The focus of this research is to study the interaction between copper and the diffusion barrier/adhesion promoter. The behavior of copper sputter-deposited onto sputter-cleaned tantalum nitride is investigated. The data show that copper growth on tantalum nitride proceeds with the formation of 3-D islands, indicating poor adhesion characteristics between copper and Ta0.4N. Post-annealing experiments indicate that copper will diffuse into Ta0.4N at 800 K. Although the data suggests that Ta0.4N is effective in preventing copper diffusion, copper's inability to wet Ta0.4N will render this barrier ineffective. The interaction of copper with oxidized tantalum silicon nitride (O/TaSiN) is characterized. The data indicate that initial copper depositions result in the formation a conformal ionic layer followed by Cu(0) formation in subsequent depositions. Post-deposition annealing experiments performed indicate that although diffusion does not occur for temperatures less than 800 K, copper "de-wetting" occurs for temperatures above 500 K. These results indicate that in conditions where the substrate has been oxidized facile de-wetting of copper may occur. The behavior of a sputter-deposited Cu0.6Al0.4 film with SiO2 (Cu0.6Al0.4/SiO2) is investigated. The data indicate that aluminum segregates to the SiO2 interface and becomes oxidized. For copper coverages less than ~ 0.31 ML (based on a Cu/O atomic ratio), only Cu(I) formation is observed. At higher coverages, Cu(0) is observed. These data are in contrast with the observed behavior of copper metal deposited onto SiO2 (Cu/SiO2). The data for Cu/SiO2 show that copper does not wet SiO2 and forms 3-D nuclei. Furthermore, post-annealing experiments performed on Cu0.6Al0.4/SiO2 show that neither de-wetting nor diffusion of copper occurs for temperatures up to 800 K, while Cu diffusion into SiO2 occurs ~ 600 K. These data indicate that aluminum alloyed with copper at the SiO2 interface serves as an effective adhesion promoter and thermal diffusion barrier.

O Cu e suas ligas têm diferentes aplicações na sociedade moderna devido as excelentes propriedades elétricas, condutividade térmica, resistência à corrosão dentre outras propriedades. Estas aplicações podem ser em válvulas, tubulações, panelas para absorção de energia solar, radiadores para automóveis, condutores de corrente e eletrônico, elementos de termostatos e partes estruturais de reatores nucleares, como, por exemplo, bobinas para campo toroidal para um reator de fusão nuclear. Dentre as ligas utilizadas em reatores nucleares, podemos destacar Cu-Be, Cu-Sn e Cu-Pt. O Ni e o Co, freqüentemente são adicionados às ligas de Cu para que a solubilidade seja deslocada para temperaturas mais elevadas com relação aos sistemas binários de Cu-Sn e Cu-Pt. A adição de Ni-Pt ou Ni-Sn ao Cu em porcentagens iguais ou inferiores a 1,5 % aliado a tratamentos termos-mecânico alteram as propriedades do Cu. Estudamos neste trabalho sete diferentes ligas: três ligas de Cu-Ni-Pt 1 (97,99 % Cu - 1,55 % Ni - 0,46 % Pt), 2 (99,33 % Cu - 0,23 % Ni -0,43 % Pt) 3 (98,01 % Cu - 0,48 % Ni - 1,51 % Pt); três ligas de Cu-Ni-Sn 4 (98,31% Cu - 1,12 % Ni - 0,58 % Sn), 5 (98,79 % Cu – 0,57 % Ni - 0,65 % Sn), 6 (98,39% Cu – 0,46 % Ni – 1,16 % Sn) e Cu eletrolítico 0 (0,0058 % Pb - 0,0007 % Fe - 0,0036 % Ni - 0,0024 % Ag). As referentes ligas foram desenvolvidas a partir de um forno a arco voltaico e passaram por tratamentos termo-mecânicos pré-determinados. As microestruturas foram analisadas diretamente por microscopia óptica e microscopia eletrônica de varredura / EDS e indiretamente por medidas de dureza Vickers e condutividade elétrica. O objetivo deste trabalho, portanto, foi observar e constatar os efeitos da mudança da microestrutura em relação às propriedades dureza e condutividade elétrica. / The Cu and its alloys have different applications in the owed modern society the excellent electric properties, thermal conductivity, resistance to the corrosion and other properties. These applications can be in valves, pipes, pots for absorption of solar energy, radiators for automobiles, current driver, electronic driver, thermostats elements and structural parts of nuclear reactors, as, for example, reels for field toroidal for a reactor of nuclear coalition. The alloys used in nuclear reactors, we can highlight Cu-Be, Cu-Sn and Cu-Pt. Ni and Co frequently are added to the Cu alloys so that the solubility is moved for temperatures more elevated with relationship to the binary systems of Cu-Sn and Cu-Pt. The addition of Ni-Pt or Ni-Sn to the Cu in the same or inferior percentages to 1,5% plus thermomechanical treatments changes the properties of the copper. We studied the electric conductivity and hardness Vickers of the Cu-Ni-Pt and Cu-Ni-Sn and compared with the electrolytic Cu. In the proposed flowcharts, breaking of the obtaining of the ingot, we proceeded with thermo mechanical treatments.

