Calcination/acid-activation treatment of an anodic oxidation TiO<Subscript>2</Subscript>/Ti film catalyst

The aim of this work was to investigate the effects of calcination/acid-activation on the composition, structure, and photocatalytic (PC) reduction property of an anodic oxidation TiO₂/Ti film catalyst. The surface morphology and phase composition were examined by scanning electron microscopy and X-ray diffraction. The catalytic property of the film catalysts was evaluated through the removal rate of potassium chromate during the PC reduction process. The results showed that the film catalysts were composed of anatase and rutile TiO₂ with a micro-porous surface structure. The calcination treatment increased the content of TiO₂ in the film, changed the relative ratio of anatase and rutile TiO₂, and decreased the size of the micro pores of the film catalysts. The removal rate of potassium chromate was related to the technique parameters of calcination/acid-activation treatment. When the anodic oxidation TiO₂/Ti film catalyst was calcined at 873 K for 30 min and then acid-activated in the concentrated H₂SO₄ for 60 min, it presented the highest catalytic property, with the removal rate of potassium chromate of 96.3% during the PC reduction process under the experimental conditions.     

Polymer-induced generation and characterization of electrophoretic properties of hollow TiOX nanospheres for electronic paper

Hollow TiO_X nanospheres have been successfully prepared using hollow core–double shell latex particles (poly(styrene-co-methyl methacrylate-co-butyl acrylate-co-methacrylic acid) (abbreviated in poly(St-co-MMA-co-BA-co-MAA)) as template, which involves the deposition of inorganic coating on the surface of hollow core–shell latex particles and subsequent removal of the latex by calcinations in air or ammonia gas. Ti(OBu)₄ was used as precursor for the preparation of hollow TiO_X nanospheres. TEM of white hollow core–double shell polymers particles with an aperture of approximately 225 nm displays the perfect characteristic hollow nanospheres structure of primary core–double shell particles. The formation of TiO_X was confirmed by XRD analysis and hollow structure of the particles was revealed by transmission electron microscopy (TEM). When the calcined temperature was at 800 °C, hollow TiO₂ nanospheres were arranged regularly with the diameter range of 130–170 nm. The electrophoretic properties were characterized by JS94J micro-electrophoresis apparatus. The electrophoretic mobility of white TiO₂ and black TiO hollow spheres in tetrachloroethylene were 1.09 × 10⁻⁵ and 3.12 × 10⁻⁵ cm²/V s, and the zeta potentials were 7.10 and 20.24 mV, respectively. The results show that white TiO₂ particles and black TiO hollow nanoparticles are suitable as electrophoretic particles and possess the application potential in the future electrophoretic display.     

Morphologies of GdBO3:Eu3+ one-dimensional nanomaterials

Europium doped gadolinium orthoborate nanorods and nanoribbons were morphology-controlled grown on the porous anodic aluminum oxide (AAO) template surface via a hydrothermal process combined with high-temperature calcination. The morphologies, crystal structures and luminescent properties of the as-prepared nanomaterials were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and photoluminescence (PL) spectra. The morphologies of the nanomaterials were controlled by the calcination temperature. If calcined at 1000 °C, the morphology of the GdBO₃:Eu³⁺ one-dimensional materials is nanorods; when calcined at 800 and 600 °C, the shapes of the Eu-doped GdBO₃ are nanoribbons. If treated at 900 °C, the as-prepared samples are composed of nanorods and nanoribbons.The changed morphologies of the as-prepared nanomaterials obtained from different calcination temperatures were explained according to the structural phase transition of GdBO₃. The PL spectrum shows that the characteristic emission of GdBO₃:Eu³⁺ one-dimensional nanomaterials is the ⁵D₀ → ⁷F₁ transition.     

Recycling of Ammonia Wastewater During Vanadium Extraction from Shale

In the vanadium metallurgical industry, massive amounts of ammonia hydroxide or ammonia salt are added during the precipitation process to obtain V₂O₅; therefore, wastewater containing a high level of NH₄⁺ is generated, which poses a serious threat to environmental and hydrologic safety. In this article, a novel process was developed to recycle ammonia wastewater based on a combination of ammonia wastewater leaching and crystallization during vanadium extraction from shale. The effects of the NH₄⁺ concentration, temperature, time and liquid-to-solid ratio on the leaching efficiencies of vanadium, aluminum and potassium were investigated, and the results showed that 93.2% of vanadium, 86.3% of aluminum and 96.8% of potassium can be leached from sulfation-roasted shale. Subsequently, 80.6% of NH₄⁺ was separated from the leaching solution via cooling crystallization. Vanadium was recovered via a combined method of solvent extraction, precipitation and calcination. Therefore, ammonia wastewater was successfully recycled during vanadium extraction from shale.     

