Solvent-free extrusion emulsification (SFEE) is new top-down technique specially suited to high viscosity polymers (100-1000 Pa.s) for producing sub-micron (100-500 nm) particles inside a twin screw extruder (TSE) without the use of hazardous solvents. SFEE has been difficult to implement in industry due to process sensitivities and a lack of mechanistic knowledge on how the polymer-water morphology must develop prior to inversion. To devise a mechanistic explanation of the critical stages of the process, an inline orifice-plate type viscometer was developed to monitor rheological changes previously witnessed in early batch studies. The general variables of study throughout the thesis included the manner by which sodium hydroxide (NaOH) can be added as well as the NaOH content necessary, resin-to-water (R/W) ratio, and surfactant content. The last study in the thesis explores the influence of matrix viscosity, which was accomplished by crosslinking the polyester. The striated lamellae morphology of the polyester-water system, critically controlling the final particle size, depended on two factors, specifically surface energy (determined by endgroup conversion and added surfactant) and matrix viscosity. Analysis of the rheological response indicated that a higher polar surface energy contribution had the greatest influence on the morphological state, demonstrating a steeper viscosity transition due to more favourable and more rapid incorporation of water within the polyester matrix. A strong correlation was repeatedly found between particle size and this viscosity transition, which has been related to the thickness of striated lamellae through a theory of lamellae coarsening (or thinning as is more relevant to the current process). The reported lamellae coarsening model in the literature, which shows the predominant effects of interfacial energy and viscosity on lamellae thickness in a mixed phase system showed excellent correspondence to the results in this thesis. Among the variables of study in this thesis, the dissolution of the sodium hydroxide species (when added as a solid particle) and the kinetics of end-groups conversion proved to be rate-limiting phenomena to generating thinner striated lamellae. The ionic strength of the system was notably important to the viscosity change occurring in the process as water was added for the first time and subsequently influenced the particle size produced, particularly when additional surfactant was not added and the system relied exclusively on the carboxylate endgroups present. Finally, with mounting evidence that SFEE showed significant sensitivity to the matrix viscosity, a final study examined the effectiveness of SFEE in the face of ever increasing viscous force by blending a crosslinked polyester into the neat resin at different weight fractions. With higher viscosity there was a corresponding decrease in interfacial area growth between the polyester and water, resulting in increased particle size but even with a viscosity near 800 Pa.s, far above a traditional oil-in-water system, it was still found possible in this study to create nano-sized particles by SFEE. / Thesis / Doctor of Philosophy (PhD)

No description available.

Granulation is an important process for industries ranging from plastics to food and pharmaceutics. In the last decades, the twin-screw extruder has been more and more studied as a continuous method for granulation. But there are many questions remaining to be answered such as the functions of kneading block and the granulation behavior in this zone, the influence of the wetting method, and also the influence of the active pharmaceutical ingredient (API) properties on the granulation process. Therefore, in this project, a series of experiments were performed based on a new technique to the granulation field named ‘screw pullout’ for understanding the granulation process within the twin-screw extruder. In order to understand the specific function of an important screw element known as a kneading block, the physical particle motion reflecting progress of granulation was monitored along the screw. Different feed rate and formulations were studied; the residence time and pressure in kneading block were measured; and the granules along the screw were characterized for their porosity and size distribution. It was found that granule consolidation and breakup within the kneading block allowed the production of granules with consistent properties and excellent mechanical strength. However, the changes produced by a kneading block are dependent upon the formulation. For example, the kneading block demonstrates no observable function with formulations containing a significant content of microcrystalline cellulose. The most notable benefit of the kneading block to all tested materials appeared to be distribution of the interstitial binding liquid rather than to compact the powders. A new wetting method using a foam binder has been studied intensively in this work to assess its influence on the granulation process. A series of studies have been performed to compare the granule development along the screws as powder formulation and screw design were varied to test for the differences induced by the two wetting methods (foam delivery or liquid injection). The evolution of the granules along the screw was characterized by analyzing the particles size distribution, porosity, and fracture strength. It was found that the wetting method had minor impact on the particle size distribution due to the strong mechanical dispersion inherent to the extruder. The major finding for the pharmaceutical industry was that the foam method reduces the required amount of liquid to granulate, thereby dropping drying time after the process. The foamed binder was also found to be preferred when the formulation contains powder components with poor spreading properties. Finally, the influence of an API’s physical properties on granulation was studied by comparing formulations with varying API hydrophobicity. It was found that the API and binder distribution was not affected by the hydrophilicity of API, while the particle size distribution, porosity and fracture strength were strongly dependent on the properties of the API. / Thesis / Master of Applied Science (MASc)

No description available.

