Simulation of the interface of (1 0 0) rutile with aqueous ionic solution

The interface of the rutile (1 0 0) surface with NaCl solutions has been simulated by classical molecular dynamics. In contrast to earlier simulations the protonation and hydroxylation equilibriums have been adjusted for different pH values (4, 7.4, and 9). The short range order close to the surface is described by two water layers with some orientational order and intermediate layers of positive or negative ions depending on the surface charge. A Stern model is confirmed with a dense layer of counterions on the charged TiO₂ surface and a diffuse layer, which only consists of few ions in our system. The increase of orientational order of the water molecules close to the surface is described by an exponential function with a decay parameter of 1.9 Å, superposed by a damped oscillation which is independent of the pH value. The diffusion is significantly slower than in the bulk within a range of 13 Å from the surface. We propose a common approach for describing the different z-dependences of orientational order and of the diffusion coefficients.     

Role of pH and calcium ions in the adsorption of an alkyl N-aminodimethylphosphonate on steel: An XPS study

The role of pH and calcium ions in the adsorption of an alkyl N-aminodimethylphosphonate on mild steel (E24) surfaces was investigated by XPS. Fe 2p_3/2 and O 1s spectra show that the oxide/hydroxide layer developed on the steel surface, immersed in the diphosphonate solution (7 ≤ pH ≤ 13, without Ca²⁺) or in a filtered cement solution (pH 13, 15.38 mmol l⁻¹ of Ca²⁺), consists of Fe₂O₃, covered by a very thin layer of FeOOH (goethite). The total thickness of the oxide/hydroxide layer is ∼3 nm and is independent of the pH and the presence/absence of Ca²⁺. In the absence of Ca²⁺ ions, the N 1s and P 2p spectra reveal that the adsorption of the diphosphonate on the outer layer of FeOOH takes place only for pH lower than the zero charge pH of goethite (7.55). At pH 7, the adsorbed diphosphonate layer is continuous and its equivalent thickness is ∼24 Å (monolayer). In the presence of Ca²⁺ ions, the C 1s and Ca 2p signals indicate that calcium is present on the steel surface as calcium phosphonate (and Ca(OH)₂, in very small amount). The adsorption of the diphosphonate molecules on the steel surface is promoted in alkaline solution (pH > 7.55) by the doubly charged Ca²⁺ ions that bridge the O⁻ of goethite and the P-O⁻ groups of the diphosphonate molecules. The measured values for the Ca/P intensity ratio are in the range 0.75-1, which suggests that the diphosphonate molecules are adsorbed on steel forming a polymer cross-linked by calcium ions through their phosphono groups. In the presence of Ca²⁺ ions in alkaline solution, the adsorbed diphosphonate layer is discontinuous and the surface coverage is found to be ∼34%.     

Comparison of the Monte Carlo estimation of surface electrostatic potential at the hematite (0 0 0 1)/electrolyte interface with the experiment

The Monte Carlo simulations of the surface electrostatic potential are presented for the hematite (0 0 0 1) crystal plane. According to the ab initio calculations, the Fe-terminated (0 0 0 1) plane contains only one type of surface groups. The charge of this surface group is predicted using quantum population analyses, and the result is very close to this of the 1-pK model assumption. The surface topology and topography were constructed using the relaxed crystal plane structure. The Monte Carlo simulations for the reduced (including only hydrogen ions) and the extended (containing also electrolyte) models give the linear non-Nernstian pH-profile of surface potential. The simulation results are in agreement with the experimental measurements carried out by Kallay et al. [N. Kallay, Z. Dojnovi?, A. Cop, J. Colloid Interface Sci. 286 (2005) 610-614.] in the point of zero charge vicinity. This suggests that in this pH-region the surface properties are basically governed by the H⁺ ions uptake/release and the electrolyte ions complexations. The discrepancy for strongly acidic and basic regions suggests that some additional processes take place in the single-crystal electrode measurement, which results in the non-linear ψ₀=f(pH) profile.     

Functionalized SBA-15 organosilicas as sorbents of zinc(II) ions

SBA-15 nanoporous silicas functionalized with amine-, thiol-, vinyl-, phenyl- and cyano surface groups were synthesized by using the amphiphilic block copolymer P123 as the structure-directing agent. The obtained materials have a well-developed porous structure - the values of specific surface area are in the range 800-950 m²/g and the sizes of cylindrical mesopores are in the range 7.4-8.6 nm. It was established that the size of the mesopores strongly depends even on small amounts of co-monomers co-condensing with TEOS. Adsorption of Zn(II) ions at the SBA-15/NaCl interface was investigated by means of the radioactive isotope tracer technique over the pH range of 3-11. Surface charge density, adsorption density, pH_50% and ΔpH_10-90% parameters for different concentrations of the carrying electrolyte were evaluated and discussed.     

