Дисертації з теми "250103 Colloid and Surface Chemistry"

The focus in this thesis has been to gain a fundamental understanding of how different type of salts affect preadsorbed polyelectrolytes, both natural and synthetic. The knowledge from the fundamental work is then applied on a commercial system to investigate if the efficiency can be enhanced. We built thin films using the synthetic polyelctrolytes by using layer-by layer (LbL) deposition. The formed film is commonly known as a polyelectrolyte multilayer. The LbL method allows the incorporation of proteins, polymers, polyelectrolytes with different functions and so on within the film, thus achieving multilayers with different functions. The major measuring technique used within this thesis is the quartz crystal microbalance with dissipation (QCM-D), which measures mass adsorbed on a surface including the trapped solvent and the viscoelastic properties of an adsorbed film. The QCM-D measurements were complemented with an optical technique, dual polarization interferometry (DPI), which measures the change in refractive index and thickness. From these parameters the dry mass and relative water content of the film can be calculated. The Atomic Force Microscopy (AFM) further gave information about forces acting between preadsorbed films. We investigated the effect of salt on synthetic polyelectrolyte poly(allylamine hydrochloride)/poly(sodium 4-styrenesulfonate) built with the LbL technique, thus forming polyelectrolyte multilayers. We concluded that the multilayer build-up was linear and that the internal structure of the multilayer is of a compact and rigid nature. However, the type of rinsing protocol (termination of adsorption by: salt, water and salt first followed by water) has a significant effect on the outer layer of the formed multilayer. Interestingly, the structural changes only applied when poly(allylamine hydrochloride) was at the outermost layer and the most significant when water was used. We suggest that it is only the top layer that swells due to the removal of counterions resulting in increased intrachain repulsion. We further performed two-layer model calculations with the Voight model to confirm the QCM-D results as well as a novel two layer model simulation for the DPI data in order to resolve the thickness. The model calculations were in good agreement with each other thus we concluded that only the outer layer swells for this particular multilayer system. In a related experiment we studied the adsorption of bovine submaxillary mucin (BSM), which has an important mucousal function, to different thiol modified gold surfaces as well as the effect of electrolytes (NaCl, CaCl2, LaCl3) on preadsorbed mucin to a hydrophobic thiol-modified Au surface. The salt induced an expansion at low concentrations; higher concentrations resulted in a compaction. Increasing the valence of the counter ion resultedin a compaction at low concentrations. The structural change of preadsorbed BSM was reversible for NaCl, partially reversible for CaCl2 and irreversible for LaCl3. Interestingly, the swelling of BSM could not be fully understood by using the QCM-D and thus AFM force curves of the same system were taken and the results showed that NaCl does decrease the tail length due to the effective screening of charged sites within the BSM molecule. Increasing the valence resulted in a notable compaction already at very low concentrations suggesting that the ions bind to the anionic sites on BSM. In the last work we attempted to combine the gained knowledge from the previous studies by using the LbL-buildup on an actual commercial health care application. The above-mentioned mutlilayer were used to coat polystyrene wells in order to increase the binding of immunoglobulin (IgG). The main goal was to increase the sensitivity of the conventional enzymelinked immunosorbent spot assay (ELISpot) and subsequently the modified polystyrene wells were used with the ELISpot test with human peripheral blood mononuclear cells (PBMC) to measure the cytokine response. We suggested that the main driving force for adsorption for IgG on a PAH terminated multilayer is electrostatic attraction, whereas on PSS terminated multilayer the driving force is hydrophobic. Further, we suggested that IgG  does not overcharge the surface and the linearity of the multilayer build-up is not altered when IgG is incorporated within the multilayer structure. We concluded that the cytokine response (spots) on the built multilayers regardless thickness or adsorbed IgG is significantly less than the regular polyvinyldiene fluoride (PVDF) backed ELISpot wells. We suggested that due to the compact and rigid nature of the PAH/PSS multilayer structure it is unable to form the kind of three-dimensional antibody-binding support found in the PVDF membrane. PSS terminated PAH/PSS multilayer did not induce any cytokine response whereas PAH terminated did, which suggests that PSS totally covers the surface from the cells point of view.
QC20100705

Paper and board are hydrophobized (sized) to control the spreading and absorption of waterbased inks and retard the absorption and edge penetration of liquid packaging by aqueous liquids. Alkenyl ketene dimers (AKD) and alkenyl succinic anhydride (ASA) are synthetic sizing agents that are generally used under neutral or slightly alkaline papermaking conditions. The overall objective of this thesis is to improve understanding of the internal sizing of paper and board by AKD and ASA by establishing a link between the sizing mechanism on one hand, and properties of sized papers, such as surface chemistry, wettability and friction, on the other. Fundamental research has been conducted in parallel with more applied research on laboratory and pilot papers. Significant effort has been expended to study the spreading behavior of AKD. The main instrument to characterize the surface chemical composition of AKD and ASA sized papers was X-ray photoelectron spectroscopy (XPS). By combination with time-of-flight secondary ion mass spectrometry (ToF-SIMS) we have been able to determine the lateral distribution and the chemical state of the sizing agent at the paper surface. Combined with contact angle measurements using liquids with different surface tensions, and other methods to analyze the amounts of size in paper, this has enabled us to obtain a deeper knowledge of the sizing mechanisms of AKD and ASA. The results indicate a definitive relationship between the redistribution of AKD at the surface of pilot papers and the drying profile used during papermaking. However, the spreading was not complete, as also seen on a model surface. Further spreading of AKD was shown to occur via surface diffusion in the form of an autophobic monolayer precursor. The spreading rate increased linearly with temperature and showed an inverse proportionality with respect to the melting point of the AKD. This monolayer spreading is relatively slow the diffusion coefficient being of the order 10-11 m2/s. AKD spreading was not hindered by hydrolyzed AKD (ketone) that spread as well. Moreover, AKD spread on the surface of crystalline calcium carbonate. In laboratory papers, the extractives present on CTMP fiber surfaces appeared to have enhanced the spreading of AKD when the fibers were in water. In spite of a slightly lower retention, ASA covered the surface of unfilled and PCC-filled pilot papers to a significantly higher extent than AKD. The ASA sized papers, however demonstrated slightly lower resistance to water. This was attributed to formation of hydrolyzed ASA products. The results obtained confirm the proposed sizing mechanism for ASA, where the hydrolyzed ASA plays a key role. The sizing level of these papers stored wrapped in aluminium foil at 23 °C and 5O %RH was nearly unchanged over prolonged storage time. In contrast, the papers exposed to ambient conditions suffered from sizing loss, most likely due to hydrolysis and migration. The reduction of the sizing degree was higher for the AKD than ASA sized unfilled papers and the catalytic effect of PCC contributed to the hydrolysis of AKD in PCC-filled papers. As expected, the use of sizing agent reduced the surface energy of paper. The higher the sizing degree of paper the lower the surface energy, and thus the higher the resistance to wetting. This was particularly seen in the contact angles with ethylene glycol having a lower surface tension than water. AKD significantly decreased the friction between unfilled papers, whereas ASA had no impact. This difference was attributed to surface chemical composition. Friction reduction for the AKD sized papers started at the AKD coverage normally found in paper produced for low water absorption. As expected, PCC filler increased paper-to-paper friction.
Papper och kartong hydrofoberas (limmas) för att kontrollera spridning och absorption avvattenbaserade tryckfärger och hindra kantinträngning av vattenbaserade vätskor ivätskekartong. Alkylketendimer (AKD) och alkylbärnstensyra anhydrid (ASA) är syntetiskahydrofoberingsmedel som allmänt används under neutrala eller något alkaliska förhållandenvid papperstillverkning.Arbetets övergripande målsättning var att förbättra förståelse för mäldhydrofobering avpapper och kartong med AKD och ASA genom att upprätta ett samband mellanhydrofoberingsmekanism på ena sida och ytkemi hos hydrofoberat papper och dessvätningsförmåga och friktion på den andra sidan. Grundläggande studier parallellt med mertillämpade undersökningar på laboratorie- och pilotpapper har utförts. En betydande strävanhar använts för att studera spridning av AKD. Huvudinstrumentet för att karakterisera kemisksammansättning av ytan av pilotpapper hydrofoberade med AKD och ASA var röntgenfotoelektron spektroskopi (XPS). Genom att kombinera det med sekundär jonmasspektrometri (ToF-SIMS) har lateral fördelning och kemiskt tillstånd av AKD och ASAvid en yta av papper kunnat bestämmas. Kombinerat med mätningar av kontaktvinkel medvätskor med olika ytspänning och andra metoder för att analysera halten avhydrofoberinsgmedel i papper har gjort det möjligt att erhålla djupare kunskap omhydrofoberingsmekanismer av AKD och ASA.Resultaten indikerar en klar koppling mellan omfördelning av AKD på ytan av pilotpapperoch torkningsprofil vid papperstillverkning. Emellertid, spridningen var inte fullständig, vilketvar fallet även på modellytor. Fortsatt spridning av AKD visades ske som ytdiffusion i formav ett autofobiskt monoskikt (precursor film). Spridningshastigheten ökade linjärt medtemperatur och visade omvänd proportionalitet med avseende på AKD:s smältpunkt. Dennamonoskiktspridning är relativt långsam, diffusionshastighet är i storleksordningen 10-11 m2/s.Hydrolyserat AKD (keton) hindrade inte AKD:s spridning utan spred även den. Dessutomspred AKD på ytan av kristallina kalciumkarbonat. I laboratoriepapper är extraktivämnennärvarande på ytor av CTMP fiber och tycktes ha förbättrat AKD:s spridning när fibrerna varunder vatten.ivTrots något lägre retention täckte ASA ytan av icke-fyllda och PCC-fyllda papper tillsignifikant högre grad än AKD. ASA-papperen visade dock något lägre motstånd mot vatten.Detta var hänvisat till bildning av hydrolyserade ASA-produkter. De uppnådda resultatenbekräftar den föreslagna hydrofoberingsmekanismen för ASA, där hydrolyserat ASA spelaren avgörande roll. Hydrofoberingsgraden av papper lagrade inlindade i aluminiumfolie vid23 °C och 50 RH var nästan oändrad över den förlängda lagringstiden. Som motsatsgenomgick papperen som exponerats mot omgivande atmosfärsförhållanden genomgick enminskning av hydrofoberingsgraden, troligen på grund av hydrolys och migrering. Minskningav hydrofoberingsgraden var större för icke-fyllda papper av AKD än av ASA. PCC:skatalytiska effekt bidrog till hydrolys av AKD i PCC-fyllda papper.Som förväntat reducerade användning av hydrofoberingsmedel reducerade ytenergin avpapper. Ju högre hydrofoberingsgrad desto lägre var ytenergin och därmed desto högremotstånd mot vätning. Detta sågs särskilt i kontaktvinklar med etylenglykol som har lägreytspänning än vatten.AKD minskade signifikant friktionen mellan icke-fyllda papper, medan ASA inte hadeinverkan. Denna skillnad hänfördes till skillnad i ytsammansättning. Minskning av friktion förAKD-hydrofoberade papperen påbörjades vid en sådan yttäckning av AKD som är normaltför papper tillverkat för låg vattenabsorption. Som förväntat ökade PCC-fyllmedel friktionenmellan papperen.
QC 20100817

