Dissertations / Theses on the topic 'Clay industries'

This Ph.D thesis describes an investigation into the operation of the Blue Circle Cauldon Works precalciner vessel. The vessel is part of the cement making plant and it serves the purpose of providing a furnace that is maintained at approximately 900C to calcine the limestone in the raw meal prior to cementation in the kiln. At Cauldon, tyre chips are used as a support fuel. It was the aim of this work to predict the likely behaviour of the gases and particles in the precalciner by using Computational Fluid Dynamics modelling. The commercial code Fluent was used. Investigation of the likely trajectories and combustion behaviour of tyre chips was particularly important. In this way it was hoped that a method of assessing the suitability of alternative waste fuels for incineration in the precalciner might be established. CFD models were constructed that simulated the precalciner with all main reactions and energy exchanges occurring. The first model predicted the behaviour of the precalciner burning coal and the full load of raw meal. Subsequent models assessed the sensitivity of the first model to changes in the boundary conditions. Further models were developed together with experimental work to assess the combustion and aerodynamic behaviour of the tyre chips. Alternative injection points for the tyre chips were investigated. This type of precalciner had not previously been modelled elsewhere. Similar models were found for the operation of the precalciner without tyre chips but the geometrical accuracy of the models was improved in this work due to improvements in commercial CFD code. No similar study of tyre chip combustion has been made elsewhere. CFD was used successfully to model a precalciner vessel with tyre chip and coal combustion and the full raw meal loading simulated. Adjustments can be made quickly to the model to assess minor geometrical alterations. Alternative fuel injection points can be quickly assessed using the model.

Both Chinese and Islamic glazed ceramics played a significant role in the history of ancient ceramic production. Moreover, it was innovation in glazes that made the Chinese and Islamic ceramics constantly innovative in various categories with different manufacturing techniques. This study applies chemical and isotopic analyses to investigate the manufacturing techniques and provenances of different types of glazes from Northern China and the Middle East, and extends the use of Sr isotopic analysis to investigate raw materials and glaze recipes used to making lime/alkaline glazes in Northern China and the Middle East for the first time. By chemical compositions of the lead glazes, the glazing techniques used to produce Chinese Tang Sancai lead glazes and splashed lead glazes from the Middle East have been identified. The mixture of lead oxide plus quartz/quartz sand was used for making both Chinese Tang Sancai glazes and Islamic splashed lead glazes. Besides, for the Chinese lead glazes, the trace element and lead isotopic analyses of them have been effective in grouping glazes made in different production kiln sites, and hence associating the Tang Sancai wares excavated from archaeological sites of unknown origin with their production centres. Furthermore, by comparing the lead isotopic ratios of Islamic lead glazes and those of lead ore deposits, the possible sources of lead used for making lead glazes can be determined, although more than one source was suggested due to the overlap of Pb isotopic ratios of different lead ore sources in some cases. This study is the first time that Sr isotopic analysis has been applied to the lime/alkaline glazes from Northern China and the Middle East. It has revealed that Sr isotopic compositions of lime/alkaline glazes from Northern China and the Middle East have been very effective in providing information on the glaze recipes and characteristics of raw materials used for making them. Based on Sr isotopic compositions, the case study of Nothern Chinese lime glaze has identified that the Yaozhou celadon glaze was probably produced by local ‘Fuping glaze stone’ combined with botanic ash. Besides, the case study of the Middle East alkaline glaze has suggested that the Raqqa ware glaze was probably made by ‘Cenozoic sand’ containing a certain content of limestone grains and feldspar and that botanic ash was used as a flux.

ZnO is a promising semiconducting material for manufacturing optoelectronic devices. Its most important properties are its wide and direct band gap and its high electron-hole binding energy. Synthesis of ZnO in bulk and thin film form has been investigated intensively over recent decades. Likewise, nanomaterials have been in the point of focus for their different properties compared to their bulk form. The vastly increased ratio of surface area to volume and change in electronic properties with great reduction in particle size enable improved performance in conventional applications where their bulk counterparts have been used for decades. As a result of this trend, research on synthesis of ZnO nanowires and their incorporation in prototype optoelectronic devices has been intensive in recent years. Therefore, synthesis of ZnO nanowires in a cost effective way and understanding the factors influencing the ZnO nanowire growth is essential for contribution to ongoing research. V In this thesis, hydrothermal synthesis of ZnO nanowires, which is a solution based method enabling vertically aligned ZnO nanowire array fabrication over large areas, is investigated. In the first part of this thesis, the effect of using various zinc salts as zinc sources on ZnO nanowires is investigated by monitoring pH, temperature and light transmittance of growth solutions. In the second part, a detailed parametric study on the use of zinc acetate dihydrate salt is provided with regard to the existence of its unique properties compared to other two zinc salts. The effect of growth time, temperature, ratio of concentration of precursor chemicals and precursor chemical concentrations is investigated. The results show that hydrothermal synthesis method could replace the conventional ZnO nanowire fabrication methods. It was shown that specific nanowire lengths for any application can be obtained simply by adjusting the parameters of hydrothermal growth system.

Global warming and the high energy demands of fossil fuel in industries have led governments to implement legislation aimed towards developing more energy efficient and sustainable processes. In the brickwork industry, the burning of coal and natural gas provides the energy to fire clay bricks in the 900-1200 oC range into high quality building materials. Microwaves powered by renewable energy sources have been suggested as a sustainable alternative to fossil fuels. Microwave heating has been considered a promising technique for the processing of clays due to the potential energy consumption and carbon footprint reductions, and for its volumetric heating nature, which enables the fast and uniform heating of a load. This could result in improving the mechanical properties of the fired products. The aims of this project were to develop an understanding of how microwaves interact with clays in order to show whether they could be used to fire clay-based building materials, and to understand how this could be achieved and the parameters that affect it. The composition of Danish clays was quantified, i.e. quartz, calcite, albite, orthoclase, kaolinite, montmorillonite and muscovite, and their thermal evolution was studied across the firing range. The dielectric properties of clays were measured at 912-2470 MHz and 20-950 oC in order to investigate the microwave/clay interaction, assess the effects of changing composition, temperature, frequency and material's density on their potential for microwave processing, and provide critical information on the design and scale up of this technology. Relating the mineralogy of a material and its evolution during heating to changes on the dielectric property trends, and thus microwave processability, was examined for the first time in this thesis. Insight into the influence of individual components on the potential for microwave heating was gained from an analogous study on clay constituents. While the dielectric constants of clays were found to be relatively stable during heating, their loss factors fluctuated with temperature. Free and physically bound water were the dominant dielectric species near room temperature, while their removal halved the loss factors until 350 oC. Beyond this temperature, a steady increase in the loss factors concurred with the mineral dehydroxylations. The loss factors sharply rose beyond 800 oC due to sintering effects, while calcite decomposition partially counteracted this growth. Montmorillonite and muscovite were the most microwave absorbing mineral species due to their water affinity and interlayer cation content, enabling the microwave treatment of the whole clay. On the other hand, a frequency shift from 2470 MHz to 912 MHz resulted in a loss factors increase. This is mainly due to the frequency shifting towards the dipolar dispersion area of physically bound water and the zone in which ionic conductivity heating effects dominate. Mixing rules were used to relate each single mineral to dielectric property variations, and thus rapidly gain knowledge of the microwave processability of any clay across the firing range based on its composition. Böttcher model provided accurate estimations when compared to experimental measurements, and with the same degree of uncertainties at the 912-2470 MHz frequencies and 0.56-0.37 void fraction ranges. The model was expanded for different compositions with clays from Spain, England and Netherlands. This was the first time that mixing rules were successful in estimating mixtures of more than three constituents. A microwave system was developed with the aim of firing clay products of comparable quality to conventional specimens. The basis of design focused on maximising the thermal uniformity of the clay load. The process design steps involved remodelling the clay load, building heat transfer models of the load, carrying out trials to study whether clays behave as expected from their dielectric properties, i.e. volumetric or selective heating, minimising thermal gradients, and assessing alternative methods for the control of the holding stage. Microwave firing cycles manufactured clays with a thermal uniformity at the height of firing of 1050±55 oC and reduced processing times to < 3 h. This is 92% faster than in brickworks, where conventional samples could not match the heating rates without cracking. High temperature (>800 oC) mineral reactions went unfinished due to the reduced holding time of the microwave treatment (30 min), which resulted in dimmer surface colorations. Enhanced thermal uniformity and reduced time for densification resulted in specimens with a 12% higher compressive strength, 38% larger water absorption and 7% higher void fraction. Clay samples three times as big were fired to gain an insight into the scale up of the technique. A tighter process control and higher reproducibility were reported, which is promising for potentially allowing longer holding times in scaled up processes, but the product quality improvement did not change. Looking into an industrial scale up, further work would be required to assess possible design concepts, and an optimal microwave firing process may require complete redesign of the furnace configuration, where several challenges need to be considered, such as brick arrangement, power availability and applicator size and shape. For the purposes of assessing the possible economic and environmental impact of implementing microwave clay firing at industrial scale, one of the most straightforward designs, i.e. retrofitting of an industrial tunnel kiln for microwave processing, was considered. Although energy expenditures would decrease from 11.6 GJ fuel/h to 6.1 GJ electricity/h when using a microwave system for the same throughput, the higher cost of electricity and microwave equipment over conventional burners made the conventional technique more economically feasible. The substitution of natural gas by electricity powered by green energy sources resulted in carbon footprint reductions of >95%, and agreed with the energy policies of numerous countries and supranational organisations worldwide.

Thesis (MScIng)--University of Stellenbosch, 2007.
ENGLISH ABSTRACT: Due to economic and environmental constraints mining operations are placed under increasing pressure to effectively manage and operate tailings disposal operations. Restrictions imposed on water usage and tailings operations footprint have led to higher density and wider particle size distribution slurries conveyed to tailings areas. One means of efficiently disposing the tailings is co-disposal. In this method a concentrated fine vehicle slurry is used to convey a coarser fraction. This produces a higher density of tailings, with a number of advantages both upstream and downstream of the tailings process. Limited research has been conducted on the effect of coarse particles on the non-Newtonian rheological properties of these slurries. This lack of information complicates the design and reliable operation of these systems. This project aims at gaining a clearer understanding as to the mechanisms involved in the addition of coarse particles to a fine clay slurry vehicle; and to provide a means of estimating the measured slurry rheological properties. A number of experiments were designed to test the slurry (both Kaolin only, and Kaolin-coarse particle mixtures) rheological properties using a Couette viscometer (for the dynamic flow properties of yield stress and plastic viscosity) and a vane instrument (for the static yield stress measurements). The slurries were prepared in varying Kaolin clay solids concentrations with reverse osmosis water. Glass beads and two types of industrial sand were used as the coarse fractions. All of the coarse particles had a similar size but varied significantly in shape. Slurry pH and temperature readings were monitored throughout the tests. Tests were done initially on clay only slurries. The rheological properties of these slurries were repeatable, and no noticeable variations of properties with time were observed. The yield stress (both static and dynamic) and plastic viscosity data were well correlated with established relationships. Coarse particles were added to the clay only slurries, and then removed. The remaining clay only slurry exhibited the same rheological properties as the initial clay only slurry. The presence of coarse particles increased all the measured rheological properties (i.e. dynamic yield stress, Bingham viscosity, and static vane yield stress) in a fashion resembling the effect of adding clay to a clay only slurry. In addition, the change in measured rheological property by addition of coarse particle was independent of the clay fraction in the clay slurry. Furthermore, with both the clay only slurries and clay and coarse sand slurries, a constant linear relationship existed between the static and dynamic yield stress. Several correlations from the literature were found to provide reasonable prediction of the rheological property variations observed. These empirical and semi-empirical models however did little to explain the mechanisms involved in coarse particle addition. A new correlation has been proposed, Residual Clay Concentration, which predicts the change in rheological property based on an additional clay concentration, which in turn is a linear function of the coarse particle concentration. The accuracy of this model further strengthens the belief that the coarse particle acts in a similar fashion to a floc. By means of a case study example the importance of selecting an appropriate model for design was illustrated. The Residual Clay Concentration method provided the most conservative results. This combined with its theoretical basis strengthens the models recommendation for use in design.
AFRIKAANSE OPSOMMING: As gevolg van ekonomiese en omgewings beperkinge word mynwese nywerhede onder toenemende druk geplaas om doeltreffende afvalstroom bestuur en operasie toe te pas. Beperkinge geplaas op water gebruik en afvalstroom area-groote ly tot hoër digthede en wyer partikel-grooteverspreidings van flodders vervoer na afval areas. Een manier om van die afval doeltreffend ontslae te raak en te berg is deur medeberging. In die metode word ‘n gekonsentreerde fyn flodder gebruik as draer van ‘n growwer partikel-fraksie. Dit ly tot ‘n hoër digtheid flodder, met verskeie voordele in beide die op – en afstroom prosesse. Beperkte navorsing is gedoen op die effek van growwe partikels op die nie-Newoniese rheolgiese eienskappe van hierdie flodders. Hierdie tekort aan informasie maak die effektiewe, betroubare bedryf en operasie van die sisteme meer ingewikkeld. Hierdie projek is daarheen gemik om ‘n beter begrip te ontwikkel met betrekking tot die meganismes betrokke in die byvoeging van growwe partikels aan ‘n fyn klei-agtige flodder draer; en om ‘n manier te voorsien wat die rheologiese eienskappe kan beraam. Verskeie eksperimente was ontwerp om die flodders (beide slegs Kaolien, en Kaoliengrowwe partikel mengsels) se rheologiese eienskappe te toets deur die gebruik van ‘n Couette-viskometer. Die Couette viskometer was gebruik om die dinamiese eienskappe (van grens-spanning, en plastiese viskositet) te meet. ‘n Vaan apparaat is gebruik om die eienskap van statiese grens-spanning te meet. Die flodders was voorberei in verskeie Kaolien konsentrasies met tru-osmosis water. Glas krale en twee tipes industriële sand is gebruik as die growwe fraksies. Al die growwe partikels het soortgelyke groottes gehad, maar het grootliks verskil in vorm. Die flodder pH en temperatuur lesings is deurentyd nagegaan. Toetse was aanvanklik gedoen op die klei-alleenlike flodders. Die gemete reologiese eienskappe van die flodders was herhaalbaar, en geen opmerkbare veranderinge van die eienskappe met betrekking tot tyd is gemeet nie. Die grens-spanning (beide statiese en dinamiese) en plastiese viskositeit is goed gekorrelleer met gevestigde verhoudinge. Growwe partikels is aan die klei-alleenlike flodders bygevoeg, en daarnae verwyder. Die oorblywende klei-alleenlike flodder het dieselfde gemete rheologiese eienskappe getoon as die oorspronklike klei-allenlike flodder. Die teenwoordigheid van growwe partikels het na ‘n toename van al die gamete rheologiese eienskappe gelei wat fisies baie soortgelyk is aan die byvoeging van klei tot ‘n klei-alleenlike flodder. Verder, met beide die klei-alleenlike en klei-growwe partikel flodders het ‘n konstante liniëre funksie tussen die statiese en dinamiese grens-spannings bestaan. Verskeie verhoudings uit die literatuur het goeie korrelasie bewerkstellig met die waargenome rheologie veranderinge. Hierdie empiriese en semi-empiriese modelle doen egter min om die megansimes betrokke in die toevoeging van growwe partikels te verduidelik. ‘n Nuwe korrelasie is voorgestel, naamlik die Residu Klei Konsentrasie. Hierdie model voorspel die verandering in reologiese eienskappe gebaseer op ‘n addisionele klei konsentrasie, wat ‘n liniëre funkise is van die growwe partikel konsentrasie. Die goeie korrelasie gesien met die model versterk die idée dat die growwe partikel in ‘n soortgelyke manier as ‘n flok gedra in die teenwoordigheid van ander flokke. Deur middel van ‘n tipiese industriële voorbeeld is die belangrikheid in die keuse van die regte korrelasie geillustreer. Die Residu Klei Konsentrasie metode het die mees konservatiewe resultate gelewer. Hierdie feit gekombineerd met die model se soliede teoreitiese beginsels versterk dit as voorgestelde korrelasie vir ontwerp.

Thesis (MBA)--Stellenbosch University, 2014.
ENGLISH ABSTRACT: For decades black South Africans suffered under apartheid, being excluded from active participation in the South African economy. Following the first democratic election in 1994, which was won by the African National Congress, the new government immediately made clear its intentions to transform the economy by including all the South Africans citizens. In 2004 the government promulgated the Broad-Based Black Economic Empowerment Act (BB-BEE), which aimed to redress the wrongs of the past and to realise the country's full economic potential whilst assisting the black majority to become part of the economic mainstream. The BB-BEE act focused primarily on the upliftment and empowerment of historically disadvantaged people, particularly black people, women, the youth and the disabled and on those living in rural communities; it aims to include these people in the management and ownership structures of South African companies. The clay brick industry, one of the oldest industries in the world, had been severely affected by the introduction of the legislation, as 75% of businesses were predominantly family owned, and 69.39% of them are predominantly white owned. The primary objective of this research assignment was to investigate the impact of Broad-Based Black Economic Empowerment (BB-BEE) on the South African clay brick industry and to make recommendations to the various stakeholders regarding the management of the introduction of BB-BEE into the industry. The methodology followed a survey approach by using specific indicators to ascertain what the perceptions and experiences of the business owners were, regarding the implementation of BB-BEE in the industry. The study found that the business owners were concerned about losing control of their businesses, that there is very little support from government for businesses entering into BB-BEE deals and that it is difficult to find the “right” empowerment partner which “fits” the culture and management style of the business. The study concluded that much uncertainty, fear and anxiety exists amongst business owners regarding the introduction of BB-BEE. The study also makes practical recommendations to the various stakeholders who may assist with facilitating the introduction of BB-BEE in the industry.