Mechanism of charging of the pyrite/aqueous interface as deduced from the surface potential measurements

Surface potential of pyrite in an aqueous environment was measured by means of a single crystal pyrite electrode. The effect of the activity of S²⁻ and Fe²⁺ ions as well as of pH, was examined. The results show that S²⁻ and Fe²⁺ ions are the dominant potential determining ions. These ions are bound to surface sites with the extent depending on their activity in the bulk of the solution. Adsorption affinity of S²⁻ ions is significantly higher than that of Fe²⁺ ions so that in most cases the pyrite surface is negatively charged. The results were explained on the basis of the surface complexation model. It was found that the surface potential depends also on pH.     

Electrochemical synthesis of Ag nanoparticles supported on glassy carbon electrode by means of p-isopropyl calix[6]arene matrix and its application for electrocatalytic reduction of H2O2

The silver nanoparticles were prepared on the glassy carbon (GC) electrode, modified with p-iso propyl calix[6]arene, by preconcentration of silver ions in open circuit potential and followed by electrochemical reduction of silver ions. The stepwise fabrication process of Ag nanoparticles was characterized by scanning electron microscopy and electrochemical impedance spectroscopy. The prepared Ag nanoparticles were deposited with an average size of 70 nm and a homogeneous distribution on the surface of electrode. The observed results indicated that the presence of calixarene layer on the electrode surface can control the particle size and prevent the agglomeratione and electrochemical deposition is a promising technique for preparation of nanoparticles due to its easy-to-use procedure and low cost of implementation. Cyclic voltammetry experiments showed that Ag nanoparticles had a good catalytic ability for the reduction of hydrogen peroxide (H₂O₂). The effects of p-isopropyl calix[6]arene concentration, applied potential for reduction of Ag⁺, number of calixarene layers and pH value on the electrocatalytic ability of Ag nanoparticles were investigated. The present modified electrode exhibited a linear range from 5.0 × 10⁻⁵ to 6.5 × 10⁻³ M and a detection limit 2.7 × 10⁻⁵ M of H₂O₂ (S/N = 3) using amperometric method.     

Soft X-ray appearance potential spectroscopy (SXAPS) study of TiO2(1 1 0)-1 × 2 and (0 0 1)-1 × 1 surfaces

A soft X-ray appearance potential spectroscopy (SXAPS) apparatus with high sensitivity was built to measure non-derivative spectra. SXAPS spectra (non-derivative) of Ti 2p and O 1s for TiO₂(1 1 0)-1 × 2 and (0 0 1)-1 × 1 surfaces have been measured using low incident currents (about 10 μA/cm²) and a photon counting mode. Density of empty states on Ti and O sites are deduced by self-deconvoluting the spectra. The self-deconvoluted SXAPS spectra are qualitatively similar to those measured by X-ray absorption spectroscopy (XAS). The Ti 2p_3/2 spectrum shows two strong peaks which correspond to t_2g and e_g states. For the O 1s spectrum two strong peaks near the threshold are also found which can be ascribed to O 2pπ and O 2pσ states. These results suggest that the spectra almost obey the dipole selection rule, so-called the “approximate dipole selection rule”. The SXAPS spectra of Ti 2p and O 1s for the (1 1 0) and (0 0 1) surfaces resemble qualitatively, which is consistent with the XAS results. The spectra measured on the (1 1 0)-1 × 2 surface at an incident angle of 45° off normal to the surface and on the (1 1 0) surface sputtered by Ar ions indicate that SXAPS is very sensitive to the surface electronic states.     

