Otimização de estruturas de destilação azeotrópica com recurso a planeamento experimental

Trabalho Final de Mestrado para obtenção do grau de Mestre em Engenharia Química e Biológica

Optimization process of polyester polymer mortars modified with recycled GFRP waste aggregates – application of factorial experiment design-

Glass fibre-reinforced plastics (GFRP), nowadays commonly used in the construction, transportation and automobile sectors, have been considered inherently difficult to recycle due to both: cross-linked nature of thermoset resins, which cannot be remolded, and complex composition of the composite itself, which includes glass fibres, matrix and different types of inorganic fillers. Presently, most of the GFRP waste is landfilled leading to negative environmental impacts and supplementary added costs. With an increasing awareness of environmental matters and the subsequent desire to save resources, recycling would convert an expensive waste disposal into a profitable reusable material. There are several methods to recycle GFR thermostable materials: (a) incineration, with partial energy recovery due to the heat generated during organic part combustion; (b) thermal and/or chemical recycling, such as solvolysis, pyrolisis and similar thermal decomposition processes, with glass fibre recovering; and (c) mechanical recycling or size reduction, in which the material is subjected to a milling process in order to obtain a specific grain size that makes the material suitable as reinforcement in new formulations. This last method has important advantages over the previous ones: there is no atmospheric pollution by gas emission, a much simpler equipment is required as compared with ovens necessary for thermal recycling processes, and does not require the use of chemical solvents with subsequent environmental impacts. In this study the effect of incorporation of recycled GFRP waste materials, obtained by means of milling processes, on mechanical behavior of polyester polymer mortars was assessed. For this purpose, different contents of recycled GFRP waste materials, with distinct size gradings, were incorporated into polyester polymer mortars as sand aggregates and filler replacements. The effect of GFRP waste treatment with silane coupling agent was also assessed. Design of experiments and data treatment were accomplish by means of factorial design and analysis of variance ANOVA. The use of factorial experiment design, instead of the one factor at-a-time method is efficient at allowing the evaluation of the effects and possible interactions of the different material factors involved. Experimental results were promising toward the recyclability of GFRP waste materials as polymer mortar aggregates, without significant loss of mechanical properties with regard to non-modified polymer mortars.

The Influence of the Media on Shaping Perceptions of Leadership in Sport: A Within and Between Groups Design

An experimental design that included both between-group and within-group designs was used to assess media influence on perceptions of sport leadership. Participants were recruited and randomly assigned to three groups, where each group completed two separate survey sessions regarding leader personality traits and behaviours. During the second survey session, experimental Groups 1 and 2 watched a video on a separate, respective sport leader prior to filling out the survey. There were a total of 104 participants (N = 104) for the first session, and 99 (N = 99) participants completed the second session. One-way ANOVA, factorial repeated measures ANOVA, and ANCOVA were used for data analysis. Results indicate a significant change in Group 2’s results after watching the video clip, thus rejecting the null hypotheses. Results and implications are discussed, highlighting their relationships to sport and media related theories and sport management practice.

Design and Development of Compact Coplanar Waveguide Fed Antennas for Wireless Applications

The need of miniaturization in the present day communication industry is challenging. In the present scenario, printed antenna technology is highly suitable for wireless communication due to its low profile and other desirable radiation characteristics. Small monopole type antennas are overruled by compact small antennas for present day mobile communication applications. Coplanar waveguides (CPW) are printed on one side of a dielectric substrate. CPW have attracted the attention of antenna designers due to their excellent properties like ease of integration with ‘MMIC’, low cost, wide bandwidth, flexibility towards multiband operation, low radiation leakage and less dispersion. The requirement of omnidirectional coverage, light weight and low cost made these CPW fed antennas a good candidate for wireless applications. The main focus of the thesis is the study of coplanar waveguide transmission line. Rigorous investigations were performed on both the ground plane and signal strip of a coplanar waveguide transmission line to create effective radiation characteristics. Good amount of works have been done to transform CPW line to antenna suitable for mobile phone applications