Yes / It has been shown that seeded granules of calcium carbonate can be produced in commercial batch high shear granulators such as the Cyclomix high-shear impact mixer. Seeded granules are attractive to the pharmaceutical industry due to their high uniformity and good mechanical properties which can assist efficient tablet manufacture. In the current study, attempts to produce seeded granules of Durcal 65 and PEG 4000 binder using hot melt granulation are reported, in response to the recent shift towards continuous pharmaceutical manufacturing. Various screw configurations and rotation speeds were investigated in a series of experiments to determine the relationship between process conditions and granule properties. Particle size analysis, strength measurement and structural characterisation were used to quantify granule properties. It was found that using a series of kneading elements arranged at a 60° staggering angle located near to the feed section of the extruder screw generated strong, spherical granules. From structural characterisation approximately 5–15% of extruded granules were found to be seeded. Twin screw melt granulation is therefore considered to be a promising technique for continuous production of seeded granules, although a more detailed investigation is required to optimise yield and quality.

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.

L’extrusion biocatalytique, ou bioextrusion, est une technique d’extrusion réactive utilisant des enzymes comme catalyseurs. Cette technique est considérée en temps qu’étape intermédiaire, subséquente au prétraitement physico-chimique et précédente à l’hydrolyse enzymatique enréacteur fermé. L’utilisation de l’extrusion permet un procédé continu, facilement modulable et adaptable à des conditions de hautes consistances, de nombreuses biomasses et facilement transférable à l’échelle industrielle. Néanmoins, les données bibliographiques font ressortir la complexité des entrants et leurs interactions lors de la bioextrusion de biomasses lignocellulosiques. Les conclusions des bioextrusions de biomasses amidonnées soulignent l’importance de l’étude de l’influence de la concentration en substrat et en enzymes. Les résultats obtenus à partir de la bioextrusion des biomasses lignocellulosiques valident l’existence d’une activité enzymatique en extrudeuse malgré la contrainte thermomécanique et le temps de séjour limité. Lors de cette étape, l’hydrolyse de la fraction cellulosique est favorisée pour des milieux concentrés en substrat et en enzymes. Des modifications significatives des fractions cellulosiques cristallines et amorphes en surface, des réductions des tailles de particules, une dégradation visuelle des structures de la biomasse et l’augmentation de la sensibilité à la décomposition thermique, sont aussi observées sur la fraction solide. L’hydrolyse enzymatique des bioextrudats est prolongée en réacteur fermé. La bioextrusion permet des améliorations significatives des taux et vitesses de conversion des sucres sur le long terme, jusqu’à 48 h. Les gains observés sont relativement constants pour la paille de blé et augmentent avec le temps pour les écorces de bouleau et les résidus de maïs. Post-extrusion, la concentration en substrat influence négativement la conversion des sucres. Cependant, les plus-values de conversion du glucose lié à la bioextrusion de paille de blé sont principalement observables pour des concentrations en substrat et en enzymes élevées. À partir de 4 h, des baisses significatives de la conversion du xylose sont observées après bioextrusion. Les déstructurations de la fraction solide, déjà observées au cours la bioextrusion, se poursuivent en réacteur fermé. Les meilleurs résultats hydrolytiques aux niveaux des hautes charges en enzymes et en substrat sont associables aux bonnes conditions de mélanges caractéristiques des éléments bilobes. L’ensemble enzymatique est probablement réparti de façon plus homogène (mélange distributif) pour cibler plus de sites disponibles. De plus, le mélangé dispersif limite la proximité entre enzymes de même type et les gênes associées. Le procédé d’extrusion permet une agitation efficace, un bon transfert de masse et probablement un meilleur contact entre enzymes et substrat. Les moins bons résultats de conversion du xylose sont probablement à relier à des phénomènes d’adsorption non-spécifique, ou encore de désactivation des hémicellulases, provoqués par l’intensité des contraintes thermomécaniques et les résidus ligneux. Les bons résultats de déstructuration après bioextrusionsont associables à une action synergétique des contraintes mécanique et biochimique. Les analyses d’autofluorescence montrent l’évolution de la fraction ligneuse dans le processus de déconstruction de la fraction solide. Une production progressive de particules très fines,visiblement associée à la fraction ligneuse, est observée. Des complexes lignine-carbohydratessont aussi détectés dans la fraction liquide. Etant peu, voire pas hydrolysable par voie enzymatique, ces fractions hétéropolymériques sont un frein à la déconstruction. Si la déstructuration des lignines est probablement majoritairement liée au prétraitement alcalin, le procédé de bioextrusion provoque une diminution de la teneur en hétéropolymères de plus hautes masses moléculaires. / Biocatalytic extrusion, also named bioextrusion, is a reactive extrusion technique using enzymes as catalysts. Bioextrusion is considered as a link between the previous physico-chemical pretreatment (like alkaline extrusion) and the subsequent enzymatic hydrolysis in batch conditions. The extrusion allows a continuous, flexible and versatile process for high consistency media, easily transferable to the industrial level. However, complexity of both lignocellulosic biomass and lignocellulolytic enzymes and their interactions during the extrusion process are underlined by the literature. Numerous response surface methodology experiments with starchy biomass indicate that bioextrusion efficiency is mainly influenced by substrate and enzymes loading. Enzymatic activity during the bioextrusion process of lignocellulosic biomass is confirmed by the experiments despite the mechanical constraints and the limited residence time. During bioextrusion, best holocellulosic fraction hydrolysis results were obtained with high substrate and enzymes loadings. Significant modifications of the solid fraction like particule size reduction, visual deconstruction of the biomass structure, increased sensibility to thermal decomposition and the evolution of the surface exposure of crystalline and amorphous cellulose were observed. Enzymatic hydrolysis of the bioextrdates is prolonged in batch conditions. Clear improvements of speeds and rates of sugars conversion up to 48 h indicate a long term influence of the bioextrusion. Gain observed are steady for the pretreated wheat straw whereas it increases with time for corn residues and birch barks. Post-extrusion, a negative influence of the substrate loading is measured. However, best enhancements for the glucose conversion of pretreated wheat straw are detected for high substrate and enzymes loadings. From 4 to 48 h, significant losses in xylose conversion are measured with previous bioextrusion. Indicators of the solid fraction deconstruction, observed during the bioextrusion step, indicate a stronger biomass degradation after 48 h. Improvements of glucose conversion rates can be associated with good mixing conditions of the extruder, especially due to the use of kneading elements. Enzymes are probably more homogeneously distributed (distributive mixing) and can access more catalytic sites available. Moreover, dispersive mixing limits the enzyme jamming due to the biocatalysts concentration. Extrusion process permits an better agitation efficiency, good mass transfer conditions and probably a higher contact between substrate and enzymes. Lower xylose conversion results may be attributed to non-specific adsorptions or inactivation phenomena due to mechanical constraints and lignin residues. Good deconstruction results on the solid fraction may be associable with a synergetic action between mechanical and biochemical constraints. Autofluorescent signal analysis of the lignin fraction show its evolution during the deconstruction of the solid residue. During the hydrolysis, a progressive production of very small particles, appearing to be associated with the lignin fraction is observed. Lignin-carbohydrate complexes are also detected in the liquid fraction. These heteropolymeric complexes, difficult or even impossible for the enzymes to hydrolyze, are an obstacle to the biomass valorization. If lignin deconstruction is mainly due to the alkaline pretreatment, bioextrusion process seems to reduce the proportion of these heteropylymers with high molecular weights.

