Considerable research has been done to improve hydrate formation rate. One of the ideas is to introduce mechanical mixing which later tend to complicate the design and operation of the hydrate formation processes. Another approach is to add surfactant (promoter) that will improve the hydrate formation rate and also its storage capacity to be closer to the maximum hydrate storage capacity. Surfactant is widely known as a substance that can lower the surface or interfacial tension of the water when it is dissolved in it. Surfactants are known to increase gas hydrate formation rate, increase storage capacity of hydrates and also decrease induction time. However, the role that surfactant plays in hydrate crystal formation is not well understood. Therefore, understanding of the mechanism through morphology studies is one of the important aspects to be studied so that optimal industrial processes can be designed. In the present study the effect of three commercially available anionic surfactants which differ in its alkyl chain length on the formation/dissociation of hydrate from a gas mixture of 90.5 % methane – 9.5% propane mixture was investigated. The surfactants used were sodium dodecyl sulfate (SDS), sodium tetradecyl sulfate (STS), and sodium hexadecyl sulfate (SHS). Memory water was used and the experiments for SDS were carried out at three different degrees of under-cooling and three different surfactant concentrations. In addition, the effect of the surfactant on storage capacity of gas into hydrate was assessed. The morphology of the growing crystals and the gas consumption were observed during the experiments. The results show that branches of porous fibre-like crystals are formed instead of dendritic crystals in the absence of any additive. In addition, extensive hydrate crystal growth on the crystallizer walls is observed. Also a “mushy” hydrate instead of a thin crystal film appears at the gas/water interface. Finally, the addition of SDS with concentration range between 242ppm – 2200ppm (ΔT =13.10C) was found to increase the mole consumption for hydrate formation by 14.3 – 18.7 times. This increase is related to the change in hydrate morphology whereby a more porous hydrate forms with enhanced water/gas contacts. / Applied Science, Faculty of / Chemical and Biological Engineering, Department of / Graduate

The techniques mostly used to decontaminate air as well as water pollutants have drawbacks in terms of higher costs, require secondary treatment, and some methods are very slow. So, emphasis has been given to water though the use of photocatalysts, which break organic pollutants to water and carbon dioxide and leave no trace of by-products at the end. Photocatalytic remediation aligns with the waste and wastewater industries’ zero waste schemes with lower cost, eco-friendly and sustainable treatment technology. The commonly used photocatalysts such as titanium oxide (TiO2), zinc oxide (ZnO), tungsten oxide (WO3) have band gap of nearly 3.2 eV. The lower energy band-gap of a semiconductor makes it a better photocatalyst. The major drawbacks of photocatalysts are its inefficiency to work under visible light and high photocorrosion which limits its uses. These limitations can be mitigated through dopants and the formation of varying morphologies like nanowires, nanoparticles, nanotubes etc. Several organic pollutants are insoluble in water, which inhibits the pollutant (insoluble) to come in contact with photocatalytic material thus hindering remediation characteristic of a photocatalyst. Binder material used to immobilize the photocatalytic material tends to decompose due to oxidative and reduction reactions around the photocatalyst which causes the loss of photocatalytic material. This investigation displays the advantage of organic remediation in visible radiation using graphene (G) doped TiO2 nanoparticles and nanowires. The nanostructured G-TiO2 nanoparticles and G-TiO2 nanowires were synthesized using sol-gel and hydrothermal methods. The nanostructured materials were characterized using scanning electron microscopy (SEM), Transmission electron microscopy (TEM), X-ray diffraction (XRD), UV-visible spectroscopy (UV-vis), Fourier transform infrared spectroscopy (FTIR) and particle analyser procedures. The remediation of organic compounds (methyl orange) in water was achieved under visible radiation using graphene doped nanostructured photocatalytic materials. The sol-gel synthesized G-TiO2 nanoparticles has shown complete remediation of methyl orange (MO) in less than four hours, thus displaying enhanced photocatalytic activity achieved through graphene doping on TiO2 nanostructures The dopant and structure introduced in zinc oxide (ZnO) nanomaterials bring foundation for enhanced