The local structure of SO2 and SO3 on Ni(1 1 1)

The normal incidence X-ray standing wave (NIXSW) technique, supported by X-ray photoelectron spectroscopy and near-edge X-ray absorption fine structure (NEXAFS), has been used to determine the local adsorption geometry of SO₂ and SO₃ on Ni(1 1 1). Chemical-state specific NIXSW data for coadsorbed SO₃ and S, formed by the disproportionation of adsorbed SO₂ after heating from 140 K to 270 K, were obtained using S 1s photoemission detection. For adsorbed SO₂ at 140 K the new results confirm those of an earlier study [Jackson et al., Surf. Sci. 389 (1997) 223] that the molecule is located above hollow sites with its molecular plane parallel to the surface and the S and O atoms in off-atop sites; corrections to account for the non-dipole effects in the interpretation of the NIXSW monitored by S 1s and O 1s photoemission, not included in the earlier work, remove the need for any significant adsorption-induced distortion of the SO₂ in this structure. SO₃, not previously investigated, is found to occupy an off-bridge site with the C_3v axis slightly tilted relative to the surface normal and with one O atom in an off-atop site and the other two O atoms roughly between bridge and hollow sites. The O atoms are approximately 0.87 Å closer to the surface than the S atom. This general bonding orientation for SO₃ is similar to that found on Cu(1 1 1) and Cu(1 0 0) both experimentally and theoretically, although the detailed adsorption sites differ.     

Inhibition of steel corrosion in 2 M H3PO4 by artemisia oil

Artemisia oil (Ar) is extracted from artemisia herba alba collected in Ain es-sefra-Algeria, and tested as corrosion inhibitor of steel in 2 M H₃PO₄ using weight loss measurements, electrochemical polarisation and EIS methods. The naturally oil reduces the corrosion rate. The inhibition efficiency was found to increase with oil content to attain 79% at 6 g/l. Ar acts as a cathodic inhibitor. The effect of temperature on the corrosion behaviour of steel indicates that inhibition efficiency of the natural substance decreases with the rise of temperature. The adsorption isotherm of natural product on the steel has been determined.     

Density functional theory investigation of the structure of SO2 and SO3 on Cu(1 1 1) and Ni(1 1 1)

Density functional theory (DFT) slab calculations, mainly using the generalised gradient approximation, have been used to investigate the minimum energy structures of molecular SO₂ and SO₃ on Cu(1 1 1) and Ni(1 1 1) surfaces. On Ni(1 1 1) the optimal local adsorption structures are in close agreement with experimental results for both molecular species obtained using the X-ray standing wavefield technique, although for adsorbed SO₂ the energetic difference between two alternative lateral positions of the lying-down molecule on the surface is marginally significant. On Cu(1 1 1) the results for adsorbed SO₂, in particular, were sensitive to the DFT functional used in the calculations, but in all cases failed to reproduce the experimentally-established preference for adsorption with the molecular plane perpendicular to the surface. This result is discussed in the context of previously published DFT results for these species adsorbed on Cu(1 0 0). The optimal geometry found for SO₃ on Cu(1 1 1) is similar to that on Ni(1 1 1), providing agreement with experiment regarding the molecular orientation but not the adsorption site.     

The corrosion behavior of intermetallic compounds Ni3(Si,Ti) and Ni3(Si,Ti) + 2Mo in acidic solutions

The corrosion behavior of the intermetallic compounds homogenized, Ni₃(Si,Ti) (L1₂: single phase) and Ni₃(Si,Ti) + 2Mo (L1₂ and (L1₂ + Ni_ss) mixture region), has been investigated using an immersion test, electrochemical method and surface analytical method (SEM; scanning electron microscope and EPMA: electron probe microanalysis) in 0.5 kmol/m³ H₂SO₄ and 0.5 kmol/m³ HCl solutions at 303 K. In addition, the corrosion behavior of a solution annealed austenitic stainless steel type 304 was studied under the same experimental conditions as a reference. It was found that the intergranular attack was observed for Ni₃(Si,Ti) at an initial stage of the immersion test, but not Ni₃(Si,Ti) + 2Mo, while Ni₃(Si,Ti) + 2Mo had the preferential dissolution of L1₂ with a lower Mo concentration compared to (L1₂ + Ni_ss) mixture region. From the immersion test and polarization curves, Ni₃(Si,Ti) + 2Mo showed the lowest corrosion resistance in both solutions and Ni₃(Si,Ti) had the highest corrosion resistance in the HCl solution, but not in the H₂SO₄ solution. For instance, it was found that unlike type 304 stainless steel, these intermetallic compounds were difficult to form a stable passive film in the H₂SO₄ solution. The results obtained were explained in terms of boron segregation at grain boundaries, Mo enrichment and film stability (or strength).     

