<p>In this thesis the interactions in cellulose systems havebeen studied with emphasis on surface forces and adsorptionphenomenon. The study was limited to surfaces and polymers ofinterest for papermaking. During papermaking both therunability of the paper machine as well as the properties ofthe final paper will depend on the molecular interactionsbetween the components present in the suspension. The objectiveof this work was to gain a better understanding of theseinteraction forces and how they are affected by solutionconditions like pH and electrolyte concentration. The maintechniques employed for this purpose were direct surface forcemeasurements using both the interferometric surface forceapparatus (SFA) and the atomic force microscopy (AFM)colloidal-probe technique. In addition, both electronspectroscopy for chemical analysis (ESCA) and AFM imaging wereused for surface characterisation and to study adsorptionbehaviour. Since a smooth and transparent surface is needed forsurface force studies using SFA, Langmuir-Blodgett films ofcellulose were employed.</p><p>The interactions between cellulose surfacesand xylansurfaces were studied. Cellulose is the main constituent of thewood fibre. In close association with cellulose in the cellwall are the hemicelluloses, xylan being a commonhemicellulose. Steric forces were found to dominate theinteractions between these substances in aqueous solutions.Still factors like charge density, solution pH and electrolyteconcentration were important. The adhesion between cellulosesurfaces in air depended on the contact area. The effect of acationic polyelectrolyte on the forces between cellulosesurfaces and between cellulose and mineral surfaces wasinvestigated to obtain a better understanding of the effects ofcationic retention and strength additives. In the presence of acationic polyelectrolyte the forces at large distances weredominated by double-layer repulsion. Bridging attraction was insome cases observed, but the presence and magnitude of thisforce was dependent on the properties of the substratesurface.</p><p>Lignin on the fibre surface affects brightness, swelling andstrength of paper. In addition, dissolved lignin interfereswith added polymers during papermaking. For this reason theadsorption of lignin on cellulose fibre surfaces was explored.The adsorption of lignin was influenced by the concentration oflignin in solution and by the electrolyte composition of thesolution. The retention of lignin was affected by the presenceof a cationic polyelectrolyte and particularly by how thepolyelectrolyte was added. The AFM imaging revealed thestructure of the adsorbed lignin, which varied with the way ofadding the polyelectrolyte, and gave an idea about theadsorption mechanism. The effect of lignin on strengthproperties of paper sheets was also evaluated.</p><p>Keywords: cellulose, hemicellulose, xylan, lignin, surfaceforces, adsorption, polyelectrolyte, SFA, AFM, ESCA,Langmuir-Blodgett films, chitosan, steric forces,bridging,adhesion</p>

<p>The main objective for the work described in this PhD thesiswas to formulate a friction model to characterize thefrictional behavior of paper. More specifically, the modelshould explain a phenomenon that is typical for paper grades,viz.: that the level of paper-to-paper friction is dependent onthe direction and the number of previous slides. The modelshould also explain the lubricating effect oflow-molecular-mass lipophilic compounds (LLC) that occur inpaper on paper-to-paper friction. Furthermore, the model shoulddescribe the types of forces that influence paper-to-paperfiction and explain the mechanism by which the LLC decreasepaper-to-paper friction.</p><p>This thesis consists of a literature review of the basicconcepts of tribology and a summary of the main results andconclusions from four studies on the frictional characteristicsof paper and a study on the friction and adhesion of cellulosesurfaces together with some unpublished material.</p><p>The purpose of the investigation described in the firstpaper was to explain a phenomenon that is typical for papergrades, viz.: the level of paper-to-paper friction is dependenton the direction and the number of previous slides. Thisbehavior is called“friction hysteresis”by theauthors, and it has its origin in the reorientation of thefibers on the surface of a paper and their alignment relativeto the sliding direction.</p><p>The second paper describes a study that was aimed atidentifying lubricants that occur natively in paper. Filterpapers were impregnated with model compounds representing woodextractives, i.e. low-molecular-weight lipophilic compounds,which are present in wood, pulp and paper, and thepaper-to-paper friction was determined. The results of thatstudy show that a wood extractive must fulfill severalstructural criteria in order to lubricate a paper surface: Itmust have a hydrophilic group that can attach to the papersurface and a linear hydrocarbon backbone of sufficientlength.