Machine vision for the automatic classification of images acquired from Non-destructive tests

This project is based on Artificial Intelligence (A.I) and Digital Image processing (I.P) for automatic condition monitoring of sleepers in the railway track. Rail inspection is a very important task in railway maintenance for traffic safety issues and in preventing dangerous situations. Monitoring railway track infrastructure is an important aspect in which the periodical inspection of rail rolling plane is required.Up to the present days the inspection of the railroad is operated manually by trained personnel. A human operator walks along the railway track searching for sleeper anomalies. This monitoring way is not more acceptable for its slowness and subjectivity. Hence, it is desired to automate such intuitive human skills for the development of more robust and reliable testing methods. Images of wooden sleepers have been used as data for my project. The aim of this project is to present a vision based technique for inspecting railway sleepers (wooden planks under the railway track) by automatic interpretation of Non Destructive Test (NDT) data using A.I. techniques in determining the results of inspection.

Homogenization of Precipitation Hardening Nickel Based Superalloys

Allvac 718 Plus and Haynes 282 are relatively new precipitation hardening nickel based superalloys with good high temperature mechanical properties. In addition, the weldability of these superalloys enhances easy fabrication. The combination of high temperature capabilities and superior weldability is unmatched by other precipitation hardening superalloys and linked to the amount of the γ’ hardening precipitates in the materials. Hence, it is these properties that make Allvac 718 Plus and Haynes 282 desirable in the manufacture of hot sections of aero engine components. Studies show that cast products are less weldable than wrought products. Segregation of elements in the cast results in inhomogeneous composition which consequently diminishes weldability. Segregation during solidification of the cast products results in dendritic microstructure with the segregating elements occupying interdendritic regions. These segregating elements are trapped in secondary phases present alongside γ matrix. Studies show that in Allvac 718Plus, the segregating phase is Laves while in Haynes 282 the segregating phase is not yet fully determined. Thus, the present study investigated the effects of homogenization heat treatments in eliminating segregation in cast Allvac 718 Plus and Haynes 282. Paramount to the study was the effect of different homogenization temperatures and dwell time in the removal of the segregating phases. Experimental methods used to both qualify and quantify the segregating phases included SEM, EDX analysis, manual point count and macro Vickers hardness tests. Main results show that there is a reduction in the segregating phases in both materials as homogenization proceeds hence a disappearance of the dendritic structure. In Allvac 718 Plus, plate like structures is observed to be closely associated with the Laves phase at low temperatures and dwell times. In addition, Nb is found to be segregating in the interdendritic areas. The expected trend of increase in Laves as a result of the dissolution of the plate like structures at the initial stage of homogenization is only detectable for few cases. In Haynes 282, white and grey phases are clearly distinguished and Mo is observed to be segregating in interdendritic areas.

Modular Product Verifications Based on Design for Assembly

The desire to conquer markets through advanced product design and trendy business strategies are still predominant approaches in industry today. In fact, product development has acquired an ever more central role in the strategic planning of companies, and it has extended its influence to R&D funding levels as well. It is not surprising that many national R&D project frameworks within the EU today are dominated by product development topics, leaving production engineering, robotics, and systems on the sidelines. The reasons may be many but, unfortunately, the link between product development and the production processes they cater for are seldom treated in depth. The issue dealt with in this article relates to how product development is applied in order to attain the required production quality levels a company may desire, as well as how one may counter assembly defects and deviations through quantifiable design approaches. It is recognized that product verifications (tests, inspections, etc.) are necessary, but the application of these tactics often result in lead-time extensions and increased costs. Modular architectures improve this by simplifying the verification of the assembled product at module level. Furthermore, since Design for Assembly (DFA) has shown the possibility to identify defective assemblies, it may be possible to detect potential assembly defects already in the product and module design phase. The intention of this paper is to discuss and describe the link between verifications of modular architectures, defects and design for assembly. The paper is based on literature and case studies; tables and diagrams are included with the intention of increasing understanding of the relation between poor designs, defects and product verifications.

