Milling is a common unit operation in industry for the purpose of intentional size reduction. Considerable amount of energy is consumed during a grinding process and much of the energy is dissipated as heat and sound, which often makes grinding into an energy-intensive and highly inefficient operation. Despite many attempts to interpret particle breakage during a milling process, the grindability of a material in a milling operation remains aloof and the mechanisms of particle breakage are still poorly understood. Hence the optimisation and refinement in the design and operation of milling are in great need of an improved scientific understanding of the complex failure mechanisms. This thesis aims to provide an in-depth understanding of particle breakage associated with stressing events that occur during milling. A hybrid of experimental, theoretical and numerical methods has been adopted to elucidate the particle breakage mechanics. This study covers from single particle damage at micro-scale to bulk comminution during the whole milling process. The mechanical properties of two selected materials, i.e. alumina and zeolite were measured by indentation techniques. The breakage test of zeolite granules subjected to impact loading was carried out and it was found that tangential component velocity plays an increasingly important role in particle breakage with increasing impact velocity. Besides, single particle breakage via in-situ loading was conducted under X-ray microcomputed tomography (μCT) to study the microstructure of selected particles, visualize the progressive failure process and evaluate the progressive failure using the technique of digital image correlation (DIC). A new particle breakage model was proposed deploying a mechanical approach assuming that the subsurface lateral crack accounts for chipping mechanism. Considering the limitation of existing models in predicting breakage under oblique impact and the significance of tangential component velocity identified from experiment, the effect of impact angle is considered in the developed breakage model, which enables the contribution of the normal and tangential velocity component to be rationalized. The assessment of breakage models including chipping and fragmentation under oblique impact suggests that the equivalent normal velocity proposed in the new model is able to give close prediction with experimental results sourced from the public literature. Milling experiments were performed using the UPZ100 impact pin mill (courtesy by Hosokawa Micron Ltd. UK) to measure the comminution characteristics of the test solids. Several parameters were used to evaluate the milling performance including product size distribution, relative size span, grinding energy and size reduction ratio etc. The collective data from impact pin mill provides the basis for the validation of numerical simulation results. The Discrete Element Method (DEM) is first used to model single particle breakage subject to normal impact loading using a bonded contact model. A validation of the bonded contact model was conducted where the disparity with the experimental results is discussed. A parametric study of the most significant parameters e.g. bond Young’s modulus, the mean tensile bond strength, the coefficient of variation of the strength and particle & particle restitution coefficient in the DEM contact model was carried out to gain a further understanding of the effect of input parameters on the single particle breakage behavior. The upscaling from laboratory scale (single particle impact test) to industrial process scale (impact pin mill) is achieved using Population Balance Modelling (PBM). Two important functions in PBM, the selection function and breakage function are discussed based on the single particle impact from both experimental and numerical methods. An example of predicting product size reduction via PBM was given and compared to the milling results from impact pin mill. Finally, the DEM simulation of particle dynamics with emphasis on the impact energy distribution was presented and discussed, which sheds further insights into the coupling of PBM and DEM.

Le comportement mécanique de matériaux granulaires est intrinsèquement lié aux propriétés individuelles des grains constitutifs ainsi qu’à leur assemblage (texture, distribution des vides, contact entre grains…). Soumis à un chargement extérieur, cet assemblage se déforme incluant le déplacement relatif entre les particules mais également la déformation propre des grains jusqu’à leur rupture si elle se produit. Pour étudier la rupture d'une seule particule, des études expérimentales et numériques ont été réalisées. Quatre particules sphériques formées de billes d’argile expansée légère ont été testées en compression à déplacement contrôlé jusqu’à la rupture (essai brésilien). Des photos ont été prises avec une fréquence d’acquisition de 4 images par seconde pour suivre la déformation des grains durant l’essai. La structure interne d'une particule a une influence significative sur l'initiation de la fissure. Pour approfondir cet effet, une micro-tomographie par rayons X a été utilisé pour scanner une particule afin d'obtenir la structure géométrique réelle en 3D. Ensuite, un modèle numérique 3D basé sur la géométrie des