Estimação em modelos de tempo de falha acelerado para dados de sobrevivência correlacionados

We presented in this work two methods of estimation for accelerated failure time models with random e_ects to process grouped survival data. The _rst method, which is implemented in software SAS, by NLMIXED procedure, uses an adapted Gauss-Hermite quadrature to determine marginalized likelihood. The second method, implemented in the free software R, is based on the method of penalized likelihood to estimate the parameters of the model. In the _rst case we describe the main theoretical aspects and, in the second, we briey presented the approach adopted with a simulation study to investigate the performance of the method. We realized implement the models using actual data on the time of operation of oil wells from the Potiguar Basin (RN / CE).

Análise de resíduos em modelos de tempo de falha acelerado com efeito aleatório

We present residual analysis techniques to assess the fit of correlated survival data by Accelerated Failure Time Models (AFTM) with random effects. We propose an imputation procedure for censored observations and consider three types of residuals to evaluate different model characteristics. We illustrate the proposal with the analysis of AFTM with random effects to a real data set involving times between failures of oil well equipment

Produtividade fabril III - método para rápido aumento da produtividade fabril: redução de tempos inativos e do tempo de espera do material em processo

O método para rápido aumento da produtividade fabril, aplicável principalmente à indústria brasileira de manufatura (17% do PIB), fundamenta-se exclusivamente na redução ou eliminação do tempo inativo do homem, da máquina e do material, que é a grande causa da ineficiência. O método exige a utilização de apenas cinco das mais simples, elementares e conhecidas técnicas e é aplicável às vinte situações mais freqüentes (objetos de estudo) na indústria de manufatura. Nossa experiência atesta que o método pode proporcionar à produtividade fabril um aumento superior a 30%, em poucos meses e de forma perene. Sua aplicação e a implantação das medidas dele decorrentes são feitas com extrema facilidade e, por isto, os resultados surgem muito rapidamente. Atinge portanto seu objetivo: proporcionar aumento da produtividade fabril em curto espaço de tempo. Este artigo (terceiro e último da série) detalhará doze objetos de estudo (situações): 1. redução dos tempos inativos causados por troca de turno, por refeição e por troca de produtos; 2. redução dos tempos improdutivos acarretados por causas mais importantes, por espera pelo serviço de manutenção, por espera pelo serviço de preparação, por espera pelo operador e por causas não apontáveis pelos procedimentos usuais; 3. redução das atividades improdutivas e das produtivas executadas num ritmo improdutivo; e 4. redução do tempo de espera do material em processamento pela redução do tamanho do lote de fabricação e pelo aumento da velocidade de manufatura.

Avaliação do programa de tutorização da EMATER-RN para servidores em estágio probatório

The present thesis evaluated the contributions and limitations of the tutorship program introduced in EMATER-RN, as a tactic of organizational socialization for civil servants in probationary stage. Tutorship was understood as an intensive and continuous relational process, in which a more experienced person in the organization the tutor offers psychosocial support, stimulates the development of the professional career and enables to the newcomer the tutee learning on job performance. The organizational socialization was considered in the perspective of the symbolic interactionism. The study was characterized as a program evaluation and as an action research. The practical interventions for the program implementation were conducted and, at the same time, the evaluations of process, results and reaction to the program were applied. Among the major contributions of the action research, it stood out: the diagnosis of reasons for the formation of the pair and of expectations of tutors and tutees, the improvement of the tutorship registration tools, the ascertainment of the success of the program in the socialization of the new civil servants, the confirmation of the importance of the compatibility among them and of the adequate performance of tutorship functions for achieving its benefits. Based in constraints of the program, one may quote as essential recommendations: the formation of a technical team supporting the program, the clear establishment of deadlines for each procedure and the reinforcement to its compliance, the investigation of the functions performed by the tutor, the sensitization of the managers to the resolution of problems that affect the program, the voluntary participation of the tutor and the continuous meetings of tutors and tutees. One settles for the relevance of the program and in favor of its continuation, provided that its improvement and systematic management are conducted.

