Chip-package interaction (CPI) has become a critical reliability issue for flip-chip packaging of Cu/low-k chip with organic substrate. The thermo-mechanical deformation and stress develop inside the package during assembly and subsequent reliability tests due to the mismatch of the coefficients of thermal expansion (CTEs) between the chip and the substrate. The thermal residual stress causes many mechanical reliability issues in the solder joints and the underfill layer between die and substrate, such as solder fatigue failure and underfill delamination. Moreover, the thermo-mechanical deformation of the package can be directly coupled into the Cu/low-k interconnect, inducing large local stresses to drive interfacial crack formation and propagation. The thermo-mechanical reliability risk is further aggravated with the implementation of ultra low-k dielectric for better electrical performance and the mandatory change from Pb-containing solders to Pb-free solders for environmental safety. These CPI-induced reliability issues in flip-chip packaging of Cu/low-k chips are investigated in this dissertation at both chip level and package level using high-resolution Moiré interferometry and Finite Element Analysis (FEA). Firstly, the thermo-mechanical deformation in flip-chip packages is analyzed using high-resolution Moiré interferometry. The effect of underfill properties on package warpage is studied and followed by a strategy study of proper underfill selection to improve solder fatigue life time and reduce the risk of interfacial delamination in underfill and low-k interconnects under CPI. The chip-package interaction is found to maximize at the die attach step during assembly and becomes most detrimental to low-k chip reliability because of the high thermal load generated by the solder reflow process before underfilling. A three-dimensional (3D) multilevel sub-modeling method combined with modified virtual crack closure (MVCC) technique is employed to investigate the CPI-induced interfacial delamination in Cu/low-k interconnects. It is first focused on the effects of dielectrics and solder materials on low-k interconnect reliability and then extended to the scaling effect where the reduction of the interconnect dimension is accompanied with an increased number of metal levels and the implementation of ultralow-k porous dielectrics. Recent studies on CPI-induced crack propagation in the low-k interconnect and the use of crack-stop structures to improve the chip reliability are also discussed. Finally, 3D integration (3DI) with through silicon vias (TSV) has been proposed as the latest solution to increase the device density without down-scaling. The thermo-mechanical reliability issues facing 3DI are analyzed. Three failure modes are proposed and studied. Design optimization of 3D interconnects to reduce the thermal residual stress and the risks of fracture and delamination are discussed. / text

Des films et revêtements composés de phases et composés intermétalliques présentent des propriétés et des combinaisons de propriétés attractives qui ne sont que très partiellement explorées aujourd’hui. Ils sont porteurs de solutions potentielles pour conférer à des matériaux avancés des multifonctionnalités nécessaires dans pratiquement toutes les industries manufacturières et deviennent ainsi source de rupture et d’innovation. Cette situation prévaut pour le système Al-Cu-Fe, au sein duquel même les binaires à base d’Al présentent des propriétés remarquables. Si des techniques de dépôt physique en phase vapeur sont le plus souvent utilisées pour l’élaboration de tels films et revêtements métalliques, l’utilisation de procédés de dépôt chimique en phase vapeur à partir de précurseurs métalorganiques (MOCVD) permettrait à terme le traitement et la fonctionnalisation de surfaces de géométrie complexe. Le présent travail s’inscrit dans cette logique. Il vise la mise au point de procédés MOCVD de films d’Al, de Cu et de Fe. Ces procédés doivent être compatibles afin de constituer la base pour l’élaboration de protocoles complexes permettant le codépôt ou le dépôt séquentiel de ces éléments. La MOCVD d’Al à partir de dimethylethyl amine alane (DMEAA) a été adaptée pour satisfaire les contraintes de codépôt, pour valider le dispositif expérimental utilisé pour le dépôt des films unaires et binaires, pour valider certains aspects mécanistiques du dépôt et pour illustrer la capacité de la technique de couvrir de manière conforme des surfaces de