</p><p>Although it is not specifically stated in the second paper,the authors proposed a type of lubrication by which woodextractives decrease paper-to-paper friction that is, ineffect, boundary lubrication. The purpose of the investigationdescribed in the third paper was to clarify whether woodextractives and other low-molecular-mass lipophilic compoundsthat occur in paper can act as boundary lubricants on papersurfaces. The main objective of that study was to investigatethe role of chemical structure of LLC for their orientationrelative to the paper surface, which is an important criterionfor boundary lubrication. Filter papers were impregnated withmagnesium salts of different lipophilic acids, which were usedfor model compounds for the LLC. The deposited layers ofmagnesium salts were characterized by X-ray photoelectronspectroscopy (XPS) and contact angle goniometry and thefriction of the impregnated paper sheets was determined. Theresults show that the degree of lubrication and the resistanceto wear of the layers of a magnesium salt increased withincreasing chain length and increasing degree of linearity ofthe lipophilic acid. Based on the results of that study and ofearlier studies, it is concluded that boundary lubrication isthe type of lubrication by which low-molecular-mass lipophiliccompounds that occur natively in paper decreasepaper-to-paper-friction.</p><p>In boundary lubrication, surfaces are covered withmonolayers of lubricant molecules that comprise an active headgroup that can attach to the surface, e.g. a carboxyl group,and an inert linear backbone, such as a long saturatedhydrocarbon chain. Such compounds form ordered monolayers onsurfaces, so that the backbone points vertically out of planeof the surface. The friction is then determined by theinteractions between the monolayers, which are weaker than theinteractions between the clean surfaces and this gives a lowerfriction.</p><p>The fourth paper describes a study on the origin of thedifferences in friction levels between different linerboardsbased on recycled fiber (old corrugated container, OCC). Thesheets were subjected to two extraction stages and analyzedwith respect to surface roughness and their content oflow-molecular-mass lipophilic compounds (LLC). The resultsshowed that a high amount of LLC in the sheets lead to lowfriction, due to lubrication.</p><p>The fifth paper describes a study that was aimed atdetermining the types of forces that influence the frictionbetween the surfaces of hydrophilic polymers and explaining themechanism by which boundary lubricants decrease the friction.The adhesion and the friction of model systems was measuredwith atomic force microscopy (AFM) using regenerated cellulosefilms and functionalised AFM tips and the effect of fatty acidsand humidity was investigated. The friction significantlyincreased with increasing humidity and that there was a strongcorrelation between the ability of a fatty acid to form ahydrophobic surface and its lubricating performance. Measuredadhesion forces at high humidity were well predicted bytheoretical models that took into account the effect of theLaplace pressure acting in a water meniscus formed aroundcontact regions due to capillary condensation. The resultsindicated that the degree of capillary condensation may beeffectively suppressed by increasing the hydrophobicity of thecontacting surfaces, causing adhesion and friction to decrease.These results suggest that friction between paper surfacesunder ambient conditions is greatly influenced by the degree ofcapillary condensation. Furthermore, lubrication by fatty acidsis achieved by the formation of a vertically oriented,hydrophobic monolayer that can withstand the stresses duringsliding and increase the hydrophobicity of the paper surfaceand thereby suppress capillary condensation.</p><p><b>Keywords:</b>Friction, paper-to-paper friction, frictionhysteresis, fibers, orientation, sliding direction, woodextractives, low-molecular-mass lipophilic compounds, boundarylubrication, adhesion, capillary condensation, Laplacepressure, surface forces, JKR theory, gas chromatography-massspectroscopy, X-ray photoelectron spectroscopy, contact angle,atomic force microscopy</p>