photocatalytic activity due to lowering of the band gap, and decreasing of photocorrosion through delaying of electron-hole recombination. The challenge to synthesize both nanowire and nanoparticle structures of ZnO doped with graphene (G) are carried out by simple and cost effective hydrothermal as well as super saturation precipitation techniques, respectively. Various nanostructures of ZnO have been synthesized using precipitation and hydrothermal methods are ZnO nanoparticles, G doped ZnO nanoparticles, ZnO nanowires, G doped ZnO nanowires, TiO2 seeded ZnO nanowires and G doped TiO2 seeded ZnO nanowires The synthesized ZnO based nanostructures were characterized using SEM, TEM, XRD, UV-vis, FTIR and particle analyser methods respectively. The standard organic pollutant methyl orange (MO) dye was employed in the water to understand the effective remediation using ZnO nanostructured materials under visible light radiation. The G-ZnO NW structure has shown effective remediation of MO in water in three hours compared to other synthesized nanostructured ZnO materials. The petroleum compounds were photocatalytically remediated from water using G- TiO2 nanoparticles material in visible light radiation. The G-TiO2 nanoparticle was synthesized using sol-gel technique and used on various petroleum-based chemicals (toluene, naphthalene and diesel) were remediated, and samples were analysed using optical and gas chromatography (GC) techniques. The importance of pollutant to come in contact with photocatalyst have been demonstrated by employing surfactant along with G-TiO2 nanoparticles to remediate naphthalene. Earlier studies in this investigation have shown that graphene (G) doping in both titanium oxide (TiO2) and zinc oxide (ZnO), has brought about a reduction in photocorrosion, and an increase in the photocatalytic efficiency for remediation of organics under visible light (λ > 400nm). However, the graphene doped photocatalysts have proven to be hard to coat on a surface, due to the strong hydrophobic nature of graphene. So, attempts have been made to use polyaniline (PANI), a conducting polymer, as a binder material by insitu polymerization of aniline over G-TiO2 nanoparticles (G-TiO2 NP) and G-ZnO nanowires (G-ZnO NW) & characterized using SEM, XRD, UV-vis and FTIR techniques. The photocatalytic, as well as photoelectrochemical catalytic performance of PANI:G-TiO2 NP and PANI:G-ZnO NW, were investigated. The standard MO in water was used for both PANI:G-TiO2 NP and PANI:G-ZnO NW electrodes on conducting substrates. 1:1 PANI:G-TiO2 NP shows an increase of 31% in the remediation of MO in water at potential of +1000 mV, and with the ease in coating PANI:G-TiO2 NP and PANI:G-ZnO NW on various substrates, on top of the visible light remediation allows for the use of these materials and process to be used for practical applications of remediation of organics from water.

L'objectif principal de ces travaux de thèse est l'étude expérimentale de la mobilisation de l'huile dans le cadre de la récupération assistée du pétrole à base de tensioactif dans un milieu poreux en deçà de la saturation en huile résiduelle. A saturation en huile résiduelle, le réseau d'huile est déconnecté et constitué de ganglions dans l'ensemble du milieu poreux. Cette huile résiduelle est difficile à produire dans les conditions classiques de récupération du pétrole à cause du piégeage capillaire des ganglions, piégeage corrélé à la tension interfaciale entre l'huile et l'eau. Le déplacement de la solution de tensioactif et sa caractérisation a été réalisé au travers d'injections en milieux poreux naturels. L'étude a été réalisée dans un premier temps en conditions monophasiques, c'est-à-dire en absence d'huile. Les courbes de percée ont été analysées pour étudier les paramètres de dispersivité et d'adsorption des échantillons. Les expériences sont ensuite utilisées pour améliorer la modélisation du transport du tensioactif en milieu poreux. Pour le cas diphasique, nous avons développé un système microfluidique avec une géométrie de pore variable, le plus représentatif possible d'un milieu poreux naturel. Il s'agit dans les expériences d'injecter un petit ganglion d'huile à travers un canal central et de balayer la puce microfluidique avec la solution tensioactive dans des conditions contrôlées. L'objectif est d'étudier le déplacement du ganglion d'huile au sein du micromodèle. De nouveaux mécanismes sont identifiés et une voie de modélisation des phénomènes physique est proposée. / The main objective of the PhD is to study experimentally the oil mobilization using surfactant in a porous media below the residual oil saturation. At the residual oil saturation, the oil network is disconnected and organized in ganglia of different sizes and