Synthesis and characterization of mesoporous Mn-MCM-41 materials

MCM-41 has been synthesized at two different pH using cetyl-trimethylammonium bromide (CTAB) surfactant as template and adding the silica precursor to aqueous solutions containing CTAB. The obtained solids were calcined at 600 °C for 4 h. Mn-MCM-41 powders with different Mn/Si molar ratios were prepared using the incipient wetness method, followed by calcination at 550 °C for 5 h. At the end of the impregnation process the powders colour changed from white to brown whose intensity depends on manganese quantity. The materials characterization was performed by X-ray diffraction, N₂ adsorption, ²⁹Si Cross Polarization-Magic Angle Spinning NMR, and X-ray Photoelectron Spectroscopy. The effects of the manganese quantity and of the structural characteristic of the MCM-41 support were studied. The catalytic activity of the prepared systems was evaluated in a complete n-hexane oxidation.     

Effects of processing parameters on the synthesis of TiO2 nanofibers by electrospinning

TiO² nanofibers were synthesized by an electrospinning technique using polyvinyl pyrrolidone and titanium tetraisopropoxide as precursors. The effects of processing parameters including the precursor ratio, calcination time, temperature and atmosphere were investigated. The calcination temperature determines the TiO₂ phases as either anatase or rutile. The diameter of the synthesized TiO₂ nanofibers is not sensitive to the calcination atmosphere or the time. However, the surface microstructure of the synthesized nanofibers depends highly on calcination atmosphere. Calcination in an N₂ atmosphere produces smooth surfaces. In contrast, surfaces that are more granular evolve when they are calcined in an O₂ atmosphere. In addition, less Ti precursor in the electrospinning solution results in slim nanofibers.     

Effect of calcination temperature and atmosphere on crystal structure of BaTiO<Subscript>3</Subscript> nanofibers

Barium titanate (BaTiO₃, BT) nanofibers with a diameter range of 160 nm to 300 nm were prepared by drying electrospun BT/polyvinylpyrrolidone (BT/PVP) composite fibers for 1 h at 80 °C in vacuum with a subsequent calcination in air for 1 h at a temperature range of 650 °C to 750 °C. The morphology and crystal structure of calcined BT nanofibers were characterized with the aid of XRD, FT-IR, SEM, and TEM. The XRD and FR-IR measurements confirm that BT nanofibers with a diameter of about 160 nm and a tetragonal perovskite structure were present in the electrospun fibers after calcination for 1 h at 750 °C. The FR-IR analysis of the BT fibers reveals that the intensity level of the O-H stretching vibration bands (at 3430 cm⁻¹ and 1425 cm⁻¹) become weaker as the calcination temperature is increased and that a broad band at 570 cm⁻¹, which represents the Ti-O vibration, appears sharper and narrower after calcination at 750 °C due to the formation of metal oxide bonds. In contrast, BT fibers prepared by a refluxing process in a nitrogen atmosphere show a dramatic change in crystal structure: the tetragonal structure changes to a cubic perovskite structure, probably due to the suppression of carbonate contamination. Thus, the calcination temperature and atmosphere appear to have a significant influence on the crystal structure of BT.     

Hydro-chemical conversion of galena in FeCl3-KCl solution

The behaviours of complexation and dissolution of PbCl₂ on the surface of galena were investigated to explore the process of hydro-chemical conversion of galena (PbS) in chloride media. By means of solution chemistry calculation, the production and dissolution of the products PbCl₂ were studied. And the passivation of the galena was studied by Tafel curve. The results show that PbCl₄²⁻ is the main form of PbCl₂ presented in the saturated potassium chloride (KCl) solution. The PbCl₂ crystal is easy to precipitate when the total concentration of chloride ion ([Cl⁻]_T) is equal to 0.92 mol/L, and it is inclined to dissolve when [Cl⁻]_T is more than 0.92 mol/L. The chloride complexing reaction rate strongly depends on the Fe³⁺ion concentration when it is less than 6×10⁻⁴mol/L, while passivation occurs on the surface of the electrode when Fe³⁺ concentration is larger than 6×10⁻⁴mol/L. The reaction rate increases obviously when KCl is added, since the activity of Cl⁻ increases; thus accelerates the dissolution of PbCl₂.     