Investigation of the inhibitive effect of triphenyltin 2-thiophene carboxylate on corrosion of steel in 2 M H3PO4 solutions

A new organic compound was synthesised and tested as corrosion inhibitor of steel in phosphoric acid medium using gravimetric, electrochemical polarisation and electrochemical impedance spectroscopy (EIS) measurements. Results obtained show that the inhibitor studied is a good cathodic inhibitor. EIS results show that the change in the impedance parameters (R_T and C_dl) with concentration of triphenyltin 2-thiophene carboxylate (TTC) is indicative of the adsorption of molecules leading to the formation of a protective layer on the surface of steel. The effect of the temperature on the steel corrosion in 2 M H₃PO₄ and with addition of various concentrations of TTC in the range of temperature 298-348 K was studied. The associated apparent activation corrosion energy has been determined.     

The local structure of SO2 and SO3 on Ni(1 1 1): A scanned-energy mode photoelectron diffraction study

O 1s and S 2p scanned-energy mode photoelectron diffraction (PhD) data, combined with multiple-scattering simulations, have been used to determine the local adsorption geometry of the SO₂ and SO₃ species on a Ni(1 1 1) surface. For SO₂, the application of reasonable constraints on the molecular conformation used in the simulations leads to the conclusion that the molecule is centred over hollow sites on the surface, with the molecular plane essentially parallel to the surface, and with both S and O atoms offset from atop sites by almost the same distance of 0.65 Å. For SO₃, the results are consistent with earlier work which concluded that surface bonding is through the O atoms, with the S atom higher above the surface and the molecular symmetry axis almost perpendicular to the surface. Based on the O 1s PhD data alone, three local adsorption geometries are comparably acceptable, but only one of these is consistent with the results of an earlier normal-incidence X-ray standing wave (NIXSW) study. This optimised structural model differs somewhat from that originally proposed in the NIXSW investigation.     

DFT study of Pt adsorption on low index SrTiO3 surfaces: SrTiO3(1 0 0), SrTiO3(1 1 1) and SrTiO3(1 1 0)

Density Functional Theory has been used to determine the energetically preferred structures of submonolayer, monolayer, and multilayer Pt films on both ideal terminations of SrTiO₃(1 0 0), SrTiO₃(1 1 1), and SrTiO₃(1 1 0). The strength of the resulting metal/metal oxide interfaces was characterized by the adsorption energy of the film and the film’s work of separation. The two polar surfaces, SrTiO₃(1 1 1) and SrTiO₃(1 1 0), form significantly stronger interfaces than the non-polar SrTiO₃(1 0 0) surface. Approximate criteria were applied to predict the growth mode of Pt on each surface.     

Influence of substrate temperature in BiFeO3-CoFe2O4 nanocomposites deposited on SrTiO3 (0 0 1)

BiFeO₃-CoFe₂O₄ epitaxial nanocomposites have been deposited on SrTiO₃ (0 0 1) substrates by pulsed laser deposition. We present here a study of the influence of the deposition temperature (T_S), in the 550-800 °C range, on the film composition, morphology and microstructure. Electron-probe microanalysis shows strong reduction of the Bi content in the films when increasing T_S. Films prepared at T_S=750 °C and above are virtually Bi-free. X-ray diffraction (XRD) data show that, due to the volatility of Bi, there is a progressive reduction in the amount of BiFeO₃. The deposition temperature and the concomitant presence of Fe_xO_y spurious phases in the nanocomposites grown at high temperature promote radical changes in film morphology and magnetization. It thus follows that a temperature range suitable for controlled modification of nanocomposites morphology would be extremely narrow.     

