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Infektionen medizinscher Titanoberflächen stellen ein aktuelles Problem in der rekonstruktiven Medizin dar. Dabei wird oft versucht, diesem Problem mit systemischer Antibiotikaanwendung zu begegnen, die jedoch Resistenzentstehung begünstigt und am Ort der Infektion nur einen oft unzureichenden Wirkspiegel ermöglicht. Eine mögliche Verbesserung wir hierbei in lokaler Wirkstofffreisetzung gesehen. Gegenstand dieser Arbeit war die Modifikation medizinischer Titanoberflächen mittels Anodisierung in fluoridhaltigen Elektrolyten und die Abschätzung ihres Potentials hinsichtlich der Einlagerung und der Freisetzung ausgewählter antibakteriell wirksamer Substanzen. Durch die Anodisierung der Titanoberflächen konnten Titannanotubes aus Titanoxiden mit Röhrenlängen von bis zu 6,54 m und Röhrendurchmessern von bis zu 160 nm erzeugt werden. Als Modellwirkstoffe wurden das noch heute als Reserveantibiotikum gegen manche Problemkeime geltende Chemotherapeutikum Vancomycin, sowie Silber als Element mit breiter antibakterieller Wirkung, verwendet. Es konnte gezeigt werden, dass durch die Oberflächenvergrößerung, die sich aus der Entstehung von nanotubeförmigem Titanoxid ergab, im Vergleich zu nicht anodisierten Referenzproben um bis zu 447 % mehr Wirkstoff eingelagert werden konnte. In der Freisetzungskinetik von Vancomycin zeigten sich oberflächenabhängig deutliche Unterschiede. Dabei setzten Titanoberflächen, die in einem Elektrolyten auf Wasserbasis anodisiert worden waren, den adsorbierten Wirkstoff schneller frei als die Referenzproben, während das Vancomycin auf Oberflächen, die in einem Elektrolyten auf Ethylenglycolbasis modifiziert worden waren, deutlich retardiert über einen Zeitraum von circa 305 Tagen freigesetzt wurde. Des weiteren wurde Silber in Proben eingelagert, die in einem Elektrolyten auf Wasserbasis anodisiert worden waren. Auch für Silber resultierte eine deutliche Steigerung der Gesamtmenge des adsorbierten Wirkstoffs um bis zu 229 %. Dabei war seine Freisetzung, verglichen mit der Referenzprobe, deutlich verzögert. Durch die Anodisierung der Titanproben in fluoridhaltigen Elektrolyten konnten Oberflächen erzeugt werden, die entsprechend ihrer Morphologie verschiedene Wirkstoffbeladungen und Freisetzungskinetiken ermöglichen. Hinsichtlich der unterschiedlichen Anforderungen in der klinischen Medizin nach Abgabemenge und Abgabekinetik antibakteriell wirksamer Substanzen zur postoperativen Infektionsprävention offerieren diese Oberflächenmodifikationen ein hohes Potential für die Erzeugung schnell verfügbarer und kostengünstiger Drug-Release-Systeme. / Infection of medical titanium surfaces is one important problem in modern medicine, especially orthepedics and dentistry. In the present work titanium surfaces were modified by anodisation. Titanium nanotube formations of different shape were obtained. These surfaces were modified with example drugs (vancomycin and silver ions) for drug-release. Drug-release was measured and compered.

