Study on growth factors of intermetallic layer within hot-dipped 25% Al-Zn alloy coating on steel

25%Al-Zn alloy coating performs better than hot dip galvanized coating and 55%Al-Zn-Si coating with regard to general seawater corrosion protection. This study deals with the interfacial intermetallic layer's growth, which affects considerably the corrosion resistance and mechanical properties of 25%Al-Zn alloy coatings, by means of three-factor quadratic regressive orthogonal experiments, The regression equation shows that the intermetallic layer thickness decreases rapidly with increasing content of Si added to the Zn-Al alloy bath, increases with rise in bath temperature and prolonging dip time. The most effective factor that determined the thickness of intermetallic layer was the amount of Si added to Zn-Al alloy bath, while the effect of bath temperature and dip time on the thickness of intermetallic layer were not very obvious.

Anticorrosion performance of polyaniline nanostructures on mild steel

Different one-dimensional nanostructured polyanilines were synthesized in sulfuric acid solutions by conventional polymerization, interfacial polymerization and direct mixed reaction, respectively. The products were characterized with SEM, UV-vis and FTIR and the anticorrosion performance of products on mild steel were studied using electrochemical measurement in 3.5% NaCl aqueous solution. Results showed that the polyaniline nanofibers synthesized by direct mixed reaction have uniform morphology with diameters of 60-100 nm and more excellent protective properties than conventional aggregated polyaniline. Comparative studies revealed that the nanostructure and morphology of polyaniline could influence its anticorrosion performance. (C) 2010 Elsevier B.V. All rights reserved.