As ligas de cobre têm grande importância na fabricação de produtos metálicos que necessitam de boa resistência à corrosão e/ou alta condutividade térmica e elétrica. A sua estrutura de grãos bruta de solidificação define diversas propriedades requeridas em serviço/processamento e o refino desta estrutura pode ser realizado a partir da inoculação do banho metálico antes do início da solidificação, aumentando o número de núcleos sólidos formados. A inoculação e os mecanismos de refino de grão em ligas de cobre foram pouco investigados e não são entendidos suficientemente para permitir o projeto de inoculantes. O presente trabalho tem como principal objetivo identificar os mecanismos fundamentais de inoculação e refino de grão das ligas do sistema Cu-Sn a partir de adições de Zr aos banhos líquidos antes da solidificação. Amostras cilíndricas foram produzidas a partir da solidificação das ligas a uma taxa de resfriamento de ~ 0,8 ?C/s. Estas amostras foram analisadas por diferentes técnicas: (a) observação da macroestrutura de grãos; (b) análise térmica das curvas de resfriamento obtidas durante a solidificação; (c) análise química; (d) exame da microestrutura em microscopia óptica, microscopia eletrônica de varredura (MEV) com emissão de campo (FEG), microscopia eletrônica de transmissão (MET) com e sem o feixe de íons (FIB) e (e) microanálise por espectroscopia de energia dispersiva (EDS). Observa-se que adições de Zr na faixa de 0,04 a 0,4% a banhos da liga Cu-8%Sn com cobertura de pó de grafita reduzem o tamanho médio de grão em até 90%, mas não causam efeito significativo sem a cobertura de grafita. Este efeito da diminuição do tamanho de grão com a adição de Zr torna-se significativo somente para teores de Sn >=4%. Esta redução de tamanho médio de grão é acompanhada do aparecimento de partículas facetadas na microestrutura, identificadas como ZrC a partir de padrões de difração de elétrons e microanálises EDS. Uma análise teórica mostra desajustes entre os reticulados do ZrC e do Cu? tão pequenos quanto 1,9%, indicando que estas partículas podem funcionar como centros efetivos para a nucleação heterogênea e causar o refino de grão em ligas de Cu. Parâmetros extraídos da recalescência das curvas de resfriamento, como a diferença entre as temperaturas mínima e máxima da recalescência, apresentaram boa correlação com o tamanho médio de grão final, indicando a possibilidade do controle do tamanho de grão em ligas Cu-Sn com adições de Zr a partir da análise térmica. / Copper alloys are important to the production of metallic parts with good corrosion resistance and high thermal and electrical conductivity. The as-cast grain structures of these alloys are closely related to the properties required in service or during processing. The refining of the grain structure can be achieved by inoculation of the metallic melt, before the beginning of solidification, increasing the number of solid nuclei. The inoculantion and grain refining of copper alloys have been poorly investigated and are not sufficiently understood to enable the design of inoculants. The objective of the present work is to identify the fundamental mechanisms underlying the inoculation and grain refining of Cu-Sn alloys by additions of Zr to the melt prior to solidification. Cylindrical samples of these alloys were cast at a cooling rate of ~0,8 ?C/s. These samples were analyzed using different techniques: (a) observation of the grain macrostructure; (b) thermal analysis of the cooling curves collected during solidification; (c) chemical analysis; (d) observation of the microstructure in the optical microscope, scanning electron microscope (SEM) with field emission gun (FEG), trasmission electron microscope (TEM) with and without the focused ion beam (FIB) for sample preparation and (e) energy dispersive spectroscopy (EDS) microanalysis. The results show that additions of Zr in the range between 0,04 and 0,4% to melts of a Cu-8%Sn alloy with a graphite powder cover decrease the average grain size by up to 90%, but have no effect without the graphite cover. The decrease in grain size obtained with Zr additions become significant only for alloys with %Sn >==4 and is followed by the appearance of faceted particles in the microstructure, identified as ZrC after examining electron difraction patterns and EDS microanalyses of the particles.

