The purpose of this thesis is to examine the potential for a more comprehensive method of analysis of coal mine dust. Respirable dust is specifically of interest due to its ability to cause occupational lung disease when miners are overexposed to airborne concentrations. A detailed standard methodology to characterize respirable mine dust is carefully investigated with the use of scanning electron microscopy with energy dispersive x-ray (SEM-EDX). In addition to a thorough description of the developed particle level characterization approach, the method is demonstrated with underground respirable dust samples collected from an underground coal mine in Central Appalachia. Results of this thesis indicate that a comprehensive dust characterization method is possible and can be efficient and effective, when standardized. This analytical approach uses measured compositions, dimensions, and shapes to produce an abundance of data in even a single sample of dust. Verification results show the method is suitable for analysis of respirable particles of common coal mine mineralogy and analysis of many samples in a timely manner. The results obtained from the underground samples in Central Appalachia reveal the quantity of information which can be generated using the developed method. The amount of data which is acquired using the more comprehensive dust characterization method may aid in understanding the health effects of various dust characteristics. / Master of Science

[EN] An integrated methodology incorporating preliminary archaeometric studies, design and performance of conservative and preventive treatments, as well as the design of an expositive support for a Montefortino helmet conserved at the Museum of Requena (Valencia, Spain), is presented. It was a bronze helmet dated back at the 3rd century B.C., providing from a terrestrial archaeological context showing intense degradation caused by cyclic corrosion associated to cuprous chlorides known as "bronze disease". The object showed advanced intergranular corrosion with deep attack of nantokite and minerals of the atacamite family, giving rise to an important structural fragility. The singularity of the object either in regard to its historic and documental value as well as in regard to its problems of mechanical and physico-chemical deterioration, have been faced from an interdisciplinary perspective around three specific aspects: i) the archaeometric study, focused on the characterization of the mechanical and physico-chemical deterioration using radiographic and analytic techniques, mainly, Optical Microscopy (OM), Scanning Electron Microscopy (SEM/EDX), X-ray Fluorescence Spectrometry (XRF) and Volammetry of Microparticles (VMP); ii) structural study on the mechanical resistance of the helmet using digital modeling techniques; iii) application of chemical decloruration conservative treatments accompanied by the study of expositive systems, including the design of a specific support. The monitoring of the conservation state of the object was carried out by means of climatic control and analytical examination after seven years of Museum exposition, showing that the helmet still maintains an acceptable level of mechanical and physico-chemical stability. / [ES] Se desarrolla una metodología integrada que atiende a los estudios arqueométricos previos, el diseño y ejecución de tratamientos conservativos y preventivos, así como el diseño del soporte expositivo de un Casco Montefortino conservado en el Museo de Requena (Valencia). Se trata de un casco de bronce de en torno a la mitad del siglo III a.C., procedente de un contexto arqueológico terrestre y que presentaba un proceso de degradación avanzado a causa de la corrosión cíclica producida por los cloruros cuprosos conocida como "enfermedad del bronce", habiéndose detectado una corrosión intergranular avanzada con ataques profundos de nantokita y minerales del grupo de la atacamita dando lugar, como consecuencia, a una fragilidad estructural importante. Tanto la singularidad de la pieza en cuanto a su valor histórico y documental, como el interés derivado de sus problemas de deterioro mecánico y químico, se han abordado desde una perspectiva interdisciplinar en torno a tres ámbitos específicos: i) el estudio arqueométrico, centrado en la caracterización de los deterioros físico-químicos y estructurales mediante técnicas radiográficas y analíticas, incorporando Microscopía Óptica (MO), Microscopía Electrónica de Barrido (SEM/EDX), Espectrometría por Fluorescencia de rayos X y Voltamperometría de Micropartículas (VMP); ii) el estudio estructural mediante técnicas de modelización digital sobre la resistencia mecánica del casco; iii) la aplicación de tratamientos conservativos de decloruración química acompañados del estudio de sistemas expositivos incluyendo el diseño de un soporte específico. Se ha procedido igualmente a un seguimiento de la pieza en exposición mediante control climático y examen analítico tras siete años de exposición, evidenciando que el Casco continúa manteniendo unos niveles de estabilidad físico-químicos y estructurales aceptables / [CA] Es presenta una metodologia integrada atenent als estudis arqueomètrics previs, el disseny i realització de tractaments conservatius i preventius així com el disseny d'un suport expositiu d'un Casc Montefortí conservat al Museu de Requena (València). Es tracta d'un casc de bronze datat al voltant de la meitat del segle III a.C., provinent d'un context arqueològic terrestre i que mostrava un procés de degradació avançat a causa de la corrosió cíclica produïda pels clorurs cuprosos coneguda com "malaltia del bronze", havent-se detectat una corrosió inter-granular avançada amb atacs profunds de nantokita i minerals del grup de l'atacamita donant lloc, com a conseqüència, a una fragilitat estructural important. Tant la singularitat de la peça en quant al seu valor històric i documental, com l'interès derivat dels seus problemes de deteriorament