géométrie complexe. Le protocole mise au point permet d’opérer à une pression de 10 Torr, dans une fenêtre de températures entre 160 °C et 240 °C. La modélisation du procédé permet son optimisation dans ces conditions, conduisant à des films d’épaisseur uniforme sur une surface de diamètre 58 mm. La microstructure désordonnée des films est améliorée par un prétraitement plasma des substrats d’acier 304L in situ avant dépôt.Le besoin d’utiliser des précurseurs de Cu et de Fe exemptes d’oxygène (en vue d’un codépôt avec Al) a conduit à tester pour ces deux éléments la famille originale des composés moléculaires à base de ligands amidinates. Il est montré que des films purs de Cu sont obtenus entre 200 °C et 350 °C à partir de [Cu(i-Pr-Me-AMD)]2 dans une phase gazeuse riche en hydrogène, la limite entre les régimes cinétique et diffusionnel étant à 240 °C. Le criblage de précurseurs analogues pour Fe a révélé que, dans les mêmes conditions, le composé [Fe(tBu-MeAMD)2] conduit à des films contenant Fe, Fe4N ainsi qu’à des carbures Fe3C et Fe4C.Des bicouches de Cu et Al ont été déposées à partir des protocoles mis au point. Leur recuit post dépôt a été suivi in situ par diffraction de rayons X et par mesure de la résistance électrique. Il a permis de stabiliser des phases θ-Al2Cu, η-AlCu et, pour la première fois reportée dans la littérature, de la phase approximante γ-Al4Cu9. Il a été démontré que la technique MOCVD associée avec des recuits post dépôt est une méthode appropriée pour obtenir des films composés d’alliages intermétalliques. Des dépôts conformes de tels films peuvent ainsi être envisagés pour des nombreuses applications. / Films and coatings intermetallic phases and intermetallic compounds present proprieties and combination of proprieties which are just partially explored today. They carry potential solutions to confer multifunctionality for advanced materials needed by industries and become a source of disruption and innovation. This situation prevails for the Al-Cu-Fe, in which even the binary Al-based exhibit remarkable properties. While techniques of physical vapor deposition are most often used for the development of such films and metallic coatings, the use of processes of chemical vapor deposition from metallorganic precursors (MOCVD) lead to the treatment and functionalization of surfaces with complex geometry. The present work joins in this logic.It aims at the development of MOCVD processes of Al, Cu and Fe films. These processes must be compatible to constitute the base for the elaboration of complex protocols allowing the codeposition or the sequential deposition of these elements. The MOCVD of Al from dimethylethyl amine alane (DMEAA) was adapted to satisfy the constraints of codeposition to validate the experimental device. Used for the deposition of unary and binary films, to validate certain aspects mechanistic of the deposition and to illustrate the capacity of the technique to cover in a shape way surfaces of complex geometry. The protocol development allows to operate at pressure of 10 Torr, in a window of temperatures between 160 °C and 240 °C. The modeling of the process allows its optimization in these conditions, leading to films with uniform thickness. The disorderly microstructure of these films is improved by a plasma pretreatment of the substrate of 304L steel in situ before deposition. The need to use precursors of Cu and Fe-free oxygen (for a co-deposition with Al) has led to testing for these two elements the original family of molecular compounds based ligands AMIDINATES. It is shown that pure Cu films are obtained between 200 ° C and 350 ° C from [Cu (i-Pr-Me-AMD)]2 in a gaseous phase rich in hydrogen, the boundary between the kinetic schemes and diffusion regyme being at 240 ° C. Screening similar to Fe precursors revealed that, under the same conditions, the compound [Fe (tBu-MeAMD)2] leads to films containing Fe, as well as Fe4N carbides Fe3C and Fe4C. Bilayers of Cu and Al were deposited from the protocols developed. Their post deposition annealing was followed by in situ X-ray diffraction and by measuring the electrical resistance. It has stabilized θ-Al2Cu, η-AlCu phases and, for the first time reported in the literature, the approximant phase γ-Al4Cu9. It was demonstrated that the MOCVD technique associated with post-deposition annealing is a suitable method to obtain films composed of intermetallic alloys. Deposits conform such films can thus be considered for many applications.

