Styrene (C2H3-C6H5) is expected to have a more complex reaction process due to active reaction sites located in both vinyl group and phenyl group. Our exploration indicates that the adsorption products are coverage dependent. At low coverage, both vinyl group and phenyl group are possible to take part in the adsorption process. A new AsymT adsorption state covered two adjacent Si dimers is identified through two [4+2] cycloaddition. At high coverage, only vinyl group can interact with Si dimer to form cis and trans stereoisomers with different thermal energies and kinetic reaction barriers. STM images and vibrational frequencies are also explored to further support the experimental observations. / The adsorption of unsaturated organic molecules on reconstructed Si(100) surface is widely applied in the modification and functionalization of silicon surface to design new semiconductor materials. The present project is devoted to explore the adsorption mechanisms and the related properties of adsorption species for unsaturated organic molecules: acetylene (C2H 2), ethylene (C2H4), vinyl bromide (C2H 3Br) and styrene (C8H8) by quantum chemical calculation, based on density functional theory (DFT) method with pseudopotentials and plane wave basis set. / The investigation of vinyl bromide (C2H3Br) chemisorption on Si(100) resolves the conflicting conclusions between previous experimental and theoretical studies. The orientation of the vinyl bromide molecule relative to the titled silicon dimer is found to be an important factor for both the stability and reactivity of the precursor state. A new precursor pi-complex is identified, which is metastable and trapped by barriers around 0.1eV. Comparisons between theoretical and experimental vibrational frequencies support the conclusion that such a pi-complex is present on the surface at very low temperature. Careful analysis on the electronic structure also demonstrates that it is indeed a pi-complex rather than a diradical as previously suggested. Reaction mechanisms at higher vinyl bromide coverage are also modeled to explain the decrease in activation barrier observed in experiments. / The reaction processes for acetylene (C2H2) and ethylene (C2H4) chemisorption on the surface silicon dimer and the sub-layer silicon atoms are compared. Acetylene can undergo a new type of cycloaddition on sub-layer Si atoms (called sub-di-sigma) with no barrier, which is identified by ab initio Molecular Dynamics. The related properties including vibrational frequencies and STM images are calculated and found to be similar with those of the end-bridge adsorption structure. The identification of such a sub-di-sigma adsorption structure explains the discrepancy between STM experiments and theoretical calculations. In addition, the analysis of calculated vibrational frequencies, simulated STM images and the reaction barriers for di-sigma and end-bridge structures indicate that inter-dimer reaction for C2H4 is possible. / Zhang, Qiuji. / Adviser: Zhi Feng Liu. / Source: Dissertation Abstracts International, Volume: 70-09, Section: B, page: . / Thesis submitted in: October 2008. / Thesis (Ph.D.)--Chinese University of Hong Kong, 2009. / Includes bibliographical references (leaves 86-87). / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Electronic reproduction. [Ann Arbor, MI] : ProQuest Information and Learning, [200-] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstracts in English and Chinese. / School code: 1307.

The aim of the research presented in this thesis was to increase the understanding of the interaction between polymeric dispersants and titania pigment particles. In particular, the effects of dispersants of varied functionalities on the pigment dispersion behaviour in both aqueous suspension and dry paint film were investigated. / thesis (PhDEng(MineralsandMaterials))--University of South Australia, 2004.

A combination of surface analytical techniques, colloid probe Atomic Force Microscopy (AFM) and X-ray Photoelectron Spectroscopy (XPS) was used to optimise the grafting density of covalently attached 5, 20 and 40 kDa methoxy-terminated PEO layers (under marginal solvation (cloud point) conditions for the PEO molecules). The combination of these techniques allowed us to relate the PEO layer density and molecular conformations to the range, magnitude and types of forces generated by coatings of various grafting densities. The key optimisation parameter was the grafting time with the concentration of PEO in solution having a weaker effect. Oxidation of the substrate occurred, but did not significantly limit the surface density of the functional groups used to chemically attach the PEO molecules. Interactions between the substrate and silica were electrostatic in origin and did not contribute to the interaction between silica and the PEO surfaces due to salt screening effects Surfaces with dense, highly stretched PEO layers (brushes) generated purely repulsive forces at all separation distances, arising from compression by the silica spherical probe used. The force profiles for lower density surfaces comprised long-ranged attractive and short-ranged repulsive forces. The attractive forces were most likely due to attractive bridging interactions between the PEO chains and the SiO2 surface. For low grafting densities, i.e. inter-chain grafting distances, s &gt ??RF, the PEO layers were not strongly stretched and free to adsorb onto the opposing silica surface. XPS analysis demonstrated that HSA and Fibrinogen adsorbed onto low density 20 kDa PEO coatings (s &gt ??RF), most likely via diffusion through the PEO layer. No protein adsorption was found (detection limit &gt 10 ng/cm2) on high density, ???strongly stretched brush??? coatings (s &lt ?? RF). Analysis of data from the more sensitive Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS) techniques indicated that low amounts of adsorbed HSA, lactoferrin, lysozyme, and IgG were present on high density 20 and 40 kDa surfaces; the most likely explanation being attractive interactions between the proteins and the PEO layers during the protein adsorption experiments. ToF-SIMS data obtained for the strongly stretched (s &lt ?? RF) 5 kDa PEO surfaces suggested that no protein was adsorbed, in line with the XPS data for the same surfaces.

