Dissertations / Theses on the topic 'Titania surface'

In this thesis, surface sensitive techniques have been employed to investigate the surface chemistry of TiC>2. A bottom-up approach was used to grow ultra-thin films of rutile TiO2(110) on Ni(110). The surface structure of this system was probed using scanning tunnelling microscopy (STM) and low energy electron diffraction (LEED), whereas the electronic structure was characterised with soft X-ray photoelectron spectroscopy (SXPS). SXPS was also used to investigate the reactivity of this system towards water. While optimising the conditions for the growth of the desired titania phase, the growth of other structures commonly found in reduced native TiC>2 crystals were apparent from STM and LEED observations. The formation of 1x2 reconstructed TiO2(110) and crystallographic shear planes are reported. These phases are assigned by comparison with previous studies of analogous phases on the native rutile TiC>2(110) surface. STM was also used to monitor chemical reactions on native TiO2(110) surfaces. The reaction of surface bridging hydroxyl groups with molecular oxygen at room temperature was imaged directly. After exposure to O2, nearly all bridging hydroxyl groups are consumed, and new, mobile adsorbates appear with a range of apparent heights. With the support of calculations performed by Hofer's group in the University of Liverpool and Fisher's group in UCL, the adsorbates left on the surface after the reaction are assigned to neutral and charged oxygen adatoms as well as terminal hydroxyls. Finally, the surface local density of states of TiO2(110) were measured using scanning tunnelling spectroscopy. Energetically localised states are found at sample biases of +0.2 V, 0.7 V and 1.9 V. Additionally, a surface state at 1.9 V is localised spatially at two adjacent titanium five-fold atoms near to the positions of surface oxygen vacancies.

This thesis presents surface science studies, investigating several aspects of titanium dioxide at the atomic scale. The greater part of this work is devoted to the preparation by chemical vapor deposition (CVD) of titanium(IV) tetraisopropoxide (TTIP) of ultrathin TiO2 or TiOx films on Au(111). Four ordered structures were growth and characterized. It was also demonstrated how the morphology of the film (wetting film vs island) can be tailored. The acquired knowledge about the CVD process was exploited to load nano porous gold with titania, enhancing its catalytic activity. The reactivity towards water adsorption of the titania structures on Au(111) was also investigated. Finally, part of this work concerned the studying of the behavior of water on the stoichiometric rutile TiO2(110) surface, combining the experiments with density-functional theory (DFT) calculations and (kinetic) Monte Carlo simulations. The main experimental techniques used in this work are low-energy electron diffraction (LEED), scanning tunneling microscopy (STM) and photoelectron spectroscopy (PES).

Wide band gap metal oxides have recently become one of the most investigated materials in surface science. Among these metal oxides especially TiO2 attracts great interest, because of its wide range applications, low cost, biocompatibility and ease of analysis by all experimental techniques. The usage of TiO2 as a component in solar cell technology is one of the most investigated applications of TiO2 . The wide band gap of TiO2 renders it inecient for isolated use in solar cells. TiO2 surface are therefore coated with a dye in order to increase eciency. This type of solar cells are called dye sensitized solar cells . The eciency of dye sensitized solar cells is directly related with the absorbed light portion of the entire solar spectrum by the dye molecule. Inspite of the early dyes, recent dye molcules, which are called wider wavelength response dye molecules, can absorb a larger portion of entire solar spectrum. Thus, the eciency of dye sensitized solar cells is increased by a considerably amount. In this thesis the electronic structure of organic rings, which are the fundamental components of the dye molecules, adsorbed on anatase (001) surface is analyzed using density functionaltheory. The main goal is to obtain a trend in the electronic structure of the system as a function of increasing ring number. Electronic structure analysis is conducted through band structure and density of states calculations. Results are presented and discussed in the framework of dye sensitized solar cells theory.

This thesis focuses on understanding the influence of defect sites in titanium dioxide that drive many types of thermal and photochemical reactions. Two of the most common defects in vacuum are titanium interstitials and oxygen vacancies. Molecular oxygen fills oxygen vacancies and creates oxygen adatoms. We broadly investigate reduction and oxidation reactions of oxygenates driven by titanium interstitials and oxygen adatoms. First, we focus on the thermal chemistry of oxygen adatoms with butyrophenone and find that it reacts with the adatoms to form a strongly bound complex. The large difference in mobility between complexed and uncomplexed butyrophenone, and the corrugated nature of the \(TiO_2(110)\) surface plane, allows a confined one-dimensional gas to persist, which is characterized by scanning tunneling microscopy (STM). Next, we focus on the reductive coupling of benzaldehyde to stilbene that is driven by titanium interstitials. The diolate intermediate of the reaction is identified by STM and the thermodynamic preference of molecular oxygen to interact with titanium interstitials is exploited to selectively reverse the benzaldehyde diolate intermediates. Additionally, we investigate the photo-oxidative coupling of methanol to methyl formate, the photo-oxidation of butyrophenone and the photo-stability of benzoate. Finally, we identify a water splitting mechanism on reduced titania that creates oxygen adatoms. We demonstrate that the photo-generated oxygen adatoms thermally react with titanium interstitials to make TiOx islands and drive the photo-oxidation of formaldehyde and butyrophenone. Methods used include temperature programmed reaction spectroscopy, STM, and density functional theory.
Chemistry and Chemical Biology

The room temperature photocatalytic oxidation of carbon monoxide in excess air was examined over silica/titania and 0.1%palladium/silica/titania catalysts under UV irradiation. The experiments were conducted in batch re-circulated reactor with the initial 1000 ppm carbon monoxide in air and 0.5 g catalyst charge and the conversion of carbon monoxide to carbon dioxide was followed by FT-IR spectro-photometer. The change in gas composition in dark and under 36 Watts of UV irradiation exposed to a catalyst area of 12.4 centimeter square indicated both adsorption of carbon monoxide and conversion of carbon monoxide to carbon dioxide over the catalyst samples. The effect of catalyst composition (silica/titania) ratio and the presence of palladium oxide were investigated. The catalyst samples were synthesized by sol-gel technique and all samples were hydrothermally treated before calcination in air. The catalyst samples were characterized by XRD and nitrogen adsorption techniques. XRD results indicated that titania is comprised of pure anatase phase and palladium oxide preferantially dispersed over titania. BET surface area of the samples were observed to increase with silica loading and the BJH results showed isotherms of Type V v with H2 hysteresis loops. The highest carbon monoxide adsorption rate constant was achieved with pure silica with the highest surface area. Photocatalytic activity measurements indicated that carbon monoxide in excess air can be successfully oxidized at room temperature over the titania photocatalyts. Higher physisorption was observed over higher silica containing samples and higher oxidation activity was observed with increasing titania/silica ratio. The optimum titania/silica ratio was determined by the titania content and surface area of catalyst. The activity tests were also indicated that the addition of palladium oxide phase synergistically increased the adsorption and oxidation activity of the catalysts.

In this study photocatalytic antibacterial and self-cleaning activities of TiO2-SiO2 thin films as a function of TiO2/SiO2 ratios were investigated. TiO2-SiO2 mixed oxides were synthesized by sol-gel method and coated over soda-lime glass plates by dip coating technique. Escherichia coli was used as a model microorganism for the photocatalytic antibacterial tests. Degradation rate of methylene blue (MB) molecules was used to characterize photocatalytic self-cleaning activities of thin film surfaces. The maximum antibacterial activity was achieved over 92 wt% SiO2 containing thin films. However, when the SiO2 content exceeds 92 wt%, photocatalytic antibacterial activity decreased considerably, which was explained by the dilution of TiO2 phase and inaccessibility of TiO2. Increase in photocatalytic antibacterial activity was attributed to increases in the relative surface area, roughness, hydroxyl (OH-) groups and bacterial adhesion. The favored bacterial adhesion enhanced direct contact of bacteria with TiO2 particles and surface reactive oxygen species. The highest initial decomposition rate of MB was obtained for 60 wt% SiO2 and the activity decreases as SiO2 concentration increases. The increase in photocatalytic activity by the SiO2 addition can be explained by the increase of the amount of MB per unit area of TiO2-SiO2 thin films. Different adsorption capability of thin films against MB molecule and E. coli cell was explained as the first reason why the antibacterial and self-cleaning activities reached their maximum values at different SiO2 ratios. The second reason could be related with the different control mechanisms of self-cleaning and antibacterial activities by different textural and surface properties.

The aim of this study was to investigate the viability of patterning by immobilization, photocatalytic removal, and re-immobilization steps of the enzyme on photocatalytically active thin films for biosensor fabrication purposes. For this aim, TiO2-SiO2-Au sol-gel colloids were synthesized and deposited on glass substrates as thin films by dip coating. Cysteamine linker was assembled on gold nanoparticles to functionalize thin films with amine groups for immobilization of model enzyme invertase. Effect of immobilization temperature, enzyme concentration of the immobilization solution and immobilization period on invertase immobilization were investigated. The immobilized invertase activity was found independent from the immobilization temperature in the range tested (4oC-room temperature). The optimum enzyme concentration and period for immobilization was determined as 10µ
g/ml and 12 hours respectively. The resulting invertase immobilized thin films showed high storage stability retaining more that 50% of their initial activity after 9 weeks of storage. Photocatalytic enzyme removal and re-immobilization studies were carried out by irradiating the invertase immobilized thin films with blacklight. Upon 30 minutes of irradiation, immobilized invertase was completely and irreversibly inactivated. Initial immobilized invertase activity (before the irradiation) was attained when invertase was re-immobilized on thin films that were irradiated for 5 hours. Thus it was inferred that with sufficient exposure, enzymes can be completely removed from the surfaces which makes the re-immobilization possible. The possibility of enzyme removal with photocatalytic activity and re-immobilization can pave the way to new patterning techniques to produce multi-enzyme electrode arrays.

