The rollers of run out table in Hot Strip Mill are operated with variable high rotational speed under a severe environment of high temperature and much cooling water around. And the table takes long space about 128 meters of length with over 330 rollers. The rollers of this area often break down, and it takes long to make urgent repair. So it costs about ten million NT dollars per year for mill shut-down. Although some improvements have been made before, the troubles still happens frequently. Then the temporary countermeasures of shortening the maintenance cycle and increasing the grease supply have been applied to prevent the break-down frequency from aggravation . But it wastes the cost and does not meet the environmental policy. This study analyzes many damage phenomena. Then it assumes that the 75% of roller running break-down is bearing damage resulting from bad lubrication condition and abnormal axial load. The cooling water which penetrates into bearing housing will result in grease emulsification and its consistency diluting. This certainly causes the bad lubrication condition and bearing rusting. In the meantime, if the floating function of roller bearing is inactive, the bearings will be operated under abnormal high axial load and without appropriate lubrication. Then the bearing will be damaged rapidly and must be repaired quickly. In order to improve bad lubrication and bearing rusting, this study modifies sealing arrangement and grease feeding circuit for bearing housing with the special functions of water obstruction, drainage and resistance to prevent water penetration. In addition, the overflow of grease will be collected to meet the environmental needs. Meanwhile, to look for better water resistance and mechanical stability for greasing, the study also discusses the relationship between consistency variation and thickening soap base after grease emulsification. During a three-month running of the new design , the water contents are stably under 1.5% which has greatly advanced. And the quantity of grease supply is under 10% of existing one. In order to improve the inactive floating function of roller bearings, this study not only analyzes the derivation of problems but also modifies the dimensional tolerance and adds cylindricity of geometric tolerance for the bore of bearing housing. This will ensure complete loose fit and shape accuracy to prevent the interference fit between the bore and bearing caused by manufacturing inaccuracy or other mistakes

Miniemulsion technology is attracting increasing interest for the preparation of nano-size particles. However, the barrier to industrialising miniemulsion-based products is the lack of an energy efficient and scalable homogenisation device. Current laboratory techniques consist of batch units, however trends are leaning towards developing continuous processes. The objective of the work presented here is to investigate the use of the rotor-stator (RS) and static mixers (SM) as homogenisation devices and ultimately develop a continuous emulsification/polymerisation process for the preparation of miniemulsions. Initially we investigated the RS as a homogenisation device and found that we were able to generate droplets ranging from 300 nm to 2 μm, at industrially pertinent solids content. Subsequently, we investigated the use of SM and compared their performance in terms of mean droplet size evolutions with the rotor-stator. We were able to generate droplets < 200 nm in size and polymerise them in a stable fashion. All the available emulsification devices were then compared in terms of power/energy consumption, droplet size distributions and shear rates. It was observed that with energy costs being of similar orders of magnitude, SM imposed less shear, produced relatively narrow distributions and were better adapted to scale-up, making them the optimal choice for miniemulsification. Energy savings were increased by reducing coalescence during the emulsification step by using in situ generated surfactants, ultimately reducing emulsification time. Neutralising a water-soluble base with an oil-soluble acid almost instantaneously generates in situ surfactants at the oil-water interface. The reduction in emulsification time was partially attributed to the elimination of the relatively slow adsorption step typical of preformed surfactants. These results were used to show that emulsifying in situ formulations at moderate flow rates in line with SMX mixers can substantially reduce emulsification time from 30 minutes, with preformed surfactants, to ~30 seconds. With such a rapid emulsification step, it was possible to test the feasibility of the continuous emulsification process followed by polymerisation in a tubular reactor. Comparing this process with a batch operation, similar results for the ratio of NP/ND and conversion were obtained, but the continuous process was accomplished in a single step. / Thesis (Ph.D, Chemical Engineering) -- Queen's University, 2010-04-19 03:32:08.766