This research deals with the modeling and control of a plasticating twin screw extruder (TSE) that will be used to obtain consistent product quality. The TSE is a widely used process technology for compounding raw polymers. Compounding creates a polymer with improved properties that satisfy the demand of modern plastic applications. Modeling and control of a TSE is challenging because of its high nonlinearity, inherent time delay, and multiple interactive dynamic behavior. A complete methodology is proposed in this thesis to design an advanced control scheme for a TSE. This methodology was used to develop a model predictive control scheme for a laboratory scale plasticating TSE and to implement the control scheme in real-time. The TSE has a processing length of 925 mm and a length to screw diameter ratio (L/D) of 37. High density polyethylenes with different melt indices were used as processing materials. Manipulated variables and disturbance variables were selected based on knowledge of the process. Controlled variables were selected using a selection method that includes a steady state correlation between process output variables and product quality variables, and dynamic considerations. Two process output variables, melt temperature (Tm) at the die and melt pressure (Pm) at the die, were selected as controlled variables. A new modeling approach was proposed to develop grey box models based on excitation in the extruder screw speed (N), one of the manipulated variables. The extruder was excited using a predesigned random binary sequence (RBS) type excitation in N and nonlinear models relating Tm and Pm to N were developed using this approach. System identification techniques were used to obtain model parameters. The obtained models have an autoregressive moving average with exogenous (ARMAX) input structure and the models explain the physics of the extrusion process successfully. The TSE was also excited using a predesigned RBS in the feed rate (F) as a manipulated variable. Models relating Tm and Pm to F were developed using a classical system identification technique; both models have ARMAX structures. The model between Pm and F was found to give excellent prediction for data obtained from a stair type excitation, indicating that the obtained models provide a good representation of the dynamics of the twin screw extruder. Analysis of the TSE open loop process indicated two manipulated variables, N and F, and two controlled variables, Tm and Pm. Thus, a model predictive controller (MPC) was designed using the developed models for this 2X2 system and implemented in real-time. The performance of the MPC was studied by checking its set-point tracking ability. The robustness of the MPC was also examined by imposing external disturbances. Finally, a multimodel operating regime was used to model Tm and N. The operating regime was divided based on the screw speed, N. Local models were developed using system identification techniques. The global model was developed by combining local models using fuzzy logic methodology. Simulated results showed excellent response of Tm for a wide operating range. A similar approach was used to design a global nonlinear proportional-integral controller (n-PI) and a nonlinear MPC (n-MPC). Both the controllers showed good set-points tracking ability over the operating range. The multiple model-based MPC showed smooth transitions from one operating regime to another operating regime. / Process Control

