Submitted by PPG Engenharia e Tecnologia de Materiais (engenharia.pg.materiais@pucrs.br) on 2017-10-26T16:09:28Z No. of bitstreams: 1 Tese Eng. Piedade.pdf: 6225051 bytes, checksum: c7f77823a538300959734acada65a861 (MD5) / Rejected by Caroline Xavier (caroline.xavier@pucrs.br), reason: Devolvido devido a 1) Arquivo PDF sem capa institucional. 2) Na primeira e segunda folha do arquivo PDF, o nome do autor est? incompleto. Na ficha catalogr?fica e publica??o enviada est? completo. 3) Nome e descri??o do arquivo na publica??o est?o em desacordo com o manual enviado. on 2017-11-07T13:03:14Z (GMT) / Submitted by PPG Engenharia e Tecnologia de Materiais (engenharia.pg.materiais@pucrs.br) on 2017-11-08T17:01:40Z No. of bitstreams: 1 final para entrega com capa.pdf: 6291908 bytes, checksum: a447082574d55fe4709b55f1c2da38fb (MD5) / Approved for entry into archive by Caroline Xavier (caroline.xavier@pucrs.br) on 2017-11-17T12:16:13Z (GMT) No. of bitstreams: 1 final para entrega com capa.pdf: 6291908 bytes, checksum: a447082574d55fe4709b55f1c2da38fb (MD5) / Made available in DSpace on 2017-11-17T12:20:52Z (GMT). No. of bitstreams: 1 final para entrega com capa.pdf: 6291908 bytes, checksum: a447082574d55fe4709b55f1c2da38fb (MD5) Previous issue date: 2017-08-18 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior - CAPES / Quasicrystals are materials that have unusual characteristics, they can not be described as crystalline, for not having long-range order, or as amorphous, have medium-range structure. Some Al-Cu-Fe family alloys presents quasicrystalline phases when have rapidly solidification. In order to obtain this alloy, ingots of the Al65Cu35-xFex family were casted with x=6 (atomic), initially in a standard mold with solidification equilibrium. To provide samples with different cooling rates, the alloy was cast in a stepped mold, containing six different steps, resulting in samples out of equilibrium state (rapidly solidification). For the analysis of the cooling curves, the CACC-TA technique was used, with cooling rates varying from170 to 540?C / s, which were obtained by dT/dt. Analyzes by optical microscopy, scanning electron microscopy (SEM), dispersive energy spectrometry (EDS), show microstructure with faceted dendrites, lamellar interdendritic formations and pentagonal precipitates (IQC). The Vickers microhardness ranged from 4.09 to 7.22 GPa and the X-ray diffraction (XRD) proved by characteristic diffractograms the icosahedral quasicrystalline phase formation. / Os quasicristais s?o materiais que apresentam caracter?sticas incomuns, pois n?o podem ser descritos como cristalinos, por n?o apresentarem ordem de longo alcance, nem como amorfos, apresentam estrutura de m?dio alcance. Algumas ligas da fam?lia Al-Cu-Fe apresentam fases quasicristalinas quando rapidamente solidificadas. Para obter-se esta liga, foram fundidos lingotes da fam?lia Al65Cu35-xFex com x=6 (at?mico), inicialmente em um molde padr?o com solidifica??o em estado de equil?brio. Para proporcionar amostras com taxas de resfriamento variadas, a liga foi vazada em um molde escalonado, contendo seis cavidades diferentes, resultando em amostras solidificadas fora do estado de equil?brio (solidifica??o r?pida). Para an?lise das curvas de resfriamento utilizou- se a t?cnica CACC-TA, com taxas de resfriamento variando entre 170 e 540?C/s, que foram obtidas por meio de dT/dt. An?lises por microscopia ?ptica, microscopia eletr?nica de varredura (MEV), espectrometria por energia dispersiva (EDS), mostram microestrutura com dendritas facetadas, forma??es interdendr?ticas lamelares e precipitados pentagonais (IQC). A microdureza Vickers variou entre 417 HV e 736 HV (4,09 e 7,22 GPa) e a difra??o de raios X (DRX) comprovou por meio de difratogramas caracter?sticos a forma??o de fase quasicristalina icosa?drica.

