Dissertations / Theses on the topic 'Fouling interaction'

Fouling is a chronic problem in many heat transfer systems and results in the need for frequent heat exchanger (HEX) cleaning. In the dairy industry, the associated operating cost and environmental impact are substantial. Antifouling coatings are one mitigation option. In this work, the fouling behaviour of fluoropolymer, polypropylene and stainless steel heat transfer surfaces in processing raw milk and whey protein solution are studied. Methodologies to assess the economics of antifouling coatings are developed and applied. Two experimental apparatuses were designed and constructed to study fouling at surface temperatures around 90 °C. A microfluidic system with a 650 x 2000 µm flow channel enables fouling studies to be carried out by recirculating 2 l of raw milk. The apparatus operates in the laminar flow regime and the capability to probe the local composition of delicate fouling deposit $\textit{in-situ}$ with histological techniques employing confocal laser scanning microscopy. A larger bench-scale apparatus with a 10 x 42 mm flow channel was built to recirculate 17 l of solution in the turbulent flow regime which is more representative of conditions in an industrial plate HEX. Experimental results demonstrate that fluoropolymer coatings can reduce fouling masses from raw milk and whey protein solution by up to 50 %. Surface properties affect the structure and composition of the deposit. At the interface with apolar surfaces raw milk fouling layers are high in protein, whereas a strongly attached mineral-rich layer is present at the interface with steel. Whey protein deposits generated on apolar surfaces are more spongy and have a lower thermal conductivity and/or density than deposits on steel. The attraction of denatured protein towards apolar surfaces and the formation of a calcium phosphate layer on steel at later stages of fouling are explained with arguments based on the interfacial free energy of these materials in water. The financial attractiveness of coatings is considered for HEX subject to linearly and asymptotically increasing fouling resistance and using a spatially resolved fouling model. An explicit solution to the cleaning-scheduling problem is presented for the case of equal heat capacity flow rates in a counter-current HEX. Scenarios where the use of coatings may be attractive or where there is no financial benefit in cleaning a fouled exchanger are identified. Finally, experimental data are used to estimate the economic potential of fluoropolymer coated HEXs in the ultra-high-temperature treatment of milk. In the considered case, the value of a fluoropolymer coating inferred from the reduction in fouling is estimated to be around 2000 US$/m².

This dissertation introduces assembly of spherical particles as a novel topography-based anti-biofouling coating. It also provides new insights on the effects of surface topography, especially local curvature, on cell–surface and cell–cell interactions during the evolution of biofilms. I investigated the adhesion, colonization, and biofilm formation of the opportunistic human pathogen Pseudomonas aeruginosa on a solid coated in close-packed spheres of polystyrene, using flat polystyrene sheets as a control. The results show that, whereas flat sheets are covered in large clusters after one day, a close-packed layer of 630–1550 nm monodisperse spheres prevents cluster formation. Moreover, the film of spheres reduces the density of P. aeruginosa adhered to the solid by 80%. Our data show that when P. aeruginosa adheres to the spheres, the distribution is not random. For 630 nm and larger particles, P. aeruginosa tends to position its body in the confined spaces between particles. After two days, 3D biofilm structures cover much of the flat polystyrene, whereas 3D biofilms rarely occur on a solid with a colloidal crystal coating of 1550 nm spheres. On 450 nm colloidal crystals, the bacterial growth was intermediate between the flat and 1550 nm spheres. The initial preference for P. aeruginosa to adhere to confined spaces is maintained on the second day, even when the cells form clusters: the cells remain in the confined spaces to form non-touching clusters. When the cells do touch, the contact is usually the pole, not the sides of the bacteria. The observations are rationalized based on the potential gains and costs associated with cell-sphere and cell-cell contacts. I concluded that the anti-biofilm property of the colloidal crystals is correlated with the ability to arrange the individual cells. I showed that a colloidal crystal coating delays P. aeruginosa cluster formation on a medical-grade stainless-steel needle. This suggests that a colloidal crystal approach to biofilm inhibition might be applicable to other materials and geometries. The results presented in appendix 1 suggest that colloidal crystals can also delay adhesion of Methicillin resistant staphylococcus aureus (MRSA) while it supports selective adhesion of this bacterium to the confined spaces.
Ph. D.