Thesis (M. S.)--Materials Science and Engineering, Georgia Institute of Technology, 2008.
Committee Chair: Sandhage, Kenneth; Committee Member: Barefield, Kent; Committee Member: Bunz, Uwe; Committee Member: Carter, Brent; Committee Member: Tannenbaum, Rina.

Sample preparation is the most error-prone step in chemical analysis. A great deal of efforts has been made to develop efficient techniques and protocols for sample preparation to accomplish important goals such as miniaturization and implementation of green analytical methodologies. Solid-phase microextraction (SPME) has successfully eliminated the use of hazardous organic solvents in extraction sampling, sample preparation, preconcentration and sample introduction to the analytical instrument in an effective manner. Ensuring thermal- and solvent-instability of traditional SPME extraction phases represented one of their main drawbacks. This was solved by the introduction of sol-gel SPME phases characterized by enhanced thermal-, solvent-, and stability over a wide pH range. Sol-gel SPME phases (sorbents) facilitated excellent preconcentration effects for a wide range of analytes. In this dissertation, hydrolytic and nonhydrolytic sol-gel routes were explored for the creation of zirconia-, titania-, and niobia-based novel hybrid organic-inorganic sorbents using sol-gel active polymeric ligands. These sorbents were prepared in the form of surface coatings for capillary microextraction and preconcentration of biologically important molecules such as catecholamine neurotransmitters and phosphopeptides. In comparison with other sorbents made only of inorganic transition metal oxides, the presented sol-gel sorbents facilitated efficient desorption of the extracted analytes by LC-MS compatible mobile phases. The sol-gel zirconia- and titania-based hybrid sorbents provided pH-stable (pH range: 0 - 14) and derivatization-free extraction media that effectively overcame the major drawbacks of traditional sorbents for the analysis of catecholamines (silica-based sorbents suffer from narrow operational pH window while polymer-based sorbents require additional sample derivatization steps). The modification of the terminal hydroxy groups in PPO with ZrCl4 or TiCl4 provided an enhanced sol-gel reactivity of the polymer modified-terminals. Such a modification procedure allowed for an efficient incorporation of the polymeric ligand into the evolving sol-gel network. The effectiveness of the PPO modification was also evaluated by a systematic thermogravimetric investigation exploring the loading of the ligand in sol-gel hybrid sorbents, which revealed an enhanced ligand-loading achieved via the nonhydrolytic sol-gel route used with modified-PPO. Sol-gel hybrid sorbents prepared by the nonhydrolytic sol-gel (NHSG) pathway provided excellent microextraction performance for catecholamines: low detection limits (5.6 – 9.6 pM), enhanced run-to-run reproducibility (RSD 0.6 – 5.1 %), excellent desorption efficiency (95.0 – 99.5 %) and high enrichment factors (EF) for epinephrine (EF ~ 1480) and for dopamine (EF ~ 2650) extracted from aqueous and synthetic urine samples at pH 10.5. Run-to-run and capillary-to-capillary reproducibility remained below 5 % when the peak area or the sorbent-mass was used as the reproducibility criterion. Niobia-based sol-gel sorbents prepared with and without organic ligand (polyethylenimine) were utilized as microextraction media for the enrichment of phosphorylated and nonphosphorylated tetrapeptide VYKA. Sol-gel niobia-based sorbents with covalently anchored polyethylenimine showed excellent selectivity toward the phosphopeptide compared to analogous titania-based sorbents. Specific extraction (SE) values were higher by 97.0 % when obtained by niobia-based sorbents. Excellent run-to-run peak area reproducibility (RSD < 5.1 %) and high EF of ~ 4000 were achieved. The sol-gel niobia-based coating facilitated excellent desorption efficiency (97.5 %), which suggests that the surface of the niobia sorbent possesses moderate-strength Lewis acid sites that avoided the need for special elution solvents that are conventionally used for the desorption of phosphorylated molecules from titania-based sorbents. The sol-gel pathway for the creation of microextraction phases is versatile and capable to provide unique control on the characteristics of the sorbents that are critically important for many sample preparation applications.

High-performance liquid chromatography (HPLC) is the most widely used analysis technique. However, its sensitivity is limited. Sample preconcentration methods, such as fiber-based solid-phase microextraction (SPME) and in-tube SPME (capillary microextraction) offer improved detection limits. It is, however, difficult to couple fiber SPME on-line with HPLC due to the need for complicated desorption devices. Such coupling is further complicated due to the limited solvent stability of the extracting phase both in the fiber and in-tube formats of SPME. In this research, surface-bonded sol-gel sorbents were developed to provide the solvent stability required for effective on-line hyphenation of capillary microextraction (CME) with HPLC. These sol-gel sorbents were prepared using (1) silica-based, (2) titania-based, and (3) germania-based sol-gel precursors. Sol-gel reactions were performed within fused silica capillaries to create a number of organic-inorganic hybrid sorbents in the form of surface-bonded coatings: (1) alkyl (methyl, octyl, octadecyl), (2) polydimethyldiphenylsiloxane, (3) titania poly(tetrahydrofuran), and (4) germania tri-block polymer. The sol-gel coated microextraction capillaries were capable of efficiently extracting a wide variety of analytes, including polycyclic aromatic hydrocarbons, ketones, aldehydes, aromatic compounds, amines, alcohols, and phenols with ng/L to pg/L detection limits. The sol-gel methyl coating demonstrated a counterintuitive ability to extract polar analytes. Sol-gel polydimethyldiphenylsiloxane coatings were found to be resistant to high temperature solvent exposure (150°C and 200°C), making them suitable for use in high-temperature liquid phase separations. To better understand how extraction takes place, effects of alkyl chain length and sol-gel precursor concentration were evaluated in the study on sol-gel alkyl coatings. The sol-gel titania poly(tetrahydrofuran) coating was also capable of extracting underivatized aromatic acids and polypeptides at pHs near their respective isolectric points. The sol-gel titania poly(tetrahydrofuran) coatings and the sol-gel germania tri-block polymer coatings demonstrated impressive resistance to extreme pH conditions, surviving prolonged exposure to 1.0 M HCl (pH approx. 0.0) and 1.0 M NaOH (pH approx. 14.0) with virtually no change in extraction behavior. Sol-gel germania tri-block polymer coatings were also stable under high temperature solvent conditions (200°C). In addition, for the first time, the analyte distribution constants between a sol-gel germania coating and the aqueous samples (Kcs) were determined.

Objective: Topography, chemistry, and energy of titanium (Ti) implants alter cell response through variations in protein adsorption, integrin expression, and downstream cell signaling. However, the contribution of surface energy on cell response is difficult to isolate because altered hydrophilicity can result from changes in surface chemistry or microstructure. Our aim was to examine a unique system of wettability gradients created on microstructured Ti on osteoblast maturation and phenotype. Method: A surface energy gradient was created on sand-blasted/acid-etched (SLA) Ti surfaces. Surfaces were treated with oxygen plasma for 2 minutes, and then allowed to age for 1, 12, 80, or 116 hours to generate a wettability gradient. Surfaces were characterized by contact angle and SEM. MG63 cells were cultured on SLA or experimental SLA surfaces to confluence on TCPS. Osteoblast differentiation (IBSP, RUNX2, ALP, OCN, OPG) and integrin subunits (ITG2, ITGA5, ITGAV, ITGB1) measured by real-time PCR (n=6 surfaces per variable analyzed by ANOVA/Bonferroni’s modified Student’s t-test). Result: After plasma treatment, SLA surface topography was retained. A gradient of wettability was obtained, with contact angles of 32.0° (SLA116), 23.3° (SLA80), 12.5° (SLA12), 7.9° (SLA1). All surfaces were significantly more hydrophilic than the original SLA surface (126.8°). Integrin expression was affected by wettability. ITGA2 was higher on wettable surfaces than on SLA, but was highest on SLA1. ITGAV and ITGB1 were decreased on hydrophilic surfaces, but ITGA5 was not affected. IBSP, RUNX2, and ALP increased and OPG decreased with increasing wettability. OCN decreased with increasing wettability, but levels on the most wettable surface were similar to SLA. Conclusion: Here we elucidated the role of surface energy on cell response using surfaces with the same topography and chemistry. The results show that osteoblastic maturation was regulated in a wettability-dependent manner and suggest that the effects are mediated by integrins.