Unspecific interactions, at the interface between a synthetic material and an aqueous biological environment, leading to irreversible protein adsorption can cause to undesired consequences. These include fouling of a boat hull or a triggered immune response. Thus, stealthy materials are a topic that has generated a great deal of interest in the scientific community. This work deals with the design of networks, nanoparticles, and surfaces containing poly(ethylene glycol) (PEG), known for its resistance to protein adsorption and non-toxic nature. Initially, PEG-based networks, hydrogels, were synthesized using photoinduced thiol-ene chemistry in order to afford coatings targeted for marine antifouling applications. By varying the length of the PEG chain, curing chemistry, cross-linker as well as hydrolytical stability, a library of hydrogel coatings was produced. The coatings were subsequently characterized with respect to curing efficiency, thermal and mechanical properties, and aqueous stability. Furthermore, the antifouling properties of coatings were evaluated using in vitro tests with proteins, marine bacteria, and diatoms. As a final test the coatings were evaluated in a four month field test. It was found that coatings comprising longer PEG chains displayed enhanced antifouling performance, compared to shorter PEGs. In addition, the choice of cross-linker, curing chemistry, and hydrolytical stability also affected the properties to a great extent. This thesis further deals with the design of amphiphilic linear dendritic hybrids, with PEG as the hydrophilic block. Using non-toxic 2,2-bis(methylol) propionic acid (bis-MPA) based dendrons, bearing click functional cores (alkyne or allyl) and peripheral hydroxyl groups, as macrointitiators for ring-opening polymerization of ε-caprolactone, a library of star branched materials was afforded. As a final step, click functional (azide or thiol) PEGs were attached using copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) or thiol-ene click chemistry. The size of the dendrons was varied from generation 0-4, along with variation of both poly(ε-caprolactone) (PCL) length and PEG length. The materials were designed in order to allow a study of the impact of the dendron generation. Finally, the hybrid materials were used for the preparation of micelles, as well as for the formation of honeycomb membranes. The micelles critical micelle concentration, size and drug loading capacity were shown to be highly dependent on the generation of the dendron. The generation of the dendron also had a profound effect on the ability of the hybrid materials to form ordered honeycomb membranes, and hybrid materials of the 3rd generation yielded the most highly ordered membranes.
Ickespecifika interaktioner vid gränsytan, mellan ett syntetiskt material och en vattenbaserad biologisk miljö, kan leda till irreversibel adsorption av proteiner. Detta kan i sin tur leda till oönskade följdeffekter, såsom beväxning på båtskrov eller trigga en immunologisk reaktion. För att motverka dessa effekter har forskare utvecklat så kallade smygmaterial. Denna avhandling behandlar design av nätverk, nanopartiklar och ytor innehållande poly(etylenglykol) (PEG), som är känt för sina smygegenskaper och för att vara icke-toxiskt. Initialt behandlar avhandlingen PEG-baserade nätverk, hydrogeler, syntetiserade med fotoinitierad tiol-enekemi, för användning som beväxningsavvisande beläggningar för marina applikationer. Genom att variera olika parametrar, såsom längden på PEG-kedjan, härdningskemin, tvärbindaren samt den hydrolytiska stabiliteten, byggdes ett bibliotek av hydrogelbeläggningar upp. Hydrogelbeläggningarna karaktäriserades sedan med avseende på härdningseffektivitet, termiska och mekaniska egenskaper, samt hydrolytisk stabilitet. Vidare studerades beläggningarnas avvisande förmåga mot proteiner, bakterier samt kiselalger. Slutligen studerades ytbeläggningarna i ett fyra månader långt fälttest. Av testerna framgick att längre PEG-kedjor gav beläggningar med bättre avvisande förmåga. Dessutom framgick att valet av tvärbindare, härdningskemi samt hydrolytisk stabilitet var av betydelse för beläggningarnas effektivitet. Denna avhandling behandlar vidare design av amfifila linjära dendritiska hybridmaterial, med PEG som den hydrofila delen. Genom att använda icke-toxiska 2,2-bis(metylol)propionsyrabaserade dendroner, med en klickfunktionalitet i kärnan (alkyne eller allyl) och perifera hydroxylgrupper, som makroinitiatorer för ringöppningspolymerisation av ε-kaprolakton byggdes ett bibliotek av material upp. För att göra materialen amfifila, kopplades klickfunktionella PEG-kedjor (azid eller tiol) till kärnan med koppar(I)-katalyserad azid-alkyn cykloadditionskemi alternativt tiol-enekemi. Storleken på dendronerna varierades från generation 0-4, dessutom varierades längden på både poly(ε-kaprolakton)- och PEG-kedjorna. Materialen designades så att inverkan av dendrongenerationen kunde studeras. Slutligen användes dessa hybridmaterial för att framställa miceller samt isoporösa filmer. Micellernas kritiska micellbildningskoncentration, storlek samt förmåga att laddas med läkemedel visade sig vara mycket beroende av dendrongenerationen. Dendrongenerationen visade sig vidare även ha stor inverkan i hybridmaterialens förmåga att självorganisera sig till en isoporös struktur och material av tredje generationen gav de mest välordnade filmerna.
QC 20101125

The environmental stability of a metal / polymer interface is essential for the durability and mechanical stability of constructions in several important areas such as the automotive, offshore, building and aerospace industries. The protective capability of a polymer film is strongly connected to its barrier properties, but the transport of water and corrosive constituents through the polymer and the subsequent processes at the metal surface are complicated to analyse in detail. The surface to be analysed is confined between two media that are impermeable to most probing particles used in conventional analytical techniques. Several methods exist to describe separate parts of the system, but few techniques work atambient pressure and have the capacity to conduct real-time analysis at relevant exposure conditions. In this work, attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) in the Kretschmann geometry was successfully employed for systematic studies of metal / polymer interfaces. This technique requires the use of thin metal films deposited on an internal reflection element (IRE). Most studies were performed on aluminium, which is an important structural light-weight material, but also zinc was analysed, being frequently used for corrosion protection of steel. Upon exposure to water and electrolytes, the ATR-FTIR Kretschmann technique was found capable to monitor and to separate early deterioration related processes at the aluminium / polymer interface, including water sorption and transport of ionic species through the polymer film. Other main processes identified were the formation of corrosion products and swelling of the surface-near polymer network. To perform more comprehensive interpretations, a spectro-electrochemical method was further developed for in situ studies of the hidden metal / polymer interfaces. The ATR-FTIR Kretschmann technique was here combined with the complementary acting technique, Electrical Impedance Spectroscopy (EIS). The integrated set-up was able to provide complementary information, with ATR-FTIR Kretschmann being sensitive to the surface-near region and EIS to the whole system. For instance, metal oxidation and delamination processes can be difficult to distinguish by EIS, while on the other hand oxidation and hydration reactions on aluminiumcan be confirmed as IR bands at distinct positions. Delamination and swelling of a polymer both result in negative bands in an IR spectrum, but these processes may be distinguished by EIS as alterations in different frequency regions. While traditional chemical pre-treatments for enhanced hydrolytic stability perform excellent, they are being phased out from industrial applications due to environmental concerns and work health issues. Today there is an intense ongoing research regarding the mechanisms and performance of environmentally friendly pretreatments to develop systems of similar performance, and the analysis of the confined metal / polymer interface is crucial for this development. The capability of the integrated in situ ATR-FTIR Kretschmann and EIS set-up was therefore further applied to systems where a surface pre-treatment had been applied to the metal prior to the organic coating. Studies were first performed on vacuum-evaporated films of zinc treated with a titanium-based conversion coating and further coated with a UV-curing polymer. Alterations of the conversion layer could be detected upon exposure to the electrolyte. Also alkaline-cleaned aluminium coated with an amino-functional silane film and a thermo-curing epoxy top-coat was thoroughlycharacterized by both ATR-FTIR and IRRAS and further investigated upon exposure toelectrolyte and humid air. Changes at the hidden interface were detected upon thermal curingof the epoxy film and during exposure in electrolyte, and the in situ ATR-FTIR Kretschm annanalysis showed a high sensitivity towards alterations in the interfacial region. Complementary studies in the absence of metal could confirm a water uptake within the silane film and water-induced alterations of the siloxane network.
QC 20101222

The aim of this thesis work was to systematically investigate the physico-chemical properties of polyelectrolyte complexes (PECs) formed by bottle brush and linear polyelectrolytes in solution and at solid / liquid interfaces. Electrostatic self-assembly of oppositely charged macromolecules in aqueous solution is a versatile strategy to construction of functional nanostructures with easily controlled properties. Bottle brush architecture, introduced into the PEC, generates a number of distinctive properties of the complexes, related to a broad range of application, such as colloidal stability and protein repellency to name a few. To utilize these materials in a wide range of applications e.g. drug delivery, the understanding of the effects of polymer architecture and solution parameters on the properties of bottle brush PECs is of paramount importance. This thesis constitutes a systematic investigation of PECs formed by a series of cationic bottle-brush polyelectrolytes and a series of anionic linear polyelectrolytes in aqueous solution. The focus of the first part of the thesis was primarily on formation and characterization of PECs in solution, whereas the adsorption properties and adsorption kinetics of bottle-brush polyelectrolytes and their complexes was investigated in the second part of the thesis work. In particular, effects of the side-chain density of the bottlebrush polyelectrolyte, concentration, mixing ratio and molecular weigh of the linearpolyelectrolyte on formation, solution properties, stability and adsorption of PECs were addressed. The pronounced effect of the side-chain density of the bottle-brush polyelectrolyte on the properties of stoichiometric and nonstoichiometric PECs was demonstrated. Formation of PECs by bottle-brush copolymers with high density of side-chains results in small, watersoluble, molecular complexes having nonspherical shape, independent of concentration. Whereas formation of PEC-aggregates was revealed by bottle-brush polyelectrolytes with low side chain density, the level of aggregation in these complexes is controlled by polyelectrolyte concentration. The structure of the PECs formed with low molecular weight polyanions is consistent with the picture that several small linear polyelectrolyte molecules associate with the large bottle-brush. In contrast, when complexation occurs between polyanions of high molecular weigh and the bottle-brush polymers considerably larger PECs are formed, consistent with several bottle-brush polymers associating with one high molecular weight polyanion.
QC 20110516

Friction forces between protein / polyelectrolyte layers, adsorption properties of proteins, and conformational changes due to variation in electrolyte concentration have been investigated. The aim was to obtain better understanding of adsorbed layer properties, with focus on the relation between layer structure and lubrication capabilities. The major techniques used were AFM (atomic force microscope) with colloidal probe for normal force and friction measurements together with QCM-D (quartz crystal microbalance with dissipation) for measurement of adsorption and conformational changes of adsorbed layers. A comparison between some techniques for calibration of the AFM instrument for friction measurements was made to find the most suitably one for colloidal probe friction measurements in aqueous solutions. It is suggested that the normal and torsional Sader methods are preferred in combination with torsional detector sensitivity measurement, for which one new methodology has been proposed. Adsorption was studied for bovine serum albumin, cytochrome c, myoglobin and mucin, whereas conformational changes of the adsorbed layer were monitored only for mucin. It was found that it was essential to take into account bulk density and viscosity changes for correct interpretations of QCM data when studying the effect of changes in electrolyte type and concentration on preadsorbed layers of mucin, and also when having different (high) concentrations of proteins in the measuring solution. The adsorbed amount of proteins appears to depend on the strength of the surface attachment, in such a manner that a too high affinity reduces the adsorbed amount. Friction properties in aqueous solution have been studied for adsorbed layers of PEO45MEMA:METAC co-polyelectrolytes, with varying density of grafted PEO45 side chains and varying charge density, as well as for a naturally occurring polyelectrolyte (chitosan) and the glycoprotein mucin. These polymers were used to cover a wide range of different types of adsorbed layers and interactions to gain a better understanding of friction mechanisms and demands on layer properties for achieving favourable lubrication. It was found that the common features of low friction layers are that no attractive forces are present, and that excluded volume and / or electrostatic forces counteract chain interpenetration under load.
QC 20100903

Aqueous silica is present in all natural waters and exhibits a high affinity for the surfaces of iron oxides. Therefore, it is expected to play an important role in environmental systems. Experiments were conducted to investigate the fundamentals of silica sorption onto pre-formed ferric hydroxide at pH 5.0-9.5 and silica concentrations of 0-200 mg/L as SiO₂. Over the entire pH range studied, sorption densities exceeding monolayer sorption were observed at silica levels typical of natural waters. Under some circumstances, sorption exceeded a monolayer while the particle zeta potential remained positive, a phenomenon which is inconsistent with available models. To address this deficiency, an extended surface complexation model was formulated in which soluble dimeric silica sorbs directly to iron surface sites. This model fits sorption density data up to 0.40 mol SiO₂/mol Fe, and it accurately predicts trends in zeta potential and the observed H⁺ release during silica sorption to ferric hydroxide at pH 5.0 and 6.0.