A liga binária Al-Cu é a base para todas as ligas da série 2xxx que são de grande importância em diversas aplicações como na indústria aeronáutica, transporte, máquinas e equipamentos. No entanto, pouco se conhece sobre os efeitos do tipo de solidificação desta liga e da deformação plástica sobre sua resistência à corrosão em meio aquoso. O escopo deste trabalho foi procurar correlacionar microestruturas da liga Al-4,5%p.Cu solidificada de maneira convencional e unidirecional vertical ascendente (brutas de fusão, deformadas plasticamente por forjamento rotativo a frio, e tratadas termicamente visando recristalização), orientações preferenciais de grãos com as características de resistência à corrosão. Foram utilizadas técnicas de microscopia eletrônica de varredura e óptica, difratometria de raios X e ensaios eletroquímicos em soluções de NaCl 0,6 M e Na2SO4 0,1M por polarização potenciodinâmica e espectroscopia de impedância eletroquímica. A taxa de corrosão foi maior em solução de NaCl 0,6 M do que em Na2SO4 0,1M para todas as amostras. O aumento da redução por deformação plástica conduziu a uma diminuição da resistência à corrosão da liga devido ao aumento das tensões internas e ao aparecimento de orientações preferenciais dos grãos de menor densidade planar como (200) e (220). As amostras recristalizadas apresentaram de uma forma geral uma resistência maior quando comparada às amostras não recristalizadas, comportamento atribuído ao alívio de tensões internas e ao desaparecimento da orientação preferencial do plano menos denso (220). / The binary Al-Cu alloy is the basis for all AA2xxx alloys, being important in several applications as aeronautical industry, transportation, machines and equipments. However, few is known about the effect of the type of solidification of this alloy and plastic deformation on the corrosion resistance in aqueous medium. The scope of this work was to correlate microstructures of the Al-4.5 % wt. Cu alloy solidified under conventional and upward direct chilling conditions (as cast condition, plastic formed by cold swaging, and heat treated seeking recristallyzation), crystallographic orientations and corrosion resistance characteristics. Scanning electron microscopy and optical, X ray diffractometry techniques and electrochemical measurements in NaCl 0,6 M and Na2SO4 0,1 M potentiodynamic polarization and electrochemical impedance spectroscopy were used. The corrosion rate in NaCl 0,6 M was higher than in Na2SO4 0,1 M for all samples. The increase of the plastic deformation led to alloy corrosion resistance decrease, due to the internal stresses increase and the arising of less dense grain preferred orientations of lower planar density as (200) and (220) orientations. The recristallyzed samples presented in a general way a higher corrosion resistance, when compared to the non recristallyzed samples, being imputed to the internal tension relieve and the extinction of the plane (220) of lower planar density to a structure of random orientation.

Neste trabalho estudou-se a formação de complexos da tirosina e de seus dipeptídeos tirosil-glicina e glicil-tirosina com o íon Cu2+. Para a caracterização destes complexos foram utilizadas as técnicas espectroscópicas de Absorção ótica na região do visível (400 a 800 nm), Ressonância paramagnética eletrônica em duas temperaturas (ambiente e &#8764-150&#176C) e a técnica de fluorescência. No caso da tyr os dados experimentais obtidos pela espectroscopia de RPE sugerem a formação de pelo menos duas espécies distintas de complexos além do cobre hidratado. Os complexos propostos foram: o CuL4 (ao redor de pH 3,5) e o CuL2 (na faixa de pH 4,0 e 12,0). Já para os dipeptídeos são evidenciados três tipos diferentes de complexos. São propostos os seguintes complexos: CuL2 (ao redor de pH 4,5), CuL (H2O) (na faixa de pH 7,0 e 12,0) e CuL(OH)22- (acima de