ca₂Cl₂(HPO₄)) and calcium pyrophosphate (Ca₂P₂O₇) phases. A glass-forming Al-based additive was applied to enhance the mechanical properties of the Cl/OH)Ap ceramic fibres and indeed resulted in the formation of (Cl/OH)Ap/Al₂O₃ fibres with improved mechanical stability. Finally, TCP, (Cl/OH)Ap and (Cl/OH)Ap/Al₂O₃ fibres were subjected to seeding with mesenchymal stem cells. Negligible cytotoxicity is observed.     

Investigation of high-temperature reactions within the ZrSiO4–Al2O3 system

Solid state reactions between ZrSiO₄ and αAl₂O₃ in powders of stoichiometric composition 3Al₂O₃·2SiO₂ were studied by X-ray diffraction and electron scanning microscopy with energy dispersive X-ray analysis (SEM + EDX). Data were obtained at temperature ranging from 1400 °C to 1600 °C for a period of time ranging from 30 min to 60 h. The results indicate that ZrSiO₄ and αAl₂O₃ react and form crystalline ZrO₂, crystalline mullite (almost 3Al₂O₃·2SiO₂ composition) and non-crystalline silicon–alumina phase (pre-mullite). At the temperature of 1600 °C the fastest stage of reaction is dissociation of ZrSiO₄. Obtained results show that dissociation of zircon is a first-order reaction. The dissolution of Al₂O₃ particles and diffusion of Al into non-crystalline phase seem to be the slowest step of the reaction.     

Conversion of carbohydrate biomass to methyl levulinate with Al2(SO4)3 as a simple,cheap and efficient catalyst

Al₂(SO₄)₃ was developed as a simple and efficient catalyst for the synthesis of methyl levulinate (MLE) from carbohydrate biomass including fructose, glucose, mannose, sucrose, cellobiose, starch, and cellulose. The maximum MLE yield of 64% from glucose could be obtained at 160 °C for 150 min. Important roles of Al^3 + and Brønsted acid sites generated by the hydrolysis/methanolysis of Al^3 + were elucidated. The reaction process was revealed using in situ real-time attenuated total reflection infrared spectroscopy. Al₂(SO₄)₃ can be regenerated easily and reused at least four times without the loss of activity.     

Decomposition behavior of CaSO4 during potassium extraction from a potash feldspar-CaSO4 binary system by calcination

The extraction of potassium from a tablet mixture of K-feldspar ore and CaSO_4by roasting was studied with a focus on the effects of the decomposition behavior of CaSO_4on the potassium extraction process.The roasted slags were characterized by X-ray diffraction(XRD),scanning electron microscopy(SEM),energy-dispersive X-ray spectroscopy,and thermogravimetric(TG)analysis.The XRD analysis revealed that hydrosoluble mischcrystal K_2Ca_2(SO_4)_3was obtained by ion exchange of Ca~(2+)in CaSO_4and K~+in KAlSi_3O_8.Meanwhile,the intermediate product,SiO_2,separated from KAl Si_3O_8and reacted with CaSO_4to decompose CaSO_4.The SEM results showed that some blowholes emerged on the surface of the CaSO_4particles when they reacted with SiO_2at 1200°C,which indicates that SO_2and O_2gases were released from CaSO_4.The TG curves displayed that pure CaSO_4could not be decomposed below 1200°C,while the mixture of K-feldspar ore and CaSO_4began to lose weight at 1000°C.The extraction rate of potassium and decomposition rate of CaSO_4were 62%and 44%,respectively,at a mass ratio of CaSO_4to K-feldspar ore of 3:1,temperature of 1200°C,tablet-forming pressure of6 MPa,and roasting time of 2 h.The decomposition of CaSO_4reduced the potassium extraction rate;therefore,the required amount of CaSO_4was more than the theoretical amount.However,excess CaSO_4was also undesirable for the potassium extraction reaction because a massive amount of SO_2and O_2gas were derived from the decomposition of CaSO_4,which provided poor contact between the reactants.The SO_2released from CaSO_4decomposition can be effectively recycled.     

Effect of Al2O3 on the structure and microwave dielectric properties of Ca0.7Ti0.7La0.3Al0.3O3

The effect of excess Al₂O₃ on the densification, structure and microwave dielectric properties of Ca_0.7Ti_0.7La_0.3Al_0.3O₃ (CTLA) was investigated. CTLA ceramics were prepared using the conventional mixed oxide route. Excess Al₂O₃ in the range of 0.1–0.5 wt% was added. It was found that Al₂O₃ improved the densification. A phase rich in Ca and Al was found in the microstructure of Al₂O₃ doped samples. Additions of Al₂O₃ coupled with the slow cooling after sintering improved the microwave dielectric properties. CTLA ceramics with 0.25 wt% Al₂O₃ cooled at 5 °C/h showed high density and a uniform grain structure with ɛ_r = 46, Q × f = 38,289 and τ_f = +12 ppm/°C at 4 GHz. XRD and TEM examinations showed the presence of (1 1 2) and (1 1 0) type twins arising from a⁻a⁻c⁺ tilt system with the presence of anti-phase domain boundaries from the displacement of A-site cations of the orthorhombic perovskite structure.     