Stress corrosion cracking of B13, a new high strength aluminium lithium alloy

The present paper focuses on the study of SCC behaviour of a new Al–Cu–Li alloy. For this purpose, two conventional media – NaCl and NaCl + H₂O₂ – were used for comparison with commercial alloys 7075 and 8090. This new alloy shows lower susceptibility to SCC than conventional alloys as it does not undergo environmentally-induced embrittlement in NaCl solutions and in 1 M NaCl + 0.3% H₂O₂ in which the 7075 and 8090 alloys, respectively, undergo environmentally-induced fracture.Solution composition was modified in order to determine the environmental conditions and strain rates under which this new alloy will crack due to a stress corrosion cracking phenomenon. The addition of 0.6 M sulphates to 1 M NaCl + 0.3% H₂O₂ solution allows the definition of a range of strain rate (between 10⁻⁷ and 10⁻⁶ s⁻¹) in which this new alloy undergoes stress corrosion cracking.     

Electrochemical characterization of the different surface states formed in the corrosion of carbon steel in alkaline sour medium

In this study the different surface states that manifest in the corrosion process of 1018 carbon steel in alkaline sour environment, solution prepared specifically to mimic the sour waters occurring in the catalytic oil refinery plants of the Mexican Oil Company (PEMEX) (0.1 M (NH₄)₂S and 10 ppm NaCN at pH 9.2) were prepared and characterized. The surface states of the carbon steel were formed by treating the surface with cyclic voltammetry at different switching potentials (E_λ+), commencing at the corrosion potential (E_corr=−0.890 V vs sulfate saturated electrode, SSE). The surface states thus obtained were characterized using electrochemical impedance spectroscopy and scanning electron microscopy techniques. It was found that for E_λ+=−0.7 and −0.6 V vs SSE a first product of corrosion formed, characterized by a high passivity. Moreover, it was very compact (with a thickness of 0.047 μm). However, at more anodic potentials (E_λ+>−0.5 V vs SSE) a second corrosion product with non-protective properties (porous with a thickness of 0.4 μm and very active) was observed. The diffusion of atomic hydrogen (H⁰) was identified as the slowest step in the carbon steel corrosion process in the alkaline sour media. The H⁰ diffusion coefficients in the first and second products that formed at the carbon steel–sour medium interface were of the order of 10⁻¹⁵ and 10⁻¹² cm²/s respectively.     

Synthesis of nano-sized Co<Subscript>3</Subscript>O<Subscript>4</Subscript> powder by spray conversion method for anode material of lithium battery

A nano-sized Co₃O₄ powder was prepared using a spray conversion method that could be applied for mass production. The spray-conversion process consisted of spray drying of a metallic liquid solution, a calcination treatment, and a ball milling process. The calcined Co₃O₄ powder consisted of agglomerated spherical clusters with nano-sized particles. After milling for 24 h, agglomerated powders were fragmented into fine powders sized below 60 nm. The lithium/cobalt oxide cell was charge-discharged at a constant current density of 0.2 mAcm⁻² and showed a first discharge capacity of 1100 mAhg⁻¹. The discharge capacity of the Li/Co₃O₄ cell drastically decreased with cycle number. By increasing the carbon content of the anode, the cycle life was improved. For a Co₃O₄ electrode containing 40 wt.% carbon, the discharge capacity was over 400 mAhg⁻¹ after 50 cycles. The spray conversion method might be a useful method to prepare nano-sized Co₃O₄ powder for the anode material of lithium batteries.     

Interfacial interaction of solid nickel with liquid Pb-free Sn–Bi–In–Zn–Sb soldering alloys

The dissolution process of nickel in liquid Pb-free 87.5% Sn–7.5% Bi–3% In–1% Zn–1% Sb and 80% Sn–15% Bi–3% In–1% Zn–1% Sb soldering alloys has been investigated by the rotating disc technique at 250–450 °C. The temperature dependence of the nickel solubility in soldering alloys obeys a relation of the Arrhenius type c_s = 4.94 × 10² exp(−39500/RT)% for the former alloy and c_s = 4.19 × 10² exp(−40200/RT)% for the latter, where R is in J mol⁻¹ K⁻¹ (8.314 J mol⁻¹ K⁻¹) and T is in K. Whereas the solubility values differ considerably, the dissolution rate constants are rather close for these alloys and fall in the range (1–9) × 10⁻⁵ m s⁻¹ at disc rotational speeds of 6.45–82.4 rad s⁻¹. Appropriate diffusion coefficients vary from 0.16 × 10⁻⁹ to 2.02 × 10⁻⁹ m² s⁻¹. With both alloys, the Ni₃Sn₄ intermetallic layer is formed at the interface of nickel and the saturated or undersaturated melt at dipping times of 300–2400 s. The other Ni–Sn intermetallic compounds are found to be missing. A simple mathematical equation is proposed to evaluate the Ni₃Sn₄ layer thickness in the case of undersaturated melts. The tensile strength of the nickel-to-alloy joints is 94–102 MPa, with the relative elongation being 2.0–2.5%.     