This dissertation investigates the emulsification of aqueous liquid in immiscible organic liquid in various microfluidic environments, and addresses both experimental characterization and theoretical interpretation of the dynamics and design guidelines, as well as an application of microfluidic emulsification in fabrication of disk-like colloidal particle suspensions for studying its sedimentation behavior. In an attempt to understand the dynamics of drop formation in flow-focusing microfluidic channels, especially for an explanation of a transition from unique drop size to bimodal oscillating drop sizes as observed in the experiments, numerical simulation is developed to use the volume-of-fraction method to model the drop formation, and the simulation results help to interpret the transition in the theory of saddle-node transition in drop formation, as well as show the importance of selecting proper orifice length in flow-focusing microfluidic channel design. The electric technique for controlling of microfluidic emulsification is explored by a detailed study on low-frequency alternating-current electro-flow-focusing (EFF) emulsification in microfluidic channels. It is found that the droplet size variation is not a monotonic function of the electric field as in the case of direct-current EFF emulsification, which originates from the relaxation oscillation of the flow rate through the Taylor cone, and a power-law droplet size distribution was obtained at the voltage ramping-up stage. This emulsification process was modeled in analog to the charge accumulation and release in a resistor-capacitor electric circuit with an adjustable resistor, and the simulated data exhibit good agreement with the experiments. As an application of the microfluidic emulsification, a method of fabricating disk-like wax colloidal particle suspensions using electrospray is reported. Based on this technique, the first measurement of the hindrance function for sedimentation and creaming of disk-shaped colloids via the analytical centrifugation is reported. Disks align with the external flow right above the volume fraction of a few percent and this effect is extremely sensitive to the aspect ratio of disks. Due to this alignment effect, disk sedimentation/creaming demonstrate distinct trends in dilute and semi-dilute region.

Low phosphorus content steels are essential for steel applications where high ductility is required, such as thin sheets, deep drawn, pipelines and automobile exteriors. In the past, phosphorus control was not considered a big challenge in steel production in the US because iron ores with low phosphorus contents were readily available and considered cheap. However, in the last decade, the iron ore price has risen by roughly 400% and lower cost iron sources generally have higher phosphorus content. In integrated steel plants, phosphorus removal usually takes place during the oxygen steelmaking process (OSM) but in Japan a intermediate step for hot metal dephosphorization is commonly used. There are various types of OSM furnaces but the most widely used remains the top-blown Basic Oxygen Furnace (BOF). The BOF slag can be recycled to a sinter plant or directly to the blast furnace, ultimately increasing the phosphorus input in the process. In order to meet new demands for phosphorus control, it is necessary to improve our understanding on the thermodynamics and kinetics of the phosphorus partitioning reaction between slag and metal melts during steelmaking. Therefore, the present work has been divided in three strongly correlated sections: phosphorus equilibrium between metal and slag; analysis of plant data; and observations of the reaction kinetics. Phosphorus equilibrium between liquid metal and slag has been extensively studied since the 1940's. It is well known that CaO and FeO are the main slag constituents that help promote dephosphorization. On the other hand, dephosphorization decreases with temperature due to the endothermic nature of the reaction. Many correlations have been developed to predict the phosphorus partition ratio as a function of metal and slag composition as well as temperature. Nevertheless, there are still disagreements in the laboratory data and the equilibrium phosphorus partition can be predicted with an uncertainty of a factor of up to 5. The first part of the present work focuses on generating more reliable equilibrium data for BOF-type slags by approaching equilibrium from both sides of the reaction. The experimental results were combined with two other sets of data from different authors to produce a new correlation that includes the effect of SiO2 on the