particules incluant la porosité interne a été construit avec Abaqus pour les mêmes conditions de chargement. Une comparaison des résultats des tests de laboratoire et des simulations a été faite. Sur la base des résultats, l’initiation des fissures, leur localisation dans le grain et la classification des ruptures de particules ont été établies. Afin d’étudier le rôle de l’anisotropie et en particulier de la fabrique d’un matériau granulaire soumis à un chargement externe, cinq essais de compression biaxiaux ont été réalisé sur un assemblage de grains quasi-sphériques placés dans une chambre confinée. Des photos ont été prises pendant les tests et ont été enregistrées selon une fréquence définie. Un programme écrit sous Matlab a été utilisé pour traiter les photos, obtenir le champ de déplacement et analyser les résultats. Un intérêt particulier a concerné l’orientation des contacts, le tenseur de fabrique et son évolution durant le chargement. L'impact de certains facteurs clés tels que la densité de compactage, la pression de confinement, la taille des plateaux de chargement, la taille des particules et l’épaisseur des échantillons sur la déformation des échantillons ont été étudiés. Une attention particulière s’est portée sur les grains subissant une rupture. Nous avons déterminé le nombre de contact sur ces grains et les avons reproduits, dans le modèle numérique (grain 3D) soumis à un chargement diamétral, par le biais de contraintes cinématiques / The mechanical behaviour of granular materials is deeply related to both the individual particle properties and to the assembly of grains (fabric, void distribution …). Subjected to an external loading, the assembly deforms which is not only dependent on relative grain displacements but also on the grain deformation and to grain breakage when occurring. Experimental and numerical studies of single particles were performed. Four approximately spherical particles of light expanded clay were tested to investigate the breakage phenomenon under diametric displacement-controlled compression load. Photos were taken with a frame rate of 4 images per second during the testing. Since the interior of a heterogeneous particle has significant influence on the failure initiation, an X-Ray micro tomography system was used to scan particles. Moreover, the post-processing enables us to obtain the real 3D volumetric structure. Then a 3D numerical model including pore structure was built in Abaqus for the same loading conditions. A comparison of results from laboratory tests and simulations was made. Based on the results, the crack initiation process, its location and classification of particle failures were set. For purpose of understanding the anisotropy and in particular fabric of packing of granular material when disturbed under external loading, five biaxial compression tests were performed on an assembly of approximately spherical particles settled in a chamber under confining pressure. During the test, photos were taken by the camera and saved to a computer at periodic intervals. Software written with Matlab codes was used to process the photos, determine the displacement field and analyse the results. Focus on contact orientation, fabric tensor and its evolution during testing were put on. Impact of some key factors such as packing density, confining pressure, sizes of the covers, sizes of the particles and thickness of samples on the packing characteristic were analysed. In order to understand mechanical behaviour and kinematic of multiple particles under external load considering particle breakage, six biaxial compression tests were performed on an assembly of approximately spherical particles. Photos were taken to record the location of each particle during the tests. Software written with of Matlab codes was used to process the photos and trace the displacement of all particles in order to analyze kinematical behaviour of the particles. A particular attention was payed to given particles subjected grain breakage within the assembly. Their contacts and relative displacements were introduced in the numerical model of single grain breakage and conclusions were derived

The liver diseases represent a relevant health problem, affecting once an organ of great importance in homeostasis maintaining. The search for herbal hepatoprotective capacity has been increasing, mainly because of the synthetic products used for this purpose may present adverse effects. Guaraná, obtained from the roasted seeds of the Amazonian plant Paullinia cupana var. sorbilis (Sapindaceae), is a product with a wide reputation as stimulant and a nutritional supplement in terms of physical and mental stress. It also presents several other biological properties, among them the antioxidant, antimicrobial, anticancer and anti-obesogenic. However, few studies focus on the potential hepatoprotective this plant. In this study, the protective effects of Paullinia cupana Mart. var. sorbilis (guaraná) on liver damage were evaluated in rats exposed to carbon tetrachloride (CCl4). Male Wistar rats were intra gastric pretreated with guaraná powder (100, 300 and 600 mg/Kg) or silymarin 100 mg/Kg daily for 14 days before treatment with a single dose of CCl4 (50% CCl4, 1 mL/Kg, intraperitoneally). Rats were sacrificed 24 h