Design and analysis of climate model experiments for the efficient estimation of anthropogenic signals

Presented herein is an experimental design that allows the effects of several radiative forcing factors on climate to be estimated as precisely as possible from a limited suite of atmosphere-only general circulation model (GCM) integrations. The forcings include the combined effect of observed changes in sea surface temperatures, sea ice extent, stratospheric (volcanic) aerosols, and solar output, plus the individual effects of several anthropogenic forcings. A single linear statistical model is used to estimate the forcing effects, each of which is represented by its global mean radiative forcing. The strong colinearity in time between the various anthropogenic forcings provides a technical problem that is overcome through the design of the experiment. This design uses every combination of anthropogenic forcing rather than having a few highly replicated ensembles, which is more commonly used in climate studies. Not only is this design highly efficient for a given number of integrations, but it also allows the estimation of (nonadditive) interactions between pairs of anthropogenic forcings. The simulated land surface air temperature changes since 1871 have been analyzed. The changes in natural and oceanic forcing, which itself contains some forcing from anthropogenic and natural influences, have the most influence. For the global mean, increasing greenhouse gases and the indirect aerosol effect had the largest anthropogenic effects. It was also found that an interaction between these two anthropogenic effects in the atmosphere-only GCM exists. This interaction is similar in magnitude to the individual effects of changing tropospheric and stratospheric ozone concentrations or to the direct (sulfate) aerosol effect. Various diagnostics are used to evaluate the fit of the statistical model. For the global mean, this shows that the land temperature response is proportional to the global mean radiative forcing, reinforcing the use of radiative forcing as a measure of climate change. The diagnostic tests also show that the linear model was suitable for analyses of land surface air temperature at each GCM grid point. Therefore, the linear model provides precise estimates of the space time signals for all forcing factors under consideration. For simulated 50-hPa temperatures, results show that tropospheric ozone increases have contributed to stratospheric cooling over the twentieth century almost as much as changes in well-mixed greenhouse gases.

The impact of maternal control on children’s anxious cognitions, behaviours and affect: an experimental study

Controlling parenting is associated with child anxiety however the direction of effects remains unclear. The present study implemented a Latin-square experimental design to assess the impact of parental control on children’s anxious affect, cognitions and behaviour. A non-clinical sample of 24 mothers of children aged 4-5 years were trained to engage in (a) controlling and (b) autonomy-granting behaviours in interaction with their child during the preparation of a speech. When mothers engaged in controlling parenting behaviours, children made more negative predictions about their performance prior to delivering their speech and reported feeling less happy about the task, and this was moderated by child trait anxiety. In addition, children with higher trait anxiety displayed a significant increase in observed child anxiety in the controlling condition. The pattern of results was maintained when differences in mothers’ levels of negativity and habitual levels of control were accounted for. These findings are consistent with theories that suggest that controlling parenting is a risk factor in the development of childhood anxiety.

Neurofuzzy design and model construction of nonlinear dynamical processes from data

A common problem in many data based modelling algorithms such as associative memory networks is the problem of the curse of dimensionality. In this paper, a new two-stage neurofuzzy system design and construction algorithm (NeuDeC) for nonlinear dynamical processes is introduced to effectively tackle this problem. A new simple preprocessing method is initially derived and applied to reduce the rule base, followed by a fine model detection process based on the reduced rule set by using forward orthogonal least squares model structure detection. In both stages, new A-optimality experimental design-based criteria we used. In the preprocessing stage, a lower bound of the A-optimality design criterion is derived and applied as a subset selection metric, but in the later stage, the A-optimality design criterion is incorporated into a new composite cost function that minimises model prediction error as well as penalises the model parameter variance. The utilisation of NeuDeC leads to unbiased model parameters with low parameter variance and the additional benefit of a parsimonious model structure. Numerical examples are included to demonstrate the effectiveness of this new modelling approach for high dimensional inputs.