Interactions between SO2 and NO on the surface of stepped Pt(3 3 2)

Interactions between S¹⁸O₂ and NO on the surface of stepped Pt(3 3 2) were studied using Fourier transform infra red reflection-absorption spectroscopy (FTIR-RAS) combined with thermal desorption spectroscopy (TDS). Adsorbed S¹⁸O₂ does not seem to have a preference for step sites on Pt(3 3 2). As such, the presence of S¹⁸O₂ molecules following exposures of ?1.6 L does not significantly block the subsequent adsorption of NO (?0.8 L) on these step sites. Adsorbed S¹⁸O₂ molecules undergo dissociation (S¹⁸O₂(a) → S¹⁸O(a) + ¹⁸O(a)) as the surface temperature is increased to 250 K and above, but the resultant ¹⁸O(a) further reacts with sulfur oxides (S¹⁸O₂(a) and S¹⁸O(a)) to form S¹⁸O_x (x > 2) species at ∼400 K and above. The S¹⁸O_x species desorb as S¹⁸O₂. Even though the presence of co-adsorbed S¹⁸O₂ suppresses NO dissociation and subsequent N₂ production, this effect is not significantly enhanced with increasing the exposures of S¹⁸O₂ in the range ?1.6 L; N₂ desorption is still detectable at an exposure of 1.6 L S¹⁸O₂, at which a considerable amount of S¹⁸O₂ desorption is detected.     

Electrochemical, theoretical and XPS studies of 2-mercapto-1-methylimidazole adsorption on carbon steel in 1 M HClO4

The inhibition of the corrosion of carbon steel in 1 M HClO₄ by 2-mercapto-1-methylimidazole (MMI) has been investigated in relation to the concentration of the inhibitor as well as the temperature using weight loss and electrochemical measurements. The effect of the temperature on the corrosion behaviour with addition of different concentrations of MMI was studied in the temperature range 30-60 °C. Polarization curves reveal that MMI is a mixed type inhibitor. The inhibition efficiency of MMI is temperature independent but increases with the inhibitor concentration. Changes in impedance parameters (charge transfer resistance, R_t, and double-layer capacitance, C_dl) were indicative of adsorption of MMI on the metal surface, leading to the formation of a protective film. Adsorption of MMI on the carbon steel surface is found to obey the Langmuir adsorption isotherm. Some thermodynamic functions of dissolution and adsorption processes were also determined. The X-ray photoelectron spectroscopy (XPS) of the carbon steel indicated that MMI is chemically adsorbed on the steel surface. Moreover, the electronic properties such as highest occupied molecular orbital (HOMO), lowest unoccupied molecular orbital (LUMO) energy levels and molecular orbital densities were calculated.     

Adsorption of NO, NO2, pyridine and pyrrole on α-Mo2C(0 0 0 1): A DFT study

Density functional theory computations have been carried out on the adsorption of NO, NO₂, pyridine and pyrrole on the α-Mo₂C(0 0 0 1) surface for understanding the hydrodenitrogenation processes. On the Mo-terminated surface, NO decomposes into surface N and O, and NO₂ dissociates into surface O and NO without any barriers, while the most stable adsorption modes of pyridine and pyrrole have π-face coordination over the three-fold molybdenum hollow sites with strongly destroyed aromatic systems. On the C-terminated surface, adsorbed surface species have been found for NO and NO₂, while destroyed ring systems are found for pyridine and pyrrole. It is found that adsorption on the Mo-terminated surface is much stronger than that on the C-terminated surface.     

Electrochemical properties of thin TiO2 electrode on Li1 + xAlxGe2 − x(PO4)3 solid electrolyte

A fabrication of all-solid-state thin-film rechargeable lithium ion batteries by sol-gel method is expected to achieve both the simplification and cost reduction for fabrication process. TiO₂ thin film electrode was prepared by PVP (polyvinylpyrrolidone) sol-gel method combined with spin-coating on Li_1 + xAl_xGe_2 − x(PO₄)₃ (LAGP) solid electrolyte which has wide electrochemical window. The thin film was composed of anatase TiO₂ that is the most active phase for Li insertion and extraction and contacted well with LAGP substrate. In the cyclic voltammogram, a redox couple was observed at 1.8 V vs. Li/Li⁺ assigned to Li insertion/extraction into/from anatase TiO₂, indicating that the thin film worked as electrode for lithium battery. The charge and discharge test in various charge and discharge rates revealed that the discharge process (delithiation) is thought to be faster than charge process (lithiation). It is attested that the sol-gel process, which derives both simplification and cost reduction for fabrication process, can be applied to thin film battery using LAGP solid electrolyte.     

