Energy requirement of ultraviolet and AOPs for the post-treatment of treated combined industrial effluent

Post-treatment was carried out to eliminate the colour and COD of treated combined industrial effluent. Ozonation at a dose of 300 mg/h for 10 min resulted in 100% colour and 96% COD removal at pH 8 and temperature 25 °C. The application of UV/H₂O₂ resulted in 91% colour and 82% COD removal. 79% colour and 60% COD removal was obtained with the Fenton process after 60-min treatment in the presence of 170 mg/l H₂O₂, while the photo-Fenton process showed an almost complete elimination of both parameters. Electrical energy consumption showed that the photo-Fenton resulted in the highest removal efficiency with 95% removal in terms of colour and COD abatement rates. The electrical energy requirements of the tested processes followed the increasing order UV/Fe/H₂O₂ < O₃ < UV/H₂O₂ < UV.     

Colour and COD removal from textile effluent by coagulation and advanced oxidation processes

The aim of this study was to compare the performance of coagulation, Fenton's oxidation (Fe²⁺/H₂O₂) and ozonation for the removal of chemical oxygen demand (COD) and colour from biologically pretreated textile wastewater. FeSO₄ and FeCl₃ were used as coagulants at varying doses and varying colour removal efficiency was measured. For the Fenton process, COD and colour removal efficiencies were found to be 78% and 95% for the Fenton process, and to be 64% and 71% for the Fenton-like process (Fe³⁺/H₂O₂), respectively. Ozonation experiments were conducted at different initial pH values and fixed ozone doses. Ozonation resulted in 43% COD and 97% colour removal whereas these rates increased to 54% and 99% when 5 mg/l hydrogen peroxide was added to the wastewater before ozonation at the same dose. The operating costs of all proposed treatment systems were also evaluated in this study.     

Effects of Palladium Dispersions on Gas-Sensitive Conductivity of Semiconducting Ga2O3 Thin-Film Ceramics

The gas sensitivity of Ga₂O₃ thin-film n -type conductors was investigated at temperatures of 500–1000°C. Palladium dispersions whose particle sizes are dependent on the preceding annealing processes were deposited by a wet-chemical technique onto Ga₂O₃ thin-film ceramics. The palladium clusters and their temperature-dependent growth were detected using scanning electron microscopy micrographs and X-ray photoemission spectroscopy measurements. The effect of the palladium dispersions on the gas-sensitive behavior of the Ga₂O₃ ceramics was investigated in various O₂/H₂ mixtures in the N₂ carrier gas at 700°C. The conductivity of the ceramics treated in this way was dependent on the O₂ partial pressure, as well as on the H₂ partial pressure of the surrounding gas atmosphere. The ceramic conductivity can be described as a function of the O₂:H₂ ratio, in accordance with the relation σ( p O₂/ p H₂/)^−1/3.     

High-Temperature Oxidation of Boron Nitride: II, Boron Nitride Layers in Composites

The oxidation of BN composite interphases was examined with a series of model materials. Oxidation was examined in both low-water-vapor (∼20 ppm H₂O/O₂) environments at 900°C and high-water-vapor (1% and 10% H₂O/O₂) environments at 700° and 800°C. The low-water-vapor case was explored with layered BN/SiC materials. This case was dominated by borosilicate glass formation, and the 20 ppm water vapor gradually removed the boron from the glass, leaving a larger amount of SiO₂ than would be expected from simple SiC oxidation. Layered SiC/BN/SiC materials were also used to study low-water-vapor oxidation effects within the composite. The high-water-vapor case was explored with SiC/BN/SiC minicomposites, and it was dominated by volatilization of BN as HBO₂( g ), H₃BO₃( g ), and H₃B₃O₆( g ). A model for recession of the BN fiber coating was developed based on the gas-phase diffusion of these species out of the annular region around the SiC fiber and concurrent sealing of this annular region by oxidation.     

Mixed Protonic–Electronic Conduction in "α-Al2O3": An Alternative Hypothesis

As an alternative, the voltage data of Kurita et al . recently published on galvanic cells with commercial α-Al₂O₃ as a solid electrolyte and with O₂, H₂O/α-Al₂O₃ as well as H₂, H₂O/α-Al₂O₃ as electrodes can be quantitatively described by assuming that α-Al₂O₃ represents a mixed sodium ionic–electronic conductor rather than a protonic–electronic conductor. From the evaluation of the experimental data, numerical values for the p -type electronic conduction parameter are obtained that agree sufficiently well with the data known to date for the sodium ion conductor Na-beta-Al₂O₃.     

