Doctor of Philosophy / Department of Grain Science and Industry / Yong Cheng Shi / The reaction of starch and octenylsuccinic anhydride (OSA) produces lipophilic starch that has the ability to stabilize oil-in-water emulsions. The functional properties of octenylsuccinate (OS) starch depend on its molecular structure and distribution of OS groups. Structures of OSA and OS starches were investigated by NMR spectroscopy. In granular OS starches, OS groups were substituted at O-2, O-3 positions, but not the O-6 position. Distribution of OS groups was investigated by enzyme hydrolysis followed by chromatography analysis. OS substitution predominantly occurred at the amorphous region of the starch granules. OS starch of degree of substitution (DS) 0.018 had OS groups located close to the branching points, whereas the OS substitution in OS starch of DS 0.092 occurred near non-reducing ends as well as the branching points. OS starches with different substitution patterns were prepared from two approaches. OS starches from the first approach had OS substitution near the branching points or non-reducing ends, whereas OS starches from the second approach had OS groups distributed randomly throughout the starch chains. A method of preparing OS starch by dry heating a mixture of waxy maize starch and OSA was developed. The optimum reaction was investigated and found to be pH 8.5 by addition of 3% NH4HCO3, 180 °C and 2 h. Reaction efficiency of ca. 90% was obtained at OSA levels from 1 to 6%. The OS starch had a DS of 0.0202 with 98% solubility when reacted with 3% OSA. Transglucosidation occurred during the reaction. The OS starch had a degree of branching of 19.8 %. The highly debranched OS starch showed excellent emulsification property for vitamin E and vitamin A. The structural changes of insoluble native waxy maize starch granules to cold watersoluble pyrodextrin during dextrinization under acidic conditions were investigated. We proposed that the starch was hydrolyzed by acid in the amorphous regions. Unwinding of the double helices also occurred, and crystallite size decreased. Starch molecules were hydrolyzed into small molecule fractions but remain in a radial arrangement. Glycosyl linkages including - (1 2), -(1 6), -(1 2), and -(1 6) linkages were formed and the majority starch chain terminals were 1,6-anhydro- -D-glucopyranose. Transglucosidation occurred during dextrinization and the resulted pyrodextrin was highly branched.

Much research has been carried out in recent years on Pickering emulsions, but understanding of the underlying physics requires considerable strengthening. This thesis seeks to address several fundamental aspects by presenting the results of recent experimental work. This work has focused on a model oil-in-water emulsion system stabilised by fluorescent colloidal silica particles and using a mixture of dodecane and isopropyl myristate as the oil phase. The phase behaviour of the particle dispersions has been altered using sodium chloride and sodium iodide, whilst sodium hydroxide and hydrochloric acid have been used to adjust the pH of samples. Comparisons are also made to emulsions stabilised by commercially available fumed silica. Conventionally, it was assumed that a weakly flocculating particle dispersion is required in order to generate a stable Pickering emulsion. It is shown in this work, however, that in some circumstances a weakly flocculating dispersion leads to the least stable emulsion. It is therefore argued that a more nuanced view of Pickering stabilisation is required, taking into account the factors affecting whether particles will adsorb to the interface during emulsification. Very recently it has begun to be suspected that Pickering emulsions sometimes aggregate due to the sharing of particles between two droplets, an effect known as bridging. In this thesis it is also shown that particle bridges can form in Pickering emulsions at high shear, and that they can subsequently be broken by low shear or by modifying the particle wettability. For the first time, electron microscopy has been used to provide direct evidence of droplets sharing particles. A simple theoretical model is developed, based on collisions between partially coated droplets, which captures the trends observed experimentally. It is argued that particle bridging may have been overlooked in the literature, and that the shear history of emulsions is a crucial determinant of subsequent behaviour. The deaggregation of bridged emulsions has been studied using a novel method where two different colours of particles are used. By starting with two emulsions which are bridged, each stabilised by a different colour of particle, and then using confocal microscopy to study them as they are mixed together and deaggregate, the processes involved in deaggregation can be elucidated. These experiments have also shown, for the first time, the dynamic nature of particles in Pickering emulsions; particles transfer readily between droplets when the samples are placed on a roller bank. It is found that a period of unbridging and rebridging takes place prior to deaggregation of the emulsions, and the timescale of deaggregation can be tuned by varying the particle wettability. The two-colour method has also been applied to the study of Pickering emulsions which are repeatedly sheared. It is found that limited coalescence is not reestablished simply by re-applying the shear rate which was used in the initial emulsification. This behaviour is attributed to the presence of an elastic shell of particles at the interface, which inhibits droplet breakup, and is in contrast to that of surfactant-stabilised emulsions, where increasing the stabiliser concentration makes droplets more liable to deform and breakup. Finally, a short study has been carried out attempting to increase the scale of the experiments presented in this thesis to sample volumes of approximately one litre. This study has demonstrated the relevance of particle bridging to industrial emulsification processes. Overall, experiments with carefully controlled model Pickering emulsions, including those using two colours of particles, have revealed the fundamental workings of these arrested systems.