Delisea pulchra is a red macroalga that produces furanones, a class of secondary metabolites that inhibit the growth and colonization of a range of micro- and macroorganisms. In bacteria, furanones specifically inhibit acyl homoserine lactone (AHL)- driven quorum sensing, which is known to regulate a variety of colonization and virulence traits. This thesis aims to unveil multiple aspects of the chemically mediated interactions between an alga and its bacterial flora. It was demonstrated that the quorum sensing genetic machinery of bacteria is laterally transferred, making traditional 16S rRNA gene based-diversity techniques poorly suited to identify quorum sensing species. Previous studies had shown that AHL-producing bacteria belonging to the roseobacter clade can be readily isolated from D. pulchra. Because of this, it was decided to use a roseobacter epiphytic isolate from this alga, Ruegeria strain R11, to conduct a series of colonization experiments on furanone free and furanone producing D. pulchra. Furanones were shown to inhibit Ruegeria strain R11's colonization and infection of D. pulchra. In addition, it was demonstrated that Ruegeria strain R11 has temperature-regulated virulence, similar to what is seen for the coral pathogen Vibrio shiloi. Rising ocean temperatures may explain bleached D. pulchra specimens recently observed at Bare Island, Australia. To assess whether quorum sensing is common within the roseobacter clade, cultured isolates from the Roseobacter, Ruegeria and Roseovarius genera were screened for AHL production. Half of the bacteria screened produced the quorum sensing signal molecules, AHLs. These AHLs were identified using an overlay of an AHL reporter strain in conjunction with thin layer chromatography (TLC). The prevalence of quorum sensing within the roseobacter clade, suggests that these species may occupy marine niches where cellular density is high (such as surface associated communities on substratum and marine eukaryotes). Diversity studies in marine microbial communities require appropriate molecular markers. The 16S rRNA gene is the most commonly used marker for molecular microbial ecology studies. However, it has several limitations and shortcomings, to which attention has been drawn here. The rpoB gene is an alternate ???housekeeping??? gene used in molecular microbial ecology. Therefore, the phylogenetic properties of these two genes were compared. At most taxonomic levels the 16S rRNA and rpoB genes offer similar phylogenetic resolution. However, the 16S rRNA gene is unable to resolve relationships between strains at the subspecies level. This lack of resolving power is shown here to be a consequence of intragenomic heterogeneity.

Aquaculture facilities involve mooring a large amount of artificial structures in offshore areas, which are colonised by a wide group of marine organisms, forming characteristic fouling communities. Many studies have focused on determining what sessile organisms are able to settle on nets, ropes and buoys, owing to the specific problems they cause and their economic cost to the aquaculture industry. Although sessile fouling communities are well-studied from the point of view of controlling this community on aquaculture facilities, little is known about the epifaunal mobile species inhabiting these artificial structures. This thesis addresses the study of crustacean amphipods, which have been scarcely studied regarding their species composition and relation to the habitats created by the sessile species and despite being detected in high abundances. After the general introduction, which sets the study framework, Chapter 1 is a preliminary study on the composition of fouling assemblages on aquaculture facilities in the Mediterranean Sea, comparing them with others such as those in harbours or offshore structures. Therein, it is shown that fouling communities are made up of mainly bivalves, algae, hydroids and bryozoans and amphipods usually represent more than 80 % of motile fauna associated with these organisms. Moreover, amphipod assemblages are characterised by seven frequent and dominant species: Elasmopus rapax, Jassa marmorata, Jassa slatteryi, Ericthonius punctatus, Stenothoe tergestina, Caprella equilibra and Caprella dilatata. A quantitative study of amphipod densities is carried out in Chapter 2, where mean amphipod densities observed in fish farm fouling amounted to 176,000 ind.m-2 and reached maxima up to 1,000,000 ind.m-2. There, the role of the macro- and microhabitat in supporting such amphipod communities is explored. The effect of the modification of marine currents on pelagic communities due to the introduction of coastal infrastructures is analysed in Chapter 3. Therein, it was detected a retention effect on planktonic amphipods near such facilities, noticeable in the increased abundance of hyperiids and migrating amphipods from different benthic and floating habitats. The influence of fouling amphipods on other habitats is analysed in Chapters 4 and 5, it is shown that fish-farm fouling acts as a source population of amphipods dispersing towards both defaunated sediments in soft-bottoms and surrounding floating habitats. Finally, in the last chapter, based on the possibility of using wild fauna already growing in fish farms, the applicability of amphipods as an accessory culture is tested in an offshore integrated multi-trophic aquaculture (IMTA) system with finfish as main fed species. Throughout this thesis it has been shown that fish-farming activities affect the amphipod assemblage in several ways such as the establishment of high population densities or the intimate connectivity between different subpopulations. As a result, a new potential commercial application arises from the possibility of using them as biofilters of aquaculture wastes, within an off-coast integrated multitrophic aquaculture system, promoting a more sustainable development of aquaculture in the marine environment.
Las estructuras artificiales que conforman las instalaciones de acuicultura en mar abierto suelen ser colonizadas por multitud de organismos marinos, que forman comunidades de fouling características en estas estructuras. Muchos estudios se han centrado en la descripción de los organismos sésiles que se desarrollan sobre cabos, redes y boyas de las instalaciones de acuicultura, debido a los problemas que generan para el cultivo y los costes adicionales que significan para la industria derivados de su necesaria eliminación. Sin embargo, aunque las comunidades de fouling sésiles han sido bien estudiadas desde el punto de vista de su control en las instalaciones de acuicultura, poco se sabe sobre la epifauna que habita estas estructuras artificiales. Esta tesis se centra en el estudio de los crustáceos anfípodos, los cuales aún no han sido estudiados en cuanto a la composición de especies y a su relación con los hábitats creados por los organismos sésiles, a pesar de haber sido detectados en grandes abundancias en las instalaciones de acuicultura. Después de una introducción general, que establece el marco de estudio, el capítulo uno es un estudio preliminar sobre las comunidades de fouling de las instalaciones de acuicultura en el Mediterráneo, comparándolas con las desarrolladas en otras estructuras artificiales como puertos o plataformas petrolíferas. En este capítulo, se demuestra que las comunidades de fouling están compuestas principalmente por bivalvos, algas, hidrozoos y briozoos y que más de un 80% de la fauna asociada a estos organismos son anfípodos. Además el poblamiento se caracteriza por la presencia de siete especies de anfípodos que son frecuentes y abundantes: Elasmopus rapax, Jassa marmorata, Jassa slatteryi, Ericthonius punctatus, Stenothoe tergestina, Caprella equilibra y Caprella dilatata. Un estudio cuantitativo de las densidades de estos anfípodos se lleva a cabo en el capítulo 2, donde se encuentra que la densidad media es de 176.000 ind.m-2, con máximos de más de 1.000.000 ind.m-2. Allí se explora también el papel de los macro y microhábitats en mantener dichas poblaciones de anfípodos. El efecto de la modificación de corrientes sobre las comunidades plantónicas debida a la instalación de las piscifactorías se analiza en el capítulo 3. En él, se detectó una retención de los anfípodos planctónicos cerca de las instalaciones, evidenciada por el incremento en las abundancias de hipéridos y de anfípodos migradores desde diferentes hábitats bentónicos flotantes. La influencia de las grandes densidades de anfípodos del fouling sobre otros hábitats se estudia en los capítulos 4 y 5, donde se observó que el fouling actúa como fuente de anfípodos migradores, exportando individuos que colonizan tanto sedimentos defaunados en el fondo marino como otros hábitats flotantes cercanos. Finalmente, en el último capítulo se analiza la posibilidad de aprovechar la producción natural y la conectividad observadas a través del cultivo de anfípodos como parte de un sistema de acuicultura multitrófica integrada (AMTI) en mar abierto con peces como especie principal. A lo largo de esta tesis, se demuestra que la acuicultura influencia las poblaciones de anfípodos marinos, tanto en el establecimiento de grandes densidades de población como en la conectividad entre las diferentes subpoblaciones. Como resultado, surge una nueva aplicación comercial de la posibilidad de usar los anfípodos del fouling como biofiltros, reciclando los residuos de la acuicultura dentro de un sistema de acuicultura multitrófica, garantizando así un desarrollo más sostenible de la acuicultura en el medio marino.