later, and blood samples were collected for assaying serum biochemical parameters. The hepatic tissue was removed to perform the comet assay. CCl4 induced liver damage and significantly increased the activities of Alanine Aminotransferase (ALT) and Aspartate Aminotransferase (AST) in serum. In addition, CCl4 increased the DNA damage index in hepatocytes. Pretreatment with guaraná in all concentrations was significantly effective in decreasing the ALT and AST activities when compared with CCl4 treated group. Furthermore, the treatment with guaraná 300 mg/Kg decreased DNA damage index. In addition, the DNA damage index showed a significant positive correlation with AST and ALT. These results indicate that guaraná has hepatoprotective activity and prevents the DNA strand breakage in CCl4-induced liver damage in rats. / As doenças hepáticas representam um grave problema de saúde, uma vez que acometem um órgão de grande importância na manutenção da homeostase. A busca por fitoterápicos com capacidade hepatoprotetora vem aumentando, principalmente pelo fato dos produtos sintéticos utilizados para esse fim apresentarem efeitos adversos. O guaraná, obtido das sementes torradas da planta amazônica Paullinia cupana var. sorbilis (Sapindaceae), é um produto com ampla reputação como estimulante e como suplemento nutricional em condições de estresse físico e mental. Além disso, apresenta outras diversas propriedades biológicas, entre estas destacam-se os efeitos antioxidantes, antimicrobianos, anticancerígenos e anti-obesogênicos. Entretanto, poucos estudos enfocam o possível potencial hepatoprotetor desta planta. Neste trabalho, os efeitos protetivos do guaraná sobre o dano hepático foram avaliados em ratos expostos ao tetracloreto de carbono (CCl4). Ratos Wistar machos foram pré-tratados (gavagem) com pó de guaraná (100, 300 e 600 mg/Kg) ou com silimaria 100 mg/Kg durante o período de 14 dias. No 14a dia, para a indução de hepatotoxidade, os animais receberam dose única, via intraperitonial de CCl4 (1 mL/Kg; 50%, diluído em azeite de oliva). Após 24 h, amostras de sangue foram coletadas via retro-orbital para avaliação de parâmetros bioquímicos, os animais sacrificados e o tecido hepático removido para a realização do ensaio cometa. O tratamento com CCl4 provocou dano hepático, demonstrado pela elevação signifivativa da atividade das enzimas aspartato aminoranferase (AST) e da alanina aminotransferase (ALT) no soro. Além disso promoveu um aumento significativo no índice de dano ao DNA. O pré-tratamento com guaraná, em todas as concentrações, foi significativamente efetivo em evitar a elevação da atividade de AST e ALT quando comparados ao grupo controle CCl4. O pré-tratamento com guaraná 300 mg/Kg promoveu uma diminuição no índice de dano ao DNA. O índice de dano no DNA mostrou signifivativa correlação positiva com as atividades de AST e ALT. Estes resultados indicam que o guaraná tem atividade hepatoprotetora e previne a quebra da fita do DNA em dano induzido por CCl4 em ratos.

Submitted by Claudia Rocha (claudia.rocha@udesc.br) on 2018-02-21T15:07:06Z No. of bitstreams: 1 PGPV16MA189.pdf: 1182946 bytes, checksum: cdac92d859fc3431d9c622f433fc3ae9 (MD5) / Made available in DSpace on 2018-02-21T15:07:06Z (GMT). No. of bitstreams: 1 PGPV16MA189.pdf: 1182946 bytes, checksum: cdac92d859fc3431d9c622f433fc3ae9 (MD5) Previous issue date: 2016-02-18 / FUMDES / Uniedu / Nitrogen is the mineral nutrient taken up in highest amounts by maize (Zea mays) and the one that has the largest impact on its grain yield. Maize requires great nitrogen rates and high plant densities to achieve elevated grain yield. However, these two management practices favor stem lodging which may decrease grain yield and quality. An alternative to avoid this problem is the use of growth regulators that restrict theinternode expansion, preventing the excessive increase of plant height. This study was carried out aiming to evaluate the use of ethyl trinexapac growth regulator as an alternative to increase the response to nitrogen side-dress fertilization of maize hybrids with contrasting cycles. The experiment was set in Lages, SC, during the 2014/2015 growing season. A randomized block experimental designarranged in split-split plots was used. Two hybrids were tested in the main plots: P1630 (hipper early cycle) and 30F53 (early cycle). Four nitrogen (N) rates were evaluated in the split plots, equivalent to 0; 0.5; 1 and 1.5 times the amount of N required to achieve a grain productivity of 21,000 kg ha-1. Thepresence and absence of the growth regulator ethy trinexapac l was assessed in the split-split plots. The plant density of 90,000 pl ha-1 and the row spacing of 0.7 m were used. The application of the growth regulatorethy trinexapac decreased 12% plant height, at the average of four N rates and two hybrids. The percentage of broken and lodged stems was lower than 1% and was not affected by the evaluated treatments. The application ofethyl trinexapac reduced 3% the 16 17 weight of 1000 grains. This contributed to the decrease of 815 kg ha-1 of maize hybrids grain yield when the growth regulator was applied, at the average of four N rates. The nitrogen efficiency use decreased linearly with the increase in N rate, both in presence and absence of the growth regulator. The