Du fait de leurs propriétés intrinsèques exceptionnelles, les nanotubes de carbone (CNTs) sont des matériaux bien adaptés pour renforcer les polymères thermodurcissables. Le nanocomposite multifonctionnel ainsi obtenu possède des propriétés électriques, thermiques et mécaniques sensiblement meilleures que le polymère seul, ce qui lui procure de nombreuses applications potentielles, et tout particulièrement dans le domaine de l’électronique ou de l’aéronautique. Le but de cette thèse de doctorat est orienté suivant deux axes. Il s’agit dans un premier temps de mettre au point un matériau nanocomposite avec des propriétés multifonctionnelles à partir de techniques d’élaborations efficaces. Puis dans un second temps, l’objectif consiste à proposer des alternatives permettant d’améliorer ces propriétés. Le premier chapitre de cette thèse établit une revue de l’état de l’art au sujet des matériaux qui ont été étudiés au cours de ce travail de recherche. Parmi ces matériaux, nous pouvons citer tout particulièrement les CNTs, les renforts hybrides nano/micrométriques constitués de CNTs et d’alumine, les polymères conducteurs électroniques et les polymères thermodurcissables. Il s’agit plus précisément de présenter pour chaque matériau les techniques d’élaboration, leurs structures et finalement leurs propriétés. Dans la seconde partie du manuscrit, nous décrivons en premier lieu les procédés d’élaboration permettant d’obtenir des nanocomposites conformes aux normes internationales. Ensuite, nous présentons les différentes techniques de caractérisation de ces nanomatériaux. Il s’agit notamment de déterminer les phénomènes de transports électriques et thermiques. Des techniques d’analyses supplémentaires permettent de mieux comprendre la structure des matériaux obtenus dans une gamme d’échelle allant de l’état macroscopique à l’atomique. Ainsi, nous avons eu recours à l’utilisation de la microscopie électronique à balayage et en transmission, et aussi la microscopie à force atomique (AFM). Différentes études spectroscopiques de types : Raman, perte d’énergie des électrons (EELS), photoélectrons X (XPS) fournissent des informations additionnelles sur ces matériaux. Les résultats obtenus sur ces nanocomposites en matière de transports électronique et thermique montrent que certaines améliorations sont nécessaires pour optimiser les propriétés multifonctionnelles de ces nanomatériaux. Nous avons concentré nos efforts sur les phénomènes physicochimiques à l’interface matrice/renfort. Par conséquent, nous avons décidé de modifier la surface des CNTs afin de favoriser la cohésion matrice/renfort, mais aussi et surtout, pour diminuer les résistances de contacts entre les CNTs lorsqu’ils sont distribués aléatoirement dans une matrice polymère. Le dernier chapitre de la thèse s’articule autour de la fonctionnalisation des CNTs par un polymère conducteur électronique (ECP). Dans un premier temps, nous avons mis au point des techniques électrochimiques permettant de déposer une couche homogène d’épaisseur nanométrique d’ECP à la surface des CNTs. Ce polymère conducteur et en même temps biocompatible est le polypyrrole (Ppy). La précision et l’efficacité de notre démarche sont démontrées par les différents outils de caractérisation, et tout particulièrement grâce à la microscopie électronique en transmission à haute résolution. Des études supplémentaires par AFM couplé à un résiscope ont montré l’évolution de la résistance électrique d’hybrides CNT-Ppy plus ou moins isolés. Dans une seconde partie, nous avons mis au point une méthode permettant de contrôler finement l’épaisseur de Ppy déposé à la surface des CNTs. / Carbon nanotubes (CNTs) are ideal candidates to reinforce thermoset polymers due to their exceptional intrinsic properties. The resulting multifunctional nanocomposite has electrical, thermal and mechanical properties sensitively higher than pristine polymer. Therefore, this new material possesses various potential applications, and particularly in the domain of electronics and aerospace. The aim of this PhD thesis is oriented towards two directions. In the first one, we establish efficient techniques to produce composite materials with multifunctional properties. Then, the objective consists in the enhancement of these properties by proposing valuable alternatives to previous results cited in the litterature. In the first chapter, we present the state of the art research concerning the materials studied during this work. Among these, there are in particular: CNTs, hybrids constituted of CNTs and alumina microparticles, electronically conducting and thermoset polymers. Moreover, this chapter deals with the characteristics of each material, i.e. elaboration techniques, structures and properties. The second chapter of the manuscript contains first, the elaboration techniques allowing the synthesis of high quality nanocomposites according to international standards. Then, we analyze the properties of these nanomaterials, and particularly in terms of electrical and thermal transports. Further characterization procedures allow better understanding of the obtained structures in a domain ranging from macroscopic to atomic scales. This is realized using scanning/transmission electron microscopy, Raman spectroscopy, EELS, XPS, and AFM. Electrical and thermal conductivity measurements obtained on these new materials give prominence to the necessity of some improvements. Thereby, we have focused our research on the physico-chemical phenomena at the matrix/filler interface. We have proposed to modify the surface of CNTs, in order to favour the matrix/filler cohesion, but also and mainly to decrease contact resistances between the randomly distributed CNTs within the polymer matrix. Finally, the last chapter deals with the surface functionalization of CNTs using electrochemistry. First, we have implemented an accurate technique to deposit a nanometric layer of electronically conducting polymer on the surface of CNTs. This conducting polymer, namely polypyrrole (Ppy) is in the meantime biocompatible. The accuracy and efficiency of our approach are demonstrated through various characterization techniques, and particularly using transmission electron microscopy. Further studies using AFM coupled with a resiscope indicate the electrical resistance distribution performed on CNT-Ppy hybrids. In the second part of this chapter, we present our method to control precisely the thickness of the Ppy layer around the CNTs.

