Дисертації з теми "Implanted diamond"

L'interaction entre les électrons et les phonons dans la matière condensée est responsable du couplage de leurs équations de transport, ce qui donne lieu à des effets d’entrainements mutuels sous l'effet d'un gradient de température (effet Seebeck) ou d'un courant de charge (effet Peltier). Dans certains matériaux, ces effets, connus sous le terme anglophone de « phonon drag », conduisent à des valeurs de coefficient Seebeck très élevées. Ils se manifestent généralement à basse température lorsque le libre parcours moyen des phonons est important, près du maximum en température de la conductivité thermique de réseau. Historiquement, ces effets de « drag » entre les électrons et les phonons ont été mis de côté dans les stratégies de recherche en thermoélectricité car ils coïncident avec un maximum de la conductivité thermique du réseau, ce qui limite l'efficacité thermoélectrique. Toutefois, des études réalisées en 2008 sur des systèmes de silicium nanostructurés ont montré que des effets Seebeck significatifs dus à ces effets de « drag » peuvent coexister avec une faible conductivité thermique du réseau. Les travaux théoriques traitant les équations de transport couplées ont apporté de nouvelles perspectives, démontrant que les états de phonons dominant le transport de chaleur sont distincts de ceux qui sont principalement impliqués dans les effets de drag. L'objectif de ma thèse était de réaliser des expériences pour explorer un nouveau concept d’effets « drag » entre les électrons et les phonons, séparés par une interface. J'ai étudié les propriétés de transport des électrons confinés dans un canal conducteur sous la surface d'un diamant cristallin agissant comme un bain de phonon externe constitué d’états de phonon propagatifs. Mon travail inclut l’élaboration des systèmes, leur caractérisation structurale et le développement de protocoles de mesure pour la conductance et le coefficients Seebeck pour des systèmes conducteurs enterrés. J'ai étudié les propriétés de transport de canaux produits dans différentes conditions d'implantation et de recuit pour comprendre les liens entre leur microstructure et leurs propriétés de transport électronique. Dans la première étude, j'ai mesuré la conductance et le coefficient Seebeck dans des canaux épais (~145 nm) enfouis à environ 200 nm sous la surface du diamant. Ces canaux, créés par implantation ionique d'hélium à une fluence modérée suivie d'un recuit à haute température, présentaient principalement une microstructure graphitique. À température ambiante, la conductance est proche de celle du graphite massif. Le coefficient Seebeck présentait un comportement à basse température similaire à celui du graphite, avec un pic négatif attribué aux effets de traînée. Toutefois, ce pic est apparu à une température nettement plus élevée que dans le cas du graphite massif, ce qui pourrait être une première indication des contributions supplémentaires des phonons du diamant. Dans la seconde étude, j'ai examiné des canaux de dimensions similaires mais soumis à une fluence d'implantation plus faible ou recuits à des températures plus basses. Ces canaux présentent une microstructure désordonnée complexe composée d'agrégats d'atomes de carbone avec une hybridation sp, sp² et sp³. La conductance et le coefficient Seebeck en fonction de la température varient de manière significative par rapport à la première étude. Le coefficient Seebeck est positif et atteint plusieurs milliers de µV/K à basse température. Les propriétés de transport ont été interprétées à l'aide de la théorie du chaos quantique. Mon travail montre la faisabilité des mesures de conductance et du coefficient Seebeck à basse température à travers des canaux conducteurs enfouis sous la surface du diamant et met en évidence la richesse des propriétés de conduction de ces canaux qui peuvent être accordées en contrôlant leur microstructure par un choix judicieux des paramètres d'implantation et de recuit
The interaction between electrons and phonons in condensed matter is responsible for the coupling of their transport equations, which gives rise to mutual drag effects between them under the effect of a temperature gradient (Seebeck effect) or a charge current (Peltier effect). In some bulk materials, these drag effects, better known as “phonon drag”, lead to very high Seebeck coefficient values at low temperatures. It usually manifests at low temperatures when the phonon mean free path is large, near the maximum in temperature of the lattice thermal conductivity in dielectric crystals, which occurs due to reduced phonon-phonon scattering. Historically, phonon drag has been overlooked in thermoelectric research as it coincides with the maximum in the lattice thermal conductivity peak, potentially reducing overall thermoelectric efficiency. However, studies in 2008 on nanostructured silicon systems contradicted this, demonstrating that significant Seebeck effects from phonon drag can coexist with low lattice thermal conductivity. Theoretical works treating the coupled transport equations offered new insights, demonstrating that phonon states dominating heat transport are distinct in phase space, in wave-vector, and energy from those mainly involved in drag effects. The aim of my thesis was to carry out experiments to explore a novel concept of phonon drag between electron and phonon gases, separated by an interface. I studied transport properties of electrons confined to a conductive channel beneath the surface of a crystalline diamond acting as an external phonon bath with propagative phonon states. My thesis involved system construction, structural characterization, development of measurement protocols for conductance and Seebeck coefficients, and adaptation of these measurements for buried conductive systems. I analyzed the transport properties of channels produced under different implantation and annealing conditions to understand how the microstructure of the channel influences electronic transport properties. In the first study, I measured conductance and the Seebeck coefficient in thick channels (~145 nm) buried about 200 nm below the diamond surface. These channels, created via helium ion implantation at moderate fluence followed by high-temperature annealing, displayed mostly a graphitic microstructure. At room temperature, the conductance was close to that of bulk graphite. The Seebeck coefficient exhibited low-temperature behavior akin to graphite, with a negative peak attributed to drag effects. However, this peak occurred at a significantly higher temperature compared to solid graphite, which could be a first indication of additional contributions from diamond phonons. In the second study, I examined channels with similar dimensions but subjected to lower implantation fluence or annealed at lower temperatures. These channels exhibited a highly disordered microstructure composed of aggregates of carbon atoms with sp, sp², and sp³ hybridization. The temperature-dependent conductance and Seebeck coefficient varied significantly from the first study. The Seebeck coefficient is positive and reached several thousand µV/K at low temperatures. The transport properties were interpreted using quantum chaos theory. My work shows the feasibility of conductance and Seebeck coefficient measurements at low temperature through conductive channels buried beneath the diamond surface and highlights the rich conduction properties of such channels which can be tuned by controlling their microstructure through a careful choice of implantation and annealing parameters