pH 12,0). Os espectros de RPE mostram claramente que com o aumento de pH, ocorre a complexação do Cu2+ com os dipeptídeos. Em pHs altos (acima de pH 10,0) surgem nestes espectros uma estrutura superhiperfina de 5 linhas típicas para a coordenação de Cu2+ com dois nitrogênios. Quanto a tirosina, o espectro de seu complexo com Cu2+, não apresenta estrutura superhiperfina, sendo o sinal obtido, típico do complexo com Cu2+. Da mesma forma que foi observado por RPE, pode-se observar pelos espectros óticos, que em pHs baixos (2,0 a 3,5) para os dipeptídeos, os espectros apresentam uma banda larga e mal-resolvida, característica do íon de Cu2+ livre em solução. Observou-se também um deslocamento do máximo das bandas para o azul, apresentando características típicas das transições d-d correspondentes às várias espécies de complexos do metal em equilíbrio. Os dados de fluorescência foram muito informativos. As titulações da tyr e dos dipeptídeos puros em função do pH permitiram a determinação dos valores de pKs dos grupos ionizáveis. O efeito de supressão de fluorescência devido ao paramagnetismo do cobre foi usado tanto para a determinação da estequiometria quanto para a determinação das constantes de associação dos complexos dos dipeptídeos com Cu2+ em dois pHs fixos (pH 7,0 e 9,0). Encontrou-se complexos com a seguinte estequiometria (ligante/metal) : 2:1 e 1:1 respectivamente para a tyr e para os dipeptídeos nestes pHs. Um modelo simples de equilíbrio foi desenvolvido e estimou-se as constantes de associação da ordem de 107M-1 para os complexos de dipeptídeos- Cu2+. / The main goal of this work was to study the formation of the complexes of tyrosine and its dipeptides tyrosil-glycil and glycil-tyrosine with the transition metal íon Cu2+. The characterization of these complexes was performed through the use of spectroscopic techniques: optical absorption, electron paramagnetic resonance at both room temperature and -150&#176C and fluorescence emission. The EPR spectroscopy suggested for tyrosine two distints species. The following complexes were proposed: CuL4 (pH 3,5) and CuL2 (in the range of pH between 4,0-12,0). Three different complexes were evidentiated for dipeptides- Cu2+: CuL2 (pH 4,5); CuL(H2O) (in the range of pH between 7,0-12,0) and CuL(OH)22- (above pH 12,0). EPR spectra shows clearly the complexation of Cu2+ to the dipeptides. Both at intermediate and high pHs and specially above pH 10,0 a superhyoerfine structure of five lines typical for coordination of copper to two nitrogens was observed. In the case of the aminoacid no superhyperfine structure is observed. EPR data suggest that in a wide pH range between 7,0 and 11,0 the complex formed by the dipeptides was CuL(H2O). Electronic optical absorption was measured at room temperature as a function of pH in the range 2,0-13,0. It was observed that at low pHs (2,0 3,5) the spectra for the dipeptides was characterized by a broad not well resolved band around 800 nm characteristic of hidrated free Cu2+ in water solution. EPR spectra are in agreement with this observation. Increase of pH leads to a blue shift in the absorption band maximum and as a consequence to typical spectra for d-d transitions of the various species of complexes of cooper in equilibrium in solution. Fluorescence data were also very informative. The pure tyr and dipeptides tritation allowed to determine pKs values of ionizable groups. The effect of fluorescence suppression due to paramagnetic copper was used both to establish the stoichiometry of the complexes and the association constants. The stoichiometry of the complexes was determined as 2:1 and 1:1 ligand:metal for tyrosine and the dipeptides respectively at pH 7,0 and pH 9,0. A simple equilibrium model was developed and the association constants for the Cu2+ dipeptides complexes at pH 7,0 and pH 9,0 were estimated to be around 107M-1.