Conselho Nacional de Desenvolvimento CientÃfico e TecnolÃgico / The structural and thermal decomposition properties of Mg-Fe and Co-Cu-Fe hy- drotalcites (HT) have been studied through thermogravimetric analysis, X ray powder difraction (XRD), Fourier transform infrared spectroscopy and 57Fe MÃssbauer spec- troscopy. In the Mg-Fe system, the destruction of the layered structure took place at about 300 oC. The broad peaks observed in the X ray difractograms suggests that the resultant oxides constitute a solid solution. For samples treated at temperatures higher than 500 oC the formation of the MgO and MgFe2O4 formation of the MgO and MgFe2O4 spinel phases is observed. 57Fe MÃssbauer spectroscopy was employed to monitor the Fe chemical environment for the samples annealed at diferent temperatures (100-900 oC). In situ XRD experiments revealed that the HTs start an interlayer contraction at about 180 oC. This phenomenon is identified as being due to a grafting process for which the interlamellar anions attach to the layers through a covalent bond. The reconstruction of the Mg-Fe HTs was also investigated and its eficiency depends on the thermal anneal- ing temperature and on the Mg/Fe ratio. The structure of the reconstructed samples was found to be exactly the same as the parent structure. The in situ 57Fe MÃssbauer experiments were performed in the 100-500 oC temperature range confirm an increasing structural disorder in this temperature range. The quadrupolar splitting indicates that the maximum disorder occurs at 300 oC. Regarding the Co-Cu-Fe ternary system we have observed that due to the strong Jahn-Teller effect the Cu-Fe layered system is stabilized only in the presence of Co2+. At low Co2+ contents, additional phases are segregated in the solids. X ray patterns diffraction show the presence of Cu(OH)2 and CuO. The decomposition process was investigated by in situ X ray, in situ MÃssbauer and FTIR experiments. By increasing the temperature from 25 oC up to 180 oC we observed that the structural disorder increases. This effect has been likely attributed to the Co2+ to Co3+ oxidation since thermal decomposition was carried out under static air atmosphere. Part of the Co3+ cations could migrate to the interlayer region, thus forming a metastable compound that still has a layered structure. Collapse of the layered structure was ob- served at about 200 oC. By further increasing the temperature the system becomes more crystalline and the formation of Co3O4 is observed in the X ray patterns. In Cu-rich HT, some of the carbonate anions are released at temperatures higher than 550 oC and this phenomenon is attributed to the formation of a carbonate-rich phase. The specific surface area data present its highest values in the temperature range where the collapse of the layered structure takes place. / As propriedades estruturais e de decomposiÃÃo tÃrmica das hidrotalcitas Mg-Fe e Co-Cu-Fe foram estudadas atravÃs de espectroscopia MÃssbauer de 57Fe, anÃlise termo- gravimÃtrica, difraÃÃo de raios X, e espectroscopia de absorÃÃo no infravermelho (FTIR). No sistema Mg-Fe a destruiÃÃo da estrutura lamelar ocorre em torno de 300 oC. O alargamento dos picos de difraÃÃo de raios X observados nos difratogramas sugerem que os Ãxidos resultantes constituem uma soluÃÃo sÃlida. Para as amostras tratadas em temperaturas maiores do que 500 oC a formaÃÃo de fases do