Objetivo: Avaliar a interface pilar protético/implante e o destorque, quando utilizados parafusos recobertos com Diamond-like carbon (DLC) e parafusos convencionais de titânio para fixação dos componentes protéticos, antes e após ação de carga cíclica. Posteriormente, avaliar a correlação entre o desajuste vertical da interface pilar UCLAimplante e o destorque dos parafusos dos pilares. Método: Trinta e seis implantes foram divididos em quatro grupos de acordo com o tipo de conexão (hexágono externo e interno) e do parafuso utilizado para fixar o pilar ao implante (titânio ou recoberto com DLC), ou seja: Grupo A: hexágono externo/parafuso titânio; Grupo B: hexágono externo/parafuso recoberto com DLC; Grupo C: hexágono interno/parafuso titânio;Grupo D: hexágono interno/parafuso recoberto com DLC. Após os implantes terem sido incluídos em resina acrílica incolor, coroas foram enceradas sobre pilares UCLA, fundidas com liga metálica de Ni-Cr-Ti e parafusadas aos implantes com aplicação do torque recomendado pelo fabricante. Em seguida, as interfaces pilar/implante foram mensuradas, em microscópio de luz, em quatro pontos de cada amostra (DV1). Após as amostras terem sido submetidas a um milhão de ciclos mecânicos, as interfaces foram novamente mensuradas (DV2). Para comparar os valores médios, intra e intergrupos, das interfaces pilar/implante, da diferença entre os mesmos e os valores de destorque, os dados foram submetidos à Análise de Variância, ao teste t de Student e ao teste de Mann Whitney (p≤0,05). E para a correlação entre os fatores estudados, os resultados foram submetidos ao teste de correlação de Pearson (p≤0,05). Resultados: Os implantes com hexágono externo apresentaram os maiores valores de desajuste vertical pilar UCLA/implante antes (DV1) e após (DV2) ciclagem mecânica (GA/DV1 = 59,81μm e GA/DV2 = 62,59μm, GB/DV1 = 73,73μm e GB/DV2 = 72,95μm). Nos grupos onde foram utilizados parafusos de titânio foi observado aumento dos valores da interface pilar/implante de DV1 para DV2 (GA = de 59.81μm para 62.50μm e GC = de 18.13μm para 22.54μm). Nos grupos onde foram utilizados parafusos de DLC foi evidenciada redução dos valores da interface pilar/implante de DV1 para DV2 (GB = de 73.73μm para 72.95μm e GD = de 16.07μm para 14.47μm. Somente o GC apresentou diferença significativa entre os valores mensurados na interface pilar/implante antes e após o carregamento cíclico (p=0,05). Para correlacionar os valores de destorque aos valores das interfaces pilar/implante, foi aplicado o teste de correlação de Pearson, porém não foi verificada diferença significativa entre os fatores estudados (p˃0,05). Conclusões: As interfaces pilar UCLA/implante foram maiores nos grupos com hexágono externo que nos grupos com hexágono interno, porém sem diferença significativa quando utilizados parafusos de titânio ou revestidos com DLC. Houve perda de torque após carga cíclica em todos os grupos. Não é possível afirmar que um maior valor de interface pilar/implante esteja correlacionado com o desaperto do parafuso.
Purpose: To evaluate the interface abutment/implant, and the loosening screws values when used screws with Diamond-like carbon (DLC) coated and conventional titanium screws for fixation of prosthetic components, before and after action of cyclic loading. After, to evaluate the connections between the values of interface abutment UCLA/implant and loosening screw. Method: Thirty six implants were divided into four groups according to the type connection (external hexagon and internal hexagon) and screw used to fix the abutment to the implant (titanium or coated with DLC): Group A: external hexagon / titanium screw; Group B: external hexagon / DLC screw; Group C: internal hexagon / titanium screw; Group D: internal hexagon / DLC screw. After the implants were included in colorless acrylic resin, crowns were waxed using UCLA type abutment, casting with metal alloy of Ni-Cr-Ti and screwed to the implants using the torque recommended by the manufacturer. Then the interfaces pillar/implant were measured with light microscope in four pre-marked points (DV1). After the sets (implant, crown and screw) were subjected to one million mechanical cycles and the interfaces measured again (DV2). Analysis of Variance, Test t Student and test Mann Whitney (p≤0,05) were applied to compare the average to the interfaces abutment/implant intra and intergroup, the difference between the same and the loosening screws values. And to evaluate the correlated between the factors studying, the Pearsons correlation test (p≤0,05). Results: The implants with external hexagon exhibited the higher values of the vertical misfit pillar UCLA/implant before (DV1) and after (DV2) cyclic loading (GA/DV1 = 59,81μm e GA/DV2 = 62,59μm, GB/DV1 = 73,73μm e GB/DV2 = 72,95μm). In groups of titanium shows screws there was an increase in interface abutment/implant after cyclic loading (GA = 59,81μm to 62,50μm and GC = 18,13μm to 22,54μm) and in groups with DLC coated screws there was a reduction the values of interface abutment/implant (GB = 73,73μm to 72,95μm and GD = 16,07μm to 14,47μm). Only group C showed a statistically significant difference to the interface abutment/implant before and after cyclic loading (p = 0.05) exhibited mean values and differences between the interfaces pillar/implant. To correlate the values of loosening to the values of pillar interfaces/implant was applied the Pearsons correlation test, but there was no significance among the studied factors (p ˃ 0.05). Conclusions: The interfaces pillar UCLA/implant were higher in groups with external hexagon connection those in groups with internal hexagon, but without significant differences when use titanium screws or coated with DLC. Always screws loosed torque after cycling load. Is not possible to affirm that a higher value of interface abutment/implant be correlated with the loosening screw.