phosphorus partition coefficient, LP . Although the quantification of phosphorus equilibrium is extremely important, most industrial furnaces do not operate at equilibrium, usually due to liquid slag formation, kinetics and time constraints. Thus, it is important to know how close to equilibrium different furnaces operate in order to suggest optimal slag compositions to promote dephosphorization. The present work analyzed four large sets of data containing the chemical compositions of both slag and metal phase as well as the tapping temperature of each heat. Each set of data corresponded to different furnaces: one AOD (Argon Oxygen Decarburization), two top-blown BOFs and one Q-BOP or OBM. It was found that the bulk slag composition can greatly \mask" the data due to solid phases coexisting with the liquid slag. The author used the software package FactSage to estimate the amount of solids in the slag and liquid slag composition. It was found that the AOD is the reactor closest to equilibrium, followed by the Q-BOP (OBM) and the two top-blown BOFs. It was noted that the stirring conditions and slag composition are two key variables to enable optimum phosphorus removal. Also, over saturating the slag with CaO and MgO does not seem to benefit the process to any extent. Lastly, interesting observations on the behavior of small metal droplets reacting with slag are presented and discussed. It was found that dynamic interfacial phenomena at the metal-slag interface is likely to play a significant role in the kinetic behavior of the system, due to the exchange of surface active elements, such as oxygen, which dramatically lowers the interfacial tension and cause spontaneous emulsification. Although this phenomenon has been studied, actual quantification of changes in interfacial area remain a challenge. The author developed an experimental method to enable better quantification of spontaneous emulsification and two sets of experiments were carried. One with an Fe containing 0.2 wt.% P and another in a P-free system where pure iron was oxidized. It was found that phosphorus did not play a role in spontaneous emulsification and it was rapidly removed before the onset of dynamic interfacial phenomena. Emulsificaion was maybe caused by de-oxidation of the metal after phosphorus removal took place and the metal became super saturated with oxygen by an unknown reason. The estimated surface area rapidly increases by over an order of magnitude during the beginning and intermediate periods of the reaction. The metal drop breaks into hundreds of small droplets, effectively emulsifying the metal into the slag. With time, the surface area decreases and the metal droplets coalesce. Similar results were observed for an Fe droplet being oxidized. Spontaneous emulsification takes place regardless of the direction of oxygen transfer and the changes in surface area are similar for both cases. The last chapter describes the industrial relevance of the present work, summarizes the findings, revisits the hypotheses and presents potential future work where further research is encouraged.

Orientador: Rosiane Lopes da Cunha / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia de Alimentos / Made available in DSpace on 2018-08-18T08:17:47Z (GMT). No. of bitstreams: 1 Reis_Cathiados_M.pdf: 2669539 bytes, checksum: 364324f89741f00357d22a38d35ee9ee (MD5) Previous issue date: 2011 / Resumo: A gelatina é uma proteína de alto interesse e valor comercial, no entanto seu uso como agente emulsificante ainda é bastante restrito devido à limitações tecnológicas. O objetivo geral deste trabalho foi investigar as alterações nas propriedades físicas, químicas e funcionais da gelatina de origem bovina quando submetida à modificação química através da reação de acilação com um cloreto de ácido graxo, bem como avaliar seu desempenho em aplicações com finalidade tecnológica de emulsificação. Para a definição das condições ótimas de reação de acilação (pH de reação e concentração do reagente), foram avaliados o grau de acilação (GA), a atividade (AE) e estabilidade emulsificante (ES), a força de gel (Bloom) e a viscosidade. As gelatinas aciladas obtidas foram também caracterizadas quanto aos teores de proteína, cinzas, umidade, cloretos, distribuição de peso molecular, ponto isoelétrico e espectroscopia de infravermelho. As emulsões (20% óleo) produzidas utilizando as gelatinas aciladas foram avaliadas através de medidas de separação visual de fases e determinação de tamanho de gota por microscopia ótica. Os resultados mostraram que a reação de acilação apenas tornou-se efetiva quando realizada em pH extremamente alcalino (pH 11,0), porém a força de gel e a viscosidade diminuíram nestas condições. As gelatinas aciladas com maior força de gel e viscosidade mostraram maior efeito na estabilização das emulsões