application of the growth regulator ethyl trinexapac was not an effective managementstrategy to increase grain yield and nitrogen efficiencyuse of maize hybrids P1630 and P30F533 / O nitrogênio é o nutriente mineral mais absorvido pelo milho (Zea mays) e o que mais interfere no rendimento de grãos. Para alcançar altas produtividades, é necessário utilizar altas doses de N e densidades de plantas elevadas na lavoura. Contudo, estas duas práticas de manejo favorecem o acamamento, podendo causar perdas significativas no rendimento e na qualidade de grãos. Uma estratégia para evitar este problema é o uso de reguladores de crescimento que restrinjam a expansão dos entrenós e o incremento excessivo na estatura da planta. Este trabalho objetivou avaliar o uso do regulador de crescimento etil trinexapac como alternativa para aumentar a resposta do milho à adubação nitrogenada em cobertura de híbridos de milho com ciclos contrastantes. O experimento foi implantado em Lages, SC, na safra 2014/2015. O delineamento experimental utilizado foi de blocos casualizados dispostos em parcelas sub-subdivididas. Na parcela principal foram testados dois híbridos: P1630 (ciclo hiperprecoce) e 30F53 (ciclo precoce). Nas subparcelas foram testadas quatro doses de nitrogênio (N), equivalentes a 0; 0,5; 1 e 1,5 vezes a dose necessária para atingir produtividade de 21.000 kg ha-1. Nas sub-subparcelas foram testadas a ausência e presença do 12 13 regulador de crescimento etil trinexapac. A densidade utilizada foi de 90.000 plantas ha-1 e o espaçamento entre fileiras de 0,7m. A aplicação do regulador de crescimentoetil trinexapac diminuiu em 12% a estatura de plantas, na média das quatro doses de N e dois híbridos usados. A percentagem de plantas acamadas e quebradas foi inferior a 1º e não foi afetada pelos tratamentos testados no trabalho. A aplicação de etil trinexapac reduziu em 3% a massa de 1000 grãos. Isto contribuiu para o decréscimo de 815 kg ha1 do rendimento de grãos dos híbridos avaliados quando se aplicou o produto, na média das doses de N. A eficiência do uso do nitrogênio diminuiu linearmente com o incremento na dose de N aplicada em cobertura, tanto na presença quanto na ausência do regulador de crescimento. A aplicação do regulador de crescimento etil trinexapac não foi uma estratégia efetiva para aumentar para aumentar o rendimento de grãos e a eficiência de uso do nitrogênio dos híbridos P1630 e P30F533

Made available in DSpace on 2016-12-08T16:44:46Z (GMT). No. of bitstreams: 1 PGPV14MA137.pdf: 748421 bytes, checksum: 74756a464b8fbc9e8e5f4b2e9987693f (MD5) Previous issue date: 2014-08-01 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The delay of maize harvesting may damage grain yield. The magnitude of these losses can be influenced by the hybrid agronomic characteristics. This work was carried out aiming to evaluate the effects of harvest time on the agronomic performance of maize hybrids with different growth cycles. The experiment was set in Lages, SC, during the 2012/13 growing season. A randomized block design with split plots was used. Six single-cross hybrids were tested on the main plots: PP32R22H and P1630H (super early); P2530 (very early); X40B143H, P30F53YH and PP30R50YH (early). Five harvest times were assessed in the split plots: 0 (physiological maturity), 10, 20, 30 and 40 days after physiological maturity. The plant density of 80,000 pl ha-1and row spacing of 0.7 m were used. Sowing was held on December 5, 2012. Delaying harvest time by 40 days decreased 8.7% grain yield in comparison to harvest performed at the crop physiological maturity. The percentage of broken and lodged stems was higher when maize was harvested 30 to 40 days after physiological maturity. The incidence of stem diseases increased proportionally to the delay in harvest time. The occurrence of rotten grains was not affected by harvest time. The super early hybrids P32R22H and P1630H presented higher percentage of stem diseases, greater occurrence of rotten grains and worst ear husk coverage. Grain average moisture at harvest was higher than 25.0%, even when this operation was performed 40 days after physiological maturity. The delay in 14 harvest time damages maize agronomic performance, regardless of maize growth cycle / O atraso na colheita do milho poder ocasionar perdas quantitativas e qualitativas aos grãos. A magnitude dessas perdas pode ser influenciada pelas características agronômicas do híbrido utilizado. Este trabalho objetivou avaliar os efeitos da época de colheita sobre o desempenho agronômico de híbridos de milho com ciclos distintos. O experimento foi implantado em Lages, SC, na safra 2012/13. O delineamento experimental utilizado foi de blocos casualizados dispostos em parcelas subdivididas. Na parcela principal foram testados seis híbridos simples: PP32R22H e P1630H (hiper-precoces); P2530 (super-precoce); X40B143H, P30F53YH e PP30R50YH (precoces). Nas subparcelas foram testadas cinco épocas de colheita: 0 (maturação fisiológica), 10, 20, 30 e 40 dias após a época 0. A densidade utilizada foi de 80.000 plantas ha-1 e o espaçamento entre fileiras de 0,7m. A semeadura foi realizada no dia 5 de dezembro de 2012. O atraso de 40 dias na colheita reduziu 8,7% a produtividade média de grãos dos seis híbridos, em comparação