tipo MgO e MgFe2O4 à observada. A espectroscopia MÃssbauer de 57Fe foi empregada para monitorar o ambiente quÃmico do Fe na faixa 100-900 oC de temperatura. As medidas in situ de difraÃÃo de raios X revelam que em 180 oC inicia-se uma contraÃÃo interlamelar. Este fenÃmeno à atribuÃdo ao processo de âgrafting" no qual os Ãnions interlamelares ligam-se nas camadas atravÃs de uma ligaÃÃo covalente. A reconstruÃÃo estrutural da hidrotalcita Mg-Fe tambÃm foi investigada. A eficiÃncia da reconstruÃÃo estrutural depende da temperatura de tratamento e da razÃo molar Mg/Fe. A estrutura das amostras reconstruÃdas sÃo as mesmas da amostra inicial. As medidas in situ de espectroscopia MÃssbauer de 57Fe foram realizadas na faixa 100-500 oC confirmaram uma desordem estrutural crescente nesta regiÃo de temperaturas. Os valores do desdobramento quadrupolar indicam que o mÃximo de desordem ocorre em 300 oC. Com relaÃÃo ao sistema ternÃrio Co-Cu-Fe observamos que devido ao efeito Jahn-Teller o sistema Cu-Fe somente à estabilizado na presenÃa de Co2+. Para baixas concentraÃÃes Co2+ fases adicionais segregadas sÃo observadas nos sÃlidos. Os padrÃes de difraÃÃo de raios X indicam a presenÃa de Cu(OH)2 e CuO. O processo de decomposiÃÃo tÃrmica foi investigado atravÃs de difraÃÃo de raios X, espectroscopia MÃssbauer de 57Fe in situ e de espectroscopia de absorÃÃo no infravermelho (FTIR). Aumentando a temperatura de tratamento tÃrmico das amostras de 25 oC a 180 oC observamos um aumento da desordem estrutural. Este efeito tem sido atribuÃdo a oxidaÃÃo Co2+ para Co3+ uma vez que a decomposiÃÃo foi realizada ao ar. Parte dos cÃtions Co3+ migram para a regiÃo interlamelar formando um composto metastÃvel que ainda possui uma estrutura lamelar. O colapso da estrutura lamelar à observado a 300 oC. Com o aumento posterior da temperatura o sistema torna-se mais cristalino e a formaÃÃo de Co3O4 à observada atravÃs do ensaio de raios X. Nas hidrotalcitas com maior teor de Cu, alguns dos Ãnions carbonato sÃo liberados somente acima de 550 oC sendo este fenÃmeno atribuÃdo a formaÃÃo de uma fase rica em carbonato. Os valores de Ãrea superficial especÃfica apresentam um mÃximo na faixa de temperatura onde ocorre o colapso da estrutura lamelar.

Les mécanismes de formation de phases dans des films minces du système ternaire Al-Cu-Fe et des systèmes binaires Al-Cu, Al-Fe et Cu-Fe ont été étudiés. Dans chacun des systèmes, plusieurs échantillons avec des compositions distinctes ont été préparés par pulvérisation cathodique. Des couches d'aluminium, de cuivre et de fer ont été déposées séquentiellement sur des substrats de silicium oxydé et ont été traités thermiquement par différentes méthodes puis caractérisés. Des mesures de diffraction de rayons X et de résistivité in-situ ont été effectuées pour suivre la formation des phases. Des recuits thermiques suivis de trempe ont été réalisés et les échantillons ont été caractérisés par diffraction des rayons X. L'analyse enthalpique différentielle a également été utilisée ainsi que des mesures simultanées in-situ de résistivité et de diffraction des rayons X. L'ensemble des résultats obtenus nous a permis de proposer des mécanismes de formation de phases pour chacun des échantillons étudiés et en utilisant des modèles théoriques de croissance de phases nous avons pu déterminer des données cinétiques sur la formation de phases dans ces films.