Humans have caused grave ecological and economic damage worldwide through the introduction of invasive species. Understanding the factors that influence community susceptibility to invasion are important for controlling further spread of invasive species. Predators have been found to provide biotic resistance to invasion in both terrestrial and marine systems. However, predators can also have the opposite effect, and facilitate invasion. Therefore, recovery or expansion of native predators could facilitate the spread of invasive species. Needles et al. (2015) demonstrated that the threatened southern sea otter (Enhydra lutris nereis) facilitated the invasion of an exotic bryozoan, Watersipora subatra. However, the underlying mechanism was not fully understood. We tested the hypothesis that sea otter predation on Romaleon antennarium crabs indirectly facilitated the abundance of W. subatra. To do this, we collected weekly data on sea otter foraging and quantified the abundance of crabs in the sea otter diet. We also conducted a caging experiment, where we experimentally manipulated crab densities and limited otter access using exclusion cages on pier pilings in Morro Bay, CA. We used photoQuad image processing software to calculate the abundance of W. subatra on PVC panels within each treatment group. We found that crabs were the second most abundant prey item in Morro Bay, comprising 25.1% of the otter diet. Through the caging experiment, we found that W. subatra abundance significantly increased as crab densities decreased. Our results indicated that sea otters indirectly facilitated the invasion of W. subatra by reducing R. antennarium crab densities and sizes. Removal of crabs may release W. subatra from the disturbance caused by crab foraging behavior. Understanding the impacts of top predators in invaded ecosystems has important management implications, as recovery of predator populations could unintentionally benefit some non-native species. Therefore, management should focus first on prevention and second on early detection and eradication of invasive species likely to benefit from predator recovery.