Carbon nanotubes (CNTs) have been the subject of intensive research for nearly two decades, and this is due to their exceptional lightness, large aspect ratio, extraordinary mechanical, electrical, thermal properties and additional multi-functional characteristics. Ceramics have high stiffness and good thermal stability with a relatively low density, and they are an important constituent in the fabrication of advanced composites where high thermal and chemical stability are important. However, brittleness has limited their application in many structural applications. The combination of ceramic (alumina in particular) and CNTs, endeavouring to develop functional composites, offers a very attractive system for research and development. The fabrication of such alumina-CNT composites at bulk scale is therefore highly desirable for industrial applications. However, the synthesis of such composites possesses many technical challenges which need to be addressed. Poor synergy between the matrix and CNTs, potential damage to CNTs, obtaining a uniform and agglomeration-free distribution of CNTs within the matrix, and high cost of CNTs and processes involved in their composite fabrication have proved to be the significant challenges. In this thesis, the focuses are laid on addressing these issues and on the fabrication of specially engineered composites for particular applications such as filter and composites with improved mechanical properties. In this regard, it has been tried to directly fabricate CNTs in different ceramic matrices based on the application requirements. After that, the critical issues and challenges in the fabrication of these functional materials have been clearly investigated and by introducing novel methods and approaches, it has been tried to solve these problems. Also, a new polymer-ceramic-CNT composite has been fabricated by using two different thermoset (epoxy resin) and thermoplastic (polyamide 12) matrices. In this regard, good interfacial bonding between the composite elements along with good wettability of ceramic and CNTs with polymer had to be addressed as critical issues and challenges in the fabrication process. If the adherence at the interface is not strong enough, the material will tear and fail easier. In contrary, a tailored functionalization of CNTs can lead to an improved wettability and as the results, strong interfacial adhesion and bonding between the composite elements. These dominating factors will improve the degree of filling which results in existence of fewer voids inside the composite. These voids will act later as stress points and reduce the composite strength. At the end, the mechanical properties of the fabricated samples have been assessed. The CNT filters have been tested in the removal of bioorganic (yeast cells) and inorganic (heavy metal ions) contaminants from water, and of particulates from air, and they all showed very promising results. More than 99.6% of the air particles (size ranges from 0.3 to 10 µm) were filtered using 300 mm long CNT filter. A complete removal of heavy metal ions from water was reported particularly for single ion. 98% of the yeast cells were filtered. Different factors involved in the filtration efficiency such as ceramic pore size, length of filters, CNT loading and injection rates have also been discussed. Furthermore, the mechanical properties (compression test, hardness and impact test) of the composite materials (including ceramic-CNT, epoxy resin-ceramic-CNT and polyamide-ceramic-CNT composites) have been assessed. During impact test, the epoxy resin-ceramic-CNT composite absorbed 117.2% and 32.7% more energy compared to the pure epoxy resin and epoxy resin-ceramic composite, respectively. The epoxy resin-ceramic-CNT composite sustained 40% more elastic deformation before breakage compared to the epoxy resin-ceramic composite as a result of the CNT reinforcement. The addition of CNTs to the polyamide12-ceramic composite increased its yield stress by 41%. All of these results represent a big leap towards practical applications for the composite reported in the thesis, which may open up new opportunities for CNT engineering at industrial scales, due to the easy fabrication methods introduced and the promising performance they have exhibited.

Thesis advisor: Thomas Chiles / Molecular recognition is an important area of research as it has far reaching applications in sensors, molecular separations, and medicine. Molecularly imprinted polymers offer an option for developing high resolution tools of detection that are both selective and sensitive. As a platform, carbon nanotubes offer a highly conductive surface and their growth and unique magnetic properties can be manipulated for our purposes. Such carbon-nanotube based sensors can afford high sensitivity, while molecular imprinting provides the selectivity of detection with the flexibility of fabrication. In order to fabricate a molecular imprint, monomeric compounds are polymerized in the presence of a target molecule of interest, which acts as the template. Once the template molecule has been removed an imprint capable of “recapturing” the target molecule is left behind. In this work we used cyclic voltammetry as a means of depositing polymer coatings doped with a target molecule. We fabricated a molecularly imprinted polymer sensor specific for ferritin using polyphenol as the polymer. The development of our imprint was monitored based on changes in impedance levels calculated by electrochemical impedance spectroscopy. After depositing ferritin-doped polyphenol layers we evaluated the effectiveness of different eluant solutions. Ultimately, deionized water was determined to be the developing solution of choice because it effectively removed the ferritin while not compromising the integrity of the remaining polymer coating. The sensor was capable of detecting ferritin at a concentration of 1x10-9 g/L (1 pg/mL). In parallel we evaluated the stability of the polyphenol coating. / Thesis (BS) — Boston College, 2009. / Submitted to: Boston College. College of Arts and Sciences. / Discipline: College Honors Program. / Discipline: Biology.