Interfacial features of polymers are a complex, fascinating topic, and industrially very important. There is clearly a need to understand interactions between polymer layers as they can be used for controlling surface properties, colloidal stability and lubrication. The aim of my Ph.D study was to investigate fundamental phenomena of polymers at interfaces, covering adsorption, interactions between polymer layers and surfactants, surface forces and friction between adsorbed layers. A branched brush layer with high water content was formed on silica surfaces by a diblock copolymer, (METAC)m-b-(PEO45MEMA)n, via physisorption. The adsorption properties were determined using several complementary methods. Interactions between pre-adsorbed branched brush layers and the anionic surfactant SDS were investigated as well. Surface forces and friction between polymer layers in aqueous media were investigated by employing the Atomic Force Microscopy (AFM) colloidal probe technique. Friction forces between the surfaces coated by (METAC)m-b-(PEO45MEMA)n in water are characterized by a low friction coefficient. Further, the layers remain intact under high load and shear, and no destruction of the layer was noted even under the highest pressure employed, about 50 MPa. Interactions between polymer layers formed by a temperature responsive diblock copolymer, PIPOZ60-b-PAMPTMA17 (phase transition temperature of 46.1 °C), was investigated in the temperature interval 25-50 °C by using the AFM colloidal probe technique. Friction between the layers increases with increasing temperature (25-45 °C), while at 50 °C friction was found to be slightly lower than that at 45 °C. We suggest that this is due to decreased energy dissipation caused by PIPOZ chains crystallizing in water above the phase transition temperature. The structure of 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) bilayers was determined by X-ray reflectometry. Surface forces and friction between DPPC bilayer-coated silica surfaces were measured utilizing the AFM colloidal probe technique. Our study showed that DPPC bilayers are able to provide low friction forces both in the gel (below ≈ 41°C) and in the liquid crystalline state (above ≈ 41°C). However, the load bearing capacity is lower in the gel state. This is attributed to a higher rigidity and lower self-healing capacity of the DPPC bilayer in the gel state. Friction forces in single asperity contact acting between a micro-patterned silicon surface and an AFM tip was measured in air. We found that both nanoscale surface heterogeneities and the µm-sized depressions affect friction forces, and considerable reproducible variations were found along a particular scan line. Nevertheless, Amontons’ first rule described average friction forces reasonably well. Amontons’ third rule and Euler’s rule were found to be less applicable to our system. / <p>QC 20141209</p>

Cette thèse de doctorat présente une étude expérimentale des propriétés rhéologiques d’électrolytes confinés et de la mécanique des doubles couches électrostatiques.Afin d’étudier simultanément les propriétés d’équilibre et de transport d’électrolytes confinés proches de parois électriquement chargées, nous avons développé un appareil à forces de surfaces dynamique. Cette technique combine à la fois des mesures à l’équilibre, à l’instar des appareils à forces de surfaces classiques, et des mesures dynamiques permettant de caractériser les phénomènes de transport.Nous avons tout d’abord étudié le cas d’électrolytes très dilués. Nous avons montré l’existence d’une sur-dissipation induite par les ions issus des électrolytes par rapport à un comportement newtonien classique. De plus, nous avons mis en évidence un comportement élastique des doubles couches électrostatiques dépendant de la fréquence. Une approche théorique vient compléter et expliquer en partie les résultats expérimentaux.Enfin nous nous sommes intéressés à la dynamique d’électrolytes concentrés : les liquides ioniques. Nous avons étudié l’influence, sur la viscosité et les propriétés du liquide à l’interface solide-liquide, d’un champ électrique intense appliqué perpendiculairement à l’écoulement, comme rencontré dans les super-condensateurs. / This thesis presents an experimental study of rheological properties of confined electrolytes and mechanics of electric double layer.In order to study simultaneously equilibrium and transport of confined electrolytes nearby charged surfaces, we developed a dynamic surface force apparatus. This technique enables both steady state measurements, as provided by common surface forces apparatus, and dynamic measurements that allow characterizing the transport phenomenona.First, we showed the existence of an over-dissipative behavior of weak electrolytes compared to a classical newtonian fluid. Furthermore we highlighted a frequency dependence of the EDL elastic behavior. Alongside, a theoretical approach completes and explains partially the experimental observations.Finally we studied the dynamics of ionic liquid, a type of concentrated electrolytes. We looked at the influence of a huge electric field, applied perpendicularly to the surfaces, on the viscosity and the properties of the liquid nearby the surfaces, as found in super-capacitors.

