n the first part of this diploma thesis there are described basic findings about superhard cutting materials (sorts, notation, structure, physical-mechanical properties, usage, production) and evaluates this tool of material from the aspect of cutting ability. The second part focused on complex data processing about assortment of superhard cutting materials of significant tools materials producers and comparison of work conditions (kind of machined ma-terials, cutting conditions), which are recommend for effective turning applica-tions by producers.

Diploma thesis is focused on cutting superhard materials (polycrystalline diamond and polycrystalline cubic boron nitride). It deals with physical, mechanical and cutting properties, production and effective use. Evaluative product range of superhard cutting materials of the prominent world producers in terms of cutting conditions and type of materials machined in turning.

Les excellentes propriétés électroniques, thermiques et mécaniques du graphène confèrent à ce matériau planaire (bi-dimensionnel) un énorme potentiel applicatif, notamment en électronique. Néanmoins, ce matériau présente de sérieux inconvénients qui pourraient limiter son champ d'applications. Par exemple, sa structure de bandes électronique sans bande interdite rend difficile le blocage du courant dans un dispositif. De plus, pour les applications thermoélectriques, sa forte conductance thermique est aussi une forte limitation. Il y a donc beaucoup de défis à relever pour rendre ce matériau vraiment utile pour des applications. Cette thèse porte sur l'étude des propriétés électroniques et thermoélectriques dans les hétérostructures planaires constituées de graphène et de nitrure de bore hexagonal (BN). Différentes configuration de ce nouveau matériau hybride permettent de moduler la bande interdite, la conductance thermique et le coefficient Seebeck. Cette étude a été menée au moyen de calculs atomistiques basés sur les approches des liaisons fortes (TB) et du modèle à constantes de force (FC). Le transport d'électrons et de phonons a été simulé dans le formalisme des fonctions de Green hors équilibre. Les résultats montrent que, grâce à la modulation de la bande interdite, des transistors à base d'hétérostructures de BN et de graphène peuvent présenter un très bon rapport courant passant / bloqué d'environ 10⁴ à 10⁵. En outre, nous montrons l'existence d'états quantiques hybrides à l'interface zigzag entre le graphène et le BN donnant lieu à des propriétés de transport électronique très intéressantes. Enfin, ce travail montre qu'en agençant correctement des nano-flocons de BN sur les côtés d'un nanoruban de graphène, la conductance des phonons peut être fortement réduite alors que l'ouverture de bande interdite conduit à un accroissement important du coefficient Seebeck. Il en résulte qu'un facteur de mérite thermoélectrique ZT plus grand que l'unité peut être réalisé à température ambiante. / Graphene is a fascinating 2-dimensional material exhibiting outstanding electronic, thermal and mechanical properties. Is this expected to have a huge potential for a wide range of applications, in particular in electronics. However, this material also suffers from a strong drawback for most electronic devices due to the gapless character of its band structure, which makes it difficult to switch off the current. For thermoelectric applications, the high thermal conductance of this material is also a strong limitation. Hence, many challenges have to be taken up to make it useful for actual applications. This thesis work focuses on the theoretical investigation of a new strategy to modulate and control the properties of graphene that consists in assembling in-plane heterostructures of graphene and Boron Nitride (BN). It allows us to tune on a wide range the bandgap, the thermal conductance and the Seebeck coefficient of the resulting hybrid nanomaterial. The work is performed using atomistic simulations based on tight binding (TB), force constant (FC) models for electrons and phonons, respectively, coupled with the Green's function formalism for transport calculation. The results show that thanks to the tunable bandgap, it is possible to design graphene/BN based transistors exhibiting high on/off current ratio in the range 10⁴-10⁵. We also predict the existence hybrid quantum states at the zigzag interface between graphene and BN with appealing electron transport. Finally this work shows that by designing properly a graphene ribbon decorated with BN nanoflakes, the phonon conductance is strongly reduced while the bandgap opening leads to significant enhancement of Seebeck coefficient. It results in a thermoelectric figure of merit ZT larger than one at room temperature.