Orientador: Vitor Baranauskas
Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Eletrica
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Resumo: O desenvolvimento de novos materiais para a produção de implantes ortopédicos tem sido uma busca constante, devido principalmente ao aumento das aplicações clínicas e à necessidade de se alcançar maior durabilidade, diminuindo assim as cirurgias de revisão. O diamante CVD obtido por deposição química da fase vapor é um novo material com grande potencial de uso devido às suas excelentes propriedades físico-químicas. Dentre elas pode-se destacar a inércia química, extrema dureza e baixo coeficiente de atrito, características importantes para materiais que necessitam resistir ao desgaste e à corrosão produzida pelos fluídos do corpo humano. O objetivo deste estudo foi avaliar pela análise ¿in vitro¿ e ¿in vivo¿ a biocompatibilidade de tubos de diamante microcristalino e diamante nanocristalino produzidos pela deposição química de vapor em filamento quente (CVD). Palavras Chave: diamante CVD, biomateriais, implantes, próteses
Abstract: The development of new materials for orthopedic implants has been a quest due to the increasing number of clinical applications and necessity of achieving larger durability for lessening the need for revision surgeries. Diamond CVD (Chemical Vapour Deposition) is a new material with larger potential of future use due its excellent physico-chemical properties like for instance, high chemical inertness, extreme hardness and low friction coefficient. The aim of this study is to evaluate by ¿in vitro¿ and ¿in vivo¿ assays the biocompatibility of microcrystalline and nanocrystalline diamond self-sustaining tubes produced by hot-filament chemical vapor deposition (CVD). Key Words: chemical-vapor-deposited diamond, biomaterials, implants, prosthesis
Mestrado
Engenharia de Computação
Mestre em Engenharia Elétrica

Le diamant dopé bore (BDD) est un matériau extrêmement prometteur pour applications biomédicales par son unique combinaison de propriétés. Cette thèse a visé le développement de nouvelles structures de micro-électrodes en BDD et l'étude de leur intérêt et leurs performances pour des applications électroanalytiques et électrophysiologiques. En dépit de leurs propriétés électroanalytiques très supérieures à d'autres matériaux d'électrodes plus conventionnels, les électrodes BDD sont sujettes au «fouling», i.e. l'apparition d'un film à la surface du diamant qui réduit la réactivité électrochimique. Ceci est très compromettant dans des milieux complexes comme l'urine, les eaux stagnantes, des boissons, le plasma sanguin etc. Ici, un nouveau traitement d'activation a été développé pour nettoyer la surface des électrodes et recouvrir leur réactivité initiale, donc il permet leur usage pour de longues périodes d'enregistrement sans dégradation du signal. Ceci permet l'usage de ce type d'électrodes, pour des domaines d'applications, pour le suivi continu d'analytes, sans entretien spécifique, en solutions complexes. La grande originalité de ces techniques d'activation est qu'elle peut être menée directement dans l'analyte lui-même. En comparaison avec leurs équivalents en macro-électrodes, les microélectrodes permettent d'obtenir de plus grandes sensibilités, des courants résiduels moindre, des pertes ohmiques moindres, et donc des rapports signal à bruit meilleurs. Un procédé robuste et fiable a été optimisé pour la fabrication de réseaux de microélectrodes (MEA MicroElectrode Arrays) et d'ultra micro-électrodes, permettant par lithographie sur 4 pouces d'offrir une large flexibilité de fabrication. Par exemple, parmi d'autres prototypes, des microélectrodes BDD ont été utilisées pour applications de biocapteurs pour quantifier l'acide urique en temps quasi-réel. Bien que le diamant possède une très bonne biocompatibilité et des propriétés électrochimiques excellentes, la faible relative capacité de double couche limite leur application pour des applications électrophysiologiques. Des procédés de nanostructuration ont ainsi été mis au point pour accroitre les limites d'injection de charge. Parmi les approches, des procédés hybrides à base de polypyrrole se sont révélés prometteurs, de même que des procédés de gravure pour former de la «nano-herbe» diamant, très intéressantes pour la fabrication de MEAs en BDD. Ces matériaux à fort rapport d'aspect apparaissent comme d'excellents candidats pour applications d'interfaces neuronales et notamment pour la fabrication d'implants rétiniens.STAR
Boron doped diamond (BDD) electrodes are extremely promising in the field of biomedical applications as they exhibit a unique combination of properties. The thesis aims at developing new types of BDD microelectrodes and exploring their interests for electro-analytical and electrophysiological applications. Despite their superior electro-analytical properties, BDD electrodes are prone to fouling, which leads to a loss of electrode reactivity when used in biological fluids such as urine, waste waters, drinks, blood plasma, etc. A novel electrochemical treatment was developed to clean the electrode surface and to retrieve the initial reactivity, thereby enabling the use of BDD electrodes to long periods of measurements without degradation of the signal, thus significantly extending the field of monitoring and surveying applications up to domains where continuous analysis is required. The real novelty of the technique is that it does not require the use of a specific media and thus can be directly performed in the probed (bio-)fluid. Microelectrodes in comparison with macro-electrodes offer higher sensitivity, lower background current, lower ohmic losses and higher signal-to-noise ratio. A robust, high-yield, reliable, and reproducible process for fabricating a thin-film BDD micro and ultra-microelectrode arrays (MEA) was developed using a novel lithographic technique, based on clean room processing on 4 inch substrates, thus offering wide flexibility. For example, among other prototypes, BDD microelectrodes were developed as biosensors to quantify uric acid in human urine in quasi-real time. Although diamond film possesses good biocompatibility and excellent electrochemical properties, the low double-layer capacitance limits its application in electrophysiological applications. Increasing the charge injection limit was investigated by surface modification and nano-structuring. These include the synthesis of hybrid diamond-polypyrrole electrodes and nanograss BDD MEAs. Such high aspect ratio materials appear as excellent candidates for neurointerfacing applications such as for retinal implants