Polystyrenes with carboxyl end-groups (PS-COOH)and poly (tert-butyl acrylates) (PtBA) of different molar mass were synthesised by anionic polymerisation using n-butyllithium as the initiator. Gel permeation chromatography (GPC) was used to calculate the molecular weight and polydispersity of these polymers. The tacticity of these polymers was determined using Carbon 13 Nuclear Magnetic Resonance Spectroscopy (13C NMR). FT-IR was used to confirm the tacticity of the samples. Matrix-assisted laser desorption ionisation time-of-flight mass spectrometry (MALDI-TOF) was used to confirm the presence of the carboxyl end-groups. All of the films studied in this project were transferred to mica substrates using the Langmuir-Blodgett deposition method. Both single layer and multiple layer films were constructed using this technique. Atomic force microscopy (AFM) was used to observe the surface topology of these films. / Doctor of Philosophy (PhD) (Science)

In order to clarify the role that water plays in the photocatalytic process, changes in the IR and Raman spectra of P25 TiO₂ thin films were observed upon exposure to liquid water. Further investigation of these spectral changes via dehydration of thin films under nitrogen and oxygen of different humidities led to the observation of spectroscopic features that have been assigned to localised surface phonon modes. When the effect of UV irradiation on these features was investigated, a broad IR absorption due to transitions of electrons in shallow traps was detected under dry nitrogen but not under dry oxygen. Further investigation of the photocatalytic properties of P25 TiO₂ showed a complete removal of a stearic acid film. The final products have been tentatively assigned to a mixture of short chain carbonyl species and adsorbed carbonates as well as carbon dioxide and water. The IR spectrum of the fuel cell membrane material Nafion is complex and literature data varies in some of the assignments. The compound perfluoro(2-ethoxyethane)sulfonic acid was used as a model compound for the Nafion side chain resulting in a clearer assignment of the Nafion IR spectrum. In light of these new assignments changes induced in the region 1100-1300 cm⁻� by variation in humidity and ion exchange have been shown to be mainly the result of changes in the sulfonate asymmetric stretching modes. By flowing a series of solutions containing tetramethylammonium ions and perchlorate ions the surface charge characteristics of a Pt black film were determined in the pH range 2-12. There proved to be a weak positive charge below pH 4 and a weak negative charge above pH 9. Between these points there appeared to be no overall charge on the surface. When perfluoro(2-ethoxyethane)sulfonic acid was adsorbed to a Pt black film changes in its IR spectrum indicated a strong binding via interactions between the sulfonate groups and the Pt surface. The nature of the adsorption of Nafion was less clear cut and, whilst adsorption is strong, it seems possible that hydrophobic interactions between the Nafion backbone and the surface are involved.

This thesis presents: 1) literature review on adhesive bonding technologies in aviation industry including surface pretreatments (pre-preparation), surface quality assurance, and surface chemistry analysis methods; and 2) development and study of a novel solid-state electrochemical sensor for surface chemistry analysis of composite surfaces. The performance of an adhesive bonding is greatly determined by the adherend?s surface pretreatments which could increase surface tension, surface roughness, and change surface chemistry thereby increasing bond strength and durability of polymer composite adhesive joints. The primary goal of the surface pretreatments is to increase the surface roughness, surface energy, chemical activity, and cleanliness of the composite adherend as much as possible. Methods of surface pretreatments are reviewed in this paper, including: (1) abrasion/solvent cleaning; (2) grit blasting; (3) peel-ply; (4) tear-ply; (5) acid etching/anodizing; (6) corona discharge treatment; (7) plasma treatment; (8) flame treatment; (9) laser treatment; (10) others. One of the critical issues in aviation industry for an adhesive bonding is to analyze the prepared composite surfaces using a nondestructive inspection (NDI) or nondestructive test (NDT) method to determine whether the quality of surfaces are ready for the following bonding processes. Existing NDI methods include: (1) Near-Infrared; (2) Electrical potential; (3) Transient thermal NDT; (4) Electrical Impedance Spectroscopy (EIS); (5) Neutron radiography; and (6) X-ray Photoelectron Spectroscopy (XPS). However, up till now, these methods cannot provide definitive analysis or online and in-field analysis. Because of the non-availability of an on-line, in-field NDI method for surface chemistry analysis, excess or inadequate surface treatment and quality control processes may exist in the current aircraft manufacture processes incurring either a high cost or potentially weak adhesive bonds. Electrochemical reactions usually occur in liquid electrolyte or on conducting electrode but not on non-conducting composite. Conventional electrochemical sensors involve liquid electrolytes which will cause contamination on composite surfaces when they are used for surface chemistry analysis. In this work, we explore an all solid-sate electrochemical sensor technology. Redox pairs or mediators are combined into a solid-state electrolyte, NafionTM. The mediators can pass electrons to or from the composite surfaces causing slight reduction or oxidation of the composite surfaces. The output current in response to cyclic polarization (cyclic potential scanning) is used as the indication of the surface contamination level. The sensors included a working or sensing electrode with mediated Nafion clusters, Nafion membrane, Pt catalyzed carbon counter electrode, and Ag|AgCl reference electrode. The working electrode and counter electrode were attached to the Nafion membrane from different sides. The sensors were tested on different kinds of surfaces: original, polished, and sulfuric acid treated acrylic samples and pristine peel ply prepared, polished, and sulfuric acid treated composite laminate surface samples. The sensors showed a high sensitivity to the surface contamination. The performances and possible mechanisms related to the electrochemical sensors are discussed.