Seasonal variations in corrosion rate and runoff rate of copper roofs in an urban and a rural atmospheric environment

This paper summarizes the results from an extensive field exposure program implemented to study possible seasonal dependencies of copper corrosion rates and runoff rates. Two-year exposures in one urban and one rural environment were performed at four different starting seasons. An extensive multi-analytical approach was undertaken of all exposed samples.Seasonal differences in corrosion product formation was observed during the first month of exposure and attributed mainly to differences in relative humidity conditions. Seasonal differences in corrosion rate at the rural site could be discerned throughout the whole two-year exposure, again, mainly attributed to differences in relative humidity. No seasonal effect could be observed at the urban site indicating that other parameters influenced the corrosion kinetics at this site. While corrosion rates exhibit a continuous decrease with exposure time, the yearly runoff rates are independent of time. Depending on starting months the yearly copper runoff rates ranged from 1.1 to 1.7 g m⁻² y⁻¹ for the urban site, and from 0.6 to 1.0 g m⁻² y⁻¹ for the rural site. These seasonal variations were primarily attributed to differences in precipitation quantity and environmental characteristics. Runoff rates are significantly lower than corrosion rates as long as the adhering copper patina is growing with exposure time.A full risk assessment requires not only information on the total amount of copper in the runoff, but also on its chemical speciation. Under present conditions, 70–90% of all copper in runoff water collected immediately after leaving the surface is present as the most bioavailable form, the hydrated cupric ion, Cu(H₂O)₆²⁺.     

Synthesis and characterization of barium hexaferrite nanoparticles

This investigation dealt with the synthesis of nanocrystalline barium hexaferrite (BaFe₁₂O₁₉) powders through the co-precipitation–calcination route. The ferrite precursors were obtained from aqueous mixtures of barium and ferric chlorides by co-precipitation of barium and iron ions using 5 M sodium hydroxide solution at pH 10 in room temperature. These precursors were calcined at temperatures of 800–1200 °C for constant 2 h in a static air atmosphere. The effect of Fe³⁺/Ba²⁺ mole ratio and addition of surface active agents during co-precipitation step on the structural and magnetic properties of produced ferrite powders were studied. It is found that the formation of single phase BaFe₁₂O₁₉ powders was achieved by decreasing the Fe³⁺/Ba²⁺ molar ratio from the stoichiometric value 12–8 and increasing the calcination temperature ≥1000 °C. In addition, the Fe³⁺/Ba²⁺ mole ratio of 8 the surface active agents promoted the formation of homogeneous nanopowders (ca. 113 nm) of BaFe₁₂O₁₉ at a low-temperature of 800 °C with resultant good magnetic saturations (50.02 emu/g) and wide intrinsic coercivities (642.4–4580 Oe).     

Influence of surfactants on co-precipitation synthesis of strontium ferrite

Strontium ferrite (SrFe₁₂O₁₉) particles were prepared by co-precipitation method. The ferrite precursors were produced from aqueous mixtures of ferric chloride and strontium nitrate by co-precipitation, using 3 mol/L sodium hydroxide aqueous solutions as precipitant. Three surfactants sodium dodecyl sulfate (SDS), polyethylene glycol 6000 (PEG-6000), cetyltrimethylammonium bromide (CTAB), were applied and the influence of surfactants on the properties of the strontium ferrite particles was studied. The ferrite precursors were first precalcined in a muffle furnace at 400 °C and then mixed with KCl and NaCl using a planetary milling machine in order to lower the calcination temperature. Subsequently the mixtures were calcined at various temperatures. Structure and magnetic properties of the particles were characterized by X-ray powder diffraction, transmission electron microscopy and vibrating sample magnetometer. In this paper, effects of Fe³⁺/Sr²⁺ mole ratio were first verified and annealing temperatures were then discussed. The results show the strontium ferrite phase begins to form at 650 °C and complete at 800 °C after calcination, and the particles prepared using CTAB exhibit the best properties with respect to particle size and dispersibility.     