Le développement de nouvelles technologies biomédicales permet d'aider les personnes souffrant de la perte de fonctions motrices ou cognitives à récupérer partiellement de leur perte. L'étude des neurones a mis en évidence la nature électrique des signaux cérébraux, conduisant à la fabrication d'implants s'interfaçant avec eux. L'enregistrement et la stimulation de différentes parties du système nerveux central ont été rendus possibles grâce à des implants. Néanmoins, l'introduction d'un corps étranger dans le corps humain n'est pas sans conséquences. Les matériaux utilisés pour fabriquer les implants doivent être suffisamment rigides pour supporter les attaques du corps, mais ne doivent pas endommager les tissus environnants. Compte tenu de ces exigences, un matériau a récemment attiré l'attention : le diamant. Il peut être synthétisé en laboratoire et utilisé dans des processus microtechnologiques classiques pour fabriquer des dispositifs à base de diamant. Le diamant peut être un isolant électrique dans son état "naturel", c'est-à-dire un simple réseau de carbone, ou acquérir une conduction de type métallique s'il est suffisamment dopé au bore. L'excellente biocompatibilité du cristal le place comme un candidat sérieux en termes de matériau d'électrode. Ses propriétés chimiques, électrochimiques et mécaniques en font un matériau inerte, solide et fiable. Le travail de thèse s'est concentré sur le matériau diamant, afin de fabriquer un implant entièrement en diamant. Cela signifie que le diamant polycristallin intrinsèque sera utilisé comme couche de protection du dispositif, tandis que les sites des électrodes seront constitués de diamant conducteur dopé au bore (BDD). Le dispositif obtenu est conçu pour enregistrer les signaux du cerveau. Pour ce faire, la maîtrise de la structuration du diamant est primordiale pour pouvoir l’utiliser au sein de processus microtechnologiques. Il a été choisi de faire des croissances localisées du diamant, aussi bien intrinsèque que dopé, en utilisant du nitrure l’aluminium (AlN) en couche de masquage. Le taux de croissance, la composition chimique et l'analyse de l'état de surface ont confirmé la bonne manipulation du processus de diamant. Un autre point essentiel à prendre en compte lors de la fabrication des implants est le choix des matériaux qui transporteront les signaux électriques. Le développement de la couche conductrice a été réalisé en combinant le nitrure de titane (TiN) et le platine (Pt) pour tirer profit des deux matériaux. L'encapsulation du platine par le TiN a donné lieu à des pistes conductrices capables de supporter les conditions de croissance du diamant sans aucun dommage. Suite à la fabrication des implants diamant, une caractérisation doit être effectuée. Deux procédures d'analyse électrochimique ont donc été utilisées pour examiner les électrodes BDD et sonder le matériau : la voltampérométrie cyclique (CV) et la spectroscopie d'impédance électrochimique (EIS). Les tests ont confirmé la présence de BDD aux emplacements des électrodes, la bonne passivation du diamant intrinsèque et la faible impédance à 1 kHz, par rapport aux implants comportant des électrodes en BDD seul. Après s'être assuré du bon fonctionnement et de la fiabilité du dispositif, les implants ont été testés in vivo sur des rongeurs pour sonder leurs voies visuelles. Une craniotomie a été pratiquée sur des rats (à l’Institut de la Vision) et des souris (à l’EPFL) afin de placer les électrodes sur leur cortex visuel. Cette intervention chirurgicale a pour but de réaliser un enregistrement aigu des potentiels évoqués visuels (VEP), qui sont déclenchés par des stimulations visuelles. L'expérience a été un succès puisque les implants en diamant ont réussi à enregistrer des VEP dans différents contextes d'expérience, dans les deux laboratoires. Ces résultats préliminaires ouvrent la voie à la future génération d'implants neuronaux en diamant afin de garantir un dispositif chronique fiable et stable
The development of new biomedical technologies permits to help people suffering from the loss of motor or cognitive functions to partially recover from their loss. Neural study highlighted the electrical nature of brain signals, leading to the fabrication of implants interfacing with them. The recording and stimulation of different parts of the central nervous system were made possible through implants. Nevertheless, introducing a foreign object into the human body is not without consequences, as materials used to fabricate implants should be stiff enough to endure the body’s attacks but should not harm the surrounding tissues. Given these requirements, a material has recently gained attention: diamond. It can be synthetized in labs and used in conventional microtechnology processes to fabricate diamond-based devices. Diamond can either be an electrical insulator in its “natural” state, meaning a simple carbon lattice, or acquire a metallic-like conduction if doped enough with boron. The excellent biocompatibility of the carbonated crystal places it as a serious candidate in terms of electrode material. The chemical, electrochemical and mechanical properties, guarantee an inert, solid and reliable material. The PhD work was focused around diamond material, to fabricate a full-diamond implant. This means that intrinsic polycrystalline diamond was used as a protection layer of the device, while the electrodes sites were made of boron-doped conductive diamond (BDD). The obtained device was designed to record signals from the brain. To do this, the control of the structuring of diamond is essential to be able to use it within microtechnological processes. It was chosen to make localized growths of diamond, both intrinsic and doped, using aluminum nitride (AlN) as a masking layer. The growth rate, the chemical composition and the analysis of the surface condition confirmed the good handling of the diamond process. Another key point to consider when fabricating the implants is the choice of materials that will carry the electrical signals. The development of the conductive layer was done by combining titanium nitride (TiN) and platinum (Pt) to take advantage of both materials. The encapsulation of platinum by TiN resulted in conductive tracks capable of withstanding the growth conditions of diamond without any damage. Following the fabrication of the diamond implants, characterization must be performed. Two electrochemical analysis procedures were therefore used to examine the BDD electrodes and probe the material: cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The tests confirmed the presence of BDD at the electrode locations, good intrinsic diamond passivation, and low impedance at 1 kHz compared to implants with BDD-only electrodes. After ensuring proper functioning and reliability of the device, the implants were tested in vivo on rodents to probe their visual pathways. A craniotomy was performed on rats (at the Vision Institute) and mice (at EPFL) in order to place the electrodes on their visual cortex. The purpose of this surgical procedure is to make an acute recording of visual evoked potentials (VEPs), which are triggered by visual stimuli. The experiment was successful as the diamond implants were able to record VEPs in different experimental settings in both laboratories. These preliminary results pave the way for the future generation of diamond neural implants to ensure a reliable and stable chronic device