Macromolecular biomaterials often require covalent crosslinking to achieve adequate stability and mechanical strength for their given application. However, the use of auxiliary chemicals may be associated with long-term toxicity in the body. Oppositely-charged polyelectrolytes (PEs) have the advantage that they can self-crosslink electrostatically and those derived from marine organisms are an inexpensive alternative to glycosaminoglycans present in the extracellular matrix of human tissues. A range of different combinations of PEs and preparation conditions have been reported in the literature. However, although there has been some work on complex formation between chitosan (CS) and carrageenan (CRG), much of the work undertaken has ignored the effect of pH on the consequent physicochemical properties of self-crosslinked polyelectrolyte complex (PEC) gels, films and scaffolds. Chitosan is a positively-charged polysaccharide with NH3+ side groups derived from shrimp shells and, carrageenan is a negatively-charged polysaccharide with OSO3- side groups derived from red seaweed. These abundant polysaccharides possess advantageous properties such as biodegradability and low toxicity. However, at present, there is no clear consensus on the cell binding properties of CS and CRG or CS-CRG PEC materials. The aim of this study was to explore the properties of crosslinker-free PEC gels, solvent-cast PEC films and freeze-dried PEC scaffolds based on CS and CRG precursors for medical applications. The objective was to characterise the effect of pH of the production conditions on the physicochemical and biological properties of CS-CRG PECs. Experimental work focused on the interaction between PEs, the composition of PECs, the rheological properties of PEC gels and the mechanical properties of PEC films and scaffolds. In addition, cell and protein attachment to the PEC films was assessed to determine their interactions in a biological environment. For biomedical applications, these materials should ideally be stable when produced such that they can be processed to form either a film or a scaffold and have mechanical properties comparable to those of collagenous soft tissues. FTIR was used to confirm PEC formation. Zeta potential measurements indicated that the PECs produced at pH 2-6 had a high strength of electrostatic interaction with the highest occurring at pH 4-5. This resulted in stronger intra-crosslinking in the PEC gels which led to the formation of higher yield, solid content, viscosity and fibre content in PEC gels. The weaker interaction at pH 7-12 resulted in higher levels of CS incorporated into the complex and the formation of inter-crosslinking through entanglements between PEC units. This resulted in the production of strong and stiff PEC films and scaffolds appropriate for soft tissue implants. The PECs prepared at pH 7.4 and 9 also exhibited low swelling and mass loss, which was thought to be due to the high CS content and entanglements. From the range of samples tested, the PECs produced at pH 7.4 appeared to show the optimum combination of yield, stability and homogeneity for soft tissue implants. Biological studies were performed on CS, CRG and PECs prepared at pH 3, 5, 7.4 and 9. All of the PE and PEC films were found to be non-cytotoxic. When the response of three different cell types and a high binding affinity protein (tropoelastin) was evaluated; it was found that the CS-CRG PEC films displayed anti-adhesive properties. Based on these experimental observations and previous studies, a mechanistic model of the anti-adhesive behaviour of PEC surfaces was proposed. It was therefore concluded that the CS-CRG PECs produced might be suitable for non-biofouling applications.

The objective of this study was to understand the mechanism of lipid fouling in chromatography through the investigation of a hydrophobic interaction chromatography (HIC) operation. This was motivated by the need to understand this phenomenon during the manufacture of biological products such as vaccines. The systematic approach and novel analytical techniques employed create a unique platform to study fouling of other chromatographic adsorbents and process feed materials. HIC is employed as a primary capture step in the purification of yeast derived hepatitis R surface antigen (HBsAg), where the required cell disruption and detergent liberation steps release high levels of lipid content into the feed stream. From lipid- rich and lipid-depleted feedstocks, comparative analysis was able to quantify the deterioration in HIC performance (binding capacities, purities and recoveries) under successive cycles. Furthermore, a full mass balance on host lipids identified the highly hydrophobic triacylglyceride as the main foulant. Intra-particle distribution and progression of lipid fouling and its effects on material adsorption and diffusion were then examined under confocal laser scanning microscopy (CLSM). In addition, high- resolution scanning electron microscopy (SEM) images of the fouled bead (after 40 cycles) confirmed that a thick lipid layer was building up on the outer bead surface. Based on these findings, the mechanism of fouling was thought to be the rapid accumulation of lipid foulant at the rim of the bead, which was aggravated by the possible diffusion hindrance resulting from multi layer adsorption. Finally, pretreatments to reduce this mechanism of chromatography fouling were evaluated in terms of improvement on feed quality and HIC performance. Selective adsorbent polystyrene XAD-4 demonstrated promising lipid removal capabilities with satisfactory HBsAg VLP recoveries. The improved feed into the column resulted in a three-fold increase in product capacity, whilst the overall yield remained constant over 40 cycles.