do que o grau de acilação. Como conseqüência, as gelatinas ¿controle¿ apresentaram melhor atuação na estabilização das emulsões. Não foram observadas diferenças significativas na distribuição de ponto isoelétrico das gelatinas e nos espectros de infravermelho obtidos. No entanto, as gelatinas aciladas em pHs mais altos (pH 10,6 e 11,0) apresentaram aumento da massa molecular média quando comparadas as gelatinas ¿controle¿ devido a introdução do grupo acila na cadeia de gelatina / Abstract: Gelatin is a protein widely used in food industry. However, its use as an emulsifier agent is still restricted due to technological limitations. The objective of this work was to investigate the alterations at physical, chemical and functional properties of bovine gelatin after it has been subjected to a chemical modification through the acylation with a fatty acid chloride. In addition, the behavior of this acylated gelatin as emulsifier was evaluated. The acylation degree (AD), the emulsifying activity (EA) and stability (ES), the gel strength (or Bloom) and the viscosity of the modified gelatins were evaluated to define the more adequate conditions of the acylation reaction (pH and reactive concentration). The acylated gelatins were characterized regarding to protein, ash, moisture, chloride content, molecular weight distribution, isoelectric point distribution and infrared spectroscopy. O/W emulsions (20% oil) stabilized with acylated gelatins were evaluated through visual phase separation measurements and determination of drop size using optical microscopy. The results showed that the acylation reaction was effective only at very high pH (around 11.0). However, the gel strength and viscosity decreased at higher pH of reaction. Acylated gelatins with higher gel strength and viscosity showed more pronounced effect on emulsions stability than the acylation degree. As a consequence, the ¿control¿ gelatins presented better emulsion stability than acylated ones. It was not observed significant differences at isoelectric point distribution and infrared spectrum obtained for the acylated gelatins. However, acylated gelatins at higher pH (pH 10.6 and 11.0) showed an increase of the mean molecular mass when compared to the ¿control¿ gelatins due to the introduction of acyl groups to the gelatin chain / Mestrado / Engenharia de Alimentos / Mestre em Engenharia de Alimentos

Orientador: Walkiria Hanada Viotto / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia de Alimentos / Made available in DSpace on 2018-08-09T21:00:08Z (GMT). No. of bitstreams: 1 Almeida_AnaPatriciaNogueira_M.pdf: 1872253 bytes, checksum: ab983ea514eb5ef7931f6e44f631b22b (MD5) Previous issue date: 2008 / Resumo: O queijo de manteiga, também conhecido como requeijão do norte, é produzido e bastante consumido na região Nordeste do Brasil. O queijo de manteiga apresenta exagerada formação de óleo livre, com liberação de gordura na superfície. Esse problema pode estar associado às variações de pH, já que este exerce papel fundamental no equilíbrio da concentração de cálcio solúvel e coloidal O objetivo deste trabalho foi avaliar a influência do pH de fusão na composição, proteólise, lipólise, perfil de textura instrumental, cor, propriedades funcionais e microestrutura do queijo de manteiga. Foram avaliados seis níveis de pH de fusão (5,1; 5,2; 5,3; 5,4; 5,5; e 5,6) e os ensaios foram realizados em triplicata. Os queijos foram analisados nos dias 5, 20 e 35 de armazenamento refrigerado (4°C) em relação a pH, acidez titulável, nitrogênio solúvel a pH 4,6 e em TCA 12%, teor de ácidos graxos livres, índice de peróxidos, formação de óleo livre, textura instrumental e cor. A capacidade de retenção de água foi avaliada nos dias 1, 5, 20 e 35 de armazenamento refrigerado (4°C) e a microestrutura dos queijos foi avaliada através da microscopia eletrônica de varredura no 45° dia após a fabricação. A alteração do pH de fusão não afetou significativamente a composição, exceto os teores de cálcio e sal. O pH de fusão influenciou significativamente o pH dos queijos, a acidez titulável, a extensão de proteólise (NS em pH 4.6), a formação de óleo livre e a textura instrumental. A fusão na faixa de pH de 5,4 a 5,6 resultou em queijos com menor formação de óleo livre, dureza, elasticidade e mastigabilidade e maior extensão de proteólise. Os índices de proteólise aumentaram significativamente com o tempo de armazenamento, apesar do aumento ter sido pequeno em relação aos normalmente encontrados em outros tipos de queijos. Os queijos apresentaram uma matriz protéica contínua, permeada por glóbulos de gordura, cujo tamanho e distribuição variaram em função do pH de fusão. A matriz protéica apresentou-se mais compacta nos pHs de fusão da massa de 5,1 a 5,3, enquanto nos valores de pH de 5,4 a 5,6 a aparência foi mais esponjosa. O