Neste trabalho são apresentados estudos em três diferentes sistemas utilizando-se as técnicas de Ressonância Paramagnética Eletrônica (RPE) e absorção eletrônica. No primeiro estudou-se a formação dos possíveis complexos entre o aminoácido aliina, extraído do alho, e o íon cobre (II). Os dados de RPE e absorção eletronica no visível (400-1100 nm) foram utilizados para caracterizar os diferentes complexos obtidos. No segundo utilizou-se o monocristal do complexo dicloro bis (benzil difenil fosfinóxido) Cobre (II) e efetuaram-se medidas de RPE variando-se a direção de aplicação do campo magnético no monocristal. Os auto-valores encontrados para as componentes do tensor g&#175 foram: g1= 2,0891; g2= 2,4554 e g3= 2,0767. Com base nos dados de RPE e cristalográficos e usando a teoria de campo cristalino foi proposto dxy como estado fundamental para o íon cobre (II) neste complexo. Fez-se também um estudo preliminar observando-se as variações no centro ativo de hemoproteínas moduladas pelo grau de hidratação. Metahemoglobina bovina e metamioglobina eqüina liofilizadas foram usadas e o sinal de RPE do íon ferro (III) monitorado. Dos espectros de RPE das duas proteínas são observadas pelo menos duas simetrias para o íon ferro (III), uma axial caracterizada por um valor de g próximo de 6 e outra caracterizada por g= 4,3 correspondendo a simetria rômbica. A intensidade dos sinais mostrou-se muito sensíveis ao grau de hidratação. Metahemoglobina e metamioglobina apresentaram comportamentos distintos dos sinais de RPE e sugeriu-se serem eles devido as diferenças estruturais entre as duas proteínas / In this work studies in three different systems using Electron Paramagnetic Resonance (EPR) and eletronic absorption techniques are presented. The formation of possible complexes between the amino acid aliin, extracted of garlic, and the copper (II) íon was studied in the first work. EPR and visible eletronic absorption (400-1100 nm) data were utilized to characterize the different complexes obtained. In the second work a crystal of the complex dichloro bis (benzyl diphenyl phosphinoxide) copper (II) was used and the EPR measures were made for different directions of application of the magnetic field in the crystal. The eigenvalues obtained for the g&#175 tensor components were: g1= 2,0891; g2= 2,4554 and g3= 2,0767. Using EPR and crystallographic data and crystal field theory dxy was proposed as the ground state of the copper (II) íon in this complex. A preliminary study was also made observing changes at the active Center of the hemeproteins modulated by the hydration degree. Lyophilized bovine methemoglobin ande quine metmyoglobin were used and the EPR signal of the iron (III) íon monitored. Or both proteins the EPR spectra corresponding to at least two iron symmetries were observed, one axial characterized by a g value near 6.0 and another characterized by g= 4,3 corresponding to rhombic symmetry. The intensity of these signals were very sensitive to the hydration degree. Metmyoglobin and methemoglobin showed distint behaviors of the EPR signals and it was suggested that they were due to structural differences between the two proteins

No presente trabalho verificou-se a precisão de um critério que prevê composições de ligas vítreas aplicado ao sistema Zr-Ni-Cu. Este critério combina o parâmetro de instabilidade topológica (\'lâmbda\'), e o parâmetro termodinâmico (\'delta\' h) entre os elementos de liga. Os dois parâmetros correlacionam quantitativamente à composição química a tendência à formação de vidros metálicos. Este critério é uma ferramenta promissora e simples para guiar e reduzir o trabalho tedioso e intensivo de encontrar composições altas tendências a vitrificação em sistemas metálicos. Para comprovar a eficiência desta ferramenta, a metodologia foi calcular o parâmetro para o sistema de interesse e preparar ligas de acordo com algumas composições fornecidas. A metodologia de preparação das ligas seguiu a fusão a arco elétrico e subsequentemente o emprego das técnicas de resfriamento rápido, melt-spinning e splat-cooling, para a produção de fitas e discos metálicos respectivamente, e o coquilhamento para a produção de amostras maciças em forma de cunha. Para as amostras confeccionadas por melt-spinning e splat-cooling, verificou-se a precisão do critério de seleção através da quantificação das porcentagens de fases vítreas a partir de análises de difratogramas de raios-X e seus comportamentos térmicos a partir dos termogramas de análises por calorimetria exploratória diferencial (DSC). Já para as ligas coquilhadas em cunha, obtiveram-se alguns resultados com indícios de estruturas vítreas que foram