mecànic i químic, se han abordat des d'una perspectiva inter-disciplinar al voltant de tres àmbits específics: i) l'estudi arqueomètric, centrat en la caracterització dels deterioraments físic-químics i estructurals mitjançant tècniques radiogràfiques i analítiques, tot i incorporant Microscòpia Òptica (MO), Microscòpia Electrònica de Escombrat (SEM/EDX), Espectrometria per Fluorescència de raigs X i Voltamperometria de Micropartícules (VMP); ii) l'estudi estructural mitjançant tècniques de modelització digital sobre la resistència mecànica del casc; iii) l'aplicació de tractaments conservatius de de-cloruració química acompanyats de l'estudi de sistemes expositius incloent el disseny d'un suport específic. S'ha procedit igualment a un seguiment de la peça en exposició mitjançant control climàtic i examen analític rere set anys de exposició, evidenciant que el Casc continua mantenint uns nivells d'estabilitat fisico-química i estructural acceptables. / Martínez Lazaro, ID. (2016). Estudios integrados de procesos analíticos y conservativos de bronce arqueológico. Aplicación a un casco montefortino y otros materiales afines [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/61456

[ES] Las piezas numismáticas constituyen un importante porcentaje de las colecciones de los museos y una de las evidencias que con mayor frecuencia se encuentra en las excavaciones, tratándose de vestigios arqueológicos e históricos fundamentales para el estudio de diferentes aspectos de las sociedades pasadas. Para la investigación y la caracterización de estos materiales es necesario el empleo de técnicas analíticas no invasivas o nanoinvasivas que no comprometan la integridad de las monedas. En este trabajo se presentan los resultados obtenidos en la exploración de las capacidades de dos técnicas instrumentales analíticas, VIMP y FIB-FESEM-EDX, ambas de carácter nanoinvasivo, en colecciones numismáticas fabricadas en aleaciones en base cobre, escasamente empleadas en el estudio de patrimonio metálico hasta la fecha. Además, y en cada caso de estudio abordado, se han diseñado estrategias multitécnica que incluye el uso de SEM-EDX, espectroscopia FTIR, M.O., colorimetría y espectroscopia Raman. En una primera parte de la investigación se han desarrollado metodologías analíticas para la identificación y discriminación de aleaciones, productos de corrosión e intervenciones previas en tres colecciones de distinta titularidad y procedentes de diferentes ambientes. La primera colección, procede de un ambiente aéreo o atmosférico y es de titularidad privada, la colección Doménech-Francés. La segunda colección, procede de un ambiente de enterramiento y pertenece al Museu de Prehistòria de València. La última colección estudiada con esta finalidad procede de un ambiente subacuático, y pertenece al Museo Nacional de Arqueología Subacuática. En la segunda parte, el trabajo se centra en el desarrollo de una metodología innovadora basada en la técnica de electroquímica en estado sólido VIMP, que permite la discriminación entre cecas y el conocimiento de las técnicas de acuñación empleadas. Esta nueva metodología se ha implementado sobre dos casos de estudio diferentes: el primero consiste en una serie de maravedís acuñados entre 1661 y 1664 por Felipe IV, y el segundo, en una colección de monedas íberas acuñadas en las cecas de Cástulo, Obulco e Iltirta entre los siglos II y I a.C., pertenecientes al Museu de Prehistòria de València. / [CA] Las peces numismàtiques constitueixen un important percentatge de les col·leccions dels museus i una de les evidències que amb major freqüència es troba en les excavacions, i es tracta de vestigis arqueològics i històrics fonamentals per a l'estudi de diferents aspectes de les societats passades. Per a la investigació i la caracterització d'aquests materials és necessari l'ús de tècniques analítiques no invasives o nanoinvasives, que no comprometen la integritat de les monedes. En aquest treball es presenten els resultats obtinguts en l'exploració de les capacitats de dues tècniques instrumentals analítiques, VIMP i FIB-FESEM-EDX, ambdues de caràcter nanoinvasiu, en col·leccions numismàtiques fabricades en aliatges amb base de coure, escassament emprades en l'estudi del patrimoni metàl·lic fins avui. A més, en cada cas d'estudi abordat, s'han dissenyat estratègies multitècnica que inclouen l'ús de SEM-EDX, espectroscòpia FTIR, M.O., colorimetria i espectroscòpia Raman. En una primera part de la investigació s'han desenvolupat metodologies analítiques per a la identificació i discriminació d'aliatges, productes de corrosió i intervencions prèvies en tres col·leccions de diferent titularitat i procedents de diferents ambients. La primera col·lecció, procedeix d'un ambient aeri o atmosfèric i és de titularitat privada, la col·lecció Doménech-Francés. La segona col·lecció procedeix d'un ambient d'enterrament i pertany al Museu de Prehistòria de València. La última col·lecció estudiada amb aquesta finalitat procedeix d'un ambient subaqüàtic i pertany al Museu Nacional d'Arqueologia Subaqüàtica. En la segona part, el treball se centra en el desenvolupament d'una metodologia innovadora basada en la tècnica d'electroquímica en estat sòlid VIMP, que permet la discriminació entre seques i el coneixement de les tècniques d'encunyació emprades. Aquesta nova metodologia s'ha implementat sobre dos casos d'estudi diferents: el primer consisteix en una sèrie de maravedís encunyats entre el 1661 i el 1664 per Felip IV; i el segon, en una col·lecció de monedes iberes encunyades a les seques de Cástulo, Obulco i Iltirta entre els segles II i I a. de C., pertanyents al Museu de Prehistòria de València. / [EN] The numismatic pieces constitute an important part of the collections of the museums and one of the evidences that more frequently found in the excavations, being archaeological and historical vestiges fundamental for the study of severe aspects of the past societies. The use of non-invasive or nanoinvasive