Nanostructured materials are the next generation of high-performance materials, harnessing the novel properties of their nanosized constituents. The controlled assembly of nanosized particles and the design of the optimal nanostructure require a detailed understanding of particle interactions and robust methods to tune them. This thesis describes innovative approaches to these challenges, relating to the determination of Hamaker constants for iron oxide nanoparticles, the packaging of nanopowders into redispersible granules, the tuning of the wetting behavior of nanocrystals and the simulation of collective magnetic properties in arrays of superparamagnetic nanoparticles. The non-retarded Hamaker constants for iron oxides have been calculated from their optical properties based on Lifshitz theory. The results show that the magnitude of vdW interactions in non-polar solvents has previously been overestimated up to 10 times. Our calculations support the experimental observations that oleate-capped nanoparticles smaller than 15 nm in diameter can indeed form colloidally-stable dispersions in hydrocarbons. In addition, a simple procedure has been devised to remove the oleate-capping on the iron oxide nanoparticles, enabling their use in fluorometric assays for water remediation, with a sensitivity more than 100 times below the critical micelle concentration for non-ionic surfactants. Nanosized particles are inherently more difficult to handle in the dry state than larger micron-sized powders, e.g. because of poor flowability, agglomeration and potential toxicity. The rheology of concentrated slurries of TiO2 powder was optimized by the addition of sodium polyacrylate, and spray-dried into fully redispersible micron-sized granules. The polymer was embedded into the granules, where it could serve as a re-dispersing aid. Monte Carlo (MC) simulations have been applied to the collective magnetic behavior of nanoparticle arrays of various thicknesses. The decrease in magnetic susceptibility with the thickness observed experimentally was reproduced by the simulations. Ferromagnetic couplings in the arrays are enhanced by the finite thickness, and decrease in strength with increasing thickness. The simulations indicate the formation of vortex states with increasing thickness, along with a change in their orientation, which becomes more and more isotropic as the thickness increases.

At the time of the doctoral defense, the following paper was unpublished and had a status as follows: Paper 2: Manuscript.

Les chambres implantables sont des dispositifs médicaux utilisés pour l’'administration de produits de chimiothérapie et/ou de nutrition parentérale. Comme la plupart des implants médicaux, ces dispositifs peuvent être à l’'origine d’infections nosocomiales. L’'objectif de la thèse a été d’'étudier la contribution des modifications physico-chimiques de surface de matériaux à base de titane sur l’'adhérence de microorganismes. Des surfaces présentant différentes caractéristiques ont été élaborées et l’'adhérence de la bactérie Staphylococcus aureus et de la levure Candida albicans a été testée in vitro en conditions statiques. Des surfaces modèles de TiO2 présentant des rugosités à l’'échelle du nanomètre et du micromètre ont été élaborées avec des wafers de silicium revêtues d’'un film mince d’'oxyde de titane déposé par pulvérisation cathodique. Des surfaces d’'alliages de titane grade 2 et grade 5 ont été modifiées par polissage, sablage ou électroérosion, créant différentes morphologies. Il est apparu que le nombre de microorganismes adhérents changeait certes avec la rugosité, mais était fonction de la morphologie de surface des matériaux et de la taille du microorganisme. Des surfaces lisses de TiO2 ont ensuite été fonctionnalisées par greffage moléculaire pour modifier le caractère hydrophile/hydrophobe de surface. L’'étude de l’'adsorption de protéines du plasma sanguin, par QCM, a permis de mieux expliquer l’'adhérence de bactéries et de levures sur ces surfaces. L’'influence de la nutrition parentérale et des produits de chimiothérapie sur les surfaces a aussi été étudiée afin de se rapprocher des conditions d’'utilisation des chambres implantables
Totally implantable venous-access ports are medical devices used for the administration of chemotherapy drugs and/or parenteral nutrition. Infections can occur and it is indispensable in modern-day medical practice to prevent and reduce the rare infectious complications. In this context, the goal of this work was to study the contribution of the modification of physico-chemical properties of titanium based surfaces on the adherence of microorganisms. Surfaces with different characteristics were produced and the adherence of the bacterium Staphylococcus aureus and the yeast Candida albicans was studied in vitro in static conditions. Model surfaces made of titanium dioxide with roughness from nanometer to micrometer were elaborated using silicon wafers recovered with a thin film of titanium dioxide deposited by plasma vapor deposition. Titanium alloy surfaces (Ti grade 2 and Ti grade 5) were modified by polishing, grit-blasting or wire erosion, to create different surface morphologies. In vitro studies were performed and it was found that the number of adhering microorganisms changed with roughness, but more importantly with the surface morphology of the biomaterials and microorganisms size. Flat titanium dioxide thin films were then functionalized by molecular grafting to modify the hydrophobicity of the surface. Study of plasma protein adsorption, by QCM, allowed to better explain the adherence of bacteria and yeast onto these surfaces. The influence of parenteral nutrition and chemotherapy drugs was also studied in order to better approach the real conditions of totally implantable venous-access ports

In this thesis two studies of reactive metal adsorption upon a low index single crystal silicon dioxide surface are presented in addition to a study of sulphur adsorption upon a low index single crystal nickel surface. Chromium growth upon the a-quartz Si02(0001) (J84xJ84) Rll 0 surface is studied at three coverages, 0.25±O.08 ML, 0.5±O.16 ML and 1.0±0.33 ML, using surface extended x-ray absorption fine structure (SEXAFS). SEXAFS measurements, from the chromium K-edge, recorded at both grazing and normal incidence show that chromium growth proceeds via the formation of mesoscopic particles with a body centred cubic (b.c.c.) like structure having an average nearest neighbour Cr-Cr distance of 2.36±O.03 A. This represents a contraction of 5.6 % from the bulk b.c.c. lattice spacing of 2.49 A. There is no evidence of a surface reaction between chromium and the surface oxygen. SEXAFS was used to study titanium reactional growth on a-quartz (0001) (J84xJ84) Rll 0 and (lx1). Three nominal coverages were studied, 0.25±O.08 ML, 0.5±O.16 ML and 1.0±O.33 ML. Both normal and grazing incidence SEXAFS data were recorded and show the formation of a spatially extensive region in which an interfacial reaction has occurred between surface oxygen and adsorbate titanium atoms. Coupled with this is the formation of subnanometre titanium clusters. The metal oxide has nearest neighbour Ti-O distances close to those of both the anatase and rutile forms of titania with the metallic titanium clusters having a Ti-Ti distance within experimental error that of bulk hexagonal close packed (h.c.p.) titanium, 2.89 A. A re-examination of the surface geometry of Ni(1l0)c(2x2)S using SEXAFS has been performed. Data out to an electron wavevector of 9 A-I are analysed with a new code to assess the influence of multiple scattering. The first shell S-Ni distance is determined to be 2.20±O.02 A with the next nearest neighbour distance being 2.29±O.02 A, giving a top-layer Ni expansion of 14±3% relative to the bulk. The influence of multiple scattering does not significantly alter these values from earlier studies.

An investigation of surface structures formed on polycrystalline and single crystal TiO2 (titania) samples having under gone various heat treatments in a controlled hydrogen bearing atmosphere was conducted. The study included the recreation and examination of the process discovered by Sehoon Yoo at Ohio State University to form nanofibers on the surface of polycrystalline TiO2 disks. Fibers were formed by heating samples to 700??in a 5%H2 95%N2 gas stream. The nanofibers formed during this processes are approximately 5-20 nanometers in diameter and can be 100??f nanometers long. The fibers do not actually grow on the surface, but are what remain of the surface as the material around them is removed by the gas stream V i.e., nanocarving. The mechanism of fiber formation and the effect of varying experimental parameters remained unknown and were explored within this study. This included changing gas composition, flow rate, and changes in sample preparation. The effect of isovalent doping and impurities within the starting powder were examined. Sintering temperature and time was investigated to determine the effect of grain size and surface morphologies prior to nanocarving. The effect of elevated temperature and 5%H2 95%N gas on the surface of TiO2 single-crystal wafers was also investigated. Test methods include Thermogravimetric Analysis (TGA), Mass Spectrometry (MS), Scanning Electron Microscopy (SEM), and X-ray diffraction (XRD) analysis.

Biomaterial surface energy, chemical composition, charge, wettability and roughness all play an important role in determining the degree of the direct bone-to-implant interface, termed osseointegration. Surface chemistry, which is influenced by surface energy, wettability, and composition, is another factor that determines osteoblast phenotype and regulates osteoblast maturation. Increased surface energy is desirable for bone implants due to enhanced interaction between the implant surface and the biological environment. The extent of bone formation in vivo is also increased with increasing water wettability of implants. The physiological role of implant surface chemistry is important in determining the success of implant osseointegration because of molecular rearrangements, surface reactions, contamination, and release of toxic or biologically active ions that are determined by the starting chemistry. However, the role of surface chemistry on osteoblast response is not fully studied. Therefore, the overall goal of this dissertation is to understand how the surface chemistry, including wettability, chemical composition, and charge density, of titanium biomaterials impacts osteoblast maturation (in vitro). This study focuses on the general hypothesis that modifications of surface chemistry of titanium surfaces with sterilization or polyelectrolyte coating on titanium surfaces regulate osteoblast response.