caracterizadas por difração de raios-X e metalografia. Desta forma chegou-se à conclusão que o critério de seleção aplicado ao sistema Zr-Ni-Cu pode ser utilizado para o desenvolvimento de composições favoráveis à formação de vidro antes da produção das ligas. Conclui-se que o critério que combina o parâmetro de instabilidade topológica (\'lâmbda\' min) e o parâmetro termodinâmico (\'delta\' h) é uma ferramenta que pode ser utilizada como guia para encontrar as composições mais fáceis de formar vidro, reduzindo assim o trabalho experimental de tentativa e erro. / In the present work it was verified the accuracy of a proposed criterion to predict compositions of glassy alloys applied in the Zr-Ni-Cu system. This criterion combines the topological instability parameter (\'lâmbda\') and a thermodynamic parameter (\'delta\' h) among the alloying elements. The two parameters correlate quantitatively the chemical composition with the glass forming ability. This criterion is a promising and simple tool to guide and reduce the tedious and intensive work of finding good compositions of glasses in metallic systems. In an attempt to prove the efficiency of such tool, the methodology was to calculate the parameter for the system of interest and prepare alloys in accordance with the compositions provided by the tool. The methodology of preparation of the alloys followed the electric arc- melting and subsequent use of fast cooling techniques, melt-spinning and splat-cooling for the production of metallic ribbons and discs, respectively, and a wedge-shaped chiller mold to produce bulk metallic samples. For samples prepared from the melt-spinning and splat-cooling, it was verified the accuracy of the selection criteria by quantifying the percentage of glassy phases from X-ray diffractograms and their thermal behaviors from thermograms produced by differential scanning calorimetry (DSC). For alloys produced from the wedge-shaped mold, some results were obtained with evidence of vitreous structures that were characterized by X-ray diffraction and metallography. Therefore the conclusion is that the selection criteria applied to the system Zr-Ni-Cu can be used to develop favorable compositions for the formation of glasses before the production of the alloys. It is concluded that the selection criterion is a good tool and can be used as a guide to find the best glass forming alloys, thus reducing the experimental procedures of trial and error.

Os vidros metálicos baseados em Cu-Zr representam uma classe bastante promissora para a categoria de materiais estruturais, tendo em vista suas interessantes propriedades resultantes da natureza amorfa. Sabe-se que o oxigênio tem grande influência na formação da estrutura amorfa e consequentemente nas propriedades dessa classe de materiais. No presente trabalho, ligas amorfas baseadas em Cu-Zr foram analisadas termicamente a fim de se observar o comportamento das mesmas frente à contaminação com oxigênio. As análises térmicas foram realizadas em um equipamento de calorimetria exploratória diferencial (DSC), e as temperaturas características como de transição vítrea, cristalização, fusão e líquidus foram determinadas. Concluiu-se que conforme a literatura apresenta, o processo de cristalização é favorecido pela presença de oxigênio, causando uma queda na energia de ativação dos processos de cristalização das ligas trabalhadas. Através de ensaios que simularam tratamentos térmicos, cristalizou-se controladamente as amostras amorfas baseadas em Cu-Zr a fim de formar compósitos entre cristais e vidros metálicos buscando diminuir a fragilidade das ligas. / Cu-Zr-based bulk metallic glasses represent a very promising class of structural materials with interesting properties resulting from the amorphous nature. It is known that oxygen has a great influence on the formation of the amorphous structure and consequently on the properties of these materials. In the present work, Cu-Zr-based amorphous alloys were thermally analyzed in order to observe their behavior against oxygen contamination. Thermal analyzis were performed on a differential scanning calorimetry (DSC) equipment, and characteristic temperatures as glass transition, crystallization, melting and liquidus were determined. It was concluded that, according to the literature, the crystallization process is favored by the presence of oxygen, causing a decrease in the activation energy of the crystallization processes of the worked alloys. Through tests that simulated heat treatments, the amorphous samples were crystallized in order to form composites between crystals and metallic glasses in order to reduce the brittleness of the alloys.