河流成因储层沉积微相与剩余油分布及形成机理研究

Based on the study of fluvial sandstone reservoir in upper of Guantao group in Gudao and Gudong oilfields, this paper first introduces A.D.Miall's(1996a) architectural-element analysis method that was summarized from ground outcrop scale into the reservoir formation research of the study area, more subtly divides sedimentary microfacies and establishes sedimentary model of research area.on this base, this paper summarizes the laws of residual oil distribution of fluvial formation and the control effect of sedimentary microfacies to residual oil distribution, and reveals residual oil formation mechanism. These results have been applied to residual oil production, and the economic effect is good. This paper will be useful for residual oil research and production and enhancement of oil recovery in similar reservoir. The major conclusions of this paper are as follows. 1. Using the architectural-element analysis method to the core data, a interfacial division scheme of the first to the dixth scale is established for the studied fluvial formation. 2.Seven architectural-elements are divided in upper of Guantao group of study area. The sandstone group 5～1+2 of Neogene upper Gutao group belongs to high sinuous fine grain meandering river, and the sandstone group 6 is sandy braided river. 3. Inter layer, the residual oil saturation of "non-main layer" is higher than "main layer", but the residual recoverable reserve of former is larger. Therefore, "main layer" is the main body of residual oil distribution. The upper and middle part of inner layer has lower permeability and strong seeping resistance. Addition to gravity effect in process of driving, its driving efficiency is low; residual oil saturation is high. Because of controlling of inside non-permeable interlayer or sedimentary construction, the residual oil saturation of non-driving or lower driving efficiency position also is high. On plane, the position of high residual oil saturation mostly is at element LV, CS, CH (FF), FF etc, Which has lower porosity and permeability, as well as lens sand-body and sand-body edge that is not controlled by well-net, non-perfect area of injection and production, lower press difference resort area of inter-well diffiuent-line and shelter from fault, local high position of small structure. 4.Microscopic residual oil mainly includes the non-moved oil in the structure of fine pore network, oil in fine pore and path, oil segment in pore and path vertical to flow direction, oil spot or oil film in big pore, residual oil in non-connective pore. 5.The most essential and internal controlling factor of fluvial formation residual oil distribution is sedimentary microfacies. Status of injection and production is the exterior controlling factor of residual oil distribution. 6. The controlling effect of formation sedimentary microfacies to residual oil distribution indicates inter-layer vertical sedimentary facies change in scale of injection and production layer-series, planar sedimentary face change and inner-layer vertical sedimentary rhythm and interbed in single layer to residual oil distribution. 7. It is difficult to clear up the inter-layer difference in scale of injection and production layer-series. The using status of minor layer is not good and its residual oil saturation is high relatively. It is obvious that inter-layer vertical sedimentary facies changes control inter-layer residual oil distribution at the same or similar conditions of injection and production. For fluvial formation, this vertical sedimentary facies change mainly is positive gyration. Namely, from down to top, channel sediment (element CHL, LA) changes into over-bank sediment (element LV, CR, CS). 8. In water-injection developing process of transverse connecting fluvial sandstone oil formation, injection water always comes into channel nearby, and breaks through along channel and orientation of high pressure gradient, does not expand into side of channel until pressure gradient of channel orientation changes into low. It brings about that water-driving status of over-bank sedimentary element formation (LV, CR, CS) is not good, residual oil saturation is high. In non-connective abandoned channel element (CH) formation with channel, because this reverse is difficult to control by injection and production well-series, its using status is not good, even terribly not good, residual oil is enrichment. 9. The rhythm and sedimentary structure, sedimentary facies change in single sand body brings about vertical changes of formation character, growth character of inner layer interbed. These are important factor of controlling and affecting vertical water spread volume and inner layer residual oil forming and distribution in single sand body. Positive rhythm, is the principal part of fluvial sandstone inner layer sedimentary rhythm. Namely, from down to upside, rock grain granularity changes from coarse to fine, seeping ability changes from strong to feebleness. It brings about that water-driving status of inner layer upside is not good, residual oil saturation is high. Inner layer interbed has different degree affecting and controlling effect to seeping of oil and water. Its affecting degree lies on interbed thickness, extending scale, position, and jeted segment of production or injection well. The effect of interbed at upside of oil formation to oil and water seeping is less; the effect of interbed at middle of oil formation to oil and water seeping is more. 10. Indoor experiment and research indicate that wettability, permeability step, vertical permeability, position of Kmax and ratio of oil viscousity and water viscousity all have great effect on the water-driving recovery ratio. 11. Microscopic residual oil distribution is affected and controlled by formation pore network structure, pressure field distribution, and oil characteristic. 12.The residual oil forming mechanism: the over-bank sedimentary element and upper part of a positive rhythm sandstone have fine pore and throat network, permeability is low, displacement pressure of pore and throat is high. The water-driving power usually falls short of displacement pressure that brings about injection water does not spread into these pore and throat network, thereby immovable oil area, namely residual oil, is formed. At underside of channel sedimentary element and positive rhythm sandstone, porosity and permeability is relatively high, connecting degree of pore and throat is high, displacement pressure of pore and throat is low. Thereby injection water is easy to enter into pore and throat, driving oil in them. Because the pore space is irregular, the surface of pore wall is coarse and non-flat. That the oil locate on concave hole of pore wall and the dead angle of pore, and the oil attaches on surface of pore wall by surface tension, are difficult to be peeled off, becoming water-driving residual oil (remaining oil). On the other hand, Because flowing section lessens, flowing resistance increase, action of capillary fore, or seeping speed decreases at process of transfer at pass narrow throat path in the course carried by driving water. The "oil drop", "oil bead", or "oil segment" peeled off by driving water is difficult to carry and to drive out by water at less pressure difference. Thereby they are enclosed in pore to form discontinuous residual oil. 13.This results described above have been applied in nine develop blocks of Gudao and Gudong oilfield. Its applying effect is marked through local injection production adjustment, deploying replacement well, repair hole, replacement envelop, block off water and profile control etc. Relative method and technology can be applied to other oil production area of Shengli oilfield, and obtain better economic and societal effect.