shapes all along the sample. This residual oil is difficult to produce in the classical conditions of water flooding because of capillary trapping created by the interfacial tension between oil and water. Injection of surfactant is able to mobilize the remaining oil at flow rates consistent with the real case of an oil mature reservoir. The use of surfactant allows lowering the interfacial tension by several orders of magnitude, towards ultra-low values (10-3 mN/m), strongly decreasing the capillary forces and so, mobilizing the oil. The first main study of the PhD work was to characterize the displacement of the surfactant injected in a sandstone sample in monophasic conditions (without oil). Breakthrough curves have been analyzed in term of dispersivity and adsorption. Experiments have shown that a better way to model the surfactant transport is to use a Langmuir kinetic adsorption model. For the diphasic case, we have developed a microfluidic 2D system with a random pore geometry of controlled conditions. The experiments are based on the injection of a small ganglia through a central channel, then, a surfactant flood is generated. The aim is to see how ganglia are displaced within the micromodel. New mechanisms have been identified and a way to model those phenomena has been proposed. A better understanding of surfactant and oil transport in porous media is key for chemical enhanced oil recovery processes.

Kyoto University (京都大学) / 0048 / 新制・課程博士 / 博士(工学) / 甲第14634号 / 工博第3102号 / 新制||工||1461(附属図書館) / 26986 / UT51-2009-D346 / 京都大学大学院工学研究科材料化学専攻 / (主査)教授 大塚 浩二, 教授 木村 俊作, 教授 松原 誠二郎 / 学位規則第4条第1項該当

L'objectif de ce travail est le développement et la caractérisation de matériaux magnétiques (magsorbants) qui pourraient être intégrés dans un procédé assisté magnétiquement dont la finalité est de compléter les procédés actuellement utilisés dans les filières de traitement des eaux. Pour s'inscrire dans une démarche d'écoconception, nos matériaux sont des billes millimétriques constituées d'une matrice biopolymère (alginate ou chitosane) dans laquelle sont encapsulées des nanoparticules magnétiques. Ces billes sont bifonctionnelles, elles possèdent des propriétés adsorbantes permettant l'extraction de polluants organiques. Mais leur originalité réside dans leurs propriétés magnétiques qui sont mises à profit pour les séparer magnétiquement de l'eau à dépolluer. Les propriétés d'adsorption des billes magnétiques vis-à-vis de polluants organiques modèles ont été étudiées en regardant l'effet de différents paramètres tels que le pH et la force ionique de la solution, la concentration initiale en polluant et le temps de contact. Dans un premier temps, les polluants modèles considérés sont des colorants chargés. Nous avons montré que les billes d'alginate sont efficaces pour adsorber le bleu de méthylène chargé positivement alors que les billes de chitosane adsorbent le méthylorange chargé négativement. Par contre, le p-nitrophénol est faiblement adsorbé par les billes d'alginate et de chitosane. Pour pallier ce problème, deux solutions ont été proposées dans le but d'augmenter l'hydrophobicité des billes. La première consiste à ajouter un tensioactif cationique aux billes d'alginate. La deuxième solution est d'encapsuler une organobentonite dans les billes. / The aim of this thesis is the development and characterization of multifunctional materials called magsorbents that could be integrated in a water-treatment process to improve current methods or to develop new methods. These materials are millimetric beads with a polymer matrix in which are encapsulated magnetic nanoparticles of maghemite; in order to develop an environment-friendly product, biopolymers such alginate and chitosan were selected for the matrix. Our materials possess adsorbing properties allowing the extraction of organic pollutants from water. The originality of these materials lies in their magnetic properties that could be exploited for their magnetic separation from the treated medium. The adsorption characteristics of the magnetics beads were assessed by using two dyes: methyl orange (negatively charged) and methylene blue (positively charged). We showed that alginate beads are efficient for the removal of positively charged pollutants while chitosan beads adsorb preferentially negatively charged pollutants. p-nitrophenol is weakly adsorbed by both, alginate and chitosan beads. To overcome this problem, two solutions have been proposed in order to increase the beads hydrophobicity. The first one is adding a cationic surfactant, cetylpyridinium chloride, into alginate beads. The second solution is to encapsulate pillared clay into alginate beads. Both solutions show their efficiency in improving p-nitrophenol adsorption by alginate beads.