a colheita feita na maturação fisiológica. A percentagem de plantas acamadas e quebradas foi maior quando a colheita ocorreu de 30 a 40 dias após a maturação fisiológica. A incidência de doenças na base de colmo aumentou proporcionalmente ao retardamento da colheita. A incidência de grãos ardidos não diferiu entre as épocas de colheita. Os híbridos hiper-precoces PP32R22H e P1630H apresentaram maior incidência de podridões de base de colmo, pior empalhamento das espigas e maior percentagem de grãos 12 ardidos do que os demais híbridos. A umidade média dos grãos na colheita foi maior do que 25%, mesmo quando esta operação foi realizada 40 dias após a maturação fisiológica. O atraso na colheita prejudica o desempenho agronômico do milho, independentemente do ciclo do híbrido utilizado

Abstract Flocculation plays a critical role in the activated sludge process, where flocs are removed by settling and where unsatisfactory flocculation is resulting in poor effluent quality. Control and operation of the process is also challenging as it is sensitive to external and internal disturbances. Furthermore, stricter environmental demands are also being placed on wastewater treatment and discharge quality thus solutions are needed to improve the current systems. A novel optical monitoring method employing a tube flow and a CCD camera was developed to characterize the flocs and filaments of the sludge, and the method was tested on samples from full-scale activated sludge plants. An online device operating on the same principle was also developed and this was tested over a period of eight months at municipal wastewater treatment plant. Optical monitoring was employed in the laboratory to study the breakage of activated sludge flocs. Based on the image analysis data, in the industrial plant the major breakage process was large-scale fragmentation. In the two municipal plants, it was surface erosion. The flocs had more filaments and were more irregular in shape in the industrial plant, which could be the reason for the large-scale fragmentation. The effect of floc morphology on the effluent clarity of the activated sludge process was studied in the industrial and municipal activated sludge plants by optical monitoring over periods of three months and eight months, respectively. The changes in floc morphology took place slowly in both plants. Four major factors that correlated with the purification results were the size and shape of the flocs and the quantities of small particles and filaments. The image analysis results suggested that the settling problem that occurred during the test periods in the industrial plant was caused by dispersed growth, whereas that in the municipal plant was caused by filamentous bulking. In conclusion, it is possible to use the developed method online in order to analyse the state of flocculation. Thus the method could be useful when developing online monitoring applications for quantifying floc characteristics and for diagnosing the causes of settling problems in the wastewater treatment plants. / Tiivistelmä Aktiivilieteprosessissa flokkulaatiolla on merkittävä rooli, sillä muodostuneet flokit poistetaan prosessista laskeutuksen avulla. Siten huono flokkulaatio johtaa puhdistetun jäteveden kiintoainemäärän lisääntymiseen. Prosessin säätö ja operointi on kuitenkin hankalaa, sillä aktiivilieteprosessi on herkkä ulkoisille ja sisäisille häiriöille. Jätevedenpuhdistukseen liittyvät ympäristövaatimukset ja päästöehdot vesistöihin ovat myös tiukentuneet, joten uusia menetelmiä tarvitaan parantamaan nykyisiä prosesseja. Tässä työssä kehitettiin uusi, optinen kuvantamismenetelmä karakterisoimaan flokkeja ja rihmoja. Menetelmä hyödyntää putkivirtausta ja CCD-kameraa ja sitä testattiin aktiivilietelaitosten näytteillä. Lisäksi kehitettiin samaa periaatetta noudattava online-laitteisto, jota testattiin kahdeksan kuukauden ajan. Optista kuvantamista testattiin laboratoriossa flokkien hajoamistutkimuksessa. Kuva-analyysitulosten perusteella kahden kunnallisen aktiivilietelaitoksen flokit hajosivat pintaeroosioon perustuvan mallin mukaan ja teollisen aktiivilietelaitoksen flokit hajosivat fragmentaatiomallin mukaan. Teollisen aktiivilietelaitoksen flokeissa oli enemmän rihmoja ja ne olivat epäsäännöllisemmän muotoisia, mikä voi olla syynä flokkien fragmentaatioon. Flokkien morfologian vaikutus jäteveden puhdistustuloksiin tutkittiin teollisessa (kolmen kuukauden ajan) ja kunnallisessa (kahdeksan kuukauden ajan) aktiivilietelaitoksessa optisella kuvantamismenetelmällä. Molemmissa laitoksessa muutokset flokkien morfologiassa tapahtuivat hitaasti. Neljä tärkeintä tekijää, jotka korreloivat puhdistustulosten kanssa, olivat flokkien koko ja muoto sekä pienten partikkelien ja rihmojen määrä. Kuva-analyysitulosten perusteella laskeutumisongelma teollisessa jätevesilaitoksessa johtui flokinmuodostajabakteerien liian pienestä määrästä ja kunnallisessa jätevesilaitoksessa rihmamaisten bakteerien liikakasvusta. Yhteenvetona voidaan todeta, että kehitettyä menetelmää on mahdollista käyttää online-mittarina sekä sen avulla voidaan arvioida flokkulaation tilannetta. Siten menetelmää on mahdollista hyödyntää flokkien ominaisuuksien karakterisoinnissa ja arvioidessa jätevedenkäsittelylaitoksen laskeutumisongelmien aiheuttajaa.

