Atomic force microscopy (AFM) is adapted to the measurement of adhesion forces between indoor-air-pollutant bioparticulates and synthetic carpet fiber materials. This novel technology is used to characterize the adhesion and release of a model bioparticulate, the bacterium E. coli on Nylon. This knowledge will lead to expanded studies of a wider range of biocontaminants, and ultimately to the ability to design carpet and rugs upholstery that reduce the spread of indoor air pollutants. Such an advance would improve life significantly for the 20+ million Americans who suffer from asthma, and countless others who are afflicted with allergies and illness spread via bioparticulates.

Using a combination of micromechanical force and flowloop measurements, hydrate deposition on a pipe wall surface was investigated for ‘dry’ hydrates formed in the bulk phase and for hydrates growing on the pipe surface. Cyclopentane ‘dry’ hydrates (without a free water phase) were used to predict whether hydrates, formed in a bulk condensate phase, would adhere to a pipe wall. Adhesion forces between cyclopentane hydrates and steel were measured using a micro-mechanical force apparatus. The average force of adhesion was measured to be very small, less than 0.01 N/m. This force was used in a particle force balance, predicting that hydrates formed in the bulk phase would not deposit on the pipe wall. It was hypothesized than in the presence of a water saturated hydrocarbon, hydrates would grow on the pipe wall as the fluid cooled below its equilibrium temperature. This hypothesis was confirmed using a single pass condensate flowloop. Water was continuously dissolved into the flowloop inlet stream as water deposited in the flowloop test section, resulting in both a pressure drop and fluid temperature increase. This work illustrates the need for a hydrate wall growth model.

Micromechanical adhesion force measurements were performed on tetrahydrofuran (THF) hydrate particles in n-decane. The experiments were performed at atmospheric pressure over the temperature range 261–275 K. A scoping study characterized the effects of temperature, anti-agglomerants, and interfacial energy on the particle adhesion forces. The adhesion force between hydrate particles was found to increase with temperature and the interfacial energy of the surrounding liquid. The adhesion force of hydrates was directly proportional to the contact time and contact force. Both sorbitan monolaurate (Span20) and poly-N-vinyl caprolactam (PVCap) decreased the adhesion force between the hydrate particles. The measured forces and trends were explained by a capillary bridge between the particles.

Friction between nanoscale objects has been a subject of great interest and intense research effort for the last two decades. However, the vast majority of the work done in this area has focused upon the sliding friction between two rigid, atomically smooth surfaces. Thus the parameter most explored has been the corrugation in the atomic potentials and how this affects the force required to slide one object across another. In truth, many nanoscale objects whose translation force is of practical interest are more spherical in nature. We hypothesize that the factors that determine the translation force will be related, not only to the interfacial adhesion, but also to the mechanical properties of the translating object and its underlying surface. The dependence on these quantities of the friction is not known. In this dissertation we have utilized Atomic Force Microscopy and Force Spectroscopy to study the tribological properties of submicron scale polymeric particles to explore how the friction between these submicron spherical objects translating over planar substrates is related to interfacial energy and the mechanical properties for these particles. A technique for modifying the mechanical properties was developed and used to provide a set of samples over which we had control of the elastic modulus without corresponding changes in the chemical bonds. The modified mechanical properties were tested against the Flory-Rehner theory. Lateral force microscopy was used to measure the force required to translate asymmetric, nanoscale particles of controlled size, surface chemistry and moduli. Silicon wafers were used as the substrate. The effects of work of adhesion, elastic modulus of polystyrene microspheres, and contact radius between particle and substrate have been studied for the different modes of particle translation under an external force.