queijo fundido a pH 5,5 apresentou glóbulos de gordura de menor tamanho e mais uniformemente distribuídos na matriz protéica, evidenciando maior emulsificação da gordura pela caseína. O maior teor de cálcio micelar nesse pH sugere que deve haver uma quantidade ótima de cálcio ligado à caseína de modo a facilitar a sua ação como agente emulsificante / Abstract: Queijo de manteiga, also knows as requeijão do norte, is usually produced and consumed in the Brazilian Northeastern region. This cheese is characterized by an excess of free oil formation, which is usually visible in its surface. Since pH has a fundamental role on the equilibrium of both soluble and colloidal calcium concentrations, this problem is probably associated to variations in pH. The objective of this work was to evaluate the influence of curd melting pH on the composition, proteolysis, lipolysis, instrumental texture, color, functional properties and microstructure of the queijo de manteiga. Six levels of curd melting pH were studied (5,1; 5,2; 5,3; 5,4; 5,5 e 5,6) and the experiments were carried out in triplicate. The cheeses were analyzed at 5, 20 and 35 days of refrigerated storage (4°C) in relation to pH, titratable acidity, soluble nitrogen in pH 4.6 and TCA 12%, free fatty acids, peroxide value, formation of free oil, instrumental texture and color. The water retention capacity was evaluated at 1, 5, 20 and 35 days of refrigerated storage and the cheeses microstructure was evaluated through scanning electronic microscopy 45° days after manufacture. Variation in curd melting pH did not affect the composition, except for calcium and salt content. The curd melting pH had a significant influence on cheese pH, titratable acidity, proteolysis extension, and lipolysis and texture. Curd melting in the pH range 5,4 to 5,6 resulted in cheese with lowest the free oil formation, hardness, elasticity and mastigability and proteolysis extension. The proteolysis increased significantly with time, although the increase was small in relation to those usually found for other types of cheese. The cheese presented a continuous protein matrix in which fat globules were entrapped, their size and distribution depending on pH of melting. The matrix protein was more compact when melting occurred in pH 5,1-5,3. However, the cheese appearance was spongy at pHs 5,4-5,6. The cheese which melted on pH 5,5 had small fat globules, uniformly distributed into the protein matrix, showing greater degree fat emulsification by casein. The greatest amount of micellar calcium in this pH suggests that a certain amount of calcium linked with casein was necessary to improve their action as an emulsifying agent / Mestrado / Mestre em Tecnologia de Alimentos

Orientador: Rosiane Lopes da Cunha / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia de Alimentos / Made available in DSpace on 2018-08-21T04:58:14Z (GMT). No. of bitstreams: 1 Moraes_MarisaCorreade_M.pdf: 1452448 bytes, checksum: cbfd0da3e6558c06281ba86e39f14050 (MD5) Previous issue date: 2012 / Resumo: O colágeno é um subproduto de matadouro sendo amplamente utilizado como ingrediente na indústria, depois de extraído e purificado. As propriedades tecnológicas do colágeno estão intimamente relacionadas com a distribuição da massa molecular de suas fibras, que varia de acordo com as características da matéria-prima e condições do processo de obtenção do material. Com o intuito de avaliar o efeito das variáveis de processo (tempo,temperatura e pH), o colágeno foi extraído da camada interna da pele bovina e submetido a hidrólise em diferentes condições de temperatura (50, 60 e 80°C) e pH (3, 5, 7 e 10) durante 6 horas. Os produtos obtidos foram avaliados quanto ao teor de proteína solúvel, carga superficial, distribuição de massa molecular, desnaturação protéica, capacidade gelificante e emulsificante. Os produtos mostraram teor de proteína solúvel entre 5 e 82% (m/m), sendo os maiores valores obtidos em tratamentos realizados em temperatura mais elevada e/ou condições mais ácidas. Produtos obtidos em condições extremas de pH (3 e 10) ou temperaturas acima ou similar à temperatura de desnaturação do colágeno (80 e 60°C, respectivamente) tiveram sua estrutura mais desnaturada. Em geral, os hidrolisados obtidos em pH ácido formaram géis mais firmes, exceto o produzido a 80°C. Já os hidrolisados obtidos nos outros valores de pH (5, 7 e 10) formaram géis com baixos valores de tensão de ruptura porém, quando tratados em temperatura acima da temperatura de desnaturação e maior tempo de processo, apresentaram uma melhora nas propriedades gelificantes. A capacidade de retenção de água (CRA) foi próxima de 100%, exceto para hidrolisados obtidos em pH igual a 7 e 10 e temperatura de 50°C. A capacidade emulsificante destes hidrolisados também foi avaliada em emulsões óleo/água (O/A). A estabilidade das emulsões aumentou com a redução do pH e com o aumento do tempo de hidrólise, porém somente a emulsão em pH 3 e 6 horas de hidrólise não apresentou separação de fases. As emulsões mais estáveis (pH 3) apresentaram gotas com baixa polidispersão e diâmetro médio entre 1,5 e 5 µm. Em valores de pH próximo ao pI do colágeno houve a formação de agregados que desestabilizaram as emulsões, o que acarretou elevados valores de diâmetro médio (entre 8 e 17 µm). As emulsões estáveis mostraram comportamento pseudoplástico, porém nas emulsões em que ocorreu a separação de fases, a fase inferior (aquosa) sempre apresentou comportamento Newtoniano, enquanto que a fase creme foi pseudoplástica. De maneira geral, o uso de temperaturas mais amenas e pH ácido, possibilita a produção de hidrolisados com boas propriedades mecânicas, no entanto, em temperatura mais elevada obtém-se um produto com alta solubilidade. Se o objetivo é a obtenção de um gel com alta capacidade de retenção de água o mais indica-se utilizar pH abaixo ou próximo do pI ou elevadas temperaturas. Para melhorar a capacidade emulsificante o uso em pH abaixo do pI é o mais indicado / Abstract: Collagen is a byproduct of the slaughterhouse that is widely used as an ingredient in industry, after being extracted and purified. The technological properties of collagen are closely related to the molecular weight distribution of the fibers, which varies with the characteristics of raw materials and process conditions used to obtain the material. In order to evaluate the effect of process variables (time, temperature and pH), collagen was extracted from the inner layer of bovine hide and subjected to hydrolysis under different conditions of temperature (50, 60 and 80°C) and pH (3, 5, 7 and 10) for 6 hours. The products were evaluated for soluble protein content, surface charge, molecular weight distribution, protein denaturation, gelling and emulsifying capacity. The products showed soluble protein content between 5 and 82% (w / w), in which the highest values were obtained in the treatments carried out at higher temperature and/or under more acidic conditions. Products obtained under extreme conditions of pH (3 and 10) or temperatures above or similar to the collagen denaturation temperature (80 and 60°C, respectively) were more denatured. In general, the hydrolysates obtained at acidic pH formed firmer gels, except that produced at 80°C. The hydrolysates obtained in the other pH values (5, 7 and 10), in turn, formed gels with low values of strain at fractures but, when treated at temperatures above the denaturation during long time, they showed an improvement in those properties. The water holding capacity (WHC) was approximately 100%, except for hydrolysates obtained at pH 7 and 10 and temperature of 50°C. The emulsifying capacity of such hydrolysates, was also evaluated in oil/water (O/W) emulsions. The stability of the emulsion increases with decreasing pH and increasing hydrolysis time, but only at pH 3 and 6 hours of process the emulsion showed no phase separation. These emulsions showed low polydispersity and droplet size between 1.5 and 5 µm. At pH values near the pI of collagen the formation of aggregates that destabilized the emulsions occurred, which resulted in higher droplet size (between 8 and 17 mm). The stable emulsions showed shearthinning behavior, but in case of emulsions in which phase separation occurred, the lower phase (aqueous) always presented Newtonian behavior, while the cream phase was a shearthinning fluid. In general, lower temperatures and acid pH, allows the production of hydrolysates with good mechanical properties, however, at higher temperature gives a product with high solubility. If the goal is to obtain a gel with high water retention capacity, it is indicated using pH below or close to the pI or elevated temperatures. To improve the emulsifying capacity the use of pH below the pI is the most suitable / Mestrado / Engenharia de Alimentos / Mestre em Engenharia de Alimentos

L'objectif a été de formuler des émulsions multiples Hydrophile/Lipophile/Hydrophile de taille nanométrique par autoémulsification, d'évaluer leurs cytotoxicités et le taux d'encapsulation. Trois formules ont été développées. La phase lipophile est composée de : triglycéride à chaine moyenne et de deux agents de surface : formules (a) Polysorbate 85 (PS85) / Labrasol®, (b) PS 85 / Cremophor® EL, (c) Glycérol / PS85. Les tailles des globules multiples des formules sont (a) 150 nm, (b) 40 nm et (c) 200 nm. La stabilité est de (a) 24 h, (b) 6 mois et (c) 2 mois. Le système multiple a été caractérisé par microscopie électronique à transmission et calorimétrie différentielle à balayage (DSC). L'évaluation de la viabilité cellulaire a montré une cytotoxicité aigüe (a) et retardé (b) et absence de