At the molecular level the entropic “hydrophobic effect” is responsible for high interfacial energies between hydrophobic solids and aqueous liquids, the low solubility of apolar solutes in aqueous solvents, and self-assembly in biological processes, such as vesicle formation and protein folding. Although it is known that a strong attraction between apolar molecules exists at the molecular level, it is not clear how this force scales up to objects with dimensions in the range 100 nm–1 m. This work sets out to measure the forces between particles with a radius of about 10 µm. Because we can only measure the total force, which includes the van der Waals force and the electrostatic forces, it is important to isolate the effect of “hydrophobicity”. We do this by measuring for systems where the particles are very hydrophobic (water contact angle, θ ~110°) and the van der Waals and electrostatic forces are very small. Under these conditions we find that the total force is very small: it is similar to the van der Waals force at separations exceeding 5 nm. Many early works on the hydrophobic force reported surface force at over 100 nm of separation. However, many of these strong, long-ranged attractive forces are likely caused by submicron interfacial bubbles, known as nanobubbles. Nanobubbles were imaged with an atomic force microscope to better understand their stability and dependence on solution properties, such as initial concentration of dissolved gas and changes in gas concentration. We found that nanobubbles still formed in degassed solutions and that lowering the dissolved gas concentration did not reduce the bubble size, implying that nanobubbles do not form from dissolved gas in the liquid phase or do not contain gas and are instead water vapor. Furthermore, addition of an oxygen scavenger agent, sodium sulfite, to a liquid phase that had been pressured with oxygen did not reduce bubble size which could be evidence that nanobubbles are impermeable to gas diffusion across the gas liquid interface, do not form from the dissolved gas in the surrounding liquid, or do not contain gas and are instead water vapor. / Ph. D.

Healthy articular joints exhibit remarkable lubrication due in large part to the complex rheological and tribological behavior of the synovial fluid (SF) that lubricates the joints. Current approaches that seek to elucidate such remarkable lubrication usually focus on the roles of high molecular weight SF components such as lubricin and hyaluronic acid but frequently overlook the role of serum albumin (SA), although it represents 90% of the protein content of SF. In this thesis, we used the Surface Forces Apparatus to investigate in detail the structural and tribological response of SA thin films when sheared between model surfaces and subjected to a large range of shearing parameters. Our data indicate that, under shear, SA films reproduce closely the shear response previously reported for SF, i.e., film thickening and formation of numerous long-lived aggregates accompanied by low friction and efficient surface protection against damage. More specifically, our detailed investigation of shear parameters reveals that (i) strong anchoring of SA to surfaces promotes the formation of large rod-like shaped aggregates that enable rolling friction and keep surfaces far apart, preventing damage, (ii) aggregation mechanism is irreversible, which makes aggregates long-lived (though mobile) in the contact, and (iii) aggregate formation only occur when SA was sheared above a ‘critical’ amplitude Ac and a critical shear velocity Vc. Collectively, our results provide experimental evidence of the role of globular proteins, such as SA, in lubrication and establish a correlation between shearing parameters, formation and stability of aggregates, low friction and wear protection. Although our findings are based on experiments involving rigid, nonporous surfaces hence can hardly be generalized to compliant and porous cartilage surfaces, they are applicable to other rigid tribosystems such as artificial joints and will certainly advance our understanding of joint implants’ lubrication in SF mediated by protein aggregation, with implications for future design of artificial joints and therapeutic interventions.

No description available.

No description available.

The hydrophobic interaction refers to a mutually attractive force experienced by hydrophobic surfaces or molecules across water. At the molecular scale, it drives the selfassembly of lipid vesicles and micelles and accelerates interfacial chemical reactions. At the macroscale, it confers upon numerous plants and insects the ability to repel water and is harnessed in practical applications, such as water-proofing and desalination. However, despite its ubiquity and significance, mechanistic insights into the hydrophobic interaction between macroscopic surfaces remain unclear. A significant body of experimental data on surface force measurements exists, which were obtained following this protocol: hydrophobic molecules (typically organosilanes) are physisorbed onto molecularly smooth mica films that are glued onto transparent rigid silica discs and driven towards each other while measuring forces and distances. We developed a protocol for functionalizing mica surfaces with perfluorodecyltrichlorosilane (FDTS) to achieve robust, ultra-smooth hydrophobic surfaces. Then we investigated the consequences of nuclear quantum effects (NQEs) in water on the hydrophobic interaction. Whereas NQEs are known to influence physical and chemical properties of water, their impact on the hydrophobic interaction has remained largely unexplored. We find that the attractive forces between FDTS-coated mica surfaces were ~ 10% higher in light water (H2O) than in heavy water (D2O) even though macroscopic measurables, such as the interfacial tensions and contact angles are indistinguishable. This is the first-ever experimental demonstration of nuclear quantum effects at play in modulating hydrophobic surface forces. Towards practical applications, we investigated the partitioning of small, amphiphilic molecules onto our molecularly smooth FDTS-coated mica films. These scenarios are relevant in wastewater treatment, bioresource processing, fermenter broths, and food & beverage industries. Water-soluble short chain alcohols (ethanol) readily partitioned onto FDTS surfaces and remained attached onto the surface. The presence of alcohols was confirmed by surface force measurements, contact angle goniometry of water drops, and gas chromatography. We investigated protocols for characterizing fouled surfaces and cleaning them. These protocols were tested on realistic desalination membranes and proved effective. Thus, our findings could be used to develop robust protocols for characterizing membrane fouling and cleaning protocols in various separation processes.