Made available in DSpace on 2014-06-11T19:26:42Z (GMT). No. of bitstreams: 0 Previous issue date: 2004Bitstream added on 2014-06-13T18:55:02Z : No. of bitstreams: 1 sisti_ke_me_araca.pdf: 3618905 bytes, checksum: 81667dd0274261a8682b5422aae8f08f (MD5)
Universidade Estadual Paulista (UNESP)
O longo tempo de espera entre a cirurgia e a instalação da prótese sobre implante dentário, sempre preocupou os pesquisadores. Proposição: Estudar a superfície de implantes utilizando discos de titânio irradiados com feixe de laser. Método: A amostra foi irradiada com feixes de laser de alta intensidade (Nd-YAG), posteriormente depositado hidróxiapatita e submetido a tratamento térmico. Foi analisada sob MEV (Microscópio Eletrônico de Varredura) e realizada análise morfológica qualitativa com microfotografias em vários aumentos. Resultados: A superfície irradiada com laser apresentou deformidade superficial e característica isomórfica; a aplicação de hidroxiapatita pelo método de biomimético aumentou quantitativamente a área da superfície de titânio; a amostra demonstrou características não encontradas nos implantes disposto no mercado. Conclusões: deposição de hidroxiapatita, melhor característica isomórfica e aumento quantitativo da área superficial estudada.
Background: Delay between surgery and dentistry prosthesis is the important factory to studier. Proposition: The aim of this study has been to analyze the surface of titanium implants in the odontology. Methods: Titanium discs were treated with laser high insensitive (Nd-YAG), and deposited hydroxyapatite with thermal treatment. Sample received Morphological analyze qualitative for micrographies with many size in SEM (Scanning Electron Microscopy). Results: Surface laser irradiation shows roughness and isomorphic characteristic. The hydroxyapatite amplified the titanium surface area by method bio mimetic. Sample shows characteristics don t have in the market. Conclusions: The treatment surface showed hydroxyapatite, good isomorphic characteristic, amplification the titanium surface area.

Titanium has been used in bio-medical implants for decades due to its superior biocompatibility. To improve the osseointegration of dental and orthopaedic implants, various surface modification techniques have been used including laser surface texturing. In particular, short-pulsed lasers, such as femtosecond and picosecond lasers, are widely used for surface modification. In this thesis, commercially pure Ti surfaces are modified by a femtosecond laser to explore the relationship between surface topography, surface chemistry, surface wettability, and biocompatibility with the goal of improving the osseointegration of implants. The laser textured surfaces consist of 1μm wide grooves spaced 10 μm, 4.8 μm, 2.4 μm and 1.2 μm apart. Gradient configurations where the groove spacing varies are also investigated. Surface morphology was characterized using Optical Microscopy (OM), Scanning Electron Microscopy (SEM) and Atomic Force Microscopy (AFM). A custom-build contact angle measurement apparatus is used to investigate the wettability of the laser textured surfaces using the sessile drop method. Freshly laser-treated commercially pure Ti surfaces are found to be super-hydrophilic and become hydrophobic over time when exposed to air. The presence of grooves can accelerate the evolution of the contact angle over time, and introduces anisotropy in the wetting behavior (along vs. across the grooves). The hydrophilicity of laser treated surfaces can be retained by storing samples in ethanol. X-ray Photoelectron Spectroscopy (XPS) shows that the relative carbon content increases over time when Ti samples are exposed to air, which results in the subsequent evolution of the contact angle and cell response to laser textured Ti surfaces. Besides, laser treatment promotes the oxidation of pure Ti, and the product, TiO2, is responsible for the better biocompatibility. In vitro experiments using MG 63s osteoblast-like cells are implemented on laser-treated Ti surfaces and polished surfaces (control) with 1 day, 3 days and 7 days of cell culture. The best cell outcome was obtained by storing samples in air for 1 week, where storing for shorter or longer times resulted in the worst outcome, especially in the early stages of cell adhesion. There does not appear to be a direct link between wettability and the fate of cells on Ti surfaces. Indeed, while samples stored in air and ethanol have drastically different contact angle measurements (the former being hydrophobic and the latter hydrophilic), the cell behavior was unaffected. In addition, while wettability and laser treatment can affect the early stages of cell adhesion, they do not have a strong effect on the number of cells at longer incubation times (3 and 7 days). Laser machining does however affect the cell morphology and alignment, where cells preferentially align themselves parallel to the direction of the laser machined grooves with an elongated morphology.

This thesis is dedicated to the exploration of fluid phases confined in nanoporous materials using Nuclear Magnetic Resonance (NMR) techniques, with an aim to benefit catalysis research. Included in this report are studies of pure fluids and their mixtures, confined in titania and silica catalyst supports. These investigations are conducted at industrially-relevant, high-temperature (≥ 180 °C) and high-pressure conditions (up to 13 bar), made possible by a pilot-scale chemical reactor unit, designed to operate inside the strong magnetic fields of an NMR spectrometer. NMR spectroscopy, relaxation and pulsed field gradient (PFG) diffusion experiments were performed on each of the systems discussed in this report. Cyclohexane was initially studied inside a porous titania catalyst support at 188 °C and various pressures up to 13 bar. The adsorption and desorption processes of the cyclohexane were observed, revealing a number of previously unobserved phenomena. In addition to an overall, averaged diffusion coefficient, a slow diffusion coefficient was observed within the PFG NMR data attributable to surface diffusive processes occurring within the material. Additionally, T1 relaxation studies were found to provide experimental evidence for the differing configurations of adsorbed layers on the adsorption and desorption branch of the isotherm. Cyclohexane was subsequently studied alongside fluorobenzene in a series of silica catalyst supports of 6 nm, 10 nm and 20 nm pore size. In doing this, it was hoped that the multiple phenomena observed in the titania experiments might be deconvoluted, allowing a greater level of insight. The diffusivities of the fluids were found to differ significantly between the materials, and greater evidence was found of the slow-diffusing surface phase in each of the materials. Additionally, concentrations of cyclohexane and fluorobenzene in the gas and adsorbed layers inside the pore space were calculated via the results of the PFG NMR experiments, providing a map of confined phase behaviour. Competitive adsorption effects were found to become more significant, the smaller the pore size of the material. The results of the cyclohexane and fluorobenzene in silica studies were modelled, using approaches available in the literature, which were found to give varying levels of prediction. The data set acquired in this thesis was found to provide a useful standard, against which current and future models of confined phase behaviour might be verified.

Les sites actifs de l’époxydation des alcènes dans les catalyseurs au titane supporté sur silice sont des ions Ti(IV) isolés. La stratégie d’isolation de site adoptée ici consiste à greffer l’isopropoxyde de titane par réaction avec les groupements silanol de surface dont la densité est diminuée par « capping » chimique remplaçant le traitement thermique usuel, très énergivore. La technique du pochoir moléculaire à motifs périodiques (PMP) a été appliquée pour forcer l’isolation de site. Dans les silices poreuses mesostructurées par un tensio-actif, c’est ce dernier, partiellement extrait, qui génère l’effet PMP lors du capping. Son élimination à l’étape suivante libère des îlots de groupements silanol sur lesquels sont greffés les ions Ti(IV). Une étude spectroscopique quantitative menée en parallèle par FT-IR et par RMN du solide du 29Si démontre que le pochoir organique inverse formé de groupement organosilyls greffés est conservé à toutes les étapes de synthèse. La spectroscopie UV en corrélation avec l’activité catalytique en époxydation du cyclohexene montent que ces surfaces originales favorisent un nombre beaucoup plus grand de sites mononucléaires isolés que les surfaces de silice non modifiées. La démonstration est faite avec une fonction de capping dipodale, 1-2-ethanebis(dimethylsilyl) (EBDMS), beaucoup plus stable que le monopodal classique, trimethylsilyl (TMS). Par ailleurs, le pochoir organique inverse issu du TMS ou de EBDMS voit sa stabilité augmentée par traitement thermique tout en préservant son effet dispersant pour le titane. Pour ce faire, un suivi quantitatif de la décomposition des organosilanes greffés a été réalisé par RMN du solide du 29Si. Finalement, une description affinée et quantitative du mode de greffage du titane a été réalisée par simulation des spectres UV sur une série de catalyseurs supposant 5 types d’espèces comprenant les sites isolés et les clusters, les derniers se différenciant par leur gamme de taille
The active sites for epoxydation of alkenes in silica supported titanium catalysts are isolated Ti(IV) ions. The strategy for site isolation consists here to graft titanium isopropoxyde by reaction with surface silanol groups, the density of which is decreased by chemical capping instead of the energy consuming thermal treatment. The molecular stencil patterning technique (MSP) is applied to enforce site isolation. In mesostructured porous silicas, the partly extracted templating surfactant plays the role of a MSP mask during capping. Then, the elimination of the remaining surfactant liberates silanol islands for the grafting of Ti(IV) ions. Quantitative FT-IR and 29Si MAS-NMR studies reveal that the inverse organic stencil made of grafted organosilyls groups is maintained at each synthesis steps. Diffuse reflectance UV spectroscopy in correlation with the catalytic activity in epoxidation of cyclohexene show that these original surfaces favor the formation of a much larger number of isolated mononuclear sites than the unmodified silica surfaces. The demonstration is obtained using a dipodal organosilyl function, 1-2-ethanebis (dimethylsilyl) (EBDMS) that is much more stable than the classic and monopodal, trimethylsilyl (TMS). Besides, it is shown that the inverse organic stencil (from EBDMS or TMS) is stabilized further by thermal treatment while its dispersive effect on titanium can be preserved. The proof relies on a quantitative 29Si solid State NMR study. Finally, a refined description of the grafting mode of titanium was realized by simulation of the UV spectra of a large series of catalysts assuming only 5 different types of species including isolated species and clusters differentiated by the range of sizes

I have developed a model of aerosol microphysics and scattering in Titan's atmosphere that incorporates the concept of irregular aggregates. By comparing models with spacecraft observations of Titan's intensity and polarization phase laws and ground-based observations of Titan's solar reflection spectrum, I have constrained several properties of the aerosols. The aerosols are assumed to be irregular aggregates of small spheres made of Titan tholin--the spheres have a radius of approximately 0.06 μm, and through most of the atmosphere the aggregates comprise 10 to 100 spheres. The aggregates form at an altitude of 250 to 300 km, and are the primary source of scattering opacity down to the lower stratosphere, where there must be some removal process, such as rain-out, although there is likely to be some scattering opacity in the troposphere. This model fits the polarization data well, in addition to being highly forward scattering. It is used to predict the penetration of sunlight into the atmosphere, and it predicts that the surface becomes visible at wavelengths longer than about 0.9 μm. I then carried out a program of 0.9-2.3 μm spectroscopy of Titan in which Titan's albedo at wavelengths sensitive to the surface was monitored. Results of this program show that Titan's albedo does vary, with the leading hemisphere consistently brighter than the trailing hemisphere, and that the variations repeat with a period equal to Titan's orbital period. The source of the variation is very likely the surface, and there is no evidence of surface absorption features. The amplitude of the light-curve at 2 μm (32 ± 3%) suggests that the bright component is unlikely to have a strong 2 μm absorption feature, and, therefore, is not pure water ice. It is clear from the existence and repetition of the variation that the surface is not homogeneous, and specifically that a global ocean is not allowed.