An experimental manipulation of responsibility in children: a test of the inflated responsibility model of obsessive-compulsive disorder

The objective of this study was to investigate whether Salkovskis (1985) inflated responsibility model of obsessive-compulsive disorder (OCD) applied to children. In an experimental design, 81 children aged 9– 12 years were randomly allocated to three conditions: an inflated responsibility group, a moderate responsibility group, and a reduced responsibility group. In all groups children were asked to sort sweets according to whether or not they contained nuts. At baseline the groups did not differ on children’s self reported anxiety, depression, obsessive-compulsive symptoms or on inflated responsibility beliefs. The experimental manipulation successfully changed children’s perceptions of responsibility. During the sorting task time taken to complete the task, checking behaviours, hesitations, and anxiety were recorded. There was a significant effect of responsibility level on the behavioural variables of time taken, hesitations and check; as perceived responsibility increased children took longer to complete the task and checked and hesitated more often. There was no between-group difference in children’s self reported state anxiety. The results offer preliminary support for the link between inflated responsibility and increased checking behaviours in children and add to the small but growing literature suggesting that cognitive models of OCD may apply to children.

A review of cashmere nutrition experiments with suggestions for improving their design and conduct

The scientific literature contains divergent views about the effects of nutrition on cashmere. The consequences of ignoring nutrition will be an increase in the number of goats suffering lower production, increased welfare risks and premature mortality. This review evaluated published reports to identify current knowledge and best practice in regard to the design and management of cashmere nutrition experiments. The ability of experiments to distinguish between treatments was evaluated based on their statistical evidence. Many experiments had serious deficiencies in their design, conduct and reporting. Six of 16 papers did not provide statistical information that would enable a reader to verify differences between treatments. For most experiments to detect nutrition affects at P < 0.05, they required a difference between treatments of 0.2–0.8 μm in cashmere mean fibre diameter and 15–42 g in clean cashmere production. Government Research Institutes research was characterised by more experienced authors conducting longer (P < 0.05) and larger (P < 0.05) experiments than those conducted by Universities. Much of the “debate” regarding the affects of nutrition on cashmere production arises from the misinterpretation of both experiments that did not detect statistically significant effects and of experiments that did detect statistically significant effects. Based on a comparison between experiments reporting responses to nutrition with those reporting no response, 13 design and management features were identified that are related to the ability of experiments to detect significant treatment affects. Methods must be adopted to reduce the variance in cashmere production within treatments, by using sufficient animals per treatment, and having replication to provide sufficient degrees of freedom to reduce error terms in analysis. The power of experimental designs should be evaluated before experiments commence. Cashmere production records from a previous full production year could be used as co-variants during statistical analyses but this requires that potential experimental goats are managed in one flock, without variations resulting from different grazing, reproduction or other management for a year prior to an experiment. It is preferable to use more productive and older goats, and goats that are used to handling, and to the conditions and feed to be used. Allocation of animals to treatments must take into account live weight. Nutrition treatments need to be sufficiently different to produce different growth curves. An appropriate control is needed such as live weight maintenance. Evidence of both nutrition intake and growth curves must be published with cashmere production data so the claims made can be verified by the actual responses. As cashmere production is an order of magnitude less than fibre production of Merino sheep or Angora goats and is more difficult to measure, the requirements for measurement, sampling and testing cashmere fleeces are summarised. The use of mid side cashmere patches to determine cashmere growth and quality is seriously biased and must be avoided, preferably by shearing goats prior to and at the end of experiments. In order to obtain higher fleece growth responses and improve the ability of experiments to detect treatment effects it is preferable to start cashmere growth experiments by midsummer and conduct experiments for at least 4 months. These requirements make it difficult for many university students to plan, undertake and complete long-term cashmere nutrition experiments without considerable management support. It is not possible for experiments to disprove the Null hypothesis regarding the effects of nutrition on cashmere production as they can only report a failure to detect treatment effects. Researchers and journals need to be more rigorous in providing statistical information including: degrees of freedom for error terms, treatment variances, standard error of differences or similar to enable readers to compare treatment effects. Publications that do not provide sufficient statistical information should be disregarded from future discussions. Claims that an experiment shows no responses to nutrition should be subject to rigorous examination using the issues identified in this review.