Thesis (MBA)--Stellenbosch University, 1992.
ENGLISH ABSTRACT: Development in the world and particularly in South Africa has resulted in change. This presents new opportunities and challenges to today's managers and entrepreneurs. As a result of our local political reform process, together with the collapse of the Soviet Union and the general deterioration of communistic ideologies, south Africans are experiencing a growing acceptance back into the world and neighbouring African communities. south African businessmen are faced with opportunities in foreign countries, especially neighbouring African countries, with South Africa cited as the key to Africa. The problem South African managers face, is how to evaluate opportunities in a neighbouring African country and to ascertain the type of trading conditions in that country. After eighteen years of communistic rule and ten years of civil war Mozambique is amongst the poorest countries in the world. World aid programs have come to the country's assistance, introducing economic recovery programs as well as replacing the out-dated socialistic ideas with western style free market principles. Although the country is suffering the effects of an ongoing civil war, indications are that a peace settlement is imminent. The Mozambique government has .introduced an attractive foreign investment package which is aimed at attracting foreign capital. A first impression indicates that this country is ready for foreign investment and exploitation, but is it? This research proj ect firstly evaluates existing feasibility models in an attempt to find a suitable model to assess the feasibility of investing in a clay brickworks located in Mozambique. Failing to find such a feasibility model, a suitable model is then presented. The feasibility model presented takes a holistic approach, acknowledging that first world structures, such as a financial or transportational infrastructure, should not be assumed to exist. The model is divided into two parts, the first evaluating the macro parameters of the country and the second evaluating the micro parameters or specifics of the opportunity. The assessment of macro parameters is divided into five sections, namely, socio- cultural, political, economic, technological and physical parameters. After the completion of each section parameters are summarised and graded. At the end of the macro parameters, an interim evaluation is required to assess whether the country is favourable for investment. If the investor believes the country is ready for investment, the following section covering the micro parameters is investigated. If, however, the investor believes that the country is not suitable for investment then further analysis is suspended. The second section which covers the micro parameters is also divided into five sections, namely, financial, manufacturing, proposed infrastructure, marketing and personnel parameters. These parameters cover the project specifically and are similar to those of a normal business plan. Following this analysis, a final evaluation is done culminating in a decision on whether the project is feasible or not . In applying this model to evaluate the feasibility of establishing a clay brickworks in Mozambique, the researchers concluded at the interim evaluation that it was premature to invest in a clay brickworks in Mozambique . This type of investment might only become attractive after a peace settlement were reached between the government and the resistance movement and with the restoration of the country's infrastructure.
AFRIKAANSE OPSOMMING: Ontwikkeling wereldwyd, en veral in Suid-Afrika, het verandering meegebring. Dit stel nuwe geleenthede en uitdagings aan vandag se bestuurders en entrepreneurs. Na aanleiding van veranderinge in die politieke bestel in Suid-Afrika, die verbrokkeling van die Sowjet-Unie en die verlies van geloofwaardigheid van die kommunistiese ideologie, beleef Suid-Afrika toenemende aanvaarbaarheid in die wereld asook met sy naburige Afrika lande. Nuwe geleenthede buitelands en veral in die naburige Afrika lande, word nou aan besigheidslui in Suid-Afrika gebied, derhalwe word Suid- Afrika gesien as die sleutel tot Afrika. Die probleem wat Suid-Afrikaanse bestuurders tans in die gesig staar, is die evaluasie van lewensvatbare geleenthede in 'n naburige Afrika land en om die handelstoestande te bepaal waaronder hulle sal moet funksioneer. Na agtien jaar van kommunistiese heerskappy en tien jaar van burgeroorloe is Mosambiek een van die armste lande ter wereld. Buitelandse noodlenigingsprogramme het tot die land se redding gekom met die daarstel van ekonomiese herstel programme sowel as die vervanging van sosialistiese idees met 'n Westerse vryemarkstelsel. Alhoewel Mosambiek nog swaar gebuk gaan onder burgeroorloe, is daar wel aanduidings dat 'n vredesooreenkoms onafwendbaar is. Die Mosambiekse regering bied tans aantreklike beleggingspakkette aan wat hoofsaaklik gerig is op die buitelandse belegger. Die eerste indrukke wat gelaat word, is dat Mosambiek gereed is vir buitelandse belegging en ontginning. Die vraag is, is dit wel so? Hierdie navorsingsprojek evalueer eerstens bestaande uitvoerbaarheidsmodelle ten einde 'n toepaslike model te vind om die uitvoerbaarheid te bepaal van investering in 'n kleibaksteenfabriek in Mosambiek. Die uitvoerbaarheidsmodel wat hier voorgestel word, neem 'n holistiese benadering aan, met die erkenning dat elemente soos die finansiele- en vervoer-infrastruktuur nie noodwendig tans bestaan nie. Die model is verdeel in twee dele waarvan die eerste die makro- parameters van die land evalueer, en die tweede die mikra-parameters, of spesifieke besonderhede aangaande die geleentheid. Die evaluering van makro- parameters word opgedeel in vyf afdelings, naamlik, die sosio-kulturele, politiese, ekonomiese, tegnologiese en fisiese parameters. Na voltooiing van elke afdeling word 'n kort opsomming en gradering gedoen. Aan die einde van die deel wat handel oor makro-parameters, is daar 'n tussentydse evaluasie gedoen om te bepaal of die land gunstig is vir beleggings. As die belegger glo dat die land gereed is vir belegging, word die volgende afdeling, naamlik mikro-parameters, ondersoek. Indien die belegger egter van mening is dat die land nie geskik is vir beleggings nie, word die ontleding na die eerste gedeelte gestaak. Die tweede afdeling, wat na mikro-parameters verwys, word ook in vyf sub- afdelings opgedeel, naamlik, finansieel, vervaardiging, voorgestelde infrastruktuur, bemarking en personeel parameters. Hierdie parameters is soortgelyk aan 'n gewone besigheidsplan en is omvattend en spesifiek. Hierdie ontleding word gevolg deur 'n finale evaluasie wat uitloop op 'n besluit of die projek uitvoerbaar is of nie. Deur middel van die toepassing van hierdie model om die lewensvatbaarheid van die vestiging van 'n kleibaksteenfabriek in Mosambiek te evalueer, het die navorsers in die tussentydse ontleding getoon dat so 'n belegging nie op hierdie stadium lewensvatbaar sal wees nie. 'n Belegging sal moontlik aantreklik wees nadat daar ' n vredesooreenkoms bereik word tussen die regering en die weerstandsbeweging, en met die herstel van die land se infrastruktuur.

Cette thèse de doctorat a été menée dans le cadre d'un partenariat entre le Laboratoire Conception de Produits et Innovation des Arts et Métiers ParisTech et l'Ecole de Biologie Industrielle. Le projet de recherche porteur de nos travaux de thèse vise à accompagner la valorisation de nouvelles particules d'argile ayant fait l'objet d'un dépôt de brevet au sein du laboratoire EBInnov®. Ce nouvel ingrédient polyfonctionnel est destiné à satisfaire de multiples applications dans les secteurs bio-industriels, notamment dans l'industrie pharmaceutique, le secteur des cosmétiques, le phytosanitaire ou encore l'environnement. L'objectif de nos travaux de thèse est d'intégrer les spécifications techniques, sensorielles et réglementaires des entreprises de ces secteurs au sein d'un modèle de conception axé innovation. Pour ce faire, les hypothèses de recherche s'appuient sur l'émergence du paradigme de l'innovation ouverte dans ces secteurs. Nous soutenons que les nouveaux intermédiaires de l'innovation sont performants dans les bio-industries et permettent la prise en compte du potentiel d'innovation dès les phases amont du processus de conception. La validité de ces hypothèses a ensuite été vérifiée en milieu industriel par le biais d'expérimentations en lien direct avec les secteurs d'application de la technologie EBISilc®. Finalement, nous proposons un modèle de conception axé innovation prenant en compte l'évolution des modèles d'innovation dans les bio-industries
This doctoral thesis was realized within the framework of a partnership between the Product Design and Innovation Laboratory of Arts et Métiers ParisTech and the Ecole de Biologie Industrielle. The research project behind our thesis aims to support the promotion of new clay particles having been patented by the EBInnov® laboratory. This new polyfunctional ingredient is designed to satisfy several applications in the bio-industries, including the pharmaceutical and cosmetic industry, the phytosanitary sector or the environment. The aim of the thesis is to integrate the technical, sensory and regulatory specifications of bio-industrial companies in an innovation-oriented design process. Thus, the research hypotheses rely on the emerging paradigm of open innovation in these sectors. We support that the new innovation intermediaries are efficient in the bio-industries and allow the integration of the innovation potential in the early stages of the design process. The validity of these assumptions was studied by means of industry-related experiments directly linked to the main application sectors of the EBISilc® technology. Finally, we propose an innovation-oriented design process taking into account the evolution of the innovation models in the bio-industries

This study investigates the physical, mineralogical and chemical characteristics of a group of pottery sherds that are mostly Miletus-ware ceramics, belonging to the Early Ottoman period and excavated during 2003 season, from the The sherds examined are mostly characterized by cobalt-blue designs which are occasionally coupled with black, green and purple paintings. After grouping the sherds according to their stylistic and color differences
petrographic, X-ray diffraction, scanning electron microscope coupled with energy dispersive X-ray and Fourier Transform Infrared analyses were carried out for investigating the mineralogical and chemical properties. Most of the ceramic samples have slip and glaze on both sides. The glaze part is mostly fresh without any devitrification products. Bodies of the ceramics have tones of reddish yellow and/or red, indicating abundant amount of iron in their raw material. Grains consist mainly of metamorphic rock fragments (quartz-mica schist), quartz, feldspar, hornblende, hematite and biotite. Pyroxene, epidote, chert, muscovite, opaque minerals, chlorite are also encountered. Micritic calcite occurs in some of the pores. Ceramic bodies investigated are usually fine-grained and well-sorted. Clay raw material used for the production of the ceramics seems to be originated from a metamorphic source. Bodies usually show a low degree of vitrification with few exceptions, indicating a rather simple technology with non-uniform and low degree of firing, probably not exceeding 900°
C. Technological characteristics of the sherds examined do not seem to have changed much between 14th and 16th century.

Clinoptilolite is the most abundant zeolite mineral in nature. In this study a reproducible synthesis recipe for clinoptilolite was established and the limits of the crystallization field were developed by changing synthesis parameters such as temperature, composition and the nature of reactants. Clinoptilolite was reproducibly synthesized as a pure phase and in high yield at 140oC using a benchmark batch composition of 2.1 Na2O:Al2O3:10SiO2:110.1 H2O. Clinoptilolite was crystallized from 10wt% or 28wt% seeded systems while it was not formed if no seeds were present. Clinoptilolite was also crystallized as a pure phase when the cation in the benchmark batch composition was Na,K mixture, or when alkali salts such as carbonates or chlorides were used besides alkali hydroxides, or when the SiO2/Al2O3 ratio was in the range of 10-12. Clinoptilolite was still crystallized as a single phase when alkali hydroxides in the batch were reduced by 20%. With the benchmark batch composition, clinoptilolite was crystallized in pure phase form at 100oC, 120oC, 140oC and 160oC while synthesis at 175oC resulted in the formation of pure mordenite. At 140oC clinoptilolite was crystallized together with Linde L when cation in the benchmark composition is only potassium. Phillipsite crystallized together with clinoptilolite at SiO2/Al2O3 ratio of 8 to 9. At SiO2/Al2O3 ratios of 6 or 4, phillipsite or analcime was formed as pure phase respectively. When the alkali hydroxides in the batch was increased by 20%, sanidine was formed. Use of reactive aluminosilicate gels enhanced the formation of clinoptilolite while attempts to use mineral raw materials were unsuccessful. For both Na and (Na,K)-clinoptilolite, Si/Al ratio of products were greater than four. Thermal stability of synthetic clinoptilolites were comparable with natural clinoptilolite and potassium ion increased thermal stability of clinoptilolite.

The effect of seeding on the properties of alumina supported MFI membranes was investigated in this study. Membranes were synthesized from clear solutions with a molar batch composition of TPAOH:9.80SiO2:0.025NaOH:0.019Al2O3: 602.27H2O:39.16C2H5OH on bare and seeded alumina supports at 130oC in autoclaves. The amount of seed on the support surface was changed between 0.6 mg/cm2 and 6.9 mg/cm2 by vacuum seeding method, which provided uniform and closely packed seed layers. Membranes were characterized by XRD and SEM, and by measuring single gas permeances of N2, SF6, n-C4H10 and i-C4H10. The quality of membranes was evaluated on the basis of N2/SF6 ideal selectivity. Membranes, which showed N2/SF6 ideal selectivity higher than 40, were considered to be good quality, comprising few defects. Good quality membranes were also used to separate butane isomers. Membranes synthesized on seeded supports had compact and uniform MFI layer if the seed amount is less than 1.0 mg/cm2 on the support surface. Membranes that were synthesized on the supports coated with higher amount of seed crystals showed an asymmetric structure with a dense and uniform MFI layer at the top, the support at the bottom and a seed layer between. Half of the membranes synthesized on seeded supports had N2/SF6 ideal selectivity higher than 40. These membranes exhibited n-C4H10/i-C4H10 separation selectivities between 5 and 27 and 8 and 21 at room temperature and at 200oC, respectively. High ideal and separation selectivities showed that membranes did not include non-zeolitic pores. Membranes synthesized on bare support had non-uniform MFI layer. Those membranes showed N2/SF6 ideal selectivities below Knudsen selectivity, indicating the existence of large non-zeolitic pores in the MFI layer.

MFI type zeolites, are the most widely studied zeolites for membrane separations. Conventionally, zeolite membranes are prepared in batch systems by hydrothermal synthesis in autoclaves. This method has several disadvantages for use in industrial scale for the synthesis of membranes with large areas and complex geometries that are commonly used in membrane modules. The objective of this study is to prepare MFI type zeolite membranes on tubular alumina supports in a continuous system where the synthesis solution is circulated through the tubular supports. Syntheses were carried out using clear solutions, at atmospheric pressure and at temperatures below 100°
C. The membranes were characterized by N2, SF6, n-butane and isobutane permeances, X-ray diffraction and scanning electron microscopy. A 2-&
#956
m membrane was synthesized using the composition 80SiO2: 16TPAOH: 1536H2O at 95°
C in the continuous system. The membrane showed N2 permeance of 4.4 x 10-7 mol/m2.s.Pa and N2/SF6 selectivity of 11. The membrane synthesized in the batch system showed a N2 permeance of 3.4 x 10-7 mol/m2.s.Pa and a N2/SF6 selectivity of 27. Both membranes showed n-butane/isobutane mixture (50%-50%) selectivities of about 6 at temperatures of 150 and 200°
C. Among many zeolite membranes reported in literature, these membranes are one of the few zeolite membranes synthesized in a flow system and the first MFI type membranes synthesized in a continuous flow system with circulation of the synthesis solution. The permeances and selectivities of the membranes synthesized in the continuous system are comparable with the MFI type membranes synthesized in batch systems in literature.

Thermal mismatch between different components of a system could cause of problems like residual stress induced cracking, thermal fatigue or even optical misalignment in certain high technology applications. Use of materials with customized thermal expansion coefficient is a counter-measure to resolve such problems. Zirconium tungstate (ZrW2O8) with negative thermal expansion coefficient is capable of being used in synthesis of composites with tailored coefficient of thermal expansion (CTE). In this work, the sol-gel method which had been already set up in our group was characterized and the sources of the factors imposing impurities in the product were distinguished in all the steps of precursor preparation and heat treatment. In the second part of study, zirconium tungstate particles synthesized by the sol-gel method were utilized as core in synthesis of ZrW2O8&ndash
ZrO2 core&ndash
shell composite particles. Shell layer was composed of ZrO2 nanocrystallites and precipitated from an aqueous solution by urea hydrolysis. Volume of the shell was effectively controlled by concentration of the initial zirconium ion in the solutions. The rate of precipitation was a function of the ratio of initial urea concentration to zirconium ion. It is hypothesized that isolation of the ZrW2O8 within a layer of ZrO2, will be a key element in solving problems associated with reactivity of ZrW2O8 towards other components in sintering of ceramic&ndash
ceramic composites with tuned or zero thermal expansion coefficient.

Alumina (Al2O3) is one of the most widely used engineering ceramic. It can be used in a wide range of applications like electrical/thermal insulation, wear resistance, structural refractories, cutting tools, abrasives, catalyst carriers and coatings. A traditional ceramic process has several steps (i.e. powder synthesis and processing, shape forming, drying, organic burnout and densification). Accessing powders with sizes in the range of a couple of micrometers down to several tens of nanometers is considered critical in attaining higher densities in the final ceramic bodies. Besides since significant shrinkage can be observed in the thermal treatment steps due to the excessive use of additives (e.g. binders, solvents and plasticizers) in the powder processing and forming steps, it is important to take remedies that would increase the solids loading in the initial mixtures. In addition, most of the conventional additives and solvents used in these steps are toxic and it is necessary to replace them with the environmentally benign aqueous-based alternatives. Alumoxanes could be used as a benign aqueous-based alternative to be used as a ceramic precursor or an agent. They are a group of compounds that have nano sized boehmite cores encapsulated with the organic groups used in its production steps. In this research work, alumoxane nano particles which can be used as precursors for nano-alumina were developed starting from aluminum trihydroxide. As a preconditioning step, grinding was applied to decrease the aluminum hydroxide particle size (&
#8804
60 &
#956
m) to submicron sizes. This process was followed by the glycothermal ageing step, and organic derivative of boehmite was obtained. The amorphous particles thus obtained were further treated mechanochemically in a high energy ball mill with organic chemicals like acetic acid, methoxy acetic acid, stearic acid and L-lysine. After this step the observed sizes of the particles were as low as 10-100 nm. The effects of organic molecules used in each step were studied by FTIR spectroscopy and their effectiveness in exfoliation of hydroxide layers were identified with dynamic light scattering from processing solutions dispersed in aqueous medium. Moreover, in each step, structural analyses were carried out by XRD.