La tendance à la miniaturisation des produits n'est pas sans influence sur l'évolution de leurs moyens de production et d'assemblage. En effet, dû à la réduction d'échelle, l'assemblage de petits composants (appelé microassemblage) est perturbé par les forces de surface comme les forces de capillarité. Ces forces, exercées par le pont liquide reliant manipulateur et composant, sont habituellement négligeables (et négligées) dans l'assemblage conventionnel dominé par les forces de gravité. L'approche originale suivie dans ce travail consiste à tirer parti de ces effets et à les utiliser pour la manipulation de microcomposants, c'est-à-dire de composants dont la taille va de quelques dizaines de microns à quelques millimètres. Ce travail tente donc d'apporter quelques réponses aux problèmes de conception posés par un tel choix: quels sont les avantages d'une telle approche? Comment ces forces `fonctionnent-elles'? Sont-elles suffisamment grandes pour manipuler des microcomposants? Comment, dans ce cas, relâcher le composant? Quel rôle la tension de surface joue-t-elle? En quoi le choix des matériaux est-il important? Comment optimiser la conception du manipulateur? Tout au long de ce travail, le lecteur trouvera un inventaire des principes de manipulation existants, les éléments nécessaires à la modélisation des forces de capillarité, ainsi que la description de la simulation et du banc d'essai développés par l'auteur dans le but d'étudier ces paramètres de conception. Les résultats présentés dans cette thèse recouvrent essentiellement deux thèmes: quelles sont les règles de conception à suivre pour maximiser les forces de capillarité (problème de la préhension) et comment choisir une stratégie de relâche adéquate (problème de la relâche)?

The surface roughness of a few asperities and their influence on the work of adhesion is of scientific interest. Macroscale and nanoscale adhesion data have given seemingly inconsistent results. Despite the importance of bridging the gap between the two regimes, little experimental work has been done, presumably due to the difficulty of the experiment needed to determine how small amounts of surface roughness might influence adhesion data lying in between the two scales. To investigate the role of few-asperity contacts in adhesion, the pull-off force was measured between different sized AFM (Atomic-Force Microscope) tips that had different roughnesses and sample surfaces that had well-controlled material properties. The spring constant of the cantilever, the deflection of the cantilever, and the radius of the cantilever tip were measured before each experiment. There were seventeen tips of four different types, with radii from 200 nm to 60 ìm. The samples were unpatterned amorphous silicon dioxide die with two types of surface conditions: untreated and treated with a few angstroms of vapor deposited diphenylsiloxane. We observed that the pull-off force was independent of the radius of the AFM tip, which was contrary to all continuum-mechanics model predictions. To explain this behavior, we assumed that the interactions between the AFM tip and sample were additive, material properties were constant, and that the AFM tip, asperities, and sample surfaces were of uniform density. Based on these assumptions, we calculated a simple correction due to the measured Root Mean Square (RMS) surface roughness of the AFM tips. The simple correction for the RMS surface roughness resulted in the expected dependence of the pull-off force on radius, but the magnitudes were higher than expected. Commercial and heat-treated AFM tips had minimal surface roughness and result in magnitudes that were more reliable. The relative uncertainty for the pull-off force was estimated to be 10% and the work of adhesion was estimated to be 15%. In this thesis, we derive how the cantilever and tip parameters contribute to the measured pull-off force, show how the corrected results compare with theory, and demonstrate how the AFM probes were calibrated. Although much work is still needed, the work presented here should expand the understanding of adhesion between the nanoscale and macroscale.