Dopant control over the crystal morphology of ceramic materials

Doping is a common way to activate the behavior of ceramics. Its effect is not limited to the bulk: segregation of dopants to the surfaces also yields a way to modify, and ultimately control the crystal morphology. We propose a model that allows us to calculate the surface energy beyond the Langmuir isotherm for doped and defective surfaces from atomic-level simulations. The model also allows us to account for different compositions between the bulk and surface. Computational materials design can thus be applied to optimize simultaneously the crystal behavior at the atomic (surface structure and composition) and mesoscopic (crystal size and shape) length scales. We exemplify the model with orthorhombic CaTiO₃ perovskite doped with Mg²⁺, Fe²⁺, Ni²⁺, Sr²⁺, Ba²⁺ and Cd²⁺ ions, by predicting the effect that different dopants and dopant concentrations have on the crystal morphology. We find that a higher proportion of reactive {0 2 1} and {1 1 1} surfaces are exposed with the presence of divalent Mg²⁺, Fe²⁺ and Ni²⁺ ions than in the undoped material and in perovskite doped with Ba²⁺ and Sr²⁺. Cd²⁺ has only minor effects on crystal morphologies. These findings have important implications for predicting the reactivity of crystals doped with different ions and we show how this can be related to a simple parameter such as the ionic radius. We have tested our newly derived model by comparison with laboratory flux grown single crystals of CaTiO₃, (Ni, Ca)TiO₃ and (Ba, Ca)TiO₃ and find excellent agreement between theory and experiment.     

Measurement of the surface charge density of CO-saturated Pt(1 1 1) electrodes as a function of potential: the potential of zero charge of Pt(1 1 1)

From measurements of the charge flowing upon immersion, at controlled potential, of a CO-covered Pt(1 1 1) electrode in a 0.1 M HClO₄ solution, the corresponding surface charge density vs. potential curve was obtained, and from this the potential of zero charge (pzc) of the CO-covered Pt(1 1 1) electrode. From these data it was estimated that the error incurred when the potential of zero total charge (pztc) of Pt(1 1 1) electrodes is determined by the CO-charge displacement method is of approximately 50 mV at pH 1 and of approximately 90 mV at pH 3. Furthermore, the experimentally determined pzc of the CO-covered Pt(1 1 1) electrode has allowed us to make an estimation of the potential of zero free charge (pzfc) of Pt(1 1 1) electrodes.     

Atomic and electronic structures of thin NaCl films grown on a Ge(0 0 1) surface

Density functional theory (DFT) with LDA and GGA have been employed to study the interface and thin film properties of NaCl on a Ge(0 0 1) surface. The atomic and electronic structures of thin NaCl films from one to ten monolayers were analyzed. The layer adsorption energies show that a quasi-crystalline (0 0 1) fcc NaCl film is built up via a layer-by-layer growth mode with NaCl thickness above 2 ML. Simulated STM images show a well-resolved (1 × 1) NaCl atomic structure for sample bias voltage V_s < −2.5 V and the bright protrusions should be assigned to the Cl⁻ ions of the NaCl film. The Ge substrate dimer is reserved and buckled like a clean Ge(0 0 1)-p(2 × 2) surface as the result of weak interface interaction between the dangling bonds coming from valence π states of the Ge substrate and the 3p states of the interfacial Cl⁻ ion. These results are consistent with the experiments of STM, LEED and EELS.     

The surface alloying behavior of martensitic stainless steel cut with wire electrical discharge machine

The surface alloying behavior of tempered martensitic stainless steel multi-cut with wire electrical discharge machine (WEDM) is studied in this paper. Before machined with WEDM, the steel specimens were quenched at 1050 °C and then tempered at 200 °C, 400 °C, and 600 °C, respectively. The microstructure and surface morphology of the multi-cut surfaces were examined with scanning and transmission electron microscopes integrated with an energy-dispersive X-ray spectrometer for chemical composition analysis. Experimental results show that the cut surfaces of the steel specimens were alloyed with wire-electrode material in various extent. Especially the cut surface was much more alloyed when the steel was cut with the first rough cutting pass by using negatively biased potential and final fine cutting using positively biased potential. Alloying degree of cut surfaces can be distinguished with their anodic polarization curves in 0.5 M HClO₄ + 0.2 wt% NaCl at 27 °C. Higher passive current density induces deeper alloyed surface. On the severely alloyed surface, a secondary anodic peak in the potential of 120 mV (versus Ag/AgCl_sat.) of its anodic polarization curve was observed. The presence of the secondary anodic peak was attributed to dissolution of copper, which was the major element of wire-electrode material from the alloyed surface.     