ABSTRACT MICROWAVE SINTERING AND CHARACTERIZATION OF ALUMINA AND ALUMINA MATRIX CERAMIC NANOCOMPOSITES Kayiplar, Burcu M.S., Department of Metallurgical and Materials Engineering Supervisor: Assist. Prof. Dr. Arcan F. Dericioglu April 2010, 106 pages Efficiency of microwave heating on the sintering of ceramic materials has been investigated in comparison to conventional processing. Monolithic alumina with or without sintering additives such as MgO, CaO, Y2O3 were fabricated by both conventional and microwave sintering at temperatures ranging from 1000°
C to 1600°
C with a constant soaking time of 1 hour. Based on the densification results on monolithic alumina, nanometer-sized SiC or stabilized ZrO2 particle-dispersed alumina matrix ceramic nanocomposites were sintered by both methods at 1300°
C and 1500°
C for 1 hour. Sintered ceramic materials were characterized in terms of densification, microstructural evolution, chemical composition and mechanical properties such as hardness and indentation fracture toughness. Microwave sintering was determined to be a remarkably effective method in the production of Al2O3 ceramics at considerably low temperatures (&
#8804
1400°
C) compared to conventional sintering in achieving enhanced relative densities reaching to ~97% with improved microstructural characteristics and mechanical properties. Usage of sintering additives at temperatures higher than 1400°
C was determined to be effective in densifiying Al2O3 by both methods. Second phase particle incorporation yielded poor densification resulting in a decrease of hardness of the fabricated ceramic nanocomposites
however, their fracture toughness improved considerably caused by the crack deflection at the dispersed particles and grain boundaries reaching to ~4 MPa·
m1/2 in the case of SiC particledispersed nanocomposites. Compared to conventional sintering, microwave sintering is more effective in the processing of alumina and alumina matrix nanocomposites leading to similar densification values along with improved microstructural and mechanical characteristics at lower temperatures in shorter soaking periods.

Ces dernières années, les problèmes d’environnement et de dépollution sont devenus cruciaux. En particulier, les industries textiles sont une source très importante de pollution des milieux aquatiques. De 60 à 70 % des colorants de l’industrie textiles contiennent une ou plusieurs fonctions azoïques et sont pour la plupart d’entre eux toxiques, mutagènes et cancérigènes. L’objectif de la thèse a été d’évaluer l’efficacité du procédé photocatalytique pour éliminer des colorants anioniques et cationiques seuls ou en mélange en présence de dioxyde de titane et d’argile pontée au titane, synthétisé au laboratoire. Trois colorants sont étudiés comme modèle le bleu de Méthylène (BM), le noir Rémazol 5 (NR5) et le réactif rouge 2 (RR2). La première partie du travail est une étude cinétique de l’adsorption, de la dégradation et de la minéralisation de ces colorants à différents pH. Plusieurs conclusions émergent (1) l’isotherme d’adsorption n’est pas une isotherme de Langmuir (2) aucune corrélation n’est observée entre les quantités adsorbées et les vitesses de dégradation et (3) à forte concentration en colorants, une partie de la lumière est absorbée et la vitesse de dégradation diminue. La seconde partie du travail concerne l’étude du mélange des deux colorants anioniques. L’influence du rapport molaire, du pH et de la concentration initiale sur l’isotherme d’adsorption, la cinétique de décoloration et de minéralisation des deux colorants dans le mélange sont étudiés et comparés à celle obtenues pour les colorants pris individuellement. Aucun complexe n’est formé. Des compétitions entre les deux colorants sont observées après saturation de la surface de TiO2. Au-delà de la saturation du catalyseur un ralentissement de la minéralisation du COT et des hétéroatomes est observé. La troisième partie de l’étude est dédiée à l’étude de la préparation, caractérisation et propriétés photocatalytique de l’argile pontée au TiO2 (MMT-TiO2) et du matériau composite : argile pontée au TiO2 dopée avec de l’argent (MMT-TiO2/Ag). Cette étude est réalisée sur le colorant cationique (BM) et le colorant anionique (NR5). Une adsorption totale du colorant BM est observée, contrairement au NR5 qui ne s’adsorbe pratiquement pas, suggérant une adsorption par liaison ionique. L’argile pontée dopée ou non ne présente pas des propriétés photocatalytiques plus importantes que celle de TiO2 mais joue un rôle important sur l’adsorption des colorants cationiques, ce qui favorise leur élimination de la solution aqueuse. La présence d’Ag diminue les propriétés d’adsorption et de photocatalyse de l’argile pontée
The problems of environment become crucial. In particular, textile industries are important sources of pollution of the aquatic system. 60% to 70% of dyes used in these textiles industries are azo dyes containing one or more; some of them are toxic, mutagenic and carcinogenic compounds. The aim was to evaluate the efficiency of photocatalytic processed for the elimination of anionic and cationic dyes alone or in combination with titanium dioxide and clay pillared with titanium, synthesized in the laboratory. The photocatalytic processing is interesting because solar flux can be used. Three dyes were studied as model: methylene blue (BM), black Remazol 5 (NR5) and reactive red 2 (RR2). The first part of this work is a kinetic study of adsorption, degradation and mineralization of these dyes at different pH. Several conclusions emerge (1) the adsorption isotherm is not of Langmuir type(2) no correlation exists between the quantities adsorbed and the degradation rates and (3) at high concentration, a part of UV is absorbed by the dye and the degradation rate decreases. The second part of the work involves the study of the mixture of two anionic dyes. The concentration of both dyes in the mixture, the influence of molar ratios, pH and initial concentration on the adsorption isotherm, kinetics of decolorization and mineralization of the two dyes in the mixture are compared to that obtained for the individual dyes. No complex is formed and competition between the two dyes occurs only after saturation of the photocatalyst surface. Beyond the saturation of the catalyst a slower mineralization of TOC and heteroatoms are observed. The third part deals with the preparation, characterization and photocatalytic properties of TiO2 pillared clay (MMT-TiO2) and of a composite material: TiO2 pillared clay doped with silver (MMT -TiO2/Ag), performed on the cationic dye (MB) and the anionic dye (NR5). A total adsorption of the BM dye is observed. Constrasting with the NR5 adsorption suggesting an adsorption by ionic bond. The pillared clay doped or not with silver but favors the elimination of dyes from the aqueous solution by adsorption. The presence of silver reduces the adsorption properties and photocatalysis properties of the pillared clay

As argilas são rochas constituídas por argilominerais e por minerais acessórios, cuja estrutura cristalina permite a adsorção de cátions e ânions conferindo-lhes propriedades físico-químicas particulares. Quimicamente os argilomineriais são formados essencialmente por silicatos hidratados de alumínio, ferro e magnésio. As bentonitas apresentam mais de 140 usos industriais, com variações particulares, seja devido ao emprego tecnológico desta argila, seja devido à origem geológica ou à composição mineralógica desta, por isso, sendo consideradas tipos especiais de argilas industriais. O termo bentonita é usado para designar uma argila com alto teor de argila esmectítica. O maior produtor mundial de bentonita são os Estados Unidos representando cerca de um terço do total da produção mundial. No Brasil, os mais importantes jazimentos de bentonitas encontram-se na Paraíba, nos municípios de Boa Vista, Cubati e Pedra Lavrada. A bentonita bruta da Paraíba é lavrada por empresas mineradoras e comercializada em grandes quantidades no próprio Estado, sendo estas destinadas a empresas que as beneficiam, ativam e posteriormente vendem para os demais mercados nacionais. Os preços da bentonita variam em função da qualidade do produto, da pureza, da função ou aplicação, e do tipo do beneficiamento e ativação a que foi submetido o minério. Considerando a expectativa de crescimento desse setor para os próximos anos, este estudo tem como objetivo complementar e atualizar dados tecnológicos existentes na literatura sobre as bentonitas do Estado da Paraíba, contribuindo com estudos tecnológicos das bentonitas da Paraíba realizados em 1976 pelo professor Dr. Pérsio de Souza Santos. Pretende-se evidenciar como estão as propriedades e os usos de 5 argilas da mina Lages após 35 anos de estudos. Para o desenvolvimento deste trabalho utilizaram-se 5 tipos diferentes de bentonitas cedidas pela empresa BENTONISA - Bentonita do Nordeste S.A. Para estas foram realizadas as caracterizações físico-químicas e mineralógicas. Através da análise dos resultados obtidos foi possível realizar algumas indicações para os usos potenciais destes materiais.
The clays are composed of clay minerals and accessory minerals, whose crystal structure allows the adsorption of cations giving them particular physical and chemical properties. Chemically, the argilomineriais are formed mainly of hydrated silicates of aluminum, iron and magnesium. The bentonites are special types of industrial clays because submitting more than 140 industrial uses, with particular variations, whether due to technological employment of clay, is due to the geological origin and the mineralogy of this clay. The term bentonite is used to designate a high clay content of montmorillonite. The world\'s largest producer of bentonite is the United States represents about one-third of total world production. In Brazil, the most important bentonite clay bentonite deposits are found in Paraiba, in the municipalities of Boa Vista, Cubati and Pedra Lavrada. The crude bentonite Paraíba is wrought by mining companies and sold in large quantities within the State, which are aimed at companies that benefit, activate and subsequently sold to other markets. Prices vary depending on the bentonite product quality, purity, function or application, and the type of processing and activation in the ore that was submitted. Considering the expected growth of this sector in the coming years, this study aims to complement existing technology and update data in the literature on bentonite clays of Paraíba State, contributing to technological studies of bentonites from Paraíba conducted in 1976 by Professor Dr. Pérsio de Souza Santos. It is intended to highlight are the properties and uses of these materials after 35 years of studies. To develop this work, we used five types of bentonite clays supplied by the company BENTONISA-Bentonita do Nordeste S.A., For these were the physical and mineralogical characterization. By analyzing the results we achieve some indication for the potential uses of these materials.

L’étude d'un matériau céramique a base d'argiles, en fonction de la température et de l'atmosphère de cuisson, nécessite une bonne connaissance de sa composition minéralogique. Les minéraux argileux et non argileux ont été analysés qualitativement et quantitativement avant et après les traitements thermiques. Les oxydes de fer sont parmi les principaux agents de coloration des matériaux céramiques cuits non émaillés, leur étude a permis d'une part de localiser les ions fe**(2+) dans les aluminosilicates, les ions fe**(3+) dans la goethite, l'hématite et les aluminosilicates, d'autre part de montrer que la formation de la magnétite n'a pas lieu à 1250**(o)c, à moins de conditions très réductrices. Une étude des transformations minéralogiques au cours de la cuisson a permis de mettre en évidence la formation de la mullite à 1100**(o)c environ et celle de la cristobalite à 1200**(o)c environ.

L'industrie de la terre cuite valorise les materiaux de la terre en extrudant des pates d'argiles. Le but de cette etude est la maitrise de la mise en forme a vitesse elevee de ces pates et des defauts d'extrusion. La caracterisation des proprietes physiques et rheologiques des pates, notamment dans des conditions non consolidees et non drainees, les fait apparaitre comme des materiaux plastiques heterogenes. Les proprietes d'interface des pates sont caracterisees grace a un tribometre concu pour l'etude des frottements a vitesse elevee. Nous proposons une loi de frottement suggerant un couplage des effets de la vitesse de glissement et de la pression normale. Une etude experimentale systematique a permis d'obtenir les proprietes d'ecoulement des pates et d'etudier les defauts generes durant l'extrusion au travers de filiere axisymetrique. Des mesures locales et directes de la vitesse a l'interface pate-paroi montrent que l'evolution de cette derniere est reliee a celle des defauts. La mise en evidence d'une evolution de la texture et des proprietes mecaniques de la pate au cours de l'extrusion oblige a tenir compte de l'histoire mecanique de la pate. L'analyse montre la necessite de prendre en compte la piezodependance sur le comportement rheologique en volume des pates et sur le comportement a l'interface. Elle a permis de proposer des mecanismes a l'origine des defauts d'extrusion qui permettent d'expliquer la morphologie des defauts dont l'evolution apparait liee a la texture anisotrope des extrudats et au comportement fortement plastique des pates d'argiles etudiees.

Rack clad building (RCB) is a type of warehouse building system built using steel storage racks. Generally, these structures are larger and taller compared to regular storage racks commonly seen in superstores. These are built in a way that the peripheral frame can be used to support cladding. These structures possess some unique properties such as the members are built using thin walled perforated steel sections and the beam column joints utilizes teardrop connector in down isle direction. The hysteretic behavior of these connections is usually pinched type. Due to these properties the structure shows unique behavior under lateral loading. Until now very little research work has been carried out to determine the seismic performance of these structures. As RCB is a new type of structure, there exists no guideline in the current building codes for designing these structures against seismic loading. Here, a force and a direct displacement based design (DDBD) procedure have been adapted for designing RCB structures in the down isle direction. Finally, the performances of RCB frames designed under these two different methods have been compared and an optimum design method has been recommended for such type of structures.

Digital clay is a virtual material that exists currently in many 3D design software applications. Coupled with the rapid development of 3D printing technology, clay forms designed with a computer can now be externalized into the physical world as 3D prints or, vice versa, as digital scans. Recently, advanced tools have become available to artists and designers as affordable systems marketed to the professional consumer. As a response to these developments, my research examines the learning that occurs for eight artists who have been asked to play with physical and digital clay. This research employs a multiple case study methodology to understand the challenges of learning to work with digital clay and the supporting role of physical material engagement in this process. By interviewing participants and thematically analyzing their responses, I presented the subjective experience of the artists through portraiture showcasing the educational role play assumes when engaging across physical and digital media. Findings of the study suggest that engaging physical and digital materials calls upon a broad scope of cognitive processes including recollection and mental wanderings that contributed to reflection and discovery of novel ideas. Details from unstructured interviews were presented through narrative reporting as this research also strives to make sense of the participants' experience and situate the details of the study’s context.