Scaling up community-based obesity prevention in Australia : background and evaluation design of the health promoting communities : being active eating well initiative

Background : There is only limited evidence available on how best to prevent childhood obesity and community-based interventions hold promise, as several successful interventions have now been published. The Victorian Government has recently funded six disadvantaged communities across Victoria, Australia for three years to promote healthy eating and physical activity for children, families, and adults in a community-based participatory manner. Five of these intervention communities are situated in Primary Care Partnerships and are the subject of this paper. The interventions will comprise a mixture of capacity-building, environmental, and whole-of-community approaches with targeted and population-level interventions. The specific intervention activities will be determined locally within each community through stakeholder and community consultation. Implementation of the interventions will occur through funded positions in primary care and local government. This paper describes the design of the evaluation of the five primary care partnership-based initiatives in the 'Go for your life' Health Promoting Communities: Being Active Eating Well (HPC:BAEW) initiative.

Methods/Design : A mixed method and multi-level evaluation of the HPC:BAEW initiative will capture process, impact and outcome data and involve both local and state-wide evaluators. There will be a combined analysis across the five community intervention projects with outcomes compared to a comparison group using a cross-sectional, quasi-experimental design. The evaluation will capture process, weight status, socio-demographic, obesity-related behavioral and environmental data in intervention and comparison areas. This will be achieved using document analysis, paper-based questionnaires, interviews and direct measures of weight, height and waist circumference from participants (children, adolescents and adults).

Discussion : This study will add significant evidence on how to prevent obesity at a population level in disadvantaged and ethnically diverse communities. The outcomes will have direct influence on policy and practice and guide the development and implementation of future obesity prevention efforts in Australia and internationally.

Os efeitos das reclamações online na lealdade dos consumidores: um estudo experimental

In an environment of constant change, technological developments, market competition and more informed consumers, the search for a lasting relationship through the conquest of loyalty has become the objective of companies. However, several authors suggest that this loyalty can be affected by negative comments available on the internet. Therefore, this dissertation has as objective to examine if the complaints are available on the internet impact the loyalty to a brand of mobile phone. The research used as the basis the Expanded NCSB model suggest by Johnson et al. (2001), studying five prominent drives of loyalty: image/brand reputation, affective commitment, calculative commitment, perceived value and trust, beyond the satisfaction construct as moderator variable. The research method adopted was the experimental design which included 285 undergraduate students, with the trial which included 285 undergraduate students, with the field study of the mobile industry, specifically, the brands of cell phones. The research approach was quantitative and methods were descriptive statistics, factor analysis, cluster analysis, linear regression and non-parametric test of Wilcoxon for data analysis. Of the 16 hypothesis stemmed from the research model proposed, 12 were confirmed. The results showed that the complaint available on the internet, here represented by the available on the site Reclame Aqui, may impact consumer perceptions about brand loyalty, as well as its antecedents, being that these complaints can affect all the consumers, regardless of historical satisfaction with the brand. It also noted the positive relationship between the independent variables trust, image/brand reputation, perceived value, affective commitment and calculative commitment and the dependent variable - loyalty, even when considering the data obtained after exposure to the complaint. However, no unanimous conclusion that the relationship between these variables was strongest in the group with satisfactory experience. At the first moment of the research, the trust was the most important variable for the formation of loyalty. However, after exposure to treatment, the image/brand reputation, was more relevant. Contributions of the study, limitations and recommendations for future researches are approached in the present investigation

Encapsulation of Local Anesthetic Bupivacaine in Biodegradable Poly(DL-lactide-co-glycolide) Nanospheres: Factorial Design, Characterization and Cytotoxicity Studies