Diese publikationsgestützte Dissertation umfasst Arbeiten zum Thema Monitoring und Feedback in der stationären Psychosomatik. In zwei Arbeiten wurde untersucht, ob die Effektivität von psychosomatischen Behandlungen gesteigert werden kann, wenn Therapeuten regelmäßig Feedbackberichte der Monitoring- und Feedbacksoftware OQ-Analyst erhalten Hier zeigte sich, dass Feedback den Outcome von Patienten mit erhöhtem Risiko einer Verschlechterung verbessern kann. Bei den restlichen Patienten dagegen konnte Feedback den Therapieprozess nur schwach und nur kurzfristig für eine Behandlungswoche verbessern. In einer weiteren Arbeit wurde untersucht, ob sich unterschiedliche Belastungsgrade im wöchentlichen Monitoring differenziell verändern. Hierfür wurde das ICD-10-Symptomrating herangezogen. Die Ergebnisse lieferten Hinweise darauf, dass sich depressive Beschwerden und Angstbeschwerden schon in der ersten Behandlungswoche verbessern, somatoforme Beschwerden jedoch erst im späteren Behandlungsverlauf. Die vierte Arbeit setze sich mit der Fragestellung auseinander, ob Therapiebeziehung, soziale Unterstützung, Motivation, und Lebensereignisse mit bedeutsamen Verbesserungen und bedeutsamen Verschlechterungen assoziiert sind. Während alle vier Bereiche mit bedeutsamen Verbesserungen verknüpft waren, waren nur soziale Unterstützung und Lebensereignisse mit bedeutsamen Verschlechterungen assoziiert. / This dissertation is based on four publications on monitoring and feedback in psychosomatic in-patient therapy. In two publication it was investigated whether the effectiveness of psychosomatic in-patient therapy can be increased when therapists routinely receive the feedback reports of the monitoring and feedback software OQ-Analyst. Feedback could improve the outcome of patients at risk of treatment failure. For the remaining patients, feedback could optimize the therapy process only slightly for one treatment week. In another publication, the ICD-10-Symptom-Rating was used to explore how different symptoms change on a weekly basis. While depressive symptoms and symptoms of anxiety disorders improved already in the first treatment week, more treatment weeks were required to improve somatoform symptoms. In a fourth publication, associations between considerable positive as well as considerable negative change and the therapeutic alliance, social support, motivation, and life events were investigated. While all four factors were associated with considerable improvements, only social support and life events correlated with considerable deteriorations.

Neste trabalho são apresentados alguns resultados relacionados a estudos sobre o comportamento eletroquímico do Cu(II) em meio contendo diferentes peptídeos (tri, tetra e pentaglicina) em função da acidez utilizando-se voltametria cíclica. Os experimentos foram realizados em uma faixa de pH entre 7,0 e 10,0. Experimentos espectrofotométricos e coulométricos também foram feitos, ambos para se caracterizar as espécies de Cu(II) e Cu(III) em solução e provar a existência da degradação dos complexos de Cu(III). Além disso, experimentos para esses sistemas também foram realizados em diferentes temperaturas utilizando eletrodo rotativo na configuração disco-anel. Estudos eletroanalíticos demonstraram a potencialidade de se empregar o sistema Cu(II)/Cu(III) no desenvolvimento de metodologia eletroanalítica para a determinação de sulfito. Neste contexto, um método amperométrico indireto para a determinação de sulfito em fluxo é proposto neste trabalho. O método baseia-se na medida amperométrica (OV vs Ag/AgCI (sat. NaCI)) do Cu(III) gerado quimicamente no processo de auto¬-oxidação do S(IV) em soluções de Cu(II)/tetraglicina na presença de traços de Ni(II) utilizando uma célula em fluxo com sistema adequado para separação de gases. A oxidação espontânea do complexo pelo oxigênio dissolvido e S(IV) é muito lenta ao contrário do que ocorre quando há traços de Ni(II). A faixa de trabalho foi de 20-100 µmoIL-1 com limite de detecção de 2µmoIL-1 (S/N=3). A repetibilidade para a determinação (100µmoIL-1) levou a um desvio de 4,9% (n = 38), valor superior aos encontrados na literatura para determinações de sulfito em vinho por FIA com detecção amperométrica indireta (1-4,6%), e a freqüência analítica foi de 40h-1, valor coerente com os dos outros métodos amperométricos. Ambas as análises de sulfito em amostras de vinhos e de sucos tiveram seus resultados comparados com aqueles obtidos utilizando-se o método padrão. / The electrochemistry of Cu(II) in aqueous solutions containing