Present PhD thesis aimed to investigate relatively unknown properties of halloysite nanoparticles, as well as to further examine HNTs as potential drug nanocarriers. NPs loading and release characteristics were studied using model active molecules: magnesium monoperoxyphthalate (MMPP), aspirin and epirubicin. The research was fulfilled with formation of complex multi-functional nanoarchitectures, which apart from ability to deliver incorporated drugs, showed the potential of controlled and sustain release of therapeutics, biocompatible and bioresorbable characteristics as well as potential targeting abilities. Great attention was dedicated to characterization of formed halloysite-based nanoarchitectures in qualitative as well as quantitative manner. Investigations performed in this thesis also faced the problem of exceeding dimensions of halloysite units, nanoparticles aggregation, poor loading capability and dose dumping effect. Subsequently, studies for trying to find a solution to these obstacles were undertaken. Fully characterized halloysite nanoconstructs were further examined in biological field, employing different cancer cell lines. Studies on pristine halloysite nanotubes: Physico-chemical and biological properties of halloysite nanoparticles were evaluated using microscopic techniques, spectroscopic analysis, surface studies regarding charge, porosity and wettability. The thermal and time-based examination of pristine halloysite was performed as well, showing stability of HNTs alumino-silicate skeletons up to ~400 ℃ and over a long period of time (2 years) at room temperature, however with a variable amount of incorporated water molecules. Biological performance of HNTs was determined in vitro in multiple cellular systems by toxicity, cellular uptake, colocalization and accumulation studies using [3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide] tetrazolium reduction (MTT) assay and set of microscopic techniques. Aiming to deeply characterize halloysite nanoparticles, the study proceeded with employment of non-standard techniques, as multiphoton microscopy that drove to discovery of novel NPs promising capabilities. It was revealed that halloysite is able to convert light to its second harmonic, at twice of the frequency (and therefore half of the wavelength) while using high intensity femtosecond pulsed laser. Halloysite Second Harmonic Generation (SHG) signal was detected over a broad wavelength range, showed stability over a long period of time, polarization properties and quadratic dependence on the intensity of incident light. The analysis also pointed out characteristic structure properties of the nanoparticle that is lack of the center of symmetry and the high crystalline structure organization. Among a wide spectrum of domains where discovered HNTs characteristics can be utilized (e.g. optoelectronics, biosensors), we have explored its application in alternative label-free bioimaging. The proposed multiphoton method of analysis showed advantages over the standard confocal microscopy, since e.g. nanoparticles did not have to be stained prior the analysis, thus no possible alterations of HNTs including size, surface chemistry and consequent cellular uptake were induced. Therefore, for the first time, halloysite nanotubes were exploited as imaging agents, taking advantage of their endogenous properties. Along the research it was revealed that the length of pristine HNTs and the strong aggregation limit their ability to pass intracellular membranes and thus minimize their effectiveness as drug nanocarriers. Therefore, efforts were devoted to the development of facile methodology to efficiently disperse and shorten HNTs units. Set of characterizations techniques, such as Scanning Electron Microscopy (SEM) analysis with size distribution profile and nitrogen adsorption Brunauer–Emmett–Teller (BET) method revealed that the applied ultrasonication procedure resulted with longest tubes breaking and favored obtaining HNTs below 300 nm in length (39.1 % to 76 % of the batch). The number of voids among the pristine nanoparticles when packing together (123–43 nm) greatly increased (total pore volume from 0.23 cm^3/g to 0.30 cm^3/g), meaning that the nanomaterial was efficiently disaggregated as well. In vitro internalization and colocalization studies by Scanning Electron and Multiphoton Microscopy demonstrated that the sonicated halloysite were preferentially internalized via macropinocytosis within 60 min and accumulated in the perinuclear region within 24 h. Halloysite application in nanomedicine: To study halloysite potential as a carrier for drugs, we set up the preparation and characterization of hybrid nanoconstructs with model molecules such as magnesium monoperoxyphthalate hexahydrate (MMPP), a negatively charged oxidizing agent, aspirin, an anti-inflammatory drug and epirubicin, a chemotherapeutic. Chosen molecules were incorporated with 3.5 %wt, 1.1 %wt and 5.1 %wt capacity, respectively for MMPP, aspirin and epirubicin. Loading efficiency (LE) improvement was achieved through the choice of the right solvent (1), enhancement of electrostatic forces between nanoparticle and the drug, via functionalization of HNT surfaces with an active linker (2), as well as NPs structure modification leading to increase of inner lumen volume (3). Specifically, the use of water: EtOH (7:3 v/v) as a solvent instead of water, increased MMPP loading capacity up to 6.1 %wt. Poor incorporation of aspirin was improved by enhancing electrostatic forces between deprotonated aspirin molecules and modified HNTs inner walls with amine-rich organosilane. It was also demonstrated that by enlarging volume of the NPs cavities, more molecules could be loaded. To do that, pristine HNTs were treated with 0.1M aqueous solution of NaOH, which resulted in an exfoliation of bilayers located inside the lumen. At the same time, outer surface of the halloysite tubules was preserved. As a consequence of the base treatment, halloysite cylinders gained more volume in the inner cavity as concluded from Transmission Electron Microscopy (TEM) and nitrogen adsorption BET analysis. The actual test on loading capacity using model MMPP molecule revealed increased MMPP incorporation from 6.1 % wt to 11.7 %wt. To evaluate if the activity of MMPP as an oxidizing agent remained unchanged upon incorporation and release from halloysite, and therefore to demonstrate the inactivity of the inorganic skeleton towards carried molecule, we tested HNT-MMPP nanoconstruct with selective fluorescent 1,3-diphenylisobenzofuran (DPBF) probe. Among available modifications of halloysite nanoparticles via covalent bond, the surface silanization is commonly recognized as one of the most efficient and widespread reaction while HNT manipulation. Up to date, the halloysite nanotubes functionalized with silanes have been used as a support for versatile applications in diverse scientific domains, including enzymes immobilization and biosensing. Willing to explore the halloysite functionalization with those active linkers, we have performed grafting reactions with representative organosilanes carrying the same backbone, while varying in the content of terminal groups, namely (3-aminopropyl)triethoxysilane (APTES), 3-(2-aminoethylamino)propyldimethoxymethylsilane (AEAPS), (3-mercaptopropyl)trimethoxysilane (MPS). Successful HNTs surfaces functionalization with organosilanes was demonstrated by means of quantitative thermogravimetric analysis (TGA) that allowed to estimate the loading capacity of organosilanes to be of 5.7 %wt for APTES, 7.4 %wt for AEAPS and 0.7 %wt for MPS. In addition, particular attention was dedicated to further quantify incorporated organosilane (APTES), since only one method has been so far reported, that is the destructive thermogravimetric analysis (TGA). For this reason, we set up and optimized a Fmoc based method by performing the following three reactions: (i) synthesis of “APTES-Fmoc” molecule; (ii) halloysite functionalization with “APTES-Fmoc”; and (iii) time-dependent Fmoc deprotection reaction in piperidine: EtOH (20 %) solution, resulting in dibenzofulvenepiperidine adduct (DBF-pip) formation. The UV-visible spectroscopic analysis of supernatant solutions demonstrated that the DBF-pip deprotection from halloysite support needs 5 h to be completed. Therefore, it was evidenced that HNT Fmoc-method showed strong coherence with already existing TGA method (± 2 % measurement error) and stood out as a valuable complementary technique for quantification of silane grafting on HNTs surface with additional low-cost and nondestructive advantages. The possibility of using halloysite nanotubes as a non-viral gene delivery nanosystem for therapeutic treatments was studied as well. Aiming to immobilize plasmid DNA (pDNA) based on the Green Fluorescent Protein (GFP) on HNTs support, the layer-by-layer (LbL) adsorption technique was applied. Obtained multi-component assembly was characterized qualitatively by monitoring variation in nanoparticle physico-chemical properties including surface charge, mass weight, presence of functional groups at each step of hybrid formation, which confirmed the successful nanoarchitecture formation. In order to additionally demonstrate the presence of GFP encoding plasmid (pGFP) on HNTs, the nanoarchitecture was treated with the bovine pancreatic deoxyribonuclease (DNase) enzyme, which induced the pGFP degradation through hydrolytic cleavage of phosphodiester linkages in DNA backbone. Thus, as expected, such nanoform with deposed genetic material varied in physico-chemical properties, expressing similar ones of the nanoconstruct without pGFP plasmid attached. The biological efficiency of HNTs-pGFP nanosystem was checked by means of Multiphoton microscopy. Successful pGFP plasmid transportation into cells was verified by detection of GFP expression, which yielded fluorescence emission. The interesting and innovative aspect of this case study was the simultaneous observation of GFP expression via fluorescence detection, and colocalization of halloysite nanoparticles by their SHG signal. This study proved that halloysite can act as an efficient carrier of genetic material, since free pGFP cannot be internalized by same cells, due to its large size and significant charge. Drug-loaded halloysite nanoconstructs (HNT-MMPP, HNT-APTES-aspirin) were also examined on the drug release kinetics, demonstrating long-term MMPP leakage taking 18 days and aspirin over 60 min. However, great drug liberation into the solvent of release was observed in the first minutes, followed by desired sustained drug release. The initial molecule liberation (dose dumping effect) is known to entail local toxicity. Herein, trying to find a solution to this problem, the coating of HNTs with the natural collagen polymer was investigated. Two strategies for the loading with this biopolymer were studied: (i) formation of a covalent bond between collagen and APTES-modified HNTs using glutaraldehyde cross-linker or (ii) noncovalent adsorption of collagen into pores of NPs. Immobilization of collagen on the surface of HNTs was estimated to be 3.7 %wt (i) and 1.8 %wt (ii). Other supplementary characterization techniques, such as water contact angle, ζ–potential analysis, Kaiser test, ultraviolet and visible (UV-vis) spectroscopy and Fourier Transform Infrared Spectroscopy (FTIR) were in accordance and proved nanoarchitectures formation. For the visualization purpose of HNTs encapsulated in collagen shell, the innovative characterization technique was implemented, namely 3D Multiphoton microscopy. It revealed that the biopolymer coating blocked the entrances of the hollow tubes thus, entrapping the drug in NPs. Mimicking tumor microenvironment (TME), the pH and/or enzyme triggered release was performed. LC-Mass analysis revealed that the collagen coating slowed down the release of aspirin from HNTs. Studies on cells showed that the collagen coating on HNTs is biocompatible and cell viability assay performed on 5637 urinary bladder and HeLa cervical cancer cell lines demonstrated the sustained release of the entrapped epirubicin chemotherapeutic agent in the biological context. Industrial application of halloysite: During a stage in BASF SE (USA), validation and properties enhancement of halloysite-based products potentially manufacturable in the company on an industrial scale were studied. In particular, the research was dedicated to aspects such as the pH-dependent dispersion behavior of halloysite nanotubes and iron coarse impurities removal from bulk samples. Applied methodologies and set of physico-chemical characterization techniques generated and revealed decreased percentage of present aggregates, maintained low shear viscosity under the threshold value and increased solids loading capacity in final halloysite-based products. Conclusions: In conclusion, PhD studies here reported contributed to the exploration of halloysite nanotubes for their application in the nanomedical and industrial fields. The investigations suggest a facile manipulation and functionalization of HNTs, useful for properties modification and improved NPs performance. Specifically, the study was directed toward formation of multi-functional nanocarriers with controlled drug delivery and release properties, together with targeting and imaging abilities. Moreover, the research was completed with halloysite-related technology transfer to the BASF SE, for the purpose of knowledge increase in the halloysite-field and bringing forward placement of halloysite-based products on the market. The systematic study on HNTs characterization and application performed in this PhD thesis will contribute to the development of HNTs as a high performance structural and functional material.

CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICO
Um amplo trabalho de pesquisa, envolvendo extensivas investigações de campo e laboratório de um depósito de argila mole localizado na Zona Industrial de Santa Cruz, Rio de Janeiro, RJ, vem sendo desenvolvido pela PUC-Rio desde meados de 2005. Evidências de recalques em estruturas construídas nessa região têm sido reportadas desde o final da década de 70. O presente trabalho apresenta resultados de estudos de laboratório realizados visando à caracterização do depósito argiloso e a determinação de seus parâmetros de compressibilidade e adensamento. Para tanto, desenvolveu- se um programa experimental compreendendo a caracterização físico-químico- mineralógica de amostras do perfil e a execução de ensaios de adensamento edométrico e triaxial hidrostático e anisotrópico. Os experimentos em células edométricas envolveram ensaios convencionais, com medida de permeabilidade e com determinação de compressão secundária. Aspectos de qualidade das amostras ensaiadas são discutidos. Os resultados obtidos propiciaram uma estimativa do K0 do material normalmente adensado, um entendimento do estágio de adensamento hoje existente e uma estimativa preliminar de recalques que podem ainda vir a ocorrer sob as presentes condições de carregamento.
A large research work comprising extensive field and laboratory investigations on a soft clay deposit located in the Industrial Zone of Santa Cruz, Rio de Janeiro, RJ, is being developed at PUC-Rio since 2005. Occurrences of settlement of structures built in this region have been reported since the end of the decade of 1970. This work presents results of laboratory studies aiming at the characterization of the soft clay deposit and the determination of compressibility and consolidation parameters of the clay. The experimental program developed comprised physical-chemical- mineralogical characterization of samples from the soil profile and the execution of oedometric consolidation tests and hydrostatic and anisotropic triaxial tests. The experiments in oedometric cells comprised conventional tests and tests with measurement of permeability and determination of secondary compression. Aspects of quality of the samples are highlighted. The obtained results propitiated an estimation of the K0 of the normally consolidated material, an understanding of the present stage of consolidation of the deposit and a preliminary assessment of settlements that may still occur in the site under the present loading conditions.

Clas Ohlson startade ett företag i Insjön när han var 23 år gammal. Det började som ett enmansföretag och har nu vuxit till ett imperium, och nya butiker öppnar varje år. Som människa har han lämnat markanta spår efter sig i det lilla samhället i Dalarna. Här berättas om hans liv, hans minne och tvisten om hans grav.

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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)
Esta dissertação teve como objetivo desenvolver processos de confecção de Jóias de Arte ecologicamente corretas em bambu e metal clay. Para tanto foram projetados e confeccionados alguns protótipos de jóias com estes materiais, aliando o material renovável bambu e o metal clay, que é proveniente da reciclagem de chapas fotográficas e outros resíduos industriais. Foram confeccionados um anel, uma pulseira e um pingente, com partes de colmos de bambu devidamente secos, da espécie Dendrocalamus giganteus, fornecidos pelo Laboratório de Bambu do Cmpus da UNESP de Bauru, e a Prata metal clay, da marca Mitsubishi materials. As jóias foram produzidas de acordo com o instrumento de análise ecológica de produtos joalheiros. Foram avaliados parâmetros como: custo, tempo de feitio, treinamento, ferramentas e maquinários utilizados, durabilidade da peça e resíduos gerados. No final foram propostas as etapas necessárias para a confecção de jóias em bambu e metal clay, associando o design a processos mais enxutos, eficazes e seguros na produção artesanal destas
This study aimed to develop eco-friendly art jewelry in precious metal clay and bamboo. Therefore, it was designed and made some art jewelry prototypes with these materials, combining renewable bamboo material and metal clay that comes from the recycling of photographic plates and others industrials wastes. Initially, a ring, a bracelet and a pendant were made using wastes of dried culms of Dendrocalamus giganteus bamboo and silver metal clay of Mitsubishi materials. The pieces were produced according produced according to the analysis chart of ecological products jewelry. The evaluated parameters were: cost, producing time, necessary training, used tools and machinery, durability and generated waste. As a result, proposals were made for the necessary procedures to make jewerly with bamboo and metal clay, combining design with streamlined, efficient and safe processes to make those pieces

In response to water quality deterioration caused by clam processing effluent, the Virginia State Water Control Board is imposing much greater effluent discharge limitations on the industry. Meeting these limits will require increased wastewater treatment and decreasing the water volume of water used and the loading of organic material and suspended solids. Disposal of sludges and solid wastes also present problems to the industry. Three processing plants were studied to characterize the nature, sources and variations in waste generation and to evaluate potential solutions. Wastewater is generated throughout the processing plants from washing operations, from splashing and overflow of tanks and flumes and from cleanup operations. Wastewater generation varied from plant to plant and at each plant over time, ranging from 80,000 gallons to almost 350,000 gallons per day and as high as 40,000 gallons per hour. The organic loading in wastewater ranged as high as 15,000 mg/L COD and averaged 3000-7000 mg/L. Total suspended solids loading ranged as high as 29,000, and were usually between 1,000 and 10,000 mg/L. Anaerobic digestion and composting of solid wastes were evaluated by bench scale experiments. Anaerobic digestion can provide reduction in COD of 75% and generate usable biogas. Composting can be used to stabilize sludges and solid wastes with destruction of the organic fraction in seven days. The proposed 90 mg/L BOD and 90 mg/L TSS limitations are not significantly stricter than the limitations imposed on similar plants in other areas.
Master of Science

Orientador: Marco Antonio dos Reis Pereira
Banca: Marizilda dos Santos Menezes
Banca: Antonio Ludovico Beraldo
Resumo: Esta dissertação teve como objetivo desenvolver processos de confecção de Jóias de Arte ecologicamente corretas em bambu e metal clay. Para tanto foram projetados e confeccionados alguns protótipos de jóias com estes materiais, aliando o material renovável bambu e o metal clay, que é proveniente da reciclagem de chapas fotográficas e outros resíduos industriais. Foram confeccionados um anel, uma pulseira e um pingente, com partes de colmos de bambu devidamente secos, da espécie Dendrocalamus giganteus, fornecidos pelo Laboratório de Bambu do Cmpus da UNESP de Bauru, e a Prata metal clay, da marca Mitsubishi materials. As jóias foram produzidas de acordo com o instrumento de análise ecológica de produtos joalheiros. Foram avaliados parâmetros como: custo, tempo de feitio, treinamento, ferramentas e maquinários utilizados, durabilidade da peça e resíduos gerados. No final foram propostas as etapas necessárias para a confecção de jóias em bambu e metal clay, associando o design a processos mais enxutos, eficazes e seguros na produção artesanal destas
Abstract: This study aimed to develop eco-friendly art jewelry in precious metal clay and bamboo. Therefore, it was designed and made some art jewelry prototypes with these materials, combining renewable bamboo material and metal clay that comes from the recycling of photographic plates and others industrials wastes. Initially, a ring, a bracelet and a pendant were made using wastes of dried culms of Dendrocalamus giganteus bamboo and silver metal clay of Mitsubishi materials. The pieces were produced according produced according to the analysis chart of ecological products jewelry. The evaluated parameters were: cost, producing time, necessary training, used tools and machinery, durability and generated waste. As a result, proposals were made for the necessary procedures to make jewerly with bamboo and metal clay, combining design with streamlined, efficient and safe processes to make those pieces
Mestre

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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior
Materials based on graphene oxide and different types of clays are two classes of materials with unique properties and with several applications, highlighting the adsorption capacity of some dyes, metals and organic compounds. The combination of these structures can lead to significant improvements in their properties through the synergism of the two species. Methylene blue, a cationic dye widely used in many types of industries, has considerable toxicity and causes biological imbalances when discarded in the wrong way. Because it is a low-cost, high-application material, it is of great concern to health organizations as it can cause irreversible damage when discarded or stored in the wrong way in the environment. Thus, the need for treatments to remove this material from nature becomes more and more and among the various available techniques, the adsorption is one of the most outstanding, due to its ability to remove the material from the contaminated medium without compromising the medium, however the materials currently used have a number of disadvantages, such as high cost and considerable efficiency. The purpose of this work was to obtain and characterize a hybrid material consisting of the deposition of graphene oxide (GO) under porcelain based on a mixture of clay and paper, and its application as adsorbent material of the dye methylene blue. The kinetic studies showed that hybrid materials with different proportions of GO (400μL and 1200μL) were tested as adsorbent matrices, showing in their results that the higher proportion of GO in the compound improves the adsorption power, reaching 98% of the dye, due to the high surface area of the carbonaceous material and its negative charge surface are attractive for the retention of the cationic dye, since the interaction between the materials is given primarily by electrostatic attraction. Another factor that influenced the retention power of the dye in the matrix was the basic medium in which the dye was, since when it immersed the matrix, the molecules of methylene blue began to interact with it. The use of paper clay as an adsorber matrix also allowed the reuse and recycling of the matrices, since after the first use there were still active sites in the matrices and after their saturation, sintering them again it was possible to eliminate the materials of its surface, allowing so its re-use with GO deposited again.
Materiais à base de óxido de grafeno e diferentes tipos de argilas são duas classes de materiais com propriedades únicas e com diversas aplicações, destacando a capacidade de adsorção de alguns corantes, metais e compostos orgânicos. A combinação destas estruturas pode levar a melhorias significativas em suas propriedades, através do sinergismo das duas espécies. O azul de metileno, um corante catiônico muito utilizado em diversos tipos de industrias, apresenta toxicidade considerável, além de causar desequilíbrios biológicos quando descartados de maneira equivocada. Por se tratar de um material de baixo custo e de grande aplicação, ele demonstra uma grande preocupação para as organizações de saúde, uma vez que podem causar danos irreversíveis quando descartados ou armazenados de forma equivocada no meio ambiente. Sendo assim a necessidade de tratamentos para remover este material da natureza se torna cada vez maior e dentre as diversas técnicas disponíveis a adsorção é uma da que mais se destaca, devido a sua capacidade de remover o material do meio contaminado sem comprometer o meio, porém os materiais utilizados atualmente apresentam uma série de desvantagens, tais como alto custo e eficiência considerável. Sendo assim este trabalho teve como finalidade a obtenção e caracterização de um material híbrido constituído pela deposição de óxido de grafeno (GO) sob uma porcelana baseada em mistura de argila e papel (paper clay - PC), e sua aplicação como material adsorvente do corante azul de metileno. Através de estudos cinéticos, os materiais híbridos com diferentes proporções de GO (400μL e 1200μL) foram testados como matrizes adsorventes, mostrando em seus resultados que a maior proporção de GO no composto, melhora o poder de adsorção, chegando a 98% de retenção do corante, devido a elevada área superficial do material carbonáceo e sua superfície de carga negativa são atrativos para a retenção do corante catiônico, uma vez que a interação entre os materiais se dá primordialmente por atração eletrostática. Outro fator que influenciou o poder de retenção do corante pela matriz foi o meio básico em que o corante se encontrava, uma vez que quando imersa a matriz, as moléculas de azul de metileno passaram a interagir com a mesma. A utilização do paper clay como matriz adsorvedora permitiu ainda a reutilização e reciclagem das matrizes, uma vez que após a primeira utilização ainda restaram sítios ativos nas matrizes e após a sua saturação, sinterizando-as novamente foi possível eliminar os materiais de sua superfície, permitindo assim a sua reutilização com GO depositado novamente.