Electron-stimulated desorption of lithium ions from lithium halide thin films

Electron-stimulated desorption of positive lithium ions from thin layers of lithium halides deposited onto Si(1 1 1) are investigated by the time-of-flight technique. The determined values of isotope effect of the lithium (⁶Li⁺/⁷Li⁺) are 1.60 ± 0.04, 1.466 ± 0.007, 1.282 ± 0.004, 1.36 ± 0.01 and 1.33 ± 0.01 for LiH, LiF, LiCl, LiBr and LiI, respectively. The observed most probable kinetic energies of ⁷Li⁺ are 1.0, 1.9, 1.1, 0.9 and 0.9 eV for LiH, LiF, LiCl, LiBr and LiI, respectively, and seem to be independent of the halide component mass. The values of lithium ion emission yield, lithium kinetic energy and lithium isotope effect suggest that the lattice relaxation is only important in the lithium ion desorption process from the LiH system. In view of possible mechanisms and processes involved into lithium ion desorption the obtained results indicate that for LiH, LiCl, LiBr and LiI the ions desorb in a rather classical way. However, for LiF, ion desorption has a more quantum character and the modified wave packet squeezing model has to be taken into account.     

Preparation, characterization and MRI application of carboxymethyl dextran coated magnetic nanoparticles

Superparamagnetic nanoparticles functionalized with carboxymethyl dextran (CM-dextran) were synthesized by a two-step method. First, the magnetic nanoparticles (MNPs) coated with dextran (M_w ≈ 20000) were prepared by co-precipitation of Fe²⁺ and Fe³⁺ ions. Then, dextran on the surface of MNPs reacted with monochloroacetic acid (MCA) in alkaline condition. The influences of temperature and reactant concentration on the amount of -COOH on the surface of nanoparticles were systematically studied. The obtained MNPs coated with CM-dextran were stable over the entire range of pH and NaCl concentration. The MRI experiment indicated that the CM-dextran MNPs could potentially be used as MRI contrast agents for magnetic resonance molecular imaging.     

Demineralisation of semi-anthracite char with molten salts/HCl: Effects on the porous texture and reactivity in air

The effects of chemical heat treatments of a semi-anthracite char (AC) on textural properties and reactivity in air of the material are investigated. The starting char was first treated with a mixture of LiCl/KCl or LiCl/KCl/CaO at 743, 873 or 1173 K and the products obtained were then washed thoroughly with distilled water. A small fraction of these samples were treated with 10⁻³ M HCl solution. Valuable information on textural modifications produced in the material was derived from the adsorption isotherms for CO₂ at 273 K. The reactivity tests were carried out at 808, 823 and 823 K. The microporosity developed and the reactivity in air increased in the partially demineralised products. The former effect was stronger for the LiCl/KCl/CaO-treated samples and the latter for a larger number of the LiCl/KCl-treated samples.     

The role of Pb ions doping in the mechanism of chromate adsorption by goethite

Pure and 0.384% Pb²⁺ ions doped goethite samples were prepared in the laboratory by the coprecipitation method. The laboratory-prepared goethite samples were characterized for pH of point of zero charge (pH_pzc), surface area, XRD, TG-DTA, TEM, SEM and FTIR analysis, which suggest that the Pb²⁺ ions are incorporated into the crystals of goethite and are also present on the surface in the hydroxylated form. Chromate adsorption studies were carried out in the concentration range 0.25-2.01 mmol L⁻¹ at pH 3, 5 and 7, which show that maximum chromate is adsorbed at the lowest pH of 3 by both the samples of goethite. Effect of temperature on the adsorption of chromate, in the range 303-323 K, shows that the process of adsorption is endothermic in case of pure goethite and exothermic in case of Pb-doped goethite. The values of isosteric heat of adsorption were positive for pure goethite and negative for Pb-doped goethite, which are consistent with the effect of temperature on the process of adsorption. Langmuir isotherm was found applicable to the experimental data. FTIR analysis and equilibrium pH changes reveal that at pH 3 outersphere while at pH 5 and 7 innersphere complexation is the dominant mechanism for chromate adsorption by both the samples of goethite.     

Water-dispersible hydroxyapatite nanorods synthesized by a facile method

A simple and effective method, using calcium nitrate and triammonium phosphate as starting materials, for the preparation of water-dispersible hydroxyapatite nanorods (HAp) was reported. The process primarily involves the preparation of HAp with the addition of sodium citrate (NaC) and the exchange of absorbed ions (NaC) with sodium hexame taphosphate (NaP). The end products were investigated using various means in order to confirm the particles’ crystal phase and morphology and to understand how to improve their stability. The results demonstrate that the resulting HAp at 90 °C is rod-like with length of 300-400 nm and width of 40-60 nm. The zeta potential values of pure HAp, HAp-NaC, HAp-NaC/NaP are from −15.20, −30.89 to −44.84 mV. The settling time test shows the HAp-NaC/NaP could keep stable above 7 months without any creaming or visible sedimentation. The amount of NaC and the reaction temperature play significant roles in the whole process due to the formation of Ca containing precipitates.     

