Synthesis of ternary zinc spinel oxides and their application in the photodegradation of organic pollutant

Ternary zinc spinel oxides such as Zn₂SnO₄, ZnAl₂O₄ and ZnFe₂O₄ were synthesized and characterized, and their activities in the photodegradation of phenol molecules were investigated. Zn₂SnO₄, ZnAl₂O₄ and ZnFe₂O₄ powders were synthesized by hydrothermal, metal–chitosan complexation and solvothermal routes, respectively. The face-centered cubic spinel structure of each material was confirmed by powder X-ray diffractometry (XRD) and its porous structure by N₂ adsorption–desorption isotherms. The characterization of spinels was complemented with Fourier transform infrared spectroscopy (FTIR) and X-rays fluorescence (XRF), revealing the formation of spinel structures with high purity. The photocatalytic activity in the degradation of phenol was observed only with Zn₂SnO₄ oxide. Mineralization degree of phenol molecules by Zn₂SnO₄ photocatalyst determined by total organic carbon analysis (TOC) reached 80% at 360 min under sunlight.     

Role of delayed release of sulphates from clinker in DEF

Two clinkers rich in sulphate burned in the pilot plant rotary kiln and cements prepared from them were investigated. Clinker richer in sulphate (SO₃=3.6%) contained independent anhydrite grains as well as inclusions of anhydrite in belite. The mortar from it expanded after heat treatment at 90 °C and the addition of Na₂SO₄ or NaOH accelerated and increased this expansion. The expansion occurred irrespective of the fact that the clinker contained only 3% of C₃A, although the C₄AF content was 13%. The second clinker with 2.6% SO₃ contained mainly calcium langbeinite and expanded only when 2% of Na₂SO₄ was added. The SEM examination of the mortars revealed the presence of numerous bands of massive ettringite around sand grains. Agglomerates of cracked ettringite in cement gel were also present. In addition, microcracks were seen inside the darker C-S-H gel. The conclusion is that anhydrite forming inclusions in belite gives an expanding mortar after heat treatment at 90 °C independently of the tricalcium aluminate content. Such clinkers are not typical of industrial conditions. The expansion is caused by the bands of massive ettringite as well as its agglomerates present in the cement gel and nanometric ettringite in the C-S-H phase.     

Preparation and characterization of multicomponent porous materials prepared by the sol-gel process

An experimental strategy was developed to obtain transparent Si-Al-Ti-Ni-Mo and Si-Zr-Ti-Ni-Mo sols via the sol-gel process. The sol was prepared from Si(OEt)₄ (TEOS), Al(OBu^s)₃ (OBu^s: C₂H₅CH(CH₃)O), Ti(OEt)₄ (OEt: OCH₂CH₃), Zr(OPrⁿ)₄ (OPrⁿ: OCH₂CH₂CH₃). In both cases nickel nitrate hexahydrate (Ni(NO₃)₂ · 6H₂O) and ammonium heptamolybdate tetrahydrate ((NH₄)₆Mo₇O₂₄ · 4H₂O) were the Ni and Mo sources, respectively. The sols were characterized by Fourier Transform Infrared Spectroscopy (FTIR). Assignments of the simultaneous formation of the Si-O-Al, Si-O-Ti, Si-O-Ni, and Si-O-Zr bonds were done. The sols were polymerized at room temperature (293 K) to obtain gels, and these were dried at 423 K and calcined at 573, 853 and 893 K in air. The characterization techniques used were small-angle X-ray scattering (SAXS), X-ray diffraction (XRD), scanning electron microscopy (SEM), and ²⁹Si and ²⁷Al magic angle spinning nuclear magnetic resonance (MAS NMR). The density of the solids was measured following ASTM method D-4892 and the porosity and surface area were determined by N₂ adsorption/desorption isotherms. The corresponding average pore diameters were evaluated using the BJH, HK, and DA methods.     