Orientadores: Meuris Gurgel Carlos da Silva, Valdinete Lins da Silva
Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica
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Resumo: As indústrias têxteis constituem fator de grande importância na economia brasileira e são agrupadas em três categorias principais de fibras: tecidos de algodão, de lã e sintéticos. O impacto ambiental provocado pelo setor, a geração de efluentes líquidos se constitui num parâmetro representativo como fator potencialmente poluidor. Além disso, é uma das tipologias industriais que mais consomem água em seu processo produtivo. Um dos maiores problemas ambientais gerados durante o processo de tingimento nas lavanderias industriais é a grande quantidade de despejos altamente poluidores, contendo elevada carga de substâncias tóxicas, dentre estas os corantes. A avaliação da remoção de cor dos efluentes é fundamental tanto para o controle ambiental, uma vez que a cor interfere nos processos biológicos dos ecossistemas aquáticos. Os objetivos propostos para o desenvolvimento da tese visam contribuir com informações para a minimização de problemas ambientais, promovendo a avaliação dos sistemas de remoção de cor de efluentes têxteis e elaborando uma proposta para um sistema técnico e economicamente viável visando sua aplicação em pequenas e médias empresas. Neste trabalho estudou-se a utilização como adsorvente uma argila esmectita, que se constitui em um resíduo de grande disponibilidade na Região do Araripe em Pernambuco - Brasil, num processo de remoção de corante em efluente típico de tingimento de lavanderias industriais através de dois métodos: o mais simples, em banho finito e posteriormente em leito fixo, mais aplicável à realidade das referidas empresas. Os resultados demonstraram um bom potencial do processo visto que foram obtidos valores de remoção de corante acima de 90%. Uma modelagem matemática foi feita a fim de obter uma equação empírica que reproduzisse o fenômeno de adsorção para diversas vazões dentro da faixa de dados experimentais disponíveis, tendo sido obtido uma equação com boa capacidade de previsão de resultados
Abstract: The textile industries constitute factor of great importance in the Brazilian economy and are grouped in three main staple fiber categories: fabrics of cotton, woolen and synthetic. The environment impact provoked by the sector, the generation of effluent liquids if constitutes in a representative parameter as potentially polluting factor. Moreover, it is one of the industrial typology that more consumes water in its productive process. One of the biggest generated environment problems during the process of dyeing in the industrial laundries is the great amount of highly polluting spilling, contends high toxic substance load, amongst these the dyes. The evaluation of the removal of color of the effluent ones is basic in such a way for the environmental control, a time that the color intervenes with the biological processes of aquatic ecosystems. The objectives considered for the development of the thesis aim at to contribute with information for the minimization of environmental problems, promoting the evaluation of the systems of dye¿s removal of textile effluent and elaborating a proposal for a system small economically viable technician and aiming at its application in small and measured companies. In this work it was studied use as adsorbent a esmectita clay, that if constitutes in a residue of great availability in the Region of the Araripe in Pernambuco ¿ Brazil, in a dye's removal process in the typical effluent of the dyeing of industrial laundries, through two methods: simplest, in batch equilibrium and later in fixed bed, more applicable to the reality of the related companies. The results had demonstrated a good potential of the process since values of removal of dyes above of 90% had been gotten. A mathematical modeling was made in order to get an empirical equation that inside reproduced the adsorption phenomena for diverse outflows of the band of experimental data available, getting an equation with high capacity of forecast of results
Doutorado
Engenharia de Processos
Doutor em Engenharia Química

The Karak mudstone, cropping out in the vicinity of Karak town, NW Pakistan, is contained within an Eocene evaporitic sequence deposited in the rapidly sinking Kohat foreland basin. It was buried beneath 5 Km of younger sedimentary rocks. Illite-smectite with 20 to 30% expandable component is the most dominant clay mineral, which has converted from detrital smectite or highly expandable illite-smectite in a diagenetic environment at ~ 100 C. Time does not seem to be have played any significant role in the conversion of smectite layers to illite layers. The A1 and K necessary for the conversion reaction was provided by the breakdown of detrital K-feldspar. Muscovite does not seem to have contributed to this process as suggested by previous studies. Direct lattice images of illite-smectite revealed that conversion of smectite layers to illite layers took place through dissolution of smectite layers and precipitation of illite layers as well as by solid state mechanism. Whole rock chemical analysis suggests that the mudstone is a product of severe weathering of the source area which was mainly composed of acidic rocks. Depleted ions like Ba, Rb, Ca and Mn were probably flushed out from the restricted basin by influx of fresh water. The swelling properties of Karak mudstone are low and even Na activation does not enhance these properties. The smectite layers may already have undergone natural Na activation due to original sea water and pore water hypersalinity. Cation exchange capacity and total surface area values are also low, which suggests this material is unsuitable for most major bentonite related uses. Owing to the higher concentration of Mg and Fe ions in the octahedral site of illite-smectite these clays were easily activated with HCl. Acid activation also increased surface area as measured by BET method. Bleaching performance of activated material measured on rapeseed oil showed optimum bleaching capacity of 90% following treatment with 2N HCl for three hours or 3N HCl for two hours. The maximum bleaching capacity was not associated with maximum surface area. Pilot plant scale tests should be carried out to investigate the potential for industrial applications of this material.

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Capes
O presente trabalho trata do estudo teórico e experimental do processo de secagem de argila bentonita em secador rotativo contínuo industrial. Foram realizados testes experimentais em campo, onde foi possível coletar e medir parâmetros geométricos do secador, fluxo mássico, temperatura do ar e do material. Foi estabelecido um modelo matemático a ser utilizado para a análise da eficiência global teórica idealizada e real do secador rotativo. Resultados teóricos do teor de umidade, temperatura do ar e do material na saída do secador, além da eficiência global do equipamento em várias condições de secagem foram apresentados e analisados. Verificou-se que o modelo real da simulação mostrou que o secador rotativo quando operado em certas condições ambientes na planta de instalação possui eficiência e desempenho adequado conforme sugere a literatura. Parâmetros como tempo de residência, velocidade rotacional e velocidade do ar quando manipulados corretamente pode-se obter melhores resultados na secagem do produto de argila bentonita visando a redução do consumo de combustível. Além dos testes dos parâmetros, sugestões para futuros estudos como, a determinação da cinética de secagem e curvas de sorção da argila são de essencial importância para garantir a especificação do teor de umidade final do produto.
The present work deals with the theoretical and experimental study of the drying process of bentonita clay in an industrial continuous rotary dryer. Experimental tests were performed in the field, where it was possible to collect and measure geometric parameters of the dryer, mass flow, air and material temperature. It was proposed a mathematical model to be used for the analysis of the idealized and real theoretical global efficiency of the rotary dryer. Theoretical results of moisture content, air temperature and material at the dryer outlet, besides the overall equipment efficiency under various drying conditions were presented and analyzed. It was verified that the real simulation model showed that the rotary dryer when operated in certain ambient conditions in the installation plant has efficiency and adequate performance as suggested by the literature. Parameters such as residence time, speed of rotation and air velocity when handled properly, better results can be obtained in the drying of the bentonita clay product in order to reduce fuel consumption. In addition to the parameter tests, as future studies, the determination of drying kinetics and sorption curves of the clay are of essential importance to ensure the specification of the final moisture content of the product.

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Particularly in Braziland in Rio Grande do Norte, companies manufacturing red ceramic, play an important role as agents of development to study the region Serid?- RN, specific place for carrying out the research. It is observed in this region a concentration of red ceramic industries of small size, which, despite its importance in the ceramic, they are unable to enjoy or use the new forms of administrative management and technological advances designed and offered by universities, centers of research and projects of governments, remained almost entirely outside the progress and modernization, technological and administrative. These companies still have outdated technology, and management processes, providing quality problems and standardization of end products. Upon these conditions are the companies going through crisis and struggling to survive alone and without assistance. The region of Serid?-RN, lets make a detailed case study of red ceramic companies in the region proposed from the existing theoretical and actual lifting of the condition of the product manufacturing red ceramic, allowing through this overview of the implementation of collect samples of raw materials, allowing the study of each ceramic industry that contributed to the participation of the research, which was determined parameters such as: analysis of the physical, chemical and technological properties of raw materials, characterization of the processes used, raising the technological resources considering equipment, machinery, supplies, raw materials and facilities available and its organization by type of products from companies involved in this study. The methodology consists of the following steps: collection of raw material, crushing and screening, characterization of raw materials (liquid limit, chemical analysis, mineralogical analysis, differential thermal analysis, sieve analysis), mixing, forming, cutting, drying and burning of ceramic bodies and bodies of evidence. The results showed that it was clay with distinct characteristics with respect to plasticity. With respect to the different compositions of mixtures of ceramic masses, we conclude that the ceramic properties showed a direct proportionality with increasing fraction of the clay not plastic. However, the compositions of the masses studied proved to be the most appropriate for the types of simulated clay for use in ceramics. Adopted in the ceramic processing made it possible to obtain products the resulted in consistent properties, and in some cases even exceeding the requirements of technical studies and standard-Brazilian clays to obtain ceramic products such as tiles, bricks and tiles to floor. Based on the discussions from the results obtained in the various processing steps of this work, one can draw conclusions according to the physico-chemical and mineralogical properties of raw materials, the properties of ceramic products burned and analysis. This work may be used by other researchers, private companies and governmental organizations, undergraduate students and graduate, can develop studies and future research to: develop projects to modify the furnaces; mapping projects develop and rationalize the exploitation of raw materials ;promoting reforestation and forest management; develop reduction projects and recovery of waste; develop training projects in manpower sector, and develop security projects, improving the conditions of work in the area pottery
No Brasil e particularmente no Estado do Rio Grande do Norte, as empresas de fabrica??o de cer?mica vermelha, representam um papel importante como agentes de desenvolvimento de estudo para a regi?o do Serid?-RN, local determinado para a realiza??o das pesquisas. Observa-se nesta regi?o uma concentra??o de ind?strias de cer?mica vermelha de pequeno porte, que, apesar de sua import?ncia no contexto cer?mico, estas n?o conseguem usufruir ou utilizar as novas formas de gerenciamento administrativo e de avan?os tecnol?gicos concebidos e propostos pelas Universidades, centros de pesquisas, bem como dos projetos dos Governos, permanecendo na sua quase totalidade ? margem dos avan?os e da moderniza??o, tanto tecnol?gico como administrativo. Estas empresas apresentam ainda processos tecnol?gicos e gerenciamentos ultrapassados, propiciando problemas de qualidade final e padroniza??o de seus produtos. Mediante estas condi??es ficam as empresas atravessando crises e lutando para sobreviverem isoladas e sem assist?ncia. A regi?o do Serid?-RN, permite efetuar um estudo de caso detalhado das empresas de cer?mica vermelha na regi?o proposta, a partir do referencial te?rico existente e do levantamento real da condi??o de fabrica??o do produto cer?mico vermelho, possibilitando atrav?s deste panorama geral a realiza??o da coleta de amostras de mat?rias primas, permitindo o estudo de cada ind?stria cer?mica vermelha que contribuiu na participa??o da pesquisa, onde foi determinado par?metros tais como: an?lise das propriedades f?sicas, qu?micas e tecnol?gicas das mat?rias primas, caracteriza??o dos processos utilizados, levantamento dos recursos tecnol?gicos considerando equipamentos, m?quinas, insumos, mat?rias primas e instala??es dispon?veis e a organiza??o dos mesmos por tipologia de produtos das empresas envolvidas neste estudo. A metodologia aplicada consta das seguintes etapas: coleta da mat?ria prima, moagem e peneiramento, caracteriza??o das mat?rias-primas (limite de liquidez, an?lise qu?mica, an?lise mineral?gica, an?lise t?rmica diferencial, an?lise granulom?trica), mistura, conforma??o, corte, secagem e queima das massas cer?micas e nos corpos de prova. Os resultados obtidos revelaram tratar-se de argilas com caracter?sticas distintas com rela??o ? plasticidade. Com rela??o ?s diversas composi??es das misturas das massas argilosas, conclu?mos que as propriedades cer?micas apresentaram uma rela??o direta de proporcionalidade com o aumento da fra??o da argila n?o pl?stica. No entanto, as composi??es das massas estudadas mostraram-se as mais adequadas para os tipos de argilas simuladas para aplica??o em cer?mica. No processamento cer?mico adotado, possibilitou obterem-se produtos que resultaram em propriedades compat?veis e, em alguns casos, at? superiores as exig?ncias das normas t?cnicas e estudos de argilas padr?o-brasileiras para a obten??o de produtos de cer?mica, tais como, telha, tijolos e lajotas para piso. Tendo como base ?s discuss?es realizadas a partir dos resultados obtidos nas diversas etapas de processamento deste trabalho, podem-se elaborar conclus?es de acordo com as caracter?sticas f?sico-qu?micas e mineral?gicas das mat?rias-primas, das propriedades cer?micas dos produtos queimados e das an?lises. O presente trabalho poder? ser utilizado por outros pesquisadores, empresas privadas e governamentais, estudantes de Gradua??o e P?s-Gradua??o, podendo desenvolver estudos e pesquisas futuras para: Desenvolver projetos de modifica??o dos fornos; Desenvolver projetos de mapeamento e racionaliza??o da explora??o de mat?rias-primas; Desenvolver projetos de reflorestamento e manejo florestal; Desenvolver projetos de redu??o e aproveitamento de res?duos; Desenvolver projetos de capacita??o da m?o-de-obra setorial, e Desenvolver projetos de seguran?a do trabalho visando ? melhoria das condi??es laborais na ?rea cer?mica