Les bioréacteurs à membranes (BAM) sont de plus en plus utilisés dans le domaine du traitement des eaux résiduaires urbaines notamment lorsque le terrain est limité ou qu’un traitement épuratoire poussé est requis. Néanmoins, la gestion de ces installations et plus particulièrement du colmatage des membranes reste difficile et constitue toujours une source de problèmes pour les exploitants. La modélisation est un outil efficace et déjà éprouvé sur les procédés conventionnels à boues activées pour l’aide à la conduite et à la compréhension de procédé avec les modèles de boues activées de type ASM. Le traitement biologique donc, et aussi les capacités de filtration des membranes (colmatage) sont deux aspects qui peuvent être modélisés sur les BAM. Au cours de ce travail, trois installations réelles ont été étudiées et l’une d’entre elles a été choisie pour le calage du modèle ASM1. La méthodologie a été adaptée aux spécificités des bioréacteurs à membranes et de l’installation modélisée en particulier (fractionnement des eaux usées, calage de l’aération) et un nouveau jeu de paramètres de l’ASM1 a pu être constitué. L’influence des propriétés des boues activées et des conditions d’opération sur les capacités de filtration des membranes reste encore l’objet de nombreuses recherches, généralement sur installations pilotes, et la modélisation dans ce domaine n’en est qu’à ses débuts. L’objectif de ce travail concernant la filtration membranaire a été de caractériser le système « membrane/boues » à travers l’étude des interactions entre les propriétés des boues, les conditions d’opération et les paramètres de la filtration (perméabilité membranaire et vitesse de colmatage) à comparer avec les résultats de la littérature scientifique. Les deux BAM étudiés ont montré des comportements et relations entre paramètres assez différents confirmant la complexité des interactions entre membrane, boues et conditions opératoires
Membrane bioreactors (MBRs) are becoming increasingly popular for the treatment of municipal wastewater especially when land is limited or when the treatment requirements are high. Nevertheless, the operation of these plants and in particular the fouling of the membrane are still difficult to manage for the operators. Modelling is an efficient tool, which has already been successfully used on conventional activated sludge processes, for the operation and the understanding of the process using Activated Sludge Models (ASM). Biological treatment and membranes filtration capacity (fouling) are two aspects that can be modeled on MBRs. In this work, three full-scale plants were investigated and one of them was chosen for the ASM1 calibration. The usual methodology was adapted to the MBR specificities and to the modeled wastewater treatment plant in particular (wastewater fractionation, oxygen calibration) and a new set of ASM1 parameters was estimated. The influence of the sludge properties and the operating conditions on the membrane filtration capacity is still the subject of numerous studies, generally on pilot-scale MBRs, and modelling is in its early stages. The objective of this work regarding membrane filtration was to characterize the “membrane/sludge” system by studying the interactions between the sludge properties, the operating conditions and the filtration parameters (membrane permeability and fouling rate) and to compare them with the results from the literature. The two studied MBRs showed quite different behaviors and correlations between parameters, validating the statement that the interactions between membranes, sludge and operating conditions are very complex

碩士
國立中央大學
化學工程與材料工程研究所
95
The characteristics of preventing nonspecific adsorption of protein has lead to extensive usage of PEG and its derivatives for biomedical applications. We consider that the interaction of water with the PEG is a major determinant of preventing protein adsorption. However, the thermodynamics aspect of the mechanism has not been well addressed. Therefore, in this study, we described the hydration behavior of PEG by measuring the dilution heat of PEG with various salt concentration, types of salt ions, temperature and molecular weight of PEG. In addition, we measured the isotherms and the interaction enthalpy between protein and Ether-650S with various salt concentrations, salt types and temperature by batch isotherms and ITC. From the results of dilution heat, we observed that all the dilution heat are exothermic at all condition (i.e. salt conc. and types, temperature, PEG MW). It indicated that the PEG molecule is prefer to hydrate with water than aggregation in the conditions investigated. At high salt concentration, temperature and molecular weight of PEG, the dilution heat of PEG is less exothermic due to the poor hydration of PEG. In thermodynamics, the dilution of PEG is more energy unfavorable at high salt concentration, temperature and molecular weight of PEG. And the extent of salt ions which affect the hydration of PEG is consistent with the Hofmeister series. Besides, we also observed that all the values of Flory-Huggins parameter(χ) are negative at each condition. It also indicated that all the solvent which we used are good solvent for PEG. From the results of isotherm, the amount of lysozyme adsorb on Ether-650 will decrease with increase the salt concentration. We considered that both of hydrophobic and electrostatic interaction affect the binding affinity of lysozyme. The enthalpy of lysozyme adsorbed on Ether-650S are almost endothermic. It indicated that the hydrophobic force is the driving force during the adsorption process. However, the enthalpy of adsorption is exothermic at 1M KCl. This lead to the suggestion that the adsorption of lysozyme with the Ether-650 is of the “nonclassical” hydrophobic type interaction at 1M KCl. In this study, we also calculated the number of water molecules released during the adsorption by preferential interaction model. From the results of P.I Model, we can conclude : (1) when we adding ammonium chloride to the solution, the system released more water molecules than add that of potassium chloride during the binding process.(2)compare with literature data, PEG ligand have stronger capability of hydration than other hydrophobic ligands.