The tensor theory is a branch of Multilinear Algebra that describes the relationship between sets of algebraic objects related to a vector space. Tensor theory together with tensor analysis is usually known to be tensor calculus. This thesis presents a formal category treatment on tensor notation, tensor calculus, and differential manifold. The focus lies mainly on acquiring and understanding the basic concepts of tensors and the operations over them. It looks at how tensor is adapted to differential geometry and continuum mechanics. In particular, it focuses more attention on the application parts of mechanics such as; configuration and deformation, tensor deformation, continuum kinematics, Gauss, and Stokes' theorem with their applications. Finally, it discusses the concept of surface forces and stress vector.

Thin liquid films (TLFs) of water are ubiquitous in daily lives as well as in many industrial processes. They can be formed between two identical phases, as in colloid films between two macroscopic surfaces and foam films between two air bubbles; and between two dissimilar phases, as in wetting films. Stability of the colloids, foams, and wetting films is determined by the surface forces in the TLFs. Depending on the nature of the surfaces involved, the stabilities can be predicted using combinations of three different forces, i.e., the van der Waals, electrical double layer (EDL), and hydrophobic forces. The objective of the present work is to study the roles of these forces in determining the stabilities of the TLFs of water confined between i) an air bubble and a hydrophobic surface and ii) an oil drop and a hydrophobic surface, with particular interest in studying the role of the hydrophobic force. The first part of the study involves the measurement of the surface forces in the TLFs confined between bitumen drops and mineral surfaces. Deformation of bitumen drops has been monitored by interferometry while it approaches a flat surface. By analyzing the spatiotemporal film profiles, both the capillary and hydrodynamic forces have been calculated using the Young-Laplace equation and the Reynolds lubrication approximation, respectively, with the surface forces being determined by subtracting the latter from the former. The results are useful for better understanding the effects of electrolyte and pH on bitumen liberation and recovery by flotation and for developing a filtration model from first principles. The second part of the study involves the surface force measurement in wetting (flotation) films. Surface forces in the TLFs of water on silica surfaces have been measured using the force apparatus for deformable surfaces (FADS) using an air bubble as a force sensor. The measurements have been conducted in the presence of various cationic surfactants such as dodecylamine hydrochloride (DAH), and alkyltrimethylammonium chloride (CnTACl), electrolytes, and polymers. The results show that film stability and hence the kinetics of film thinning can be greatly improved by the control of bubble ζ-potentials, whose role in flotation has long been neglected in flotation studies. Force measurements have also been conducted in the TLFs of water confined between oil drops and hydrophobic surfaces. Stability of this type of film plays an important role in a process of using oil drops rather than air bubbles to collect hydrophobic particles from aqueous phase. The force measurements conducted in the present work show that hydrophobic forces are much stronger in water films formed between oil drops and hydrophobic surfaces than in water films formed between air bubbles and hydrophobic surfaces, which can be attributed to the differences in the Hamaker constants involved. / Doctor of Philosophy / When two macroscopic surfaces in water are brought to a close proximity, a thin liquid film (TLF) is formed in between, with its stability being determined by the surface forces present in the film. TLFs are ubiquitous in daily lives and play a decisive role in many industrial processes such as mineral flotation, food processing, oil extraction, heat transfer, etc. In the present work, the surface forces present in wetting films have been measured by approaching an air bubble (or an oil drop) slowly toward a flat surface while monitoring the curvature changes during film thinning by interferometry and calculating the capillary forces using the Young-Laplace equations. By analyzing the results in view of the Frumkin-Derjaguin isotherm and the extended DLVO theory, it was possible to determine the changes in the van der Waals, electrical double-layer (EDL), and hydrophobic forces during film thinning. The results show that both the EDL and the long-range component of the hydrophobic force control the kinetics of film thinning and rupture while the contact angle formation is controlled by the van der Waals force and the short-range hydrophobic force. It has been found also that n-alkane drops form substantially larger contact angles than air bubbles on a hydrophobic surface due to the fact that the van der Waals force is attractive in the drop-surface interactions while the same is repulsive in the bubble-surface interactions. These observations have a profound implication in flotation, that is, oil drops can recover hydrophobic particles from an aqueous phase better than air bubbles.