A second phase of research was aimed at identifying the practical implications of silica sorption to iron hydroxide in natural and engineered systems. Two types of surfaces were prepared by exposing pre-formed Fe(OH)₃ to aqueous silica (0-200 mg/L as SiO₂) for periods of 1.5 hours or 50 days. The concentration of pre-formed iron passing through a 0.45 micron pore size filter at pH 6.0-9.5 increased as the solids aged in the presence of silica. Consistent with formation of small, stable colloids, "soluble" iron concentrations exceeded 0.2 mg/L only at zeta potentials < -15 mV. When arsenate was added to iron hydroxide particles equilibrated with silica for 1.5 hours, percentage arsenate removals were high. In contrast, arsenate removals decreased markedly as pH and silica concentrations increased if silica was pre-equilibrated with the iron for 50 days. Trends in percentage removal of humic substances were similar. Competition for sorption sites was the main cause of hindered anionic contaminant removal. However, interference with hydrolysis and precipitation are expected to be important under some circumstances, particularly during water treatment.
Master of Science

In Sweden the encapsulated nuclear waste will be surrounded by compacted bentonite in the granitic host rock. In contact with water-bearing fractures the bentonite barrier may release montmorillonite colloids that may be further transported in groundwater. If large amounts of material are eroded from the barrier, the buffer functionality can be compromised. Furthermore, in the scenario of a leaking canister, strongly sorbing radionuclides, can be transported by montmorillonite colloids towards the biosphere. This thesis addresses the effects of groundwater chemistry on the generation, stability, sorption and transport of montmorillonite colloids in water bearing rock fractures. To be able to predict quantities of montmorillonite colloids released from the bentonite barrier in contact with groundwater of varying salinity, generation and sedimentation test were performed. The aim is first to gain understanding on the processes involved in colloid generation from the bentonite barrier. Secondly it is to test if concentration gradients of montmorillonite colloids outside the barrier determined by simple sedimentation experiments are comparable to generation tests. Identical final concentrations and colloid size distributions were achieved in both types of tests. Colloid stability is strongly correlated to the groundwater chemistry. The impact of pH, ionic strength and temperature was studied. Aggregation kinetics experiments revealed that for colloid aggregation rate increased with increasing ionic strength. The aggregation rate decreased with increasing pH. The temperature effect on montmorillonite colloid stability is pH-dependent. At pH≤4, the rate constant for colloid aggregation increased with increasing temperature, regardless of ionic strength. At pH≥10, the aggregation rate constant decreased with increasing temperature. In the intermediate pH interval, the aggregation rate constant decreased with increasing temperature except at the highest ionic strength, where it increased. The relationship between the rate constant and the ionic strength allowed the critical coagulation concentration (CCC) for Na- and Ca-montmorillonite to be determined. In order to distinguish the contribution of physical filtration and sorption to colloid retention in transport, the different retention mechanisms were quantified. Sorption on different representative minerals in granite fractures was measured for latex colloids (50, 100, 200 nm) and montmorillonite colloids as a function of ionic strength and pH. Despite of the negative charge in mineral surfaces and colloids, sorption was detected. The sorption is correlated to the mineral point of zero charge and the zeta potential of the colloids, and increases with increasing ionic strength and decreasing pH. In transport experiments with latex colloids in columns packed with fracture filling material, the retention by sorption could clearly be seen. In particular at low flow rates, when the contact time for colloids with the mineral surfaces were the longest, sorption contributed to retention of the transport significantly. The retention of latex colloids appeared to be irreversible in contrary to the reversible montmorillonite colloid retention. Generation, stability and sorption of the montmorillonite colloids are controlled by electrostatic forces; hence, the results were in qualitative agreement with DLVO.

This thesis deals with the use of electric fields for evaluation and control of chemical systems. An electric field can result in the flow of charge across an interface between a metal and a solution, by means of chemical reactions. This interplay between electricity and chemistry, i.e. electrochemistry, is a field of crucial importance both within research and industry. Applications based on electrochemical principles encompass such diverse areas as batteries and fuel cells, pH electrodes, and the glucose monitor used by people suffering from diabetes.A major part of the present work concerns the use of static electric fields in solutions containing a non-contacted metal surface. In such a setup it is possible to control the extent of electrochemical reactions at different positions on the metal. This allows the formation and evaluation of various types of gradients on electrodes, via indirectly induced electrochemical reactions. This approach is a new and simple way of forming for instance molecular gradients on conducting surfaces. These are very advantageous in biomimetic research, because a gradient contains a huge amount of discrete combinations of for example two molecules. The basis for the technique is the use of bipolar electrochemistry. Briefly, a surface can become a bipolar electrode (an electrode that acts as both anode and cathode) when the electric field in the solution exceeds a certain threshold value, thereby inducing redox reactions at both ends. In our experiments, the driving force for these reactions will vary along the electrode surface. Since the result of an electrochemical reaction can be the deposition or removal of material from an electrode, bipolar electrochemistry can be used to create gradients of that material on a surface. In order to gain a deeper understanding of these processes, the potential and current density distributions at bipolar electrodes were investigated with different methods. Especially the use of imaging techniques was important for the visualization and analysis of the gradients. Using this knowledge, the formation of more complex gradients was facilitated, and the results were further compared to simulations based on simple conductivity models. These simulations also provided us with means to predict the behavior of new and interesting setup geometries for pattering applications.The other major part is more application driven and deals with the use of alternating electric fields for chemical analysis, a technique known as electrochemical impedance spectroscopy (EIS). In this work, EIS has been applied for the analysis of engine oils and industrial cutting fluids. Emphasis was placed on practical aspects of the measurement procedure, and on the evaluation of the results using statistical methods. It was for example shown that it was possible to simultaneously determine the amount of different contaminants in low conducting solutions. Generally, EIS is used to measure the impedance of a solution or a solid, often as a function of the frequency of the alternating electric field. The impedance of a system is closely correlated to its complex dielectric constant, and EIS can therefor be used to examine many chemical and physical processes. It is further well suited for characterizing low conducting media with little or no redox-active species. The evaluation of impedance data is often a quite complex task, which is why we have made use of statistical methods that drastically reduce the effort and quickly reveal significant intrinsic parameters.

With increasing environmental awareness, the desire to protect human beings and the environment from adverse effects induced by dispersed metals has become an issue of great concern and interest. New policies, such as REACH (Registration, Evaluation, Authorisation and Restriction of Chemicals) within the European Community, have been implemented to reduce hazards posed by the use of chemicals on producers and downstream users. The generation of exposure assessment data and relevant test procedures able to simulate realistic scenarios are essential in such legislative actions. This doctoral study was initiated to fill knowledge gaps related to the metal release process of stainless steels. A wide range of stainless steel grades, fourteen in total, were investigated. They cover a very broad range of applications, and the focus in the thesis was to simulate a few selected exposure scenarios: precipitation, the human body and food intake. Comparisons were made between metal release from stainless steel alloys and the pure metals that constitute each stainless steel in order to explore the differences between alloys and pure metals, and to provide quantitative data on metal release rates of different alloy constituents. Because of similar surface properties between stainless steel and pure chromium, this metal exhibits similar release rates, whereas iron and nickel exhibit significantly lower release rates as alloy components than as pure metals. Detailed studies were also performed to elucidate possible relations between metal release and steel surface properties. Key parameters turned out to be chromium enrichment of the self-passivating surface film, surface roughness, the electrochemically active surface area and the microstructure of the steel substrate. The degree of metal release increased with decreasing chromium content in the surface oxide, increasing surface roughness, and increasing presence of inhomogeneities in the bulk matrix. More detailed studies were initiated to possibly correlate the nucleation of metastable pits and the extent of metal release. Evidence was given that metastable pits exist even when the stainless steel is passive, and may cause extremely short-lived bursts of released metal before the surface film repassivates again.
QC 20100810

The cellular response to a biomaterial, such as a dental implant, is mainly governed by the surface properties, and can thus be altered by the introduction of a surface coating. In this thesis the buildup of a biomacromolecule-based coating formed by layerby-layer (LbL) deposition of the charged polypeptides poly(L-lysine) (PLL) and poly(L-glutamic acid) (PGA) has been studied. In an attempt to make these coatings bioactive and useful for bone-anchored implants, an amelogenin protein mixture (EMD), has been immobilized in these thin polyelectrolyte multilayer (PEM) films. Multilayers were also built by LbL deposition of the natural biomacromolecules collagen (Col) and hyaluronic acid (HA). Multilayer films of these two extra-cellular biomacromolecules should be of interest for use as a scaffold for tissue engineering.

The buildup of the multilayer films has been followed in situ, using ellipsometry, quartz crystal microbalance with dissipation (QCM-D), and dual polarization interferometry (DPI). The studied PLL/PGA multilayers were found to be highly hydrated, and to exhibit a two-regime buildup behavior, with an initial “slow-growing” regime, and a second “fast-growing” regime with a linear growth in film thickness and more than linear growth in mass. A net diffusion of polypeptides into the film during the buildup led to an increase in density of the films for each layer adsorbed. A change in density was also observed in the Col/HA film, where HA penetrated and diffused into the porous fibrous Col network.

The formed PLL/PGA films were further found to be rather stable during drying, and post-buildup changes in temperature and pH, not losing any mass as long as the temperature was not raised too rapidly. The film thickness responded to changes in the ambient media and collapsed reversibly when dried. A swelling/de-swelling behavior of the film was also observed for changes in the temperature and pH.

The EMD protein adsorbed to silica surfaces as nanospheres, and could by itself form multilayers. The adsorption of EMD onto PLL/PGA multilayer films increased at lower pH (5.0), and EMD could be immobilized in several layers by alternate deposition of EMD and PGA.