Graduation date: 1991

The dissociative adsorption of three carboxylic acids (acetic acid, propanoic acid, and acrylic acid), allyl alcohol, and allyl aldehyde on Si(100)2×1 at room temperature has been investigated by X-ray photoelectron spectroscopy (XPS) and temperature programmed desorption (TPD), as well as density-functional theory (DFT) calculations. The C 1s features obtained by XPS measurement for acetic acid, propanoic acid, and acrylic acid show that formation of bidentate carboxylate at a low exposure is followed by that of unidentate carboxylate at a higher exposure, with approximately equal population for both adstructures. The signatures of C 1s features attributed to methyl (285.7 eV), ethyl (285.3 eV), ethenyl (285.0 eV), and bidentate carboxyl (286.8 eV) and unidentate carboxyl (289.8-289.3 eV) carbons were observed for the studied carboxylic acids. The results showed that the carboxyl group is more reactive than the alkyl or alkenyl group towards the Si(100)2×1 surface, with O−H dissociation preferred over [2+2] C=C cycloaddition and the other plausible reaction products. This was also supported by our DFT calculation which showed that the bidentate carboxylate adstructure is the most stable configuration among the calculated adstructures for the aforementioned carboxylic acids. The combined temperature-dependent XPS and TPD studies provided strong evidence for the formation of ketene, acetaldehyde and CO from acetic acid, CO and ethylene from propanoic acid, and CO, ethylene, acetylene, and propene from acrylic acid. Furthermore, the TPD results provided further evidence for the preferred structure of the adsorbate from each of the carboxylic acid on the surface. In addition to carboxyl group, reactivity of the hydroxyl and carbonyl functional groups relative to that of ethenyl group was studied by investigating the reaction of allyl alcohol and allyl aldehyde on Si(100)2×1 at room temperature. The C 1s XPS results supported O−H dissociation for allyl alcohol and [2+2] C=O cycloaddition for allyl aldehyde over the [2+2] C=C cycloaddition. The similarity between the observed C 1s features for allyl alcohol and allyl aldehyde helped to identify the structure of the adsorption products of these two molecules on the surface. The presence of the related C 1s feature of C=C for allyl alcohol and allyl aldehyde, and the absence of C 1s feature of C=O for allyl aldehyde provided strong evidence to support that [2+2] C=C cycloaddition does not occur in the presence of hydroxyl or carbonyl groups. Furthermore, by comparing the experimental results and the adsorption energies of the adstructures calculated by DFT, it was concluded that these molecules do not react with the Si dimers through both of their functional groups, while the reaction of only one of the two functional groups is preferred on the surface. Formation of ethylene, acetylene, and propene from allyl alcohol and allyl aldehyde, simultaneously to CO from allyl alcohol, was concluded from the corresponding TPD results, which also confirm the structure of the adsorbates on the surface. The present research shows that reactions involving oxygen-containing functional groups are favoured over the other plausible reactions including [2+2] C=C cycloaddition on the Si(100)2×1. The preference of the surface to react with one of the two functional groups calls for future studies for the selective functionalization of Si(100)2×1 with potential applications in molecular electronics.