Aquest treball neix amb l’objectiu de descriure les aules intel·ligents analitzant-ne els elements diferenciadors, les dimensions i les interrelacions, per comprendre quines són les tendències que poden proporcionar millores en els processos d’ensenyament-aprenentatge dels estudiants del segle XXI. Per fer-ho, s’utilitza una metodologia d’investigació exploratòria que permet recollir dades i concatenar resultats per ampliar-ne el marc referencial. Atenent que el present document compendia un total de dotze publicacions, les tècniques i els instruments de recerca utilitzats són variats, tant des del punt de vista qualitatiu com quantitatiu: revisions sistemàtiques de la literatura i aproximacions teòriques amb valoració d'experts, entrevistes, grups focals, anàlisi documental i tests objectius. La fonamentació teòrica permet contextualitzar la Quarta Revolució Industrial i el seu potencial en educació. Com a resultat, s’introdueix una definició de les escoles intel·ligents, que han d’estar dotades de sistemes de gestió integral i solucions automatitzades, han d’estar centrades en les persones i ser inclusives, i han de ser sostenibles, amb l’objectiu d’acollir una educació intel·ligent tot adoptant de manera eficient noves metodologies d’aprenentatge i avenços de la Quarta Revolució Industrial. També es conceptualitzen i es defineixen les aules intel·ligents mitjançant la dimensionalització de les seves característiques, i es descriuen les característiques principals que han de tenir quant a tecnologia, factors ambientals i processos pedagògics. Es posa especial èmfasi en les condicions ambientals, ja que es detecta que són influents en els processos d’ensenyamentaprenentatge i representen un camí rellevant per a la innovació a les aules. S’estudien en profunditat els dos temes més rellevants: il·luminació i acústica. Els resultats emergents de la recollida de dades mostren diverses implicacions de les smart classrooms i el seu nivell de maduresa. Val a destacar, d’una banda, que els centres educatius de Catalunya estan disposats a respondre a les innovacions pedagògiques que comporti l’arribada de la Indústria 4.0, però encara no estan preparats per obtenir uns resultats eficients. D’altra banda, es destaca l’efectivitat de sistemes dinàmics per controlar la il·luminació a l’aula.
Este trabajo nace con el objetivo de describir las aulas inteligentes analizando sus elementos diferenciadores, sus dimensiones y sus interrelaciones, para comprender cuáles son las tendencias que pueden proporcionar mejoras en los procesos de enseñanza-aprendizaje de los estudiantes del siglo XXI. Para hacerlo, se utiliza una metodología de investigación exploratoria que permite recoger datos y concatenar resultados para ampliar el marco referencial. Atendiendo que el presente documento compendia un total de doce publicaciones, las técnicas e instrumentos de investigación utilizados son variados, tanto de carácter cualitativo como cuantitativo: revisiones sistemáticas de la literatura y aproximaciones teóricas con valoración de expertos, entrevistas, grupos focales, análisis documental y tests objetivos. La fundamentación teórica permite contextualizar la Cuarta Revolución Industrial y su potencial en educación. Como resultado, se introduce una definición de las escuelas inteligentes, que deben estar dotadas de sistemas de gestión integral y soluciones automatizadas, deben estar centradas en las personas y ser inclusivas, y deben ser sostenibles, con el objetivo de acoger una educación inteligente adoptando de manera eficiente nuevas metodologías de aprendizaje y avances de la Cuarta Revolución Industrial. También se hace una conceptualización y definición de las aulas inteligentes mediante una dimensionalización de sus características, y se describen las características principales que deben tener en cuanto a tecnología, factores ambientales y procesos pedagógicos. Se pone especial énfasis en las condiciones ambientales, ya que se detecta que son influyentes en los procesos de enseñanza-aprendizaje y representan un camino relevante para la innovación en las aulas. Se estudian en profundidad los dos temas más relevantes: iluminación y acústica. Los resultados emergentes de la recogida de datos muestran varias implicaciones de las smart classrooms y su nivel de madurez. Cabe destacar, por un lado, que los centros educativos de Cataluña están dispuestos a hacer frente las innovaciones pedagógicas que comporte la llegada de la Industria 4.0, pero aún no estarían preparados para obtener unos resultados eficientes. Por otra parte, se destaca la efectividad de sistemas dinámicos para controlar la iluminación.
This work started with the aim of describing smart classrooms by analyzing their differentiating elements, their dimensions and their interrelationships, in order to understand what are the trends that can provide improvements in the teaching and learning processes of 21st century students. To do this, an exploratory research methodology is used to collect data and concatenate results to expand the reference framework. Given that this work summarizes a total of twelve publications, the research techniques and instruments used are varied, both qualitative and quantitative: systematic literatura reviews and theoretical approaches with expert assessment, interviews, focus groups, documentary analysis and objective tests. The theoretical foundation allows to contextualize the Fourth Industrial Revolution and its potential in education. As a result, a definition of smart schools is introduced, which must be equipped with comprehensive management systems and automated solutions, must be people-centered and inclusive, and must be sustainable, with the goal of hosting smart education while efficiently adopting new learning methodologies and advances from the Fourth Industrial Revolution. There is also a conceptualization and definition of smart classrooms through a dimensionalization of their characteristics, and describe the main characteristics they must have in terms of technology, environmental factors and pedagogical processes. Special emphasis is placed on environmental conditions, as they are found to be influential in teaching and learning processes and represent a relevant path for innovation in classrooms. The two most important topics are studied in depth: lighting and acoustics. The emerging results of data collection show various implications of smart classrooms and their level of maturity. It is worth noting, on the one hand, that the educational centers of Catalonia are ready to face the pedagogical innovations that the arrival of Industry 4.0 entails, but they would not yet be prepared to obtain efficient results. On the other hand, the effectiveness of dynamic systems for controlling lighting in the classroom is highlighted, as a first step in automating environmental conditions in a smart classroom.

CNPq; Fundação Araucária
A região Sul do Brasil, em especial, os estados do Paraná e Santa Catarina destacam-se pelo cultivo de uvas e maçãs para consumo in natura e, visando agregar valor a estes produtos, processam o material para a elaboração de vinhos, sucos e geleias. Como resultado grandes quantidades de coprodutos, como cascas, sementes e bagaço, são produzidos tornando-se problemas ambientais. Estudos de reaproveitamento desses coprodutos têm despertado interesse, pois têm demonstrado um elevado potencial biológico, em virtude da presença de altos teores de compostos fenólicos, que são associados a uma menor incidência de doenças ocasionadas pelo estresse oxidativo, devido as suas propriedades antioxidantes, anti-inflamatórias e antibacterianas. Atualmente, poucos estudos são apresentados sobre a composição fenólica e potencial biológico dos resíduos de uvas da variedade Bordô (Vitis labrusca) e maçã (Malus domestica) variedade Gala, cultivadas na região Sul do Brasil. Dentro deste contexto, os objetivos desse estudo foram: comparar a eficiência da extração sólido-líquido e líquido-líquido, realizar a otimização e validação de metodologia analítica por CLAE-DAD para a separação, identificação e quantificação de compostos fenólicos multiclasses, avaliar a atividade antioxidante pelos métodos de sequestro dos radicais livres 2,2 difenil-1- picrilhidrazina (DPPH) e 2,2-azino-bis-(3-etil-benzotiazolina-6-ácido sulfônico) (ABTS), método de redução do Fe3+ a Fe2+ (FRAP), ORAC, CLAE-FR-ABTS on-line, Rancimat e determinação de compostos fenólicos totais de três coprodutos agroindustriais, bagaço e engaço de uva Bordô produzidos na região Sudoeste do Paraná e bagaço de maçã Gala oriundo do Oeste de Santa Catarina. A otimização e validação do método cromatográfico apresentaram parâmetros de qualidade satisfatórios para os compostos de interesse e a extração sólido-líquido foi o mais eficiente em extrair os fenólicos avaliados. Os três coprodutos avaliados apresentaram teores significativos de compostos fenólicos quando analisados por CLAE, principalmente os flavonoides catequina e epicatequina, além de apresentaram significativa capacidade antioxidante. O extrato do engaço de uva apresentou a maior capacidade de sequestro dos radicais DPPH e ABTS e redução do ferro, além de elevado teor de compostos fenólicos totais. O extrato do bagaço de maçã apresentou a melhor resposta para o método Rancimat, o que indica elevado potencial em proteger o óleo da oxidação lipídica, não apresentado diferença significativa quando comparado ao antioxidante sintético TBHQ. Os resultados obtidos neste estudo demonstraram que os coprodutos agroindustriais analisados, são ricos em compostos fenólicos de alta capacidade antioxidante e, portanto, devem ser melhor explorados pelas indústrias de alimentos e farmacêutica.
The southern region of Brazil, especially the states of Parana and Santa Catarina stand out for growing grapes and apples for fresh consumption and in order to add value to these products, process the material for the production of wine, juices and jellies . As a result large quantities of by-products, such as peels, seeds and pulp are produced becoming environmental problems. Studies reuse of these by-products have attracted interest because they have shown a high biological potential, due to the presence of high levels of phenolic compounds, which are associated with a lower incidence of disease caused by oxidative stress, due to its antioxidant, antiinflammatory and antibacterial properties. Currently, few studies are presented on the phenolic composition and biological potential of waste grape variety Bordô (Vitis labrusca) and apple (Malus domestica) Gala variety, cultivated in southern Brazil. Within this context, the objectives of this study were: compare the efficiency of solidliquid and liquid-liquid extraction, perform the optimization and validation of analytical methodology by HPLC-DAD for the separation, identification and quantification of multiclass phenolic compounds, evaluate the activity antioxidant by sequestering methods of free radical 2,2-diphenyl-1 picrilhidrazina (DPPH) and 2,2-azino-bis (3- ethyl-benzthiazoline-6-sulphonic acid) (ABTS) solution, reduction of Fe3+ in Fe2+ method (FRAP), ORAC, RP-HPLC-ABTS online, Rancimat and determination of total phenolics three agro-industrial byproducts, pomace and stems grape Bordô produced in Paraná Southwest region and Gala apple pomace coming from the Santa Catarina West. Optimization and validation of chromatographic method showed satisfactory quality parameters for the compounds of interest and the solidliquid extraction was more efficient in extracting phenolic evaluated. The three byproducts evaluated showed significant levels of phenolic compounds when analyzed by HPLC, especially flavonoids, catechin and epicatechin besides that showed significant antioxidant capacity. The grape stems extract had the highest sequestration capacity of DPPH and ABTS radical and reduced iron, and high content of phenolic compounds. The apple pomace extract showed the best response to the Rancimat method, which indicates a high potential to protect the oil from lipid oxidation, was no significant difference when compared to synthetic antioxidant TBHQ. The results of this study showed that the agro-industrial coproducts analyzed are rich in phenolic compounds of high antioxidant capacity and therefore must be better explored by the food and pharmaceutical industries.

The present work has the objective to characterize technologically five clays used in ceramics sectors in Brazil. Its potential to produce synthetic aggregate of calcined clay to replace brittle in concrete production was evaluated. The clays were characterized by granulometry, plasticity index, X - ray diffraction, differential thermal and gravimetric analysis, dilatometric analysis, X - ray fluorescence, organic matter content, cation exchange capacity, specific area. Test specimens were produced by uniaxial pressing at 30 MPa in a rectangular (60x20x12 mm3) and cylindrical (20 in height and 20 mm in diameter) and fired at 1100oC. It was observed that 1-PIN, 2-IN and 4 -MA were the ones that presented better results of water absorption, compressive strength and apparent specific mass due to the range of flux oxides presented (4.5 to 5.9%), fire loss between (3.8 and 8.8 %) and low organic matter content (<3.4%). The specimens of the ceramic formulations without and with incorporation of 5,10 and 20% of packaging glass waste were fired and subsequently characterized. It was observed that, after fired at 1100oC, all the formulations presented parameters of mechanical resistance to compression, water absorption and specific mass comparable to those of the gravel, with the exception of the mass containing 20% of waste that presented the same results when fired at 1000oC, contributing to reduce the fired temperature and reduce the environmental impact.
O presente trabalho tem por objetivo caracterizar tecnologicamente cinco argilas utilizadas em setores de cerâmica no Brasil. Sua potencialidade para produzir agregado sintético de argila calcinada para substituir britas na produção de concreto foi avaliada. As argilas foram caracterizadas por ensaios de granulometria, índice de plasticidade, difração de raios X, análise térmica diferencial e gravimétrica, análise dilatométrica, fluorescência de raios X, teor de matéria orgânica, capacidade de troca de cátions, área específica. Corpos de prova foram produzidos por prensagem uniaxial a 30 MPa, em formato retangular (60x20x12 mm3) e cilíndrico (20 de altura e 20 mm de diâmetro) e queimados a 1100oC.Foi observado que as argilas 1-PIN, 2-IN e 4-MA foram as que apresentaram melhores resultados de absorção de água, resistência a compressão e massa específica aparente devido à faixa de óxidos fundentes apresentados (4,5 a 5,9%), perda ao fogo entre (3,8 e 8,8%) e baixo índice de matéria orgânica (< 3,4%). Os corpos das formulações cerâmicas sem e com incorporção de 5,10 e 20% de resíduo de vidro de embalagem, foram queimados e posteriormente caracterizados. Foi observado que, após queima a 1100oC todas as formulações apresentaram parâmetros de resistência mecânica a compressão, absorção de água e massa específica comparáveis aos da brita, com excessão da massa contendo 20% de resíduo que apresentou os mesmos resultados quando queimados a 1000oC, contribuindo para redução da temperatura de queima e o impacto ambiental provocado pelo resíduo descartado.
São Cristóvão, SE

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Capes
O aumento da produção industrial tem proporcionado à geração de efluentes aquosos contaminados com íons de metais pesados. Esses devem ser tratados antes de serem descartados no meio ambiente. Por este motivo é muito importante à utilização de processos para reduzir ou eliminar metais pesados presentes em efluentes industriais. Dentre os vários processos existentes, a adsorção apresenta grande eficiência na remoção de metais presentes em baixas concentrações. As argilas têm apresentado ótimos resultados em processos de adsorção de metais pesados, o que motiva a busca por argilas que possuam maior afinidade com cada tipo de metal. Neste trabalho as argilas naturais esmectiticas Chocobofe e Chocolate B proveniente do estado da Paraíba foram investigadas com o objetivo de avaliar sua afinidade e capacidade para remoção de cádmio, chumbo e zinco. Realizou-se, inicialmente, a caracterização das argilas pelas técnicas: Difração de Raios X; Análises químicas; Análises térmicas (diferencial e gravimétrica); Espectroscopia na região do infravermelho; Adsorção Física de Nitrogênio; Microscopia eletrônica de varredura e capacidade de troca de cátions. Depois de caracterizadas, as argilas foram avaliadas quanto a sua capacidade de remoção (qeq) e seu percentual de remoção (%Rem) para os metais (Cádmio, Chumbo e Zinco), presentes em efluente sintético, através de sistema de banho finito. De forma a se obter uma maior eficiência na remoção dos metais, foi realizado um planejamento fatorial 22 avaliando duas variáveis de entrada: concentração inicial de metais pesados (10, 30 e 50 ppm) e pH (3, 4 e 5), para determinar as melhores condições de trabalho, no qual se verificou que o pH= 5 e concentração inicial de 50 mg/g foram as condições que apresentaram melhores resultados alcançando Valores de 88,54-99,44% de percentagem de remoção e 3,36-4,43 mg/g de capacidade de remoção. A partir desses dados foram desenvolvidos estudos cinéticos e isotermas de equilíbrio que serviram de dados para avaliar a capacidade de adsorção das argilas com ajustes feitos através dos modelos de Langmuir, Freundlich e Redlich-Peterson. Os resultados dos testes cinéticos indicaram que o processo de remoção dos íons Cd2+, Pb2+ e Zn2+ pelas argilas se aplicam ao mecanismo do modelo de velocidade de pseudo-segunda ordem, sendo necessário um tempo de 10 minutos para alcançar o equilíbrio. Os modelos matemáticos adotados para a modelagem dos dados experimentais descreveram adequadamente a dinâmica da adsorção, produzindo isotermas teóricas com comportamento bastante próximos daqueles encontrados com as isotermas experimentais e que dos modelos utilizados, verifica-se que os modelos de Langmuir e Redlich-Peterson apresentaram melhor ajuste aos dados experimentais. A capacidade máxima de adsorção obtida pelas argilas Chocobofe e Chocolate B foram: 18,35 -21,88 mg. g-1 para o Pb2+; 10,0-11,20 mg. g-1 para o Cd2; 8,64-8,69 mg.g-1 para o Zn2, indicando uma seletividade das argilas em relação aos metais em estudo uma sequência de afinidade: Pb2+ > Cd2 > Zn2. Assim, os resultados experimentais indicaram que as argilas bentonitas podem ser utilizadas como adsorventes para a eliminação dos metais Cádmio, Chumbo e Zinco de aguas e efluentes contaminados por meio do mecanismo de adsorção.
The increase in industrial production has provided the generation of wastewater contaminated with heavy metal ions. These must be treated before disposal into the environment. For this reason it is very important to the use of processes to reduce or eliminate heavy metals from industrial effluents. Among the many existing processes, adsorption has great efficiency in the removal of metals present in low concentrations. Clays have shown excellent results in heavy metal adsorption processes, which motivates the search for clays having higher affinity with each type of metal. In this work the smectite clays natural Chocobofe and Chocolate B from the state of Paraíba were investigated in order to evaluate their affinity and capacity for the removal of cadmium, lead and zinc. Held, initially, the characterization of clays by techniques: X-ray diffraction; Chemical analysis; Thermal analysis (differential and gravimetric); Spectroscopy in the infrared region; Adsorption Nitrogen Physics; Scanning electron microscopy and capacity of cation exchange. After characterized the clays were evaluated for removal capacity (q and q) and its removal percentage (% Rem) to metals (cadmium, lead and zinc) present in synthetic wastewater through finite bath system. In order to achieve greater efficiency in the removal of metals a 22 factorial experimental design was conducted to evaluate two input variables: initial concentration of heavy metals (10, 30 and 50 ppm) and pH (3, 4 and 5) to determine the best working conditions, which revealed that the pH = 5 and initial concentration of 50 mg/g were the conditions that showed better results from 88.54 to 99.44% reaching values of percentage removal and 3,36- 4.43 mg/g of removability. From these data were developed kinetic and equilibrium isotherms that served data to evaluate the adsorption capacity of clays with adjustments made through the Langmuir, Freundlich and Redlich-Peterson. The results of the kinetic tests indicated that the removal of Cd2+ ions, Pb2+ and Zn2+ the clay are applied to the mechanism of the pseudo-second-order rate model, a time of 10 minutes is required to reach equilibrium. The mathematical models used to model the experimental data adequately describe the dynamics of adsorption, producing theoretical isotherms quite close to those found behavior with experimental isotherms and that of the models used, it appears that the Langmuir and Redlich-Peterson showed better fit to the experimental data. The maximum adsorption capacity obtained by clays Chocobofe and Chocolate B were 18.35 -21.88 mg. g-1 for Pb2+; 10.0 to 11.20 mg. g-1 for Cd2+; 8.64 to 8.69 mg.g-1 for Zn2+, indicating a selectivity of clays in relation to studying a metal affinity sequence: Pb2+> Cd2+> Zn2+. Thus, the experimental results indicate that the bentonite clays can be used as adsorbents for the removal of metals cadmium, lead and zinc contaminated water and effluent by adsorption mechanism.