The influence of pH and bath composition on the properties of Fe-Co alloy film electrodeposition

Fe-Co films were electrodeposited on ITO glass substrates from the electrolytes with different molar ratio of Co²⁺/Fe²⁺ and different pH values (2.1, 2.9, 3.7, and 4.3) at 25 °C. The properties of Fe-Co alloy films depend on both Co²⁺ and Fe²⁺ concentrations in electrolyte and pH values was studied. The content of Co increases from 40% to 85% as the mole ratio of CoSO₄/FeSO₄ increasing from 0.50/0.50 to 0.90/0.10 in electrolyte and slightly decreases from 77% to 63% as the pH values increasing from 2.1 to 4.3. The X-ray diffraction analysis reveals that the structures of the films strongly depend on the Co content in the binary films. The surface morphologies of the films are influenced by the combined action of composition and phase structure. The saturation magnetization reaches a maximum value of 2974.03 emu/cm³ and coercivity reaches a minimum value of 42.72 Oe of the Fe_0.30Co_0.70. The saturation magnetization reaches a maximum values of 2974.03 emu/cm³ and coercivity reaches a minimum values of 42.72 Oe of the Fe_0.30Co_0.70 at pH = 2.9.     

Characterization of rare-earth conversion films formed on the AZ31 magnesium alloy and its relation with corrosion protection

Two pre-treatments were studied for AZ31 Mg alloy substrates, consisting of immersion in cerium nitrate and lanthanum nitrate solutions for various immersion times. The surface composition was investigated by X-ray photoelectron spectroscopy and Auger electron spectroscopy that revealed the presence of a surface film containing the rare-earth cation, with a composition which was time dependent in the case of the cerium pre-treatment.The corrosion behaviour of the pre-treated substrates in 0.005 M NaCl solutions was assessed by potentiodynamic polarization, open circuit potential monitoring and the scanning vibrating electrode technique (SVET). The electrochemical results show that the pre-treatments reduced the corrosion activity of the AZ31 Mg alloy substrates in the presence of chloride ions. The corrosion protection efficiency is dependent on the treatment time.     

Optimization of nickel adsorption from aqueous solution by using activated carbon prepared from waste apricot by chemical activation

Waste apricot supplied by Malatya apricot plant (Turkey) was activated by using chemical activation method and K₂CO₃ was chosen for this purpose. Activation temperature was varied over the temperature range of 400-900 °C and N₂ atmosphere was used with 10 °C/min heat rate. The maximum surface area (1214 m²/g) and micropore volume (0.355 cm³/g) were obtained at 900 °C, but activated carbon was predominantly microporous at 700 °C. The resulting activated carbons were used for removal of Ni(II) ions from aqueous solution and adsorption properties have been investigated under various conditions such as pH, activation temperature, adsorbent dosage and nickel concentration. Adsorption parameters were determined by using Langmuir model. Optimal condition was determined as; pH 5, 0.7 g/10 ml adsorbent dosage, 10 mg/l Ni(II) concentration and 60 min contact time. The results indicate that the effective uptake of Ni(II) ions was obtained by activating the carbon at 900 °C.     

Photo-electrochemical analysis of passive film formed on X80 pipeline steel in bicarbonate/carbonate buffer solution

Photo-electrochemical measurement was used to explore the formation potential, formation time, chloride ions concentration, applied potential and pH value of the solution on the electronic property of passive film formed on X80 pipeline steel in 1 M NaHCO₃/0.5 M Na₂CO₃ buffer solution. The results showed that the photocurrent is positive, indicating an n-type semiconductor character of the passive film, the photocurrent increased with increasing the formation potential, prolonging the formation time, decreasing chloride ions concentration, rising applied potential and decreasing the pH value of the solution. Capacitance measurement exhibited a positive slope of Mott-Schottky plot, and the slopes of Mott-Schottky plots increased with the increasing formation potential, showing a decrement of the donor density of the passive film.