Cellulose nanocrystals (CNCs) are rod-shaped nanoparticles derived from cellulose, the most abundant polymer in the world. CNCs are as strong as Kevlar™, have a high aspect ratio (traditional nanoparticles are spherical) and thus, a higher surface area, which makes them ideal for use in nanocomposites. In addition, CNCs are considered the only safe nanomaterial according to Health Canada. In this thesis, CNCs were used to produce nanocomposites via in situ semi-batch emulsion polymerization. The target application for these nanocomposites was as pressure sensitive adhesives (PSAs). In the past, CNCs have been blended with polymers rather than added in situ. Emulsion polymerization is considered a more sustainable method to synthesize polymers compared to say, solution polymerization. However, adhesives synthesized using this method tend to have a lower shear strength due to poor gel network formation. As a result, conventional emulsion-based PSAs suffer from the inability to increase certain adhesive properties (e.g., tack and peel strength) while simultaneously increasing shear strength. In this thesis, we demonstrate how the use of CNCs via in situ emulsion polymerization overcomes this classic problem. Two polymer systems were tested: isobutyl acrylate (IBA)/n-butyl acrylate (BA)/methyl methacrylate (MMA) and 2-ethylhexyl acrylate (EHA)/BA/MMA. The use of CNC with IBA, a relatively hydrophilic monomer, rather than with EHA, a highly hydrophobic monomer, resulted in the simultaneous improvement of tack, peel strength and shear strength of the PSA films. Dynamic mechanical analysis (DMA) also indicated improved storage and loss moduli with increasing CNC content, further supporting the reinforcing effect of the CNCs within the PSA. EHA followed similar trends as IBA for conversion, particle size, viscosity, pH, glass transition temperature and gel content. On the other hand, the use of CNC with EHA yielded less improvement in adhesive properties due to poor dispersion of the CNCs because of the hydrophobic repulsion by the EHA.

Colloidal Microcapsules (MCs), i.e. capsules stabilized by nano-/microparticle shells are highly modular inherently multi-scale constructs with applications in many areas of material and biological sciences e.g. drug delivery, encapsulation and microreactors. These MCs are fabricated by stabilizing emulsions via self-assembly of colloidal micro/nanoparticles at liquid-liquid interface. In these systems, colloidal particles serve as modular building blocks, allowing incorporation of the particle properties into the functional capabilities of the MCs. As an example, nanoparticles (NPs) can serve as appropriate antennae to induce response by external triggers (e.g. magnetic fields or laser) for controlled release of encapsulated materials. Additionally, the dynamic nature of the colloidal assembly at liquid-liquid interfaces result defects free organized nanostructures with unique electronic, magnetic and optical properties which can be tuned by their dimension and cooperative interactions. The physical properties of colloidal microcapsules such as permeability, mechanical strength, and biocompatibility can be precisely controlled through the proper choice of colloids and preparation conditions for their This thesis illustrates the fabrication of stable and robust MCs through via chemical crosslinking of the surface engineered NPs at oil-water interface. The chemical crosslinking assists NPs to form a stable 2-D network structure at the emulsion interface, imparting robustness to the emulsions. In brief, we developed the strategies for altering the nature of chemical interaction between NPs at the emulsion interface and investigated their role during the self-assembly process. Recently, we have fabricated stable colloidal microcapsule (MCs) using covalent, dative as well as non-covalent interactions and demonstrated their potential applications including encapsulation, size selective release, functional devices and biocatalysts.

No description available.

Master of Science / Department of Food Science Institute / Fadi M. Aramouni / To find an optimal formulation of oil-in-water (O/W) emulsion pourable dressings containing 60% and 70% soybean oil, nine stabilizers common to the dressing industry were tested, each at three concentrations. The stabilizers tested were xanthan gum, propylene glycol alginate (PGA), a xanthan gum/guar gum/sodium alginate blend, a viscosifying modified corn starch, an emulsifying modified corn starch, microcrystalline cellulose (MCC), liquid salted egg yolks, liquid salted whole eggs, and dried egg whites (DEW). The emulsions were made with a laboratory high shear disperser and evaluated over 8 weeks by measurement of creaming in 100- mL graduated cylinders and by change in viscosity as measured by a Brookfield viscometer. The stabilizers and concentrations most effective at preventing separation and maintaining viscosity were MCC at 1%, 2%, and 3% in the 60% oil emulsion and 0.25% xanthan gum in the 70% oil emulsion. Average viscosities ranged from 3300 - 23,400 centipoise (cP). The emulsifying starch and dried egg whites were also effective at preventing creaming, but failed to maintain viscosity. The other ingredients showed some initial emulsion stability followed by either a gradual or sudden decrease in stabilization, as seen by decreasing viscosity and eventual separation.