Les composites SiC/SiC à renfort fibreux à base de SiC, et à matrice SiC sont développés pour applications aéronautiques. En vue d’améliorer leur durée de vie en atmosphère oxydante à haute température, l’utilisation d’interphase BN est préconisée,puisque l’oxyde de bore liquide permet de protéger le matériau. Cependant, sous atmosphère humide, la volatilisation de B2O3 sous forme d’hydroxyde HxByOz est non négligeable. L’objectif de ce travail est d’optimiser l’organisation structurale de BN élaboré par CVD/CVI, pour améliorer sa résistance à l’oxydation, et d’évaluer l’intérêt de l’ajout d’élément(s) au nitrure de bore permettant la stabilisation thermodynamique de B2O3 à haute température, en présence d’humidité. Ce travail a permis d’établir des liens entre composition chimique de la phase gazeuse, cinétique et mécanisme de dépôt, et degré d’organisation du nitrure de bore. Malheureusement, si la résistance à l’oxydation de BN augmente perpendiculairement à ses plans (002) avec son organisation structurale, elle est à peine améliorée le long des plans (002). Néanmoins, l’intérêt de l’ajout d’aluminium à l’interphase BN pour améliorer la stabilité chimique de B2O3 en présence d’humidité a été démontré à une température suffisamment élevée pour permettre la formation de cristauxAl4B2O9. Ainsi, il semble que ces cristaux permettent une cicatrisation efficace des fissures matricielles dans des composites SiC/SiC. Des essais supplémentaires d’oxydation dans des conditions plus complexes, comme sous cyclage thermique, sont nécessaires pour conclure catégoriquement en faveur de l’amélioration de la durée de vie de ces matériaux. / SiC/SiC composites with SiC-based fibres and SiC matrix are developed for aeronautic applications. In order to improve their life time in an oxidizing atmosphere at high temperature, the use of BN interphase is recommended, as far as liquid boron oxide can protect the material. However, this glassy material is known to be very sensitive to moisture because boron oxide volatilizes quickly under high temperature. The aims of this work are (i) to maximise the structural organization of BN deposited by CVD/CVI to improve its oxidation resistance and (ii) to assess the interest of elemental addition to boron nitride allowing thermodynamic retention for B2O3 under wet air. Relationships between gas phase composition, deposition rates, and microstructure have been established in this work. Unfortunately, if the oxidation resistance of BN perpendicular to its (002) crystal planes increases with its structural organization, it appears to be hardly improved along the (002) planes. Nevertheless, aluminium addition to BN has led to Al4B2O9 crystals generation, asAl2O3 reacts together with B2O3 under high temperature. These materials therefore appear tobe able to seal SiC matrix cracks. As a result, the global oxidation resistance under wet air of SiC/SiC composites with B(Al)N interphases can been significantly improved. Additional oxidation tests, especially under thermal cycling, are needed to definitively conclude about this point.

In this research thermal properties enhancement of phase change material (PCM) using boron nitride nanomaterials such as nanoparticles and nanotubes is studied through experimental measurements, finite element method (FEM) through COMSOL 5.3 package and molecular dynamics simulations via equilibrium molecular dynamics simulation (EMD) with the Materials and Process Simulations (MAPS 4.3). This study includes two sections: thermal properties enhancement of inorganic salt hydrate (CaCl2∙6H2O) as the phase change material by mixing boron nitride nanoparticles (BNNPs), and thermal properties enhancement of organic phase change material (paraffin wax) as the phase change material via encapsulation into boron nitride nanotubes (BNNTs). The results of the proposed research will contribute to enhance the thermal transport properties of inorganic and organic phase change material applying nanotechnology for increasing energy efficiency of systems including electronic devices, vehicles in cold areas to overcome the cold start problem, thermal interface materials for efficient heat conduction and spacecraft in planetary missions for efficient thermal managements.