Ionic liquids (ILs) present new approaches for controlling interactions at the solid-liquid interface. ILs are defined as liquids consisting of bulky and asymmetric ions, with a melting point below 373 K. Owing to their amphiphilic character they are powerful solvents but also possess other interesting properties. For example, ILs can self-assemble and are attracted to surfaces due to their charged nature. As a result, they are capable of forming nanostructures both in bulk and at interfaces. This thesis describes how the solid-IL interface responds to external influences such as elevated temperatures, the addition of salt and polarisation. An improved understanding of how these factors govern the surface composition can provide tools for tuning systems to specific applications such as friction. Normal and friction forces are measured for ethylammonium nitrate (EAN) immersed between a mica surface and a silica probe, at different temperatures or salt concentrations. The results demonstrate that an increase in temperature or low concentrations of added salt only induce small changes in the interfacial structure and that the boundary layer properties remain intact. In contrast, at sufficiently large salt concentrations the smaller lithium ion prevails and the surface composition changes. The interfacial layer of a similar IL is also investigated upon the addition of salt and the results reveal that lithium ions affect the surface composition differently depending on the ion structure of the IL. This demonstrates that the surface selectivity strongly depends on the ion chemistry. Remarkably, a repulsive double layer force manifests itself for EAN at 393 K, which is not observed for lower temperatures. This indicates a temperature dependent change in EAN’s microscopic association behaviour and has general implications for how ILs are perceived. A new method is developed based on a quartz crystal microbalance to investigate how the surface compositions of ILs respond to polarisation. The approach demonstrates that interfacial layers of both a neat IL and an IL dissolved in oil can be controlled using potentials of different magnitudes and signs. Furthermore, the method enables two independent approaches for monitoring the charges during polarisation which can be used to quantify the surface composition. The technique also provides information on ion kinetics and surface selectivity. This work contributes to the fundamental understanding of the solid-IL interface and demonstrates that the surface composition of ILs can be controlled and monitored using different approaches. / Jonvätskor möjliggör nya tillvägagångssätt för att kontrollera interaktioner vid gränsskiktet mellan fasta ytor och vätskor. Jonvätskor definieras som vätskor som består av stora och asymmetriska joner med en smältpunkt under 373 K. På grund av sin amfifila karaktär är de starka lösningsmedel men har också andra intressanta egenskaper. Jonvätskor kan till exempel självorganisera sig och attraheras till ytor på grund av sin laddning. En följd av detta är att de bildar nanostrukturer både i bulk och på ytor. Denna avhandling beskriver hur gränsskiktet mellan fasta ytor och jonvätskor svarar på yttre påverkan såsom en ökning i temperatur, tillsättning av ett salt samt polarisering. En ökad förståelse för hur dessa faktorer styr ytkompositionen av jonvätskor kan bidra med verktyg för att kontrollera system till specifika applikationer såsom friktion. Normala- och friktionskrafter mäts för etylammonium nitrat (EAN) mellan en glimmeryta och en kolloidprob vid olika temperaturer eller saltkoncentrationer. Resultaten visar att en ökning av temperatur eller låga koncentrationer av tillsatt salt bara marginellt framkallar ändringar i strukturen på gränsytan och att det adsorberade lagret förblir intakt. När saltkoncentrationen emellertid var tillräckligt hög får den mindre litiumjonen överhanden och ytsammansättningen ändras. Ytlagret av en liknande jonvätska undersöks också vid tillsättning av salt och resultaten avslöjar att litiumjoner påverkar ytsammansättningen annorlunda beroende på jonstrukturen av jonvätskan. Detta visar att ytselektiviteten starkt beror på jonkemin. En repulsiv dubbellagerkraft yttrar sig anmärkningsvärt för EAN vid 393 K vilket inte observeras vid lägre temperaturer. Detta indikerar en ändring i EANs mikroskopiska sammansättningsbeteende och har generella återverkningar för hur jonvätskor uppfattas. En ny metod har utvecklats baserad på en kvartskristall mikrovåg för att undersöka hur ytsammansättningen av jonvätskor reagerar på polarisering. Denna metod visar att det adsorberade lagret av både en ren jonvätska och en jonvätska löst i olja kan kontrolleras genom att applicera spänningar med olika tecken och storlekar. Dessutom möjliggör metoden två oberoende tillvägagångssätt för att övervaka laddningarna under polarisering vilket kan användas för att kvantifiera ytsammansättningen. Tekniken ger också information om jonkinetik och ytselektivitet. Detta arbete bidrar till den grundläggande förståelsen av gränsskiktet mellan fasta ytor och jonvätskor och visar att ytsammansättningen av jonvätskor kan kontrolleras och övervakas med olika tillvägagångssätt. / <p>QC 20160518</p>