Zugl.: Stuttgart, Univ., Diss., 2008

Thesis (PhD)--Stellenbosch University, 2004. / ENGLISH ABSTRACT: The study presented in this dissertation had as primary aim to develop pathways to heterogeneous aqueous polymerizations that had living characteristics. To this end, the reversible addition fragmentation chain transfer (RAFT) process was investigated in predispersed and ab initio emulsions as well as homogeneous media. The synthesis of RAFT agents was carried out. The compounds prepared provided varied behaviour in reaction. In situ IH nuclear magnetic resonance (NMR) increased understanding of homogeneous RAFT mediated polymerizations. The early behaviour of RAFT mediated polymerizations led to the definition of initialization; a period before pre-equilibrium in a polymerization where degenerate behaviour occurs. Stable miniemulsion preparation methods were developed that provided living polymer latexes using high surfactant concentrations. The effect of surfactant concentration on particle size and latex stability was investigated. Living polymer characteristics were shown by the use of size exclusion chromatography, and 2- dimensional chromatography conclusively showed block polymer formation. In situ NMR spectroscopy of emulsions in deuterated water was used to provide evidence on the role of initiator solubility in polymerization. Secondary nucleation in high surfactant concentration miniemulsions systems was investigated using both particle size and molar mass analysis techniques and a means of eliminating secondary particle nulceation was shown through the use of aqueous phase radical traps. The role of the RAFT agent used in the polymerization was shown to be significant in determining the extent to which multiple polymer distributions formed in the polymerization in that radical exit from particles was affected. Finally, a new form of emulsion polymerization, which has been termed proto-seeded emulsion, has been developed. The proto-seed latex is formed by using a monomer whose polymer has chain length dependent water solubility. This process allows ab initio RAFT mediated emulsion polymerization to be conducted successfully without transport of RAFT agents in heterogeneous media. / AFRIKAANSE OPSOMMING: Die primerê doel in hierdie dissertasie is die ontwikkeling van roetes na heterogene water-gebaseerde polimerisasies met lewende eienskappe. Om hierdie doel te bereik is die omkeerbare addisie fragmentasie ketting oordrag proses (eng reversible addition fragmentation chain transfer (RAFT)) ondersoek in vooraf verspreide en direkte emulsies sowel as homogene media. Die sintese van RAFT agente is uitgevoer. Die verbindings wat voorberei is het verskillende einskappe in reaksies getoon. In situ IH kern magnetiese resonansie (KMR) het die kennis en begrip van homogene RAFT polimerisasies uitgebrei. Die vroeë gedrag van RAFT polimerisasies het tot die definisie van inisialisasie gelei; 'n periode voor die pre-ekwilibrium in 'n polimerisasie waartydens "degenerate" gedrag plaasvind. Stabiele miniemulsie voorbereidings metodes is ontwikkel wat lewende polimeer latekse verskaf het met gebruik van hoë seep konsentrasies. Die effek van seep konsentrasie op partikel grootte en lateks stabilitiet is ondersoek. Lewende polimeer eienskappe is bewys deur gebruik te maak van grootte-uitsluiting vloeistof chromatografie, en 2-dimensionele chromatografie het duidelik blok-polimeer vorming gewys. In situ KMR spektroskopie van emulsies in gedeutereerde water is gebruik om bewys te lewer van die rol van initieerder-oplosbaarheid in polimerisasie. Sekondêre nukleasie in hoë seep konsentrasie miniemuisie sisteme is ondersoek met die gebruik van beide partikel grootte sowel as molêre massa analise tegnieke. 'n Metode om sekondêre partikels te verhoed is verskaf deur gebruik te maak van waterfase radikaal lokvalle. Die rol van die RAFT agent in die polimeerisasie is beduidend in die graad van vorming van meer as een polimeer distribusie in die sin dat radikal uitgang van partikels beinvloed was. Ten slotte is 'n nuwe vorm van emulsie polimeerisasie ontwikkel wat proto-gesaaide emulsie genoem is. Die proto-gesaaide lateks is gevorm deur gebruik te maak van 'n monomeer waarvan die polimeer water-oplosbaarheid afhanklik is van die kettinglengte. Die proses laat ab initio RAFT emulsie polimerisasie toe om suksesvol uitgevoer te word sonder die vervoer van RAFT agente in heterogene media.

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No description available.