Thesis. 1975. Sc.D.--Massachusetts Institute of Technology. Dept. of Materials Science and Engineering. / Vita. / Includes bibliographical references. / Sc.D.

As propriedades mecânicas, de corrosão e a condutividade térmica e elétrica, aliadas à relativa facilidade de fundir atribuem grande relevância ao cobre e suas ligas. Algumas destas propriedades podem ser significativamente melhoradas com a diminuição do tamanho de grão da estrutura bruta de solidificação a partir do tratamento de inoculação do banho líquido. Este tratamento aumenta o número de núcleos sólidos, diminuindo assim o tamanho médio de grão. Neste trabalho, foi realizado um estudo do refino de grão da estrutura bruta de solidificação a partir da inoculação com adições de C, P e Zr a ligas do sistema Cu-Zn com teores de até 30% de Zn. Três séries de experimentos principais foram realizadas. Na primeira, o teor de Zr na liga Cu- 30%Zn foi gradativamente aumentado até 0,4% para mostrar o efeito do Zr. Na segunda, o teor de Zr foi mantido constante em 0,08%, enquanto o teor de Zn foi elevado gradativamente até 30% para mostrar o efeito do Zn. Na terceira foram testadas adições isoladas e conjuntas de C, P e Zr para verificar o efeito de cada elemento no refinamento de grãos. As amostras foram caracterizadas e analisadas por diferentes técnicas: (a) observação da macroestrutura de grãos; (b) análise química; (c) análise térmica; (d) microscopia óptica; (e) microscopia eletrônica de varredura; (f) microanálise EDS; g) microanálise WDS e h) difração de raios X. Os resultados mostram que o tamanho médio de grão diminui significativamente nas ligas do sistema Cu-Zn (6% <= Zn <= 30%) quando Zr e P são adicionados simultaneamente. Isoladamente, estes elementos quando adicionados, não reduzem significativamente o tamanho de grão. Nota-se também que o tamanho de grão é cada vez menor à medida que o teor de Zn aumenta de 0 a 30% com a adição de 0,08%Zr, porém não se observa uma correlação entre tamanho de grão e teor de Zn quando Zr não é adicionado. Uma análise da microestrutura dos lingotes utilizando as técnicas mencionadas mostra que a diminuição do tamanho médio de grão a partir de adições de Zr e P coincide com o aparecimento de precipitados facetados ricos em Zr e P. Esta análise indica que um possível mecanismo de inoculação dos latões é a nucleação heterogênea da fase sólida Cu-µ, com estrutura cristalina cúbica de faces centradas, sobre partículas sólidas de ZrP, com estrutura hexagonal compacta, formadas no banho líquido após as adições de Zr e P. / Good mechanical and corrosion properties, large thermal and electrical conductivities, as well as relatively large castability are characteristics that contribute to the importance of copper and copper alloys. Some of these properties are enhanced when the average grain size of the as-cast structure decreases by inoculation of the melt. The inoculation treatment increases the number of solid nuclei, causing a reduction in the average grain size. In the present work, an investigation of the grain refinement by inoculation with Zr and P additions to Cu-Zn melts with contents of Zn up to 30%(mass) was carried out. Three series of experiments were conducted. In one the Zr content of the Cu-30%Zn alloy was gradually increased up to 0.4% to reveal the effects of Zr, while in the second series, the concentration of Zr was constant, equal to 0.08%, but the Zn content was gradually increased to 30% to show the effect of Zn. The third one was to test separate and conjunct addition of C, P and Zr in order to understand each elements effect on grain refinement. The resulting samples were characterized and analyzed by several techniques: (a) visual observation of the grain macrostructure; (b) chemical analysis; (c) thermal analysis; (d) optical microscopy; (e) scanning electron microscopy; (f) EDS microanalysis; (g) WDS microanalysis; and (h) X-Ray diffraction. The results show that the average grain size of the Cu-Zn alloys (6% <= Zn <= 30% mass) decreases significantly when Zr and P are both added to the melt. Nevertheless, average grain size is not reduced significantly when either Zr or P are added separately to the melt. When 0.08%Zr is added, the average grain size decreases as the concentration of Zn increases from 0 to 30%Zn, but without Zr additions, the Zn content and the average grain size are uncorrelated. The microstructural analysis with the techniques listed before show that the decrease in average grain size caused by Zr and P additions coincide with the observation of faceted precipitates rich in Zr and P. This analysis indicates that the inoculation mechanism is probably the heterogeneous nucleation of solid Cu-µ, of face-centered-cubic lattice structure, on solid particles of ZrP, with hexagonal compact structure, formed in the melt after Zr and P additions.