Abstract Respiratory syncytial virus (RSV) is one of the most common pathogens for early childhood respiratory tract infections. Most children are infected by RSV, approximately 1% of infants require hospital care. RSV infections are often accompanied by otitis media (OM). Surfactant proteins A and D (SP-A and SP-D) are involved in lung function and innate immunity. The proteins are capable of recognizing surface patterns in pathogens and function as a defense before the acquired immunity is developed. The Toll-like receptor (TLR) family is associated to several pathogens. The role of the TLR-family is to recognize pathogens and activate the immune defense. The aim of the thesis was to investigate the genetic association of RSV and OM infections in infants. A candidate gene approach was used study SP-A, SP-D and TLR4 in severe RSV bronchiolitis. Association between SP-A and OM was also studied. A case-control study setup was used for all studies. 1700 samples were collected for the studies. The results revealed genetic association between SP-A gene variation and severe RSV infections. SP-A allele 1A3 was overrepresented in RSV infants, the allele 1A was present more often in the control population. SP-D allele Met11 and genotype Met/Met were predisposing to severe RSV infections. The TLR4 gene did not show direct association with severe RSV. However, we showed for the first time difference in association in two separate epidemics. In the OM study, an association was shown between SP-A gene variations and otitis media in children. The present results have brought new information about innate defense and the genetic variations and associations involved. The results will help understand the mechanisms of innate defense and predisposition to infections. The results also present possibilities to investigate and develop new treatment strategies.

Abstract The Eustachian tube (ET) connects the upper respiratory tract and the middle ear. It equilibrates the pressure in the middle ear and prevents the harmful impact of the airways. Middle ear infection, or otitis media, is one of the most common illnesses in childhood and affects nearly all children at least once. ET dysfunction is considered to be a major pathogenic factor in the development of otitis media. Surfactant proteins A (SP-A) and D (SP-D) have an important role in the pulmonary host defence system, and interactions with bacteria that also cause middle ear infections raised a question about the expression of surfactant proteins in ET. The local defence system could be significant in preventing ear infections. The purpose of the study was to increase our basic knowledge of the putative ET surfactant system. ET and lung epithelia are both of endodermal origin, and ET epithelium with its mucociliary system resembles that of the lower airways. The aim was to determine whether SP-A, SP-B and SP-D are expressed in ET. The expressions were characterized with reverse transcriptase polymerase chain reaction (RT-PCR), Northern hybridizations and in situ hybridizations. The surfactant proteins were localized using immunohistochemistry and immunoelectron microscopy. The proteins were characterized with Western analyses, and the properties of the ET surfactant were evaluated using electrospray ionization mass spectrometry and a pulsating bubble surfactometer. SP-A, SP-B and SP-D were found to be expressed in porcine ET epithelium, and the cDNA sequences were homologous to those detected in lung tissue. The proteins were localized to specific ET epithelial cells, and their sizes were characteristic of lung SP-A, SP-B and SP-D. ET lavage fluid contained the surfactant proteins and phospholipid. However, the phospholipid molecular species and surface tension measurements showed the structure and function of the surfactant in ET to be different from lung surfactant, suggesting that a very low surface tension is not a critical determinant of ET surfactant function. As a conclusion, surfactant proteins in ET are likely to be involved in the local host defence system and may contribute to the mucociliary function of the tube.