Identidade, espaço e tempo: negociações de sentido sobre a "gente de rua"

This research examines the street children s identity construction processes. Recently, the research about this population has focused on the socialization processes that organize their everyday, their situations of interaction, the meanings of their social practices, their street experience. The concept of identitary forms gives coherence to the set of these phenomena, articulating them theoretically, in order to describe their life conditions and details of their trajectories. This research utilized an ethnographic approach with a group of 11 street people, 9 of them boys and girls 16-18 years old, during 3 months. It included participant observation, informal and formal interviews, that resulted in young s narratives of lifestory. These narratives were interpreted according to the principles of positioning analysis and the Labovian Analysis model of oral narratives of personal experience. The observation of interaction among the studied group and other groups has showed that their social practices, supported on many particular bodily technologies, recreate space and time of these interactions semantically, as mediation of meaning negotiations among groups. Such meanings transform again the environment of these interactions, disclosing interpretative systems by means of which the groups apprehend this interaction in a particular way. These street children s bodily technologies imply identitary forms based on scarcity and abandonment, paradoxicalally related to their self-concept. The analysis of narratives revealed diversity and complexity in the meanings assembly for their street experience; it showed that the semantic arrangements reconstruct the temporal experience, creating a moral climate for each lifestory, and determining more or less aperture of identitary forms to change. The study concludes that space and time, builders of interaction regimes, produce identitary forms; that the narratives and the social practices of the studied group are sustained upon a master discourse that opposes the meanings of the home and the life in the streets

Desenvolvimento de um biossensor potenciométrico, à base de soja, para a determinação de uréia

In this work, the objective in study was the development of a biossensor potencyometric for urea detection, starting from the extracted urease of soy grains. Initially, was made a chemometrics study, through a planning factorial 24, objectified to find great conditions for the extraction of the urease without its properties were affected. Starting from this study, the best conditions were determined for the obtaining of rich extracts in urease, allowing the biossensors making with good characteristics. These were made using a platinum electrode as transducer with the dispersed urease in chitosan head office and reticulated in glutaraldehyde vapor. The biossensors obtained presented a limit of urea detection the same to 0,33 mM and lineal strip between 0,33 and 3 mM of the substratum. The time of answer was considered loud, mainly, in low concentrations of the substratum, where it was taken about 5 minutes by analysis. For high concentrations that time was reduced for not more than one minute. The time of life was limited by the adherence of the enzymatic membrane to the transducer, but it was possible to maintain the biossensor with operation for one month with about 50 accomplished measures. Application of the biossensor for analyses of fertilizers to the urea base presented excellent result for a sample with few interfering, but it was different when the used fertilizer was originating from of a complex sample. Even so the label was not expressed the text of nitrogen it was totally coming of the urea. An evaluation of the kinetic parameters of the catalytic reaction of the biossensor showed coherence with the results exposed in the literature

Degradação catalítica de polietileno de alta densidade sobre a zeólita HZSM

In last years it has talked a lot about the environment and the plastic waste produced and discarded. In last decades, the increasing development of research to obtain fuel from plastic material, by catalytic degradation, it has become a very attractive looking, as these tailings are discarded to millions worldwide. These materials take a long time to degrade themselves by ways said natural and burning it has not demonstrated a viable alternative due to the toxic products produced during combustion. Such products could bring serious consequences to public health and environment. Therefore, the technique of chemical recycling is presented as a suitable alternative, especially since could be obtain fractions of liquid fuels that can be intended to the petrochemical industry. This work aims to propose alternatives to the use of plastic waste in the production of light petrochemical. Zeolites has been widely used in the study of this process due to its peculiar structural properties and its high acidity. In this work was studied the reaction of catalytic degradation of high-density polyethylene (HDPE) in the presence HZSM-12 zeolites with different acid sites concentrations by thermogravimetry and pyrolysis coupled with GC-MS. The samples of the catalysts were mixed with HDPE in the proportion of 50% in mass and submitted to thermogravimetric analyses in several heating rates. The addition of solids with different acid sites concentrations to HDPE, produced a decrease in the temperature of degradation of the polymer proportional the acidity of the catalyst. These qualitative results were complemented by the data of activation energy obtained through the non-isothermal kinetics model proposed by Vyazovkin. The values of Ea when correlated to the data of surface acidity of the catalysts indicated that there is a exponential decrease of the energy of activation in the reaction of catalytic degradation of HDPE, in function of the concentration of acid sites of the materials. These results indicate that the acidity of the catalyst added to the system is one of the most important properties in the reaction of catalytic degradation of polyethylene

Hidrólise e caracterização de poliacrilamida hidrofobicamente modificada: avaliação da aplicabilidade na recuperação de petróleo