Dielectric Relaxation of La-Doped Zirconia Caused by Annealing Ambient

La-doped zirconia films, deposited by ALD at 300°C, were found to be amorphous with dielectric constants (k-values) up to 19. A tetragonal or cubic phase was induced by post-deposition annealing (PDA) at 900°C in both nitrogen and air. Higher k-values (~32) were measured following PDA in air, but not after PDA in nitrogen. However, a significant dielectric relaxation was observed in the air-annealed film, and this is attributed to the formation of nano-crystallites. The relaxation behavior was modeled using the Curie–von Schweidler (CS) and Havriliak–Negami (HN) relationships. The k-value of the as-deposited films clearly shows a mixed CS and HN dependence on frequency. The CS dependence vanished after annealing in air, while the HN dependence disappeared after annealing in nitrogen.     

Synthesis and electrochemical properties of monoclinic Li3V2(PO4)3/C composite cathode material prepared from a sucrose-containing precursor

Monoclinic structure Li₃V₂(PO₄)₃/C composite powders are synthesized via a novel homogeneous mixing route followed by a one-step heat treatment. The composites were characterized by X-ray diffraction (XRD) and galvanostatic charge/discharge, CV measurements. The influence of the heat treatment on the electrochemical properties of Li₃V₂(PO₄)₃/C composites was investigated. To examine the effect of residual carbon content on the properties of the composites, six samples with 1.2, 2.3, 3.4, 4.4, 5.8, and 7.0 wt% carbon were prepared. The sample with 4.4 wt% carbon exhibited good cycling performance and rate capability in the range of 3.0–4.8 V.     

ZnO/Cr2O3 catalyst for reverse-water-gas-shift reaction of CAMERE process

The stability and the activity of Fe₂O₃/Cr₂O₃ and ZnO/Cr₂O₃ catalysts were examined for a reverse-watergas-shift reaction (RWReaction). The initial activities of those catalysts were quite high so that the conversion reached close to equilibrium. The activity of Fe₂O₃/Cr₂O₃ catalyst decreased from 33.5 to 29.8% during the RWReaction for 75 h at 873 K with GHSV (ml/gcat · h) of 100,000. Moreover, the coke formation on the Fe₂O₃/Cr₂O₃ catalyst caused clogging in the RWReactor of the CAMERE process. On the other hand, the ZnO/Cr₂O₃ catalyst showed no coke formation and no deactivation for the RWReaction at 873 K with GHSV (ml/gcat · h) of 150,000. The ZnO/Cr₂O₃ was a good catalyst for the RWReaction of the CAMERE process.     

A comparative study of different leaching processes for the extraction of Cu,Ni and Co from a complex matte

The extraction behaviors of Cu, Ni and Co from a complex matte under different leaching conditions have been discussed. The synthetic Cu-Ni-Co-Fe-S matte was prepared by melting the pure metals. The matte contained 24.95% Cu, 35.05% Ni, 4.05% Co, 11.45% Fe, 24.5% S, similar composition as is expected to be obtained by reduction smelting of the Pacific Ocean nodules followed by sulphidisation of the alloy. The different phases identified are CuFeS₂, CuS₂, (FeNi)₉S₈, (FeNi)S₂, Ni₉S₈, Ni₃S₂, (CoFeNi)₉S₈ and Co metal. The merits and demerits of each process of dissolution i.e., H₂SO₄/oxygen pressure leaching, atmospheric FeCl₃ leaching, NH₄OH/(NH₄)₂SO₄ pressure leaching are discussed in detail. Out of the three, the H₂SO₄/oxygen pressure leaching process is found to be the most suitable with more than 99% metal extraction efficiency within 1 h of leaching time. From the X-ray diffraction analysis, the different undissolved phases corresponding to different leaching processes have been identified. The metal extraction efficiency decreased in case of atmospheric FeCl₃ leaching and NH₄OH/(NH₄)₂SO₄ pressure leaching processes due to the formation of product layer such as elemental sulfur and goethite, respectively.     