analytical techniques that do not compromise the integrity of the coins is essential for the investigation and characterization of these materials. This PhD presents the results obtained in the exploration of the capabilities of two nanoinvasive analytical instrumental techniques, VIMP and FIB-FESEM-EDX, in numismatic collections made of copper-based alloys, scarcely used in the study of heritage metallic so far. In addition, and in each study case discussed, multi-technical strategies have been designed that include the use of SEM-EDX, FTIR spectroscopy, O.M., colorimetry and Raman spectroscopy. In the first part of the investigation, analytical methodologies for the identification and discrimination of alloys, corrosion products and previous interventions in three collections of different ownership and coming from different environments have been developed. The first collection, comes from an air or atmospheric environment, is privately owned, the Doménech-Francés collection, the second collection, comes from a burial environment and belongs to the Museum of Prehistory of Valencia, and the last collection studied for this purpose, comes from an underwater environment and belongs to the National Museum of Underwater Archaeology. In the second part, the work focuses on the development of an innovate methodology based on the technique of solid-state electrochemistry VIMP that allows the discrimination between mints and the knowledge of the coinage techniques used. This new methodology has been implemented on two different case studies: the first consists of a series of maravedís coined between 1661 and 1664 by Philip IV, and the second, in a collection of iberian coins minted in the mints of Cástulo, Obulco and Iltirta between the 2nd and 1st centuries BC, and belonging to the Museum of Prehistory of Valencia. / Agradecer todo el apoyo institucional que he tenido: al contrato FPI del Ministerio de Economía, Industria y Competitividad del que he podido disfrutar durante estos cuatro años (referencia de la ayuda BES-2015-072439) enmarcado dentro de los proyectos CTQ2014-53736- C3-1-P y CTQ2014-53736-C3-2-P, al proyecto CTQ2017-85317-C2-1-P, del Ministerio de Ciencia, Innovación y Universidades y cofinanciado por el Fondo Europeo de Desarrollo Regional (ERDF) y la Agencia Estatal de Investigación (AEI) / Álvarez Romero, C. (2020). DESARROLLO DE MÉTODOS DE CARACTERIZACIÓN Y CONTROL DE TRATAMIENTOS DE CONSERVACIÓN DE COLECCIONES NUMISMÁTICAS MEDIANTE TÉCNICAS DE MICROSCOPÍA ELECTRÓNICA Y NANOELECTROQUÍMICA [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/140316

Grâce à ses propriétés d’antioxydant, d’anti-usure et éventuellement d’extrême pression le dithiophosphate de zinc (ZDDP) fait partie des additifs les plus utilisés dans les lubrifiants pour moteurs thermiques. De nos jours, dans un souci de respect de l’environnement, de nouveaux lubrifiants possédant de bonnes performances en lubrification (frottement faible et usure limitée) sont développés en prenant compte des limitations d’utilisations actuelles du ZDDP. L’idée étant de réduire dans ceux-ci les teneurs en phosphore et soufre (Normes euros VI), éléments essentiels du ZDDP qui endommagent les pots catalytiques. L’objectif de cette thèse est l’étude du comportement tribologique du phosphate de zinc di alkyl (ZP) en comparaison avec le ZDDP. La méthodologie expérimentale étudiée pour comprendre le mécanisme d’action de ces additifs, associe des essais de frottement à descaractérisations physico-chimiques des surfaces frottantes après essais.Cette comparaison a été effectuée en fonction de la température (25°C et 100°C), la vitesse de glissement (25, 50 et 100 mm/s) et la concentration en additif (200 et 600 ppm dephosphore). Les meilleures actions anti-usure sont obtenues avec le ZDDP pour une température de 100°C et une vitesse de glissement de 100 mm/s et le ZP pour une température de 25°C et une vitesse de glissement de 25 mm/s. Les analyses de surface XPS, AES, XANES et MET-EDX ont permis de mettre en évidence la présence d’un film protecteur constitué principalement de phosphate de zinc, ceci pour les deux additifs.Une synergie de comportement tribologique a été mise en évidence avec un lubrifiantconstitué de ZP (usure faible) et d’oléate d’urée (frottement faible). Des essais complémentaires sur un tribomètre dynamique ont permis d’étudier le niveau de frottement du tribofilm formé à partir du ZDDP. Le caractère visqueux du tribofilm de ZDDP a été mis en évidence. / Thanks to its antioxidant, anti-wear and extreme pressure properties, zinc dialkyldithiophosphate (ZDDP) is nowadays the most used anti-wear additives in engine oil. Due to environmental protection concerns, new lubricants with good tribological performances (low friction and low wear) are developed. This research aims to evaluate the current limitations of ZDDP and to find alternative environmentally friendly solutions. Thus, the target is to reduce the quantity of phosphorus and sulphur in lubricants, two essential elements of ZDDP molecule that damage catalytic. The objective of this thesis is to study tribological behavior of zinc phosphate di alkyl (ZP) in comparison to ZDDP. The experimental method performed is the coupling of friction test with surface physico-chemical characterisation of rubbing surface after tests.This comparison carried out according to the temperature (25°C and 100°C), the sliding speed (25, 50, 100 mm/s) and additives concentrations (200 and 600 ppm). The best anti-wear efficiency is obtained with the ZDDP additive at 100°C - 100 mm/s and with the ZP at 25°C - 25 mm/s. For both additives and under these conditions, tribofilms are mainly made of zinc phosphate.A tribological synergy are obtained with a lubricant contained ZP (low wear) and oleyl urea (low friction). Complementary tests were made on a original dynamic tribometer for a better understanding of ZDDP tribofilm friction behavior. The viscous character of ZDDP tribofilm was obtained.