Electrical Evaluation of a Low Concentrating PVT Collector Based on Performance Ratio

Photovoltaic Thermal/Hybrid collectors are an emerging technology that combines PV and solar thermal collectors by producing heat and electricity simultaneously. In this paper, the electrical performance evaluation of a low concentrating PVT collector was done through two testing parts: power comparison and performance ratio testing. For the performance ratio testing, it is required to identify and measure the factors affecting the performance ratio on a low concentrating PVT collector. Factors such as PV cell configuration, collector acceptance angle, flow rate, tracking the sun, temperature dependence and diffuse to irradiance ratio. Solarus low concentrating PVT collector V12 was tested at Dalarna University in Sweden using the electrical equipment at the solar laboratory. The PV testing has showed differences between the two receivers. Back2 was producing 1.8 energy output more than Back1 throughout the day. Front1 and Front2 were almost the same output performance. Performance tests showed that the cell configuration for Receiver2 with cells grouping (6- 32-32-6) has proved to have a better performance ratio when to it comes to minimizing the shading effect leading to more output power throughout the day because of lowering the mismatch losses. Different factors were measured and presented in this thesis in chapter 5. With the current design, it has been obtained a peak power at STC of 107W per receiver. The solar cells have an electrical efficiency of approximately 19% while the maximum measured electrical efficiency for the collector was approximately 18 % per active cell area, in addition to a temperature coefficient of -0.53%/ ˚C. Finally a recommendation was done to help Solarus AB to know how much the electrical performance is affected during variable ambient condition and be able to use the results for analyzing and introducing new modification if needed.

Visualization of spirography-based objective measures in Parkinson's disease

Objective: To investigate whether advanced visualizations of spirography-based objective measures are useful in differentiating drug-related motor dysfunctions between Off and dyskinesia in Parkinson’s disease (PD). Background: During the course of a 3 year longitudinal clinical study, in total 65 patients (43 males and 22 females with mean age of 65) with advanced PD and 10 healthy elderly (HE) subjects (5 males and 5 females with mean age of 61) were assessed. Both patients and HE subjects performed repeated and time-stamped assessments of their objective health indicators using a test battery implemented on a telemetry touch screen handheld computer, in their home environment settings. Among other tasks, the subjects were asked to trace a pre-drawn Archimedes spiral using the dominant hand and repeat the test three times per test occasion. Methods: A web-based framework was developed to enable a visual exploration of relevant spirography-based kinematic features by clinicians so they can in turn evaluate the motor states of the patients i.e. Off and dyskinesia. The system uses different visualization techniques such as time series plots, animation, and interaction and organizes them into different views to aid clinicians in measuring spatial and time-dependent irregularities that could be associated with the motor states. Along with the animation view, the system displays two time series plots for representing drawing speed (blue line) and displacement from ideal trajectory (orange line). The views are coordinated and linked i.e. user interactions in one of the views will be reflected in other views. For instance, when the user points in one of the pixels in the spiral view, the circle size of the underlying pixel increases and a vertical line appears in the time series views to depict the corresponding position. In addition, in order to enable clinicians to observe erratic movements more clearly and thus improve the detection of irregularities, the system displays a color-map which gives an idea of the longevity of the spirography task. Figure 2 shows single randomly selected spirals drawn by a: A) patient who experienced dyskinesias, B) HE subject, and C) patient in Off state. Results: According to a domain expert (DN), the spirals drawn in the Off and dyskinesia motor states are characterized by different spatial and time features. For instance, the spiral shown in Fig. 2A was drawn by a patient who showed symptoms of dyskinesia; the drawing speed was relatively high (cf. blue-colored time series plot and the short timestamp scale in the x axis) and the spatial displacement was high (cf. orange-colored time series plot) associated with smooth deviations as a result of uncontrollable movements. The patient also exhibited low amount of hesitation which could be reflected both in the animation of the spiral as well as time series plots. In contrast, the patient who was in the Off state exhibited different kinematic features, as shown in Fig. 2C. In the case of spirals drawn by a HE subject, there was a great precision during the drawing process as well as unchanging levels of time-dependent features over the test trial, as seen in Fig. 2B. Conclusions: Visualizing spirography-based objective measures enables identification of trends and patterns of drug-related motor dysfunctions at the patient’s individual level. Dynamic access of visualized motor tests may be useful during the evaluation of drug-related complications such as under- and over-medications, providing decision support to clinicians during evaluation of treatment effects as well as improve the quality of life of patients and their caregivers. In future, we plan to evaluate the proposed approach by assessing within- and between-clinician variability in ratings in order to determine its actual usefulness and then use these ratings as target outcomes in supervised machine learning, similarly as it was previously done in the study performed by Memedi et al. (2013).