The dissociative adsorption of three carboxylic acids (acetic acid, propanoic acid, and acrylic acid), allyl alcohol, and allyl aldehyde on Si(100)2×1 at room temperature has been investigated by X-ray photoelectron spectroscopy (XPS) and temperature programmed desorption (TPD), as well as density-functional theory (DFT) calculations. The C 1s features obtained by XPS measurement for acetic acid, propanoic acid, and acrylic acid show that formation of bidentate carboxylate at a low exposure is followed by that of unidentate carboxylate at a higher exposure, with approximately equal population for both adstructures. The signatures of C 1s features attributed to methyl (285.7 eV), ethyl (285.3 eV), ethenyl (285.0 eV), and bidentate carboxyl (286.8 eV) and unidentate carboxyl (289.8-289.3 eV) carbons were observed for the studied carboxylic acids. The results showed that the carboxyl group is more reactive than the alkyl or alkenyl group towards the Si(100)2×1 surface, with O−H dissociation preferred over [2+2] C=C cycloaddition and the other plausible reaction products. This was also supported by our DFT calculation which showed that the bidentate carboxylate adstructure is the most stable configuration among the calculated adstructures for the aforementioned carboxylic acids. The combined temperature-dependent XPS and TPD studies provided strong evidence for the formation of ketene, acetaldehyde and CO from acetic acid, CO and ethylene from propanoic acid, and CO, ethylene, acetylene, and propene from acrylic acid. Furthermore, the TPD results provided further evidence for the preferred structure of the adsorbate from each of the carboxylic acid on the surface. In addition to carboxyl group, reactivity of the hydroxyl and carbonyl functional groups relative to that of ethenyl group was studied by investigating the reaction of allyl alcohol and allyl aldehyde on Si(100)2×1 at room temperature. The C 1s XPS results supported O−H dissociation for allyl alcohol and [2+2] C=O cycloaddition for allyl aldehyde over the [2+2] C=C cycloaddition. The similarity between the observed C 1s features for allyl alcohol and allyl aldehyde helped to identify the structure of the adsorption products of these two molecules on the surface. The presence of the related C 1s feature of C=C for allyl alcohol and allyl aldehyde, and the absence of C 1s feature of C=O for allyl aldehyde provided strong evidence to support that [2+2] C=C cycloaddition does not occur in the presence of hydroxyl or carbonyl groups. Furthermore, by comparing the experimental results and the adsorption energies of the adstructures calculated by DFT, it was concluded that these molecules do not react with the Si dimers through both of their functional groups, while the reaction of only one of the two functional groups is preferred on the surface. Formation of ethylene, acetylene, and propene from allyl alcohol and allyl aldehyde, simultaneously to CO from allyl alcohol, was concluded from the corresponding TPD results, which also confirm the structure of the adsorbates on the surface. The present research shows that reactions involving oxygen-containing functional groups are favoured over the other plausible reactions including [2+2] C=C cycloaddition on the Si(100)2×1. The preference of the surface to react with one of the two functional groups calls for future studies for the selective functionalization of Si(100)2×1 with potential applications in molecular electronics.

Adsorption at metal electrodes is usually a very fast process and it plays a most important role in many areas of industry. The thermodynamics of the process are well known for many systems. However, there is currently no good method that allows a determination of very fast kinetics of adsorption to be made. Previously, many attempts at evaluation of kinetic parameters of adsorption were made, but in moat cases, due to the inadequacy of the experimental methods used, the parameters obtained were much lower than expected. This thesis aims at providing the means for determining the kinetics of adsorption at metal electrodes. The methods herein described are based on two different experimental techniques. These techniques are: (i) fast cyclic voltammetry (FCV, potential sweep rate up to 100000 V/s) and (ii) high frequency AC and FFT SW (Fast Fourier Transform Square-wave) voltammetry (frequency up to 50 MHz) at ultramicroelectrodes (5 or 6.25 ìm in radius). A theoretical description of the adsorption process for both kinds of experiments is presented. A simulation program was written to provide a better understanding of the process and to elucidate the development of methods for determining the kinetics of adsorption. Thermodynamic and kinetic descriptions of the process are based on the Frumkin adsorption isotherm. Both the equilibrium constant and the adsorption rate constant are treated as functions of potential and the electrode coverage. Comparison of results for different systems is presented as an analysis of the dependence of the adsorption rate constant on the equilibrium constant. FCV proved to be useful in the evaluation of kinetics of chemisorption (standard rate constant in the range of 10⁶ s$\sp{-1})$ but the results for adsorption of aliphatic alcohols were unreliable. High frequency AC methods allowed the determination of kinetics of physical adsorption. It was found that the activation energy of the adsorption process can be expressed as a linear combination of the electrical component of the standard free energy of adsorption (a major contribution) and the energy of lateral interactions (a minor contribution). At the zero charge potential the rate constant reaches the maximum value of $\rm(4.6\pm0.3)10\sp9\ s\sp{-1}.$