The hydrolysis reaction in alkaline conditions of the commercial polymer poly(acrylamide-co-metacrylate of 3,5,5-trimethyl-hexane) called HAPAM, containing 0.75 % of hydrophobic groups, was carried out in 0.1 M NaCl and 0.25M NaOH solutions, varying the temperature and reaction time. The polymers were characterized by 1H and 13C Nuclear Magnetic Resonance (NMR), Elemental Analysis and Size Exclusion Chromatography (SEC). The values of the hydrolysis degree were obtained by 13C NMR. The viscosity of HAPAM and HAPAM-10N-R solutions was evaluated as a function of shear rate, ionic strength and temperature. At high polymer concentration (Cp), the viscosity of HAPAM solutions increased with the ionic strength and decreased with the temperature. The viscosity of HAPAM-10N-R solutions increased significantly in distilled water, due to repulsions between the carboxylate groups. At high Cp, with the increase of ionic strength and temperature, occurred a decrease of viscosity, due to mainly the high hydrolysis degree and the low amount of hydrophobic groups. These results indicated that the studied polymers have properties more suitable for the application in Enhanced Oil Recovery (EOR) in low salinity and moderate temperature reservoirs

Obtenção de biodiesel através da transesterificação do óleo de farelo de arroz utilizando KI/Al2O3

This study proposes to find a biodiesel through transesterification of rice bran oil with KI/Al2O3 checking the influence of two types of alumina (Amorphous and Crystalline) for conversion into methyl esters. The catalyst was synthesized by the wet impregnation method. Adding 30 mL of 35% KI(aq.) in 10 g of alumina, under stirring at 80 °C for 3 hours. The reaction conditions used in this study were optimized, with a molar ratio methanol:oil of 15:1, 8 h of reaction time and reflux temperature. The catalyst amount was varied in the range of 1 to 5 % wt. The solid catalysts materials were analyzed by: x-ray diffraction (XRD), thermogravimetry (TG), N2 adsorption/desorption, scanning electron microscopy (SEM) and basicity, for the identification of its structure and composition, verifying the presence of basic sites. The results showed that Al2O3(A) presents an amorphous structure, high surface area and a better catalytic activity, in relation to the catalyst synthesized with Al2O3(C) support that proved to have a more crystalline structure, having as well, a lesser surface area, enabling difficulties for the incorporation of active sites. The obtained biodiesel with 5% wt. KI/Al2O3(A) presented physicochemical properties within the standards specified by the Resolution No 7/2008 ANP and obtained the best reaction yield with 95.2%, according to quantitative measurement from the TG, which showed 96.2% conversion into methyl esters. It was furthermore found that with the increasing amount of the quantity of the catalyst in the reaction, there was also an increase in the ester content obtained. The specific mass and the kinematic viscosity were reduced with the increase of the amount of quantity of the catalyst, indicating an increase in the conversion of triglycerides

Síntese e caracterização de carreadores de oxigênio para combustão com recirculação química obtidos via reação de combustão assistida por microondas

Perovskites oxides win importance by its properties and commercials applications, they have a high thermal stability, have conductive properties, electrical, catalytic, electro catalytic, optical and magnetic, and are thermally stable. Because of these properties, are being widely studied as carriers of oxygen in the process of power generation with CO2 capture. In this work, the base carrier system La1-xMexNiO3 (Me = Ca and Sr) were synthesized by the method via the combustion reaction assisted by microwave. were synthesized from the combustion reaction method by microwave process. This method control the synthesi`s conditions to obtain materials with specific characteristics. The carriers calcined at 800 ° C/2h were analyzed by thermal analysis (TG-DTA), to verify its thermal stability, X-ray diffraction (XRD) to verify the phase formation, with subsequent refinement by the Rietveld method, to quantify the percentage of phases formed, the surface area by BET method was determined, scanning electron microscopy (SEM) was obtained to evaluate the material morphology and temperature programmed reduction (TPR) was done to observe the metallic phase of the nickel. After all proposed characterization and analysis of their results can be inferred to these oxides, key features so that they can be applied as carriers for combustion reactions in chemical cycles. The final products showed perovskite-type structures K2NiF4 (main) and ABO3.

Patogenicidade cruzada de Ceratobasidium spp. do caquizeiro (Diospyros kaki) e do chá(Camellia sinensis) e reação de cultivares de caqui ao patógeno

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Avaliação oxidativa do biodiesel de pinhão manso em diferentes processos de purificação