Magister Chirurgiae Dentium
Dental implants are artificial fixtures that are surgically inserted into the jaws to replace missing teeth. The success of dental implant treatment is dependent on achieving successful osseointegration (Branemark et al. 2001). Drills used for implant site preparation are made of different materials such as stainless steel (SS), zirconia and ceramic. Most of them do not have sufficient cutting efficiency and wear resistance (Oliveira et al. 2012). Recently diamond-like carbon coating (DLC) has been added as a drill coating to increase the cutting efficiency, increase wear resistance and drill hardness (Batista Mends et al. 2014).

Diamond is a promising material with unique chemical properties. In this thesis, nano-scale diamond quantum size effects were investigated using several chemical property indicators. The results show that the chemical properties are strongly dependent on size for film thicknesses smaller than 1 nm (1D), and for nanodiamond particle diameters less than 2 nm (3D). When the sizes exceed these ranges there are no longer any quantum effects. The influence of surface termination coverage on the surface chemical properties has been calculated for the 2×1 reconstructed diamond (100) surface and for the diamond (111) surface. The terminating species included COOH and NH2 groups, which both are beneficial for the immobilization of biomolecules. The results of the calculations show that it is energetically possible to terminate the diamond surfaces up to 100% with NH2, while it is only possible to cover the surfaces up to 50% with COOH species. The reason for the latter result is most probably the larger sterical hindrance amongst the adsorbates. Both types of termination species were shown to influence the diamond surface electronic properties (e.g., HOMO/LUMO levels). In order to extend the diamond utility for biomedical applications, especially implant design, interactions of various growth factors with the diamond surfaces were also simulated. For non-solvent diamond-biomolecule systems, the results show that adhesion affinities are strongly dependent on biomolecule molecular weights. When including a water based solvent in the systems, the results show good physisorption affinities between proteins and diamond. Proteins structures, before and after physisorption, were visualized, and further investigated with respect to electrostatic properties and functional groups. By comparing the biomolecular structural changes during the adhesion processes, it can be concluded that both the general structures, as well as the binding pocket structures, were kept intact after the adhesion to the diamond surfaces (regardless of the adhesion affinities). In addition, the surface electronic potential distributions were maintained, which indicate preserved biomolecule functionalities.
Vascubone

Today, it is possible to restore hearing in congenitally deaf children and severely hearing-impaired adults through cochlear implants (CIs). A CI consists of an external sound processor that provides acoustically induced signals to an internal receiver. The receiver feeds information to an electrode array inserted into the fluid-filled cochlea, where it provides direct electrical stimulation to the auditory nerve. Despite its great success, there is still room for improvement, so as to provide the patient with better frequency resolution, pitch information for music and speech perception and overall improved quality of sound.  A better stimulation mode for the auditory nerves by increasing the number of stimulation points is believed to be a part of the solution. Current technology depends on strong electrical pulses to overcome the anatomical gap between neurons and the CI. The spreading of currents limits the number of stimulation points due to signal overlap and crosstalk. Closing the anatomical gap between spiral ganglion neurons and the CI could lower the stimulation thresholds, reduce current spread, and generate a more discrete stimulation of individual neurons. This strategy may depend on the regenerative capacity of auditory neurons, and the ability to attract and guide them to the electrode and bridge the gap. Here, we investigated the potential of cultured human and murine neurons from primary inner ear tissue and human neural progenitor cells to traverse this gap through an extracellular matrix gel. Furthermore, nanoparticles were used as reservoirs for neural attractants and applied to CI electrode surfaces. The nanoparticles retained growth factors, and inner ear neurons showed affinity for the reservoirs in vitro. The potential to obtain a more ordered neural growth on a patterned, electrically conducting nanocrystalline diamond surface was also examined. Successful growth of auditory neurons that attached and grew on the patterned substrate was observed. By combining the patterned diamond surfaces with nanoparticle-based reservoirs and nerve-stimulating gels, a novel, high resolution CI may be created. This strategy could potentially enable the use of hundreds of stimulation points compared to the 12 – 22 used today. This could greatly improve the hearing sensation for many CI recipients.