As metaloproteinases da matriz (MMPs) foram identificadas na saliva, na placa dental, na dentina e no cemento. Este trabalho teve como objetivos: Estudo I (I) - avaliar a expressão de MMP-2 e MMP-9 presentes na saliva total e parotidiana e no fluido gengival crevicular (FGC) de pacientes portadores e não portadores de lesões cervicais não cariosas (LCNC); Estudo II (II) - investigar se a presença de MMP-8 e -9/TIMPs poderia influenciar a remineralização de lesões artificialmente criadas na superfície radicular, com ou sem desgaste por abrasão. Os métodos utilizados foram: (I) Coleta de amostras de saliva e do FGC de 32 pacientes, com (n=16) e sem LCNC (n=16). A atividade gelatinolítica das MMPs foi avaliada através de análise zimográfica e Western Blot. (II): Espécimes de dentina humana radicular foram obtidos. O grupo controle G1(10) não sofreu nenhum tratamento. Os demais segmentos radiculares foram desmineralizados G2(60). O Grupo A não foi submetido à escovação e o Grupo B foi submetido à abrasão por escovação em uma máquina de escovação simulada. G2(10) foi apenas desmineralizado, G3(10) desmineralizado e remineralizado, e os Grupos G4(10), G5(10), G6(10), G7(10) foram desmineralizados e remineralizados em presença de tampão neutro, TIMP, MMP-8 e -9, MMP-8,-9 e TIMP, respectivamente. Para a análise elemental, as concentrações de Ca+2, P, Mg+2 assim como a relação molar Ca/P e Mg/Ca foram determinadas através de uma sonda eletrônica para microanálise (EPMA). A análise qualitativa por retrodispersão (BSE) foi realizada para demonstrar a distribuição global da densidade mineral. Os resultados (I) mostraram que a principal gelatinase presente, tanto na saliva total quanto no FGC, é a proMMP-9. Na saliva secretada pela glândula parótida, não foram detectadas bandas indicando a presença de gelatinases. Os resultados do estudo (II) indicaram que os espécimes escovados apresentaram maior conteúdo de Ca+2 a 20µm e maior conteúdo de Mg+2 a 30 e 50µm. Em presença de TIMPs, ocorreu uma redução do conteúdo de Ca+2 a 20µm. Para os espécimes não escovados, em todas as profundidades, as amostras incubadas com MMPs apresentaram maiores valores de Ca+2. Portanto, pode-se concluir que (I) a comparação entre pacientes com e sem LCNC mostrou não haver diferença estatisticamente significante quanto à atividade gelatinolítica; (II) quando não inibidas pelos TIMPs, as MMPs degradaram o colágeno completamente desmineralizado na superfície radicular, permitindo melhor recalcificação na superfície subjacente. Esse fenômeno foi também facilitado pela abrasão por escovação. / Matrix metalloproteinases (MMPs) have been identified in saliva, plaque, gingival crevicular fluid (GCF), dentin and cementum. Study (I) aimed at evaluating the presence and quantity of gelatinases MMP-2 and MMP-9 in total and parotid saliva and in GCF (GCF) of subjects with and without NCCL. Study (II) aimed at investigating whether the presence of matrix metalloproteinase (MMP)-8 and - 9/TIMPs would influence the remineralization of artificial root lesions with and without mechanical wear. (I) Total stimulated saliva, parotid saliva, and GCF from patients with (n=16) and without NCCL (n=16) were collected and assessed for gelatin zymography and for western immunoblot analysis. (II) Human root segments from Group A (n=35) were not brushed and from Group B (n=35) were subjected to machine-controlled brushing, simulating mechanical wear. Specimens from Group 1 (control, n=10) were left untreated. Group 2 (n=10), was just demineralized; Group 3 (n=10) was demineralized and remineralized. The other samples G4 (n=10), G5 (n=10), G6 (n=10), G7 (n=10) were subjected to remineralization with HEPES buffer, tissue inhibitor of matrix metalloproteinase-2 (TIMP-2), activated MMP-8 and MMP-9 and activated MMP-8, MMP-9 and TIMP-2, respectively. Ca+2, P, Mg+2 concentrations as well as Ca/P and Mg/Ca molar ratios were determined through an Electron Probe Microanalyser (EPMA). (I) Densitometric analysis revealed that the main gelatinase was proMMP-9. No statistically significant difference was observed for MMP-2 and MMP-9 levels, separately. In parotid saliva, gelatinolytic activity was very low or absent. Western immunoblots revealed that, while little immunoreactivity was detected for MMP-2, there was positive immunoreaction for MMP-9, both in total saliva and in GCF. Gelatinases do not seem to originate from parotid gland. (II) The results indicated that the brushed specimens presented higher Ca+2 levels at 20 µm and higher Mg+2 content at 30 and 50 µm. Ca+2 content at 20 µm decreased in the presence of TIMPs. For the non-brushed specimens, in all depths, samples incubated with MMPs showed highest Ca+2 values. It can be concluded that (I) the main gelatinase present in the oral cavity is MMP-9. No significant differences were found in total gelatinolytic activity among NCCL+ and NCCL- patients. (II) When not inhibited by TIMPs, MMPs degraded the completely demineralized collagen in the root surface, allowing for better recalcification in the deeper areas. This phenomenon was also facilitated by the brushing procedure.