The aim of this work is to study the interfacial properties of amphiphilic compounds at the liquid–air interface in an attempt to develop a comprehensive understanding of their orientation as well as the influence of their interaction with the solvent on the interfacial layer properties. Using Vibrational Sum Frequency Spectroscopy (VSFS) as the main tool, the molecular structure of the amphiphilic layer and the amphiphile–solvent relation can be illuminated in great detail – it is arguably the most sensitive surface spectroscopy currently available. Due to its second order nature, the VSFS technique is capable of distinguishing molecules at the interface even in the presence of a vast excess of similar molecules in the bulk.Ionic liquids (Ils) form a class of solvent which are increasingly receiving attention as ``green solvents´´. Some of these, such as ethyl ammonium nitrate (EAN), a protic IL, have the capacity to hydrogen bond extensively which is one of the important features they share with water. Since the interaction with solvent is an important consideration for self assembly and it is known that surfactant self assembly in the EAN bulk is analogous to in water, it was considered of interest to probe self assembly at EAN–air interface. To this end the interfacial structure of the pure EAN interface was probed, as was the conformation and ordering of nonionic surfactants. These studies reveal that EAN is highly ordered at the interface, exposing the ethyl moiety to the gas phase. Additionally, polarization studies have enabled the average orientation of the ethyl group to be determined. Adsorption of nonionic surfactants at the interface appears to significantly displace the EAN from the interface. The headgroup of the surfactant, a linear ethylene oxide group, appears to be highly disordered.The disorder of the linear ethylene oxide groups has led to difficulties in their surface spectroscopic fingerprinting in this and other works. In an attempt to study the interfacial behaviour of ethylene oxide and the temperature dependence of its hydration, closed loop structures of PEO attached to hydrophobic groups were also probed. This essentially locks their conformation. Such molecules are known as crown ethers and display interesting interfacial behaviour and also the ability to bind cations. The presence of even small amounts of adsorbed crown ethers at the water interface is shown to considerably perturb the water structure. The NO, CN, COC and CH vibrational modes of these compounds at the air-water interface as well as OH vibrational modes of the surface water hydrating this compound have been targeted in order to obtain molecular information about arrangement and conformation. The CH2 vibrational modes of crown ethers have been identified and found to be split due to their interaction with ether oxygen. The spectra provide evidence for the existence of a protonated crown complex moiety at the surface leading to the appearance of strongly ordered water species. The orientation of Nitrobenzo crown (NB15C5) was monitored as a function of solution concentration, by targeting the ratio of peak intensities of the CN and NO2 vibrational modes. The water of hydration has also been probed as a function of crown concentration, salt concentration, and temperature. The latter study strongly suggests that the surface can be treated as a charged interface, and that the associated ordered water decreases with increasing ionic strength of the bulkFinally, insoluble monolayers of fatty acids spread on a water surface have also been studied in an effort to further understand the relationship between molecular architecture and film structure. Fatty acid (Arachidic Acid – AA and Eicosenoic Acid – EA) monolayers are compared to investigate the effect on the monolayer structure of introducing unsaturation into the alkyl chain. For AA, at very large area per molecule, floating domains of crystalline nature exist rather than any classical gaseous phase. The measured conformational disorder in EA decreases continuously with monolayer compression and no crystalline domains are observed at low density. Addition of NaCl to the subphase does not affect the monolayer order for either of the compounds; instead, a dramatic increase in the signal of the water hydrating the headgroups is observed. The effect of introducing further unsaturations (up to three) was also studied in order to probe the resulting interfacial structure. Remarkably the double bonds appear to adopt the same orientation, irrespective of how many they are in the chain. By monitoring the vinyl CH stretch it was possible to study the film stability towards oxidative degradation and it was found that all three unsaturated species studied showed rapid degradation. The rate of degradation could be controlled by adjusting the film pressure. However, the monolayers could be stabilised by performing the experiments in an inert nitrogen atmosphere.
QC20100629

In the research presented in this licentiate thesis the surface specific technique Vibrational Sum Frequency Spectroscopy, VSFS, combined with the Langmuir trough has been utilized to investigate Langmuir monolayers and Langmuir-Blodgett (LB) deposited mono- and bilayers of phospholipids. Their molecular structure, stability, and hydration were probed to gain additional understanding of important properties aiming at facilitating the use of such layers as model systems for biological membranes.

VSFS was applied to in situ studies of the degradation of Langmuir monolayers of 1,2-diacyl-phosphocholines with identical C-18 chains having various degrees of unsaturation. The time-dependent change of the monolayer area at constant surface pressure as well as the sum frequency intensity of the vinyl-CH stretch at the C=C double bonds were measured to monitor the degradation. It was shown that a rapid degradation of the monolayers of unsaturated phospholipids occurred when exposed to the laboratory air compared to the fully saturated lipid, and that the degradation could be inhibited by purging the ambient air with nitrogen. The degradation was attributed to oxidation mediated by reactive species in the air.

The molecular structure and order of Langmuir monolayers of 1,2-distearoyl-phosphocholine (18:0 PC) and their hydrating water were investigated at different surface pressures using VSFS. The spectroscopic data indicated a well ordered monolayer at all surface pressures with a more intense signal at higher pressures attributed to the subsequent increase of the number density and more ordered lipid molecules due to the tighter packing. Water molecules hydrating the headgroups or being in contact with the hydrophobic parts were observed and distinguished by their vibrational frequencies, and found to have different average orientations.

Additionally, monolayers of 18:0 PC, its fully deuterated analogue, and 1,2-distearoyl-phosphoserine (18:0 PS) were Langmuir-Blodgett (LB) deposited on CaF₂ substrates and VSFS was used to investigate the structure and order of the films as well as the hydrating water. The CH-region, water region, and lower wavenumber region containing phosphate, ester, carboxylic acid, and amine signals were probed to obtain a complete picture of the molecule. The data indicates that all deposited monolayers formed a well ordered and stable film and the average orientation of the aliphatic chains was determined using the antisymmetric methyl stretch.

I forskningen som presenteras i denna licentiatavhandling har den ytspecifika vibrationssumfrekvensspektroskopin, VSFS, använts tillsammans med Langmuirtråget för att studera Langmuir-monolager och Langmuir-Blod-gett (LB) deponerade monolager och bilager av fosfolipider. För att utvidga förståelsen av egenskaper som är viktiga för att underlätta användandet av dem som modellsystem för biologiska membran undersöktes såväl deras molekylära struktur som stabilitet och hydratisering.

VSFS användes för att genomföra in situ-studier av nedbrytningen av Langmuir-monolager av 1,2-diacyl-fosfokoliner med identiska 18 kolatomer långa sidokedjor med varierande antal omättade kol-kol-bindningar. För att övervaka nedbrytningen mättes såväl den tidsberoende förändringen av monolagernas area vid konstant yttryck som sumfrekevensintensiteten från dubbelbindningarnas CH-vibration. När monolagerna bestående av omättade fosfolipider utsattes för laboratorieluften bröts de ner hastigt jämfört med det helt mättade monolagret. Denna nedbrytning som sannolikt orsakades av reaktiva ämnen i luften kunde inhiberas fullständigt genom att ersätta den omgivande luften med kvävgas.

Den molekylära strukturen och ordningen hos Langmuir-monolager av 1,2-distearoyl-fosfokolin (18:0 PC) och deras hydratiseringsvatten undersöktes vid olika yttryck med VSFS. Den spektroskopiska datan visar att monolagerna är välordnade vid alla yttryck samt att sumfrekvenssignalens styrka ökar med ökande yttryck på grund av såväl det större antalet molekyler per ytenhet som den högre ordningen då molekylerna packas tätare. Vattenmolekyler som hydratiserar huvudgrupperna eller är i kontakt med hydrofoba delar och har olika medelorientering observerades och kunde identifieras genom sina vibrationsfrekvenser.

Vidare deponerades monolager av 18:0 PC, dess fullt deuterade analog och 1,2-distearoyl-fofsfoserin (18:0 PS) på substrat av CaF₂ och VSFS användes för att undersöka filmernas struktur och ordning såväl som hydratiseringsvattnet. CH- och vattenregionerna samt lågvågtalsområdet som innehåller fosfat-, ester-, karboxylsyra- och aminsignaler undersöktes för att få en fullständig bild av den molekylära strukturen. Data visar att alla deponerade monolager bildade en välordnad och stabil film och kolvätekedjornas medelorientering bestämdes med hjälp av signalen från den antisymmetriska metylvibrationen.

QC 20100924

In this thesis the structure and hydration of small organic and amphipilic compounds adsorbed at the air-liquid interface, have been studied using the nonlinear optical technique Vibrational Sum Frequency Spectroscopy (VSFS). The second order nature of the sum frequency process makes this technique particularly surface sensitive and very suitable for interfacial studies, as molecules at the surface can be distinguished even in the presence of a vast excess of the same molecules in the bulk. Particular emphasis was given to the surface water structure and how it is affected by the presence of small model compounds such as acetic acid and formic acid, and also non-ionic surfactants with sugar based and ethylene oxide based polar headgroups. Understanding the structure of water at these interfaces is of considerable fundamental importance, and here VSFS provided unique information. Upon addition of tiny amounts of these surface active compounds, the ordered surface structure of water was found to be significantly perturbed, as revealed by the changes observed in the characteristic spectroscopic signature of the dangling OH bond of water molecules, which vibrate free in air and are present in the top monolayer. Dramatic differences between the different compounds were also observed in the bonded OH region, providing a valuable insight into the hydration of polar groups at interfaces. Additionally, by employing different polarization combinations of the laser beams involved in the sum frequency process, information about the different water species present at the surface and their average orientation were extracted. In particular an unusual state of water was found with a preferred orientation in a non-donor configuration in close proximity to the hydrophobic region formed by the hydrocarbon tails of the surfactant molecules.

The conformation and orientation of the different adsorbates were also characterized, targeting their specific vibrational frequencies. Noteworthy is the orientation of the fluorocarbon chain of ammonium perfluorononanoate (APFN), which in contrast to the hydrocarbon chains of the other surfactant molecules studied, remained constant over a wide range of surface densities. This behaviour was also observed for the anionic headgroup of sodium dodecyl sulphate (SDS). Other interesting findings were the formation of a cyclic dimer bilayer at the surface of concentrated aqueous solutions of acetic acid and the water structuring effect induced by poly(ethylene-oxide) headgroups, in spite of being themselves disordered at the air-liquid interface.