High-Temperature Automotive Catalytic Nitrogen Oxide Reduction over Copper–Lanthanum–Alumina

The synthesis and nitrogen oxide (NO) removal activities of composite powders in the copper-lanthanum-alumina(Cu-La-Al₂O₃)system were studied, in regard to their high-temperature application as an automotive lean-burn exhaust catalyst. The solid-state reaction between the copper, the lanthanum, and the Al₂O₃support, at elevated temperature, was examined by X-ray diffractometry and electron-spin resonance. Lanthanum impregnation into the Al₂O₃support successfully helped to form active composite powders that could remove nitrogen oxides and consisted of gamma-Al₂O₃and LaAlO₃, after heat treatment at 900°C, and mainly CuLaAl11O19 at 1000°C. Cu²⁺cations were observed to be isolated in the present powders, even after heat treatment up to 1000°C. The evaluation of NO removal activity over lanthanum-modified copper-Al2O₃ catalysts that were subjected to harsh heat treatment was performed using a model exhaust-gas mixture of NO, carbon monoxide (CO), propene (C₃H₆), carbon dioxide (CO₂), water vapor (H₂O), and an excess of oxygen (O₂). The catalyst that was composed of 20 mol% copper, 10 mol% lanthanum, and Al2O₃ and heat treated at 900° and 1000°C in air showed NO removal conversion efficiencies of 14% and 8%, respectively, under the lean-burn conditions of an air:fuel (A/F) ratio of 18 and a space velocity (SV) of 100000 h-1. Lanthanum-modified copper-Al2O₃ powders are potentially useful as a NO removal catalyst, when applied to an automotive lean-burn exhaust.     

Near-Net-Shaped Calcium Hydroxyapatite by the Oxidation of Machinable, Calcium-Bearing Precursors (the Volume Identical Metal Oxidation, or VIMOX, Process)

A novel VIMOX (volume identical metal oxidation) route to near-net-shaped calcium hydroxyapatite, Ca₁₀(PO₄)₆(OH)₂, is demonstrated: the oxidation of machinable Ca—Ca₂P₂O₇ precursors. Mechanically alloyed mixtures of Ca and β-Ca₂P₂O₇ were compacted into disk- and bar-shaped preforms. The latter preforms could be machined into cylinders using a metalworking lathe (200 rpm, hardened steel tooling). After oxidation at 600°C in O₂, and then postoxidation annealing in H₂O/O₂ mixtures at 850°C and 1150°C, phase-pure hydroxyapatite was obtained. Because of offsetting volume changes from calcium oxidation and hydroxyapatite formation, porous hydroxyapatite bodies were produced that retained the shapes and dimensions (within 1%) of the machined precursors.     

Oxidation/Vaporization Kinetics of Cr2O3

The weight loss of Cr₂O₃ in oxidizing environments (Po₂= 1 to 10⁻³ atm) at 1200°C was measured. Both hot-pressed and sintered Cr₂O₃ pellets were investigated in O₂/Ar gas mixtures, and the dependence of the weight loss on the O₂ partial pressure, the gas flow rate, and the total pressure was determined independently. The experimentally determined O₂ partial pressure dependence (rate ∝ PO₂^3/4) corresponds to that expected for the reaction Cr₂O₃(s)+3/2O₂⇌2CrO₃(g). The flow rate and total pressure dependencies show that mass transport through a gaseous boundary layer is the rate-controlling step in the oxidation/vaporization of Cr₂O₃. Evaporation coefficients for the loss of CrO₃(g) under the experimental conditions were <0.01.     

Preparation, Structure, and Selected Catalytic Properties of the System LaMn1-xCuxO3-y

Samples of LaMn_1-xCu_xO_3-y in the range 0≤x≤0.8 were prepared from freeze-dried solutions of the nitrates. Samples with x≤0.6 were single-phase perovskites. At higher values of x , the samples contained La₂CuO₄ and CuO as well as the perovskite phase. Samples of LaMn_1−x,Cu_x,O_3−y supported on ceramic monoliths or when mixed with powdered A1₂O₃ exhibit catalytic activity for the oxidation of CO. Greatest activity is shown for 0.4≤x≤0.7. Although the catalysts are severely poisoned by SO₂, 2% H₂O in the gas stream causes only slight deactivation. Activities of other oxide catalysts were also measured and compared. Rate constants per unit surface area at 200° to 400°C follow the order Co₃O₄>Pt>LaMn_1−xCu_xO_3−y (0.4≤x≤0.7)>copper chromite>La_1−xSr_x,MnO₃≤ other substituted LaMnO₃ materials, CuO, or La₂CuO₄. The perovskite catalyst is more stable than Co₃O₄ or copper chromite when heated in 10% H₂+ 90% N₂.     