The aim of this thesis is concerned with the influence of sliding velocity on capillary adhesion at the nanometer scale. In ambient conditions, capillary condensation which is a thermally activated process, allows the formation of a capillary meniscus at the interface between an atomic force microscope (AFM) probe and a substrate. This capillary meniscus leads to a capillary force that acts as an additional normal load on the tip, and affects the adhesion and friction forces. The Atomic Force Microscopy (AFM) offers interesting opportunities for the measurement of surface properties at the nanometer scale. Nevertheless, in the classical imaging mode, limitations are encountered that lead to a non stationary state. These limitations are overcome by implementing a new AFM mode (called Circular AFM mode). By employing the Circular AFM mode, the evolution of the adhesion force vs. the sliding velocity was investigated in ambient conditions on model hydrophilic and hydrophobic surfaces with different physical-chemical surface properties such as hydrophilicity. For hydrophobic surfaces, the adhesion forces or mainly van der Waals forces showed no velocity dependence, whereas, in the case of hydrophilic surfaces, adhesion forces, mainly due to capillary forces follow three regimes. From a threshold value of the sliding velocity, the adhesion forces start decreasing linearly with the logarithm increase of the sliding velocity and vanish at high sliding velocities. This decrease is also observed on a monoasperity contact between a atomically flat mica surface and a smooth probe, thus eliminating the possibility of the kinetics of the capillary condensation being related to a thermally activated nucleation process as usually assumed. Therefore, we propose a model based on a thermally activated growth process of a capillary meniscus, which perfectly explains the experimental results. Based on these results, we focused on directly investigating with the Circular mode the role of capillary adhesion in friction mechanisms. We investigated the influence of the sliding velocity on the friction coefficient, and a decrease following three regimes, similar to the sliding velocity dependence of the capillary adhesion, was observed for hydrophilic surfaces that possess a roughness higher than 0.1 nm. Whereas, an increase of the friction coefficient was observed on hydrophilic (Mica) or hydrophobic (HOPG) atomically flat surfaces that posses a roughness lower than 0.1 nm. However, in this latter case, the three regimes are not established. Finally, on a rough hydrophobic surface, the friction coefficient was sliding velocity independent. A direct comparison with capillary adhesion behavior with the sliding velocity is expected to give new insights to explain this interplay. / The aim of this thesis is concerned with the influence of sliding velocity on capillary adhesion at the nanometer scale. In ambient conditions, capillary condensation which is a thermally activated process, allows the formation of a capillary meniscus at the interface between an atomic force microscope (AFM) probe and a substrate. This capillary meniscus leads to a capillary force that acts as an additional normal load on the tip, and affects the adhesion and friction forces. The Atomic Force Microscopy (AFM) offers interesting opportunities for the measurement of surface properties at the nanometer scale. Nevertheless, in the classical imaging mode, limitations are encountered that lead to a non stationary state. These limitations are overcome by implementing a new AFM mode (called Circular AFM mode). By employing the Circular AFM mode, the evolution of the adhesion force vs. the sliding velocity was investigated in ambient conditions on model hydrophilic and hydrophobic surfaces with different physical-chemical surface properties such as hydrophilicity. For hydrophobic surfaces, the adhesion forces or mainly van der Waals forces showed no velocity dependence, whereas, in the case of hydrophilic surfaces, adhesion forces, mainly due to capillary forces follow three regimes. From a threshold value of the sliding velocity, the adhesion forces start decreasing linearly with the logarithm increase of the sliding velocity and vanish at high sliding velocities. This decrease is also observed on a monoasperity contact between a atomically flat mica surface and a smooth probe, thus eliminating the possibility of the kinetics of the capillary condensation being related to a thermally activated nucleation process as usually assumed. Therefore, we propose a model based on a thermally activated growth process of a capillary meniscus, which perfectly explains the experimental results. Based on these results, we focused on directly investigating with the Circular mode the role of capillary adhesion in friction mechanisms. We investigated the influence of the sliding velocity on the friction coefficient, and a decrease following three regimes, similar to the sliding velocity dependence of the capillary adhesion, was observed for hydrophilic surfaces that possess a roughness higher than 0.1 nm. Whereas, an increase of the friction coefficient was observed on hydrophilic (Mica) or hydrophobic (HOPG) atomically flat surfaces that posses a roughness lower than 0.1 nm. However, in this latter case, the three regimes are not established. Finally, on a rough hydrophobic surface, the friction coefficient was sliding velocity independent. A direct comparison with capillary adhesion behavior with the sliding velocity is expected to give new insights to explain this interplay.