The aim of this thesis work was to gain understanding of the interactions between talc mineral and surfaces, liquids and chemicals relevant for industrial applications, such as pulp and paper. Talc is used in the pulp and paper industry as a filler pigment, in control of pitch (lipophilic extractives) deposits and as a coating pigment. A deeper understanding of talc interactions will be beneficial in optimizing its use. Long-range attractive interactions between talc and hydrophobic model probes, as well as pitch probes, have been measured using the atomic force microscope (AFM) colloidal probe method. Two procedures for preparation of pitch colloidal probes were developed to allow these studies. Model hydrophobic, nanorough surfaces with surface energy characteristics similar to talc have also been prepared and their interactions with hydrophobic model probes compared to interactions between hydrophobic model probes and talc. It is demonstrated that talc mineral interacts with model hydrophobic particles, as well as with pitch, by long-range attractive forces, considerably stronger than the expected van der Waals force. The possible origin of the measured interaction forces is discussed, and the conclusion is that the main cause is an attractive capillary force due to formation of a gas/vapor capillary between the surfaces. Force measurements using model hydrophobic, nanorough surfaces show that a large-scale waviness does not significantly influence the range and magnitude of the capillary attraction, but large local variations in these quantities are found. It is demonstrated that a large variation in adhesion force corresponds to a small variation in local contact angle of the capillaries at the surfaces. The nature of the surface topographical features influences the capillary attraction by affecting the local contact angle and by pinning of the three-phase contact line. The effect is clearly dependent on the size of the surface features and whether they exist in the form of crevices or as extending ridges. Entrapment of air also affects the imbibition of water in pressed talc tablets. The effects of wetting and dispersion agents on the interactions between talc and hydrophobic probes have also been investigated. It is demonstrated that a common dispersing agent used for talc, poly(acrylic acid), does not affect the capillary attraction between talc and non-polar probes. In fact, the results strongly suggest that poly(acrylic acid) does not adsorb on the basal plane of talc. From this finding it is inferred that the stabilizing effect of this additive most likely is due to adsorption to the edges of talc. In contrast, a wetting agent (the non-ionic triblock copolymer Pluronic PE6400) removes the long-range capillary attraction. It is suggested that such an ability to replace air at the talc surface is of great importance for an efficient wetting agent. The Hamaker constant for talc has also been estimated by using optical data obtained from spectroscopic ellipsometry. It is demonstrated that a nanocrystalline talc mineral, cut in different directions displays very small differences in Hamaker constant between the different crystallographic orientations, whereas a microcrystalline sample displays a significantly higher value. The estimated Hamaker constants are discussed for different material combinations of relevance for the pulp- and paper industry, such as cellulose and calcium carbonate.
Målet med detta avhandlingsarbete var att öka förståelsen för interaktioner mellan talkmineral och ytor, vätskor och kemikalier relevanta för industriella applikationer, såsom papper och massa. Talk används i pappers- och massaindustrin som fyllmedel, för kontroll av hartsrika (lipofila extraktivämnen) avsättningar och som bestrykningspigment. En djupare förståelse för talkinteraktioner kommer att vara användbart för att optimera dess användning. Långväga attraktiva interaktioner mellan talk och hydrofoba modellpartiklar, såväl som mellan talk och hartspartiklar, har uppmätts med hjälp av atomkraftsmikroskopi (AFM) genom att fästa kolloidala partiklar på kraftsensorn. Två metoder för att framställa partiklar gjorda av harts har utvecklats för att möjliggöra dessa studier. Hydrofoba, nanostrukturerade modellytor med ytenergier liknande de för talk har också tillverkats och deras växelverkan med hydrofoba modellpartiklar har jämförts med dem mellan talk och hydrofoba modellpartiklar. Studierna visar att talkmineral växelverkar med hydrofoba modellpartiklar, såväl som med harts, genom långväga attraktiva krafter som är betydligt starkare än den förväntade van der Waals kraften. Möjliga orsaker till de uppmätta växelverkanskrafterna diskuteras och slutsatsen blir att huvudorsaken är en attraktiv kapillärkraft som uppkommer genom att en gas-/ångkapillär bildas mellan ytorna. Kraftmätningar gjorda med hydrofoba nanostrukturerade modellytor visar att en storskalig vågighet inte nämnvärt påverkar storleken av kapillärattraktionen, men stora lokala variationer existerar. Det demonstreras att en stor variation i adhesionskraft motsvaras av en liten variation i lokal kontaktvinkel för kapillärerna på ytorna. Ytornas topografi påverkar kapillärattraktionen genom att påverka den lokala kontaktvinkeln samt genom att trefaskontaktlinjen inte kan röra sig fritt över ytan. Effekten är tydligt beroende av huruvida ytojämnheterna existerar i form av nedsänkningar eller upphöjningar. Instängd luft påverkar också pressade talktabletters uppsugningsförmåga av vatten. Vätnings- och dispergeringsmedels inverkan på växelverkan mellan talk och hydrofoba partiklar har undersökts. Resultaten visar att ett vanligt dispergeringsmedel för talk, polyakrylsyra, inte påverkar kapillärattraktionen. I själva verket tyder data på att polyakrylsyra inte adsorberas på talks basalplan. Utifrån dessa resultat dras slutsatsen att polyakrylsyra stabiliserar talkdispersioner genom att adsorbera på talkkanterna. Ett vanligt vätmedel (nonjonisk triblock sampolymer Pluronic PE6400) tar å andra sidan bort långväga kapillärattraktion. Detta antyder att egenskapen att ersätta luft på talkytan är av stor betydelse för effektiva vätmedel. Hamakerkonstanten för talk har uppskattats genom att utnyttja optiska data från ellipsometrimätningar. Det demonstreras att ett nanokristallint talkmineral kapat i olika riktningar uppvisar mycket små skillnader i Hamakerkonstant mellan de olika kristallografiska orienteringarna, medan ett mikrokristallint prov uppvisar ett betydligt högre värde. De beräknade Hamakerkonstanterna diskuteras för olika materialkombinationer relevanta för pappersindustrin, såsom cellulosa och kalciumkarbonat.
QC 20100813

This thesis focuses on the study of the interactions between polyelectrolytes and surfactants in aqueous solutions and at interfaces, as well as on the structural changes these molecules undergo due to that interaction. Small–angle neutron scattering, dynamic, and static light scattering were the main techniques used to investigate the interactions in bulk. The first type of polymer studied was a negatively charge glycoprotein (mucin); its interactions with ionic sodium alkyl sulfate surfactants and nonionic surfactants were determined. This system is of great relevance for several applications such as oral care and pharmaceutical products, since mucin is the main component of the mucus layer that protects the epithelial surfaces (e.g. oral tissues). Sodium dodecyl sulfate (SDS) on the other hand, has been used as foaming agent in tooth pastes for a very long time. In this work it is seen how SDS is very effective in dissolving the large aggregates mucin forms in solution, as well as in removing preadsorbed mucin layers from different surfaces. On the other hand, the nonionic surfactant n-dodecyl β-D-maltopyranoside (C12-mal), does not affect significantly the mucin aggregates in solution, neither does it remove mucin effectively from a negatively charge hydrophilic surface (silica). It can be suggested that nonionic surfactants (like the sugar–based C12-mal) could be used to obtain milder oral care products. The second type of systems consisted of positively charged polyelectrolytes and a negatively charged surfactant (SDS). These systems are relevant to a wide variety of applications ranging from mining and cleaning to gene delivery therapy. It was found that the interactions of these polyelectrolytes with SDS depend strongly on the polyelectrolyte structure, charge density and the solvent composition (pH, ionic strength, and so on). Large solvent isotopic effects were found in the interaction of polyethylene imine (PEI) and SDS, as well as on the interactions of this anionic surfactant and the sugar–based n-decyl β-D-glucopyranoside (C10G1). These surfactants mixtures formed similar structures in solutions to the ones formed by some of the polyelectrolytes studied, i.e. ellipsoidal micelles at low electrolyte concentration and stiff rods, at high electrolyte and SDS concentrations.
QC 20100901

Hydrogen is the smallest element in the periodical table. It has been shown in several studies that hydrogen has a large influence on the corrosion and cracking behaviour of stainless steels. Hydrogen is involved in several of the most common cathode reactions during corrosion and can also cause embrittlement in many stainless steels. Some aspects of the effect of hydrogen on corrosion and hydrogen-induced stress cracking, HISC, of stainless steels were studied in this work. These aspects relate to activation of test specimens for uniform corrosion testing, modification of a test cell for dewpoint corrosion testing and the mechanism of hydrogen-induced stress cracking. The results from uniform corrosion testing of superduplex stainless steels indicated that there is a large difference between passive and activated surfaces in hydrochloric acid and in lower concentrations of sulphuric acid. Hence, initial activation of the test specimen until hydrogen evolution can have a large influence on the results. This may provide another explanation for the differences in iso-corrosion curves for superduplex stainless steels that have previously been attributed to alloying with copper and/or tungsten. In concentrated sulphuric acid, potential oscillations were observed; these oscillations activated the specimen spontaneously. Due to these potential oscillations the influence of activation was negligible in this acid. An experimental set-up was developed for testing dewpoint corrosion of stainless steels in a condensate containing 1 % hydrochloric acid. There was an existing experimental set-up that had to be modified in order to avoid azeotroping of the water and hydrogen chloride system. A separate flask with hydro chloric acid was included in the experimental set-up. The final set-up provided reasonably good agreement with field exposures in contrary to much higher corrosion rates in the original set-up. Relaxation and low temperature creep experiments have been performed with several stainless steels in this work. The aim was to understand how creep and relaxation relates to material properties and the relative ranking between the tested materials. For low temperature creep with a load generating stresses below the yield strength, as well relaxation at stress levels above and below the yield strength, the same ranking with respect to changes in mechanical properties of the steel grades was found. For low temperature creep with a load level above the yield strength, the same ranking was not obtained. This effect can most probably be explained by annihilation and generation of dislocations. During low temperature creep above the yield strength, dislocations were generated. In addition, low temperature creep experiments were performed forone superduplex stainless steel in two different product forms with differentaustenite spacing in the microstructure. The superduplex material experienced low temperature creep at a lower load level for the material with large austenite spacing compared to the one with smaller austenite spacing. Also this differenceis influenced by dislocations. In a material with small austenite spacing the dislocations have more obstacles that they can be locked up against. Studies of the fracture surfaces of hydrogen induced stress cracking, HISC, tested duplex stainless steels showed that HISC is a hydrogen-enhanced localised plasticity, HELP, mechanism. Here a mechanism that takes into account the inhomogeneous deformation of duplex stainless steels was proposed. This mechanism involves an interaction between hydrogen diffusion and plastic straining. Due to the different mechanical properties of the phases in a superduplex stainless steel, plastic straining due to low temperature creep can occur in the softer ferrite phase. A comparison between low temperature creep data showed that for the coarser grained material, HISC occurs at the load levelwhen creep starts. However, in the sample with small austenite spacing, HISC did not occur at this load level. Microhardness measurements indicated that the hydrogen level in the ferrite was not high enough to initiate cracking in the coarser material. The proposed mechanism shows that occurrence of HISC is an interaction between local plasticity and hydrogen diffusion.
QC20100618

Adsorption on solid surfaces from solution is a fundamental property of a surfactant. It might even be the most important aspect of surfactant behavior, since it influences many applications, such as cleaning, detergency, dispersion, separation, flotation, and lubrication. Consequently, fundamental investigations of surfactant adsorption are relevant to many areas.

The main aim of this thesis has been to elucidate the adsorption properties, primarily on the solid/water interface, of a particular class of polyhydroxyl based surfactants: the alkyl glucosides. By the use of ellipsometry, the equilibrium and kinetic aspects of adsorption on titanium dioxide with respect to structural effects has been studied. Furthermore, the effects of small amounts of cationic surfactant additives on the adsorption on silica have been investigated. The results have been compared with similar studies for other nonionic surfactants.

We have found that the surfactant structure has a strong effect on the adsorption properties. An increase in the surfactant chain length increases the cooperativity of the system. An increase in the head group polymerization decreases the cooperativity and the plateau adsorbed amount at equilibrium. The effect of surfactant structure on the adsorption kinetics depends on the concentration relative to the cmc, while the there is a decrease in the rate of desorption with increasing hydrophobic chain length independent of the concentration. The adsorption/desorption process is concluded to be diffusion driven, as suggested by the model used. When comparing these results with studies on ethylene oxide based surfactants, we conclude that the two types of surfactants exhibit similar trends on surfaces onto which they adsorb.

Adsorption from binary surfactant solutions is even more interesting than adsorption from single surfactant solutions, since it brings us one step closer to the systems used in applications. In addition, adsorption from a mixture can be very different from adsorption from any of the single surfactants in the mixture. Alkyl glucosides alone do not adsorb on silica, but addition of small amounts of a cationic surfactant to the alkyl glucoside solution allows for adsorption on silica. A comparison between the adsorption and bulk properties has shown that mixed micellization explains most, but not all, effects of the coadsorption properties. Changing the pH in the mixed systems reveals that a surfactant with a pH-dependent charge and the ability to adapt its charge to the environment, e.g. a surface, enhances the adsorbed amount over a wider range of pH values than a purely cationic surfactant.

It is well known that alkyl glucosides and ethylene oxides adsorb differently on different types of hydrophilic surfaces. As a consequence, replacing ethylene oxides with alkyl glucosides might not be all straight-forward; however, we have shown that the effect of the surface can be eliminated by the use of a cosurfactant.

