Characteristics of sulfide corrosion products on 316L stainless steel surfaces in the presence of sulfate-reducing bacteria

It has been found that microbial communities play a significant role in the corrosion process of steels exposed in aquatic and soil environments. Biomineralization influenced by microorganisms is believed to be responsible for the formation of corrosion products via complicated pathways of electron transfer between microbial cells and the metal. In this study, sulfide corrosion products were investigated for 316L stainless steel exposed to media with sulfate-reducing bacteria media for 7 weeks. The species of inorganic and organic sulfides in the passive film on the stainless steel were observed by epifluorescence microscope, environmental scanning electron microscope combined with energy dispersive spectroscopy and X-ray photoelectron spectroscopy. The transformation from metal oxides to metal sulfides influenced by sulfate-reducing bacteria is emphasized in this paper. (c) 2005 Elsevier B.V. All rights reserved.

Effect of nano-TiO(2)on MP-25 resin

MP-25 resin is a chlorine-containing polymer widely used in coatings. The effects of two types of nano-TiO2 (P-25 and RM301 LP) on MP-25 were studied with saline immersion, UV irradiation, and electrochemical impedance spectroscopy. UV irradiation was evaluated in terms of gloss change and X-ray photoelectron spectroscopy (XPS). The results indicate that, compared to pigment R-930 TiO2, P-25 reduced the immersion resistance and accelerated UV aging of the MP-25 coating, whereas RM301 LP showed the opposite effects. XPS analysis showed that MP-25 resin degraded under UV irradiation via dechlorination and C-C bond breakage, similarly to poly(vinyl chloride), but RM301 LP could inhibit the aging of MP-25 to a certain extent. A skin effect of oxygen and chlorine was identified in MP-25 resin by XPS. RM301 LP could improve the impedance of the MP-25 coating because of its excellent fill capacity. Hence, rutile nano-TiO2 RM301 LP represents an excellent additive for MP-25 resin. (c) 2007 Wiley Periodicals, Inc.