Lors des interventions humaines pendant les arrêts de tranche des installations nucléaires d’EDF, on remarque une remise en suspension de certains radionucléides sous forme d’aérosols (1 µm < dp < 10 µm). Dans le cadre d’une augmentation des interventions effectuées de façon simultanée en bâtiment réacteur, il devient important de mieux comprendre la remise en suspension due à l’activité des opérateurs pour adapter leur radioprotection. Le but des travaux de cette thèse est de quantifier la remise en suspension des particules suite à la marche des opérateurs sur un sol faiblement contaminé. Pour cela, la démarche suivie consiste à coupler un modèle de remise en suspension aéraulique avec des calculs numériques d’écoulement sous une chaussure, puis à caractériser expérimentalement certains paramètres d’entrée du modèle (diamètre de particule, forces d’adhésion, mouvement de la chaussure).Le modèle de remise en suspension Rock’n’Roll proposé par Reeks et Hall (2001) a été choisi car il décrit de manière physique ce mécanisme et est basé sur le moment des forces appliquées à une particule. Il nécessite la maîtrise de paramètres d’entrée tels que la vitesse de frottement de l’air, la distribution des forces d’adhésion et le diamètre des particules.Concernant le premier paramètre, des simulations numériques d’écoulement ont été réalisées, à l’aide du code de calcul ANSYS CFX, sous une chaussure de sécurité en mouvement (numérisée par CAO 3D) ; les cartographies des vitesses de frottement obtenues donnent des valeurs de l’ordre de 1 m.s⁻ ¹ pour une vitesse angulaire moyenne de 200 °.s⁻ ¹ .Concernant le deuxième paramètre, des mesures AFM (Atomic Force Microscope) ont été réalisées avec des particules d’alumine ainsi que des particules d’oxyde de cobalt en contact avec des surfaces en époxy représentatives de celles rencontrées dans les installations d’EDF. L’AFM permet d’obtenir la distribution des forces d’adhésion et révèle une valeur moyenne bien plus faible que ce qui peut être calculé de façon théorique en utilisant par exemple le modèle JKR proposé par Johnson et al. (1971). De plus, cette technique, tenant compte des rugosités de surface, montre que plus la taille de la particule augmente, plus la moyenne des forces d’adhésion diminue. Enfin, l’analyse des mesures AFM a permis d’obtenir une corrélation liant la distribution des forces d’adhésion au diamètre des particules, remplaçant celle de Biasi et al. (2001) initialement utilisée dans le modèle Rock’n’Roll et permettant ainsi d’adapter le modèle aux particules et aux revêtements de sol étudiés. Le couplage, effectué dans le code de calcul ANSYS CFX, entre les calculs de vitesses de frottement et le modèle de remise en suspension, a permis de déterminer des taux de remise en suspension théoriques pour le cas d’un cycle unique de marche. Ce couplage a été dans un premier temps validé par une comparaison à l’expérience pour le cas simple d’une plaque en rotation dans un volume contrôlé. En complément, des expériences à l’échelle d’un local ventilé de 30 m³ ont été réalisées en marchant sur un revêtement époxy ensemencé en particules de tailles calibrées (1,1 µm et 3,3 µm). Ces expériences ont permis de mettre en évidence les paramètres influant la remise en suspension des particules, tels que la fréquence de pas et la taille des particules. / In nuclear facilities, during normal operations in controlled areas, workers could be exposed to radioactive aerosols (1 µm < dp < 10 µm). One of the airborne contamination sources is particles that are initially seeded on the floor and could be removed by workers while they are walking. During the outage of EDF nuclear facilities, there is a resuspension of some radionuclides in aerosol form (1 µm < dp < 10 µm). Since the number of co-activity will increase in reactors buildings of EDF, it becomes important to understand particle resuspension due to the activity of the operators to reduce their radiation exposure. The purpose of this Ph.D thesis is to quantify the resuspension of particles due to the progress of operators on a contaminated soil. Thus, the approach is to combine an aerodynamic resuspension model with numerical calculations of flow under a shoe, and then to characterize experimentally some input parameters of the model (particle diameter, adhesion forces, shoes motion).The resuspension model Rock'n'Roll proposed by Reeks and Hall (2001) was chosen because it describes physically the resuspension mechanism and because it is based on the moment of forces applied to a particle. This model requires two input parameters such as friction velocity and adhesion forces distribution applied on each particle.Regarding the first argument, numerical simulations were carried on using the ANSYS CFX software applied to a safety shoe in motion (digitized by 3D CAO); the mapping of friction velocity shows values of about 1 m.s⁻ ¹ for an angular average velocity of 200 °.s⁻ ¹ . As regards the second parameter, AFM (Atomic Force Microscopy) measurements were carried out with alumina and cobalt oxide particles in contact with epoxy surfaces representative of those encountered in EDF power plants. AFM provides the distribution of adhesion forces and reveals a much lower value than what can be calculated theoretically using JKR model (Johnson et al. (1971)). Moreover, this technique, taking into account the surface roughness, shows that adhesion forces decrease while particle diameter increase. Finally, the analysis of AFM measurements gives a correlation linking the distribution of adhesion forces to the particle diameter, replacing the one given by Biasi et al. (2001) originally used in the Rock'n'Roll model and thereby adapt the model to particles and flooring studied in our case.Coupling, performed in ANSYS CFX software, between the calculations of friction velocity and model of particle resuspension, gives theoretical resuspension rate during shoe motion. This coupling was initially validated by comparison to the experience for the simple case of a rotating plate in a controlled volume. Secondly, experiments at the scale of a ventilated room of 30 m³ were performed by walking on an epoxy coating initially seeded by calibrated particle size (1,1 µm and 3,3 µm). These experiments highlight the parameters influencing the suspension of particles, such as step frequency and particle size.