Catalytic Production of Carbon Nanotubes by Decomposition of CH4 over the Pre-reduced Catalysts LaNiO3, La4Ni3O10, La3Ni2O7 and La2NiO4

A large amount of more graphitic carbon nanotubes with a narrow size distribution was produced from catalytic decomposition of CH₄ over pre-reduced LaNiO₃, La₄Ni₃O₁₀, La₃Ni₂O₇ and La₂NiO₄. The structure and component of fresh and reduced LaNiO₃, La₄Ni₃O₁₀, La₃Ni₂O₇ and La₂NiO₄ were determined by X-ray diffraction (XRD). The carbon nanotubes obtained were characterized by means of transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). Thermal oxidation of carbon nanotubes in air was made by thermogravimetric experiments (TG). The results revealed that the value of La/Ni in different catalyst precursors influences the diameter distribution and graphitic degree of carbon nanotubes. Lower La/Ni leads to wider diameter and higher graphitic degree of carbon nanotubes.     

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.     

A comparative study of ordinary and mineralised Portland cement clinker from two different production units Part II: Characteristics of the calcium silicates

Portland cement clinkers from two production units were investigated in order to determine the effects of mineralisation on alite and belite; Plant 1: ordinary clinker (P1) and clinker mineralised with CaF₂₊CaSO₄ (P1m); Plant 2: ordinary clinker (P2) and two clinkers mineralised with CaF₂₊CaSO₄ (P2m, P2m′).The polymorphism of alite was studied using synchrotron X-ray powder diffraction (XRD), wavelength 1.5227 Å, and electron diffraction (ED) in a transmission electron microscope. The substitutions of minor elements in alite and belite were determined using electron microprobe analysis. Clinkers P1 and P1m both contained apparent rhombohedral alite (XRD) with an incommensurately modulated structure (ED), while clinkers P2, P2m, and P2m′ all contained monoclinic alite (XRD). The addition of mineralisers in the process caused increased content of fluoride in alite and increased substitution of Si(4+) by Al(3+) and S(6+) in both calcium silicates. The latter effect was most pronounced in clinker P1m due to its high molar SO₃ to alkali oxide ratio (R=2.18).The improved hydraulic activity of P1m compared to P1 was caused by substitutions rather than a change in symmetry. The decreased hydraulic activity of P2m and P2m′ compared to P2 was explained by the high levels of fluorine, which had a retarding effect on the hydration.     

Preparation of bao-pbo-nd2o3-tio2 powders by hydrothermal synthesis

Homogeneous and nano-sized BPNT [(Ba_1-xPb_x)Nd₂Ti₅O₁₄] powders were prepared under various hydrothermal conditions. Crystallinity and homogeneity of the synthetic powders were investigated. The microwave dielectric properties of the filters prepared with hydrothermal powders were compared with those of the filters prepared with conventional powders. The microwave dielectric properties of the filter prepared with the hydrothermal powders were also better than those of the filter manufactured with the conventional powders. The dielectric constant, quality constant and temperature coefficient of resonance frequency of hydrothermally prepared filter under optimum condition and measured at 3.5 GHz around were about 93, 6067 and 0 ppm/°C, respectively.     

Anomalous fluorescence in near-infrared Raman spectroscopy of cementitious materials

The results of near-infrared Fourier transform Raman spectral examination of cement minerals, several commercial Portland cements, and hydrating Portland cements are critically examined. It is shown that structured fluorescent effects dominate the observed spectra for C₃S, C₂S, and cement, and none of the bands generated by this mode of examination is a true Raman band. The apparent bands for the Portland cements are in different positions to those for the individual cement minerals. The fluorescence-derived spectra for different cements are similar to each other but vary enormously in intensity for different cements. Hydration progressively reduces the intensity of the bands, but does not generate bands at new locations. It is tentatively suggested that the fluorescence effect may be somehow associated with the status of the cement components as orthosilicates (i.e., composed of isolated silica tetrahedra. Samples of high-purity C₂S exhibit the fluorescence effect, but samples of CS (wollastonite) of similar purity do not. The latter are metasilicates (i.e., composed of linked chains of silica tetrahedra). They exhibit normal Raman Stokes and anti-Stokes bands.     