太阳耀斑和日食期间电离层行为的统计和模拟研究

The ionosphere is the ionized component of the Earth's upper atmosphere. Solar EUV radiation is the source of ionospheric ionization. Thus the ionosphere is affected strongly by the variations in solar radiation. Solar flares and solar eclipses can induce remarkable short time changes in solar radiation: the solar radiation would increase suddenly during solar flares and decrease significantly during solar eclipses. Solar flare and eclipse events not only affect directly the photochemical processes, but also affect the dynamic processes, and even affect the neutral atmosphere, which is strongly coupled with the ionosphere. The study on the ionospheric response to solar flares and eclipses can advance our knowledge on the ionosphere and its photochemical and dynamic processes and help us to evaluate the ionospheric parameters (such as ion loss coefficients). In addition, the study on the ionospheric responses to solar flares and eclipses is an important part of the ionospheric space weather, which can provide guides for space weather monitoring. This thesis devotes to the study on the ionospheric responses to solar flares and solar eclipses. I have developed two models to simulate the variations of solar EUV radiation during solar flares and solar eclipses, and involved in developing a 2D mid- and low-latitude ionospheric model. On the basis of some observed data and the ionospheric model, I study the temporal and spatial variations of the ionosphere during solar flares and eclipses, and investigate the influences of solar activity, solar zenith angle, neutral gas density, and magnetic dip angle on the ionospheric responses to solar flares and solar eclipses. The main points of my works and results are summarized as follows. 1. The ionospheric response to the X17.2 solar flare on October 28, 2003 was modeled via using a one-dimension theoretical ionospheric model. The simulated variation of TEC is in accordance with the observations, though there are some differences in the amplitude of the variation. Then I carried out a series of simulations to explore the local time and seasonal dependences of the ionospheric responses to solar flares. These calculations show that the ionospheric responses are largely related with the solar zenith angle (SZA). During the daytime (small SZA), most of the increases in electron density occur at altitudes below 300 km with a peak at around 115 km; whereas around sunrise and sunset (SZA>90°), the strongest ionospheric responses occur at much higher altitudes. The TEC increases slower at sunrise than at sunset, which is caused by the difference in the evolution of SZA at sunrise and sunset: SZA decreases with time at sunrise and increase with time at sunset. The ionospheric response is largest in summer and smallest in winter, which is also related to the seasonal difference of SZA. 2. Based on the observations from the ionosondes in Europe and the ionospheric model, I investigated the differences of the ionosphere responses to solar eclipses between the E-layer and F1-layer. Both the observation and simulation show that the decrease in foF1 due to the solar eclipses is larger than that in foE. This effect is due to that the F1 region locates at the transition height between the atomic ion layer and the molecular ion layer. With the revised model of solar radiation during solar flares, our model calculates the radiations from both the inside and outside of photosphere. Large discrepancy can be found between the observations and the calculations with an unrevised model, while the calculations with the revised model consist with the observations. 3. I also explore the effects of the F2-layer height, local time, solar cycle, and magnetic dip angle on the ionospheric responses to solar eclipses via using an ionospheric model and study on the solar zenith angle and the dip dependences by analyzing the data derived from 23 ionosonde stations during seven eclipse events. Both the measured and simulated results show that these factors have significant effect on the ionospheric response. The larger F2-layer height causes the smaller decrease in foF2, which is because that the electron density response decreases with height. The larger dip results in the smaller eclipse effect on the F2 layer, because the larger dip would cause the more diffusion from the top ionosphere which can make up for the plasma loss. The foF2 response is largest at midday and decreases with the increasing SZA. The foF2 response is larger at high solar activity than at low solar activity. The simulated results show that the local time and solar activity discrepancy of the eclipse effect mainly attribute to the difference of the background neutral gas density. 4. I carried out a statistical study on the latitudinal dependence of the ionospheric response to solar eclipses and modeled this latitudinal dependence by the ionospheric model. Both the observations and simulations show that the foF2 and TEC responses have the same latitudinal dependence: the eclipse effects on foF2 and TEC are smaller at low latitudes than at middle latitudes; at the middle latitudes (>40°), the eclipse effect decreases with increasing latitude. In addition, the simulated results show the change in electron temperature at the heights of above 300 km of low latitudes is much smaller than that at the same heights of middle latitudes. This is due to the smaller decrease in photoelectron production rate at its conjugate low heights. 5. By analyzing the observed data during the October 3, 2005 solar eclipse, I find some significant disturbances in the conjugate region of the eclipse region, including a decrease in Te, an increase in foF2 and TEC, and an uprising in hmF2. I also simulated the ionosphere behavior during this eclipse using a mid-low latitude ionospheric model. The simulations reproduce the measured ionospheric disturbances mentioned above in the conjugated hemisphere. The simulations show that the great loss of arriving photoelectron heat from the eclipse region is the principal driving source for the disturbances in the conjugate hemisphere.

Epoxidation of propylene on NaCl-modified silver catalysts with air as the oxidant

Propylene epoxidation by air was carried out on NaCl-modified silver (NaCl/Ag) catalysts, and the catalysts were characterized by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The effects of NaCl loadings, propylene to oxygen ratio, and the reaction time on the catalytic performance were investigated. It was found that the addition of NaCl to silver significantly increases the propylene oxide (PO) selectivity. The PO yield has a maximum when the NaCl loading is about 10 wt.%. Also 12.4% conversion of propylene and 31.6% selectivity to PO are obtained on the NaCl/Ag (10 wt.%) catalyst at 350 degreesC, space velocity 1.8 x 10(4) h(-1) and C3H6:O-2 = 1:2. XPS and XRD characterizations show that AgCl formed on the silver catalyst was favorable to propylene epoxidation. A compound with highly oxidized Ag ion was also found, which may be effective for the reaction. (C) 2002 Elsevier Science B.V. All rights reserved.

Coadsorption of nitric oxide and oxygen on the Ag(110) surface

The coadsorption of NO and O-2 on Ag(110) surface has been studied by X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS) and in situ Raman spectroscopy. The existence of oxygen enhances the adsorption of NO by forming the NOx species, that is, NO2 and NO3, and the NO in turn as a promotor facilitates the cleavage of the dioxygen bond, forming the surface atomic oxygen species having the same spectral characteristics as those produced using oxygen at high pressure. The oxygen species generated by the interaction is composed of two parts. One is produced directly by the decomposition of surface NO-O-2 complex at ca 625 K, which raised an O 1s feature at 530.5 eV and is absent at ca 800 K, while the another with an O 1s binding energy of 529.2 eV emerges at higher temperatures and shows similar properties as the reported gamma-state oxygen which bound tightly on restructured silver surface. The exposure to NO and O-2 causes noticeable changes in the morphology of the Ag(110) surface and the flat terraces superseded by small (ca 0.1 mu m) pits, and particles with typical diameters of a few micrometres were formed at elevated temperatures. (C) 1999 Elsevier Science B.V. All rights reserved.