Thesis (Ph. D.)--University of Alabama at Birmingham, 2008.
Additional advisors: Yogesh K. Vohra, Xu Feng, Jack E. Lemons, Timothy M. Wick. Description based on contents viewed July 8, 2009; title from PDF t.p. Includes bibliographical references.

Le diamant dopé bore (BDD) est un matériau extrêmement prometteur pour applications biomédicales par son unique combinaison de propriétés. Cette thèse a visé le développement de nouvelles structures de micro-électrodes en BDD et l'étude de leur intérêt et leurs performances pour des applications électroanalytiques et électrophysiologiques. En dépit de leurs propriétés électroanalytiques très supérieures à d'autres matériaux d'électrodes plus conventionnels, les électrodes BDD sont sujettes au "fouling", i.e. l'apparition d'un film à la surface du diamant qui réduit la réactivité électrochimique. Ceci est très compromettant dans des milieux complexes comme l'urine, les eaux stagnantes, des boissons, le plasma sanguin etc. Ici, un nouveau traitement d'activation a été développé pour nettoyer la surface des électrodes et recouvrir leur réactivité initiale, donc il permet leur usage pour de longues périodes d'enregistrement sans dégradation du signal. Ceci permet l'usage de ce type d'électrodes, pour des domaines d'applications, pour le suivi continu d'analytes, sans entretien spécifique, en solutions complexes. La grande originalité de ces techniques d'activation est qu'elle peut être menée directement dans l'analyte lui-même. En comparaison avec leurs équivalents en macro-électrodes, les microélectrodes permettent d'obtenir de plus grandes sensibilités, des courants résiduels moindre, des pertes ohmiques moindres, et donc des rapports signal à bruit meilleurs. Un procédé robuste et fiable a été optimisé pour la fabrication de réseaux de microélectrodes (MEA MicroElectrode Arrays) et d'ultra micro-électrodes, permettant par lithographie sur 4 pouces d'offrir une large flexibilité de fabrication. Par exemple, parmi d'autres prototypes, des microélectrodes BDD ont été utilisées pour applications de biocapteurs pour quantifier l'acide urique en temps quasi-réel. Bien que le diamant possède une très bonne biocompatibilité et des propriétés électrochimiques excellentes, la faible relative capacité de double couche limite leur application pour des applications électrophysiologiques. Des procédés de nanostructuration ont ainsi été mis au point pour accroitre les limites d'injection de charge. Parmi les approches, des procédés hybrides à base de polypyrrole se sont révélés prometteurs, de même que des procédés de gravure pour former de la "nano-herbe" diamant, très intéressantes pour la fabrication de MEAs en BDD. Ces matériaux à fort rapport d'aspect apparaissent comme d'excellents candidats pour applications d'interfaces neuronales et notamment pour la fabrication d'implants rétiniens.STAR

Orientador: Cecilia A. C. Zavaglia
Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecanica
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Resumo: O carbono tipo diamante ("diamond-like carbon" - DLC) tem demonstrado características, como alta dureza, baixo atrito, resistência ao desgaste e à corrosão, e biocompatibilidade, que podem melhorar as propriedades de implantes sólidos e articulados. O processo de imersão em plasma vem sendo usado para depositar DLC em substratos tridimensionais, pois, com esta técnica, se consegue melhor adesão do que com as técnicas convencionais. Neste trabalho, filmes de DLC foram depositados, pelo processo de imersão em plasma, em lamínulas de vidro, silício e liga de titânio Ti-13Nb-13Zr. A caracterização da microestrutura, morfologia, dureza e adesão dos filmes de DLC foi feita por espectroscopia Raman, microscopia eletrônica de varredura (MEV), microscopia de força atômica (MFA), nanoindentação e ensaio de puxamento. Como exemplos de peças tridimensionais, filmes de DLC foram depositados em implantes osteoarticulares de quadril e joelho, titânio poroso (esponja de célula-aberta, semelhante à estrutura do osso esponjoso, expandida a vácuo), facas industriais, bisturi cirúrgico, engrenagem de motor, tubos de quartzo e de alumínio, e outros objetos. O filme obtido apresentou boas propriedades mecânicas, aumentando em 2 vezes a dureza da liga de Ti, alta adesão (filme sem interface definida e sem delaminação), resistência ao desgaste, baixa rugosidade e uniformidade de deposição em superfícies tridimensionais. Os resultados de corrosão (polarização de Tafel e espectroscopia de impedância eletroquímica em fluido corporal simulado) mostraram que o revestimento de DLC melhora a resistência da liga de Ti à corrosão. No ensaio de biocompatibilidade in vitro, com células fibroblásticas, foram estudados a citotoxicidade, adesão e morfologia celular (estudo citoquímico, microscopia de contraste de fase, MEV e MFA). No ensaio de biocompatibilidade in vivo, a liga de Ti-13Nb-13Zr, revestida com DLC, foi investigada em tecido muscular e ósseo de ratos após 4 e 12 semanas do procedimento cirúrgico. A interface formada entre o DLC e o tecido foi investigada por histologia convencional, e os implantes retirados por MEV. A interface entre o implante e o tecido ósseo, não descalcificado, foi estudada por MEV na modalidade retroespalhamento. Os resultados mostraram a biocompatibilidade in vitro e in vivo do filme de DLC, e foi verificado também que os implantes revestidos com DLC possuem resposta biológica mais favorável do que os implantes não revestidos
Abstract: Diamond-like carbon (DLC) films are often considered a suitable coating material for orthopaedic applications. It has proven characteristics, such as hardness, wear resistance, low friction coefficient and biocompatibility that improve the properties of solid and articulated implants. Recently, the plasma immersion process was used to deposit DLC films with superior adhesion properties to those prepared with conventional techniques. DLC coatings were deposited on glass coverslips, silicon (Si) and Ti-13Nb-13Zr substrates using the plasma immersion process. The microstructure, morphology, roughness, hardness and adhesion of DLC films were characterized using Raman spectroscopy, scanning electron microscopy (SEM), atomic force microscopy (AFM), nanoindentation and pull-test. As examples, DLC films produced by plasma immersion were deposited on industrial knives, surgical knives, knee implants, femoral heads (of hip prostheses), titanium foams, transmission gears of motorcycles, aluminium pipes, quartz pipes, and others objects. The corrosion susceptibility of DLC coatings produced by plasma immersion was studied in a simulated body fluid environment (Hanks' solution) using polarization test and electrochemical impedance spectroscopy (EIS). Electrochemical results showed that DLC coating produced by plasma immersion could improve corrosion resistance, and no significant damage has been observed. Vero cells (fibroblasts) were utilized for the in vitro biocompatibility studies, by cytotoxicity, adhesion and cell morphology (phase contrast microscopy, SEM, AFM, and cytochemical study). DLC-coated Ti-13Nb-13Zr was investigated in an animal model using the muscular tissue and femoral condyles of rats for intervals of 4 and 12 weeks postoperatively. The interface between the implants and tissue were analysed by light microscopy, and the removed implants by SEM. The SEM by backscattering was used to access the interface between the implants the bone tissue without decalcifying. Our results indicate that DLC coatings are biocompatible in vitro and in vivo
Doutorado
Materiais e Processos de Fabricação
Doutor em Engenharia Mecânica