Effect of Heat-Treatment on the Constitution and Mechanical Properties of Some Hydrated Aluminous Cements

The compound compositions of four aluminous cements were determined on anhydrous as well as hydrated specimens which had been heat-treated at temperatures between room temperature and 1400° C. Phases were identified by X-ray diffraction and differential thermal analysis. Specimens were also tested for transverse strength, dynamic modulus of elasticity, and thermal length change. A study of the dehydration characteristics of CaO - Al₂O₈ - 10H₂O₃ 3CaO.Al₂O₃. 6H₂O, and Al₂O₃. 3H₂O was included. The data indicated that CaO. Al₂O₃ 10H₂O was the primary crystalline hydrate formed in the cements at room temperature. At 50° C., 3 CaO Al₂O₃-6H₂O and Al₂O₃. 3H₂O were formed as by-products of the dehydration of CaO.Al₂O₃.10H₂O. When heated alone in an open system, CaO.Al₂O₃.10H₂O did not convert to 3CaO. Al₂O₃. 6H₂O and A1₂O₃. 3H₂O. A correlation between the mechanical properties and compound compositions was noted.     

Chemical Vapor Deposition of Polycrystalline Al2O3

Polycrystalline Al₂O₃ was chemically vapor-deposited onto sintered Al₂O₃ substrates by reaction of AlCl₃ with (1) H₂O, (2) CO:H₂, and (3) O₂ at 1000° and 1500°C and 0.5 and 5.0 torr. Although the thermodynamics of all these reactions predict the formation of solid Al₂O₃, the deposition rate of the first reaction was considerably greater than that of the second. The third reaction was so slow that no measurable deposit was formed in 6 h at 1500°C. Formation of dense deposits of α-Al₂O₃ was favored by increasing temperature and decreasing pressure. Microstructural examination of the dense deposits showed long columnar grains, the largest of which extended through the deposit from the substrate to the surface.     

Ractions of SiC with H2/H2O/Ar Mixtures at 1300°C

The reactions of a sintered α-SiC with 5% H₂/H₂O/Ar at 1300°C were studied. Thermomchemical modeling indicates that three reaction regions are expected, depending on the initial water vapor or equivalently oxygen content of the gas stream. A high oxygen content ( P (O₂) > 10⁻²² atm) leads to a SiO₂ formation. This generally forms as a protective film and limits consumption of the SiC (passive oxidation). An intermediate oxygen content (10⁻²² atm > P (O₂) > 10⁻²⁶ atm) leads to SiO and CO formation. These gaseous products can lead to rapid consumption of the SiC (active oxidation). Thermogravimetric studies in this intermediate region gave reaction rates which appear to be controlled by H₂O gas-phase transport to the sample and reacted microstructures showed extensive grain-boundary attack in this region. Finally, a very low oxygen content ( P (O₂) < 10⁻²⁶ atm) is thermochemically predicted to lead to selective removal of carbon and formation of free silicon. Experimentally low weight losses and iron silicides are observed in this region. The iron silicides are attributed to reaction of free silicon and iron impurities in the system.     

Thermodynamic Properties of Manganese Oxides

Transposed temperature drop calorimetry and hightemperature drop solution calorimetry in molten 2PbO·B₂O₃ at 977 K were used to study the energetics of some manganese oxides, namely pyrolusite (MnO₂), bixbyite (Mn₂O₃), hausmannite (Mn₃O₄), and manganosite (MnO). The enthalpies of oxidation at 298 K in the manganeseoxygen system, which were determined by appropriate thermodynamic cycles, were (in kJ/mol of oxygen): –441.4 ± 5.8 for the reaction 6MnO + O₂→ 2Mn₃O₄, –201.8 ± 8.7 for the reaction 4Mn₃O₄+ O₂→ 6Mn₂O₃, and –162.1 + 7.2 for the reaction 2Mn₂O₃+ O₂→ 4MnO₂. These values agreed very well with previous data that were obtained using equilibrium measurements that were reported in the literature. Thus, direct calorimetric measurements were well suited to obtain reliable enthalpy of formation data for oxides that contain manganese in the 2+, 3+, and 4+ states. Using these new values of enthalpies and reliable standard entropies, the phase-stability diagram of the manganeseoxygen system was constructed.     