Ein Spezialgebiet der modernen Mikroelektronik ist die Miniaturisierung und Entwicklung von neuen nanostrukturierten und Komposit-Materialen aus 3d-Metallen. Durch geeignete Zusammensetzungen können diese sowohl mit einer hohen Sättigungsmagnetisierung und Koerzitivfeldstärke als mit besserer Oxidationsbeständigkeit im Vergleich zu den reinen Elementen erzielt werden.<br /> <br /> In der vorliegenden Arbeit werden neue Methoden für die Herstellung von bimetallischen kolloidalen Nanopartikeln vor allem mit einer Kern-Hülle-Struktur (Kern@Hülle) präsentiert. Bei der überwiegenden Zahl der vorgestellten Reaktionen handelt es sich um die thermische Zersetzung von metallorganischen Verbindungen wie Kobaltcarbonyl, Palladium- und Platinacetylacetonate oder die chemische Reduktion von Metallsalze mit langkettigem Alkohol in organischem Lösungsmittel. Daneben sind auch Kombinationen aus diesen beiden Verfahren beschrieben. Es wurden Kolloide aus einem reinen Edelmetall (Pt, Pd, Ag) in einem organischen Lösungsmittel synthetisiert und daraus neue, bisher in dieser Form nicht bekannte Ag@Co-, Pt@Co-, Pd@Co- und Pt@Pd@Co-Nanopartikel gewonnen.<br /> <br /> Der Kobaltgehalt der Ag@Co-, Teilchen konnte im Bereich von 5 bis 73 At. % beliebig eingestellt werden. Der mittlere Durchmesser der Ag@Co-Partikel wurde von 5 nm bis 15 nm variiert. Bei der Herstellung von Pt@Co-Teilchen wurde eine unterschiedlich dicke Kobalt-Hülle von ca. 1,0 bis 2,5 nm erzielt. Im Fall des Palladiums wurden sowohl monodispere als auch polydisperse Pd-Nanopartikel mit einer maximal 1,7-2,0nm dicken Kobalthülle synthetisiert.<br /> <br /> Ein großer Teil dieser Arbeit befasst sich mit den magnetischen Eigenschaften der kolloidalen Teilchen, wobei die SQUID-Magnetometrie und Röntgenzirkulardichroismus (XMCD) dafür eingesetzt wurden. Weil magnetische Messungen alleine nur indirekte Schlüsse über die untersuchten Systeme erlauben, wurde dabei besonderer Wert auf die möglichst genaue strukturelle Charakterisierung der Proben mittels moderner Untersuchungsmethoden gelegt. Röntgendiffraktometrie (XRD), Röntgenabsorptionsfeinstruktur- (EXAFS) und UV-Vis-Spektroskopie sowie Transmissionselektronenmikroskopie (TEM) in Kombination mit Elektronen Energieverlustspektroskopie (EELS) und energiedispersive Röntgenfluoreszensanalyse (EDX) wurden verwendet. / Magnetic colloidal particles are attractive because of their possible application to ultra-high-density magnetic data storage media, sensors, electronic devices and medical diagnostics. The properties of small particles depend on their composition, shape, and method of preparation. The combination of 3d-metals (Fe, Co, Ni) with noble metals improves the stability of the colloids and leads to new properties of the magnetic systems, often distinct from those of the corresponding monometallic particles. Core-shell particles, where dia- or paramagnetic noble metal-cores are surrounded by a ferromagnetic Co-shell, are an interesting system to study surface and interfacial magnetism such as an induced polarization or a giant magnetoresistance effect. <br /> <br /> In this work, new synthetic routes for the preparation of monometallic (Pt, Pd, Ag) and bimetallic magnetic nanocrystals (Ag@Co, Pt@Co, Pd@Co) with core-shell structure are presented. Stable colloids with a narrow particle size distribution were obtained in organic solvents using methods of wet chemistry. The method of preparation of Ag@Co is based on the thermal decomposition of dicobalt octycarbonyl in combination with a transmetalation reaction with water free AgClO4. The cobalt amount in the Ag@Co system could be tuned from 5 to 73 at. %. The average diameter of the particles was varied from 5 to 15 nm. <br /> <br /> The reduction of platinum and palladium salts in organic solution using long chained alcohol as the reductant leads to stable metal nanostructures. Monodisperse Pd and Pt particles with average sizes of 1.7 to 7.0 nm were synthesized via thermal decomposition of metal-surfactant complexes too. Alkylamines and alkylphosphines were used in this procedure. The thickness of the Co-shell was controlled by a simple high-temperature thermolysis of dicobalt octacarbonyl at the presence of Pd and Pt seeds and was tunable from 0.5 to 2.5 nm. <br /> <br /> The crystalline structure of the samples was characterized by transmission electron microscopy (TEM), energy dispersive x-ray spectroscopy (EDX), UV-VIS and electron-energy loss spectroscopy (EELS). SQUID magnetometry, x-ray magnetic circular dichroism (XMCD) and extended x-ray absorption fine structure (EXAFS) measurements gave information about the magnetic properties of the bimetallic systems and revealed their dependency on the particle size and the chemical composition. A high spin to orbital moments ratio µL/µS of 0.26±0.06 for Ag@Co and 0.22±0.05 for Pt@Co nanocrystals was observed at XMCD measurements due to the lowered dimensionality the investigated systems.