This thesis presents an investigation of the dynamic properties of wide range of interfacial systems, from colloidal particles in solution, through the realm of aerosols and onto studies of molecular adsorption at an interface. The primary experimental technique utilized is optical tweezers. An exploration of the history of the use of radiation pressure to manipulate matter is presented, followed by an introduction to how optical tweezers work. Some of the more advanced methods of tweezing are discussed, with an emphasis on the use of spatial light modulators (SLMs) to realise dynamic holographic optical tweezers (DHOTs), an example of which has been constructed within our laboratory using off-the-shelf optical components, and combined with a spectrometer to facilitate high resolution spectroscopic studies of microscopic systems. The spectroscopic analysis of microparticles is greatly enhanced by optical feedback generated when the wavelength of light utilized is an integer number of wavelengths around the circumference of the microsphere. Enhanced signal occurs at these wavelengths, termed whispering gallery modes (WGMs). The absolute position of these resonances depends strongly upon the shape, size and refractive index of the particle, and is predicted by Mie theory. A discussion of the concepts behind Mie theory, as well as how to use an experimental WGM spectrum to deduce the size and composition of a microparticle, is provided. This technique is then put to use in a detailed study on the properties of single aerosols, comprised of sodium chloride solution, and generated using a handheld medical nebulizer. Studies have been carried out on both evaporating and growing droplets trapped with a Gaussian beam; in the latter case, periods of size stability are observed, owing to resonant absorption of radiation at the trapping laser wavelength. The SLM can be used to change the trapping laser to a Laguerre-Gaussian (LG) mode, and an investigation of how this affects the dynamics of the droplet is presented. It is found that the use of LG modes with $ellgeq10$ produced Raman spectra with significantly more intense WGMs, and also suppressed droplet evaporation. Through observations made with fluorescent polystyrene microspheres, it is argued that the LG modes are more efficient at coupling into WGMs of the droplets. Leading on from these experiments on salt water droplets, experiments have been conducted using ionic liquids (ILs). These fluids have many fascinating properties and potential applications. The optical trapping of droplets comprised of aqueous solutions of the ionic liquid ethylammonium nitrate (EAN) and water has been demonstrated for the first time. These droplets are analysed spectroscopically by illuminating them with the output from a broadband LED; WGMs that are observed in the backscattered light are used to determine their size and composition. The response of the droplets to conditions of varying relative humidity has also been investigated. In order to characterise the relative humidity experienced by both the salt water and IL droplets, the concentration of water vapour within the trapping cells has been measured using diode laser absorption spectroscopy. The spatially modulated laser beam is then utilized in a different fashion; instead of optically tweezing a sample, a low numerical aperture objective lens is utilized to focus the laser onto the surface of a gold coated microscope slide. When a colloidal sample is placed on this surface, the thermal gradients cause the particles to form two dimensional crystals. The SLM is utilized to form multiple nucleation sites, and the dynamics of the crystals are directly observed in real time using video microscopy. It is found that grain rotation-induced grain coalescence (GRIGC) occurs, with the rotation of both crystals before coalescence. Control over the grain size is achieved by altering the separation of the laser spots, and shows that the time scale for grain boundary annealing in our system is in good agreement with theoretical expressions formulated for nanocrystal growth. Finally, as a complimentary technique to the microparticle spectroscopy previously discussed, a bulk interface is probed by using evanescent wave broadband cavity enhanced absorption spectroscopy (EW-BBCEAS) specifically to study the adsorption of cytochrome c (cyt c) to a fused silica surface. Visible radiation from a supercontinuum source is coupled into an optical cavity consisting of a pair of broadband high reflectivity mirrors, and a total internal reflection (TIR) event at the prism/water interface. Aqueous solutions of cyt c are placed onto the TIR footprint on the prism surface and the subsequent protein adsorption is probed by the resulting evanescent wave. The time integrated cavity output is directed into a spectrometer, where it is dispersed and analysed. The broadband nature of the source allows observation of a wide spectral range (ca 250 nm in the visible). The system is calibrated by measuring the absorption spectra of dyes of a known absorbance. Absorption spectra of cyt c are obtained for both S and P polarized radiation, allowing information about the orientation of the adsorbed protein to be extracted.

It is widely known that surfaces play an important role in numerous biological processes and technological applications. Thus, being able to modify surface properties provides an opportunity to control many phenomena occurring at interfaces. One way of controlling surface properties is to adsorb a polymer film onto the surface, for example through layer-by-layer (LbL) deposition of polyelectrolytes. This simple but versatile technique enables various polymers, proteins, colloidal particles etc. to be incorporated into the film, resulting in a multifunctional coating. Due to recent legislations and a consumer demand for more environmentally friendly products, we have chosen to use natural polymers (biopolymers) from renewable resources. The focus of this thesis has been on the adsorption of biopolymers and their layer-by-layer formation at solid-liquid interfaces; these processes have been studied by a wide range of techniques. The main method was the quartz crystal microbalance with dissipation monitoring (QCM-D), which measures the adsorbed mass, including trapped solvent and the viscoelastic properties of an adsorbed film. This technique was often complemented with an optical method, such as ellipsometry or dual polarization interferometry (DPI), which provided information about the “dry” polymer or protein adsorbed mass. From this combination, the solvent content and density of the layers was evaluated. In addition, the surface force apparatus (SFA), X-ray photoelectron spectroscopy (XPS), total internal reflection fluorescence (TIRF), and fluorescence resonance energy transfer (FRET) were utilized, providing further information about the film structure, chemical composition, and polymer inter-layer diffusion. Adsorption studies of the glycoprotein mucin, which has a key role in the mucousal function, showed that despite the net negative charge of mucin, it adsorbed on negatively charged substrates. The adsorbed layer was highly hydrated and the segment density on the substrate was low. We showed the importance of characterizing the mucin used, since differences in purity, such as the presence of albumin, gave rise to different adsorption behaviours in terms of both adsorbed amount and structure. The adsorbed mucin layer was to a large extent desorbed upon exposure to the anionic surfactant sodium dodecyl sulfate (SDS). In order to prevent desorption, we demonstrated that a protective layer of the cationic polysaccharide chitosan could be adsorbed onto the mucin layer and that the mucin-chitosan complexes resisted the desorption normally induced by association with SDS. Moreover, the association between chitosan and SDS was examined at the solid-liquid interface, in the bulk, and at the air-water interface. In all these environments chitosan-SDS complexes were formed and a net charge reversal of the complexes from positive to negative was observed when the concentration of SDS was increased. Furthermore, the LbL deposition method could be used to form a multilayer-like film by alternate adsorption of mucin and chitosan on silica substrates. The LbL technique was also applied to two proteins, lysozyme and β-casein with the aim of building a multilayer film consisting entirely of proteins. These proteins formed complexes at the solid-liquid interface, resulting in a proteinaceous layer, but the build-up was highly irregular with an increase in adsorbed amount per protein deposition cycle that was far less than a monolayer.Continuing with chitosan, known to have antibacterial properties we assembled multilayers with an anti-adhesive biopolymer, heparin, to evaluate the potential of this system as a coating for medical implants. Multilayers were assembled under various solution deposition conditions and the film structure and dynamics were studied in detail. The chitosan-heparin film was highly hydrated, in the range 60-80 wt-% depending on the deposition conditions. The adsorbed amount and thickness of the film increased exponential-like with the number of deposition steps, which was explained by inter-diffusion of chitosan molecules in the film during the build-up. In a novel approach, we used the distant dependent FRET technique to prove the inter-layer diffusion of fluorescent-labelled chitosan molecules within the film. The diffusion coefficient was insignificantly dependent on the deposition pH and ionic strength, and hence on the film structure. With the use of a pH sensitive dye buried under seven chitosan-heparin bilayers, we showed that the dye remained highly sensitive to the charge of the outermost layer. From complementary QCM-D data, we suggested that an increase in the energy dissipation does not necessarily indicate that the layer structure becomes less rigid.
Det är välkänt att ytor spelar en viktig roll i många biologiska processer och tekniska tillämpningar. Att kunna modifiera en ytas egenskaper ger därför en möjlighet att kunna kontrollera många fenomen som sker på ytor. Ett sätt att kontrollera ytegenskaperna är genom att adsorbera en polymerfilm på ytan, till exempel genom att växelvis adsorbera olika polyelektrolyter (LbL-teknik). Denna enkla men mångsidiga teknik möjliggör att många olika material kan införlivas i filmen, vilket resulterar i en multifunktionell beläggning. På grund av dagens lagstiftning och konsumenters ökade efterfrågan på miljövänliga material beslutade vi oss för att använda biologiska polymerer (biopolymerer) i detta projekt. Fokus i den här avhandlingen har varit på adsorption av biopolymerer och deras LbL-formation på gränsytan vätska-fast fas, där adsorptionsförloppet och det adsorberade skiktet bestående av biopolymerer studerats med en mängd olika tekniker. Huvudtekniken var kvartskristallmikrovåg med energidissipations-registrering (QCM-D), som mäter massan inklusive inkorporerat vatten, samt de viskoelastiska egenskaperna hos ett adsorberat skikt. Som komplement till denna teknik användes ofta optiska metoder, till exempel ellipsometri och ”dubbel polarisationsinterferometri (DPI)”, två tekniker som endast mäter massan av de adsorberade biopolymererna. Genom denna kombination av metoder kunde massan av inkorporerat vatten i filmen och filmens densitet bestämmas. Dessutom användes ytkraftsapparaten (SFA), röntgenfotoelektronspektrometri (XPS), och fluorescens-spektroskopiteknikerna TIRF och FRET i några undersökningar för att erhålla information om skiktens struktur, kemiska sammansättning och polymerernas diffusion inom skiktet.Adsorptionsstudier av glycoproteinet mucin, som har en central roll i funktionen av slemhinnan, avslöjade att trots att mucinet har en negativ nettoladdning adsorberade det ändå på negativt laddade substrat. Det adsorberade lagret var väldigt hydratiserat och hade en låg andel mucin i direkt kontakt med ytan. Vi påvisade vikten av att noga undersöka mucinet som användes, eftersom olika renhet, till exempel i form av förekomsten av albumin gav upphov till olika adsorptionsbeteende gällande både adsorberad mängd och struktur. En stor andel av det adsorberade mucinlagret desorberade när det exponerades för den anjoniska tensiden natriumdodecylsulfat, SDS. Vi visade att ett skyddande lager av den katjoniska polysackariden chitosan kunde adsorberas på mucinet och att mucin-chitosan-komplexen inte desorberade när SDS tillsattes. Därtill studerades växelverkan mellan chitosan och SDS på gränsytan vätska-fast fas, i bulken och på luft-vattengränsytan. Komplex av chitosan-SDS bildades i samtliga miljöer och en nettoladdningsomsvängning från positiv till negativ observerades när koncentrationen av SDS ökades.Vidare kunde LbL-tekniken nyttjas för att skapa ett multilagerlikt skikt genom att alternerande adsorbera mucin och chitosan på kiseldioxidsubstrat. Denna teknik användes även med två proteiner, lysozym och β-kasein, med målet att skapa ett multilager bestående av endast proteiner. Dessa proteiner bildade komplex på gränsytan vätska-fast fas i form av ett blandat proteinlager, men uppbyggnaden var väldigt oregelbunden med en ökning i adsorberad mängd per proteindeponeringscykel som var avsevärt mindre än ett monolager.Inom området för biomaterial utgör de antibakteriella och antihäftande egenskaperna hos chitosan respektive heparin en lovande blandning för beläggningar av medicinska implantat. Baserat på detta konstruerade vi multilagerfilmer av chitosan och heparin med olika deponeringslösningar och undersökte dynamiken och filmens struktur i detalj. Chitosan-heparin-filmen var starkt hydratiserad, bestående av cirka 60-80 vikt-% vatten beroende på deponeringsbetingelserna. Den adsorberade mängden och tjockleken på filmen ökade nästan exponentiellt med antal deponeringar, vilket förklarades med chitosanets förmåga att diffundera genom filmen under uppbyggnaden. Med ett nytt angreppssätt använde vi FRET för att bevisa diffusionen av fluorescerande färgmärkt chitosan i filmen under uppbyggnaden. Diffusionskoefficienten var i princip oberoende av pH och jonstyrka under deponeringen och följaktligen av filmens struktur. Genom att använda ett pH-känsligt färgämne begravt under sju biskikt av chitosan-heparin visade vi att färgämnet i hög grad påverkades av laddningen på det yttersta lagret. Från QCM-D-data lade vi fram teorin om att en ökning av energidissipationen för ett lager inte nödvändigtvis indikerar att lagrets struktur har blivit mindre styvt.
QC 20100729

Emulsions are commonly found both in nature and industry. Due to the complex nature of emulsion systems, their interfacial properties and stability are poorly understood, particularly the influence of droplet deformability on the colloid and interfacial behaviour. This study has highlighted the role of emulsion droplet cross-linking (deformability and penetrability) on droplet surface chemistry, droplet colloidal stability and adsorption at the droplet-water interface and provides insight into methods for enhancing the performance of emulsion formulations.