Structure and properties of samarium overlayer and Sm/Rh surface alloy on Rh(100)

The structure and properties of Sm overlayer and Sm/Rh surface alloy have been investigated with Auger electron spectroscopy (AES), low energy electron diffraction (LEED), X-ray photoelectron spectroscopy (XPS), and temperature programmed desorption spectroscopy (TDS). The growth of Sm on Rh(100) at room temperature (RT) appears following the Stranski-Krastanov growth mode and only the trivalent state Sm is observed from XPS results. Thermal treatment of the Sm film at 900 K leads to the formation of ordered surface alloy which shows the c(5 root2 x root2)R45 degrees and c(2 x 2) LEED patterns. Annealing the Sm film at temperature above 400 K makes the binding energy (B.E.) of Sm 3d(5/2) shift to higher energy by 0.7 eV, which indicates charge transfer from Sm to Rh(100) substrate, causing the increase of CO desorption temperature.

Reversible regeneration of molybdenum carbonyl species on an alumina thin film

The thin alumina film-supported metallic molybdenum model catalyst was prepared by thermal decomposition of MO(CO)6, and CO chemisorption on the catalyst was investigated in-situ by thermal desorption spectroscopy (TDS) and X-ray photoelectron spectroscopy (XPS). The results showed that a molybdenum-carbonyl-like species was formed on the alumina surface at low temperature by high coordination of CO with the surface metallic molybdenum nanoparticles, indicating a reversible regeneration of molybdenum carbonyl on the alumina surface. CO chemisorption on the model catalyst surface caused the Mo 3d XPS peak to shift toward higher binding energy. The formed molybdenum carbonyl species appeared at about 240 K in the TDS. The supported metallic molybdenum nanoparticles were quite different from the bulk molybdenum in chemical properties, which indicated a prominent particle-size effect of the clusters.

Copper phthalocyanine on InSb(111)A?interface bonding, growth mode and energy band alignment

Copper phthalocyanine on InSb(111)A?interface bonding, growth mode and energy band alignment, D.A. Evans, H.J. Steiner, S. Evans, R. Middleton, T.S. Jones, S. Park, T.U. Kampen, D.R.T. Zahn, G. Cabailh and I.T. McGovern, J. Phys.: Condens. Matter, 15, S2729?S2740, (2003)

A fully integrated multi-channel detector for electron spectroscopy

Langstaff, David; Bushell, A.; Chase, T.; Evans, D.A., (2005) 'A fully integrated multi-channel detector for electron spectroscopy', Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms 238 pp.219-223 RAE2008 Synchrotron Radiation in Materials Science ? Proceedings of the 4th Conference on Synchrotron Radiation in Materials Science 4th Conference on Synchrotron Radiation in Materials Science

Multi-scale modelling of atomic layer deposition

High-permittivity ("high-k") dielectric materials are used in the transistor gate stack in integrated circuits. As the thickness of silicon oxide dielectric reduces below 2 nm with continued downscaling, the leakage current because of tunnelling increases, leading to high power consumption and reduced device reliability. Hence, research concentrates on finding materials with high dielectric constant that can be easily integrated into a manufacturing process and show the desired properties as a thin film. Atomic layer deposition (ALD) is used practically to deposit high-k materials like HfO2, ZrO2, and Al2O3 as gate oxides. ALD is a technique for producing conformal layers of material with nanometer-scale thickness, used commercially in non-planar electronics and increasingly in other areas of science and technology. ALD is a type of chemical vapor deposition that depends on self-limiting surface chemistry. In ALD, gaseous precursors are allowed individually into the reactor chamber in alternating pulses. Between each pulse, inert gas is admitted to prevent gas phase reactions. This thesis provides a profound understanding of the ALD of oxides such as HfO2, showing how the chemistry affects the properties of the deposited film. Using multi-scale modelling of ALD, the kinetics of reactions at the growing surface is connected to experimental data. In this thesis, we use density functional theory (DFT) method to simulate more realistic models for the growth of HfO2 from Hf(N(CH3)2)4/H2O and HfCl4/H2O and for Al2O3 from Al(CH3)3/H2O.Three major breakthroughs are discovered. First, a new reaction pathway, ’multiple proton diffusion’, is proposed for the growth of HfO2 from Hf(N(CH3)2)4/H2O.1 As a second major breakthrough, a ’cooperative’ action between adsorbed precursors is shown to play an important role in ALD. By this we mean that previously-inert fragments can become reactive once sufficient molecules adsorb in their neighbourhood during either precursor pulse. As a third breakthrough, the ALD of HfO2 from Hf(N(CH3)2)4 and H2O is implemented for the first time into 3D on-lattice kinetic Monte-Carlo (KMC).2 In this integrated approach (DFT+KMC), retaining the accuracy of the atomistic model in the higher-scale model leads to remarkable breakthroughs in our understanding. The resulting atomistic model allows direct comparison with experimental techniques such as X-ray photoelectron spectroscopy and quartz crystal microbalance.