Quasikristallines Al-Cu-Fe (i-Phase) wurde ueber den Weg der amorphen (a-) Phase in Form duenner Schichten hergestellt und ein Vergleich elektronischer Transporteigenschaften der isotropen a-Phase in verschiedenen Anlassstufen mit der schliesslich entstehenden fast isotropen i-Phase durchgefuehrt (Leitfaehigkeit, Magnetoleitfaehigkeit, Hall-Effekt und Thermokraft). Die Auswirkungen einer Hume-Rothery-Stabilisierung auf den elektronischen Transport standen dabei im Vordergrund. Es wurden in der i-Phase auch die Auswirkungen einer systematischen Aenderung des Fe-Gehalts untersucht. Die a-Phase und die i-Phase sind in vielen wichtigen Trends miteinander verwandt, z.B. ist die inverse Matthiesen-Regel sowohl in der a- als auch in der i-Phase gueltig. Thermokraft und Hall-Effekt, die sehr empfindlich auf Aenderungen der Bandstruktur sind, zeigen drastischere Aenderungen beim Uebergang amorph-quasikristallin. Die Aenderungen der Eigenschaften in der i-Phase als Funktion der Temperatur und des Fe-Gehalts koennen in einem Zweibandmodell quantitativ erfasst werden. Mit dem Konzept der Spektralleitfaehigkeit, in das im Prinzip das Zweibandmodell uebergeht, koennen die Eigenschaften sowohl der i-Phase als auch der a-Phase quantitativ beschrieben werden. In der a-Phase fuehrt dieses Konzept auf eine sich von der frisch praeparierten a-Phase durch Tempern bis hin zur i-Phase kontinuierlich aendernde Spektralleitfaehigkeit, die schon unmittelbar nach dem Aufdampfen durch ein breites und ein, diesem ueberlagertes, schmales Minimum beschrieben werden kann. Beim Tempern wird das schmale Minimum immer tiefer. Im Ortsraum wird insgesamt ein Szenario vorgeschlagen, das von sphaerischer Ordnung ausgeht, zu der schon in der frisch praeparierten a-Phase eine Winkel- und Abstandsordnung hinzukommt. Diese verstaerkt sich beim Tempern bis hin zur perfekt geordneten Struktur in der i-Phase. Das Verschwinden magnetischer Effekte und die damit verbundenen Aenderungen der Tieftemperatur-Leitfaehigkeit beim Tempern deuten ebenfalls auf eine sich bereits in der a-Phase vollziehende kontinuierliche Aenderung der lokalen Umgebung der Fe-Atome, deren Anordnung hauptsaechlich die elektronischen Transporteigenschaften bestimmt.

Copper based alloys play important role in high heat flux applications, particularly in rocket technology, the liner of the combustion chamber, and also in other heat transfer vessels. In these applications, one needs excellent high-temperature strength without sacrificing the thermal conductivity significantly. However, it is a challenging and difficult task to significantly improve the balance between strength and conductivities (electrical and thermal) of Cu-based alloys. In general, microstructural attributes, responsible for increasing mechanical strength of the alloy, also affect the transport properties by creating scattering centers. Hence, delicate optimization is needed for developing balanced alloy system for better performance. A substantial amount of research efforts has therefore been focused on devising methodologies to synthesize copper based alloys with a good combination of strength and conductivity. The present thesis deals with the development of a newer class of high strength high conductivity copper base alloy through tuning of phase transformation and careful additions of ternary and quaternary alloying elements and ultimately by microstructural engineering. In this thesis, we report the development of novel high strength high conductivity Cu-based alloy series in the Cu-Fe-Si system through rapid solidification process using suction casting apparatus. We have also optimized the alloys by altering and fine tuning the alloy compositions in order to achieve balanced and optimum properties. The strength of copper can be increased by various strengthening mechanisms. In general, precipitation hardening, dispersion strengthening and solid solution strengthening are the three most effective mechanisms for improving the strength of copper. Among these, solid solution strengthening has the most detrimental effect on the transport properties due to the presence of solute atoms which act as prominent scattering centres. Precipitation hardened copper alloys are often unable to retain strength at high temperatures, due to the coarsening of the precipitates. Currently, efforts are being made to develop newer dispersion strengthened copper alloys. These alloys contain a fine dispersion of nanometer sized oxides or other intermetallic compounds in the copper matrix. Dispersion strengthened copper alloys show impressive mechanical strength as well as thermal stability. In this thesis, we have explored the possibility of obtaining structurally ordered intermetallic dispersions through exploiting immiscibility of solutes in copper based alloys. The