Local anesthetic agents cause temporary blockade of nerve impulses productiong insensitivity to painful stimuli in the area supplied by that nerve. Bupivacaine (BVC) is an amide-type local anesthetic widely used in surgery and obstetrics for sustained peripheral and central nerve blockade. in this study, we prepared and characterized nanosphere formulations containing BVC. To achieve these goals, BVC loaded poly(DL-lactide-co-glycolide) (PLGA) nanospheres (NS) were prepared by nanopreciptation and characterized with regard to size distribution, drug loading and cytotoxicity assays. The 2(3-1) factorial experimental design was used to study the influence of three different independent variables on nanoparticle drug loading. BVC was assayed by HPLC, the particle size and zeta potential were determined by dynamic light scattering. BVC was determined using a combined ultrafiltration-centrifugation technique. The results of optimized formulations showed a narrow size distribution with a polydispersivity of 0.05%, an average diameter of 236.7 +/- 2.6 nm and the zeta potential -2.93 +/- 1,10 mV. In toxicity studies with fibroblast 3T3 cells, BVC loaded-PLGA-NS increased cell viability, in comparison with the effect produced by free BVC. In this way, BVC-loaded PLGA-NS decreased BVC toxicity. The development of BVC formulations in carriers such as nanospheres could offer the possibility of controlling drug delivery in biological systems, prolonging the anesthetic effect and reducing toxicity.

Estudo da secagem do feijão verde (Vigna unguiculata L. Walp) - análise experimental do processo combinado leito fixo/leito de jorro

Green bean is considered as one of most traditional Brazilian Northeast dishes. Green beans drying preliminary experiments show that combine processes, fixed-bed/spouted bed, resulted in dehydrated beans with uniform humidity and the recovery of the beans properties after their rehydration. From this assays was defined an initial humidity suited for the spouted bed process. A fixed-bed pre-drying process until a level of 40% humidity gave the best results. The spouted bed characteristic hydrodynamic curves were presented for different beans loads, where changes in the respective beans physical properties were evidenced during the fluidynamic assay, due simultaneous drying process. One 22 factorial experimental design was carried out with three repetition in the central point, considering as entry variables: drying air velocity and temperature. The response variables were the beans brakeage, water fraction evaporated during 20 and 50 minutes of drying and the humidity ratio. They are presented still the modeling of the drying of the green beans in fine layer in the drier of tray and the modeling of the shrinking of the beans of the drying processes fixed-bed and spouted bed

Comparação entre planejamento estatístico experimental e análise dimensional em operações de mistura e separação para sistema óleo-água

This work aims to determine a better methodology to help predicting some operational parameters to a new design of mixer-settler on treating wastewater produced by petroleum industry, called MDIF (Misturador-Decantador à Inversão de Fases/ Mixer-Settler based on Phase Inversion MSPI). The data from this research were obtained from the wastewater treatment unit, called MSPI-TU, installed on a wastewater treatment plant (WTP) of PETROBRAS/UO-RNCE. The importance in determining the better methodology to predict the results of separation and extraction efficiency of the equipment, contributes significantly to determine the optimum operating variables for the control of the unit. The study was based on a comparison among the experimental efficiency (E) obtained by operating MSPI-TU, the efficiency obtained by experimental design equation (Eplan) from the software Statistica Experimental Design® (version 7.0), and the other obtained from a modeling equation based on a dimensional analysis (Ecalc). The results shows that the experimental design equation gives a good prediction of the unit efficiencies with better data reliability, regarding to the condition before a run operation. The average deviation between the proposed by statistic planning model equation and experimental data was 0.13%. On the other hand, the efficiency calculated by the equation which represents the dimensional analysis, may result on important relative deviations (up 70%). Thus, the experimental design is confirmed as a reliable tool, with regard the experimental data processing of the MSPI-TU

Comparison of the univariate and multivariate methods in the optimization of experimental conditions for determining Cu, Pb, Ni and Cd in biodiesel by GFAAS

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