In this thesis, bulk and local scale spectroscopic and microscopic tools have been applied to investigate the purified raw material of SWCNT and synthesized MWBNNT, BN-nanocapsules, B-doped SWCNT and SiC nanostructures. Using bulk scale sensitive techniques, including optical absorption spectroscopy, Raman spectroscopy, high-resolution electron energy-loss spectroscopy, the average response of the whole sample is obtained. On the other hand, on a local scale transmission and scanning electron microscopy as well as TEM-electron energy-loss spectroscopy provide information on single tubes or other nanostructures. First, diverse chemical and oxidation methods for the purification of as-produced SWCNT were presented. Purified samples were investigated using TEM and OAS. The analysis of the optical absorption spectra in the UV-Vis energy range revealed that some of the chemical treatments are harmful to nanotubes. In contrast to the chemical treatments an oxygen burning procedure was used on the raw material in high vacuum and a temperature range 450?650oC. The purification processes of SWCNT by HNO3 and oxygen burning procedures resulted in SWCNT comprised of selected diameters and a reduced diameter distribution. Both HNO3 and oxygen burning treatments can be used to selectively remove SWCNT with smaller diameters from the samples. In addition, an adapted substitution reaction was used for the synthesis of multiwall boron nitride nanotubes. It was shown that the IR-response of MWBNNT can be used as a fingerprint to analyse MWBNNT. As in h-BN for the analysis one has to be aware of the sample texture and the LO-TO splitting of the IR-active modes. TEM images and B1s and N 1s excitation edges of the grown material reveal the presence of multiwall BN nanotubes with an inner diameter of 3.1 nm and with a larger interplanar distance than in h-BN. The electronic properties of the multiwall BN nanotubes as derived from the q-dependent dielectric function e(w,q) are dominated by the band structure of the hexagonal-like BN sheets, as revealed by the large degree of momentum dispersion observed for the p and s+p plasmons, in agreement with that previously reported for different graphitic allotropic forms. Moreover, a fast and highly efficient synthesis route to produce BN nanocapsules with a narrow size distribution was developed. This was achieved by an adapted substitution process using SWCNT as templates followed by a rapid cooling treatment. The IR responses reveal the strong dipole active fingerprint lines of h-BN with distinct differences, which are due to texturing effects and which highlight the BN nanocapsules potential application as a reference source when deriving the sp2 to sp3 ratio in BN species due to their random orientation Furthermore, the idea of substitution was used for the systematic studies of B-doped SWCNT. The experiments carried out have resulted in 1, 5, 10, and 15 % boron incorporated into the single wall carbon nanotubes. Core level excitation spectroscopy of the B1s and C1s edges revealed that the boron atoms substitute carbon atoms in the tube lattice keeping an sp2-like bond with their nearest C neighbour atoms. Our results show that a simple rigid band model as has been applied previously to intercalated SWCNT is not sufficient to explain the changes in the electronic properties of highly doped B-SWCNT and a new type of a highly defective BC3 SWNT with new electronic properties is obtained. Finally, different silicon carbide nanostructures were produced. The spectroscopic and microscopic data led to a good understanding of the formation process. NH3 acts as a source of hydrogen that plays a key role in the formation of the structures through its ability to decompose SiC at high temperature such that along with the stacking faults that arise from the many polytypes of SiC the produced SiC nanorods become porous then hollow and eventually are completely decomposed.