A web-based system for visualizing upper limb motor performance of Parkinson’s disease patients

Objective To design, develop and set up a web-based system for enabling graphical visualization of upper limb motor performance (ULMP) of Parkinson’s disease (PD) patients to clinicians. Background Sixty-five patients diagnosed with advanced PD have used a test battery, implemented in a touch-screen handheld computer, in their home environment settings over the course of a 3-year clinical study. The test items consisted of objective measures of ULMP through a set of upper limb motor tests (finger to tapping and spiral drawings). For the tapping tests, patients were asked to perform alternate tapping of two buttons as fast and accurate as possible, first using the right hand and then the left hand. The test duration was 20 seconds. For the spiral drawing test, patients traced a pre-drawn Archimedes spiral using the dominant hand, and the test was repeated 3 times per test occasion. In total, the study database consisted of symptom assessments during 10079 test occasions. Methods Visualization of ULMP The web-based system is used by two neurologists for assessing the performance of PD patients during motor tests collected over the course of the said study. The system employs animations, scatter plots and time series graphs to visualize the ULMP of patients to the neurologists. The performance during spiral tests is depicted by animating the three spiral drawings, allowing the neurologists to observe real-time accelerations or hesitations and sharp changes during the actual drawing process. The tapping performance is visualized by displaying different types of graphs. Information presented included distribution of taps over the two buttons, horizontal tap distance vs. time, vertical tap distance vs. time, and tapping reaction time over the test length. Assessments Different scales are utilized by the neurologists to assess the observed impairments. For the spiral drawing performance, the neurologists rated firstly the ‘impairment’ using a 0 (no impairment) – 10 (extremely severe) scale, secondly three kinematic properties: ‘drawing speed’, ‘irregularity’ and ‘hesitation’ using a 0 (normal) – 4 (extremely severe) scale, and thirdly the probable ‘cause’ for the said impairment using 3 choices including Tremor, Bradykinesia/Rigidity and Dyskinesia. For the tapping performance, a 0 (normal) – 4 (extremely severe) scale is used for first rating four tapping properties: ‘tapping speed’, ‘accuracy’, ‘fatigue’, ‘arrhythmia’, and then the ‘global tapping severity’ (GTS). To achieve a common basis for assessment, initially one neurologist (DN) performed preliminary ratings by browsing through the database to collect and rate at least 20 samples of each GTS level and at least 33 samples of each ‘cause’ category. These preliminary ratings were then observed by the two neurologists (DN and PG) to be used as templates for rating of tests afterwards. In another track, the system randomly selected one test occasion per patient and visualized its items, that is tapping and spiral drawings, to the two neurologists. Statistical methods Inter-rater agreements were assessed using weighted Kappa coefficient. The internal consistency of properties of tapping and spiral drawing tests were assessed using Cronbach’s α test. One-way ANOVA test followed by Tukey multiple comparisons test was used to test if mean scores of properties of tapping and spiral drawing tests were different among GTS and ‘cause’ categories, respectively. Results When rating tapping graphs, inter-rater agreements (Kappa) were as follows: GTS (0.61), ‘tapping speed’ (0.89), ‘accuracy’ (0.66), ‘fatigue’ (0.57) and ‘arrhythmia’ (0.33). The poor inter-rater agreement when assessing “arrhythmia” may be as a result of observation of different things in the graphs, among the two raters. When rating animated spirals, both raters had very good agreement when assessing severity of spiral drawings, that is, ‘impairment’ (0.85) and irregularity (0.72). However, there were poor agreements between the two raters when assessing ‘cause’ (0.38) and time-information properties like ‘drawing speed’ (0.25) and ‘hesitation’ (0.21). Tapping properties, that is ‘tapping speed’, ‘accuracy’, ‘fatigue’ and ‘arrhythmia’ had satisfactory internal consistency with a Cronbach’s α coefficient of 0.77. In general, the trends of mean scores of tapping properties worsened with increasing levels of GTS. The mean scores of the four properties were significantly different to each other, only at different levels. In contrast from tapping properties, kinematic properties of spirals, that is ‘drawing speed’, ‘irregularity’ and ‘hesitation’ had a questionable consistency among them with a coefficient of 0.66. Bradykinetic spirals were associated with more impaired speed (mean = 83.7 % worse, P < 0.001) and hesitation (mean = 77.8% worse, P < 0.001), compared to dyskinetic spirals. Both these ‘cause’ categories had similar mean scores of ‘impairment’ and ‘irregularity’. Conclusions In contrast from current approaches used in clinical setting for the assessment of PD symptoms, this system enables clinicians to animate easily and realistically the ULMP of patients who at the same time are at their homes. Dynamic access of visualized motor tests may also be useful when observing and evaluating therapy-related complications such as under- and over-medications. In future, we foresee to utilize these manual ratings for developing and validating computer methods for automating the process of assessing ULMP of PD patients.