Des formes galéniques spécialement étudiées permettent l'administration topique d'un médicament ou d'un actif cosmétique afin d'obtenir un effet local ou une action systémique. Les excipients présents dans la formulation, comme les tensioactifs dans les solutions micellaires, émulsions, microémulsions, nanoémulsions, nanostructures, peuvent être alors des éléments influençant la pénétration et la perméation de l'actif. L'étude de leurs effets sur la barrière cutanée peut être utile afin de choisir au mieux les différents composés de la formulation. L'objectif de cette thèse a été d'étudier l'effet de différents tensioactifs (alkylpolyglucosides, lipoaminoacides, alcools gras éthoxylés et copolymères à blocs de type Poloxamer) en solution aqueuse sur la structure et la fonction barrière de la peau, grâce à des techniques d'infrarouge à transformée de Fourier, de calorimétrie différentielle à balayage, de mesure de la perte insensible en eau et de microscopie électronique à transmission. L'objectif spécifique de ce travail a porté sur l'étude de l'absorption cutanée ex vivo de trois principes actifs de lipophilie différente (caféine, kétoprofène et progestérone) à travers un modèle de peau animale co-traitée par différents tensioactifs. Plus spécifiquement, la pénétration de la progestérone au sein des différentes couches de la peau a été étudiée compte tenu de sa lipophilie élevée limitant son passage dans les couches cutanées plus hydrophiles. A l'issue de ces travaux, nous montrons que les tensioactifs peuvent exercer non seulement des effets sur l'organisation lamellaire des lipides intercornéocytaires mais aussi sur les cornéocytes du stratum corneum (SC). Par ailleurs, ces différents résultats ont permis de définir les structures chimiques des tensioactifs favorisant l'absorption cutanée de principes actifs. Les tensioactifs anioniques comportant une chaîne aliphatique de 12 carbones augmentent sélectivement la perméation cutanée de principes actifs hydrophiles et la pénétration de principes actifs lipophiles dans les tissus cutanés. La pénétration cutanée de principes actifs est étroitement corrélée à la taille des micelles de tensioactif susceptible de s'incorporer dans les espaces intercornéocytaires du SC. Enfin, la valeur de concentration micellaire critique est une propriété physico-chimique permettant d'expliquer en partie l'effet des tensioactifs sur leur perméabilité cutanée / Dosage forms specially designed allow the topical administration of drugs or cosmetic active ingredients to obtain a local effect or a systemic action. Excipients, such as surfactants in micellar solutions, emulsions, microemulsions, nanoemulsions, nanostructures can influence the drug penetration and permeation. Understanding their effects on skin barrier is helpful in the choice of surfactant. The aim of this thesis was to study the effect of different surfactants (alkylpolyglucosides, lipoaminoacids, ethoxylated fatty alcohol and copolymers blocks) in aqueous solution on the skin barrier structure and function, using techniques like infrared Fourier transform, differential scanning calorimetry, transepidermal water loss measurement and transmission electron microscopy. The specific aim of this work focused on the ex vivo cutaneous absorption of three drugs showing different lipophilicity (caffeine, ketoprofen and progesterone) through animal skin co-treated by different surfactants. More specifically, the penetration of progesterone in the different skin layers has been studied due to its high lipophilicity limiting its permeation in the most hydrophilic layers (viable epidermis and dermis). At the outset, we showed that surfactants could provide not only an effect on lamellar organization of intercorneocyte lipids but also on the corneocytes into the stratum corneum (SC). Moreover, these different results allowed to define surfactant chemical structure increasing drug cutaneous absorption. Anionic surfactant with a C12 chain length increased significantly cutaneous permeation of hydrophilic drug and penetration of lipophilic drug into cutaneous tissue. Drug penetration is correlated with micelle size allowed its incorporation into SC intercorneocyte spaces. Finally, the value of its critical micellar concentration is a physico-chemical properties allowed to partially explain the surfactant effect on their cutaneous permeability