Includes bibliographical references (leaves 97-101)
Two routes of Oxygen Diffusion Hardening (ODH) have been investigated on two alloys of titanium, Ti-6AI-4V and Ti-6AI-7Nb (by weight). The first route involves a controlled atmosphere where argon saturated with water was used to transport water into the test pieces at elevated temperatures. The controlled atmosphere would encourage the generation of mono-atomic oxygen through the dissociation of water vapour, and therefore change the kinetics of physical absorption and diffusion of oxygen into titanium. The second route of ODH investigated was the Oxygen Boost Diffusion Hardening (OBDH). The oxygen boost diffusion hardening process was carried out in two steps. The first step was oxidation of the samples in air at elevated temperatures and the second step was to further diffusion treat the pre-oxidised test pieces III a vacuum or argon. Various temperature and time combinations were used on both steps of OBDH.The results revealed that the ODH heat-treatment in a controlled saturated argon environment was unsuccessful in developing a significant oxygen diffusion hardened layer. The OBDH process can be carried out to modify the surface properties of titanium and alloys. Both steps of this process play a vital role in achieving a thick modified layer for improved tribological properties of titanium and alloys. Performing the oxidation step of OBDH heat-treatment at higher temperatures results in higher surface hardness and deeper diffusion zone than carrying the oxidation step at lower temperatures for longer times provided there is no peeling of the oxide scale during the high temperature oxidation. The Ti-6AI-4V achieves higher surface hardness than the Ti-6AI-7Nb upon the same OBDH heat-treatment. The second step of the OBDH can also be carried out in an argon environment instead of vacuum. Carrying out the second step in an argon atmosphere allowed for higher surface hardness and thicker hardened zone than carrying the same step in vacuum. The effect of the OBDH on the underlying microstructures of two alloys under investigation is the depletion of the ɑ phase on the modified surface as a result of the diffused oxygen which stabilises the ɑ phase. Although higher surface hardness was achieved for the Ti-6AI-4V alloy than the Ti-6AI-7Nb alloy after the same heat treatment, the Ti-6AI-7Nb alloy achieved higher wear resistance due to more adherence of the oxide scale after the oxidation step. Despite achieving higher surface hardness and thicker hardened zone upon carrying out the second step of OBDH in an argon atmosphere than in vacuum, samples which underwent the second step of OBDH heat-treatment in vacuum exhibited higher wear resistance. Performing a twin cycle OBDH heat-treatment results in even higher surface hardness and higher wear resistance despite the severe scaling of the alloys upon the heat treatments.

L’étude et le développement des matériaux goniochromes reste un challenge aussi bien pour la recherche scientifique que pour l’industrie. Dans le domaine industriel, le contrôle qualité de la couleur est rendu difficile par les effets colorés de ces matériaux. Le développement d’un étalon de matériaux goniochromes avec des effets colorés référencés pourrait permettre de simplifier ce control qualité de la couleur. Le challenge pour la recherche scientifique consiste à être capable de contrôler l’évolution de la couleur avec les conditions d’illumination et d’observation et de définir les géométries de caractérisation en accord avec les effets colorés perçus.Une revue bibliographique a montré que l’anodisation du titane est un candidat prometteur pour produire des échantillons goniochromes de référence. Afin d’obtenir des échantillons avec différents niveaux de brillant, des échantillons avec des substrats ayant une rugosité comprise entre quelques et deux cents nanomètres ont été préparés soit par un décapage à l’acide fluorhydrique soit par succession de polissages mécaniques et chimiques. La couleur du titane anodisé est liée à l’épaisseur de la couche d’oxyde et à l’indice de réfraction du matériau. Ces paramètres ont été estimés à l’aide de différentes techniques, en particulier une technique basée sur la lecture des extrema du spectre de réflectance du matériau mais aussi par ellipsométrie et réflectométrie par rayons X. Ces paramètres ont été utilisés dans un modèle optique afin de simuler la réflectance spéculaire du matériau. Les réflectances diffuse et spéculaire ont été comparées et un premier modèle de réflectance diffuse a été proposé. Les fonctions de distribution bidirectionnelle de la réflectance (BRDF) spectrales et angulaires ont été utilisées pour caractériser le goniochromisme et l’aspect diffus de ces échantillons en fonction de la rugosité du substrat et du potentiel d’anodisation
The study and the development of goniochromic materials remains a challenge both for industry and for scientific research. In the industry, the color quality control is rendered difficult by the complex color effects of these materials. The development of standard goniochromic materials with referenced color effects could simplify this color quality control. By comparing the manufactured materials to the reference ones by for example acquiring pictures of both materials in given geometries could be an easy process for color quality control. The challenge for scientific research consists to be able to control the color evolution with the illumination and observation conditions and define color characterization geometries in agreement with perceived color effects. A bibliographic review showed that anodized titanium is a promising candidate for reference goniochromic samples. In order to obtain samples with different levels of gloss, samples with substrate roughnesses ranging from a few to two hundred nanometers obtained through hydrofluoric etching or different mechanical and chemical polishing were prepared. Anodized titanium color is linked to the oxide layer thickness and the material refractive index. These parameters were estimated through different techniques in particular a technique based on the extrema of the material reflectance spectrum as well as ellipsometry and X-ray reflectometry. These parameters were put into an optical model in order to simulate the material specular reflectance. The diffuse and specular reflectances of the samples are also compared and a first simple model of the diffuse reflectance is presented. The Bidirectional Reflectance Distribution Function (BRDF) spectral and angular variations are used to characterize the diffuse appearance and goniochromism of the samples versus the substrate preparation and the anodizing cell potential

The (110) surface of TiO$\sb2$ is examined using a 9.92 keV oxygen ion beam. The positions of the peaks in the emitted ion energy spectrum are consistent with those predicted by ion-surface scattering theory for O$\sp{+}$-O and O$\sp{+}$-Ti collisions. Upon examination of the peaks present in the ion energy spectrum, information about the surface crystallographic structure can be determined. This includes studying the shadowing/blocking effects as the azimuthal and elevation angles are varied. Using this information the dimensions of the surface unit cell are found to be consistent with the bulk dimensions. The height of the oxygen rows that are present above the surface can also be determined and is found to be lower than predicted by the bulk.

Titanium and Its alloys have been used for many years as the material of choice for fabrication of dental, orthopaedic and maxillofacial implants, due to their excellent mechanical properties, biocompatibility, and the ability to osseointegrate with the surrounding bone. In order to improve the bioactivity and osseointegration of titanium implants, especially in compromised bone, surface modification of the implant surface and surface coatings have been introduced. There are different kinds of surface modification, such as, grinding, plasma spraying, sputter coatings, and alkaline treatment. More significantly, immobilization of drugs, such as, bisphosphonates, played an important role in enhancing the bone healing process. The main aim of the study is to develop and identify a facile surface modification method of immobilizing bisphosphonate molecules on commercially pure titanium and its alloy. 10mm discs of commercially pure titanium (CpTi) and titanium-aluminium-vanadium (Ti-6Al-4V) alloy were subjected to different surface treatments experiments; 1) the CpTi and Ti64 alloy surfaces were invested in phosphate bonded investment (Deguvest) and heated up to 900°C simulating superplastic forming process (SPF) creating an interaction layer on the surface upon which they were subjected to immersion in simulated body fluid (SBF) for 7 and 10 days, 2) the titanium surfaces were subjected to alkali treatment with 5M NaOH at 60°C for 24 hours, further more immersed in SBF solution for 7 and 10 days, 3) immobilization of sodium alendronate bisphosphonate on the pre treated titanium surfaces using microseeding method, and 4) tethering of Bioglass® and sodium alendronate bisphosphonate on the titanium surfaces using the electrohydrodynamic spraying method. The surface characterization of the treated surfaces was assessed using scanning electron microscopy (SEM/EDAX), Raman spectroscopy, surface roughness profilometer, and atomic force microscopy (AFM). In vitro cellular bioactivity and cytotoxicity were evaluated on the treated surfaces. This study established that both the interaction layer and its treatment further with simulated body fluids created a favourable interaction layer on the titanium surfaces, which induced the formation of apatite like layer on the surfaces when soaked in SBF solution. The interaction layer so formed was stable and not lost after physical methods of cleaning, thus can be considered to be a quick and inexpensive method of surface modification of titanium implants, during processing itself, which can enhance the bone healing and result in improved osseointegration. The surface modification of CpTi and Ti64 achieved with SPF and sodium hydroxide treatment and further treatment with SBF were further used to immobilize alendronate successfully, which yielded a simple method of incorporating bisphosphonates on implant surfaces, without causing any damage to the drug as no heat treatment or chemical crosslinking was required. Based on the cellular response to the investment treated titanium samples, sodium hydroxide treated samples followed by SBF treatment it can be concluded that these surfaces provide favourable conditions for cell growth, proliferation and differentiation when compared to the non-invested samples.