The objective of this study was to analyze the oxidative stability of biodiesel from jatropha obtained from different purification processes, three wet processes with different drying (in a vacuum oven, conventional oven and in anhydrous sodium sulfate) and dry (purification with magnesium silicate adsorbent). Raw materials of different qualities (jatropha crop ancient and recent crop) were used. The Jatropha oil was extracted by mechanical extraction and refined. The Jatropha biodiesel was obtained by the transesterification reaction in ethyl route using alkaline catalysis. The biodiesel samples were characterized by analysis of water content, carbon residue, Absorption Spectroscopy in the Infrared Region and Thermogravimetry. Thermogravimetric curves of purified PUsv* PUsq* and had higher initial decomposition temperatures, indicating that the most stable, followed by samples PU* and PUSC*. Besides the sample SP* is a smaller initial temperature, confirming the sample without purification to be less thermally stable. The percentage mass loss of the purified samples showed conversion of about 98.5%. The results of analyzes carbon residue and infrared suggested that contamination by impurities is the main factor for decreased oxidative stability of biodiesel. The oxidative stability was assessed from periodic monitoring, using the techniques of Rancimat, peroxide index, acid value and Pressurized Differential Scanning Calorimetry. Samples of biodiesel from jatropha which showed better oxidative stability were of the best quality raw material and wet scrubbing: PUsq* with dry chemical, using anhydrous sodium sulfate and PUsv* with vacuum drying, which had oxidative stability 6 hours in Rancimat time 0 days, within the limits established by the Technical Regulation No. 4/2012 of the ANP, without the addition of antioxidant, suggesting that these procedures the least influence on the oxidative stability of biodiesel

Estudo do desempenho de catalisadores tipo Ni/CexM1-xO2 (M = Zr ou Mn) na reação de oxidação parcial do metano

One of the main applications of methane is in the production of syngas, a mixture of hydrogen and carbon monoxide. Procedures used in this process are steam reforming, CO2 reforming, partial oxidation and autothermal reforming. The present study evaluated and compared the behavior of nickel catalysts supported on mixed oxides of cerium and manganese in the partial oxidation of methane with that of nickel catalysts supported on mixed oxides of cerium and zirconium. Mixed oxides of cerium and zirconium or cerium and manganese were synthesized using two different preparation methods, the polymeric precursor based on Pechini method and combustion reaction using a microwave. This was followed by impregnation with nickel content of 15 %. Samples were calcined at 300, 800 and 900 °C and characterized by specific surface area (SSA), X-ray fluorescence (XRF), X-ray diffraction (XRD), scanning electron microscopy (SEM), temperature programmed reduction (TPR) and the reaction of partial oxidation of methane. The specific areas of samples decrease with the rise in calcination temperature and after nickel impregnation. Metal-cerium solid solution was formed and the presence of other manganese species outside the solid solution structure was confirmed in the compound with the highest amounts of manganese oxides showed. With regard to scanning electron microscopy, supports based on cerium and zirconium prepared by Pechini method exhibited agglomerated particles without uniform geometry or visible pores on the surface. However, compounds containing manganese presented empty spaces in its structure. Through synthesis by combustion reaction, morphology acquired independently of the proposed composition demonstrated greater porosity in relation to Pechini synthesis. Although catalysts were prepared using different synthesis methods, the insertion of nickel showed very similar reduction profiles (TPR). In relation to nickel catalysts supported on mixed oxide of cerium and zirconium, there is an initial reduction of NiO species that present certain interaction with the support. This is followed by the reduction of Ce4+ in Ce3+ surface, with subsequent bulk reduction. For catalysts containing manganese, a reduction of nickel oxide species occurs, followed by two stages of reduction for species Mn2O3 in Mn3O4 and Mn3O4 in MnO, with subsequent reduction of bulk. With respect to partial oxidation reactions, the nickel catalyst supported on mixed oxide of cerium and zirconium, prepared using the Pechini method, exhibited CH4 conversion of approximately 80 %, with conversion of 81 % when prepared by combustion. This behavior continued for 10 hours of reaction. Manganese content was also found to directly influence catalytic activity of materials; the greater the manganese oxide content, the faster deactivation and destabilization occurred in the catalyst. In both synthesis methods, the nickel catalyst supported on mixed oxide of cerium and zirconium maintained an H2/CO ratio very close to 2 during the 10 hours of partial oxidation reaction. Samples containing manganese displayed smaller H2/CO ratios and lower performance in partial oxidation.