Interactions between two invasive alien species, Procambarus clarkii and Dreissena polymorpha, in the aquatic ecosystems of central Italy (DOTTORATO DI RICERCA IN ETOLOGIA, ECOLOGIA ANIMALE ED ANTROPOLOGIA)

Sootblowing is a process in which supersonic steam jets are used to periodically blast deposits off heat transfer tubes in kraft recovery boilers. However, sootblowing significantly consumes the valuable high pressure steam generated by the boiler, hence it should be optimized. A recovery boiler consists of three convective sections - superheater, generating bank and economizer. The tube arrangement in these sections, particularly the tube spacing is different from each other. Moreover, tubes in an economizer are finned. A sootblower jet will interact differently with these tube arrangements, potentially affecting its strength, and hence deposit removal capability. The objective of this work was to characterize jet/tube interaction in the three sections of a recovery boiler. Lab-scale experiments were conducted in which these interactions were visualized using the schlieren technique coupled with high-speed video, and were quantified by pitot pressure measurements. This work is the first to visualize the interactions. The offset between the jet and tube centrelines, the nozzle exit diameter relative to the tube diameter, and the distance between the nozzle and tube were varied to examine their effects on jet/tube interaction. Results showed that due to the very low spreading rate of a supersonic jet, a jet (primary jet) stops interacting with a superheater platen when the jet is only a small distance away from it. When the jet impinges on a tube, the jet deflects at an angle, giving rise to a weaker ‘secondary’ jet. Due to the large inter-platen spacing, a secondary jet has an insignificant impact in a superheater. In a generating bank, the primary jet weakens between the closely spaced tubes due to increased mixing. However, a secondary jet impinges on the adjacent tubes exerting a high impact pressure on those tubes. The primary jet also weakens between finned economizer tubes, but remains stronger for a greater distance than in a generating bank. As in the case inside a generating bank, a secondary jet also impinges on adjacent rows of tubes in an economizer. The results imply that in a superheater, a sootblower jet must be directed close to the platens to yield useful jet/deposit interactions, and to avoid wasting steam by blowing between the platens. In a generating bank, deposits beyond the first few tubes of a row experience a weaker sootblower jet, and thus may not be removed effectively. However, secondary jets may contribute to removing deposits from the first few adjacent tubes. They may also induce erosion-corrosion of those tubes. Secondary jets may also help remove deposits from adjacent rows in a finned tube economizer. In an economizer, the strength and hence, the deposit removal capability of a sootblower jet diminish only slightly beyond the supersonic portion of the jet. A mathematical model was also developed to determine the feasibility of using inclined sootblower nozzles in recovery boiler superheaters, and suggests that it may be possible to clean superheater platens more effectively with slightly inclined nozzles.

博士
中原大學
化學工程研究所
101
A systematic group of hyper-brush PEGylated diblock copolymers containing poly(ethylene glycol) methacrylate (PEGMA) and polystyrene (PS) was synthesized using an atom transfer radical polymerization (ATRP) method and varying PEGMA lengths. This study demonstrates the anti-biofouling membrane surfaces by self-assembled anchoring PEGylated diblock copolymers of PS-b-PEGMA on the microporous polyvinylidene fluoride (PVDF) membrane. Two types of copolymers are used to modify the PVDF surface, one with different PS/PEGMA molar ratios in a range from 0.3 to 2.7 but the same PS molecular weights (MWs , ~5.7 kDa), the other with different copolymer MWs (~11.4, 19.9, and 34.1 kDa) but the similar PS/PEGMA ratio (~1.70.2). It was found that the adsorption capacities of diblock copolymers on PVDF membranes decreased as molar mass ratios of PS/PEGMA ratio reduced or molecular weights of PS-b-PEGMA increased because of steric hindrance. The increase in styrene content in copolymer enhanced the stability of polymer anchoring on the membrane, and the increase in PEGMA content enhanced the protein resistance of membranes. The optimum PS/PEGMA ratio was found to be in the range between 1.5 and 2.0 with copolymer MWs above 20.0 kDa for the ultra-stable resistance of protein adsorption on the PEGylated PVDF membranes. The PVDF membrane coated with such a diblock copolymer owned excellent biofouling resistance to proteins of BSA and Lysozyme as well as bacterium of E. coli and S. epidermidis, and high stable microfiltration operated with domestic wastewater solution in a membrane bioreactor. For the part of interaction force analysis, a molecular simulation method was used to investigate the interaction between organic foulants and fluoropolymeric membranes, such as humic acid (HA) and dextran interacted with PVDF, polytetrafluoroethylene (PTFE) and polyvinyl fluoride (PVF) materials. The result indicated the hydrophilicity with water molecules followed the order: PVF＞PVDF＞PTFE. The simulated trend was consistent with experimental data of contact angle. Forthurmore, the result of RDF analysis implied that PVF material had more irreversible fouling due to higher interaction of hydrogen-bond with dextran. PVDF material easily attracted with HA because of hydrophobic interaction through energy calculation. PTFE reveal the lowest surface energy to resist water and foulants adsorbed on surface. Finally, the PEGylated copolymer improved hydrophilicity of PVDF membranes to reduce the foulants adsorption because of interaction with water molecules.