El conocimiento de las interacciones entre célula/proteína/biomaterial es fundamental para la ingeniería de superficies debido a las numerosas aplicaciones biomédicas y biotecnológicas que se están desarrollando así como al éxito clínico que han alcanzado muchos implantes. La respuesta biológica final inducida por los implantes está fuertemente influenciada por las interacciones superficiales entre los componentes biológicos y el material sintético. Las propiedades físicas y químicas de la superficie de un biomaterial, en lugar de las propiedades en su masa, influyen directamente en la capa de proteínas que se adsorben sobre el biomaterial y, como consecuencia de ello, en la respuesta celular a la misma, tanto in vitro como in vivo.

El objetivo de esta tesis doctoral es profundizar en el conocimiento de las interacciones material-biosistema, con el énfasis en el descubrimiento de relaciones entre las propiedades superficiales de las superficies de titanio y su respuesta biológica in vitro.

El titanio comercialmente puro (Ti c.p.) está siendo ampliamente utilizado con éxito durante muchos años como biomaterial para implantes en cirugía ósea. Su excelente biocompatibilidad se basa en sus adecuadas propiedades mecánicas y, con mayor importancia, en su excelente resistencia a la corrosión. Esta última se debe principalmente a la formación espontanea de una fina película de óxido de titanio que le confiere protección natural contra los ataques degradativos. La modificación de la topografía de la superficie del titanio ha sido objeto de investigación en el pasado con el fin de mejorar la osteointegración. El granallado de partículas es una de las tecnologías más utilizadas para conferir rugosidad a las superficies del titanio. La rugosidad óptima y el tipo de partículas abrasivas del granallado para una respuesta óptima in vitro e in vivo fue previamente determinada en nuestro laboratorio. Sin embargo, todavía están por determinar cuáles son las causas últimas que llevan al biomaterial a su exitosa respuesta biológica.

En este trabajo se han estudiado superficies pulidas y rugosas de Ti c.p. obtenidas mediante el granallado con partículas abrasivas de diferente composición química(Al2O3 y SiC) y diferentes tamaños (212-300μm; 425-600μm; 1000-1400μm). La completa caracterización de las propiedades física y química de la superficie, incluyendo la rugosidad, la composición química, la mojabilidad/energía libre y la carga eléctrica de las superficies ensayadas ha llevado a una serie de relevantes conclusiones. Entre ellas, cabe destacar que a) la composición química de las partículas de granallado, así como el método de esterilización fueron los principales factores que influyeron en la mojabilidad y la energía libre superficial de las superficies de titanio estudiadas, b) el método de esterilización cambió en la energía superficial el carácter de donante de electrones de las superficies mediante el cambio de la cantidad y la naturaleza de las sustancias adsorbidas, y c) la composición química de las partículas de granallado no influyó en la carga eléctrica a pH fisiológico ni en el punto isoeléctrico de las superficies.

Un segundo paso consistió en el uso de una microbalanza de cristal de cuarzo con monitorización de la energía de disipación, para el estudio de la cinética de adsorción (cantidad y conformación) y de los procesos de adsorción competitiva de tres proteínas de especial interés en los procesos de curación del hueso - la albúmina de suero bovino (BSA), el fibrinógeno (Fbg), y la fibronectina (Fn)- en sensores lisos recubiertos de TiO2. Se determinaron diferentes modelos de procesos de adsorción con una, dos o múltiples pasos distinguibles en función de las proteínas en solución. La capa adsorbida de BSA mostró los cambios más significativos en sus propiedades mecánicas, de conformación y de incorporación de agua hasta que se alcanzaron las condiciones estables de adsorción de proteínas. La BSA, la más pequeña de las proteínas ensayadas, desplazó la Fn y el Fbg cuando se ensayó en condiciones de la competencia por la adsorción, indicando su mayor afinidad por las superficies de TiO2. También se emplearon técnicas de marcaje fluorescente para el estudio de la adsorción proteica en superficies rugosas granalladas. En este estudio, por un parte, se pudo determinar que la cantidad de Fn y BSA adsorbidas en las superficies granalladas está directamente correlacionada con su energía superficial. Por otra parte, se visualizó la adsorción de fibronectina en solución sobre muestras granalladas rugosas de Ti. La Fn formó un patrón irregular de adsorción con una mayor cantidad de proteína adsorbida en los picos que en los valles de la topografía.

También se evaluó la organización espacial de la matriz extracelular de los osteoblastos, ECM, sobre superficies de Ti lisas y rugosas por medio de la visualización de las fibrillas de Fn teñidas con marcador fluorescente. Las células osteoblásticas depositaron las fibrillas de Fn con un determinado patrón organizado dentro de la matriz total secretada. Aparecen como una película que cubre la parte superior de las diferentes superficies rugosas de titanio. Un resultado relevante es que el espesor de esta capa aumentó con la rugosidad de la topografía subyacente. Sin embargo no más de la mitad de la máxima distancia pico-valle se cubrió con la proteína secretada y/o reorganizada.

Por último, teniendo en cuenta las diferencias en la organización de la ECM y la
adsorción de Fn en las superficies ensayadas de Ti, se realizó un estudio de qRT-PCR para determinar la influencia de las propiedades superficiales del titanio, con y sin preadsorción de Fn, en la respuesta osteoblástica. La expresión génica de la subunidad 5 de la integrina celular, como marcador de la adhesión celular, se incrementó en las superficies granalladas con SiC en comparación con las granalladas con alúmina. Este resultado fue correlacionado con la mayor cantidad de Fn adsorbida debido a la mayor energía superficial de las superficies granalladas con SiC. El aumento de la rugosidad, así como la presencia de partículas de alúmina en las superficies rugosas incrementó la actividad de ALP y la expresión génica de ALP mRNA por los osteoblastos, y por lo tanto su diferenciación.
The understanding of cell/protein/biomaterial interactions is critical to the engineering of substrates for numerous biomedical and biotechnological applications and to the clinical success of implants. The final biological response induced by implants is strongly influenced by the biological-components/synthetic-material surface interactions. It is well accepted that the physical and chemical surface properties of a biomaterial rather than its bulk properties will influence the protein adlayer and then the cell response to it, both in vitro and in vivo.

The aim of this PhD thesis is to gain an increased understanding of the materialbiosystem interactions, with an emphasis on establishing correlations between surface properties of titanium surfaces and its in vitro biological response.

Commercially pure titanium (c.p. Ti) is being widely and successfully used implant biomaterial in bone surgery over many years. Its excellent biocompatibility is based in its appropriate mechanical properties and, more importantly, in its excellent corrosion resistance, which is mainly due to the presence of a naturally-occurring thin protective titanium oxide film. Modification of titanium surface topography has been a subject of research in the past with the purpose of improving its osseointegration. Grit blasting is one of the most used technologies to roughen titanium surfaces for this purpose. The optimal roughness and type of abrasive blasting-particles for a better in vitro and in vivo response was previously determined in our lab. However, which and how different relevant surface properties of the blasted titanium surfaces induce that optimal biological behavior is still poorly understood.

Smooth/polished and rough c.p. Ti surfaces obtained by blasting with abrasive
particles of different chemical composition (Al2O3 and SiC) and different sizes (212-300μm; 425-600μm; 1000-1400μm) were studied. The comprehensive characterization of physical and chemical surface properties, including roughness, chemical composition, wettability/free energy and electrical charge of the tested surfaces led to a series of relevant conclusions. Among them, it is worth noting that a) the chemical composition of the grit-blasting particles as well as the method of sterilization were found the main factors influencing wettability and surface free energy of the titanium surfaces; b) the sterilization method changed the electron donor character of the surfaces by changing the amount/nature of physisorbed substances on the surfaces, and c) the chemical composition of the blasting particles did not influence on the electrical charge at physiological pH and the isoelectric point of the surfaces.

A second step consisted in the use of a quartz crystal microbalance with monitoring of the energy dissipation to study the adsorption kinetics (amount and conformation) and adsorption competition processes of three proteins of special interest in the healing processes of bone -bovine serum albumin (BSA), fibrinogen (Fbg), and fibronectin (Fn)-on smooth TiO2-coated sensors. Different patterns of adsorption with processes in one, two or multiple distinguishable steps were determined depending of the protein in solution. The BSA adlayers showed the most significant changes in their mechanical properties/conformation/incorporation of water until steady protein-adsorption conditions were reached. BSA, the smallest of the tested proteins, displaced Fn and Fbg when in competition for adsorption, which is an indication of its higher affinity for TiO2 surfaces. Fluorescent labelling techniques where used to study protein adsorption on blasted rough surfaces. Most significantly, the amount of Fn and BSA adsorbed on blasted surfaces was positively correlated with their surface energy. The adsorption of fibronectin from solution on shot-blasted rough titanium surfaces resulted in an irregular pattern of adsorption with a higher amount of protein adsorbed on peaks than on valleys of the topography.