Water-in-oil (w/o) microemulsion systems, stabilised by either an anionic surfactant or a cationic surfactant were studied. The anionic system consisted of ethoxylated nonylphenol phosphate esters (Atpol), Shellsol oil and an alcohol. These microemulsions tolerated an increase in ionic strength of the water phase up to a point: Beyond this point no microemulsion could be obtained. However, adding amine salts, e.g. diethanolamine nitrite, improved the emulsification of the aqueous phase. Increasing the alcohol (cosurfactant) chain length up to octanol also increased the uptake of the aqueous phase. Thus octanol yielded the best results in terms of emulsifying large volumes of the water-phase, particularly at high salt concentrations. A key objective was to prepare stable microemulsions with high nitrite content. The maximum microemulsion nitrite contents (expressed as NaNO2equivalent by mass) achieved were: -- About 10% when a 30% NaNO2solution was emulsified -- 23% when neat diethyl ethanolamine nitrite (DEEAN) was solubilized, and -- 23% for mixtures of diethanolamine nitrite (DEtOHAN) and NaNO2 in water. The cationic microemulsion system was based on the double-chain cationic surfactant, didodecyldimethyl ammonium chloride (DDAC). In this case the solubilization of the following acetate salts were investigated: ammonium, sodium, magnesium, zinc and manganese. As with the Atpol system, it was found that increasing the ionic strength is detrimental to microemulsification of the aqueous phase. In the DDAC system, an increase in the alcohol chain length beyond butanol led to reduced aqueous phase uptake. Thus the natures and concentrations of the surfactant and the cosurfactant as well as the ionic strength of the aqueous phase determine the stability and the emulsification of large volumes of aqueous phase. In general there is an optimum ionic strength at which the salt content of the microemulsion formulation is maximised. / Dissertation (MSc (Chemistry))--University of Pretoria, 2007. / Chemistry / unrestricted

Fedmis Pty (Ltd) situated in Palaborwa, South Africa produces phosphoric acid using the wet process production process. For this study, two main areas of concern in the wet process phosphoric acid production were investigated. The first area is the formation of sludge in the system due to impurities that reduces the grade of the acid produced, thereby lowering the selling price. The second area is the crystallisation of the gypsum that influences filtration and thereby affects plant productivity. These two aspects were investigated separately as they occur in different steps of the production process at different acid concentrations. A major component of the acid sludge is known as x-compound, ((Fe,Al)3KH)14 (PO4)8.4H2O). The purpose of the investigation of x-compound is to determine what effects different ionic impurities have on its precipitation and to determine if these effects could be used to decrease the amount of sludge formation. Due to the complexity of the system and the wide variety of impurities only the major impurities were considered in this study. These impurities included potassium (K+), sodium (Na+), magnesium (Mg2+), aluminium (Al3+) and iron (Fe3+). For all the experiments investigating the effect of impurities, analytical reagents were used on laboratory scale. For the silica experiments, commercially available samples were used. For the experiments investigating the impurity effects on the precipitation of x-compound it was found that: <ul> <li> Agitation increases x-compound precipitation and can be used commercially to increase the precipitation rate to a point where sludge can be removed before transportation.</li> <li> Adding x-compound seeding crystals or magnesium ions also increases precipitation.</li> <li> Adding gypsum, sodium, hexafluorosilicates or fluorosilic acid reduces the precipitation, with sodium ions producing the lowest yield. This reduction is however not sufficient to be used commercially.</li> </ul> From the Raman study it became clear why x-compound precipitation is such a slow process. E At low acid concentrations, more H2PO4 - ions are present that form a complex with iron and aluminium. E As the acid concentration increases the concentration of H2PO4- ions decrease as the degree of dissociation of phosphoric acid decreases. The ferric- H2PO4- and aluminium- H2PO4- complexes become less stable and ultimately precipitation of the x-compound is favoured above solvation. E Addition of potassium impurities to the solutions had no visible effect on the Raman spectra and is suspected not to form a complex with the acid. From the silica sources investigated namely Dicalite, Serina Kaolin, Foskor silica and Aerosil 200 it can be concluded that none of the sources will be useful for the removal of potassium