One-dimensional (1D) nanomaterial self-assembly offers an excellent approach to the fabrication of highly complex nanodevices. Despite considerable effort and research, precisely controlling the orientation and positioning of nanowires (NWs) on a large-scale area and assembling into a functional device is still a state of the art problem. This thesis focuses on the dimensionally controlled copper nanowires (Cu NWs) synthesis, and magnetic field assisted self-assembly of cupronickel nanowires (Cu/Ni NWs) into interconnect structures on a carbon doped silicon dioxide (CDO) wafer. CDO is a low dielectric constant (k) material used for copper interconnects in multilayered complex integrated circuits (ICs). Here, a strong affinity of copper (Cu) and nickel (Ni) to thiol (-SH) functional groups were exploited to strongly adhere the nanowires (Cu/Ni NWs) onto the CDO substrate. Thiol (-SH) functionalization of the CDO surface was achieved via a series of reactions involving (1) esterification of the surface exposed ≡Si-OH functional group to its triflate (≡Si-O-Tf), (2) reduction of triflate to ≡Si-H using DIBAL-H, and (3) hydrosilylation of ≡Si-H using 2-propene thiol (≡Si-(CH2)3-SH) in a photochemical reaction. The thiol functionalization of CDO surface enhances the interaction of Cu/Ni NWs with strong chemical bonds. The same reaction scheme was also used in the functionalization of the hydrophilic (Si-OH) surface to the hydrophobic long alkyl chain derivatized (≡Si-CH2-(CH2)16-CH3) surface. This long alkyl chain modified surface acts as an excellent moisture resistant film, which helps to maintain the low-k value of CDO. The dimensionally controlled Cu NWs were synthesized by a wet chemical approach. Optimization of the reducing agent, hydrazine (N2H4), controlled the surface morphology of nanowires (NWs). Interestingly, the high concentration of reducing agent produced particle decorated and/or with a rough NW surface, and conversely decreasing its concentration resulted in a comparatively thin, particle-free and smooth surface. The reaction temperature affected the aspect ratio (Length/Diameter) of the NWs. As the reaction temperature increased from 60 to 90 °C, the aspect ratio decreased from 140 to 21. Controlling the orientation of Cu NWs in a magnetic field was accomplished by coating them with a thin layer (~20 nm) of ferromagnetic nickel (Ni). This Ni-coated NWs showed an excellent degree of alignment (half-width ≈10 degrees) in the direction of an applied magnetic field over a large surface area at field strength as low as 2500 Gauss. Also, the Ni coating helped in protecting the copper core from oxidation resulting in better electrical wire-to-wire contacts. A nanowire-based interconnect channel was fabricated by combining magnetic field assisted alignment and deposition of aligned NWs on a thiol-modified and photolithography patterned CDO substrate. The NWs, deposited in the trenches, strongly bonded to the thiol-derivatized CDO substrate while an acetone wash removed loosely bound NWs on the photoresist surface. In electrical characterization, the directionally well-aligned Cu/Ni NWs channel displayed surprisingly two-fold higher conductivity than randomly arranged NWs channel.