Dans ce travail de thèse a été développé et étudié un nouveau type d'objet semiconducteur magnétique : des boîtes quantiques de CdMnTe insérées dans des nanofils de ZnTe/ZnMgTe constituant une structure de type cœur-coquille. L'objectif était d'étudier la croissance par épitaxie par jets moléculaires et les propriétés fondamentales de ces hétéro-structures complexes. Dans ce but deux aspects principaux ont été abordés : i) la qualité et le contrôle des propriétés structurales, électroniques et magnétiques de ces objets, grâce à une maîtrise de leur croissance et ii) l'obtention d'informations quantitatives locales sur la composition chimique de ces nanostructures inhomogènes. Pour atteindre ces objectifs, nous avons divisé notre étude en quatre étapes. La première étape de ce travail a été concentrée sur l'étude quantitative de la formation des particules d'or servant de catalyseurs à la croissance des nanofils. La seconde étape a porté sur l'analyse des mécanismes de croissance et des paramètres gouvernant la croissance des fils de ZnTe. En particulier deux types de fils ont été observés : des fils cylindriques de structure wurtzite et des fils coniques de structures zinc-blende. Un modèle de croissance guidée par la diffusion a été utilisé pour rendre compte de certains des résultats quantitatifs présentés dans cette partie. La troisième étape a concerné l'insertion de boîtes quantiques de CdMnTe dans des nanofils de structure cœur-coquille ZnTe/ZnMgTe. Une étude préalable des paramètres pertinents influençant les propriétés magnéto-optiques de ces objets, tels que le confinement de la boîte quantique, l'incorporation du Mn et l'anisotropie de contrainte créée par la structure, a été menée. La quatrième et dernière étape de ce travail a porté sur l'interprétation quantitative de mesures d'analyse dispersive en énergie effectuées sur des nanofils de structure cœur-multicoquille. Un modèle géométrique a été proposé, permettant de retrouver la forme, les dimensions et la composition chimique des boîtes quantiques et des coquilles. Cette étude a été couplée à des mesures de caractérisation telles que la cathodo-luminescence, la micro-photo-luminescence et la spectroscopie magnéto-optique effectuées sur le même nanofil. / In this PhD work a novel type of magnetic semiconductor object has been developed: Cd(Mn)Te quantum dots embedded in ZnTe/ZnMgTe core-shell nanowires. The goal was to investigate the growth, by molecular beam epitaxy, and the fundamental properties of these complex heterostructures. For that purpose, two main issues were addressed: i) gaining control of the structural, electronic and magnetic properties of these quantum objects by mastering their growth; and ii) obtaining quantitative local knowledge on the chemical composition of those non-homogeneous nanostructures. To tackle these topics, our research was divided into four stages. The first stage was devoted to perform a quantitative study of the formation process of the Au particles that catalyze the growth of nanowires. The second stage involved the analysis of the mechanisms and parameters governing the growth of ZnTe nanowires. In particular, two different types of nanowires were found: cone-shaped nanowires with the zinc-blende crystal structure and cylinder-shaped nanowires with the hexagonal wurtzite structure. A diffusion-driven growth model is employed to fit some of the quantitative results presented in this part. The third stage focused on the insertion of pure CdTe quantum dots containing Mn ions in the core-shell nanowires. An initial study of the relevant parameters influencing the magneto-optical properties of these objects, such as the quantum dot confinement, the Mn incorporation, and the strain anisotropy, was performed. The four and last stage of this work concerned the quantitative interpretation of Energy-Dispersive X-ray spectroscopy measurements performed on single core-multishell nanowires. A geometrical model was proposed to retrieve the shape, the size and the local composition of the quantum dot insertions and of the multiple layers of the heterostructures. This study was coupled to other complementary characterization measurements on the same nanowire, such as cathodo-luminescence, micro-photo-luminescence and magneto-optical spectroscopy.