Cette thèse s’intéresse à l’analyse de structures de machines électriques non conventionnelles destinées à la production d’électricité par des groupes électrogènes. Les topologies recherchées doivent utiliser moins de matières actives et/ou simplifier la procédure de fabrication par rapport aux machines actuelles.Une des structures est dédiée au système d’excitation de la machine. Elle possède un stator à griffes avec un bobinage toroïdal. Son dimensionnement est réalisé à l’aide d’un modèle de calcul par éléments finis en 3D, qui a été validé expérimentalement. Cette structure permet d’obtenir une réduction significative de la quantité de cuivre dans le bobinage.Les deux autres structures traitées concernent l’alternateur principal. Une machine synchro-réluctante à barrières deflux et à rotor bobiné a été proposée. L’objectif est d’augmenter la densité de couple grâce au couple de saillance. Elle est dimensionnée et comparée avec la structure conventionnelle. Ce cas met en évidence les limitations des structures proches de la structure actuelle.La dernière structure est une nouvelle topologie de machine électrique. Elle combine les caractéristiques des machines à flux axial et des machines à griffes, permettant de simplifier le système d’excitation. Une approche de modélisation originale a été développée pour l’analyse de cette topologie 3D en vue de son dimensionnement par optimisation. Le système d’excitation a un rôle important dans les performances de cette machine.Cette thèse constate aussi que l’évolution future des matériaux magnétiques pourrait tirer meilleur profit des structures non-conventionnelles avec des trajets de flux tridimensionnels
The PhD project aims to analyse nonconventional structures of electric machines for electric power generation with diesel gensets. The researched topologies should use less active materials and/or simplify the manufacturing process compared to today’s machines.One of the structures is intended for the excitation system of the electric machine. It is composed of a claw-pole stator and a toroidal winding. It is designed using a 3D Finite Element model, previously validated by a prototype. This structure allows a significant reduction of the quantity of copper of the field winding.The other two structures under study are proposed for the main generator. A synchronous-reluctance machine with flux-barriers and a field winding in the rotor is analysed. The objective is to increase the torque density by increasing the reluctance torque. The designed machine is compared to the conventional structure. This case shows the limitations of structures similar to the current structure.The last structure is a new topology of electric machine. It combines the characteristics of claw-pole machines andaxial-flux machines. An original modelling approach is developed to analyse this 3D structure for its design based on an optimization algorithm. The study shows that the excitation system has a key role in its performances.This work also notes that the future evolution of magnetic materials should benefit the use of non-conventional structures with 3D flux paths

Streptomyces clavuligerus is a Gram-positive, filamentous bacterium which produces several important secondary metabolites, including isopenicillin N, cephamycin C and the &beta
-lactamase inhibitor clavulanic acid. Among these compounds, clavulanic acid is being used in combination with commonly used &beta
-lactam antibiotics in order to fight against bacterial infections that are resistant to such antibiotics. Among these combinations, Augmentin, composed of amoxicillin and clavulanic acid, is the most widely prescribed drug and has a market value of more than one billion dollars per year. There are two genes that act in regulation of clavulanic acid biosynthesis: ccaR located in cephamycin C gene cluster and claR located in clavulanic acid gene cluster. The goal of this study is to improve clavulanic acid production capacities of both wild type and industrial S. clavuligerus strains by integrating extra copies of claR gene into S.clavuligerus genome and its overexpression via a multicopy plasmid. Although previously has shown to be quite effective on wild type S. clavuligerus strains, claR overexpression in the industrial strain used in this study yielded only 1.4-fold increase in volumetric and 1.7-fold increase in specific CA production by the recombinant strains MA28 and MA16, respectively.

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The WTP produce many kinds of residue on your treatment stages, but the sludge is the more problematic from the final disposition point view. The actual rate of residue production deriving from technological evolution and the crescent population needs prevents the subtle equilibrium generation between consumption and recycling/reuse, creating problems of pollution resulting from inappropriate management of residues. Thus, is necessary achieve a new equilibrium between the grow from raw materials and energy and the residue generation. This equilibrium should be achieved by technical and economic feasibility of environmental supported models through recycling and reuse. The red ceramic industry stand out in residue absorption question as raw material due their clay mass heterogeneity, constituted by clay minerals and non-clay minerals with wide mineralogical variation, allowing residue inclusion which act like plastic or non-plastic materials, contributing to retain heavy metals contained in residues in the vitreous mass formed during the burning of the ceramic bodies. This work propose the study of the influence of incorporation of 25 wt.% sludge from wastewater treatment plant, according preliminary results, in the mass to produce ceramic bodies. The raw materials was characterized through chemical composition analyses by XRF, mineralogical analyses by XRD, thermal analyses by TG and DTA, Atterberg limits and thermodilatometry. Subsequently was composed the mass with 75 wt.% of clay and 25 wt.% of dried wastewater sludge from UFRN WWTP. Samples with 6,0 x 2,0 x 0,5 cm was produced with unidirectional compacting under pressure of 20MPa and burned in temperatures between 950 and 1,200?C. After fired, the ceramic bodies have been submitted to physical and mechanical analyses through the measure of firing shrinkage, water absorption, density, apparent porosity and flexural strength; crystallographic analyses through XRD and microstructure analyses by SEM. The technological properties obtained was satisfactory to production of roof tiles with 25 wt.% at 1,200 ?C, but the production of others products at lower temperatures was not feasible
As ETE produzem v?rios tipos de res?duos em suas etapas de tratamento, mas o lodo ? o res?duo mais problem?tico do ponto de vista de disposi??o final. A atual taxa de gera??o de res?duos, acarretada da evolu??o tecnol?gica e da crescente demanda populacional, impede a gera??o de um equil?brio h?bil entre o consumo e a reciclagem/reuso, gerando problemas de polui??o resultantes da gest?o inadequada dos res?duos. Dessa forma, ? necess?rio atingir um novo equil?brio entre o crescimento das demandas por mat?rias e energia e a gera??o de res?duos. Este equil?brio, s? pode ser alcan?ado atrav?s da viabiliza??o t?cnica e econ?mica de modelos de sustentabilidade ambiental, atrav?s da reciclagem e do reuso. A ind?stria de cer?mica vermelha se destaca no quesito absor??o de res?duos como mat?ria-prima em virtude da heterogeneidade das massas argilosas, constitu?das de argilominerais e minerais n?o argilosos com ampla varia??o mineral?gica, permitindo a inclus?o de res?duos que atuem como plastificantes ou desplastificantes, e contribuindo tamb?m para a reten??o de metais pesados presentes nos res?duos na massa v?trea formada nos corpos cer?micos. Este trabalho prop?e estudar a influ?ncia da incorpora??o de 25% de lodo de esta??o de tratamento de esgoto, baseado em resultados preliminares, ? massa para produ??o de corpos cer?micos. As mat?rias-primas foram caracterizadas atrav?s de an?lise da composi??o qu?mica por FRX, an?lise mineral?gica por DRX, an?lise t?rmica por TG e DTA, an?lise dos limites de Atterberg e an?lise dilatom?trica. Em seguida foi composta a massa com 75% de argila e 25% em peso de lodo da ETE UFRN. Foram prensados corpos-de-prova com dimens?es 6,0 x 2,0 x 0,5 cm atrav?s de prensagem uniaxial sob press?o de 20MPa e queimadas nas temperaturas entre 950 e 1200?C. Ap?s a sinteriza??o, os corpos-de-prova foram submetidos a ensaios f?sico-mec?nicos atrav?s de medida de retra??o linear, absor??o de ?gua, massa espec?fica aparente, porosidade aparente e tens?o de ruptura ? flex?o; an?lise cristalogr?fica atrav?s de DRX e an?lise microestrutural atrav?s de MEV. As propriedades tecnol?gicas obtidas mostraram-se satisfat?rias para fabrica??o de telhas com 25% de lodo na temperatura de queima de 1.200 ?C, n?o sendo vi?vel a fabrica??o de outros produtos em temperaturas inferiores

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Existe uma gama de processos que podem ser empregados no tratamento de compostos orgânicos tóxicos como o fenol presente em efluentes líquidos. Todavia, restrições como alto custo de instalação e tempo de contato relativamente longo devem ser levadas em consideração para a escolha do processo a ser utilizado. Uma nova técnica de tratamento de efluentes contaminados por compostos fenólicos, denominada de tratamento térmico por contato direto (Direct Contact Thermal Treatment - DiCTT), vem atraindo o interesse de vários grupos de pesquisa. O Departamento de Engenharia Química da UFPE possui um protótipo de planta experimental deste processo. O método DiCTT tem como atrativo principal a utilização do gás natural como fonte energética, a capacidade demonstrada de oxidar compostos fenólicos a baixas temperaturas e pressão atmosférica, e sua natureza em empregar uma configuração de reator muito compacta. Nesta pesquisa, foram avaliados os efeitos das variáveis operacionais: vazão de alimentação do efluente líquido, concentração inicial de fenol, a taxa de reciclagem dos gases de combustão, razão molar estequiométrica fenol/peróxido de hidrogênio, vazão do gás natural e excesso do ar. Após estudos preliminares, envolvendo duas etapas (Etapa 1 e Etapa 2) e dois modos operatórios do processo (MO1 e MO2), foi efetuado um planejamento experimental do tipo Delineamento Composto Central Rotacional com fatorial (k) de (23) considerando a taxa de evaporação da fase líquida (inferior à 12%) e a temperatura do efluente líquido (75-790C) (Etapa 3). Com os resultados obtidos, foi realizado um planejamento fatorial (k) completo de (32) para identificação das condições operacionais ótimas do processo, nas faixas de variação estudadas (Etapa 4). As análises envolveram a oxidação termoquímica do fenol e dos seus respectivos intermediários de degradação até a mineralização do composto orgânico e formação de ácidos, com monitoramento das concentrações de fenol e seus intermediários por Cromatografia em fase Líquida de Alta Eficiência, medições do teor de Carbono Orgânico Total com um analisador COT e do potencial hidrogeniônico, com um medidor de pH, respectivamente. Aplicando a superfície de respostas e curvas de contorno com uso do software Statistica versão 8.0, foram identificadas as condições ótimas, nos intervalos de variação estudados, para a degradação do fenol, até 100%, e a conversão de COT, até 40%: vazão de gás natural de 4 m3/h, excesso de ar de 10%, razão molar estequiométrica fenol/peróxido de hidrogênio de 75% e taxa de reciclagem dos gases de combustão de 100%, valores satisfatórios para a degradação do fenol, porém, necessita-se ainda de melhorar as taxas de mineralização. Na etapa final desta pesquisa, foi usada a modelagem via Redes Neurais Artificiais (RNAs), com o software Statistica 8.0 e o módulo “Neural Networks” para predizer os resultados experimentais da degradação do fenol, conversão do COT e da velocidade de degradação do fenol, em função do tempo. Com os resultados obtidos, possibilitou-se concluir que o modelo mais representativo é o Modelo de Regressão e a forma da rede é a Multi Layer Perceptron. Verifica-se ainda que as correlações observadas variaram entre 95,33% até 99,58%, indicando um modelo satisfatório na predição dos resultados experimentais.

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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
O propósito deste estudo foi verificar alterações na estrutura e em algumas propriedades funcionais de biofilmes produzidos com zeína adicionados de argilas modificadas. As argilas modificadas Cloisite® 15A e Cloisite® 30B foram adicionadas na solução filmogênica sob agitação nas proporções de 1, 2 e 4% em relação à massa de zeína e os filmes formados pelo método “casting”. Ácido oléico e glicerol foram utilizados como agentes plasticizantes. Para a caracterização da microestrutura dos biofilmes foram realizadas as análises de Microscopia Eletrônica de Varredura (MEV), Ótica (MO) e Espectroscopia no Infravermelho (FTIR) e as propriedades funcionais avaliadas foram Opacidade, Solubilidade e Permeabilidade ao Vapor d’Água. Por meio das imagens obtidas na MEV observou-se que os acréscimos de argilas nos filmes resultaram na formação de uma microestrutura heterogênea, ou seja, estrutura de fase separada chamada de microcompósito ou tactóide, uma vez que as argilas não dispersaram no filme, o que proporcionou a formação de agregados. No entanto, por meio das imagens obtidas com a MO, observou-se uma distribuição uniforme dos glóbulos de lipídeos na matriz protéica, para todos os filmes. Em concordância com a característica da microestrutura dos filmes elaborados identificados na MEV, o FTIR foi capaz de identificar número de onda referente às argilas, indicando que a mesma não estabeleceu estruturação com a proteína, confirmando a formação de uma estrutura de fase separada tipo tactoide. Todos os filmes elaborados apresentaram maior opacidade quando comparados com o polietileno em razão da presença de pigmentos carotenóides. Pequenas diferenças na espessura das amostras e a quantidade de argila adicionada não influenciaram na transparência dos materiais. Os testes...
The purpose of this study was to evaluate changes in the structure and some functional properties of zein edible films added with modified clays. The modified clays Cloisite® 15A and Cloisite® 30B were added in the solution under agitation in the proportions of 1, 2 and 4% based on the weigh of zein. The films were formed pouring the solution on a surface to dry by casting method. Oleic acid and glycerol were used as plasticizer agents. Analyses of Scanning Electron Microscopy (SEM), Optical Microscopy (MO) and Infrared Spectroscopy (FTIR) were performed to characterize the microstructure of biofilms. The functional properties evaluated were opacity, solubility and permeability of water vapor. SEM images showed that the additions of clays in the films resulted in the formation of a heterogeneous microstructure, i.e. the phase separated structure called microcomposite or tactoids, since the clays were not dispersed in the film, which forms points of aggregates. However, the images obtained with MO showed an even distribution of lipids globules in the protein matrix, for all films. In agreement with the characteristic of the microstructure of the films showed by SEM, FTIR analyses pointed out the absence of wave number related to the clays, indicating that it was not established a really binding of the clays with the protein molecule. This confirms the formation of a material with phase separated, tactoid type. All the films prepared showed higher opacity when compared with polyethylene because of the presence of carotenoid pigments. Little differences in thickness of the samples and the amount of clay added did not influence the transparency of materials. Statistical mean tests of water solubility of the samples showed no differences among those films added with clay and the control. Water... (Complete abstract click electronic access below)

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Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior
The production of waste from urban and industrial activities is one of the factors of environmental contamination and has aroused attention of the scientific community, in the sense of its reuse. On the other hand, the city of Salvador/Ba, with approximately 262 channels, responsible for storm water runoff, produces every year, by the intervention of cleaning and clearing channels, a significant volume of sediments (dredged mud), and thus an appropriate methodology for their final destination. This study aims to assess the influence of incorporation of these tailings in arrays of clay for production of interlocked block ceramic, also known as ceramic paver. All the raw materials from the metropolitan region of Salvador (RMS) were characterized by x-ray fluorescence, x-ray diffraction, thermal analysis (TG and TDA), particle size analysis and dilatometry. With the use of statistical experimental planning technique, ternary diagram was defined in the study region and the analyzed formulations. The specimens were prepared with dimensions of 60x20x5mm?, by uniaxial pressing of 30 MPa and after sintering at temperatures of 900?, 1000? and 1100?C the technological properties were evaluated: linear shrinkage, water absorption, apparent porosity, apparent specifies mass, flexural rupture and module. For the uniaxial compression strength used cylindrical probe body with ? 50 mm. The standard mass (MP) was prepared with 90% by weight of clay and 10% by weight of Channel sediment (SCP), not being verified significant variations in the properties of the final product. With the incorporation of 10% by weight of manganese residue (PFM) and 10% by weight of the Ceramic waste (RCB) in the mass default, in addition to adjusting the plasticity due to less waste clay content, provided increased linear firing shrinkage, due the significant concentration of K2O, forming liquid phase at low temperature, contributing to decreased porosity and mechanical resistance, being 92,5 MPa maximum compressive strength verified. After extract test leachate and soluble, the piece containing 10% of the PFM, was classified as non-hazardous and inert material according to NBR10004/04 ABNT. The results showed the feasibility on using waste, SCP, RCB and PFM clay mass, at temperatures above 900?C, paver ceramic production, according to the specifications of the technical standards, so that to exceed the 10% of the PFM, it becomes imperative to conduct studies of environmental impacts
A produ??o de res?duos provenientes das atividades urbanas e industriais ? um dos fatores de contamina??o ambiental e tem despertado aten??o da comunidade cientifica, no sentido do seu reaproveitamento. Por outro lado, a cidade do Salvador/Ba, com aproximadamente 262 canais, respons?veis pelo escoamento de ?guas pluviais, produz todo ano, pela necessidade de interven??o de limpeza e desobstru??o de canais, um volume significativo de sedimentos (lama dragada), impondo dessa forma uma metodologia adequada para sua destina??o final. Este trabalho tem como objetivo avaliar a influ?ncia da incorpora??o desses rejeitos em matrizes de argila para produ??o de bloco intertravado cer?mico, tamb?m conhecido como paver cer?mico. Todas as mat?rias primas oriundas da Regi?o Metropolitana de Salvador (RMS) foram caracterizadas por fluoresc?ncia de raios -X, difra??o de raios -X, analise t?rmica (TG e TDA), analise granulom?trica e dilatometria. Com a utiliza??o da t?cnica estat?stica de planejamento experimental, foi definida em diagrama tern?rio a regi?o de estudo e as formula??es analisadas. Foram preparados os corpos de prova com dimens?es de 60x20x5mm3, por prensagem uniaxial de 30 MPa e, ap?s sinteriza??o nas temperaturas de 900?, 1000? e 1100?C, as propriedades tecnol?gicas avaliadas foram: retra??o linear, absor??o de ?gua, porosidade aparente, massa especifica aparente, m?dulo de ruptura ? flex?o. Para a resist?ncia ? compress?o uniaxial utilizou-se o corpo de prova cil?ndrico com ? de 50mm. A massa padr?o (MP) foi preparada com 90% em peso de argila e 10% em peso do sedimento de canais (SCP), n?o sendo verificadas varia??es significativas nas propriedades do produto final. Com a incorpora??o de 10% em peso do res?duo de mangan?s (PFM) e 10% em peso do rejeito cer?mico (RCB) na massa padr?o, al?m do ajuste da plasticidade, em fun??o de menor teor de argilominerais dos res?duos, proporcionou aumento da retra??o linear de queima, devido a significativa concentra??o de K2O, formando fase liquida em baixa temperatura, contribuindo para diminui??o da porosidade e aumento da resist?ncia mec?nica, sendo 92,5 MPa a m?xima resist?ncia ? compress?o verificada. Ap?s teste do extrato lixiviado e solubilizado, a pe?a contendo 10% do PFM, foi classificada como material n?o perigoso e inerte segundo NBR10004/04 da ABNT. Os resultados mostraram viabilidade na utiliza??o dos res?duos SCP, RCB e PFM em massa argilosa, em temperaturas acima de 900?C, para produ??o de bloco intertravado, paver cer?mico, de acordo com as especifica??es das normas t?cnicas, de forma que, para teores superiores a 10% do PFM, torna-se imperativo a realiza??o de estudos de impactos ambientais