Predictive models for chronic renal disease using decision trees, naïve bayes and case-based methods

Data mining can be used in healthcare industry to “mine” clinical data to discover hidden information for intelligent and affective decision making. Discovery of hidden patterns and relationships often goes intact, yet advanced data mining techniques can be helpful as remedy to this scenario. This thesis mainly deals with Intelligent Prediction of Chronic Renal Disease (IPCRD). Data covers blood, urine test, and external symptoms applied to predict chronic renal disease. Data from the database is initially transformed to Weka (3.6) and Chi-Square method is used for features section. After normalizing data, three classifiers were applied and efficiency of output is evaluated. Mainly, three classifiers are analyzed: Decision Tree, Naïve Bayes, K-Nearest Neighbour algorithm. Results show that each technique has its unique strength in realizing the objectives of the defined mining goals. Efficiency of Decision Tree and KNN was almost same but Naïve Bayes proved a comparative edge over others. Further sensitivity and specificity tests are used as statistical measures to examine the performance of a binary classification. Sensitivity (also called recall rate in some fields) measures the proportion of actual positives which are correctly identified while Specificity measures the proportion of negatives which are correctly identified. CRISP-DM methodology is applied to build the mining models. It consists of six major phases: business understanding, data understanding, data preparation, modeling, evaluation, and deployment.

Mapeamento e caracterização geomecânica das unidades geotécnicas de solos oriundos dos granitos, gnaisses e migmatitos de Porto Alegre