Phase formation of Na+-beta-aluminas synthesized by double zeta process

Na⁺-beta-aluminas in the Na₂O–Al₂O₃–Li₂O ternary system were synthesized by double zeta process and the dependence of the crystal phase formation on the composition and the calcination temperature was studied. For the synthesis of Na⁺-β/β″-alumina, sodium aluminate varying compositions of [Na₂O]:[Al₂O₃] = 1:4–1:6 and lithium aluminate in the forms of Li₂O·5Al₂O₃ with different amounts of Li₂O (0.35–0.45 wt%) were well-mixed and calcined at temperatures ranging between 1300 and 1600 °C for 2 h. The β″-alumina fraction appeared to be approximately 10% higher compared to the conventional solid state reaction, showing around 70% of β″-alumina fraction. These values increased about 10–15% by additional heating near the binary eutectic temperature for a short time.     

Carbon nanotube/boehmite-derived alumina ceramics obtained by hydrothermal synthesis and spark plasma sintering (SPS)

Preparation, structure and properties of hydrothermally treated carbon nanotube/boehmite (CNT/γ-AlOOH) and densification with spark plasma sintering of Al₂O₃ and CNT/Al₂O₃ nanocomposites were investigated. Hydrothermal synthesis was employed to produce CNT/boehmite from an aluminum acetate (Al(OH)(C₂H₃O₂)₂) and multiwall-CNTs mixture (200 °C/2 h.). TEM observations revealed that the size of the cubic shape boehmite particles lies around 40 nm and the presence of the interaction between surface functionalized CNTs and boehmite particles acts to form ‘nanocomposite particles’. Al₂O₃ and CNT/Al₂O₃ compact bodies were formed by means of spark plasma sintering (SPS) at 1600 °C for 5 min using an applied pressure of 50MPa resulting in the formation of stable α-Al₂O₃ phase and CNT–alumina compacts with nearly full density. It was also found that CNTs tend to locate along the alumina grain boundaries and therefore inhibit the grain coarsening and cause inter-granular fracture mode. The DC conductivity measurements reveal that the DC conductivity of CNT/Al₂O₃ is 10^?4 S/m which indicate that there is a 4 orders of magnitude increase in conductivity compared to monolithic Al₂O₃. The results of the microhardness tests indicate a slight increase in hardness for CNT/Al₂O₃ (28.35 GPa for Al₂O₃ and 28.57 GPa for CNT/Al₂O₃).     

Resistance to sulfidation of the catalytic reduction of NOx over Ag/Al2O3 by controlling the loadings of Ag and Ag+

SO₂ strongly decreased the catalytic activities of low loading Ag/Al₂O₃ below 500 °C in selective catalytic reduction (SCR) of NO_x by propene with or without the assistance of non-thermal plasma (NTP), which was mainly attributed to the competition between SO₂ and NO. By controlling the loadings of Ag and Ag⁺ over alumina, the resistance of SO₂ was remarkably enhanced between 400 °C and 500 °C in thermal SCR. In the NTP-assisted SCR, most of the NO_x conversions were also apparently recovered from 250 °C to 500 °C.     

Phase-transformation and grain-growth kinetics in yttria-stabilized tetragonal zirconia polycrystal doped with a small amount of alumina

Microstructure development during sintering in 3 mol% Y₂O₃-stabilized tetragonal zirconia polycrystal doped with a small amount of Al₂O₃ was investigated in the isothermal sintering conditions of 1300–1500 °C. At the low sintering temperature at 1300 °C, although the density was relatively high, the grain-growth rate was much slow. In the specimen sintered at 1300 °C for 50 h, Y³⁺ and Al³⁺ ions segregated along grain boundaries within the widths of about 10 and 6 nm, respectively. In grain interiors, the cubic-phase regions were formed by not only a grain-boundary segregation-induced phase-transformation mechanism but also by spinodal decomposition. The grain-growth behavior was kinetically analyzed using the grain-size data in 1300–1500 °C, which indicated that the grain-growth rate was enhanced by Al₂O₃-doping. These phase-transformation and grain-growth behaviors are reasonably explained by the diffusion-enhanced effect of Al₂O₃-doping.     

Molten salt synthesis of zinc aluminate powder

ZnAl₂O₄ powder was synthesised by reacting equimolar ZnO and Al₂O₃ powders in alkaline chlorides (LiCl, NaCl or KCl). Formation of ZnAl₂O₄ started at about 700 °C in LiCl and 800 °C in NaCl and KCl. With increasing temperature, the amounts of ZnAl₂O₄ in the resultant powders increased with a concomitant decrease of ZnO and Al₂O₃. ZnAl₂O₄ powder was obtained by water-washing the samples heated for 3 h at 1000 °C (LiCl) or 1050 °C (NaCl and KCl). ZnAl₂O₄ formed in situ on Al₂O₃ grains from the surface inwards. The synthesised ZnAl₂O₄ grains retained the size and morphology of the original Al₂O₃ powders, indicating that a template formation mechanism dominated formation of ZnAl₂O₄ by molten salt synthesis.     

The effect of Si–Bi2O3 on the ignition of the Al–CuO thermite

The ignition temperature of the Al–CuO thermite was measured using DTA at a scan rate of 50 °C min^?1 in a nitrogen atmosphere. Thermite reactions are difficult to start as they require very high temperatures for ignition, e.g. for Al–CuO thermite comprising micron particles it is ca. 940 °C. It was found that the ignition temperature is significantly reduced when the binary Si–Bi₂O₃ system is added as sensitizer. Further improvement is achieved when the reagents are nano-sized powders. For the composition Al + CuO + Si + Bi₂O₃ (65.3:14.7:16:4 wt.%), with all components nano-sized, the observed ignition temperature is ca. 613 °C and a thermal runaway reaction is observed in the DTA.