The System Alumina-Gallia-Water

A study of the system Al₂O₃–Ga₂O₃–H₂O has resulted in the determination of equilibrium diagrams for the systems Al₂O₃–Ga₂O₃ and Al₂O₃.-H₂O–Ga₂O₃.H₂O. Extensive solid solution characterizes the α -Al₂O₃ and β -Ga₂O₃ structures at high temperatures, but it is shown that below 810°C. a compound, GaAlO₃, and a new series of (Al, Ga)₂O₃ structures are stable. Among the hydrates, a complete series of diaspore solid solutions extends from Al₂O₃.H₂O to Ga₂O₃.H₂O. Boehmite solid solutions extend to approximately the composition 70Al₂O₃.H₂O, 30Ga₂O₃.H₂O.     

Phase Relations in the System UO2-UO3– Y2O3

The phase relations in the system U02-U03-Yz03, particularly in the Y203-rich region, were examined by X-ray and chemical analyses of reacted powders heated at temperatures up to 1700°C in H₂, CO₂-CO₂ and air. Four phases were identified in the system at temperatures between 1000° and 1700°C: U308, face-centered cubic solid solution, body-centered cubic solid solution, and a rhombohedral phase of composition (U,Y)₇O₂ ranging from 52.5 to 75 mole % Y₂O₃. The rhombohedral phase oxidized to a second rhombohedral phase with a nominal composition (U,Y), at temperatures below 1000°C. This phase transformed to a face-centered cubic phase after heating in air above 1000° C. The solubility of UO, in the body-centered cubic phase is about 14 mole % between 1000° and 1700°C but decreases to zero as the uranium approaches the hexavalent oxidation state. The solubility of Yz03 in the face-centered cubic solid solution ranges from 0 to 50 mole % Y2O3 under reducing conditions and from 33 to 60 mole % Y2O3 under oxidizing conditions at 1000°C. At temperatures above 1000° C, the face-centered cubic solid solution is limited by a filled fluorite lattice of composition (U,Y)O₂. For low-yttria content, oxidation at low temperatures (<300°C) permits additional oxygen to be retained in the structure to a composition approaching (U,Y)O_2.25 A tentative ternary phase diagram for the system UO₂-UO₃-Y₂O₃ is presented and the change in lattice parameter and in cell volume for the solid-solution phases is correlated with the composition.     

Microstructural Changes During Heat Treatment of Sintered Al2O3

Samples of both high-purity and Mg-doped Al₂O₃ sintered in H₂, N₂, O₂, or vacuum were annealed at 1650° to 1850°C for times up to 64 h. In pore-free systems, grain growth is limited by the mobility of Mg-rich second-phase inclusions; in samples annealed in H₂, grain growth is limited by pore dragging with a transition toward limitation by solid-inclusion dragging at high dopant levels; in samples annealed in N₂ and O₂, grain growth is characterized by a transition from an "anchoring effect" of the pores toward a combination of pore dragging by and unpinning from the grain boundaries. Time-dependence of grain growth is insufficient to determine the mechanisms and provide an adequate foundation for model-based calculations. Observations of microstructure and its change with time, together with the rate of grain growth as a function of composition, allow elimination of alternate hypotheses and determination of the process which controls the rate of grain growth and change in pore size.     

Oxidation of HIPed TiC Ceramics in Dry O2, Wet O2, and H2O Atmospheres

Isothermal oxidation of dense TiC ceramics, fabricated by hot-isostatic pressing at 1630°C and 195 MPa, was performed in Ar/O₂ (dry oxidation), Ar/O₂/H₂O (wet oxidation), and Ar/H₂O (H₂O oxidation) at 900°–1200°C. The weight change measurements of the TiC specimen showed that the dry, wet, and H₂O oxidation at 850°–1000°C is represented by a one-dimensional parabolic rate equation, while the oxidation in the three atmospheres at 1100° and 1200°C proceeds linearly. Cross-sectional observation showed that the dry oxidation produces a lamellar TiO₂ scale consisting of many thin layers, about 5 μm thick, containing many pores and large cracks, while H₂O-containing oxidation decreases pores in number and diminishes cracks in scales. Gas evolution of CO₂ and H₂ with weight change measurement was simultaneously followed by heating the TiC to 1400°C in the three atmospheres. Cracking in the TiO₂ scale accompanied CO₂ evolution, and the H₂O-containing oxidation produced a small amount of H₂. A piece of single crystal TiC was oxidized in ¹⁶O₂/H₂¹⁸O to reveal the contribution of O from H₂O to the oxidation of TiC by secondary ion mass spectrometry.     