L'augmentation de la sensibilite des multidetecteurs 4, tels eurogam ou diamant, engendre egalement une augmentation des debits de donnees a l'entree du systeme d'acquisition. Si au niveau de l'electronique, le flux de donnees a ete reparti sur plusieurs chaines d'acquisition fonctionnant en parallele, il est necessaire, au niveau de l'informatique, d'augmenter la puissance de traitement. Ce travail concerne la conception et le developpement du logiciel implante dans une architecture de processeurs paralleles. Des methodes d'analyse objet et formelle ont ete utilisees ; les performances ont ete mesurees et les perspectives d'evolution de cette architecture sont proposees.

The sub-surface region of chemical vapour deposition (CVD) diamond was transformed by C+ ion implantation followed by isochronal annealing up to 1200 oC. Different implantation regimes and with different energies at different implantation temperatures would give different thicknesses were studied. This enabled a study in the evolution of the stiffness of the damaged layer as a function of annealing. The technique of choice for this study was the non-destructive Brillouin light scattering (BLS) utilizing two scattering geometries; indirectly scattered phonons (Kr¨uger-type geometry) for temperature anneals up to 600 oC, and the conventional surface ripple mechanism up to 1200 oC. It has been argued that surface acoustic waves (SAW) on a transparent medium are enhanced by applying a thin metallic reflective layer on the surface, this study has showed that opacity of the substrate is key. In fact, bulk modes with SAW-like characteristics emanating from indirect photon scattering off phonons after reflection at the smooth reflective back of the sample dominated down to transmission below 5% which was observed after annealing between 500-600 oC (low annealing temperatures). The other complementing techniques employed to understand the changing structure of the ion implanted diamond were Raman spectroscopy, electromagnetic transmission in the visible range, electron energy loss spectroscopy (EELS) and high-resolution transmission electron microscopy (HRTEM) in addition to theoretical techniques: transport of ions in matter (TRIM), finite element modelling (FEM) and elastodynamic Green’s functions. Although the electronic techniques showed a structurally changing material at the low annealing temperatures, the optical ones did not show significant changes in the ion-damaged material possibly due to lack of distinct interface between the pristine diamond and the ion irradiated region at these lower annealing temperatures.

A thesis submitted to the Faculty of Science, University of the Witwatersrand, Johannesburg, in fulfillment of the requirements for the degree of Doctor of Philosophy.
High purity natural type Il a diamond specimens were used in this study. Conducting layers in the surfaces of these diamonds were generated using low-ion dose multiple implantation-annealing steps. The implantation energies and the ion-doses were spread evenly to intermix the point-defects, thereby increasing the probability of interstitialvacancy recombinations and promoting dopant-interstitial-vacancy combination resulting in activated dopant sites in the implanted layers. The process used to prepare our samples is known as cold-implantation-rapid-annealing (CIRA). Carbon-ion and boron-ion implantation was used to prepare the diamond specimens, and de-conductivity measurements in the temperature range of 1.5-300 K were made following each CIRA sequence. An electrical conductivity crossover from the Mott variable range hopping (VRH) to the Efros-Shklovskii VRH conduction was observed when the temperature of insulating samples was lowered. The conductivity crossover temperature Tcross decreases with increasing concentration of the boron-ion dose in the implanted layers, indicating the narrowing of the Coulomb gap in the single-particle density of states near the Fermi energy. (Abbreviation abstract)
Andrew Chakane 2019