Thesis advisor: Lawrence T. Scott / Carbon nanotubes have demonstrated unique characteristics of strength, flexibility, and electrical conductivity. The ultimate goal of this research is to develop a chemical synthesis of a [5,5] carbon nanotube endcap. Three different projects were undertaken in an effort to realize this goal. The first was the production of appreciable quantities of tetrabromocorannulene, a precursor to the endcap. The second was an exploration of a proof of principle C44H14 bowl, and the third was the development of a boronic acid that would add functionality to tetrabromocorannulene, and ultimately a bowl. / Thesis (BS) — Boston College, 2009. / Submitted to: Boston College. College of Arts and Sciences. / Discipline: College Honors Program. / Discipline: Chemistry.

Ever since the discovery of carbon nano materials like carbon nanotube (CNT) and graphene, this class of materials has gained significant attention due to their exotic properties. The principle idea of my present research project is to understand the novel improvements induced in polymer matrices with inclusion of the nanofillers. This thesis is thematically divided into three parts. In the first part we introduce principle materials that we use for preparation of composites. Methods of nanofiller preparation and different nanocomposites as previously reported in literature are discussed to formulate the basis of our study. Different dispersion techniques are discussed which facilitate uniform nanofiller distribution. A variety of experimental methods are described which were employed to investigate the structure and properties of the composites. In the second part we discuss in details polyamide-12 (PA12) composites using CNT and graphene as fillers. A marked improvement is recorded in the toughness of the films with incorporation of CNT, dispersed in PA12 using a surfactant. Electrical percolation is also achieved in the otherwise insulating matrix. With PA-12 fibers we explored the effect of fiber processing and CNT incorporation in the mechanical properties. Extensive wide angle x-ray diffraction was carried out to interpret the structural modifications brought about by CNT in the matrix. The final part of the thesis deals with a thermosetting polymer, epoxy composites. CNT, Graphene and also a mixture of the two nanofillers were used as reinforcing agents. Appreciable improvement was recorded in the mechanical properties, electrical and thermal conductivity of the composites. Detailed optical and electron microscopy was carried out to get a vivid idea of the micro-structure and dispersion. The presented work demonstrates the significant ability of carbon nanofillers to reinforce polymer matrices enhancing their mechanical, electrical and thermal properties and opening a wide horizon for a variety of applications.

Preventative immunotherapeutic treatments have been an area of great interest to combat infectious disease because of the ability to stimulate the hosts immune system which prepares the host to fight pathogenic microbes. The immunotherapeutic approach requires the use of an immune stimulating molecule that is able to boost the hosts immune response. A major problem exists that these immune stimulating molecules are often very expensive and require a large dose to be effective. To reduce the cost of using these molecules, a delivery system can be used which is able to lower the effective dose of the immune stimulant while not causing any toxic effects towards the hosts health. In this study, the immune stimulating molecules synthetic unmethylated cytidine-phosphate-guanosine oligodeoxynucleotides were attached non-covalently to multi-walled carbon nanotubes. The use of carbon nanotubes as a delivery mechanism could result in a lower effective dose able to stimulate a protective immune response in a chicken model. In this study, we first assessed which of the non-covalant linkages was ideal for linking the immune stimulant to the carbon nanotubes. This was conducted by looking at which method of linkage would allow the best cellular proliferation and transcriptional activation of selected innate immune genes. Once an appropriate linkage method had been selected, cellular uptake studies were conducted to establish that cytidine-phosphate-guanosine oligodeoxynucleotides were delivered to intracellular target receptors. After cellular uptake was demonstrated, it was important that the carbon nanotubes linked to the immune stimulant do not cause toxicity towards the host. To measure toxicity, in vitro studies were conducted to observe cell viability post treatment with carbon nanotube linked immune stimulant. Further studies were conducted on any alterations to the immune stimulants ability to activate immune cells by studying the pathway of macrophage activation. The protective ability of the molecules was then measured by the ability to protect chickens from a lethal challenge with S. typhimurium. Once the protective nature of the molecules was established, the mechanism of immune stimulation was examined by in vivo cell recruitment and in vitro cytokine production. These studies indicate that linking cytidine-phosphate-guanosine oligodeoxynucleotides to carbon nanotubes can lower the effective dose of the immune stimulant without altering the biological function of the molecule.