Further, the spatial organization of the osteoblast extracellular matrix, ECM, on smooth and rough Ti surfaces was evaluated by visualizing fluorescently-stained Fn-fibrils. Osteoblast-like cells deposited Fn- fibrils in a specific facet-like pattern that was organized within the secreted total matrix. It appeared as a film overlying the top of the different rough titanium surfaces. Interestingly, the thickness of this layer increased with the roughness of the underlying topography, but no more than half of the total maximum peak-to-alley distance was covered.

Finally, taking into consideration the differences in ECM organization and Fn adsorption on the tested Ti surfaces a qRT-PCR study was carried out to elucidate the influence of titanium surface properties with and without Fn-precoatings on the osteoblast response. The expression of 5 integrin subunit gene, as a marker for cell adhesion, was increased in SiC-blasted surfaces compared to alumina-blasted surfaces. This was related to the higher amount of adhesive-protein Fn adsorbed caused by the higher surface energy of SiC-blasted surfaces. The increase of roughness as well as the presence of alumina particles on blasted surfaces increased ALP activity and ALP mRNA gene expression by osteoblasts, and so their differentiation.

This research work contribute to increase our knowledge on the interactions taking place at the bio/non-bio interface between different biological components -water, proteins, cells- and materials of clinical relevance, such as rough titanium. The
intertwined effects of the different properties of the synthetic surfaces appear as a challenge to unravel the ultimate causes that determine the fate of cells on synthetic biomaterials.

The aim of this thesis is to understand the interactions of peptides with surfaces so that we can potentially exploit this information in the control of adsorption of biomolecules on surfaces. The study concentrates on titania surfaces which have specific applications, e.g. in biosensors and titania implants. A peptide, RKLPDA, which was experimentally found to be strong-binding to titania is studied by molecular dynamics [1]. The interaction of the rutile (110) surface with water is considered and molecular dynamics simulations are performed using the Bandura/Predota model for titania [2, 3] and TIP3P water [4, 5]. It is found that there is significant water structuring both perpendicular to the surface and in the orientation of the water molecules due to the surface. It is shown that the results agree with X-ray truncation rod experiments [6] and other simulations that use SPC/E water. MD simulations of the RKLPDA peptide in water are made using the Charmm27/TIP3P force-field. It is found that the water structuring at the charged groups, Asp, Arg and Lys is significant and likely to influence its behaviour, especially when close to the structured water at titania. Experimental decreases in binding affinity of the peptide on titania upon mutation of the Pro for Ala have been suggested in terms of an increase in the flexibility of the backbone. The work described in this thesis suggests that the Lys-backbone carbonyl and Lys/Asp interactions are responsible for experimentally observed increases of the Lys-mutant compared to the unmutated peptide. MD simulations of the RKLPDA peptide adsorbed onto the titania surface with explicit water molecules are performed. It is shown that the charged groups bind to the structured water layers, not the surface itself, in a 'horseshoe' structure first proposed by Sano and Shiba [1]. Examples are shown where the Lys-mutant stays bound to the surface but the unmutated peptide does not, and where the unmutated peptide binds to the surface but the Pro-mutant does not. These follow the trends shown by experiment and indicates a conformational aspect to binding.

Saturn's moon, Titan is a geomorphologically active planetary object, and its surface is influenced by multiple processes like impact cratering, fluvial and aeolian erosion, lacustrine processes, tectonics, cryovolcanism and mantling. Disentangling the processes that compete to shape Titan's landscape is difficult in the absence of global topography data. In this thesis, I utilize techniques in topographic statistics, fractal theory, study of terrestrial analogs and landscape evolution modeling to characterize Titan's topography and surface roughness and investigate the relative roles of surface processes in sculpting its landscape. I mapped the shorelines of 290 North Polar Titanian lakes using the Cassini Synthetic Aperture Radar dataset. The fractal dimensions of the shorelines were calculated via the divider/ruler method and box-counting method, at length scales of (1-10) km and found to average 1.27 and 1.32, respectively. The inferred power-spectral exponent of Titan's topography (β) was found to be ≤ 2, which is lower than the values obtained from the global topography of the Earth or Venus. In order to interpret fractal dimensions of Titan's shorelines in terms of the surficial processes at work, I repeated a similar statistical analysis with 114 terrestrial analogous lakes formed by different processes, using C-band radar backscatter data from the Shuttle Radar Topography Mission (SRTM). I found different lake generation mechanisms on Earth produce 'statistically different' shorelines; however, no specific set of processes could be identified for forming Titanian lake basins. Using the Cassini RADAR altimetry data, I investigated Titan's global surface roughness and calculated median absolute slopes, average relief and Hurst exponent (H) for the surface of Titan. I detected a clear trend with latitude in these roughness parameters. Equatorial regions had the smallest slopes, lowest values of H and smallest intra-footprint relief, compared to the mid-latitudes and polar regions of Titan. I used steady state models of relief generation (tectonic activity) and relief reduction (diffusive mass wasting and advective bedrock channel erosion) to generate synthetic landscapes and simulate Titan's topography. I provided constraints on two environmental variables for Titan that influence surface roughness: diffusivity and erodibility coefficient.

The exploration of Saturn's giant satellite Titan is considered, with particular reference to its surface which is hidden beneath a thick atmosphere. Groundbased observations, in which great progress has been made recently, and the measurements made by the Pioneer and Voyager spacecraft, are reviewed. Concepts for spacecraft to perform in-situ measurements on Titan are reviewed, as is the development of the NASA/ESA Cassini mission, how the mission constrains scientific investigations, and in tum how the mission has been constrained by funding pressures. The capabilities of the Cassini payload for investigating Titan's surface are critically assessed, and the ability of the Surface Science Package (SSP) on the Huygens probe to determine the composition of surface liquids is examined. Some thoughts on payload selection and the value of individual measurements are presented. The development of an impact penetrometer, and the interpretation of penetrometer and accelerometer data to measure surface mechanical properties, is described. It should be noted that Huygens is not a vehicle expressly designed as a lander, so the impact dynamics are complex. Additionally, the examination of the prospects offered by acoustic instrumentation are investigated. Modelling of a number of Titan surface processes is presented, including rainfall, photochemical and meteoric deposition, tidal dissipation in the interior, regolith processes such as volatile heat transport, annealing and aeolian transportation and the effects of tidal and crustal processes on lakes. A key subtopic of the thesis addresses the theme of planetary exploration as a whole, with the interaction between and the limitations of the exploration 'triad' of observations, insitu measurements and theory. Note is made of the remarkably significant role played by individuals and their perceptions.

L'optimisation des états de surface constitue un enjeu majeur pour les biomatériaux utilisés dans le domaine biomédical. Le titane (Ti) et ses alliages à base de nickel (NiTi) restent à ce jour les biomatériaux métalliques de prédilection dans nos applications cliniques en Odontologie (implants dentaires, instruments endodontiques, et arcs orthodontiques). Le but de nos recherche est d'optimiser les surfaces du Ti et NiTi en les fonctionnalisant par des films multicouches de polyélectrolytes (FMP). Notre travail propose d'étudier différents paramètres devant être impérativement validés avant d'envisager une quelconque application biomédicale in vivo avec ce type de revêtement. Une recherche bibliographique exhastive appuie notre recherche expérimentale. Le premier axe du travail propose de déterminer si des FMP peuvent effectivement s'adsorber chimiquement sur le Ti et le NiTi. qui plus est, une étude biologique est réalisée avec des cellules humaines pour tester la biocompatibilité des ces surfaces fonctionnalisées. La deuxième partie se concentre sur la biocompatibilité de la couche précurseur des FMP à base de polyéthyléneimine (PEI). Les résultats mettent en lumière une certaine cytotoxicité de la PEI envers des ostéoblastes et des fibroblastes gingivaux humain. Pour clore ce travail, nous réalisons des essais de stérilisation afin d'évaluer l'influence d'un tel procédé sur les FMP en terme de caractérisations physico-chimique et biologique des surfaces. La perspective d'une application biomédicale avec les FMP semble prometteuse, notamment en y introduisant des molécules bioactives. Cependant, bien d'autres paramètres sont encore à étudier avant d'envisager une application expérimentale et/ou clinique in vivo. Nous pouvons citer par exemple, le vieillissement des FMP, leur comportement en milieu salivaire ou fluoré, ou encore leur résistance à l'usure. Ces différents éléments rentrent dans les perspectives d'un projet post-doctoral.