O trabalho consta do estudo do meio físico geotécnico do município de Porto Alegre visando a identificação e caracterização de unidades geotécnias, formadas por associações de solos com características físico-morfológicas e origem semelhantes. As unidades geotécnicas são definidas por um estudo de escritório baseado em levantamentos geológicos, pedológicos, topográficos e geográficos e também com o auxílio de fotografias aéreas, acompanhado de uma investigação de campo com a amostragem de perfis das diferentes unidades estimadas. Uma carta com a ocorrência das unidades geotécnicas e com a representação das estruturas geológicas de maior importância geotécina é construída. Destaque é dado ás unidades geotécnicas de solos subtropicais oriundos dos granitos, gnaisses e migmatitos. E executada uma avaliação das características físicas (mineralogia, granulometria, plasticidade, e índices físicos) e propriedades geotécnicas (compressibilidade, colapsividade e resistência ao cisalhamento) dos solos dos principais horizontes de perfis típicos destas unidades. São utilizados ensaios de caracterização, análises mineralógicas de rochas por lâminas delgadas, análises mineralógicas de argilas por meio de difratograma de raio X, ensaios de compressão confinada e ensaios de cisalhamento direto. Os resultados são apresentados em função dos principais horizontes de solos das unidades geotécnicas , são eles horizontes saprolíticos, formados por solo residual que ainda apresentam minerais primários e vestígios estruturais da rocha de origem e horizontes superficiais muitas das vezes laterizados. A análise foi feita à luz dos processos de formação e dos decorrentes fatores que determinam o comportamento geotécnico destes solos de intemperismo subtropical.

Análise numérica e experimental do comportamento de fundações superficiais assentes em solo melhorado

O presente trabalho tem como objetivo estudar o comportamento de camadas superficiais de solo melhorado como base de fundações superficiais. Nesta pesquisa foram realizados ensaios de placa de 30 cm de diâmetro sobre camadas de solo residual compactado e de solo tratado com cimento (teor de 5% de cimento), ambas com 60 cm de espessura. O programa experimental também incluiu a retirada de amostras de campo das camadas de solo melhorado para a execução de ensaios triaxiais drenados (CID) com medida interna de deformações, a fim de obter parâmetros constitutivos para a realização de simulações numéricas. Uma comparação entre os resultados dos ensaios triaxiais com amostras retiradas em campo e moldadas em laboratório (Rohlfes Junior, 1996) é apresentada. A diferença entre os resultados dos ensaios triaxiais com amostras de campo e laboratório foi significativa para o caso das amostras de solo melhorado com cimento, tal fato é atribuído principalmente a dificuldade de mistura em campo. O Método dos Elementos Finitos foi utilizado para simular o comportamento carga x recalque das placas assentes sobre camadas de solo melhorado. O modelo Pseudo-Elástico Não Linear (Hiperbólico) foi empregado na análise numérica para modelar o comportamento dos novos materiais. Os resultados dos ensaios de placa sobre camadas de solo melhorado demonstraram que houve um aumento significativo da capacidade de suporte, além de uma redução considerável dos recalques, quando comparados ao comportamento carga x recalque do solo natural (Cudmani, 1994). A analise do comportamento de fundações superficiais assentes em solos estratificados, através de simulações numéricas, demonstrou ser eficiente para a previsão do comportamento carga x recalque das mesmas.

Efeitos da variação da carga por eixo, pressão de inflação e tipo de pneu na resposta elástica de um pavimento

