No description available.

An atomic force microscope (AFM) has been used to conduct force measurements to better understand the role of hydrophobic forces in flotation. The force measurements were conducted between a flat mineral substrate and a hydrophobic glass sphere in aqueous solutions. It is assumed that the hydrophobic glass sphere may simulate the behavior of air bubbles during flotation. The results may provide information relevant to the bubble-particle interactions occurring during flotation. The glass sphere was hydrophobized by octadecyltrichlorosilane so that its water contact angle was 109 degrees. The mineral systems studied include covellite (CuS), sphalerite (ZnS) and hornblende (Ca₂(Mg, Fe)₅(Si₈O₂₂)(OH,F)₂). The collector used for all the mineral systems studied was potassium ethyl xanthate (KEX). For the covellite-xanthate system, a biopotentiostat was used in conjunction with the AFM to control the potential of the mineral surface during force measurements. This was necessary since the adsorption of xanthate is strongly dependent on the electrochemical potential (Eₕ) across the solid/liquid interface. The results show the presence of strong hydrophobic forces not accounted for by the DLVO (named after Derjaguin, Landau, Verwey and Overbeek) theory. Furthermore, the potential at which the strongest hydrophobic force was measured corresponds to the potential where the flotation recovery of covellite reaches a maximum, indicating a close relationship between the two. Direct force measurements were also conducted to study the mechanism of copper-activation of sphalerite. The force measurements conducted with unactivated sphalerite in 10⁻³ M KEX solutions did not show the presence of hydrophobic force while the results obtained with copper-activated sphalerite at pH 9.2 and 4.6 showed strong hydrophobic forces. However, at pH 6.8, no hydrophobic forces were observed, which explains why the flotation of sphalerite is depressed in the neutral pH regime. Direct force measurements were also conducted using hornblende in xanthate solutions to study the mechanism of inadvertent activation and flotation of rock minerals. The results show the presence of long-range hydrophobic forces when hornblende was activated by heavy metal cations such as Cu²⁺ and Ni²⁺ ions. The strong hydrophobic forces were observed at pHs above the precipitation pH of the activating cation. These results were confirmed by the XPS analysis of the activated hornblende samples. Force measurements were conducted between silanated silica surfaces to explore the relationship between hydrophobicity, advancing contact angle (CA), and the magnitude (K) of hydrophobic force. In general, K increases as Contact Angle increases and does so abruptly at Contact Angle=90°. At the same time, the acid-base component of the surface free energy decreases with increasing CA and K. At CA>90°, GammaS^AB approaches zero. Based on the results obtained in the present work a mathematical model for the origin of the hydrophobic force has been developed. It is based on the premise that hydrophobic force originates from the attraction between large dipoles on two opposing surfaces. The model has been used successfully to fit the measured hydrophobic forces using dipole moment as the only adjustable parameter. However, the hydrophobic forces measured at CA>90° cannot be fitted to the model, indicating that there may be an additional mechanism, possibly cavitation, contributing to the appearance of the long-range hydrophobic force. / Ph. D.