Dans ce travail de thèse a été développé et étudié un nouveau type d'objet semiconducteur magnétique : des boîtes quantiques de CdMnTe insérées dans des nanofils de ZnTe/ZnMgTe constituant une structure de type cœur-coquille. L'objectif était d'étudier la croissance par épitaxie par jets moléculaires et les propriétés fondamentales de ces hétéro-structures complexes. Dans ce but deux aspects principaux ont été abordés : i) la qualité et le contrôle des propriétés structurales, électroniques et magnétiques de ces objets, grâce à une maîtrise de leur croissance et ii) l'obtention d'informations quantitatives locales sur la composition chimique de ces nanostructures inhomogènes. Pour atteindre ces objectifs, nous avons divisé notre étude en quatre étapes. La première étape de ce travail a été concentrée sur l'étude quantitative de la formation des particules d'or servant de catalyseurs à la croissance des nanofils. La seconde étape a porté sur l'analyse des mécanismes de croissance et des paramètres gouvernant la croissance des fils de ZnTe. En particulier deux types de fils ont été observés : des fils cylindriques de structure wurtzite et des fils coniques de structures zinc-blende. Un modèle de croissance guidée par la diffusion a été utilisé pour rendre compte de certains des résultats quantitatifs présentés dans cette partie. La troisième étape a concerné l'insertion de boîtes quantiques de CdMnTe dans des nanofils de structure cœur-coquille ZnTe/ZnMgTe. Une étude préalable des paramètres pertinents influençant les propriétés magnéto-optiques de ces objets, tels que le confinement de la boîte quantique, l'incorporation du Mn et l'anisotropie de contrainte créée par la structure, a été menée. La quatrième et dernière étape de ce travail a porté sur l'interprétation quantitative de mesures d'analyse dispersive en énergie effectuées sur des nanofils de structure cœur-multicoquille. Un modèle géométrique a été proposé, permettant de retrouver la forme, les dimensions et la composition chimique des boîtes quantiques et des coquilles. Cette étude a été couplée à des mesures de caractérisation telles que la cathodo-luminescence, la micro-photo-luminescence et la spectroscopie magnéto-optique effectuées sur le même nanofil. / In this PhD work a novel type of magnetic semiconductor object has been developed: Cd(Mn)Te quantum dots embedded in ZnTe/ZnMgTe core-shell nanowires. The goal was to investigate the growth, by molecular beam epitaxy, and the fundamental properties of these complex heterostructures. For that purpose, two main issues were addressed: i) gaining control of the structural, electronic and magnetic properties of these quantum objects by mastering their growth; and ii) obtaining quantitative local knowledge on the chemical composition of those non-homogeneous nanostructures. To tackle these topics, our research was divided into four stages. The first stage was devoted to perform a quantitative study of the formation process of the Au particles that catalyze the growth of nanowires. The second stage involved the analysis of the mechanisms and parameters governing the growth of ZnTe nanowires. In particular, two different types of nanowires were found: cone-shaped nanowires with the zinc-blende crystal structure and cylinder-shaped nanowires with the hexagonal wurtzite structure. A diffusion-driven growth model is employed to fit some of the quantitative results presented in this part. The third stage focused on the insertion of pure CdTe quantum dots containing Mn ions in the core-shell nanowires. An initial study of the relevant parameters influencing the magneto-optical properties of these objects, such as the quantum dot confinement, the Mn incorporation, and the strain anisotropy, was performed. The four and last stage of this work concerned the quantitative interpretation of Energy-Dispersive X-ray spectroscopy measurements performed on single core-multishell nanowires. A geometrical model was proposed to retrieve the shape, the size and the local composition of the quantum dot insertions and of the multiple layers of the heterostructures. This study was coupled to other complementary characterization measurements on the same nanowire, such as cathodo-luminescence, micro-photo-luminescence and magneto-optical spectroscopy.

As metaloproteinases da matriz (MMPs) foram identificadas na saliva, na placa dental, na dentina e no cemento. Este trabalho teve como objetivos: Estudo I (I) - avaliar a expressão de MMP-2 e MMP-9 presentes na saliva total e parotidiana e no fluido gengival crevicular (FGC) de pacientes portadores e não portadores de lesões cervicais não cariosas (LCNC); Estudo II (II) - investigar se a presença de MMP-8 e -9/TIMPs poderia influenciar a remineralização de lesões artificialmente criadas na superfície radicular, com ou sem desgaste por abrasão. Os métodos utilizados foram: (I) Coleta de amostras de saliva e do FGC de 32 pacientes, com (n=16) e sem LCNC (n=16). A atividade gelatinolítica das MMPs foi avaliada através de análise zimográfica e Western Blot. (II): Espécimes de dentina humana radicular foram obtidos. O grupo controle G1(10) não sofreu nenhum tratamento. Os demais segmentos radiculares foram desmineralizados G2(60). O Grupo A não foi submetido à escovação e o Grupo B foi submetido à abrasão por escovação em uma máquina de escovação simulada. G2(10) foi apenas desmineralizado, G3(10) desmineralizado e remineralizado, e os Grupos G4(10), G5(10), G6(10), G7(10) foram desmineralizados e remineralizados em presença de tampão neutro, TIMP, MMP-8 e -9, MMP-8,-9 e TIMP, respectivamente. Para a análise elemental, as concentrações de Ca+2, P, Mg+2 assim como a relação molar Ca/P e Mg/Ca foram determinadas através de uma sonda eletrônica para microanálise (EPMA). A análise qualitativa por retrodispersão (BSE) foi realizada para demonstrar a distribuição global da densidade mineral. Os resultados (I) mostraram que a principal gelatinase presente, tanto na saliva total quanto no FGC, é a proMMP-9. Na saliva secretada pela glândula parótida, não foram detectadas bandas indicando a presença de gelatinases. Os resultados do estudo (II) indicaram que os espécimes escovados apresentaram maior conteúdo de Ca+2 a 20µm e maior conteúdo de Mg+2 a 30 e 50µm. Em presença de TIMPs, ocorreu uma redução do conteúdo de Ca+2 a 20µm. Para os espécimes não escovados, em todas as profundidades, as amostras incubadas com MMPs apresentaram