The influence of polymers on the hydration of portland cement phases analyzed by soft X-ray transmission microscopy

The soft X-ray transmission microscope, which allows the in situ observation of wet samples of cement at normal pressures with high spatial resolutions (25 nm), was used to observe and compare the effects of two polymers — a water soluble polymer (HPMC — hydroxypropyl methylcellulose) and a latex [EVA-poly(ethylene-co-vinyl acetate)] on the early hydration of C₃S and C₃A. These polymers are used to modify the properties of fresh and hardened mortars and concretes, especially when adhesive characteristics are required. The images show that the cellulose ether delays the hydration of the cementitious particles and promotes the formation of inner products rather than outer products. On the other hand, EVA particles agglomerate around the hydrating C₃S grains, and act as nucleation agents in the development of the composite microstructure. While HPMC slightly changed the aspect of C₃A hydration, EVA inhibited or even prevented the formation of ettringite crystals during the early stage of hydration, and resulted in a cloud of small, bright particles concentrated around the hydrating C₃A grains.     

Mixed oxides as catalysts for the selective reduction of nitrobenzene

The catalytic behaviour of the PbO-Mn₃O₄ and the Bi₂O₃-MoO₃ systems was investigated in the selective reduction of nitrobenzene to nitrosobenzene. Lead compounds appeared to be good catalysts, and co-catalysts when used with Mn₃O₄. Different from oxidations by di-oxygen, Bi₃O₃ alone is a good catalyst and formation of mixed Bi-Mo-O compounds does not enhance the catalytic activity. It is suggested that the difference between these catalysts in the mentioned reaction is related to the way in which the oxygen vacancy is represented by the oxygen donor.     

Acid-Base Properties of Alumina-Supported M2O3 (M=B, Ga, In) Catalysts

The acid-base properties of -Al₂O₃ and alumina-supported B₂O₃, Ga₂O₃ and In₂O₃ have been determined by microcalorimetry of ammonia and sulfur dioxide adsorption. From the adsorption of NH₃, it was found that the addition of B₂O₃ on alumina leads to an increase of the number of acid sites, while Ga₂O₃ and In₂O₃ additives caused a decrease in the acidity of alumina. Using SO₂ as a probe molecule to study the basicity, the number of surface basic sites on alumina was found to be strongly decreased by the addition of boron oxide, while it was only slightly affected by the addition of gallium oxide and decreased by the addition of indium oxide. The differential heats of adsorption are discussed as a function of the coverage by the probe molecules. The electronic properties of the oxides are examined in order to explain the acid-base properties of the supported oxides.     

Hydrothermal solvothermal synthesis and microwave absorbing study of MCo2O4 (M = Mn,Ni) microparticles

ABSTRACT

MCo₂O₄ (M?=?Mn,Ni) microparticles were synthesised by a simple hydrothermal solvothermal method. The samples were characterised by X-ray diffraction, X-ray energy dispersive spectroscopy and scanning electron microscopy, which showed that MnCo₂O₄ microparticles with spherical particles aggregated by a large number of small cubes and cubic shaped NiCo₂O₄ microcubes were obtained. The microwave absorption properties of these products were systematically investigated by vector network analysis. Results indicated that the minimum reflection loss value of MnCo₂O₄ microparticles was ?26.34?dB at 11.04?GHz with the absorber thickness of 2.5?mm, which was much lower than that of NiCo₂O₄ microcubes with the same absorber thickness. The possible mechanism was analysed, indicating that the geometry and size of MCo₂O₄ (M?=?Mn,Ni) microparticles played a key role in microwave absorption.     