O presente trabalho é uma análise experimental que procura investigar os efeitos dos fatores carga por eixo, pressão de inflação e tipo de pneu sobre o desempenho de pavimentos. Os dados e informações existentes sobre o quadro de cargas por eixo praticada pela frota de veículos pesados é razoável. A ação conjunta dos referidos fatores é ainda uma questão pouco explorada. Assim, para compensar a escassez de dados sobre pressão de inflação e tipo de construção de pneus utilizados na frota de carga, programou-se uma pesquisa de campo na rodovia estadual RS/240. As informações oriundas da pesquisa demonstram que há um acréscimo generalizado no valor da pressão dos pneus e um aumento de uso dos pneus de fabricação radial em relação aos pneus convencionais. Os dados de campo subsidiaram a programação de um experimento fatorial cruzado executado na Área de Pesquisas e Testes de Pavimentos da UFRGS/DAER. A variação dos níveis dos fatores deu-se através de um simulador linear de tráfego atuando sobre uma pista experimental com 20 m de comprimento por 3,5 m de largura. Tendo como resposta estrutural do pavimento a máxima deflexão superficial recuperável medida com uma viga Benkelmam, determinou-se como significantes os efeitos dos fatores carga por eixo e pressão de enchimento dos pneus. Os cálculos estatísticos indicam também que não há diferenças significativas entre os pneus tipo 9.00R20 e 9.00x20 e que todas interações não exercem efeitos significativos sobre a variável de resposta. Em seqüência, determinaram-se as áreas de contato do rodado duplo do simulador de tráfego com a superfície do pavimento ensaiado para as combinações dos níveis dos fatores. Pode-se, então, comparar área de contato medida com área circular calculada, considerada em muitos modelos de dimensionamento de pavimentos. Relacionou-se a variação da pressão de contato com a deflexão recuperável e procedeu-se uma comparação da mesma com a pressão de inflação nominal dos pneus. Apresenta-se um modelo de análise do desempenho do pavimento em função da carga por eixo e da pressão de inflação, nos limites do experimento. Os dados decorrentes do experimento viabilizaram a determinação dos Fatores de Equivalência de Cargas para os níveis dos fatores, considerando-se o pavimento ensaiado. Avaliou-se, via evolução das deflexões e dos Fatores de Equivalência de Cargas, a redução da vida do pavimento, obtendo-se, para a combinação de níveis mais críticos de carregamento, resultados significativos de até 88 % de redução. Propõe-se, por último, uma formulação para o Fator de Equivalência de Cargas que considere também a ação da pressão de inflação.

Estudo do comportamento de um solo residual melhorado atraves de tecnicas mecanicas e fisico-quimicas e sua aplicacao a analise de fundacoes superficiais

O presente trabalho tem como objetivo estudar o comportamento de um solo residual melhorado através do uso de técnicas mecânicas de compactação e da adição de cimento. Complementarmente foram realizadas análises numéricas destes materiais tratados quando utilizados como base de fundações superficiais. O programa experimental incluiu a retirada de amostras intactas e de material amolgado para a execução de ensaios triaxiais saturados drenados com medida interna de deformações, a fim de estudar o comportamento do solo natural e do solo tratado, quer por compactação, quer por adição de cimento e compactação. Além disto, tais ensaios são determinantes na obtenção de parâmetros constitutivos para a realização de simulações numéricas. O Método dos Elementos Finitos foi utilizado para simular o comportamento carga versus recalque de placas assentes sobre o solo natural e sobre camadas de solo melhorado. O modelo Hiperbólico foi empregado na análise numérica para modelar o comportamento tensãodeformação dos materiais. Os resultados das simulações dos ensaios de placa sobre camadas de solo melhorado demonstraram que houve um aumento significativo da capacidade de suporte, além de uma redução considerável dos recalques, quando comparados ao comportamento do solo natural.