In this thesis, the relationship between the elastic modulus of PDMS and the base/agent ratio (the amount of crosslinking) is studied. Reliable macroscopic compression test instrument was developed. Preload method was applied for the nanoindentation flat punch test to develop full contact. In chapter 2, an easy instrument setup for macroscopic compression test is described. A series of PDMS samples with different base/agent ratios were tested using the macroscopic compression method. The relationship between PDMS elastic modulus and its base/agent ratio was established. In chapter 3, PDMS nanoindentation DMA tests provide stable data with different test control models. The storage modulus collected using nanoindenting DMA tests is comparable with elastic modulus collected in PDMS compression test in chapter 2. Nanoindentation experiments with flat punch were also done to test the elastic modulus of PDMS network 5:1. The adhesion force tests with different nanoindentation tips, which are Berkovich tip, conical tip and cube corner tip, show that PDMS's adhesion force is related to the sample's base/agent ratio, the nanoindentating depth and the tip's geometrical shape.

Cyclopentane hydrate interparticle adhesion force measurements were performed in pure cyclopentane liquid using a micromechanical force apparatus. Cyclopentane hydrate adhesion force measurements were compared to those of cyclic ethers, tetrahydrofuran and ethylene oxide, which were suspected to be cyclic ether-lean and thus contain a second ice phase. This additional ice phase led to an over-prediction of the hydrate interparticle forces by the capillary bridge theory. The adhesion forces obtained for cyclopentane hydrate at atmospheric pressure over a temperature range from 274-279 K were lower than those obtained for the cyclic ethers at similar subcoolings from the formation temperature of the hydrate. The measured cyclopentane interparticle adhesion forces increased linearly with increasing temperature, and are on the same order of magnitude as those predicted by the Camargo and Palermo rheology model.