No description available.

In some applications the stress across the entire cross-section of a component is not uniform but varies with position. For example, maximum shear stress is highest at the inner surface of a thick-walled cylinder subjected to uniform internal pressure and it decreases continuously towards the outer surface. In such applications it would be more appropriate for the component, too, to have varying strength across the cross-section matching with the stress profile it is subjected to. The present work deals with obtaining such a functionally graded material (FGM), characterizing it and testing its mechanical properties in compression. Differential aging heat treatment was used to produce the functionally graded material in a precipitation hardenable Al-4.6%Cu alloy by changing the microstructure. Temperature gradient furnace was used to achieve the gradation in microstructure from one end of the sample to the other end by differential aging of the solution treated sample. Mechanical properties can be varied in any precipitation hardenable alloy by means of producing various precipitates, which will form during the aging sequence. In Al-4.6%Cu alloy one end of the solution treated sample was aged for 38 hours at 170°C and the other end at 70°C by means of a temperature gradient furnace in which the coil density varies along the axis of the furnace. Thus we achieved a difference in mechanical properties from 70°C side to 170°C side as the precipitation during differential aging varied from GP zones at one end to θ' precipitate at the other end. Characterization was done on isothermally aged samples and in FGM using XRD (X-ray diffraction) and TEM (Transmission Electron Microscopy). XRD result showed that the final equilibrium precipitate θ was not formed in any of the heat-treated samples. TEM result showed the various precipitation sequences from GP zones to θ' in the isothermally aged samples and the same was confirmed in the gradient sample by cutting the samples form 70°C side towards the 170°C side and doing TEM on each sample. The properties of FGM in compression were studied using a 9mmx9mmxl8mm-compression sample using DARTEC machine and it was compared with those of isothermally aged samples. For 70°C the 0.2% proof stress was 141MPa and for 170°C it was 226MPa. The corresponding ductility values at the point of inflection on the engineering stress-strain curve for 70°C sample was higher (33%) than the 170°C (22%) sample. For the gradient sample it gave a proof stress of 163MPa and a ductility value of 30%.

No description available.

Aluminum-silicon-copper cast alloys of the 319-type have attained a commercially important status because of their widespread use. Artificial aging treatments are routinely applied to these alloys in order to obtain precipitation hardening and improve their mechanical properties. Standard treatments may not always yield the optimum achievable properties, thus Mg and Sr are commonly added to improve the response of the alloy to aging and to modify the eutectic Si morphology from acicular to fibrous, respectively. The present study was carried out to investigate aging behavior of four 319-type alloys in regard to such mechanical properties as their ultimate tensile strength, yield strength, microhardness, percent elongation and impact toughness. Non-conventional aging cycles were applied so as to evaluate the degree of the improvement in strength obtainable. These treatments, labeled in this study as T6- and T7-type multi-temperature and interrupted aging treatments, involve several heating stages at different temperatures, as opposed to the single stage at constant temperature specifications of the standard T6 or T7 heat treatment regimes. Scanning electron microscopy was used to examine the fracture surfaces of selected tensile-tested samples to compare the fracture behavior. Transmission electron microscopy was used to reveal and identify the tiny precipitates which appear in the microstructure as a result of the precipitation-hardening process due to artificial aging. It was found that the main strengthening phase is theta-Al2Cu in the form of needles; other phases were observed as minor constituents in this alloy, including the binary beta-Mg2Si, the ternary S-CuAlMg 2 and the quaternary Q-Al5Cu2Mg7Si 7. The results show that while Mg and Sr additions improve the properties of the alloy, the standard T6 treatment may not be the best available option to produce optimum properties. In fact, when the peak-aged (T6) condition is desired, the optimum treatment consists of a continuous artificial treatment at 170°C for 8 h; when the overaged (T7) condition is desired, a T7-type multi-temperature treatment consisting of underaging at 170°C for 1 h, then at 190°C for 1 h, and finally overaging at 240°C for 2 h is the best option.