Estudo geotécnico sobre a erodibilidade de solos residuais não saturados

A erodibilidade, particularizada como a susceptibilidade a erosão hídrica por fluxo superficial concentrado, é uma das propriedades de comportamento dos solos de maior complexidade pelo grande número de variáveis intervenientes. Estudada por diferentes áreas do conhecimento (Agronomia, Hidráulica, Geologia de Engenharia e Engenharia Geotécnica), tem no meio geotécnico a maior lacuna na sua quantificação e entendimento dos mecanismos envolvidos. O presente trabalho apresenta um estudo sobre a erodibilidade de solos residuais tropicais e subtropicais não saturados a partir de quatro perfis representativos dos processos erosivos e solos envolvidos na Região Metropolitana de Porto Alegre. Os solos dos principais horizontes de cada um destes perfis foram caracterizados física, química e mineralogicamente. As propriedades de resistência ao cisalhamento e colapsibilidade foram avaliadas por ensaios de cisalhamento direto convencionais e com controle de sucção e por ensaios de colapsibilidade em oedômetros, respectivamente. A erodibilidade foi avaliada em laboratório, diretamente por meio de ensaios de Inderbitzen e indiretamente por diferentes critérios e parâmetros baseados em outras características físicas e propriedades dos solos. A análise conjunta do comportamento dos solos em campo frente a erosão, da avaliação direta e indireta da erodibilidade e das propriedades geomecânicas investigadas conduziram à formulação de uma proposta de abordagem geotécnica para a erodibilidade dos solos residuais tropicais e subtropicais não saturados. Nesta proposta destaca–se a avaliação direta da erodibilidade por ensaios de Inderbitzen e a indicação de solos potencialmente erodíveis baseada no teor de finos, na plasticidade, no parâmetro K da USLE, na Razão de Dispersão de Middleton, na classificação e critério de erodibilidade MCT e na variação da coesão com a saturação pelo parâmetro variação de coesão (Δc) proposto. A proposta de abordagem geotécnica para a previsão da erodibilidade dos solos visa dotar o engenheiro geotécnico de uma ferramenta destinada à avaliação do potencial erosivo dos terrenos antes de uma iniciativa de ocupação urbana ou implantação de qualquer outra obra de engenharia. Esta avaliação é o passo inicial no direcionamento de medidas preventivas e que visem minimizar o impacto da obra ao meio físico natural, no que se refere a erosão hídrica por fluxo superficial concentrado.

Purchasing power parity and the unit root tests: a robust analysis

Empirical evidence suggests that real exchange rate is characterized by the presence of near-unity and additive outliers. Recent studeis have found evidence on favor PPP reversion by using the quasi-differencing (Elliott et al., 1996) unit root tests (ERS), which is more efficient against local alternatives but is still based on least squares estimation. Unit root tests basead on least saquares method usually tend to bias inference towards stationarity when additive out liers are present. In this paper, we incorporate quasi-differencing into M-estimation to construct a unit root test that is robust not only against near-unity root but also against nonGaussian behavior provoked by assitive outliers. We re-visit the PPP hypothesis and found less evidemce in favor PPP reversion when non-Gaussian behavior in real exchange rates is taken into account.

Testing unit root based on partially adaptive estimation

This paper proposes unit tests based on partially adaptive estimation. The proposed tests provide an intermediate class of inference procedures that are more efficient than the traditional OLS-based methods and simpler than unit root tests based on fully adptive estimation using nonparametric methods. The limiting distribution of the proposed test is a combination of standard normal and the traditional Dickey-Fuller (DF) distribution, including the traditional ADF test as a special case when using Gaussian density. Taking into a account the well documented characteristic of heavy-tail behavior in economic and financial data, we consider unit root tests coupled with a class of partially adaptive M-estimators based on the student-t distributions, wich includes te normal distribution as a limiting case. Monte Carlo Experiments indicate that, in the presence of heavy tail distributions or innovations that are contaminated by outliers, the proposed test is more powerful than the traditional ADF test. We apply the proposed test to several macroeconomic time series that have heavy-tailed distributions. The unit root hypothesis is rejected in U.S. real GNP, supporting the literature of transitory shocks in output. However, evidence against unit roots is not found in real exchange rate and nominal interest rate even haevy-tail is taken into a account.