Modifying alumina red mud to support a revegetation cover

Alumina red mud, a fine-textured, iron-rich, alkaline residue, is the major waste product of bauxite digestion with caustic soda to remove alumina. The high alkalinity and salinity as well as the poor nutrient status are considered to be the major constraints of red mud revegetation. This research was conducted to evaluate the ameliorating effect of gypsum, sewage sludge, ferrous sulfate, ammonium sulfate, ammonium nitrate, and calcium phosphate on alumina red mud. The effectiveness of the mixtures was evaluated by applying extraction tests and performing experiments using six plant species. Gypsum amendment significantly reduced the pH, electrical conductivity, and sodium and aluminum content of red mud. Sewage sludge application had an extended effect in improving both the soil structure and the nutrient status of the gypsum-amended red mud. Together with the gypsum and sewage sludge, calcium phosphate application into red mud enhanced plant growth and gave the most promising results. For more information, contact A. Xenidis, National Technical University of Athens, Laboratory of Metallurgy, School of Mining Engineering and Metallurgy, GR 157 80 Zografos, Athens, Greece; axen@central.ntua.gr.     

Effect of catalyst calcination temperature on the synthesis of MWCNT-alumina hybrid compound using methane decomposition method

This work focuses on synthesis of MWCNT-alumina hybrid compound via methane decomposition process using Ni-Al₂O₃ catalyst. The catalysts prepared through in situ process by using nickel salt and aluminium powder which are then calcined at three different calcination temperatures (700 °C, 900 °C and 1100 °C). The catalyst calcined at 900 °C followed by methane decomposition process successfully yielded MWCNT-alumina hybrid compound. No trace of CNT was detected for catalyst calcined at 700 °C and 1100 °C. The scanning electron microscopy (SEM) and high resolution transmission electron microscopy (HRTEM) micrograph confirmed the formation of MWCNT with homogenous dispersion on alumina particles.     

Synthesis and electrochemical properties of porous LiV3O8 as cathode materials for lithium-ion batteries

In this paper, we report on the synthesis of porous LiV₃O₈ by using a tartaric acid-assisted sol-gel process and their enhanced electrochemical properties for reversible lithium storage. The crystal structure, morphology and pore texture of the as-synthesized samples are characterized by means of XRD, SEM, TEM/HRTEM and N₂ adsorption/desorption measurements. The results show that the tartaric acid plays a pore-making function and the calcination temperature is an important influential factor to the pore texture. In particular, the porous LiV₃O₈ calcined at 300 °C (LiV₃O₈-300) exhibits hierarchical porous structure with high surface area of 152.4 m² g⁻¹. The electrochemical performance of the as-prepared porous LiV₃O₈ as cathode materials for lithium ion batteries is investigated by galvanostatic charge-discharge cycling and electrochemical impedance spectroscopy. The porous LiV₃O₈-300 displays a maximum discharge capacity of 320 mAh g⁻¹ and remains 96.3% of its initial discharge capacity after 50 charge/discharge cycles at the current density of 40 mA g⁻¹ due to the enhanced charge transfer kinetics with a low apparent activity energy of 35.2 kJ mol⁻¹, suggesting its promising application as the cathode material of Li-ion batteries.     

The kinetics and mechanism of cathodic oxygen reduction on zinc and zinc–aluminium alloy galvanized coatings

A rotating disk electrode technique is used to investigate the kinetics and mechanism of O₂ reduction as it occurs at the surface of various hot-dip Al–Zn alloy coatings (on steel) immersed in weakly alkaline (pH 9.6) aqueous sodium chloride. The zinc component of coatings behaves electrochemically as though it were free zinc and the O₂ reduction pathway is determined by the potential dependent state of zinc. A 2e⁻ reduction to H₂O₂ predominates at potentials near the free corrosion potential, where zinc is (hydr)oxide covered. A 4e⁻ reduction to OH⁻ predominates at potentials where zinc is bare. Tafel slopes (∂E/∂log i) of 0.058 V dec⁻¹ and 0.132 V dec⁻¹ are determined for 2e⁻ and 4e⁻ O₂ reduction on pure zinc, respectively. Aluminium is virtually inert and varying aluminium content between 0.1% and 55% exerts little influence on O₂ reduction kinetics. However, all the Zn–Al alloy surfaces give very much higher O₂ reduction currents at low polarization than does pure zinc and it is proposed that this arises through an electrocatalysis of 2e⁻ O₂ reduction by traces of substrate derived iron.     

Synthesis and electrochemical properties of Li4Ti5O12

The spinel compound Li₄Ti₅O₁₂ was synthesized by a solid state method. In this synthesizing process, anatase TiO₂ and Li₂CO₃ were used as reactants. The influences of reaction temperature and calcination time on the properties of products were studied. When calcination temperature was 750 °C and calcination temperature was 24 h, the products exhibited good electrochemical properties. Its discharge capacity reached 160 mAh g⁻¹ and its capacity retention was 97% at the 50th cycle when the current rate was 1 C. When current rate increased to 10 C, its first discharge capacity could reach 136 mAh g⁻¹, and its capacity retention was 85% at the 50th cycle.