Modification of GaAs Schottky diodes by thin organic interlayers

Modification of GaAs Schottky diodes by thin organic interlayers, A.R. Vearey-Roberts and D.A. Evans, Appl. Phys. Lett. 86, 072105 (2005)

Li+ Diffusion and its Structural Basis in the Nanocrystalline and Amorphous Forms of Two-dimensionally Ion-conducting LixTiS2

Winter, Rudolf; Heitjans, P., (2001) 'Li+ Diffusion and its Structural Basis in the Nanocrystalline and Amorphous Forms of Two-dimensionally Ion-conducting LixTiS2', Journal of Physical Chemistry B 105(26) pp.6108-6115 RAE2008

Involvement of incipient hydrous oxide species in electrocatalysis at some metal electrode surfaces

In this thesis a novel theory of electrocatalysis at metal (especially noble metal)/solution interfaces was developed based on the assumption of metal adatom/incipient hydrous oxide cyclic redox transitions. Adatoms are considered as metastable, low coverage species that oxidise in-situ at potentials of often significantly cathodic to the regular metal/metal oxide transition. Because the adatom coverage is so low the electrochemical or spectroscopic response for oxidation is frequently overlooked; however, the product of such oxidation, referred to here as incipient hydrous oxide seems to be the important mediator in a wide variety of electrocatalytically demanding oxidation processes. Conversely, electrocatalytically demanding reductions apparently occur only at adatom sites at the metal/solution interface - such reactions generally occur only at potentials below, i.e. more cathodic than, the adatom/hydrous oxide transition. It was established that while silver in base oxidises in a regular manner (forming initially OHads species) at potentials above 1.0 V (RHE), there is a minor redox transition at much lower potentials, ca. o.35 v (RHE). The latter process is assumed to an adatom/hydrous oxide transition and the low coverage Ag(l) hydrous oxide (or hydroxide) species was shown to trigger or mediate the oxidation of aldehydes, e. g. HCHO. The results of a study of this system were shown to be in good agreement with a kinetic model based on the above assumptions; the similarity between this type of behaviour and enzyme-catalysed processes - both systems involve interfacial active sites - was pointed out. Similar behaviour was established for gold where both Au(l) and Au(lll) hydrous oxide mediators were shown to be the effective oxidants for different organic species. One of the most active electrocatalytic materials known at the present time is platinum. While the classical view of this high activity is based on the concept of activated chemisorption (and the important role of the latter is not discounted here) a vital role is attributed to the adatom/hydrous oxide transition. It was suggested that the well known intermediate (or anomalous) peak in the hydrogen region of the cyclic voltanmogram for platinum region is in fact due to an adatom/hydrous oxide transition. Using potential stepping procedures to minimise the effect of deactivating (COads) species, it was shown that the onset (anodic sweep) and termination (cathodic sweep) potential for the oxidation of a wide variety of organics coincided with the potential for the intermediate peak. The converse was also shown to apply; sluggish reduction reactions, that involve interaction with metal adatoms, occur at significant rates only in the region below the hydrous oxide/adatom transition.

Atomic layer deposition of interface control layers for the fabrication of III/V MOS devices