La structure spécifique des nanotubes rend ce matériau très intéressant dans l’élaboration de nanohybrides. La cavité interne des nanotubes permet l’encapsulation de molécule laissant la paroi externe libre pour une fonctionnalisation. Les nanotubes de carbone sont déjà bien connus pour l’élaboration de nanosondes Raman. Les molécules de colorants encapsulé dans leurs cavité interne sont protégées de l’irradiation du laser. Les propriétés électroniques de cette structure en carbone permettent le transfert d’énergie entre le colorant et le nanotube engendrant ainsi une extinction de la fluorescence du colorant. La surface du nanotube de carbone est libre pour réaliser des fonctionnalisations permettant de modifier certaines propriétés de la nanosonde. L’élaboration de nanohybride à partir de cette structure permet les analyses de « multiplexage » en changeant simplement le colorant encapsulé dans la cavité interne du nanotube et la fonctionnalisation en surface. La structure des nanotubes de nitrure de bore (BNNTs) est très similaire à celle de leurs homologues en carbone. La cavité interne permet également l’encapsulation de colorant cependant les propriétés électroniques résultantes de cette structure ne permet pas le transfert d’énergie. Les molécules de colorant encapsulé dans les BNNTs conservent donc leurs fluorescences. Des études précédentes démontrent qu’après encapsulation, le spectre de fluorescence du colorant α-sexithiophène (6T) est élargi et décalé vers les longueurs d’ondes plus grandes, c.-à-d. vers le rouge. L’hypothèse la plus probable, quant à la raison de ce phénomène, est que la grande distribution de taille de diamètre de l’échantillon de BNNTs permet différentes agglomérations de 6T. Les nanosondes résultantes sont composées d’un mélange d’agglomération de colorant absorbant à différentes longueurs d’onde. Afin de confirmer cette hypothèse, nous allons procéder au triage en taille de diamètre des BNNTs. Pour cela, plusieurs étapes sont nécessaires, comme la fonctionnalisation de la surface des BNNTs pour les rendre dispersible dans l’eau, l’encapsulation du colorant de 6T selon un protocole déjà connus dans la littérature et enfin le test d’une méthode de triage de nanotubes en fonction de leurs diamètres et donc de leurs densités. La méthode de triage sélectionnée parmi les méthodes découvertes dans la littérature, a démontré son efficacité sur les nanotubes de carbone mais n’a cependant jamais été testée sur les BNNTs. Ce mémoire présente les premiers résultats d’une séparation de nanosondes fluorescentes en fonction de leurs tailles de diamètre. / The specific structure of nanotubes is interesting for the synthesis of nanohybrides. Molecules are encapsulated in the internal cavity of the tube while the external wall remain free for further manipulation. Carbon nanotubes are already known for synthesizing Raman nanoprobes. Dyes encapsulated inside the nanotube are protected from irradiation. The electronic properties of the carbon structure lead to energy transfer between the dyes and the nanotubes, this result by the the extinction of the dye’s fluorescence. The carbon nanotube’s surface is free for functionalisation that can add some properties to the nanoprobe. The preparation process of nanohybrides with that structures permit some analyse in « multiplexing » by easily change the dye encapsulated or the functionalisation on the surface of the nanotube. The structure of boron nitride nanotubes (BNNTs) is similar to the carbon one. The internal cavity can encapsulate dyes but the electronic properties don’t permit the energy exchange. Encapsulated dyes inside BNNTs emit some fluorescence. Previous studies show some changes in the fluorescence spectrum of α-sexithiophene (6T) after encapsulation inside BNNTs. The spectrum shows larger bands and a red shift. This caracteristic can come from a large distribution of diameter sizes in the BNNT sample. Différent diameter sizes of nanotubes results in different agglomeration of dyes inside their internal cavities, and these differents nanoprobes are absorbing at different wavelengths. To confirm this hypothesis, we will separate BNNTs into their diameter sizes. Before that some manipulation is necesary, like the functionnalisation of the nanotubes’ surfaces for a better dispersion in water, the encapsulation of 6T realized with the process already known and the experience of a new method to separate nanotubes by size. This separating method is chose from all the method of separating carbon nanotubes but has never been tested on BNNTs. This document shows the first results of separating fluorescents nanoprobes by diameter size.

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Nanokompositfilmer med fem olika sammansättningar av hexagonala bornitrid nanosheet och TEMPO-CNF tillverkades med hjälp av vakuumassisterad filtreringsteknik. sond-ultraljudsteknik användes som en grön väg för exfoliering av bornitridpulver i vattenhaltigt medium. TEMPO-CNF spelade nyckelroller som både matris och dispergeringsmedel för stabilisering av bornitrid nanosheets i kompositen. Nanokompositfilmerna var flexibla och formbara och de visade höga mekaniska egenskaper inklusive hög draghållfasthet och god brottöjning. / Nanocomposite films with five different compositions of hexagonal boron nitride nanosheets and TEMPO-CNF were fabricated using vacuum-assisted filtration technique. probe-ultrasonication technique was applied as a green route for exfoliation of boron nitride powder in aqueous medium. TEMPO-CNF played key roles as both matrix and dispersant agent for stabilization of the boron nitride nanosheets in the composite. The nanocomposite films were flexible and ductile, and they showed high mechanical properties including high tensile strength and good elongation at break.