A research report submitted to the Faculty of Science, University of the Witwatersrand, Johannesburg, in partial fulfilment of the requirements for the degree of Master of Science
The role of intersite electron correlation effects and the possible occurrence of the metal-insulator transition in carbon-ion implanted type IIa diamond samples have been studied at very low temperatures, using four- and two-point probe contact electrical conductivity measuring techniques. The measurements were extended to ruthenium oxide thin films in the presence and absence of a constant magnetic field of B = 4.0 T down to 100 mK, using a 3He-4He dilution refrigerator. The effect of the Coulomb gap in the variable range hopping regime has been well studied by other workers. The results tend to follow the Efros-Shklovskii behaviour with a trend towards the Mott T- 114 law for diamond samples far removed from the metal insulator transition, on the insulating side at low temperatures.
Andrew Chakane 2019

碩士
淡江大學
物理學系碩士班
103
We have performed x-ray absorption near edge structure (XANES) study on Cu ion implanted, fluence varies from 1x1015 to 1x1017 ions/cm2, ultra-nano crystalline diamond (UNCD) films. From the XANES of C K-edge of the films, we found that the absorption intensity of sp3 structure decreased tremendously. In the meantime, the exciton peak and the second band gap are completely disappeared. We also observed the absorption intensities due to sp2 structure, C-OH bond, C-H bond and the surface defect peaks all increase. As the Cu-ion fluence reached 1x1016 ions/cm2, the absorption intensity of sp2 peak decreases, the intensities of C-H bond and the surface defect peaks increase. When the Cu-ion fluence reached 5x1016 ions/cm2, the sp2 peak shifts to lower energy, which may be related to the formation of amorphous carbon. Also the intensity of C-OH peak increases, and the intensities of C-H and the surface defect peaks decrease at fluence of 5x1016 ions/cm2. From the spectra of Cu K-edge, the intensity of the main peak, due to Cu 1s to 4p transition, decreases as the Cu-ion fluence increases. From Cu L2,3-edge we found an obvious broadening of the main absorption peaks at the highest fluence. When the fluence increases, sp3 structure decreases and sp2 structure increases. While the fluence exceeds 5x1016 ions/cm2, sp2 structure decreases and the amorphous carbon forms. At the highest fluence, Cu 3d-4s-4p hybridization increases.

碩士
國立高雄應用科技大學
機械與精密工程研究所
93
Amorphous diamond-like carbon (DLC) films have attracted much attention in recent years because of their unique properties which are similar to those of diamond. DLC is also an attractive biomaterial, for instance, in artificial heart valves, stents, and rotary blood pumps due to their high inertness and excellent mechanical properties. The unique characteristic of DLC is that carbon atoms exist in both sp3-type tetrahedral and sp2-type trigonal bonds in a predominantly amorphous state coexisting with 20-40 at. % of hydrogen. By using different deposition methods and conditions, the fraction of sp3 bonds and hydrogen content of the films can be modulated to cater to different materials needs, for example, hardness and tribological properties. In this study, an interlayer approach was adopted to achieve adequate adhesion by reactive radio frequency (RF) magnetron sputter deposition between a Ti-DLC coating deposited and titanium substrate. The interlayer and Ti-DLC were use to reduce residual stress and increased adhesion. The various parameters such as pressure, gas flow ratio, power, substrate temperature and deposition time. The Ti-DLC thickness was 400nm~700nm. In addition to, hardness test, X-ray diffraction (XRD), Transmission Electron Microscope (TEM) and Scanning Electron Microscope (SEM) to obtain phases and film morphology. Inquire into biocompatibility of Ti-DLC were performed by cell attachment and cell proliferation by MG-63. The experiment result shows increasing along with power cluster will larger, the thickness can not linear raise with the power increment. Join the interlayer, the roughness was increase. The twin of TiC was obtained between Ti and TiC by TEM. The Ti atoms order structures were into amorphous carbon. The ID/IG ( ID: Intensity of D-Band, IG: Intensity of G-Band ) ratio changes as power changer, and when ID/IG ratio were lower, hardness were increase. The Ti-DLC films possess the better biocompatibility with MG-63 cell.

碩士
國立高雄應用科技大學
模具工程系
97
Diamond-like carbon film with sp3 and sp2 bonding has the merits of high hardness, low friction coefficient, chemical stability, hydrophobic and high biocompatibility. It may be getting highly focused on implant applications while doped with Cu elements which have the antibacterial effect. This study is investigate the properties of Cu-doped DLC films (Cu-DLC) made by reactive magnetron sputtering. The ratios of argon to methane gas (Ar/CH4) were controlled to obtain different characteristic of 1-2μm thick DLC films. The properties such as film hardness, electric resistivity, roughness and microstructures of DLC were measured by hardness tester, 4-point probe resistivity tester, atomic force microscope (AFM), X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM) and Raman spectroscope. The associated effects of Cu-DLC on antibacterial were evaluated by biological experiment in which Escherichia coli (E. coli) were used as bacterial source. The results indicate that the ordered crystals distribute among amorphous graphite matrix and the crystalline orientation is getting obvious while the Ar/CH4 ratio decreased from XRD and TEM analysis, the ID/IG reach the top value when Ar/CH4 ratio is 0.75. The surface roughnesses are getting better with the decreasing Ar/CH4 ratio due to the small and less amount of copper clusters formation. The hardness and electric resistivity also increase with Ar/CH4 ratios decreasing. For the antibacterial testing of Escherichia coli (E. coli), it appear that the efficiency can rise up to the high value of 99.99% with the 27.85% of Cu concentration in DLC.