The continued advancement of metal oxide semiconductor field effect transistor (MOSFET) technology has shifted the focus from Si/SiO2 transistors towards high-κ/III-V transistors for high performance, faster devices. This has been necessary due to the limitations associated with the scaling of the SiO2 thickness below ~1 nm and the associated increased leakage current due to direct electron tunnelling through the gate oxide. The use of these materials exhibiting lower effective charge carrier mass in conjunction with the use of a high-κ gate oxide allows for the continuation of device scaling and increases in the associated MOSFET device performance. The high-κ/III-V interface is a critical challenge to the integration of high-κ dielectrics on III-V channels. The interfacial chemistry of the high-κ/III-V system is more complex than Si, due to the nature of the multitude of potential native oxide chemistries at the surface with the resultant interfacial layer showing poor electrical insulating properties when high-κ dielectrics are deposited directly on these oxides. It is necessary to ensure that a good quality interface is formed in order to reduce leakage and interface state defect density to maximise channel mobility and reduce variability and power dissipation. In this work, the ALD growth of aluminium oxide (Al2O3) and hafnium oxide (HfO2) after various surface pre-treatments was carried out, with the aim of improving the high-κ/III-V interface by reducing the Dit – the density of interface defects caused by imperfections such as dangling bonds, dimers and other unsatisfied bonds at the interfaces of materials. A brief investigation was performed into the structural and electrical properties of Al2O3 films deposited on In0.53Ga0.47As at 200 and 300oC via a novel amidinate precursor. Samples were determined to experience a severe nucleation delay when deposited directly on native oxides, leading to diminished functionality as a gate insulator due to largely reduced growth per cycle. Aluminium oxide MOS capacitors were prepared by ALD and the electrical characteristics of GaAs, In0.53Ga0.47As and InP capacitors which had been exposed to pre-pulse treatments from triethyl gallium and trimethyl indium were examined, to determine if self-cleaning reactions similar to those of trimethyl aluminium occur for other alkyl precursors. An improved C-V characteristic was observed for GaAs devices indicating an improved interface possibly indicating an improvement of the surface upon pre-pulsing with TEG, conversely degraded electrical characteristics observed for In0.53Ga0.47As and InP MOS devices after pre-treatment with triethyl gallium and trimethyl indium respectively. The electrical characteristics of Al2O3/In0.53Ga0.47As MOS capacitors after in-situ H2/Ar plasma treatment or in-situ ammonium sulphide passivation were investigated and estimates of interface Dit calculated. The use of plasma reduced the amount of interface defects as evidenced in the improved C-V characteristics. Samples treated with ammonium sulphide in the ALD chamber were found to display no significant improvement of the high-κ/III-V interface. HfO2 MOS capacitors were fabricated using two different precursors comparing the industry standard hafnium chloride process with deposition from amide precursors incorporating a ~1nm interface control layer of aluminium oxide and the structural and electrical properties investigated. Capacitors furnished from the chloride process exhibited lower hysteresis and improved C-V characteristics as compared to that of hafnium dioxide grown from an amide precursor, an indication that no etching of the film takes place using the chloride precursor in conjunction with a 1nm interlayer. Optimisation of the amide process was carried out and scaled samples electrically characterised in order to determine if reduced bilayer structures display improved electrical characteristics. Samples were determined to exhibit good electrical characteristics with a low midgap Dit indicative of an unpinned Fermi level

Computational study of the growth of copper thin films by atomic layer deposition

Copper is the main interconnect material in microelectronic devices, and a 2 nm-thick continuous Cu film seed layer needs to be deposited to produce microelectronic devices with the smallest features and more functionality. Atomic layer deposition (ALD) is the most suitable method to deposit such thin films. However, the reaction mechanism and the surface chemistry of copper ALD remain unclear, which is deterring the development of better precursors and design of new ALD processes. In this thesis, we study the surface chemistries during ALD of copper by means of density functional theory (DFT). To understand the effect of temperature and pressure on the composition of copper with substrates, we used ab initio atomistic thermodynamics to obtain phase diagram of the Cu(111)/SiO2(0001) interface. We found that the interfacial oxide Cu2O phases prefer high oxygen pressure and low temperature while the silicide phases are stable at low oxygen pressure and high temperature for Cu/SiO2 interface, which is in good agreement with experimental observations. Understanding the precursor adsorption on surfaces is important for understanding the surface chemistry and reaction mechanism of the Cu ALD process. Focusing on two common Cu ALD precursors, Cu(dmap)2 and Cu(acac)2, we studied the precursor adsorption on Cu surfaces by means of van der Waals (vdW) inclusive DFT methods. We found that the adsorption energies and adsorption geometries are dependent on the adsorption sites and on the method used to include vdW in the DFT calculation. Both precursor molecules are partially decomposed and the Cu cations are partially reduced in their chemisorbed structure. It is found that clean cleavage of the ligand−metal bond is one of the requirements for selecting precursors for ALD of metals. 2 Bonding between surface and an atom in the ligand which is not coordinated with the Cu may result in impurities in the thin film. To have insight into the reaction mechanism of a full ALD cycle of Cu ALD, we proposed reaction pathways based on activation energies and reaction energies for a range of surface reactions between Cu(dmap)2 and Et2Zn. The butane formation and desorption steps are found to be extremely exothermic, explaining the ALD reaction scheme of original experimental work. Endothermic ligand diffusion and re-ordering steps may result in residual dmap ligands blocking surface sites at the end of the Et2Zn pulse, and in residual Zn being reduced and incorporated as an impurity. This may lead to very slow growth rate, as was the case in the experimental work. By investigating the reduction of CuO to metallic Cu, we elucidated the role of the reducing agent in indirect ALD of Cu. We found that CuO bulk is protected from reduction during vacuum annealing by the CuO surface and that H2 is required in order to reduce that surface, which shows that the strength of reducing agent is important to obtain fully reduced metal thin films during indirect ALD processes. Overall, in this thesis, we studied the surface chemistries and reaction mechanisms of Cu ALD processes and the nucleation of Cu to form a thin film.