immiscibility promotes precipitation and decrease the solid solubility of solute elements in the matrix which in turn minimizes the scattering process and thus offers the possibility of improved transport properties. These ordered and coherent dispersion of intermetallic particles in the continuous copper matrix, dispersed during solidification, are believed to be the main contributor to the improvement of mechanical strength of the alloy. Crystallographically ordered structure and the coherency strain associated with the intermetallic particles in the copper matrix, together contribute to the mechanical strength through the mechanism of order hardening and coherency strengthening. These also, promote a low interfacial energy between precipitates and matrix in the alloy. This low interfacial energy reduces the driving force for coarsening process and thus helps in retaining the mechanical strength at elevated temperatures. Releasing of coherency strain at the precipitate-matrix interface with increasing temperature also yields a dramatic effect on the enhancement of thermal conductivity at high service temperatures. In the current study, we have selected three alloy compositions in the Cu-Fe-Si system at the higher end of copper. These are Cu-20Fe-5Si (at%), Cu-2.5Fe-2.5Si (at%) and Cu-1.0Fe-1.0Si (at%) respectively. We have systematically increased the concentration of copper, and altered the ratio of Fe and Si in order to achieve the better combination of properties (mechanical and transport) through fine tuning the microstructure. The present sets of alloys have been chill cast by the suction casting technique. This rapid solidification process, associated with moderate undercooling, is capable of accessing the submerged metastable miscibility gap of the Cu-Fe binary system. The higher quenching rate moves the system far away from equilibrium and hence, the solidification process occurs at the non-equilibrium regime. Rapid solidification of a copper rich Fe-Cu melt promotes the precipitation of the γFe from copper solid solution due to the immiscibility of Fe and Cu. In this scenario, the addition of a small quantity of silicon as a ternary element leads to its partition to both copper and iron rich phases. However, the larger chemical affinity between Fe and Si, leads to the formation of an ordered structure. However, the FCC crystal field of the copper matrix tends to promote an FCC based novel L12 ordered structure of the Fe3Si intermetallic particles instead of the ordered DO3 structure of Fe3Si composition normally observed in the bulk alloy. This nano meter sized L12 ordered particles maintain a cube-on-cube orientation relationship with the surrounding copper matrix and are associated with large coherency strain. A good lattice matching between these L12 ordered particles and copper matrix will promote a low interfacial energy and thus, a low driving force for particle coarsening. The present thesis is divided into eight chapters. The first chapter introduces the present work and the organization of the thesis. In the second chapter, current status in the development of the copper alloys and the general principle of alloy developments has been described. This includes both experimental and theoretical developments that can be used for developing high strength Cu based alloys. Chapter three, titled as „experimental procedure‟, describes the detailed description of materials and experimental techniques, adopted for the current studies. There are three chapters that deal with the main results of the thesis. Chapter eight, describes the suggestion for future work. The fourth chapter, titled as „Chill cast Cu75Fe20Si5 alloy: Microstructural Evolution and Properties‟, explores the detailed microstructural evolution of the Cu75Fe20Si5 alloy. This chapter also discusses the microstructure-property correlations. The microstructure of the alloy exhibits a multi-scale hierarchical structure during rapid solidification. The solidified microstructure contains Fe-rich globules with DO3 ordered structure, embedded in the continuous Cu-rich matrix. The continuous copper matrix also contains nanometer sized (average diameter 12 nm) coherent particles that exhibit Ashby-Brown strain contrast. Characterization of these phases has been carried out by a combination of X-ray diffraction, electron probe microanalysis and transmission electron microscopy coupled with energy dispersive spectroscopy. This multi-scale complex copper alloy (Cu75Fe20Si5 ) has achieved a remarkable yield and ultimate tensile strength at both room temperature and elevated temperatures in comparison to other copper based alloys. The yield strength and ultimate tensile strength at room temperature are 516±17 MPa and 635±14 MPa respectively whereas yield strength and ultimate tensile