cytotoxicité (c). La stabilité de la formulation (c) a été améliorée par ajout d'un glycéride hémisynthétique (Suppocire®DM). Différentes méthodes d'évaluation du taux d'encapsulation ont été testées, des méthodes usuelles (ultracentrifugation, dialyse) et d'autres méthodes (dégradation enzymatique, intercalant de l'ADN) avec des résultats montrant une interaction. La mise en évidence de la formation de micelles de PS85 dans la phase aqueuse externe a permis d'expliquer cette interaction. L'ultrafiltration a montré que le PS85 encapsulait du principe actif dans la phase aqueuse externe. L'évaluation de l'encapsulation de DTPA-Europium par DSC a permis détecter un taux d'encapsulation de 68 %. Du DTPA-Gadolinium incorporé dans la phase aqueuse interne a montré une supériorité comme agent de contraste positif par imagerie par résonnance magnétique par rapport à la solution de référence. / The aim was to formulate nanoscale Water/Oil/Water (W/O/W) multiple emulsion (ME) byself-emulsification, to evaluate their cytotoxicity and the encapsulation rate of DTPAEuropiumsolution. Three W/O/W ME have been developed. The lipophilic phase is composed of medium chain triglyceride (MCT) and two surfactants (ratio 7/3), which are : formulations:(a) Polysorbate 85 (PS85) / Labrasol ®, (b) PS85 / Cremophor EL®, (c) Glycerol / PS85. The sizes of multiple droplets are (a) 150 nm, (b) 40 nm and (c) 200 nm. Stabilities are (a) 24 h, (b)6 months and (c) 2 months. Multiple system has been characterized by transmission electronmicroscopy and differential scanning calorimetry (DSC). Evaluation of cell viability showacute cytotoxicity (formulation a), delayed cytotoxicity (formulation b) and no cytotoxicity(formulation c). The stability of formulation (c) has been improved by adding to the oily phase a hemisynthetic glycerid (Suppocire® DM). Different methods of evaluation of encapsulation rate have been tested: conventional methods (ultracentrifugation, dialysis, conductivity) and methods used for other nanosystems (enzymatic degradation, DNA intercalating). Results have shown an interaction. The demonstration of the formation of micelles or an emulsion ofPS85 in the external aqueous phase allowed explaining this interaction. Ultrafiltration was used to characterize it and to show that the PS85 encapsulates the active subtance in the external aqueous phase. Evaluation of the encapsulation of a solution of DTPA - Europium byDSC has overcome this interaction, and detecting an encapsulation rate of about 68 %. The incorporation of a solution of DTPA - Gadolinium in the internal aqueous phase has shown superiority as a positive contrast agent in magnetic resonance imaging as compared to a reference solution.

Sucrose esters have an established use in food industry as emulsifiers. Two novel lactose esters (lactose monodecanoate and lactose monomyristate) were synthesized and studied for their antimicrobial and emulsification properties. Lactose is a byproduct in cheese production and is an inexpensive carbohydrate source. The antimicrobial activity of lactose monodecanoate (LMD) and lactose monomyristate (LMM) was tested against the growth of seven different bacteria. Both esters, when dissolved in dimethoxy sulfoxide (DMSO), proved bactericidal against Bacillus cereus, Mycobacteria KMS and Streptococcus suis. LMM/DMSO was bactericidal against B. cereus at concentrations between 1 and 3 mg/ml. LMM/DMSO was bactericidal against M. KMS and S. suis at concentrations between 3 and 5 mg/ml. LMD/DMSO was bactericidal against B. cereus and S. suis at concentrations between 1 and 3 mg/ml and against M. KMS at concentrations between 0.1 and 1 mg/ml. LMM/DMSO and LMD/DMSO were not effective in inhibiting the growth of Listeria monocyotgenes and Enterococcus faecalis. The antimicrobial effects of LMD on the growth of Listeria monocytogenes and Enterococcus faecalis were found to be solvent dependent. LMD, when dissolved in 30% ethanol, was able to inhibit the growth of L. monocytogenes at concentration between 1 and 3 mg/ml and E. faecalis at concentration between 3 and 5 mg/ml. The growth of Streptococcus mutans and Escherichia coli O157:H7 remained unaltered in the presence of LMD/ETOH, LMD/DMSO and LMM/DMSO up to 5 mg/ml. LMM was also analyzed for its emulsification properties. The destabilization rates and droplet size of the emulsion were determined for five consecutive days. At a concentration of 0.5%, LMM produced 20% oil in water emulsion with destabilization rate of 1.1 mm/day, which can be considered a stable emulsion. The droplet size of the emulsion was also within the range of 0-10 μm. Lower droplet size range signifies the effective work of the LMM as an emulsifier. Also the droplet size of the emulsion was found to be consistent over five days, which is indicative of a stable emulsion.