Reforma a vapor catalítica do metano: Otimização da produção e seletividade em hidrogênio por absorção in situ do CO2 produzido

Topics of research related to energy and environment have significantly grown in recent years, with the need of its own energy as hydrogen. More particularly, numerous researches have been focused on hydrogen as energy vector. The main portion of hydrogen is presently obtained by reforming of methane or light hydrocarbons (steam, oxy, dry or auto reforming). During the methane steam reforming process the formation of CO2 undesirable (the main contributor to the greenhouse effect) is observed. Thus, an oxide material (sorbent) can be used to capture the CO2 generated during the process and simultaneously shifting the equilibrium of water gas shift towards thermodynamically more favorable production of pure hydrogen. The aim of this study is to develop a material with dual function (catalyst/sorbent) in the reaction of steam reforming of methane. CaO is well known as CO2 sorbent due to its high efficiency in reactions of carbonation and easy regeneration through calcination. However the kinetic of carbonation decreases quickly with time and carbonation/calcination cycles. A calcium aluminate (Ca12Al14O33) should be used to avoid sintering and increase the stability of CaO sorbents for several cycles. Nickel, the industrial catalyst choice for steam reforming has been added to the support from different manners. These bi-functional materials (sorbent/catalyst) in different molar ratios CaO.Ca12Al14O33 (48:52, 65:35, 75:25, 90:10) were prepared by different synthesis methodologies, among them, especially the method of microwave assisted self-combustion. Synthesis, structure and catalytic performances of Ni- CaO.Ca12Al14O33 synthesized by the novel method (microwave assisted selfcombustion) proposed in this work has not being reported yet in literature. The results indicate that CO2 capture time depends both on the CaO excess and on operating conditions (eg., temperature and H2O/CH4 ratio). To be efficient for CO2 sorption, temperature of steam reforming needs to be lower than 700 °C. An optimized percentage corresponding to 75% of CaO and a ratio H2O/CH4 = 1 provides the most promising results since a smaller amount of water avoids competition between water and CO2 to form carbonate and hydroxide. If this competition is most effective (H2O/CH4 = 3) and would have a smaller amount of CaO available for absorption possibly due to the formation of Ca(OH)2. Therefore, the capture time was higher (16h) for the ratio H2O/CH4 = 1 than H2O/CH4 = 3 (7h) using as catalyst one prepared by impregnating the support obtained by microwave assisted self-combustion. Therefore, it was demonstrated that, with these catalysts, the CO2 sorption on CaO modifies the balance of the water gas-shift reaction. Consequently, steam reforming of CH4 is optimized, producing pure H2, complete conversion of methane and negligible concentration of CO2 and CO during the time of capture even at low temperature (650 °C). This validates the concept of the sorption of CO2 together with methane steam reforming

Aplicabilidade da voltametria de pulso diferencial na quantificação de ácido fólico e ácido oxálico: um método comparativo

The development of more selective and sensitive analytical methods is of great importance in different areas of knowledge, covering, for example, food, biotechnological, environmental and pharmaceutical sectors. The study aimed to employ the technique electroanalytical differential pulse voltammetry (DPV) as an innovative and promising alternative for identification and quantification of organic compounds. The organic compounds were investigated in this study oxalic acid (OA) and folic acid (FA). The electrochemical oxidation of oxalic acid has been extensively studied as a model reaction in the boundary between the organic and inorganic electrochemistry. Since the AF, an essential vitamin for cell multiplication in all tissues, which is essential for DNA synthesis. The AF has been investigated using analytical techniques, liquid chromatography and molecular absorption spectrophotometry. The results obtained during the experimental procedure indicated that the process of electrochemical oxidation of oxalic acid is strongly dependent on the nature of the anode material and the oxidation mechanism, which affects their detection. Efficient removal was observed in Ti/PbO2 anodes, graphite, BDD and Pt 90, 85, 80 and 78% respectively. It was also shown that the DPV employing glassy carbon electrode offers a fast, simple, reliable and economical way to determine the AO during the process of electrochemical oxidation. Furthermore, electroanalytical methods are more expensive than commonly used chromatographic analysis and other instrumental methods involving toxic reagents and higher cost. Compared with the classical method of titration and DPV could be a good fit, confidence intervals and detection limits confirming the applicability of electroanalytical technique for monitoring the degradation of oxalic acid. For the study of AF was investigated the electrocatalytic activity of the carbon paste electrode for identification and quantification in pharmaceutical formulations by applying the DPV. The results obtained during the experimental procedure showed an irreversible oxidation peak at 9.1 V characteristic of FA. The carbon paste sensor showed low detection limit of 5.683×10−8 mol L-1 reducing matrix effects. The spectrophotometric analysis showed lower concentrations of HF compared with those obtained by HPLC and DPV. The levels of AF were obtained according to the methodology proposed by the Brazilian Pharmacopoeia. The electroanalytical method (DPV) proposed is cheaper than GC analysis commonly used by the pharmaceutical industry. The results demonstrated the potential of these electroanalytical techniques for future applications in environmental, chemical and biological sensors