strength at 6000C turn out to be 95±11 MPa and 105±12 MPa respectively. In spite of achieving good mechanical strength, this alloy suffers from deterioration of electrical and thermal conductivity due to the presence of high volume fraction of the second phase and alloying elements. The room temperature electrical resistivity of this alloy shows that it is 10 times higher than that of pure copper (alloy resistivity = 1.70E-05 Ohm-cm at 250C and pure Copper- 1.68 × 10-6 Ohm-cm at 200C ). The thermal conductivity of this alloy turns out to be 88 W/m.K at 500C and 161 W/m.K at 6000C respectively which is much smaller in comparison to pure copper ( pure copper ≈ 401 W/m.K at 50 to 6000C). Attempts have been made to overcome the lowering of the transport properties by careful alteration of alloy compositions and fine tuning the microstructure. A new alloy with composition Cu-2.5Fe-2.5Si (at %) has been synthesized in order to achieve better transport properties without significantly sacrificing the mechanical strength. In this new alloy, we have reduced the volume fraction of the second phase (Fe-rich DO3 ordered globules) by lowering the addition of the alloying elements. We have also tried to alter the Fe to Si ratio in such a way that we can retain nanometer sized coherent particles in the matrix that provides strengthening. We arrived at a Fe and Si atom ratio of 1:1. The study of this alloy is presented in chapter five titled as „Chill cast Cu95Fe2.5Si2.5 alloy: Microstructural Evolution and Properties‟. Microstructural characterization indicates that the alloy contains only the nano meter sized coherent L12 ordered particles in the copper matrix. These particles show the Ashby-Brown strain contrast and are rich in iron and silicon. The absence of the high volume fraction of DO3 ordered Fe-rich globular phase and the smaller addition of the alloying elements ensure an improvement in the transport properties. The average resistivity value of this alloy at 250C is 3.5053 × 10-6 (Ohm-cm). This value represents a dramatic improvement in electrical properties in comparison to the Cu75Fe20Si5 alloy (Cu75Fe20Si5 alloy: 1.70E-05 Ohm-cm at 250C). The result is even better when we consider the temperature dependent thermal conductivity of the Cu95Fe2.5Si2.5 alloy. The thermal conductivity of this alloy turns out to be 236 W/m.K at 500C and 313 W/m.K at 6000C respectively. Though the thermal conductivity at room temperature is lower than pure copper, the gap reduces with increasing temperature (pure copper ≈ 401 W/m.K at 50 to 6000C and Cu75Fe20Si5 alloy: 88 W/m.K at 500C and 161 W/m.K at 6000C). This trend of temperature dependent thermal conductivity has made this alloy as one of the potential candidates for high-temperature applications. In situ heating experiment using transmission electron microscope (up to 4500C) and the heat treatment analysis at 6000C confirm that these L12 ordered particles are structurally stable at high temperatures and believed to be the main contributor to high mechanical strength in the alloy through the mechanism of order hardening and coherency strengthening. Coherent nature of the interface between the ordered particles and copper matrix also promotes low interfacial energy in the alloy and thus offers resistance to coarsening at elevated temperatures. Along with the attractive transport properties, this alloy also exhibits its success of retaining mechanical strength at both ambient and high temperatures as compared to the earlier alloy. The room temperature yield strength and ultimate tensile strength of this alloy are recorded as 580±18 MPa and 690±16 MPa respectively whereas the yield strength and ultimate tensile strength at 6000C of this alloy obtained as 128±8 MPa and 150±10 MPa respectively. Thus newly modified alloy exhibits an excellent balance between mechanical strength and conductivity (electrical and thermal) and can be regarded as a promising alloy for high strength high heat flux applications. The possibilities of the Cu95Fe2.5Si2.5 alloy as a potential candidate for high strength high conductivity application has provided the motivation for further optimization of the composition of this class of alloy. Mechanical strength and transport properties of a precipitation strengthened alloy always depends on the structure, shape, volume fractions and the number densities of the precipitate particles. Electrical and thermal conductivity are also sensitive to the presence of third elements and the number densities of the precipitates in the alloy. Thus, optimization of the volume fraction and the number density of the precipitates can yield a better alloy. With this objective, we have further increased the concentration of copper while keeping the Fe and Si atom ratio fixed at 1:1. Chapter six, titled as „Chill