SiH4 adsorption on SiGe(0 0 1)

The adsorption process of silane (SiH₄) on a SiGe(0 0 1) surface has been investigated by using infrared absorption spectroscopy in a multiple internal reflection geometry. We have observed that SiH₄ dissociatively adsorbs on a SiGe(0 0 1) surface at room temperature to generate Si and Ge hydrides. The dissociation of Si- and Ge-hydride species is found to strongly depend on the Ge concentration of the SiGe crystal. At a low Ge concentration of 9%, Si monohydride (SiH) and dihydride (SiH₂) are preferentially produced as compared to the higher Si hydride, SiH₃. At higher Ge concentrations of 19%, 36%, on the other hand, monohydrides of SiH and GeH and trihyderide SiH₃ are favorably generated at the initial stage of the adsorption. We interpret that when SiH₄ adsorbs on the SiGe surface, hydrogen atoms released from the SiH₄ molecule stick onto Ge or Si sites to produce Si or Ge monohydrides and the remaining fragments of -SiH₃ adsorb both on Si and Ge sites. The SiH₃ species is readily decomposed to lower hydrides of SiH and SiH₂ by releasing H atoms at low Ge concentrations of 0% and 9%, while the decomposition is suppressed by Ge in cases of 19% and 36%.     

Chloromethane surface chemistry on Fe3O4(1 1 1)-(2 × 2): A thermal desorption spectrometry comparison of CCl4, CBr2Cl2, and CH2Cl2

The surface chemistry of CBr₂Cl₂ on the Fe₃O₄(1 1 1)-(2 × 2) selvedge of single-crystal α-Fe₂O₃(0 0 0 1) has been investigated using temperature programmed reaction and desorption (TPR/D) measurements. The spectra obtained in this case show that strong chemisorption occurs and that a series of adsorbed halogenated reaction products are present. By comparison, studies of the adsorbed phase of CH₂Cl₂ show that only physisorption occurs. The TPR/D spectra of CBr₂Cl₂ show that dissociative formation of CCl₂ followed by its reaction with lattice oxygen is central to the monolayer reaction chemistry in this chloromethane. The branching ratios of the various desorbed products are compared with those obtained from CCl₄ adsorbed on the same (2 × 2) surface.     

DFT study on dissociative adsorption of SiH4 and GeH4 on SiGe(1 0 0)-2 × 1 surface

SiH₄ and GeH₄ dissociative adsorptions on a buckled SiGe(1 0 0)-2 × 1 surface have been analyzed using density functional theory (DFT) at the B3LYP level. The Ge alloying in the Si(1 0 0)-2 × 1 surface affects the dimer buckling and its surface reactivity. Systematic Ge influences on the reaction energetics are found in SiH₄ and GeH₄ reactions with four dimers of Si^∗-Si, Ge^∗-Si, Ge^∗-Ge, and Si^∗-Ge (∗ denotes the protruded atom). On a half H-covered surface, the energy barriers for silane and germane adsorption are higher than those on the pristine surface. The energy barrier for silane adsorption is higher than the corresponding barrier for germane adsorption. Rate constants are also calculated using the transition-state theory. We conclude that the SiGe surface reactivity in adsorption reaction depends on the Ge presence in dimer form. If the surface Ge is present in form of Ge^∗-Ge, the surface reactivity decreases as the Ge^∗-Ge content increases. If the surface Ge prefers to be in form of Ge^∗-Si at low Ge contents, the surface reactivity increases first, then decreases at high Ge surface contents when Ge^∗-Ge prevails. The calculated rate constant ratio of GeH₄ adsorption on Si^∗-Si over Ge^∗-Ge at 650 °C is 2.1, which agrees with the experimental ratio of GeH₄ adsorption probability on Si(1 0 0) over Si(1 0 0) covered by one monolayer Ge. The experimental ratio is 1.7 measured through supersonic molecular beam techniques. This consistency between calculation and experimental results supports that one monolayer of Ge on Si(1 0 0) exists in form of Ge^∗-Ge dimer.     