The relationship between the amount and conformation of apolymer at the solid-liquid interface, and the resultinginteraction forces between two such surfaces has beeninvestigated. With a degree of control of the polymerconformation, by varying the temperature, solvent quality,polymer charge density etc, it has been possible to measure andinterpret the resulting changes in the surface interactions.The recurring themes of dynamics and hydrodynamics have beencontinually considered due to the large range and viscoelasticnature of the polymeric systems. The polymeric systems investigated in this thesis are, poly(N-isopropylacrylamide), poly (12-hydroxystearate) and a seriesof AM-MAPTAC polyelectrolytes with variable chargedensities. Adsorption and conformation of polymers have beeninvestigated by the novel QCM instrument. By comparison tosimultaneously measured energy loss information, a greaterunderstanding of the conformation of the polymer has beengained, both as a function of layer build-up during initialadsorption, and as a result of induced conformational changes.Comparing the results toin situsurface plasmon resonance and subsequent x-rayphotoelectron spectroscopy measurements, the relativeconcentration of polymer within the layer is determined. Inaddition, efforts have been made to extend the scope of thetechnique, in such ways as measuring with QCM as a function oftemperature and deriving viscoelastic properties. The later isstill to be achieved in absolute terms for polymer layers inliquid environments, yet both the principle and experimentalcapabilities have been shown. Normal interaction forces have been measured as a functionof solvation of the polymer layer, for both adsorbed andgrafted polymer layers. For fully solvated (steric) polymerlayers, which can act as colloidal stabilisers, the dynamics ofthe repulsive force, including hydrodynamics have beeninvestigated. The same has been achieved for collapsed polymerlayers, in which the dynamic adhesion has also beeninvestigated. The effect on the adhesion of three differentdynamic mechanisms has been determined (which, like the surfaceforces, depend on the polymer conformation andviscoelasticity). These dynamic mechanisms are based onbridging forces, polymer entanglement and a viscoelastic‘bulk’response from the surface layers. Lateral or friction measurements have also been completed.The effect of load and rate have been investigated as afunction of both the polymer charge density and the underlyingsubstrate, which result in a variable conformation and bindingstrength to the substrate. This has resulted in a complexaddition of numerous mechanisms, the dominant mechanism beingdetermined by the binding strength to the surface, polymerconformation and viscoelasticity. The results have shown thatadsorbed polymer layers can be used to both increase anddecrease friction, and to change the direction of the ratedependence.

Colloidal particles are ideal models for studying the behavior of atomic and molecular systems. They resemble their atomic and molecular analogues in that their dynamics are driven by thermal energy and their equilibrium properties are controlled by inter-particle interactions. Based on this analogy, it is reasonable to construct colloidal chains, where each particle represents a repeat unit, as models for polymers. The advantages of this system over molecular systems are its controllable rigidity, contour length and diameter, as well as the convenience to capture its instantaneous shape and position via video microscopy, which are not trivial to realize in molecular systems. By utilizing the dipolar properties of magnetic colloids, a number of groups have assembled semiflexible and rigid colloidal chains by cross-linking magnetic beads under a magnetic field using polymer linkers. Recently, efforts in constructing colloidal chains led even to anisotropic magnetic colloidal chains that mimic the detailed atomic arrangements of polymers. These properties make colloidal chains possible candidates for the classic bead-spring or bead-rod model systems for semiflexible and rigid polymers. In my thesis, I present a method for generating linear colloidal chain structures by linking surface functionalized paramagnetic particles using DNA. First, I investigate the force interactions between individual magnetic particles under different conditions to optimize the resulting chain stability. A systematic study the bending and rotational diffusion dynamics of the chains and their relationship with the DNA linking chemistry is presented. I then demonstrate their use as a ideal model system to study polymer dynamics In addition, a technique to measure short-range repulsive surface forces between these colloids with high precision was developed. Building on these repulsive force studies, a colloidal system to study 2-D phase transitions was created. This thesis provides insights into understanding and engineering the directed-assembly of magnetic colloids with specific surface interactions, as well as using the assemblies as model systems to study molecular level phenomena.

The hypothesis behind this research is that Atomic Force Microscopy (AFM) can be used to capture changes in the surface interaction force caused by sorption of ions, and thereby can be employed as a tool to study sorption at the nano-scale. The Derjaguin??dau??wey??rbeek (DLVO) theory was used to explain surface interactions and probe DLVO and other interparticle forces. In the first part of the work, sorption of copper ions onto a silica particle resulted in charge reversal detected by AFM. Transient measurements of the interaction force between the silica particle and a flat glass surface can be related to the kinetics of copper ion sorption. In the second part, the force-volume AFM mode was used to detect heterogeneously charged regions on quartz silica surfaces resulting from copper ion sorption. Conditions of copper ion concentration and pH were varied to confirm the sorption mechanism. The surprising result of this study was the observation of growing islands during sorption indicating a heterogeneous behavior of the surface. In the third part, AFM was used to measure interaction forces between a gold sample and the silicon nitride tip of the AFM in aqueous electrolyte solutions under various values of applied electrostatic potential. Along with the applied potential, pH conditions were also varied. Experimental results were compared to theoretical calculations using the non-linear Poisson-Boltzmann equation. This work showed a relationship between the surface potential and the externally applied potential. Finally, the total interaction force between a standard silicon nitride AFM tip and a gold-coated plate in the presence of cationic surfactant, cetyltrimethylammonium bromide (CTAB), was measured under various conditions of applied potential. The interaction force-distance profile between the surface and the tip can be related to the structure of surfactant molecules sorbed onto the surface, which is influenced by the magnitude of the applied potential. The results presented in this work are of importance in natural and engineered systems involving colloidal particles and charged species with implications in separations as well as naturally occurring facilitated transport.