The main objective of this thesis work was to gain understanding of the layer properties and polymer structures that were able to aid lubrication in aqueous media. To this end, three types of polyelectrolytes: a diblock copolymer, a train-of-brushes and two brush-with-anchor mucins have been utilized. Their lubrication ability in the boundary lubrication regime has been examined by Atomic Force Microscopy with colloidal probe. The interfacial behavior of the thermoresponsive diblock copolymer, PIPOZ60-b-PAMPTAM17,on silica was studied in the temperature interval 25-50 ˚C. The main finding is that adsorption hysteresis, due to the presence of trapped states, is important when the adsorbed layers are in contact with a dilute polymer solution. The importance of trapped states was also demonstrated in the measured friction forces, where significantly lower friction forces, at a given temperature, were encountered on cooling than on the preceding heating stage, which was attributed to increased adsorbed amount. On the heating stage the friction force decreased with increasing temperature despite the worsening of the solvent condition, and the opposite trend was observed when using pre-adsorbed layers (constant adsorbed amount) as a consequence of increased segment-segment attraction. The second part of the studies was devoted to the interfacial properties of mucins on PMMA. The strong affinity provided by the anchoring group of C-PSLex and C-P55 together with their more extended layer structure contribute to the superior lubrication of PMMA compared to BSM up to pressures of 8-9 MPa. This is a result of minor bridging and lateral motion of molecules along the surface during shearing. We further studied the influence of glycosylation on interfacial properties of mucin by utilizing the highly purified mucins, C-P55 and C-PSLex. Our data suggest that the longer and more branched carbohydrate side chains on C-PSLex provide lower interpenetration and better hydration lubrication at low loads compared to the shorter carbohydrate chains on C-P55. However, the longer carbohydrates appear to counteract disentanglement less efficiently, giving rise to a higher friction force at high loads. / <p>QC 20170407</p>

Thèse numérisée par la Division de la gestion de documents et des archives de l'Université de Montréal.

The use of hydrophobic surfaces is important for many processes both in nature and industry. Interactions between hydrophobic species play a key role in industrial applications such as water-cleaning procedures and pitch control during papermaking but they also give information on how to design surfaces like hydrophobic mineral pigments. In this thesis, the influence of surface properties on wetting and interaction forces has been studied. Surfaces with close-packed particles, pore arrays, randomly deposited nanoparticles as well as reference surfaces were prepared. The atomic force microscope (AFM) was utilized for force and friction measurements while contact angles and confocal Raman microscopy experiments were mainly used for wetting studies. The deposition of silica particles in the size range of nano- to micrometers using the Langmuir-Blodgett (LB) technique resulted in particle coated surfaces exhibiting hexagonal close-packing and close to Wenzel state wetting after hydrophobization. Force measurements displayed long-range interaction forces assigned to be a consequence of air cavitation. Smaller roughness features provided larger forces and interaction distances interpreted as being due to fewer restrictions of capillary growth. Friction measurements proved both the surface structure and chemistry to be important for the observed forces. On hydrophobic pore array surfaces, the three-phase contact line of water droplets avoided the pores which created a jagged interface. The influence of the pores was evident in the force curves, both in terms of the shape, in which the three-phase contact line movements around the pores could be detected, as well as the depth of the pores providing different access and amount of air. When water/ethanol mixtures were used, the interactions were concluded to be due to ethanol condensation. Confocal Raman microscopy experiments with water and water/ethanol mixtures on superhydrophobic surfaces gave evidence for water depletion and ethanol/air accumulation close to the surface. Force measurements using superhydrophobic surfaces showed extremely long-range interaction distances. This work has provided evidence for air cavitation between hydrophobic surfaces in aqueous solution. It was also shown that the range and magnitude of interaction forces could, to some extent, be predicted by looking at certain surface features like structure,roughness and the overall length scales. / <p>QC 20121011</p>