through formation of potassium hexafluorosilicates. For the determination of the concentration of impurities present in the production of phosphoric acid, the Fedmis monitoring program was initiated. It included the monitoring of Foskor rock analyses on a daily basis, and the monitoring of the 27%, 39% and 54% P2O5 phosphoric acid and precipitate, from these acid solutions on a weekly basis. From the investigation of the effect of these impurities on the solubility of potassium hexafluorosilicates, it was found that magnesium causes K2SiF6 to be the most soluble and fluoride the least. Unfortunately, the impurities did not help to reduce the potassium concentrations in the acid to below the required amount for sludge formation. For the calcium sulphate dihydrate surfactant experiments, the purpose of the investigation was to determine whether higher crystallisation qualities could be obtained to improve plant productivity. The investigation was limited to using surfactants with sulphate or phosphate functionalities and experiments were done on laboratory scale using analytical reagents. Atphos E3205, Atpol E3202 and Atpol E1231 are polyethoxylated alkyl phenol phosphate esters that had no visible effect on the crystal structure of the precipitated gypsum, but differences in the crystal sizes were observed. Smaller crystal structures with relatively equal masses compared to reference experiments are an indication of a growth inhibitor and a nucleation promoter as seen with Atphos E3205 and Atpol E3202. Increased crystal sizes were obtained using Atpol E1231. The use of Calsoline Oil caused a wider crystal size distribution in the precipitated crystals as thin and broad crystals with approximately the same length are found. The crystal mass obtained is also approximately the same as that of the reference experiment. Thus, it can be concluded that the surfactant affects the growth of the crystals and not the nucleation. Arlatone 1489, calcium gluconate monohydrate, Dowfax Hydrotrope and Tamol NN 8906 had no visible effect on the structure or size of the precipitated gypsum crystals. With the use of Nansa SS30, drastic effects were seen on the crystallisation of the calcium sulphate as small hexagonal rods were found. With an increase in surfactant concentration, there is a clear decrease in the mass of crystals obtained as well as crystal size. An increase in the crystal size distribution and a decrease in crystal size reduced the filtration rate dramatically. Experiments carried out for 24 hours exhibited the same trends where there is a decrease in yield with an increase in surfactant concentration. Higher yields were however obtained proving that mass transfer barriers were overcome. The results from these experiments again indicate that the surfactant affects crystal growth and nucleation. With the use of Dowfax 3B2 there is definite reduction in yield with an increase in surfactant concentration reaching a minimum at approximately 70% yield. Due to the presence of large amounts of smaller crystals and the almost constant yield obtained compared to the reference experiment, it can be concluded that this surfactant is a growth and not a nucleation inhibitor. As with Nansa SS30, experiments where Empicol LZ/D was used show a continuous decrease in the yield obtained with an increase in the surfactant concentration. At higher concentration of Empicol LZ/D, it seems as if this surfactant changed from a growth promoter to a growth inhibitor because although broad longer crystals are present, there are now also much smaller crystals formed. The crystal size distribution also broadens considerably. Overall, very high yields were obtained using Empimin KSN70 and the observed crystal size distributions were very narrow. The only difference was that the crystals appeared to be more porous or fibrous compared to the reference experiment. It is recommended that the experiments showing promise as crystal habit modifiers like Nansa SS30 and Empicol LZ/D be investigated in more detail as well as combinations of surfactants. Both the areas of concern in the process were investigated successfully. For the sludge formation problem, it is now clear what effects the precipitation of x-compound as well as what affect the impurities and operating conditions have. For the crystallisation of gypsum using surfactants, it was proven that surfactants could be used to affect crystal growth, shape and distribution and in this way influence filtration. / Dissertation (MSc(Chemical Engineering))--University of Pretoria, 2005. / Chemical Engineering / unrestricted