In this study, a novel polyimide (PI) film, consisting of multiwall carbon nanotubes (MWCNTs) dispersed in an Ionic Liquid (IL), were demonstrated to be high shielding effectiveness (SE). The film was potentially useful for screening electromagnetic interference(EMI) in an optical transceiver module. The experimental results showed MWCNT-PI composite dispersed well in IL exhibits a high far-field SE of 38 ~ 45 dB within the frequency range of 1 ~ 3 GHz. It was also demonstrated the MWCNT-PI composite prepared with IL dispersed process have higher SE and lower weight percentage of MWCNTs than those with non-IL-dispersed process. Their intermolecular forces were carefully examined in order to understand dispersion mechanisms among MWCNTs. The aggregation phenomenon of MWCNTs was known, resulting from van der Waals forces. In our study, IL was employed to disperse MWCNTs. A proposal reason was that the attractive force between cation of the IL and £k electrons of MWCNTs is greater than the van der Waals forces among MWCNTs. From conductivity measurement, percolation threshold of the IL-dispersed MWCNT-PI composite was 5.2 wt%; percolation threshold of the non-IL-dispersed MWCNT-PI composite was 11.5 wt%. Given the lower percolation threshold ,we demonstrated the successful dispersion of MWCNT by adding IL. From the results of Raman spectrometer analyses, the IL dispersion was proved to be a physical interaction. Furthermore, the IL-dispersed MWCNT-PI composite was used as package material in monopole antenna and got a near-field SE of 37dB within the frequency of 2.8 GHz. It implied that the IL-dispersed MWCNT-PI composite has an excellent EMI performance.The IL-dispersed MWCNT-PI composite is suitable for packaging low-cost and high-performance optical transceiver modules in the application of the fiber-to-the-home (FTTH) lightwave transmission systems.

This dissertation presents research on synthesis, high-power microwave post-synthetic purification and high frequency characterization of Carbon Nanotubes (CNT). First, CNTs are synthesized using a Chemical Vapor Deposition system. The impact of substrate and methane flow rate on CNT growth is studied using Scanning Electron Microscopy, Transmission Electron Microscopy and Raman microscopy. Second, the microwave irradiation effects on purified HiPCO and CoMoCat Single-Walled CNT thin films are investigated. The measured drastic THz power transmission increase (>10 times) indicates a significant metallic content reduction after the irradiation. The Raman spectra also confirm the metallic-to-semiconducting ratio of Raman-active CNTs decreases by up to 33.3%. The observed microwave-induced effects may potentially lead to a convenient scheme for CNT demetalization. Third, Multi-Walled CNT papers are characterized from 8 to 50 GHz by rectangular waveguide measurements using a vector network analyzer. A rigorous algorithm is developed to extract the samples' effective complex permittivity and permeability from the measured S-parameters. Unlike other reported work, this method does not impose the unity permeability assumption. The algorithm is verified by finite-element simulations and the uncertainties for the characterization method are analyzed. The effective medium theory is then applied to obtain the intrinsic CNT properties. Furthermore, Terahertz Time-Domain Spectroscopy is used to characterize the samples from 50 to 370 GHz. Both transmission and reflection experiments are performed to simultaneously extract the permittivity and permeability. The extracted permittivity is fitted with a Drude-Lorentz model from 8 to 370 GHz. Finally, individual CNT characterizations at microwave frequency are studied. The impacts from impedance mismatching and parasitics on measurement sensitivity are systematically studied, revealing that the parasitic effect is possibly dominant above 10 GHz. A tapered coplanar waveguide test fixture is designed using Advanced Design System (ADS) to improve the impedance mismatching and minimize the test fixture parasitics, therefore optimize the measurement sensitivity. A de-embedding procedure to obtain the CNT's intrinsic electrical properties is presented and demonstrated with ADS simulations. In addition, the test fixture fabrication process is discussed, which is an ongoing research work. At the end, the conclusions of this dissertation are drawn and possible future works are discussed.