Novel catalyst systems based on Ni(II), Ti(IV), and Cr(III) complexes for oligo-and polymerization of ethylene

The complex of Brookhart Ni(α-diimine)Cl2 (1) (α-diimine = 1,4-bis(2,6- diisopropylphenyl)-acenaphthenediimine) has been characterized after impregnation on silica (S1) and MAO-modified silicas (4.0, 8.0 and 23.0 wts.% Al/SiO2 called S2, S3 and S4, respectively). The treatment of these heterogeneous systems with MAO produces some active catalysts for the polymerization of the ethylene. A high catalytic activity has been gotten while using the system supported 1/S3 (196 kg of PE/mol[Ni].h.atm; toluene, Al/Ni = 1000, 30ºC, 60 min and atmospheric pressure of ethylene). The effects of polymerization conditions have been tested with the catalyst supported in S2 and the best catalytic activity has been gotten with solvent hexane, MAO as cocatalyst, molar ratio Al/Ni of 1000 and to the temperature of 30°C (285 kg of PE/mol[Ni].h.atm). When the reaction has been driven according to the in situ methodology, the activity practically doubled and polymers showed some similar properties. Polymers products by the supported catalysts showed the absence of melting fusion, results similar to those gotten with the homogeneous systems by DSC analysis. But then, polymers gotten with the transplanted system present according to the GPC’s curves the polydispersity (MwD) varies between 1.7 and 7.0. A polyethylene blend (BPE/LPE) was prepared using the complex Ni(α-diimine)Cl2 (1) (α-diimine = 1,4-bis(2,6-diisopropylphenyl)-acenaphthenediimine) and {TpMs*}TiCl3 (2) (TpMs* = hydridobis(3-mesitylpyrazol-1-yl)(5-mesitylpyrazol-1-yl)) supported in situ on MAO-modified silica (4.0 wts. -% Al/SiO2, S2). Reactions of polymerization of ethylene have been executed in the toluene in two different temperatures (0 and 30°C), varying the molars fraction of nickel (xNi), and using MAO as external cocatalyst. To all temperatures, the activities show a linear variation tendency with xNi and indicate the absence of the effect synergic between the species of nickel and the titanium. The maximum of activity have been found at 0°C. The melting temperature for the blends of polyethylene produced at 0 °C decrease whereas xNi increases indicating a good compatibility between phases of the polyethylene gotten with the two catalysts. The melting temperature for the blends of polyethylene showed be depend on the order according to which catalysts have been supported on the MAO-modified silica. The initial immobilization of 1 on the support (2/1/S2) product of polymers with a melting temperature (Tm) lower to the one of the polymer gotten when the titanium has been supported inicially (1/2/S2). The observation of polyethylenes gotten with the two systems (2/1/S2 and 1/2/S2) by scanning electron microscopy (SEM) showed the spherical polymer formation showing that the spherical morphology of the support to been reproduced. Are described the synthesis, the characterization and the catalytic properties for the oligomerization of the ethylene of four organometallics compounds of CrIII with ligands ([bis[2-(3,5-dimethyl-1-pyrazolyl)ethyl]amine] chromium (III) chloride (3a), [bis[2-(3,5- dimethyl-l-pyrazolyl)ethyl]benzylamine] chromium (III) chloride (3b), [bis[2-(3,5-dimethyl-lpyrazolyl) ethyl]ether] chromiun(III)chloride (3c), [bis[2-(3-phenyl-lpyrazolyl) ethyl]ether]chromiun(III)chloride (3d)). In relation of the oligomerization, at exception made of the compounds 3a, all complex of the chromium showed be active after activation with MAO and the TOF gotten have one effect differentiated to those formed with CrCl3(thf)3. The coordination of a tridentate ligand on the metallic center doesn't provoke any considerable changes on the formation of the C4 and C6, but the amount of C8 are decrease and the C10 and C12+ have increased. The Polymers produced by the catalyst 3a to 3 and 20 bar of ethylene have, according to analyses by DSC, the temperatures of fusion of 133,8 and 136ºC respectively. It indicates that in the two cases the production of high density polyethylene. The molar mass, gotten by GPC, is 46647 g/mols with MwD = 2,4 (3 bar). The system 3c/MAO showed values of TOF, activity and selectivity to different α-olefins according to the pressure of ethylene uses. Himself that shown a big sensibility to the concentration of ethylene solubilized.