Solvent-free extrusion emulsification (SFEE) is a novel emulsification technology that operates without solvent to produce sub-micron sized particles (100–200 nm) using a twin-screw extruder (TSE) with high viscosity polymers (up to 600 Pa.s has been tested to date) and only water as the liquid medium. Surfactants have always been known to play a key role in the success of the SFEE process, however very little work has been done to investigate the mechanisms by which they operate, along with isolating the region of the process to which they play the most vital role. The first part of this thesis focused on an investigation into how different surface-active properties impacted the mechanism of SFEE. Three ionic (SDBS, Unicid 350, Calfax DB-45) and three non-ionic surfactants (Igepal CO-890, Brij 58, Synperonic F-108), each with differing surface-active properties were tested in solvent emulsification (SE) prior to their evaluation in SFEE. Synperonic F-108 was the only surfactant found unsuccessful in the SE process, and was therefore disregarded prior to SFEE testing. Of the three ionic surfactants, SDBS and Calfax were the only ones found to successfully create a stable emulsion in SFEE; the latter species doing so with 50% reduced molar loading. Igepal and Brij were found to produce very low amounts of emulsified material (5-25% of the total solids mass), requiring molar loadings that greatly exceed those of SDBS and Calfax to do so. Particles generated by both SE and SFEE were tested at extreme operating conditions to compare their relative stabilities, and were found to experience similar stability behaviours. This result reinforces previous findings that the dispersion stage controls the SFEE technique. The second part of this thesis continued the investigation on the use of non-ionics in SFEE, with a focus on the impact of their molecular structure on the overall process. Non-ionic surfactants with varying hydrophilic end group chain lengths were tested in SFEE, and it was determined that the optimal hydrophilic chain length was between 10–12 ethoxy units, where shorter chains resulted in coarse particle generation. The structure of the hydrophobic end group was tested as well, and through experimentation it was determined that a branched end group structure was slightly more beneficial than a linear end group to emulsion stabilization. As seen in the first part of this thesis, none of the new selection of non-ionic surfactants were capable of inducing sufficient phase inversion to result in a high percentage of emulsion leaving the extruder. The most promising ionic surfactant, Calfax DB-45, was combined with various promising non-ionic surfactants to create binary surfactant mixtures, and were tested in SFEE. Initial results yielded the most promising blend as Calfax/Igepal CA-630. After manipulation of both molar ratio and total surfactant loading, it was determined that a minimum Calfax loading of 0.06 mmol/g resin was required in the blend to achieve a stable 100 – 200 nm emulsion in both SE and SFEE processes, regardless of non-ionic concentration. The benefits of adding a non-ionic surfactant in the blend were seen with the substantial reduction of Calfax entrapped in the final latex particles, apparent by the distinct decrease in overall particle charge. A mini-study examining the impacts of increasing the viscosity of the water phase by hydrocolloid addition for the dilution stage has shown that positive changes to emulsion properties can be seen by this approach, but further experimentation is required before concrete conclusions can be made. / Thesis / Master of Applied Science (MASc) / The creation of nanoparticles has been a growing area of research in recent years, with numerous different means of generation being developed. Extruders have seldom been used for the generation of nanoparticles due to issues related to controlling generated particle characteristics. Previous work has shown that twin-screw extruders are capable of generating 100–200 nm particles, but the process has shown minimal robustness to variations in operating conditions. The aim of this study has been to continue the work of nanoparticle generation within a twin-screw extruder, with a specific focus on the impacts that special soap-like particles (surfactants) have on the process. Surfactants are special particles consisting of both a hydrophilic (“water-loving”) and hydrophobic (“water-hating”) end group that allows multiple substances to combine on a chemical level. Variations in the molecular structure and electronic charge of these surfactants, along with blends of different types of surfactants have been tested to gain a better understanding of their role in the process, and hopefully increase the overall robustness of the process. Overall, it was determined that surfactants with a negative charge were more successful in creating polyester latex particles than ones with a neutral molecular structure. The blending of a charged and neutral surfactant has been shown in this study to not only be successful in generating particles of desired size, but have also shown the ability to reduce the overall charge of the final latex particles.