Synthesis and characterization of oxide materials

Nanostructured materials are central to the evolution of future electronics and biomedical applications amongst other applications. This thesis is focused on developing novel methods to prepare a number of nanostructured metal oxide particles and films by a number of different routes. Part of the aim was to see how techniques used in nanoparticle science could be applied to thin film methods to develop functional surfaces. Wet-chemical methods were employed to synthesize and modify the metal oxide nanostructures (CeO2 and SiO2) and their structural properties were characterized through advanced X-ray diffraction, electron microscopy, photoelectron spectroscopy and other techniques. Whilst particulates have uses in many applications, their attachment to surfaces is of importance and this is frequently challenging. We examined the use of block copolymer methods to form very well defined metal oxide particulate-like structures on the surface of a number of substrates. Chapter 2 describes a robust method to synthesize various sized silica nanoparticles. As-synthesized silica nanoparticles were further functionalized with IR-820 and FITC dyes. The ability to create size controlled nanoparticles with associated (optical) functionality may have significant importance in bio-medical imaging. Thesis further describes how non-organic modified fluorescent particles might be prepared using inorganic oxides. A study of the concentrations and distributions of europium dopants within the CeO2 nanoparticles was undertaken and investigated by different microscopic and spectroscopic techniques. The luminescent properties were enhanced by doping and detailed explanations are reported. Additionally, the morphological and structural evolution and optical properties were correlated as a function of concentrations of europium doping as well as with further annealing. Further work using positron annihilation spectroscopy allowed the study of vacancy type defects formed due to europium doping in CeO2 crystallites and this was supported by complimentary UV-Vis spectra and XRD work. During the last few years the interest in mesoporous silica materials has increased due to their typical characteristics such as potential ultra-low dielectric constant materials, large surface area and pore volume, well-ordered and uniform pores with adjustable pores between 2 and 50 nm. A simple, generic and cost-effective route was used to demonstrate the synthesis of 2D mesoporous silica thin films over wafer scale dimensions in chapter 5. Lithographic resist and in situ hard mask block copolymer followed by ICP dry etching were used to fabricate mesoporous silica nanostructures. The width of mesoporous silica channels can be varied by using a variety of commercially available lithographic resists whereas depth of the mesoporous silica channels can be varied by altering the etch time. The crystal structure, morphology, pore arrangement, pore diameters, thickness of films and channels were determined by XRD, SEM, ellipsometry and the results reported. This project also extended work towards the study of the antimicrobial study of nanopatterned silver nanodot arrays formed using the block copolymer approach defined above. Silver nanodot arrays were successfully tested for antimicrobial activity over S. aureus and P. aeruginosa biofilms and results shows silver nanodots has good antimicrobial activity for both S. aureus and P. aeruginosa biofilms. Thus, these silver nanodot arrays shows a potential to be used as a substitute for the resolution of infection complications in many areas.