Dissolution kinetics of octadecanethiolate monolayers electro-adsorbed on Au(1 1 1)

Monolayers of octadecanethiolate on Au(1 1 1) surface were formed under electrochemical control. The influence of the formation time on the reductive desorption process was studied by cyclic voltammetry and chronoamperometry. When the formation time is increased, the reductive desorption peak observed on the voltammograms is significantly shifted in the negative direction, while the cathodic charge is only slightly affected. This behaviour is attributed to a higher degree of organisation of the monolayers for longer formation times, highlighting the role of defect sites in promoting the dissolution. A good agreement was found between our experimental chronoamperograms and theoretical models describing the dissolution process by a shrinkage mechanism. It is demonstrated that a reorganisation process takes place, consisting in the merging of small condensed domains into larger ones. This annealing phenomenon is time and potential dependent, the largest condensed domains being obtained for the longest formation times and least negative potentials. © 2008 Elsevier B.V. All rights reserved.

Mixed self-assembled monolayers of 2-mercaptobenzimidazole and 2-mercaptobenzimidazole-5-sulfonate: determination and control of the surface composition

The behaviour towards electron transfer of self-assembled monolayers of 2-mercaptobenzimidazole (MBI) and 2-mercaptobenzimidazole-5-sulfonate (MBIS) on Au(1 1 1) was examined by cyclic voltammetry. The influence of the monolayers was drastically dependent on the charge of the redox probe used. When [Ru(NH3)6]3+ is used, a post-adsorption peak characteristic of the adsorption of the redox probe is detected only at the MBIS modified electrode. Taking advantage of this difference, ac voltammetry has been used to determine the surface composition when mixed monolayers are formed by immersion of the gold substrate in mixtures of different molar fractions of MBI and MBIS. Results clearly indicate that the ionic strength of the immersion solution plays a key role in the surface composition when a charged surfactant is mixed with non-charged surfactant. © 2006 Elsevier B.V. All rights reserved.

Adsorption of 2-mercaptobenzimidazole on a Au(1 1 1) electrode

The description of the monolayer formed at Au(1 1 1) by 2-mercaptobenzimidazole (MBI) under potential control has been based on electrochemical data (charge measurements) and spectroscopic information from the subtractively normalized interfacial Fourier transform infrared spectroscopy method (SNIFTIRS). From the quantitative analysis of the SNIFTIR spectra, a surface coverage Γ/Γmax was extracted for each sample potential. The evolution of the coverage with potential was in full agreement with the charge density curve. The shift of the pzc in the presence of MBI indicates that the adsorbed molecules have a nonzero component of the permanent dipole moment in the direction perpendicular to the electrode surface. Thanks to the high quality of the spectra, it was possible to determine the orientation of MBI molecules at the surface in the monolayer and submonolayer range. The angle between the C2-axis of the molecule and the direction normal to the surface is close to 64 ± 4° and its small change (<15°) with potential indicates that the orientation of the molecules is chiefly controlled by the chemical interaction between the sulphur atom and the gold surface. © 2005 Elsevier Ltd. All rights reserved.