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In the industrial segment the comprehension of the characteristics of solid and liquid materials used as raw materials, whether dangerous or not, is key to their sustainable management in manufacturing products, knowing that the heterogeneity of the wastes generated limit their reuse. This work adressed the characterization of sludges and effluents derived from tests in the quality control department of a beneficiation of clays industry, aiming to present treatment and disposal alternatives in accordance with the National Policy on Solid Waste (PNRS). Analyses of pH, salinity, conductivity, total dissolved solids (TDS), bulk density, moisture content and total solids (TS – fixed and volatile) were conducted. It was observed that the sludges had high load inorganic material (L1, L2, L4 and L5), being only the sludge L3 with high load volatile organic matter, due to the solvents present. From the characterization of wet sludge (“in natura”) and dried (dehydrated and calcinated) by X-ray diffraction (XRD) and IR spectroscopy, it was found that there was preservation of the typical character of clay and the presence of activating agent. According to BET analyses and point of zero charge (PZC), various sludges had low surface areas, indicating that there would be difficulty in applying them as an adsorbent for the removal of pollutants in wastewater, but they can be incorporated into cementitious materials and glasses. Moreover, sludge L3 can be indicated as a source of energy for coprocessing in cement industry. As for the effluents, tests for specific reuse of three effluents (E1, E3 and E5) were conducted, indicating preliminarily that each of them can be reused, either in the laboratory, as a fuel, or in the original process.
No âmbito industrial o entendimento das características dos materiais sólidos e líquidos usados como matérias-primas, perigosos ou não, é fundamental para a gestão sustentável dos mesmos na fabricação de produtos, sabendo-se que a heterogeneidade dos resíduos gerados limita o seu reúso. Este trabalho abordou a caracterização de lodos e efluentes provenientes de ensaios no setor de controle de qualidade de uma indústria de beneficiamento de argilas, visando propor alternativas de tratamento e disposição final conforme a Política Nacional de Resíduos Sólidos (PNRS). Foram realizadas as análises pH, salinidade, condutividade, sólidos totais dissolvidos (STD), densidade aparente, teor de umidade e sólidos totais (ST – fixos e voláteis). Observou-se que os lodos tiveram alta carga de material inorgânico (L1, L2, L4 e L5), sendo apenas o lodo L3 com alta carga de matéria orgânica volátil, devido aos solventes presentes. A partir das caracterizações dos lodos úmidos (“in natura”) e secos (desidratados e calcinados) por difração de raios-X (DRX) e espectroscopia no IV constatou-se que houve preservação do caráter típico de argilas e da presença de agente ativante. De acordo com as análises superficiais de BET, e ponto de carga zero (PCZ) vários dos lodos apresentaram baixas áreas superficiais, ou seja, indicando que haveria dificuldade de aplicação como adsorvente na remoção de poluentes em efluentes, mas eles podem ser incorporados em materiais cimentícios, vidros, e ainda, o lodo L3 pode ser indicado como fonte de energia para coprocessamento na indústria cimentícia. Quanto aos efluentes foram realizados testes de reutilização específicos para três efluentes (E1, E3 e E5), indicando-se preliminarmente que cada um pode ser reutilizado, seja em laboratório, como combustível, ou no próprio processo de origem.

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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior
The paper entitled "Socio-Economic and Environmental Process Extraction of Kaolin in the Municipality of Junco do Seridó/PB" is a guided study on the extraction of kaolin in the municipality of Junco do Seridó/PB, which is the largest production center of this mineral in the state Paraíba. This activity is the basis of an extensive and complex supply chains that clay mineral widely used in industry, ceramics, refractories, rubber, paper and paint systems. The extraction of mineral resources is the main source of jobs and income for local people. Currently, about eight hundred men work in mines kaolin, risking their lives in the face of imminent dangers and risks of landslides and still subject to a daily wage of only thirty dollars. Other features consist of the use of tools craft inefficient production, lack of appropriate mining techniques, the expenditure of physical effort in excess, beyond the dismissal of personal protective equipment, even aware of the dangers of underground excavations. Workers are exposed to health hazards and even cases of fatal accidents inside the mines. In most cases, workers are relegated to the margins of legality and informality. To address the socio-economic-environmental process of extracting the kaolin in the municipality of Junco do Seridó/PB. Emphasized that the working conditions of miners in the extractive areas relating them to the sustainability indicators. To set the characterization of aspects, interviews with professionals in the areas of health, education, social class and cooperative. As a result, site visits were conducted to investigate the facilities and working conditions during the extraction process. This activity was characterized as being unsustainable for most of the indicators of sustainability. In light of this concept was performed to analyze the data collected during this study. Based on the Socio-Economic and Environmental extraction of kaolin indicated in this study showed the need for a scientific and technical contribution, planning and strategic management, public policy, training for operation and efficient organization in cooperatives to ensure this type of extraction a sustainable supply chain Junco do Seridó/PB.
O trabalho intitulado Aspectos Sócio-Econômico-Ambientais do Processo de Extração do Caulim no Município de Junco do Seridó/PB é um estudo pautado na extração do caulim no município de Junco do Seridó, que é o maior pólo produtor desse mineral no estado da Paraíba. Essa atividade é a base de uma extensa e complexa cadeia produtiva desse argilomineral muito utilizado nos setores industriais, cerâmicas, refratários, borrachas, papel e sistemas de tintas. A extração desse recurso mineral é a principal fonte geradora de trabalho e renda para a população local. Atualmente, cerca de oitocentos homens trabalham nas minas de caulim, arriscando suas vidas diante dos iminentes perigos e riscos de desabamentos e ainda submetidos a uma remuneração diária de apenas trinta reais. Outras características consistem na utilização de ferramentas artesanais pouco eficientes na produção, carência de técnicas de lavra adequadas, dispêndio de esforços físicos em excesso, além do desprovimento de equipamentos de proteção individual, mesmo conscientes dos perigos das escavações subterrâneas. Os trabalhadores se expõem aos danos à saúde e até mesmo casos de acidentes fatais dentro das minas. Na maioria dos casos, os trabalhadores estão postos à margem da legalidade e na informalidade. Para apontar os aspectos sócio-econômico-ambientais do processo de extração do caulim no município de Junco do Seridó/PB, enfatizaram-se as condições de trabalho dos garimpeiros nas áreas extrativistas relacionando-as com os indicadores de sustentabilidade. Para definir a caracterização dos aspectos, foram realizadas entrevistas com profissionais das áreas da saúde, educação, assistência social e cooperativa da classe. Na sequência, foram realizadas visitas in loco para averiguar as instalações e condições de trabalho durante o processo de extração. Essa atividade caracterizou-se como sendo insustentável na maioria dos componentes indicadores de sustentabilidade. À luz desse conceito foi realizada a análise dos dados coletados durante esta pesquisa. Com base nos aspectos Sócio-Econômico-Ambientais da extração do caulim apontados neste estudo, constatamos a necessidade de um aporte técnico-científico, planejamento e gestão estratégica, políticas públicas, capacitação para operacionalização e organização em cooperativas eficientes para que esse tipo de extrativismo garanta uma cadeia produtiva sustentável em Junco do Seridó/PB.

Este trabalho objetivou determinar os principais constituintes fenólicos e avaliar o potencial antioxidante das folhas de dez cultivares de Ipomoea batatas, todas provenientes de melhoramento genético direcionado para a produção industrial de etanol. Para tanto, coletaram-se folhas de plantas adultas, as quais foram secas, reduzidas a pó e submetidas a extrações por refluxo em aparelho de Soxhlet com etanol 70 %, seguido de liofilização. Realizaram-se prospecções fitoquímicas do extrato por diferentes reações químicas e CCD, as quais revelaram a presença de compostos fenólicos gerais, antraquinonas, alcaloides, saponinas, flavonas, flavonol, xantonas, catequinas, taninos gerais, taninos gálicos, e flavonoides. Os teores de fenóis totais determinado pelo método Folin-ciocalteu e de flavonoides totais pela reação com cloreto de alumínio correlacionaram-se entre si e variaram entre as cultivares, sendo menor na cultivar Duda e maior na cultivar Lívia com teores de fenóis entre 54,7170 ± 4,354 e 112,288 ± 3,653 mg EAT/g, teores de flavonoides variando de 29,155 ± 3,725 a 97,358 ± 2,128 mg ER/g. Os teores destes compostos correlacionaram-se com as atividades antioxidantes determinadas pelos métodos DPPH e FRAP que também variaram entre as cultivares e apresentaram-se boa em todas, exceto na cultivar Duda que tal atividade mostrou-se moderada. Por outro lado, houve baixa correlação entre os teores de fenóis e flavonoides totais com a atividade quelante determinada pela reação com ferrozina e sulfato ferroso. Esta variou entre as cultivares e foi mais eficiente na cultivar Duda. A análise por CLAE UV–VIS a 280 nm revelou uma matriz complexa de compostos fenólicos no extrato das cultivares estudadas e possibilitou identificar 10 substâncias, ácido elágico, ácido gálico, (-)- galocatequina, (+)-catequina, rutina, quercetina, naringina, (+/-)-naringenina, miricetina, morina e luteolina. Os resultados revelaram grande potencial de utilização dos compostos fenólicos das folhas de I. batatas, como opção de diversificação de produtos derivados da cultura de batata-doce, fato que torna estas partes da planta atraente para contínuas pesquisas e talvez futura aplicação na medicina.
This study aimed to determine the main phenolic constituents and evaluate the antioxidant potential of the leaves of ten cultivars of Ipomoea batatas, all directed from improvement genétic for the industrial production of ethanol. To that end, leaves were collected from mature plants, which were dried, reduced to powder and subjected to extraction by refluxing in Soxhlet with ethanol 70 %, followed by lyophilization. There were prospects of phytochemical extracts by different chemical reactions and CCD, which revealed the presence of phenolic general, anthraquinones, alkaloids, saponins, flavones, flavanols, xanthones, catechins, general tannins, gallic tannins and flavonoids. The total phenolic content determined by the Folin-Ciocalteu and total flavonoids by reaction with aluminum chloride correlated with each other and varied among cultivars, being lower in Duda and cultivate greater in cultivar Lívia with phenols between 54.7170 ± 4.354 and 112.288 ± 3.653 mg ATE/g, flavonoids ranging from 29.155 ± 3.725 to 97.358 ± 2.128 mg RE/g. The levels of these compounds correlated with the antioxidant activities determined by DPPH and FRAP methods also varied among cultivars and showed up in all good except the cultivar Duda that such activity was moderate. Moreover, there was a low correlation between phenol content and total flavonoids with activity determined by reaction with chelating ferrozina and ferrous sulfate. This varied among cultivars and cultivar was more efficient in Duda. Analysis by HPLC-UV VIS at 280 nm revealed a complex array of phenolic compounds in the extract of the cultivars under study and identify possible 10 substances, ellagic acid, gallic acid, (-)-gallocatechin, (+)-catechin, rutin, quercetin, naringin, (+ / -)-naringenin, myricetin, luteolin and morin. Results showed great potential use of phenolic compounds from the leaves of I. batatas as an option for diversification of products derived from the culture of sweet potato, a fact that makes these parts of the plant attractive to continuous research and perhaps future application in medicine.

Kent was a key component of Roman Britain, featuring aspects it held in common with the rest of this north-western fringe of Empire, but also elements unique to the region. With economic activity for much of the occupation concentrated in three specific areas - the industrial zone of the Weald, a region ranging from Canterbury to Folkestone on the Channel coast, and the upper Medway Valley - the area covered by the modern county was particularly important for the exploitation of natural resources. These included ferrous-ores for iron production in the Weald, greensands for quern production around Folkestone and ragstone quarrying in the upper Medway Valley (the latter providing much of the building stone used in the occupation-period South East). This study brings together a wide range of research findings to present a picture of the economic use and associated organisation of this landscape. The study shows there to have been a hitherto unrecognized depth of economic exploitation, demonstrated by the variety of evidence types assembled in these pages. These activities had an important role within the Imperial, commercial and personal agendas of the time, with the thesis aiming to address the question of how and why these enterprises were brought into being in the area of Kent, and their links to wider spheres within the Empire. Establishing the details of change and continuity regarding this exploitation provides a unique insight into the narrative of Roman Britain. It also allows some specific themes and theories to be explored, informing our wider knowledge of the occupation. These include the concept of the region as being more militarised than a 'normal' civitas, the links between elite settlement, individual agency and industry, the changing balance of importance between industry and agriculture, and what remained of Romanitas in Kent at the end of the occupation.

Corrosion represents the single most frequent cause for product replacement or loss of product functionality with a 5% coat to the industrial revenue generation of any country in this dissertation the efficacy of using filled coatings as a protection coating are investigated. Fillers disrupt the polymer-substrate coating interfacial area and lead to poor adhesion. Conflicting benefits of increasing surface hardness and corrosion with long term durability through loss of adhesion to the substrate are investigated. The effects of filler type, filler concentration and exposure to harsh environments such as supercritical carbon dioxide on salt water corrosion are systematically investigated. The constants maintained in the design of experiments were the substrate, AISI-SAE 1018 steel substrate, and the corrosive fluid synthetic sea salt solution (4.2 wt%) and the polymer, Bismaleimide (BMI). Adhesion strength through pull-off, lap shear and shear peel tests were determined. Corrosion using Tafel plots and electrochemical impedance spectroscopy was conducted. Vickers hardness was used to determine mechanical strength of the coatings. SEM and optical microscopy were used to examine dispersion and coating integrity. A comparison of fillers such as alumina, silica, hexagonal boron nitride, and organophilic montmorillonite clay (OMMT) at different concentrations revealed OMMT to be most effective with the least decrease in adhesion from filler-substrate contact. Subsequently examining filler concentration, a 3 wt% OMMT was found to be most effective. A comparison of unmodified and modified BMI with 3 wt% OMMT exposed and not exposed to supercritical carbon dioxide showed that the BMI provided better corrosion protection; however, OMMT provided better wear, shear, and hardness performance.

Les floculants à base de polyacrylamide (PAM) sont produits à partir du monomère toxique : l’acrylamide (AMD) et peuvent en contenir des quantités résiduelles (jusqu’à 0,1% en Europe). Après utilisation pour faciliter la séparation solide/liquide des eaux de procédés dans les industries de granulat, ces floculants sont stockés avec les boues de décantation dans des lagunes à partir desquelles une dissémination de l’AMD et du PAM vers les eaux de surface ou les eaux souterraines peut avoir lieu. Dans ces travaux de thèse, les interactions du PAM et de l’AMD avec des particules de boue et des phases argileuses (kaolinite et illite, utilisées pour étanchéifier les lagunes de décantation) ont été étudiées. Pour pouvoir quantifier correctement l’AMD, une méthode d’analyse basée sur la HPLC/MS/MS en injection directe a été développée. Cette méthode a été validée avec les normes Afnor NF T 90-210 et NF T 90-220 avec une limite de quantification égale à 1 µg/L. L’étude de l’interaction de l’AMD avec des particules de boue d’un site de granulat et deux argiles (kaolinite et illite) a mis en évidence une faible adsorption de l’AMD sur ces phases solides (<10%), indépendante du temps, de la concentration en AMD et du pH. Inversement, le PAM s’adsorbe fortement et irréversiblement sur la boue, la kaolinite et l’illite avec une cinétique rapide de 1er ordre. Les isothermes d’adsorption sont bien corrélées avec les modèles de Langmuir et de Freundlich. Les quantités d’adsorption du PAM sont indépendantes du pH des suspensions mais fortement impactées par la force ionique qui influence les interactions électrostatiques entre le PAM et les surfaces solides
Polyacrylamide (PAM) based floculants are produced from the highly toxic acrylamide (AMD) monomer and can contain residual amounts (up to 0.1% in Europe) of AMD. After they are used to facilitate liquid/solid separation of process water in aggregate quarries, PAM floculants are stored, with the sewage sludge, in decantation lagoons. Dissemination of AMD and PAM to groundwater and surface water from these lagoons can occur. In this work, we aimed to study the interactions of AMD and PAM with sludge particles and clays (kaolinite and illite used for decantation lagoon sealing) from aggregate quarry. To correctly quantify the AMD, analytical method based on HPLC/MS/MS with direct injection was developed. This method was validated according to the Afnor guidelines (NF T 90-210 and NF T 90-220) with a limit of quantification of 1 µg/L. Results of AMD adsorption experiments showed a low adsorption of AMD to sludge and clay (kaolinite and illite) particles, which is independent of time, AMD concentration and pH. Inversely, PAM was found to adsorb strongly and irreversibly to sludge, kaolinite and illite with a rapid kinetic of adsorption which consists of first order kinetic. Adsorption isotherms are well correlated with Langmuir and Freundlich models. PAM adsorption quantities are independent on the pH of suspensions, but are strongly impacted by the ionic strength which affects electrostatic interactions between PAM and solid surfaces