Gold nanoparticles, are one of the most widely investigated nanoparticles (NP) and are normally synthesized by the reduction of metal salts in citrate solution. The reason for studying this nanostructured material from a technological standpoint is mainly the anticipated application in different areas based on optical properties explained with plasmon resonance. The main work of this study was to develop different sensing systems using gold nanoparticles. Three techniques have been utilized, being lateral flow immunoassay (LFIA), surface plasmon resonance (SPR), and surface-enhanced Raman scattering (SERS). A one-step semi-quantitative LFIA strip test was developed using colloidal gold coated by a partially-purified polyclonal antibody (pAb) raised in sheep as a signal generator, and bovine serum albumin-Estriol-16-glucuronide (BSA-E3-16G) conjugates as the capture agent spotted onto a nitrocellulose membrane as the test line. In this system, gold nanoparticles were applied for visualising the response. The application of the strip sensor to urinary samples from pregnant woman proved successful. A quantitative evaluation of low levels of E3-16G in liquid media was developed based on SPR, which used the same pAb-nanogold conjugates employed for the LFIA analysis. The assay can be carried out directly on any urine samples without sample pretreatment. In this system, gold nanoparticles were utilized as high mass label to improve the sensitivity of the assay. A SERS probe was developed which comprised of Raman reporter molecules (RRM) and gold NPs. Results showed that the conducting polymer materials of 3’-[(E)-2-(4-R-phenyl)ethenyl]-2’2’:5’,2”-terthiophene (R-pe3T, where R is NO2 or NH2) showed significant enhancement. Moreover, high bio-activity groups included in the compounds make them potential candidates for the development of a SERS based sensing system.

The thesis focuses on elastic polymer material that is biodegradable and compatible with human cells and tissues. The presented research describes polymer synthesis, material processing, physico-chemical investigation and biological tests performed on this novel biomaterial.

The hydrophobicity of a surface is an important property in many areas of science and engineering. This is especially the case in mineral processing, where differences in surface hydrophobicity lie at the heart of the separation process of flotation. Chemicals are used to increase and decrease the natural hydrophobicity of minerals to attain a better separation between valuable and worthless material. Polymers are often used to reduce mineral surface hydrophobicity. Decades of empirically based decision making have produced a list of effective depressants. However the detailed study of how these polymer depressants affect surface hydrophobicity and mineral recovery lags behind applied investigations. The aim of this thesis was to study the adsorption of commonly used depressants on model surfaces and to interrogate the action of these polymers in reducing surface hydrophobicity. We have modelled the degree of hydrophobicity of common minerals in order to study polymer depressants with methods not commonly used in studies of surface characterisation in flotation. The model surfaces (self-assembled monolayers, SAMs) allowed us to use the quartz crystal microbalance with dissipation monitoring (QCM-D) to study the adsorption of polymers. The QCM-D can be used to obtain adsorption isotherms, adsorption kinetics, water content of adsorbed layers, and information on the conformation of the adsorbed polymer. The results from the QCM-D were correlated with the contact angle data from the captive bubble measurements, with which we assessed the hydrophobicity of the surface before and after polymer adsorption. Three of the polymers layers were probed with dynamic dewetting studies, in order to test other modes of depressant action. Three types of polymers were studied - a polyacrylamide (Polymer-H), a polyelectrolyte CMC (carboxymethyl cellulose) and a group of dextrins (Dextrin-TY, a phenyl succinate substituted dextrin (PS Dextrin) and a styrene oxide substituted dextrin (SO Dextrin)). These polymers are commonly used or have potential to be used in the depression of talc and graphite. Polymer-H was used to investigate the hydrophobic bonding between a non-ionic polymer depressant and chemically inert and non charged surfaces by probing the influence of substrate hydrophobicity on polymer adsorption and reduction of contact angle. Three different model surfaces were used (mixed self-assembled 0.5 SAM, 0.7 SAM or single self-assembled 1.0 SAM monolayers) with advancing contact angles between 75?? and 119??. The study of Polymer-H found that the substrate hydrophobicity is an important factor in adsorption of this polymer and the change in contact angle upon adsorption depends on adsorbed amount. The effectiveness of Polymer-H to reduce surface hydrophobicity was established to correlate with its conformation and morphology. CMC was investigated to find out how a stimulus responsive polymer depressant can be used in flotation. It was established that the adsorbed amount and rate of adsorption of CMC increase with decreasing of pH or increasing of ionic strength. It was shown that the surface hydrophobicity of a CMC pre-adsorbed layer changes with the environment and these alterations are fully reversible. A switch of ionic strength (from 10-2 M KCl to 10-1 M KCl) caused partial dehydration of the adsorbed layer and a decrease of the receding contact angle by 20??. A pH switch (pH = 9 to pH = 3) resulted in a 40?? change in receding contact angle. The CMC investigation showed that the use of a stimulus responsive polymer presents opportunities for exploiting solution conditions as a means to effect a better mineral separation in flotation The adsorption of three dextrin-based polymers on a model hydrophobic surface has been characterized using the quartz crystal microbalance with dissipation monitoring (QCM-D). The three polymers (one standard dextrin and two dextrins with different aromatic group substitutions) exhibited varying affinities and capacity for adsorption on the hydrophobic substrate. The effect of the three polymers on the static contact angle of the surface was studied using captive bubble contact angle measurements. The three polymers were seen to reduce the receding contact angle by similar amounts (approximately 14 degrees) in spite of having varying adsorbed amounts and differences in adsorbed layer water content. Although no differences were observed in the ability of the polymers to reduce the static contact angle, measurements of the dewetting dynamics between a rising air bubble and the polymer covered substrate yielded stark differences between the polymers, with one polymer slowing the dewetting dynamics by an order of magnitude more than the other two polymers. The differences in dewetting behaviour correlate with the adsorbed layer characteristics determined by QCM-D.
Thesis (PhD)--University of South Australia, 2010

Monolayer protected nanoparticles (MPNs) display fascinating size-dependent electronic, optical and catalytic properties. They are promising candidates to be used as building blocks with which to construct new generation nanoarchitectures and nanodevices for sensing, electronic and optoelectronic applications. The aggregation and dispersion of colloidal nanoparticles is one of the key issues closely related to their potential applications. Our knowledge of the colloid stability of nanoparticle dispersions with small sizes is still in its infancy, however, thymine is one of the bases in DNA, and is a pH sensitive and chromatic molecule. In the present study, thymine-functionalized self-assembled monolayer protected gold nanoparticles were synthesized. Their morphology and surface structure were characterized using TEM, UV-vis, FTIR, DSC-TGA and XPS techniques. The colloid stability of thymine-capped gold nanoparticle dispersions as a function of the type and concentration of monovalent salt, pH and particle size in alkaline aqueous solution were investigated. The manipulation of colloid stability with light was further explored. The results and conclusions are summarized inthis thesis.

The surface force apparatus (SFA) has been an important technique for making direct force measurements and has contributed enormously to our understanding of colloidal interactions. The conventional SFA has been limited to measuring forces between solid surfaces, until recently when a modified SFA was developed at the Ian Wark Research Institute [1]. A fluid drop (mercury) is introduced into the apparatus which allows a range of deformable surfaces to be studied in the SFA. This project is an extension of this technique. Interactions between a mica sheet and a mercury drop are studied, including the modification of mercury with self-assembled monolayers (SAMs) of thiol surfactants, and the drop deformation due to non-equilibrium adsorption effects and hydrodynamic forces.

Hydrophobic colloidal suspensions are common in nature and industry. DLVO theory has been used to model the interactions between colloidal particles for decades, however the origin of long-ranged attractive forces observed between hydrophobic colloids remains the subject of much debate. In an effort to understand these forces and improve the prediction of colloidal stability, the colloidal stability of synthetic silica and titania was studied at various concentrations of dissolved gas, KCl electrolyte and pH.
Thesis (PhD)--University of South Australia, 2003

The role of mechanical forces in the fate and function of adherent cells has been revealed to be a pivotal factor in understanding cell biology. Cells require certain physical cues to be present in their microenvironment or the cell will begin apoptosis. Mechanical signals from the environment are interpreted at the cellular level and biochemical responses are made due to the information from outside the cell, this process is known as mechanotransduction. Misinterpretation of physical cues has been indicated in many disease states, including heart disease and asthma. When a cell is bound to the ECM, proteins such as integrins are engaged at static and stable adhesion sites. These tight and static anchoring points found at the ECM exist in stark contrast to the dynamic conditions seen at intercellular junctions. Intercellular junctions, such as gap and adherens junctions, are formed between cells to act as a mechanism to relay information and exchange material. Due to the important role intercellular junctions play in processes of wound healing, epithelial-mesenchymal transition and cancer metastasis developing more sophisticated levels of understanding of these mechanisms would provide valuable insight.

Complex biological processes, including immune cell signaling and cellular ECM adhesions, have been effectively replicated in model systems. These model systems have included the use of solid supported lipid bilayers and polymeric hydrogels that display cell adhesion molecules. Studies of cellular mechanotransduction at ECM adhesion sites has also been completed with covalently functionalized polymeric substrates of adjustable elasticity. However, developing model systems that allow the accurate reproduction of properties seen at intercellular junctions, while also allowing the investigation of cellular mechanosensitivity has proven to be a difficult task. Previous work has shown that polymer-tethered lipid bilayers (PTLBs) are a viable material to allow the replication of the dynamics and adhesion seen at intercellular junctions. Although efforts have been made to produce PTLBs with different mechanical properties, there is currently not a material with sufficient tunable elastic properties for the study of cellular mechanotransduction.

To establish a system that allows the study of stiffness effects across a biologically relevant range (~0.50 – 40 kPa) while maintaining the dynamic properties seen at cell-to-cell junctions, polymer gel-tethered bilayers (PGTBs) were developed. A fabrication strategy was established to allow the incorporation of a hydrogel support with easily tunable stiffness and a tethered lipid bilayer coating, which produced a powerful platform to study the effects of stiffness at intercellular junctions. Careful attention was given to maintain the beneficial properties of membrane diffusion, and it was shown that on different linking architectures lipid bilayers could be established and diffusion was preserved. Microscopy-based FCS and FRAP methodology were utilized to measure lipid diffusion in these systems, while confocal microscopy was used to analyze cell spreading and adhesion. Three distinct architectures to link the lipid membrane to the underlying polyacrylamide hydrogel were pursued in this work, a non-covalent biotin-streptavidin system, a covalently linked design with fibronectin, and a direct covalent linkage utilizing crosslinker chemistry. In this work, it was shown that cells were able to spread and adhere on these substrates, with cell adhesion zones visualized under plated cells that demonstrate the capability of the cell to rearrange the presented linkers, while maintaining a stable material. Also confirmed is the tunability of the polymer hydrogel across a wide range of stiffness, this was shown by quantitative changes in cell spreading area in response to polymer properties.