3D vanadium oxide inverse opal growth by electrodeposition

Three-dimensional vanadium pentoxide (V2O5) material architectures in the form of inverse opals (IOs) were fabricated using a simple electrodeposition process into artificial opal templates on stainless steel foil using an aqueous solution of VOSO4.χH2O with added ethanol. The direct deposition of V2O5 IOs was compared with V2O5 planar electrodeposition and confirms a similar progressive nucleation and growth mechanism. An in-depth examination of the chemical and morphological nature of the IO material was performed using X-ray crystallography, X-ray photoelectron spectroscopy, Raman scattering and scanning/transmission electron microscopy. Electrodeposition is demonstrated to be a function of the interstitial void fraction of the artificial opal and ionic diffusivity that leads to high quality, phase pure V2O5 inverse opals is not adversely affected by diffusion pathway tortuosity. Methods to alleviate electrodeposited overlayer formation on the artificial opal templates for the fabrication of the porous 3D structures are also demonstrated. Such a 3D material is ideally suited as a cathode for lithium ion batteries, electrochromic devices, sensors and for applications requiring high surface area electrochemically active metal oxides.

Deposition of silver nanoparticles in geochemically heterogeneous porous media: predicting affinity from surface composition analysis.

The transport of uncoated silver nanoparticles (AgNPs) in a porous medium composed of silica glass beads modified with a partial coverage of iron oxide (hematite) was studied and compared to that in a porous medium composed of unmodified glass beads (GB). At a pH lower than the point of zero charge (PZC) of hematite, the affinity of AgNPs for a hematite-coated glass bead (FeO-GB) surface was significantly higher than that for an uncoated surface. There was a linear correlation between the average nanoparticle affinity for media composed of mixtures of FeO-GB and GB collectors and the relative composition of those media as quantified by the attachment efficiency over a range of mixing mass ratios of the two types of collectors, so that the average AgNPs affinity for these media is readily predicted from the mass (or surface) weighted average of affinities for each of the surface types. X-ray photoelectron spectroscopy (XPS) was used to quantify the composition of the collector surface as a basis for predicting the affinity between the nanoparticles for a heterogeneous collector surface. A correlation was also observed between the local abundances of AgNPs and FeO on the collector surface.

Properties of InAlN/GaN Heterostructures Prepared by Molecular Beam Epitaxy

InAlN thin films and InAlN/GaN heterostructures have been intensively studied over recent years due to their applications in a variety of devices, including high electron mobility transistors (HEMTs). However, the quality of InAlN remains relatively poor with basic material and structural characteristics remain unclear.

Molecular beam epitaxy (MBE) is used to synthesize the materials for this research, as MBE is a widely used tool for semiconductor growth but has rarely been explored for InAlN growth. X-ray photoelectron spectroscopy (XPS) is used to determine the electronic and chemical characteristics of InAlN surfaces. This tool is used for the first time in application to MBE-grown InAlN and heterostructures for the characterization of surface oxides, the bare surface barrier height (BSBH), and valence band offsets (VBOs).

The surface properties of InAlN are studied in relation to surface oxide characteristics and formation. First, the native oxide compositions are studied. Then, methods enabling the effective removal of the native oxides are found. Finally, annealing is explored for the reliable growth of surface thermal oxides.

The bulk properties of InAlN films are studied. The unintentional compositional grading in InAlN during MBE growth is discovered and found to be affected by strain and relaxation. The optical characterization of InAlN using spectroscopy ellipsometry (SE) is also developed and reveals that a two-phase InAlN model applies to MBE-grown InAlN due to its natural formation of a nanocolumnar microstructure. The insertion of an AlN interlayer is found to mitigate the formation of this microstructure and increases mobility of whole structure by fivefold.

Finally, the synthesis and characterization of InAlN/GaN HEMT device structures are explored. The density and energy distribution of surface states are studied with relationships to surface chemical composition and surface oxide. The determination of the VBOs of InAlN/GaN structures with different In compositions are discussed at last.

Tailoring the morphology of WO₃films with substitutional cation doping: Effect on the photoelectrochemical properties

With the aim of improving the performance and extending the range of applications of mesoporous WO₃films, which were initially developed for the photoelectrochemical oxidation of water, we investigated the effect of a number of dopants (lithium, silicon, ruthenium, molybdenum and tin) upon the transparency, crystallinity, porosity and conductivity of the modified films. Tin, molybdenum and silicon were shown to improve the electrochromic behaviour of the layers whereas ruthenium enhanced considerably the electronic conductivity of the WO₃films. Interestingly, most of the dopants also affected the film morphology and the size of WO₃nanocrystals. X-ray photoelectron spectra revealed absence of significant segregation of doping elements within the film. Raman analyses confirmed that the monoclinic structure of WO₃films does not change upon substitutional cation doping; thus, the crystallinity of WO₃films is maintained.