Abstract The chemicals currently used for wastewater treatment are mainly based on synthetic inorganic or organic compounds. Oil-derived polyelectrolytes are used for the removal of colloidal solids from wastewater by flocculation and coagulation, for example, while activated carbon adsorbents are typically used to remove soluble impurities such as heavy metals and recalcitrance organic matter. Many of these chemicals have associated negative health impacts, and use of activated carbon has proved to be expensive. Moreover, the present synthetic chemicals are not readily biodegradable or renewable. Thus there is a high demand for “green” water chemicals which could offer a sustainable solution for achieving high-performance, cheap water purification. Water chemicals of a new type based on nano-scale particles (nanofibrils) derived from cellulose, i.e. nanocelluloses, are examined as possible bio-based chemicals for wastewater treatment. Two anionic nanocelluloses (dicarboxylic acid, DCC, and sulphonated ADAC) were tested as flocculants in the coagulation-flocculation treatment of municipal wastewater, while the flocculation performance of cationic nanocellulose (CDAC) was studied with model kaolin clay suspensions, and nanocelluloses produced from sulphonated wheat straw pulp fines (WADAC) were tested for the adsorption of lead (Pb(II)). The anionic nanocelluloses (DCC and ADAC) showed good performance in treating municipal wastewater in a combined coagulation-flocculation process with a ferric coagulant. In the case of both anionic nanocelluloses the combined treatment resulted in a lower residual turbidity and COD in a settled suspension with highly reduced total chemical consumption relative to coagulation with ferric sulphite alone. Likewise, the CDACs resulted in powerful aggregation of kaolin colloids and maintained effective flocculation performance over wide pH and temperature ranges. The capacity of the nanofibrillated and sulphonated fines cellulosics (WADAC) for the adsorption of Pb(II) was 1.2 mmol/g at pH 5, which is comparable to the capacities of commercial adsorbents. / Tiivistelmä Jätevesien kemiallinen käsittely pohjautuu pääsääntöisesti synteettisten epäorgaanisten ja orgaanisten kemikaalien käyttöön. Öljypohjaisia polyelektrolyytteja käytetään kolloidisten partikkeleiden poistamiseen jätevesistä koaguloimalla ja flokkuloimalla, kun taas liuenneita epäpuhtauksia, kuten raskasmetalleja, poistetaan useimmiten adsorboimalla ne aktiivihiileen. Synteettiset vesikemikaalit valmistetaan uusiutumattomista luonnonvaroista ja niiden hajoaminen luonnossa voi olla hidasta, minkä lisäksi monet näistä käytetyistä synteettisistä vesikemikaaleista ovat terveydelle haitallisia. Aktiivihiilen käyttö puolestaan on kallista, johtuen sen korkeista valmistus- ja käyttökustannuksista. Uusille ”vihreille vesikemikaaleille, jotka tarjoavat ympäristöystävällisempiä, halpoja sekä tehokkaita ratkaisuja vedenpudistukseen, onkin suuri kysyntä. Tässä työssä selluloosasta valmistettuja nanokokoisia partikkeleita, eli nanoselluloosia, on tutkittu yhtenä varteenotettavana biovaihtoehtona uusiksi kemikaaleiksi jätevesien puhdistukseen. Kahden anionisen nanoselluloosan (dikarboksyyli, DCC, ja sulfonoitu, ADAC) flokkauskykyä testattiin koagulointi-flokkulointi reaktioissa kunnallisen jäteveden puhdistuksessa. Kationisen nanosellun (CDAC) flokkauskykyä tutkittiin puolestaan kaoliinisaven malliliuoksilla ja vehnän korsisellun hienoaineista nanofibrilloimalla sekä sulfonoimalla valmistetuilla (WADAC) nanoselluloosamateriaaleilla testattiin lyijyn (Pb(II)) adsorptiota vesiliuoksista. Anioniset nanoselluloosat (DCC ja ADAC) toimivat tehokkaasti kunnallisen jäteveden flokkauksessa ferri-sulfaatin kanssa yhdistetyissä koagulointiflokkulointi reaktioissa. Yhdistetyissä reaktioissa molemmat anioniset nanoselluloosat vähensivät sameutta sekä COD pitoisuutta laskeutetuissa jätevesinäytteissä huomattavasti pienemmillä kemikaalikulutuksilla paremmin kuin pelkästään ferri-sulfaatilla koaguloitaessa. Myös CDAC:t toimivat tehokkaasti flokkauksessa keräten tehokkaasti kaoliinin kolloidipartikkeleita yhteen laajalla pH- ja lämpötila-alueella. Nanofibrilloidun ja sulfonoidun vehnäsellun hienoaineen (WADAC) adsorptiokapasiteetti lyijylle Pb(II) oli 1.2 mmol/g pH:ssa 5, mikä on verrannollinen kaupallisten adsorptiomateriaalien kapasiteettiin.