cast Cu98Fe1.0Si1.0 alloy: Microstructural Evolution and Properties‟ describes the microstructural evolution and microstructure-property correlation of this new alloy. Characterization analysis (X-ray diffraction, electron probe microanalysis and transmission electron microscopy) confirms that the microstructure of this alloy contains similar kind of nanometer sized L12 ordered particles with lower number density as compared to Cu95Fe2.5Si2.5 alloy (Relative planar number density of the particles: Cu98Fe1.0Si1.0 = 0.13 and Cu95Fe2.5Si2.5 = 0.20). This nano sized coherently ordered particles show the similar Ashby-Brown strain contrast and are rich in iron and silicon similar to the Cu95Fe2.5Si2.5 alloy. This dilute alloy exhibits slight improvement in transport properties in comparison to the earlier Cu95Fe2.5Si2.5 alloy. The electrical resistivity of this alloy at 250C is 3.438E-6 Ohm-cm (Cu95Fe2.5Si2.5 = 3.5053 × 10-6 Ohm-cm at 250C). The thermal conductivity values of this alloy are 243 W/m.K and 338 W/m.K at 500C and 6000C respectively (Cu95Fe2.5Si2.5 = 236 W/m.K at 500C and 313 W/m.K at 6000C). This increase in transport properties is associated with further compositional dilution and the presence of lower number density of the ordered particles in the copper matrix. The mechanism of strengthening is similar to the earlier alloys. The only difference lies in the fact that this present alloy contains lower number density of the L12 ordered particles in the copper matrix. This lower number density is responsible for the loss in mechanical strength of this alloy. The room temperature yield strength and the ultimate tensile strength of this present alloy are 467±16 MPa and 558±12 MPa whereas yield strength and ultimate tensile strength at 6000C are recorded as 102±13 MPa and 110±12 MPa respectively. Though the alloy exhibits some loss in mechanical strength, the values are still attractive in comparison to other commercially available copper based alloys. Both the alloy Cu98Fe1.0Si1.0 and Cu95Fe2.5Si2.5 demonstrate an excellent balance of mechanical strength and transport properties and have the potential to become a high strength and high conductivity materials for high temperature applications. Chapter seven is entitled as „Comparison between the alloy systems‟. In this chapter, we have presented a comparison of our new alloys with other commercially available Cu-base alloys. The thesis ends with a chapter titled as “Suggestions for future work”. We have included a descriptive note for possible future extension of our current work in this chapter.

Quasikristallines Al-Cu-Fe (i-Phase) wurde ueber den Weg der amorphen (a-) Phase in Form duenner Schichten hergestellt und ein Vergleich elektronischer Transporteigenschaften der isotropen a-Phase in verschiedenen Anlassstufen mit der schliesslich entstehenden fast isotropen i-Phase durchgefuehrt (Leitfaehigkeit, Magnetoleitfaehigkeit, Hall-Effekt und Thermokraft). Die Auswirkungen einer Hume-Rothery-Stabilisierung auf den elektronischen Transport standen dabei im Vordergrund. Es wurden in der i-Phase auch die Auswirkungen einer systematischen Aenderung des Fe-Gehalts untersucht. Die a-Phase und die i-Phase sind in vielen wichtigen Trends miteinander verwandt, z.B. ist die inverse Matthiesen-Regel sowohl in der a- als auch in der i-Phase gueltig. Thermokraft und Hall-Effekt, die sehr empfindlich auf Aenderungen der Bandstruktur sind, zeigen drastischere Aenderungen beim Uebergang amorph-quasikristallin. Die Aenderungen der Eigenschaften in der i-Phase als Funktion der Temperatur und des Fe-Gehalts koennen in einem Zweibandmodell quantitativ erfasst werden. Mit dem Konzept der Spektralleitfaehigkeit, in das im Prinzip das Zweibandmodell uebergeht, koennen die Eigenschaften sowohl der i-Phase als auch der a-Phase quantitativ beschrieben werden. In der a-Phase fuehrt dieses Konzept auf eine sich von der frisch praeparierten a-Phase durch Tempern bis hin zur i-Phase kontinuierlich aendernde Spektralleitfaehigkeit, die schon unmittelbar nach dem Aufdampfen durch ein breites und ein, diesem ueberlagertes, schmales Minimum beschrieben werden kann. Beim Tempern wird das schmale Minimum immer tiefer. Im Ortsraum wird insgesamt ein Szenario vorgeschlagen, das von sphaerischer Ordnung ausgeht, zu der schon in der frisch praeparierten a-Phase eine Winkel- und Abstandsordnung hinzukommt. Diese verstaerkt sich beim Tempern bis hin zur perfekt geordneten Struktur in der i-Phase. Das Verschwinden magnetischer Effekte und die damit verbundenen Aenderungen der Tieftemperatur-Leitfaehigkeit beim Tempern deuten ebenfalls auf eine sich bereits in der a-Phase vollziehende kontinuierliche Aenderung der lokalen Umgebung der Fe-Atome, deren Anordnung hauptsaechlich die elektronischen Transporteigenschaften bestimmt.