Effect of copper ions implantation on corrosion behavior of zircaloy-4 in 1 M H2SO4

In order to study the effect of copper ion implantation on the aqueous corrosion behavior, samples of zircaloy-4 were implanted with copper ions with fluences ranging from 1 × 10¹⁶ to 1 × 10¹⁷ ions/cm², using a metal vapor vacuum arc source (MEVVA) operated at an extraction voltage of 40 kV. The valence states and depth distributions of elements in the surface layer of the samples were analyzed by X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES), respectively. Glancing angle X-ray diffraction (GAXRD) was employed to examine the phase transformation due to the copper ion implantation. The potentiodynamic polarization technique was employed to evaluate the aqueous corrosion resistance of implanted zircaloy-4 in a 1 M H₂SO₄ solution. It was found that a significant improvement was achieved in the aqueous corrosion resistance of zircaloy-4 implanted with copper ions when the fluence is smaller than 5 × 10¹⁶ ions/cm². The corrosion resistance of implanted samples declined with increasing the fluence. Finally, the mechanism of the corrosion behavior of copper-implanted zircaloy-4 was discussed.     

Growth of highly-oriented CaCu3Ti4O12 thin films on SrTiO3 (1 0 0) substrates by a chemical solution route

Highly-oriented CaCu₃Ti₄O₁₂ (CCTO) thin films deposited directly on SrTiO₃ (1 0 0) substrates have been developed successfully using a chemical solution coating method. X-ray diffraction (XRD), scanning electron microscopy (SEM), and atomic force microscopy (AFM) were employed to characterize the structure and the morphology. It was observed that the CCTO thin films had the 1 μm × 1 μm domain-like microstructure that consists of compact grains of about 0.1 μm in size. The cross sectional SEM image shows that the CCTO grains grow regularly close to the clear interface between the CCTO film and the SrTiO₃ substrate. The result was discussed in terms of lattice mismatch between CCTO and SrTiO₃.     

First principle study of SrTiO3 (0 0 1) surface and adsorption of NO on SrTiO3 (0 0 1)

The results of first-principles calculations about the two possible terminations of (0 0 1) surface of SrTiO₃ perovskite and adsorption of NO on SrTiO₃ (0 0 1) surface were presented. Both surface parameters (atomic structures and electronic configurations) and adsorption parameters (bond, energy and charge) of NO on SrTiO₃ (0 0 1) surface, which have never been investigated before as far as we know were investigated using density functional theory calculations with the local-density approximation (DFT-LDA). It was found that the two possible terminations of SrTiO₃ (0 0 1) surface have large surface relaxation, which leads to surface polarization and exhibits different reactivity toward the dissociative adsorption of NO. The electronic states of TiO₂-terminated surface have larger difference than that of bulk, so it is more favorable for adsorption of NO than SrO-terminated surface.     

Comparative study of Pt, Au and Ag growth on Fe3O4(0 0 1) surface

The epitaxial growth of Pt, Au and Ag layers on Fe₃O₄(0 0 1) as a function of temperature and thickness have been studied. The layers were deposited by sputtering in an ultra high vacuum chamber and the structural properties were investigated by Reflection High Energy Electron Diffraction, X-ray reflectivity and diffraction, High Resolution Transmission Electron Microscopy and Atomic Force Microscopy. Our studies give evidence for three different growth behaviours depending both on the nature of the metals and the temperature. Comparison between the growth modes of the three metals will be discussed in relation with surface and interfaces energies.     

Theoretical study of the electronic structure of the Si3N4(0 0 0 1) surface

Density functional theory has been applied to a study of the electronic structure of the ideally-terminated, relaxed and H-saturated (0 0 0 1) surfaces of β-Si₃N₄ and to that of the bulk material. For the bulk, the lattice constants and atom positions and the valence band density of states are all in good agreement with experimental results. A band gap of 6.7 eV is found which is in fair accord with the experimental value of 5.1-5.3 eV for H-free Si₃N₄. Using a two-dimensionally-periodic slab model, a π-bonding interaction is found between threefold-coordinated Si and twofold-coordinated N atoms in the surface plane leading to π and π* surface-state bands in the gap. A surface-state band derived from s-orbitals is also found in the gap between the upper and lower parts of the valence band. Relaxation results in displacements of surface and first-underlayer atoms and to a stronger π-bonding interaction which increases the π-π* gap. The relaxed surface shows no occupied surface states above the valence band maximum, in agreement with recent photoemission data for a thin Si₃N₄ film. The π* band, however, remains well below the conduction band minimum (but well above the Fermi level). Adsorbing H at all dangling-bond sites on the ideally-terminated surface and then relaxing the surface and first underlayer leads to smaller, but still finite, displacements in comparison to the clean relaxed surface. This surface is more stable, by about 3.67 eV per H, than the clean relaxed surface.