Les structures en enrochements sont parmi les ouvrages les plus usuels de génie civil (barrages, murs de soutènement,. . . ). Des tassements importants peuvent apparaître tout au long de leur durée de vie et sont principalement dus à la rupture des blocs rocheux. Cette thèse propose un modèle numérique permettant de simuler le comportement de matériaux granulaires présentant des ruptures de grains. Afin de prendre en compte la nature discontinue de ces milieux, la méthode des éléments discrets est utilisée. La modélisation adoptée est de type "Non-Smooth Contact Dynamics", où les grains et particules sont supposés rigides. Afin de générer des blocs ayant des formes complexes, un modèle de grain 3D est proposé. Ce modèle de grain est ensuite discrétisé en sous-éléments de forme tétraédrique liés par des liaisons cohésives afin de pouvoir représenter la rupture. Un critère de rupture de Mohr-Coulomb est utilisé. Le modèle est implémenté sur la plateforme logicielle LMGC90. Le modèle est d’abord éprouvé lors de simulations d’écrasement de blocs cassables entre deux plaques. Plusieurs paramètres contrôlant la résistance du grain sont étudiés : cohésion intergranulaire, taille, discrétisation, forme et orientation du grain. L’effet d’échelle observé sur ce type de matériau est vérifié. Le modèle est ensuite testé lors de simulations numériques de compression œdométrique d’enrochements. L’effet des paramètres du modèle et de l’assemblage du milieu granulaire est également étudié. Les simulations œdométriques sont confrontées à des résultats expérimentaux et présentent une bonne concordance. Enfin, des expérimentations numériques sont menées afin d’étudier les énergies mises en jeu dans ces essais. L’énergie de création de surface est estimée pour ce type de matériau. Les résultats sont proches des données de la littérature. / Rockfill structures are very popular among civil engineering structures (dams, retaining walls, . . . ). Important settlements can take place during the lifetime of these structures, settlements mainly caused by the breakage of rockfill grains. This thesis proposes a numerical model that allows the simulation of the behavior of granular materials exhibiting grain breakage. To take into account the discrete nature of these media, the discrete element method is chosen. The adopted strategy is the Non-Smooth Contact Dynamics method, where grains are considered to be rigid. To generate blocks having complex shapes, a 3D grain model is suggested. This grain model is then discretized into tetrahedral subgrains, joined together using cohesive bonds so that breakage can be simulated. A Mohr-Coulomb failure criterion is used for the cohesive bonds. The model is implemented into the LMGC90 software platform. At first, the model is tested in single grain crushing simulations between two plates. Multiple parameters controling the strength of the grain are studied : the intra-granular cohesion, the size, the discretization and the orientation of the grain. The scale effect that characterizes this type of material is verified. Then the model is tested in numerical simulations of œdometric compression of rockfill. The influence of the parameters of the model and of those of the granular medium are studied. The results of œdometric simulations are compared to experimental results, and present a good agreement. Lastly, numerical experimentations are conducted in order to study the energies that are brought into play in the simulations. The surface creation energy is estimated for this type of material. Results are close to the data provided in the literature.