Fabrication of Thin-Film SrCe0.9Eu0.1O3−δ Hydrogen Separation Membranes on Ni–SrCeO3 Porous Tubular Supports

SrCe_0.9Eu_0.1O_3−δ thin-film (∼30 μm) tubular hydrogen separation membranes were developed in order to obtain high hydrogen fluxes. Fifteen centimeters long, one end closed, NiO–SrCeO₃ tubular supports were fabricated by tape casting, followed by rolling the green tape on a circular rod. SrCe_0.9Eu_0.1O_3−δ powders were prepared by the citrate process and coated on partially sintered NiO–SrCeO₃ tubular supports. Leakage-free hydrogen membrane cells were obtained by adjusting the presintering and final sintering temperatures to reduce the difference of linear shrinkage rates between SrCe_0.9Eu_0.1O_3−δ thin films and NiO–SrCeO₃ supports. A hydrogen flux of 2.2 cm³/min was obtained for the SrCe_0.9Eu_0.1O_3−δ on Ni–SrCeO₃ tubular hydrogen separation membranes at 900°C using 25% H₂ balanced with Ar and 3% H₂O as the feed gas and He as the sweep gas. Thus, a 40% single pass yield of pure H₂ was achieved with this membrane.     

Alumina/Epoxy Interpenetrating Phase Composite Coatings: I, Processing and Microstructural Development

Interpenetrating phase composite (IPC) coatings consisting of continuously connected Al₂O₃ and epoxy phases were fabricated. The ceramic phase was prepared by depositing an aqueous dispersion of Al₂O₃ (0.3 μm) containing orthophosphoric acid, H₃PO₄, (1–9.6 wt%, solid basis) and heating to create phosphate bonds between particles. The resulting ceramic coating was porous, which allowed the infiltration and curing of a second-phase epoxy resin. The effect of dispersion composition and thermal processing conditions on the phosphate bonding and ceramic microstructure was investigated. Reaction between Al₂O₃ and H₃PO₄ generated an aluminum phosphate layer on particle surfaces and between particles; this bonding phase was initially amorphous, but partially crystallized upon heating to 500°C. Flexural modulus measurements verified the formation of bonds between particles. The coating porosity (and hence epoxy content in the final IPC coating) decreased from ∼50% to 30% with increased H₃PO₄ loading. The addition of aluminum chloride, AlCl₃, enhanced bonding at low temperatures but did not change the porosity. Diffuse reflectance FTIR showed that a combination of UV and thermal curing steps was necessary for complete curing of the infiltrated epoxy phase. Al₂O₃/epoxy IPC coatings prepared by this method can range in thickness from 1 to 100 μm and have potential applications in wear resistance.     

Damage Tolerance of Silicon Carbide- and Alumina-Matrix Surface Composites

A method for the fabrication of a ceramic-matrix composite (CMC) layer on the surface of a monolithic substrate via chemical vapor infiltration (CVI) is described. Preforms consisted of tows of fibers wound onto the surface of monolithic cylindrical tubes. Nicalon fibers were wound onto mullite substrates and infiltrated with β-SiC from CH₃SiCl₃/H₂ gas mixtures in a cylindrical cold-wall reactor. Similarly, Nextel fibers were wound onto A1₂O₃ substrates and infiltrated with α-Al₂O₃ from AlCl₃/H₂/CO₂/N₂ gas mixtures. Composites with densities as high as 88% of the theoretical value were fabricated in 8 h. The effective fracture strength of the SiC- and Al₂O₃-matrix surface composites, as determined from diametral compression tests of C-ring specimens, was found to be insensitive to damage caused to the outer diameter by a Vickers indentation. The tolerance of the SiC-matrix surface composites to surface damage was retained in specimens subjected to oxidation at 1000°C for 6 h.