Polymer brushes are extremely versatile materials, as monomer choice allows the user to design a material with the desired physiochemical properties. Given the wide variety in monomer functionality, polymers can be fine-tuned for a specific application. In this work, polymer brushes bound to a silica support are designed and utilized to enhance performance of protein extraction and chromatographic separations.
The effectiveness of an analytical method is strongly affected by matrix composition, however, the presence of species other than the target analyte is usually unavoidable. An excellent technique will be able to identify and/or quantify the analyte even when its concentration is low compared with interfering molecules. Protein analysis is particularly challenging, since many proteins of clinical and scientific significance are present in complicated matrices such as plasma or cell lysates.
A common method to specifically separate a protein from a complicated matrix is solid phase extraction. In this method, a species (such as an antibody) with high specificity towards the target is immobilized onto a solid substrate (commonly beads or small particles for greater surface area). Next, the target is collected onto the surface, bound by the species. The solid substrate is rinsed of the liquid matrix, before elution of the target. Only the active species should interact with the analyte, and the surface should be otherwise inactive. However, nonspecific interactions lead to binding/adsorption of undesirable compounds. Therefore, an optimal substrate for protein extraction must be 1) easily and completely removable from the liquid phase, 2) have a high concentration of active sites for specific binding, and 3) exhibit low nonspecific binding. As part of this work, commercial magnetic particles were coated with a nonporous silica layer that tolerates the acid bath and silane coating necessary to attach a polymer layer. On the silane coating, a polymer layer was covalently bound; this layer contains epoxide active groups for immobilizing antibodies. These antibodies bind to the target molecule with high specificity, and low nonspecific binding. Obtained particles were evaluated for protein extraction, where antibodies as well as specifically engineered drug compounds were successfully bound to the particle surface.
Glycosylation influences several physiopathological processes in proteins. Glycans can act as receptors, modify protein solubility, and participate in folding conformation. Altered glycosylation is a common feature in tumorous cells. As such, many modifications in glycoproteins have been related to cancer, including increased branching of N-glycans or augmented units of sialic acid. Therefore, characterization of glycoproteins is important not only as a diagnostic tool, but also to monitor patients’ response to treatment. Furthermore, it is important in the growing field of monoclonal antibodies as drug carriers.
Among different methods used for glycosylation analysis, Hydrophilic Interaction Liquid Chromatography (HILIC) has showed important advantages over time-consuming digestion-MS based techniques. An adequate HILIC stationary phase can be used to rapidly differentiate glycoforms present in a sample. In the second part of this work, a polymer brush based bonded phase was developed as a HILIC stationary phase. The new polymer improved the separation of a model glycoprotein compared with a commercial HILIC column, while also exhibiting enhanced stability over a previous bonded phase synthetized in our group.

The combination of analytical sensitivity and selectivity provided by time-of-flight secondary ion mass spectrometry (ToF-SIMS), with advanced statistical interrogation by principal component analysis (PCA), has allowed a significant advancement in the forensic discrimination of pen, pencil and glass materials based on trace characterisation.

The unprecedented properties of 2D materials such as graphene and MoS2 have been researched extensively [1,2] for a range of applications including nanoscale electronic and optoelectronic devices [3–6]. Their unique physical and electronic properties promise them as the next generation materials for electrodes and other functional units in nanostructured devices. However, successful incorporation of 2D materials into devices entails development of high resolution patterning techniques that are applicable to 2D materials. Patterning at the sub-10 nm scale is particularly of great interest as the next technology nodes require patterning of (semi)conductors and insulators at 7 nm and 5 nm scales for nanoelectronics. It will also benefit organic photovoltaic cells as phase segregation of p/n-type semiconducting polymers on 2D electrodes at length scales smaller than the typical exciton diffusion length (10 nm)

is expected to improve the charge separation efficiency [7].

Characterizing locally modulated properties of non-ovalently functionalized 2D materials requires high-resolution imaging techniques capable of extracting measurements of various physical/chemical properties. One such method is scanning probe microscopy (SPM) [18–21]. In Chapter 1, we present a brief review of SPM modalities, some of which are used to characterize interfacial properties, such as conductivity and local contact potential differences that can be modulated by amphiphilic assemblies [17, 22]. Atomic force microscopy (AFM) is one of main techniques that we use to determine topography. All imaging in this work were performed in attractive AC mode [23,24] in order to minimize disruption to the self-assembly of the amphiphiles by the scanning tip.

One challenge of using SAMs for locally modulated functionalization is that the proximity to the nonpolar interface can modify the behavior of the functionalities present on the surface in conjunction with the steric hindrance of 2D molecular assemblies. For instance, ionizable functional groups, one of the strongest local modulators of surface chemistry, undergo substantial pKa shifts (in some cases, > 5 units) at nonpolar interfaces, limiting their ability to ionize. In order to apply molecular assembly to create 2D chemical patterns, we needed to design alternative structures that can avoid such penalties against the intrinsic properties of functionalities present in the assemblies. Among amphiphiles, we observed that the chiral centers of phospholipids have the potential of elevating the terminal functional group in the head from the surface for improved accessibility. We refer to this type of assembly as a ’sitting’ phase. Chapter 2 describes sitting phase assembly of phospholipids; the projection of the terminal functionality allows it to maintain solution phase-like behavior while the dual alkyl tails provide additional stabilizing interactions with the substrates. Given the diversity of phospholipid architecture [25], the sitting phase assembly suggests the possibility of greatly diversifying the orthogonality of the chemical patterns, allowing highly precise control over surface functionalities.

While a variety of methods including drop-casting [26–28] and microcontact printing [29] have been used previously by others for noncovalent assembly of materials on the surface, they mostly address patterning scale in the sub-μm range. Here, we utilize Langmuir-Schaefer(LS) transfer, which has been historically used to transfer standing phase multilayers [30], and lying-down domains of PCDA at < 100 nm scales in the interest of molecular electronics [14, 31–33], as our sample preparation technique. LS transfer is remarkable in that the transferred molecules relinquish their pre-existing interactions in the standing phase at air-water interface to undergo ∼ 90◦ rotation and assemble into the striped phase on a substrate. This introduces the possibility of modulating local transfer rate across the substrate by manipulating local environment of the molecules. Thus, LS transfer has the potential to offer spatial control over the noncovalent chemical functionalization of the 2D substrate, essential in device applications.

In Chapter 3 and 4, We make comparative studies of various experimental factors such as surface pressure, temperature and molecular interactions that affect the efficiency of LS conversion. Considering the energetics of the transfer process, we predicted that the rate of transfer from the air-water interface to the substrate should be the highest from the regions around defects, which would be the energetically

least stable regions of the Langmuir film [34, 35]. In Langmuir films, two phases of lipid assemblies—liquid expanded (LE) and liquid condensed (LC)—often coexist at the low surface pressures (< 10 mN/m) used for sample preparation. Hence, we hypothesized that the microscale structural heterogeneity of Langmuir films could be translated into microscale patterns in the transferred film on HOPG. We compare the transfer rates between LE and LC phases and investigate the impacts of physical conditions during LS transfer such as temperature, packing density, dipping rate and contact time to conclude that local destabilization of Langmuir films leads to increased transfer efficiency. (Chapter 3)

As in the case of lipid membranes that reorganize routinely based on the structure of the constituent molecules [36–38], the structure of Langmuir films is strongly dependent on the molecular structures of the constituent molecules [39–43]. Accordingly, we expected the molecular structures/interactions to provide additional control over the LS transfer process. In Chapter 4, we compare domain morphologies and the average coverages between three single chain amphiphiles and two phospholipids, each

of which contain hydrogen bonding motifs of varying strengths. We show that by influencing the adsorption and diffusion rates, molecular architecture indeed influences LS conversion efficiency and subsequent assembly on the substrate. The presence of strong lateral interactions limits transfer and diffusion, forming vacancies in the transferred films with smaller domain sizes while weaker intermolecular interactions enabled high transfer efficiencies.

In der vorliegenden Dissertation werden verschiedene plasmonisch aktive Kern/Schale- Nanopartikel synthetisiert, experimentell und theoretisch charakterisiert und in analytischen Anwendungen der oberflächenverstärkten Raman-Spektroskopie (engl. surface-enhanced Raman scattering, SERS) eingesetzt. Es werden die optischen Eigenschaften von Gold/Silber-Nanoschalen mit durchstimmbaren Plasmonbanden behandelt. Motivation dafür ist die Frage nach optimalen SERS-Markern für die rote Laseranregung (λ = 632.8 nm). In SERS-Anwendungen gibt es die Möglichkeit mehrere Marker-Moleküle auf die Oberfläche der Nanopartikel aufzubringen, um so eine erhöhte Multiplexing-Kapazität zu generieren. Diese Option der gemischten Monolagen wird in der vorliegenden Arbeit untersucht. Es werden SERS-Marker-Konzepte für die rote Laseranregung basierend auf einzelnen Nanopartikeln gezeigt. Außerdem wird dargestellt, inwieweit sich durch die Anordnung von Nanopartikeln in allen drei Raumdimensionen neue SERS-Marker- Konzepte mit sehr guten plasmonischen Eigenschaften realisieren lassen. In den oben beschriebenen Kapiteln übernehmen Nanopartikel die Rolle des SERS-Substrats für den selektiven Nachweis eines bestimmten Zielmoleküls (z.B. Antigens). Neben diesen Anwendungen können Nanopartikel jedoch auch noch als SERS-Substrat für die markierungsfreie Detektion von Analytmolekülen eingesetzt werden. In dieser Dissertation wird die Herstellung, Charakterisierung und der Einsatz eines integrierten SERS-Substrats für die kombinierte Festphasensynthese und Analytik mittels plamonisch aktiver Gold/Glas-Kern/Schale-Nanopartikel auf Harz-Mikrokugeln behandelt.

The objective of this research is to develop and apply a HILIC UHPLC stationary phase that allows for separation of intact glycoproteins. In Chapter 1 I give an overview of the problems of current glycosylation profiling with regards to biotherapeutics, and my strategy to separate the intact glycoprotein with HILIC. Chapter 2 describes the methods used to produce the nonporous packing material and stationary phase. In Chapter 3 I describe previous work in developing a HILIC polyacrylamide stationary phase, and further improvements I have made. Chapter 4 describes development of an assay in collaboration with Genentech of therapeutic mAb glycosylation. In Chapter 5, I show HILIC-MS of digested ribonuclease B as a beginning step to analyze glycosylated biomarkers.

Despite the central importance of porous electrodes to any advanced electrochemical system, there is no clear answer to “How to make the best electrode?”. The source of ambiguity lies in the incomplete understanding of convoluted material interactions at smaller – difficult to observe length and timescales. Such mesoscopic interactions, however, abide by the fundamental physical principles such as mass conservation. The porous electrodes are investigated in such a physics-based setting to comprehend the interplay among structural arrangement and off-equilibrium processes. As a result, a synergistic approach exploiting the complementary characteristics of controlled experiments and theoretical analysis emerges to allow mechanistic insights into the associated mesoscopic phenomena. The potential of this philosophy is presented by investigating three distinct electrochemical systems with their unique peculiarities.

Attractive particle interactions which lead to the hetero-aggregation or 'sliming' of silicate clay gangue and valuable sulphide mineral particles are encountered in a number of hydrometallurgical and flotation processes. Sliming leads to poor recovery of the valuable minerals and high recovery of the clay gangue minerals in flotation concentrates. In the present work, the hetero-aggregation mechanism of hydrophilic mica clay mineral sericite (or muscovite) and hydrophobic chalcocite was investigated by probing the particle interactions and the prevailing interfacial chemistry under dispersion conditions where the individual chalcocite and sericite particles displayed negative zeta potentials. The mitigation/suppression of the hetero-aggregation was examined via the prudent control of dispersion conditions and pulp chemistry (i.e., pH modification and solution speciation control) and the use of two, anionic, polymeric dispersants with different molecular weight and functionality (carboxylate-substituted polyacrylamide, Cyquest 3223 and sulphonate-substituted polymaleic acid, P80 co-polymers) as dispersants. The adsorption behaviour of both polymers onto both minerals under industrially relevant suspension conditions have been quantified in terms of the polymer adsorption density and the adsorbed layer characteristics. These interfacial layer properties which impact on the mineral particles' zeta potentials and interactions, and also underpin the dispersion efficacy of polymers were characterized, using interfacial and solution analytical methods and TM-AFM imaging analysis.