The populations of the ghost-crab Ocypode quadrata have been evaluated as bioindicators at sandy beaches, but for this purpose some shortcomings need to be addressed. This study assessed several features of the species biology, from daily activity cycles to effectively its role as bioindicator. Between that, the occupation of burrows was evaluated at several morphodymically distinct beaches and it differed temporally, among the areas and within beach strata, indicating that assessing these populations through the indirect method require more caution. The period of the year after major cold fronts showed the most similar values between individuals and burrows, followed by the greater entrance of young recorded. No trend according to beach type was identified for mean size, dissipative beaches tended to have higher densities, while body growth performance index was higher at reflective beaches, gathering therefore both similarities and differences concerning the trends known for other crustaceans from these environments. The use of the species as bioindicator was effective and gathered distinct areas, through the use of a new method. Increasing levels of erosion were associated to increasing mean densities and mean sizes, followed by a sharp decrease of both, especially mean size. Connectivity breakage, e.g., armoring and vegetation removal, proved to be a threat to the populations structure, worsened when associated to erosion process, to an extent that compromise the populations viability. / As populações do caranguejo Ocypode quadrata, conhecido no Brasil como guaruçá ou maria-farinha, têm sido exploradas como bioindicadores da qualidade de praias arenosas, mas para tal algumas lacunas precisam ser preenchidas. Este trabalho levantou diversas características da espécie no litoral sudeste brasileiro, desde ciclos diários de atividade até sua aplicação como bioindicador. Nesse entremeio, as taxas de ocupação das tocas foram avaliadas em diversas praias morfodinamicamente distintas, sendo que houve variação temporal, entre praias e mesmo entre estratos de uma mesma praia, indicando que avaliações dessas populações através do método indireto requerem maior cautela. O período pós frentes frias teve o número de tocas e de animais mais semelhante, seguido da maior entrada de recrutas. O tamanho médio dos indivíduos não apresentou tendências de acordo com o tipo praial, a densidade de indivíduos foi maior nas praias dissipativas e a performance de crescimento estimada foi maior em praias reflexivas, agregando características tanto similares quanto opostas aos outros crustáceos desses ambientes. O uso da espécie como bioindicador foi válido e incorporou áreas distintas, através do emprego de um novo método. Níveis crescentes de erosão foram associados a um inicial aumento de densidade e tamanho médios, seguido de um decréscimo severo de ambos, especialmente de tamanho. A quebra de conectividade, e.g. construções e remoção da vegetação, foi também responsável pela alteração da estrutura das populações, sendo a condição agravada em casos de associação com erosão, a ponto de comprometer a viabilidade das populações.

The populations of the ghost-crab Ocypode quadrata have been evaluated as bioindicators at sandy beaches, but for this purpose some shortcomings need to be addressed. This study assessed several features of the species biology, from daily activity cycles to effectively its role as bioindicator. Between that, the occupation of burrows was evaluated at several morphodymically distinct beaches and it differed temporally, among the areas and within beach strata, indicating that assessing these populations through the indirect method require more caution. The period of the year after major cold fronts showed the most similar values between individuals and burrows, followed by the greater entrance of young recorded. No trend according to beach type was identified for mean size, dissipative beaches tended to have higher densities, while body growth performance index was higher at reflective beaches, gathering therefore both similarities and differences concerning the trends known for other crustaceans from these environments. The use of the species as bioindicator was effective and gathered distinct areas, through the use of a new method. Increasing levels of erosion were associated to increasing mean densities and mean sizes, followed by a sharp decrease of both, especially mean size. Connectivity breakage, e.g., armoring and vegetation removal, proved to be a threat to the populations structure, worsened when associated to erosion process, to an extent that compromise the populations viability. / As populações do caranguejo Ocypode quadrata, conhecido no Brasil como guaruçá ou maria-farinha, têm sido exploradas como bioindicadores da qualidade de praias arenosas, mas para tal algumas lacunas precisam ser preenchidas. Este trabalho levantou diversas características da espécie no litoral sudeste brasileiro, desde ciclos diários de atividade até sua aplicação como bioindicador. Nesse entremeio, as taxas de ocupação das tocas foram avaliadas em diversas praias morfodinamicamente distintas, sendo que houve variação temporal, entre praias e mesmo entre estratos de uma mesma praia, indicando que avaliações dessas populações através do método indireto requerem maior cautela. O período pós frentes frias teve o número de tocas e de animais mais semelhante, seguido da maior entrada de recrutas. O tamanho médio dos indivíduos não apresentou tendências de acordo com o tipo praial, a densidade de indivíduos foi maior nas praias dissipativas e a performance de crescimento estimada foi maior em praias reflexivas, agregando características tanto similares quanto opostas aos outros crustáceos desses ambientes. O uso da espécie como bioindicador foi válido e incorporou áreas distintas, através do emprego de um novo método. Níveis crescentes de erosão foram associados a um inicial aumento de densidade e tamanho médios, seguido de um decréscimo severo de ambos, especialmente de tamanho. A quebra de conectividade, e.g. construções e remoção da vegetação, foi também responsável pela alteração da estrutura das populações, sendo a condição agravada em casos de associação com erosão, a ponto de comprometer a viabilidade das populações.