triglycine, tetraglycine and pentaglycine had been investigated at glassy carbon surfaces. Experiments were carried out in the pH range between 7.0 and 10.0. A correlation between voltammetric waves and the nature of the Cu(II) species involved in the electrochemical steps was performed. Spectrophotometric and coulometric studies were also done to characterise Cu(II) and Cu(III) species in solution and prove the existence of a degradation step related to Cu(III) complexes. Rotating ring-disc voltammetry was employed to follow this chemical step coupled to the electrode reaction, at three different temperatures. Data show that Cu(III)/triglycine species degrade, with faster kinetics, when the results are compared with those obtained for tetraglycine and pentaglycine. An indirect amperometric method for the determination of sulfite in a flow injection configuration is described. The method is based on the amperometric measurement (OV vs Ag/AgCI (sat. NaCI)) of Cu(III) chemically generated by the sulfite induced autoxidation of Cu(II)/tetraglycine complex in the presence of traces of Ni(II) with a manifold that incorporates flow extraction of sulfite as SO2 through a PTFE membrane. The operational range was 2µmoIL-1 with a detection limit of 2µmolL-1 (S/N = 3). The repeatability for the determination (100 2µmolL-1) was evaluated to be 4.9% (n = 20) and the analytical frequency was 40h-1. Results for 3 wines and 2 juices samples showed excellent agreement with those obtained by using a recommended procedure for sulfite analysis.

A liga binária Al-Cu é a base para todas as ligas da série 2xxx que são de grande importância em diversas aplicações como na indústria aeronáutica, transporte, máquinas e equipamentos. No entanto, pouco se conhece sobre os efeitos do tipo de solidificação desta liga e da deformação plástica sobre sua resistência à corrosão em meio aquoso. O escopo deste trabalho foi procurar correlacionar microestruturas da liga Al-4,5%p.Cu solidificada de maneira convencional e unidirecional vertical ascendente (brutas de fusão, deformadas plasticamente por forjamento rotativo a frio, e tratadas termicamente visando recristalização), orientações preferenciais de grãos com as características de resistência à corrosão. Foram utilizadas técnicas de microscopia eletrônica de varredura e óptica, difratometria de raios X e ensaios eletroquímicos em soluções de NaCl 0,6 M e Na2SO4 0,1M por polarização potenciodinâmica e espectroscopia de impedância eletroquímica. A taxa de corrosão foi maior em solução de NaCl 0,6 M do que em Na2SO4 0,1M para todas as amostras. O aumento da redução por deformação plástica conduziu a uma diminuição da resistência à corrosão da liga devido ao aumento das tensões internas e ao aparecimento de orientações preferenciais dos grãos de menor densidade planar como (200) e (220). As amostras recristalizadas apresentaram de uma forma geral uma resistência maior quando comparada às amostras não recristalizadas, comportamento atribuído ao alívio de tensões internas e ao desaparecimento da orientação preferencial do plano menos denso (220). / The binary Al-Cu alloy is the basis for all AA2xxx alloys, being important in several applications as aeronautical industry, transportation, machines and equipments. However, few is known about the effect of the type of solidification of this alloy and plastic deformation on the corrosion resistance in aqueous medium. The scope of this work was to correlate microstructures of the Al-4.5 % wt. Cu alloy solidified under conventional and upward direct chilling conditions (as cast condition, plastic formed by cold swaging, and heat treated seeking recristallyzation), crystallographic orientations and corrosion resistance characteristics. Scanning electron microscopy and optical, X ray diffractometry techniques and electrochemical measurements in NaCl 0,6 M and Na2SO4 0,1 M potentiodynamic polarization and electrochemical impedance spectroscopy were used. The corrosion rate in NaCl 0,6 M was higher than in Na2SO4 0,1 M for all samples. The increase of the plastic deformation led to alloy corrosion resistance decrease, due to the internal stresses increase and the arising of less dense grain preferred orientations of lower planar density as (200) and (220) orientations. The recristallyzed samples presented in a general way a higher corrosion resistance, when compared to the non recristallyzed samples, being imputed to the internal tension relieve and the extinction of the plane (220) of lower planar density to a structure of random orientation.