Le procédé de fabrication directe par projection laser (FDPL), est un procédé de fabrication additive qui permet de fabriquer des pièces de forme complexe directement à partir d'un fichier CAO, sans outil et sans moule. L'un de ses inconvénients majeurs est la mauvaise qualité des états de surface obtenus (Ra supérieur à 15 μm) qui nécessite systématiquement des étapes de ré-usinage. Dans ce contexte, et dans le cadre du projet ANR « ASPECT », cette thèse a pour double objectif une meilleure compréhension de l'origine des états de surface dégradés, et le développement de différentes solutions expérimentales innovantes permettant d'améliorer les états de surface.Dans un premier temps, en considérant des géométries simples (murs) en alliage de titane Ti-6Al-4V, nous avons étudié l'interaction faisceau laser / jet de poudre / bain liquide métallique par différents diagnostics (caméra rapide, caméra thermique, pyrométrie…) pour comprendre l'évolution de la géométrie, la thermique et l'hydrodynamique de la zone fondue (ZF). Ces analyses nous ont permis de corréler les évolutions des ZF à celles des états de surface, et de mettre en évidence, sur le Ti-6Al-4V la prépondérance des effets de tension superficielle sur les effets de gravité, dans l'équilibre des ZF, et l'effet bénéfique de zones fondues larges et profondes combinées à de faibles hauteurs par couche, dans la réduction des micro et macro-rugosités. La réduction du débit massique local Dm* en vis-à-vis des parois latérales et l'augmentation du rayon de courbure des ZF avec l'élargissement des ZF (donc avec des rapports El= P/V (J/m) élevés) sont à l'origine des effets bénéfiques obtenus. Différents modèles analytiques et numériques ont également été utilisés ou développés, en complément des résultats expérimentaux, pour décrire le procédé (modèle d'interaction laser-poudre, modèle numérique thermique 3D du procédé, modèle de calcul des ondulations périodiques).En utilisant un large spectre de conditions expérimentales, et une caractérisation rigoureuse des conditions de fabrication (analyses de faisceau, de jet de poudre …) nous avons également apporté des améliorations notables à la qualité des états de surface obtenus. Ainsi, l'utilisation d'un éclairement laser uniforme plutôt que quasi-Gaussien, ou l'utilisation d'un régime quasi-pulsé plutôt que continu ont permis, sur le Ti-6Al-4V de réduire significativement les gradients thermiques en ZF et les mouvements de convection de Marangoni associés, et d'obtenir des qualités d'états de surface fortement améliorées (Ra< 3 µm) par rapport aux études antérieures sur le sujet.Pour finir, une partie de l'étude s'est concentrée sur l'utilisation d'un autre matériau: l'acier inoxydable 316L, afin d'analyser l'influence de la nature chimique et des propriétés thermo-physiques de la poudre projetée sur la qualité des états de surface. Les résultats ont montré que, contrairement à l'alliage de titane, les meilleures rugosités étaient obtenues pour les énergies linéiques El (J/m) les plus faibles, en raison de la formation, à El élevé, de macro-agglomérats de poudre sur les parois des murs. Ce résultat confirme la difficulté d'une approche prédictive globale des états de surface à partir des paramètres thermo-physiques des matériaux projetés
The process of direct manufacturing by projection laser ( FDPL), is a process of additive manufacturing which allows to make rooms(parts,plays) of complex shape directly from a file CAD, without tool and without mold(mussel). One of its major inconveniences is the bad quality of the states of surface obtained (Ra upper to 15 µm) which requires systematically stages of remanufacturing. In this context, and within the framework of the project ANR " aspect ", this thesis(theory) has for double objective a better understanding of the origin of the degraded states of surface, and the development of various innovative experimental solutions allowing to improve the states of surface. At first, by considering simple geometries (walls) in alloy of titanium Ti-6Al-4V, we studied the interaction

Surface modification is a process that is applied to the surfaces of titanium substrates in order to improve the biocompatibility after implanting in the body. Two methods were used in the present work: Anodisation and gel oxidation. Anodisation was performed at room temperature in strong mineral acids (sulphuric acid (H2SO4) and phosphoric acid (H3PO4)), an oxidising agent (hydrogen peroxide (H2O2)), mixed solutions of the preceding three, and a weak organic acid mixture (β-glycerophosphate + calcium acetate). The parameters used in anodisation were: Concentrations of the electrolytes, applied voltage, current density, and anodisation time. Gel oxidation was carried out by soaking titanium substrates in sodium hydroxide (NaOH) aqueous solutions at different concentrations (0.5 M, 1.0 M, 5.0 M, and 10.0 M) at 60??C for 24 h, followed by oxidation at 400??, 600??, and 800??C for 1 h. Conceptual models representing changes in the microstructure as a function of the experimental parameters were developed using the anodisation data. The relevant parameters were: Applied voltage, current density, acid concentration, and anodisation time: ?? The model for anodisation using the strong acid (H2SO4) illustrates the growth rate of the film, identification of the threshold for the establishment of a consistent microstructure, and prediction of the properties of the film. ?? For the oxidising agent (H2O2), two models were developed: Current-control and voltage-control, the applicability of which depends on the scale of the current density (high or low, respectively). These models are interpreted in terms of the coherency/incoherency of the corrosion gel, arcing, and porosity. ?? The model for the strongest acid (H3PO4) is similar to that of H2O2 in current-control mode, although this system showed the greatest intensity of arcing and consequent pore size. ?? Anodisation in mixed solutions uses Ohm??s law to explain four stages of film growth in current-control mode. These stages describe the thickness of the gel, its recrystallisation, and the achievement of a consistent microstructure. ?? Anodisation in weaker organic acids allows the most detailed examination of the anodisation process. Both current density and voltage as a function time reveal the nature of the process in six stages: (1) instrumental response, (2 and 3) gel thickening, (4) transformation of the amorphous gel to amorphous titania, (5) recrystallisation of the amorphous titania, and (6) subsurface pore generation upon establishment of a consistent microstructure. Gel oxidation was done at low and high NaOH concentrations followed by oxidation. Three models were developed to represent the gel oxidation process: (1) Low concentration, (0.5 M and 1.0 M NaOH), (2) Medium concentration (5.0 M NaOH), and (3) high concentration (10.0 M NaOH). For the low concentrations with increasing temperature, the model involves: (1) amorphous sodium titanate forms over a layer of amorphous anatase and (2) a dense layer of rutile forms. For the high concentrations with increasing temperature, the model involves: (1) amorphous sodium titanate forms over a layer of amorphous anatase, (2) a dense layer of anatase forms and raises up the existing porous anatase layer, and (3) the dense and porous anatase layers transform to dense and porous rutile layers, respectively. The main difference between the two is the retention of crystalline sodium titanate in the higher NaOH concentration. Anodised and gel oxidised samples subsequently were soaked in simulated body fluid in order to study the precipitation of hydroxyapatite in the absence and presence of long UV irradiation, which has not been investigated before. With the anodised surfaces, the porous and rough titania coating facilitated both the precipitation of hydroxyapatite and the attachment of bone-like cells. UV irradiation showed greatly enhanced hydroxyapatite precipitation, which is attributed to its photocatalytic properties. With the gel oxidised surfaces, the greatest amount of hydroxyapatite precipitation occurred with the presence of both anatase and amorphous sodium titanate. Rutile suppressed precipitation.

Les alliages de titane sont largement utilisés dans le secteur de l’aéronautique. Cependant,ces alliages sont très sensibles aux gammes d’élaboration et de mises en forme. Cesdernières ont une grande influence sur l’intégrité de surface des produits finis, ce qui aun impact sur la durée de vie des pièces en service. Il est donc nécessaire de maîtriser lesprocédés afin de pouvoir définir la tenue en service des pièces.Dans ces travaux, les différentes intégrités de surface sont décrites en termes d’évolutionmicrostructurale, de contraintes résiduelles et de micro-géométrie. Des essais de fatigueen flexion 4 points sont réalisés pour tester les performances mécaniques de ces surfaces.Nous avons remarqué une bonne cohérence entre les modèles reliant l’intégrité de surfaceet la tenue en fatigue déterminée expérimentalement.De plus, étant donné que les alliages de titane ont des microstructures complexes etpeuvent être multiphasés, nous nous sommes aussi intéressés au caractère hétérogènede ces matériaux principalement dans l’analyse de contraintes résiduelles déterminées àl’aide de la diffraction des rayons X. Nous avons remarqué que ces hétérogénéités ontun impact sur la détermination des contraintes résiduelles. De fait une méthodologiede détermination de contraintes non standard a été mise en place et validée par dessimulations utilisant un modèle d’homogénéisation auto-cohérent.Ces modèles d’homogénéisation sont intéressants d’un point de vue de la déterminationdes contraintes résiduelles par diffraction des rayons X car ils permettent la prise encompte de l’aspect multiphasé des matériaux ainsi que leur caractère anisotrope
Titanium alloys are widely used in aeronautics industries. However, these alloys are highlysensitive to the method for elaboration and transformation processes. These processesimpact on the surface integrity of products. Therefore, they have to be controlled inorder to predict life time of structures.In this work, the study of surface integrity is focused on the description of microstructalevolution, residual stresses and micro-geometry. Four points bending tests were performedin order to determined the fatigue limit of the different studied processes. We find outa good consistency between models used to determinate lifetime from surface integrityinvestigation and experimental results.Moreover, microstructures of titanium alloys are highly complex and they often are twophasedmaterials. Consequently, we studied the heterogeneous behaviour of such materialby X-ray diffraction investigation.We found out that these heterogeneities have an impacton residual stresses determination. Therefore, a non-standard methodology was definedand validate by simulation using a micro-mechanic model : a self-consistent model.Micro-mechanical models are interesting for the residual stresses determination using Xraydiffraction because they allow to take into account heterogeneous and anisotropicbehaviours through anisotropic elasticity and anisotropic texture