In dairy processing, dairy ingredients need to be thermally treated to ensure product quality and safety for an extended shelf life. During thermal processes, milk protein denatures and interacts with other dairy ingredients to form a layer of deposit on heated surfaces, known as fouling which can deteriorate process efficiency and product safety. Milk is a complex mixture of proteins, fats, carbohydrates, minerals and vitamins. The heat-sensitive B-lactoglobulin (B-lg) is known to be a key component in fouling formation (constituting 50% of type A fouling deposits) during milk pasteurization, as B-lg unfolds when heated and exposes the reactive sulfhydryl groups that can interact with other proteins and ingredients to form deposits. Although casein (80% of milk proteins) is known to interact with denatured B-lg, no fouling studies have been performed with particular focus on the effect of casein on whey protein fouling.

Carbohydrates are an ingredient widely added in various dairy products as sweetener, stabilizer, texturizer, and fat replacer. Simple sugars have a protective effect on whey protein denaturation, but their effect on dairy fouling is not known. Polysaccharides can interact with milk proteins through electrostatic and hydrophobic interactions, as well as hydrogen bonding. The addition of polysaccharide (carrageenan) has been reported to cause opposite effects on protein deposition, however, no conclusive mechanism has been proposed to elucidate how protein-polysaccharide interaction at pasteurization temperatures affects the fouling behavior of dairy products.

In this dissertation, different model dairy solutions and real dairy products were used to study the effect of composition, including protein distribution and additions of simple sugars and polysaccharides, on dairy fouling. Fouling deposits were formed and analyzed using a bench-top spinning disc apparatus operating under well-controlled temperatures and shear stresses characterized by computational fluid dynamics simulations. By studying the fouling behavior of camel milk and comparing with bovine milk, milk without B-lg was found to still foul and form deposits containing casein, α-lactalbumin, serum albumin with a reduced thermal resistance due to a more porous structure. Results also showed that the addition of 10 wt% sugar reduced whey protein fouling by more than 30% and affected the structure and adhesion strength of deposits. Furthermore, the presence of carrageenan in dairy solutions can promote the denaturation of B-lg when heated and form a more compact deposit, resulting in more severe fouling. Overall, this dissertation provides a fundamental understanding of the fouling characteristics of complex dairy products. The knowledge gained is expected to help the dairy industry select suitable ingredients to mitigate or prevent the fouling problem.

Produced water (PW), or water associated with crude oil extraction, is the largest oily wastewater stream generated worldwide. The reuse and reclamation of these important water volumes are critical for more sustainable operation in the oilfield. Ceramic membrane filtration is a promising technology for PW treatment; however, fouling is the major drawback for a broader application. Fouling leads to higher resistance to flow, reducing membrane lifetime, and ultimately leading to higher capital expenditures and operating expenses. Further understanding of the interactions between PW foulants and the ceramic materials is needed for designing fouling control strategies and cleaning protocols for ceramic membranes. This work explored different techniques to characterize, visualize, and quantify the submicron PW contaminants content and its adsorption interactions with metal oxides. We visualized and characterized submicron oil droplets in oilfield PW samples by applying suitable advanced microscopy techniques. For the first time, crude oil droplets as small as 20 nm were found in oilfield PW together with other submicron contaminants. The adsorption studies performed by quartz crystal microbalance with dissipation (QCM-D) showed that the interactions of organic surface-active compounds with the metal oxides are driven by the nature of the surfactant and not by the surface properties. This has implications in the selection of the ceramic membrane material, wherein electrostatic interactions should not be taken as the only predicting factor of adsorption and fouling during PW treatment. Furthermore, our results suggested that the more fluid or viscoelastic-like the contaminant layer, the more difficult the cleaning process from the metal oxide. It demonstrates that the mechanical property of the attached films is a crucial factor in designing appropriate cleaning protocols for ceramic membranes. Finally, QCM-D and advanced microscopy techniques were applied to analyze adsorption and cleaning of contaminants in a complex Bahraini PW into alumina as a case study. Bacteria were found to attach irreversibly on the alumina surface, promoting nucleation points for calcium precipitates. The protocols developed in this work are suitable for understanding membrane fouling phenomena in the micron scale and could be implemented before filtration pilot testing to save time and expenses at larger scales.