L'attention de la communauté scientifique, ainsi que le développement, pour les bioprocédés dédiés à la culture et à l'expansion de cellules souches mésenchymateuses (MSCs) pour la thérapie cellulaire et la médecine régénérative a considérablement grandi pendant ces dernières décennies. Une plus ample compréhension du lien entre la structure, la fonction et les propriétés des suspensions de cellules mésenchymateuses est devenue de première importance. Dans cette thèse, nous présentons tout d'abord les résultats d'une étude expérimentale portant sur l'écoulement de suspensions concentrées de cellules vivantes d'origine mésenchymateuse pour une grande gamme de concentration cellulaire. Nous caractérisons l'évolution de la viscosité relative en fonction de la contrainte de cisaillement appliquée pour des fractions volumiques cellulaires allant de 20 à 60%. Ces matériaux ont des empreintes rhéologiques compliquées mais très reproductibles, incluant des comportements de fluide à seuil, rhéofluidifiants ainsi que des fractures liées à la contrainte de cisaillement. Les propriétés rhéologiques de la suspension sont ensuite étudiées avec l'addition d'acide hyaluronique (HA), une biomolécule avec des séquences d'adhésion pour des récepteurs à la surface des cellules étudiées. Nous montrons que l'addition d'acide hyaluronique modifie substantiellement le comportement de la suspension et nous permet de contrôler les propriétés d'écoulement de la suspension à toutes les fractions volumiques. Cytométrie de flux et imagerie confocal à l'appui, nous montrons que l'effet observé est dû à un important changement dans la formation d'agrégats cellulaires dans la suspension, et donc dans l'envergure du réseau correspondant. La troisième partie de cette thèse porte sur l'ajout de polyéthylène glycol, une molécule qui n'est pas naturellement présente dans l'organisme mais fréquemment utilisée dans la formulation d'hydrogel. En utilisant trois types de PEG, l'influence de la charge des molécules est étudiée. Les résultats montrent que la charge est un paramètre important dans le contrôle des propriétés d'écoulement de suspensions cellulaires, car déterminant dans la formation et la compacité des agrégats. En considérant les agrégats comme des objets fractals, nous montrons qu'en prenant en compte les modifications de fractions volumiques avec le cisaillement, nous pouvons obtenir une courbe maitresse pour l'ensemble des conditions testées, et en extraire la force d'adhésion moyenne entre les cellules, au travers une population de plusieurs millions de cellules. Cette étude livre de nouveaux aspects sur la complexité des propriétés en écoulement de suspensions de cellules méchymateuses, adhérentes et concentrées, sur leur sensibilité à l'ajout de molécules, qu'elles soient naturellement présentes dans les tissues ou non, ainsi qu'une nouvelle méthode pour mesurer la force d'adhésion entre les cellules. / With the rapidly growing interest in the development of bioprocess systems to culture and expand mesenchymal stromal cells (MSCs) for cell therapy and regenerative medicine applications, greater understanding of the structure-function-property characteristics of mesenchymal cell suspensions is required. In this thesis, the results of a detailed experimental study into the flow behaviour of concentrated suspensions of living mesenchymal cells over a wide range of cell concentrations and in the presence of two macromolecules (hyaluronic acid and polyethylene glycol) often used in cellular therapy applications are presented. The change in the shear viscosity as a function of shear stress and shear rate for cell volume fractions varying from 20 to 60% are firstly presented, showing that these suspensions exhibit highly complex but reproducible rheological footprints, including yield stress, shear thinning and shear-induced fracture behaviours. The rheological properties of the suspension with the addition of hyaluronic acid (HA), a biomolecule with adhesion sequences for receptors on these types of cells, was then investigated. With the addition of HA, the rheology of these cell suspensions is significantly modified at all volume fractions. Using FACS and confocal imaging, we show that the observed effect of HA addition is due to it significantly modulating the formation of cellular aggregates in these suspensions, and thus the resultant volume spanning network. This understanding permits the rheology of concentrated mesenchymal cell suspensions to be tailored to suit particular processing scenarios. The third part of this project focused on the addition of polyethylene glycol, a molecule which is not naturally present in tissues but commonly utilised in hydrogels as injectable delivery vehicles for cells to sites of tissue damage. Using three different kinds of PEG, the influence of the charge of the molecules is investigated. The results show the charge is also a crucial parameter to tailor the flow behaviour of cell suspension when biomacromolecules are added, influencing the formation and the compactness of the cellular aggregates. Considering the aggregates as fractal structures, and by taking into account the changes in volume fractions with shear, a master curve for the range of conditions investigated was successfully achieved through the use of an analytical model. Critically, this model also permitted the estimation of the average adhesion force between cells, across a population of millions of cells. The outcomes of this study not only provide new insight into the complexity of the flow behaviours of concentrated, dynamically adhesive mesenchymal cell suspensions, and their sensitivity to associative biomolecule and synthetic molecule addition, but also a novel, rapid method by which to estimate adhesion forces between cells.

Capillarity is often exploited in self-cleaning, drag reducing and fluid absorption/storage (sanitary products) purposes just to name a few. Formulating the underlying physics of capillarity helps future design and development of optimized structures. This work reports on developing computational models to quantify the capillary pressure and capillary forces on the fibrous surfaces. To this end, the current study utilizes a novel mass-spring-damper approach to incorporate the mechanical properties of the fibers in generating virtual fibrous structures that can best represent fibrous membranes. Such virtual fibrous structures are then subjected to a pressure estimation model, developed for the first time in this work, to estimate the liquid entry pressure (LEP) for a hydrophobic fibrous membrane. As for accurate prediction (and not just estimation) of the capillary pressure, this work also presents an energy minimization method, implemented in the Surface Evolver code, for tracking the air–water interface intrusion in a hydrophobic fibrous membrane comprised of orthogonally oriented fibers. This novel interface tracking algorithm is used to investigate the effects of the membrane’s microstructure and wetting properties on its resistance to water intrusion (i.e., LEP). The simulation method developed in this work is computationally affordable and it is accurate in its predictions of the air–water interface shape and position inside the membrane as a function of pressure. Application of the simulation method in studying effects of fiber diameter or contact angle heterogeneity on water intrusion pressure is reported for demonstration purposes. Capillary forces between fibrous surfaces are also studied experimentally and numerically via the liquid bridge between two parallel plates coated with electrospun fibers. In the experiment, a droplet was placed on one of the polystyrene- or polyurethane-coated plates and then compressed, stretched, or sheared using the other plate and the force was measured using a sensitive scale. In the simulation, the liquid bridge was mathematically defined for the Surface Evolver finite element code to predict its 3-D shape and resistance to normal and shearing forces, respectively, in presence of the contact angle hysteresis effect. Despite the inherent non-uniformity of the fibrous surfaces used in the experiments and the simplifying assumptions considered for the simulations, reasonable agreement was observed between the experiments and simulations. Results reveal that both normal and shear force on the plates increase by increasing the liquid volume, or decreasing the spacing between the plates.