maiores valores de Ca+2. Portanto, pode-se concluir que (I) a comparação entre pacientes com e sem LCNC mostrou não haver diferença estatisticamente significante quanto à atividade gelatinolítica; (II) quando não inibidas pelos TIMPs, as MMPs degradaram o colágeno completamente desmineralizado na superfície radicular, permitindo melhor recalcificação na superfície subjacente. Esse fenômeno foi também facilitado pela abrasão por escovação. / Matrix metalloproteinases (MMPs) have been identified in saliva, plaque, gingival crevicular fluid (GCF), dentin and cementum. Study (I) aimed at evaluating the presence and quantity of gelatinases MMP-2 and MMP-9 in total and parotid saliva and in GCF (GCF) of subjects with and without NCCL. Study (II) aimed at investigating whether the presence of matrix metalloproteinase (MMP)-8 and - 9/TIMPs would influence the remineralization of artificial root lesions with and without mechanical wear. (I) Total stimulated saliva, parotid saliva, and GCF from patients with (n=16) and without NCCL (n=16) were collected and assessed for gelatin zymography and for western immunoblot analysis. (II) Human root segments from Group A (n=35) were not brushed and from Group B (n=35) were subjected to machine-controlled brushing, simulating mechanical wear. Specimens from Group 1 (control, n=10) were left untreated. Group 2 (n=10), was just demineralized; Group 3 (n=10) was demineralized and remineralized. The other samples G4 (n=10), G5 (n=10), G6 (n=10), G7 (n=10) were subjected to remineralization with HEPES buffer, tissue inhibitor of matrix metalloproteinase-2 (TIMP-2), activated MMP-8 and MMP-9 and activated MMP-8, MMP-9 and TIMP-2, respectively. Ca+2, P, Mg+2 concentrations as well as Ca/P and Mg/Ca molar ratios were determined through an Electron Probe Microanalyser (EPMA). (I) Densitometric analysis revealed that the main gelatinase was proMMP-9. No statistically significant difference was observed for MMP-2 and MMP-9 levels, separately. In parotid saliva, gelatinolytic activity was very low or absent. Western immunoblots revealed that, while little immunoreactivity was detected for MMP-2, there was positive immunoreaction for MMP-9, both in total saliva and in GCF. Gelatinases do not seem to originate from parotid gland. (II) The results indicated that the brushed specimens presented higher Ca+2 levels at 20 µm and higher Mg+2 content at 30 and 50 µm. Ca+2 content at 20 µm decreased in the presence of TIMPs. For the non-brushed specimens, in all depths, samples incubated with MMPs showed highest Ca+2 values. It can be concluded that (I) the main gelatinase present in the oral cavity is MMP-9. No significant differences were found in total gelatinolytic activity among NCCL+ and NCCL- patients. (II) When not inhibited by TIMPs, MMPs degraded the completely demineralized collagen in the root surface, allowing for better recalcification in the deeper areas. This phenomenon was also facilitated by the brushing procedure.

La pollution atmosphérique urbaine pose des problèmes au niveau de l'environnement et de la santé publique pour plus de la moitié de la population mondiale. Afin de réduire la pollution de fond dans les villes, un matériau cimentaire innovant a été développé et permet de dégrader les polluants atmosphériques grâce à ses propriétés photocatalytiques induites par l'ajout de TiO2. Ce travail a porté sur la corrélation entre les propriétés physico-chimiques et l'efficacité photocatalytique d'un mortier enrichi en TiO2 lors de la dégradation de 2 composés organiques volatils (COV), le formaldéhyde et le toluène ainsi que sur un mélange d'oxydes d'azote (NOx). Le taux de présence de la surface en dioxyde de titane, le pourcentage relatif de titane et l'absorbance des photons UV par TiO2 ont été respectivement déterminés par spectroscopie Raman, microscopie électronique à balayage couplé à une analyse X et spectroscopie UV-visible par réflexion diffuse. La proportionnalité entre ces 3 grandeurs a été démontrée. L'efficacité photocatalytique des matériaux cimentaires enrichis en TiO2 a été mise en évidence pour la dégradation des 2 COV et des NOx. L'efficacité photocatalytique est reliée à la présence de TiO2 en surface ainsi qu'à la capacité de TiO2 à absorber des photons UV. La matrice cimentaire permet également, à l'obscurité, de réduire significativement la concentration en formaldéhyde. L'étude de l'influence des paramètres matériaux et environnementaux a montré l'importance de la teneur en TiO2, du flux lumineux et de l'humidité relative sur les propriétés photocatalytiques du mortier et permis de contribuer à une meilleure compréhension des réactions intervenant lors de la dégradation des polluants par un matériau cimentaire photocatalytique / More than half of the world population is exposed to urban air pollution which poses problems for the environment and human health. To reduce the background of the pollution in cities, an innovative cementitious material has been developed and used to degrade pollutants thanks to its photocatalytic properties induced by the addition of TiO2. This work was focused on the correlation between physicochemical properties and the photocatalytic efficiency of a mortar enriched with TiO2 during the degradation of two volatile organic compounds (VOCs), formaldehyde and toluene as well as a mixture of nitrogen oxides (NOx). The occurence rate of of titanium dioxide on the surface, the relative percentage of titanium and the absorptance of UV photons by TiO2, respectively, were determined by Raman spectroscopy, scanning electron microscopy coupled with X-ray analysis and UV-visible diffuse refectance spectroscopy. Proportionality between these three variables has been demonstrated. The photocatalytic efficiency of TiO2-rich cementitious materials has been demonstrated for the degradation of the 2 VOCs and also for NOx. The photocatalytic efficiency is related to the presence of TiO2 on the surface and the ability of TiO2 to absorb UV photons. The cement matrix can also, in the dark, reduced significantly the concentration of formaldehyde. The study of the influence of materials and environmental parameters showed the importance of the TiO2 content, the luminous flux and relative humidity on the photocatalytic properties of the mortar and allowed to contribute to a better understanding of the reactions occurring during the degradation of pollutants by a photocatalytic cementitious material