Effect of Y2O3 and Er2O3 co-dopants on phase stabilization of bismuth oxide

Bi₂O₃ compositions were prepared to investigate the effect of rare earth metal oxides as co-dopants on phase stability of bismuth oxide. Compositions containing 9-14 mol% of Y₂O₃ and Er₂O₃ were synthesized by solid state reaction. The structural characterization was carried out using X-ray powder diffraction. The XRD results show that the samples containing 12 and 14 mol% total dopants had cubic structure, whereas the samples with lower dopant concentrations were tetragonal. Comparing the lattice parameters of the cubic phases of (Bi₂O₃)_0.88(Y₂O₃)_0.06(Er₂O₃)_0.06 and (Bi₂O₃)_0.86(Y₂O₃)_0.07(Er₂O₃)_0.07 revealed that lattice parameter decreases by increasing the dopant concentration. The XRD pattern and the powder density results indicated the formation of solid solution in the studied systems. After annealing samples with cubic phase at 600 °C for various periods of time, phase transformation to tetragonal and rhombohedral occurs.     

The contribution of class-F fly ash to the strength of cementitious mixtures

The contribution of fly ash to the physical properties of cementitious mixtures has received considerable attention since its inclusion as an essential ingredient of High Performance Concrete (HPC). However, the chemical contribution to the overall structure development has not been fully understood because of the masking of its hydration products by those of cement. In a mixture of class-F fly ash and lime (Ca/Si=2), portlandite diminishes and C₄AH₁₃ forms due to addition of Al to solution. The latter converts to hydrogarnet and C₃ASH₄. CSH is detected at 3 days and continues to increase in intensity. The ²⁹Si magic angle spinning nuclear magnetic resonance spectroscopy (MAS NMR) showed that the Al/Si ratio is 0.24 and the average chain length is 10 units. The presence of Al as approximately one-fifth of the Si in a chain length of 10 units suggests that Al tetrahedra may be present in bridging positions.     

Study on the Poisoning Mechanism of Sulfur Dioxide for Perovskite La0.9Sr0.1CoO3 Model Catalysts

The reaction and poisoning mechanism of SO₂ with La_0.9Sr_0.1CoO₃ model catalysts have been investigated. The structure and the chemical states of the model catalysts have been studied by using AES, XPS and XRD techniques. The results indicated that SO₂ diffused into the La_0.9Sr_0.1CoO₃ film during poisoning. La₂(SO₄)₃ species was formed on the surface of the film and La₂(SO₄)₃, La₂(SO₃)₃, La₂O₂SO₄ and CoO species were found in the interior. The perovskite structure of La_0.9Sr_0.1CoO₃ was destroyed by invasion of SO₂. The concentration of sulfur in the film layer was related to the reaction temperature and time. After the sample was poisoned for a fairly long time, the distribution of sulfur in the La_0.9Sr_0.1CoO₃ layer became homogeneous, suggesting that a dynamic equilibrium was achieved between the poisoning reaction and the decomposition of the sulfates. XRD and catalytic activity test results proved that the destruction of perovskite structure and the formation of sulfates were the main causes of deactivation.     

Reduced strength degradation of alumina–aluminium titanate composite subjected to low-velocity impact loading

The impact behaviour of monophase alumina and alumina–aluminium titanate monolithic composite ceramics that present flaw tolerant behaviour was studied. Low-velocity impact loading tests were performed on bending bars and the residual strength after the impact was evaluated by four-point bending tests. The impact tests were monitored using an instrumented drop-weight machine. During impact, the composites absorbed higher energy than the monophase material. The strength retention, in percentage, after the impact was significantly higher for the composite that presented damage tolerance for impact energy levels higher than monophase alumina. These results are discussed and fractographic analysis was used to identify the mechanisms responsible for the lower strength degradation of the composite.