No description available.

One of the current problems faced by mankind is the problem of safe disposal of waste rubber. Statistics show that the number of waste tires is continuously increasing at a very rapid rate. Since rubber materials do not decompose easily (due to their crosslinked structure), they end up being a serious ???environmental problem???. An intuitive solution to prevent the accumulation of the scrap tires is to continuously reuse them. A new patented reclamation method was discovered in our laboratory, which makes use of a twin screw extruder (TSE) in order to produce reclaimed rubber (referred as devulcanized rubber (DR) from here on) of very high quality. Also, this method has proven to be more economical than other commercial reclaiming methods. Products made solely from a reclaimed material face challenges from those made by virgin materials because of relatively poor properties. However, the striking advantage of using reclaimed rubbers is the cost reduction. Hence, it is important to work on establishing methods by which these reclaimed rubbers could be efficiently used and incorporated into present day products. The deterioration of properties could be minimized by blending them with varying amounts of other materials. A possibility in this direction is manufacturing of thermoplastic vulcanizates (TPVs) using reclaimed rubber and general purpose thermoplastics. In accordance with this idea, the focus of this research is to prepare DR and polypropylene (PP) based TPVs. DR is unique as the rubber itself consists of two phases- one phase consisting of uncrosslinked (including devulcanized rubber molecules), and the other phase consisting of crosslinked (un-devulcanized) rubber. These un-devulcanized crumbs act as stress concentrators because they do not break-up easily, and lead to poor physical properties. Hence, this project tries to find out ways to increase the interfacial adhesion between the rubber and PP by using reactive and non-reactive techniques. Preliminary experiments were carried out in a batch mixer to compare DR and rubber crumb (CR). DR based TPVs showed better properties than CR based TPVs, however, the properties were not useful for commercial applications. Sulphur based dynamic vulcanization was studied in a batch mixer and found to be not effective in improving the properties of DR based blends. On the other hand, DCP/ sulphur based curing system was found to show significant improvement in properties. Therefore, DCP/sulphur based curing package was studied in detail on the blends consisting of DR and PP. The optimum ratio of DCP/sulphur was found to vary depending on the ratio of DR/PP. A hypothesis regarding the mechanism of DCP/sulphur curing has been proposed, which seem to correlate well with the experimental results observed. Additionally, it was determined that DR prepared from tire rubber (DRT) performed better than DR prepared from waste EPDM (DRE) for the curing system used. Accordingly, experiments on a TSE were carried out using DRT and a combination of compatibilizing resins and curatives. This combination showed a drastic improvement in blends properties and once again the optimum ratio of compatibilizing resins seemed to depend on the ratio of DRT/PP. As a result of the work, successful strategies based on reactive compatibilization techniques were developed in order to prepare useful TPVs having up to 70% DR. A series of compatibilization techniques has been evaluated using design of experiments and various characterization techniques such as mechanical tests, scanning electron microscopy, thermal analysis and crosslink density measurements. This led to the development of a formulation, which could improve the blend properties significantly. A tensile strength of around 10 MPa and an elongation-at-break of 150-180 % could be achieved for devulcanized rubber (70%) based TPVs, which has broadened the scope for its commercial applications. In addition to that, the process was established on a TSE that has enabled a continuous and steady production of these TPVs with reasonable throughputs.