Membrane filtration is a promising advanced treatment method that has the technological capability to treat waters containing contaminants that typically escape traditional water treatment methods, including trace micro-pollutants as well as high salt concentrations. The accurate prediction of nanofiltration and reverse osmosis membrane performance in industrial applications is dependent upon understanding the fouling behavior of representative feed solutions. Combining conventional crossflow filtration experiments and characterization of foulant-foulant and foulant-membrane interactions, three mechanisms involved in combined fouling of organic and inorganic colloidal foulants are identified: increased hydraulic resistance of the mixed cake layer structure, hindered foulant diffusion due to interactions between solute concentration polarization layers, and changes in colloid and membrane surface properties due to organic adsorption. A range of typical organic foulants that exhibited different interactions in the membrane system were studied in combination with inorganic silica on low and high salt-rejecting membranes. Autopsying of the fouled membrane using iii transmission electron microscopy (TEM) helped identify combined fouling layer structure. Direct organic adsorption of BSA onto inorganic colloids was shown to cause the greatest synergistic fouling through creation of an aggregated fouling layer structure. A stratified, active salt-rejecting layer of natural organic matter minimizes cake enhanced osmotic pressure (CEOP) and reduces fouling. The presence of divalent ions can lead to the creation of salt concentrating layers by causing aggregation of alginate molecules and enabling CEOP. The effect of membrane surface chemistry on adsorptive fouling by organics was studied using self-assembled monolayers (SAMs) with different ending functionalities. Surfaces were characterized by hydrophobicity and surface free energy incorporating van der Waals and Lewis acid-base interactions. Acid-base interactions were dominant for all model membrane surfaces tested and total interfacial energies predicted natural organic matter and polysaccharide adsorption, but do not account for protein adsorption. Specific interactions, such as hydrogen bonding and electrostatic interaction between specific functionalities, playa more important role than non-specific electrostatic and hydrophobic interactions in adsorption of and irreversible fouling by proteins. Therefore, surface modifications of NF and RO membranes that minimize -COOH and -NHz as well as other charged sites may be an effective approach to develop fouling resistant membranes.

Protein-protein and protein-molecule interactions are complicated phenomena due to the tendency of proteins to change shape and function in response to their environment. Protein aggregation whether onto surfaces or in solution, can pose numerous problems in industry. Surface plasmon resonance (SPR) devices and quartz crystal microbalances (QCM) are two real-time, label free methods that can be used to detect the interactions between molecules on surfaces. These devices often employ self-assembled monolayers (SAMs) to produce specific surfaces for studying protein-protein interactions. The objective of this work was to develop methodologies utilizing SPR to better understand protein-protein and protein-molecule interactions with possible applications in the food and separation industrial sectors. A very well characterized whey protein, β-lactoglobulin (BLG), is used in numerous applications in the food industry. BLG can undergo different types of self-aggregation due changes in external environment factors such as buffer strength, pH or temperature. In this work, a hydrophilic SAM was developed and used to study the interaction and non-specific adsorption of BLG and palmitic acid (PA), a molecule which is known to bind to BLG. It was found that PA tended to reduce BLG conformational changes once on the surface, resulting in a decrease in its surface adhesion. Fluorescent excitation emission matrices (EEM’s) using a novel fluorescence probe technique were utilized to detect protein on the surface as well as conformational changes on the surface of the sensor, although the extent these changes could not be quantified. Another whey protein, α-lactoglobulin (AL), was utilized as a surrogate protein to study the adsorption of colloidal/particulate and protein matter (CPP) extracted from filtration studies of river water. A large fraction of natural organic matter (NOM), the major foulant in membrane based water filtration, is CPP and protein. Understanding the interactions between these components is essential in abating NOM membrane fouling. Several SPR methods were investigated in order to verify the interactions. A mixture of AL and CPP particles in solution prevented the non-specific adsorption of AL to the SAM surface. This change in association was then detected through SPR. Fluorescent EEM’s of the sensor surface verified that CPP and AL bound to the surface. This finding has fundamental significance in the interpretation of NOM-based membrane fouling. To better understand the mechanisms behind non-specific adsorption, a mechanistic mathematical model was developed to describe the adsorption of BLGs onto the hydrophilic SAM. The resulting model performed well in terms of predicting adsorption based on SPR data. The model incorporated the monomer-dimer equilibrium of BLG in solution, highlighting the impact of protein aggregation on non-specific adsorption mechanisms. For future studies, improvement in fluorescent FOP surface scan methodology would help identify different protein/molecules and conformations on the surface.

Work has been completed in the modeling of pressure-driven channel flow with particulate volume fractions ranging from one to ten percent. Transport of particles is influenced by Brownian and shear-induced diffusion, and convection due to the axial crossflow. The particles in the simulation are also subject to electrostatic double layer repulsion and van der Waals attraction both between particles and between the particles and channel surfaces. These effects are modeled using Hydrodynamic Force Bias Monte Carlo (HFBMC) simulations to predict the deposition of the particles on the channel surfaces. Hydrodynamics and the change in particle potential determine the probability that a proposed, random move of a particle will be accepted. These discrete particle effects are coupled to the continuum flow via an apparent local viscosity, yielding a dynamically updating quasi-steady-state velocity profile. Results of this study indicate particles subject to combined hydrodynamic and electric effects reach a highly stable steady-state condition when compared to systems in which particles are subject only to hydrodynamic effects.