Electrochemical and FTIR characterization of the self-assembled monolayer of 2-mercaptobenzimidazole on Au(1 1 1)

The behaviour of a self-assembled monolayer of 2-mercaptobenzimidazole (MBI) at the Au(111) electrode has been examined using cyclic voltammetry and in situ FTIR spectroscopy. The charge associated with the reductive desorption is pH independent while the oxidative partial redeposition charge increases when the pH is lowered. This is due to differences between the nature and the solubility of the MBI desorption product. In alkaline and neutral media MBI desorbs as the thiolate. In contrast, in acidic solutions the thiol is the desorbed product. Subtractively normalized interfacial reflection Fourier transform absorption spectroscopy (SNIFTIRS) has been applied to investigate the MBI monolayer in contact with aqueous solutions of different pH. The SNIFTIRS data are in agreement with the electrochemical results. Moreover, quantitative analysis of the IR data provided evidence that adsorbed MBI molecules assume a tilted orientation with an angle of 60±5° between the C2 axis of the molecule and the direction normal to the gold surface. © 2003 Elsevier B.V. All rights reserved.

Photoelectrocatalysis: Principles, nanoemitter applications and routes to bio-inspired systems

An overview on processes that are relevant in light-induced fuel generation, such as water photoelectrolysis or carbon dioxide reduction, is given. Considered processes encompass the photophysics of light absorption, excitation energy transfer to catalytically active sites and interfacial reactions at the catalyst/solution phase boundary. The two major routes envisaged for realization of photoelectrocatalytic systems, e.g. bio-inspired single photon catalysis and multiple photon inorganic or hybrid tandem cells, are outlined. For development of efficient tandem cell structures that are based on non-oxidic semiconductors, stabilization strategies are presented. Physical surface passivation is described using the recently introduced nanoemitter concept which is also applicable in photovoltaic (solid state or electrochemical) solar cells and first results with p-Si and p-InP thin films are presented. Solar-to-hydrogen efficiencies reach 12.1% for homoepitaxial InP thin films covered with Rh nanoislands. In the pursuit to develop biologically inspired systems, enzyme adsorption onto electrochemically nanostructured silicon surfaces is presented and tapping mode atomic force microscopy images of heterodimeric enzymes are shown. An outlook towards future envisaged systems is given. © 2010 The Royal Society of Chemistry.

Suppression of conformational heterogeneity at a protein-protein interface.

Staphylococcal protein A (SpA) is an important virulence factor from Staphylococcus aureus responsible for the bacterium's evasion of the host immune system. SpA includes five small three-helix-bundle domains that can each bind with high affinity to many host proteins such as antibodies. The interaction between a SpA domain and the Fc fragment of IgG was partially elucidated previously in the crystal structure 1FC2. Although informative, the previous structure was not properly folded and left many substantial questions unanswered, such as a detailed description of the tertiary structure of SpA domains in complex with Fc and the structural changes that take place upon binding. Here we report the 2.3-Å structure of a fully folded SpA domain in complex with Fc. Our structure indicates that there are extensive structural rearrangements necessary for binding Fc, including a general reduction in SpA conformational heterogeneity, freezing out of polyrotameric interfacial residues, and displacement of a SpA side chain by an Fc side chain in a molecular-recognition pocket. Such a loss of conformational heterogeneity upon formation of the protein-protein interface may occur when SpA binds its multiple binding partners. Suppression of conformational heterogeneity may be an important structural paradigm in functionally plastic proteins.

Experimental investigation of thermal structures in regular three-dimensional falling films

Interfacial waves on the surface of a falling liquid film are known to modify heat and mass transfer. Under non-isothermal conditions, the wave topology is strongly influenced by the presence of thermocapillary (Marangoni) forces at the interface which leads to a destabilization of the film flow and potentially to critical film thinning. In this context, the present study investigates the evolution of the surface topology and the evolution of the surface temperature for the case of regularly excited solitary-type waves on a falling liquid film under the influence of a wall-side heat flux. Combining film thickness (chromatic confocal imaging) and surface temperature information (infrared thermography), interactions between hydrodynamics and thermocapillary forces are revealed. These include the formation of rivulets, film thinning and wave number doubling in spanwise direction. Distinct thermal structures on the films’ surface can be associated to characteristics of the surface topology.