Après un chapitre d’introduction à propos des alliages métalliques complexes et leurs surfaces, le manuscrit est divisé en deux parties distinctes. La première partie (Chap.II) porte sur la détermination structurale de la surface d’ordre 2 de la phase décagonale Al-Cu-Co par LEED et STM. Les conclusions de ce chapitre indiquent (i) que la surface observée expérimentalement correspond à des terminaisons denses et riches en l’élément de plus faible énergie de surface (Al) et (ii) que la phase serait stabilisée par le terme entropique de l’énergie libre de Helmotz. Dans la deuxième partie de la thèse (Chap.III, IV et V), on applique une approche originale de science des surfaces pour résoudre un problème applicatif : l’adhérence des revêtements quasicristallins sur les substrats métalliques. On propose d’insérer une couche d’accrochage entre le revêtement et le substrat. L’alliage ?-Al4Cu9 est un bon candidat pour réaliser cette interface car il possède des propriétés structurales et électroniques intermédiaires entre un métal et un quasicristal. On élabore donc par MBE des interfaces modèles par adsorption puis recuit de Cu sur le quasicristal i-Al-Cu-Fe, puis d’Al sur Cu(111). Les expériences de photoémission, STM et LEED, ainsi que les calculs de DFT, démontrent la faisabilité d’une interface cohérente entre l’alliage de surface ?-Al4Cu9 et le Cu d’une part, et entre ?-Al4Cu9 et le quasicristal, d’autre part. Ces résultats fondamentaux sont reproduits avec succès dans le domaine applicatif, par l’élaboration de revêtements de phase ? par pulvérisation cathodique magnétron (Chap.V) / After an introductive chapter on complex metallic alloys and surfaces, the thesis is divided into two distinct parts. The first part (Chap.II) concerns the structural determination of the 2-fold surface of d-Al-Cu-Co quasicrystal, by using LEED and STM. The results show (i) that the experimental terraces correspond to dense and Al-rich terminations -the element with the lowest surface energy- and (ii) that this decagonal phase could be entropically stabilized. In the second part of the manuscript (Chap.III, IV and V), we apply a surface science approach to solve a technological bottleneck: the adherence of quasicrystalline coatings on metallic substrates. We propose to grow a buffer layer that would accommodate the differences between the two materials. For that purpose, the ?-Al4Cu9 phase is a good candidate as it shares electronic and structural properties with both substrate and coating. Hence, we synthesize model interfaces by using MBE, first by adsorption and annealing of Cu on the 5-f surface of i-Al-Cu-Fe quasicrystal and then in the Al on Cu(111) system. Photoemission, STM and LEED experiments, along with DFT calculations show that a coherent interface can be grown between the ?-Al4Cu9 surface alloy and both the Cu and the quasicrystal. Those fundamental results are successfully reproduced in the real world, by growing similar interfaces using magnetron sputterring (Chap.V)

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