Within a colloidal dispersion, the presence of negatively adsorbing material can produce a variety of effects on the dispersion properties and interactions. With increasing concentration, the negatively adsorbing material induces both depletion and structural forces on the dispersion, which can dramatically affect both colloidal stability and near-contact hydrodynamics. This project focused on expanding our understanding of the effects of such negatively adsorbing materials on both equilibrium and dynamic interactions between particles. The effects of charged, hard spheres (silica nanoparticle) on the hydrodynamic drag force a particle experiences as it approaches a flat plate were measured experimentally using colloid probe atomic force microscopy (CP-AFM). Deviation was found between the measured drag force and predictions for the drag force in a simple, Newtonian fluid. The measured drag force was always smaller than the predicted drag force as the particle approached contact with the plate. An effective viscosity, that approached the dispersing fluid viscosity at contact and the bulk viscosity at large separations, was determined for the system. This effective viscosity displayed similar characteristics to those predicted theoretically by Bhattacharya and Blawzdziewicz (J. Chem. Phys. 2008, 128, 214704.). The effects of both anionic and cationic micelles on the depletion and structural forces in a colloidal dispersion were studied both experimentally (with CP-AFM) and theoretically. The depletion and structural forces between a microparticle and a flat plate were measured and compared with the depletion force predicted by the force-balance model of Walz and Sharma (J. Colloid Interface Sci. 1994, 168, 485-496.). Consistent with previous work, the measured depletion force for both micelles was smaller in magnitude than that predicted by the Walz and Sharma model for hard, charged spheres. It is theorized that rearrangement of the micelle surfaces charges or physical deformation of the micelles may be responsible for the observed result. An effective surface potential for the micelles is proposed as a correction to the Walz and Sharma model. Finally, the stability of colloidal dispersions was studied macroscopically in solutions of ionic micelles. The colloidal dispersions displayed clear flocculation behavior in both cationic and anionic micelles. This flocculation behavior was compared with energy profiles determined from CP-AFM experiments between a single particle and a flat plate. A simple phase diagram was proposed for predicting the stability of colloidal dispersions based solely on the depth of the depletion energy well and the height of the repulsive energy barrier. / Ph. D.

This study describes the covalent and the electrostatic attachment of molecules, nano-particles, and proteins to patterned self-assembled monolayers. A scanning probe nanografting technique was employed to produce patterns of various sizes, down to 10 nm. Thus, we are able to demonstrate a degree of surface patterning which is an order of magnitude smaller than that used in the semiconductor industry. One efficient strategy for creating chemically specific nanostructures is to use the extraordinary catalytic properties of enzymes. However, as the dimension of a catalyst patch is reduced down to nanometer scale, it is difficult to detect the very low concentration of product. This study resolves the problem by developing a new strategy: the surface trapping of a product generated by a nanometer-scale patch of surface-bound enzyme. An array of proteins finds use when the array contains a number of different proteins. Toward this end, a new and convenient method for immobilizing enzymes is developed, which will allow the preparation of thin films containing several different catalytically-active enzymes on the nanoscale. The disadvantage of scanning probe nanografting technique is that the AFM tip loses resolution through wear during the patterning procedure. This study examines the possibility of developing a new AFM lithographic method to avoid wear: the use of enzymes covalently attached to a tip as a site-specific catalyst. / Ph. D.

This thesis presents work done investigating methods for constructing patterns on the nanometer scale. Various methods of nanolithography using atomic force microscopes (AFMs) are investigated. The use of AFMs beyond their imaging capabilities is demonstrated in various experiments involving nanografting and surface electrochemical modification. The use of an AFM to manipulate a monolayer of thiols deposited on a gold substrate via nanografting is shown in our work to enable chemical modification of the surface of the substrate by varying the composition of the monolayer deposited on it. This leads to the selective deposition of various polymers on the patterned areas. Conditions for enhancing the selective deposition of the self-assembled polymers are studied. Such conditions include the types of polymers used and the pH of the polyelectrolyte solutions used for polymer deposition. Another method of nanolithography is investigated which involves the electrochemical modification of a monolayer of silanes deposited on a silicon substrate. By applying a potential difference and maintaining the humidity of the ambient environment at a certain level we manage to change the chemical properties of select areas of the silane monolayer and thus manage to establish selective deposition of polymers and gold nanoparticles on the patterned areas. Parameters involved in the patterning process using surface electrochemical modification, such as humidity levels, are investigated. The techniques established are then used to construct circuit elements such as wires. / Ph. D.

This thesis addresses development of a new force spectroscopy tool, correlation force spectroscopy (CFS), for the measurement of the mechanical properties of very small volumes of material (molecular to µm³) at kHz-MHz time-scales. CFS is based on atomic force microscopy (AFM) and the principles of CFS resemble those of dual-trap optical tweezers. CFS consists of two closely-spaced micro-cantilevers that undergo thermal fluctuations. Measurement of the correlation in thermal fluctuations of the two cantilevers can be used to determine the mechanical properties of the soft matter, e.g. a polymeric molecule, that connects the gap between the two cantilevers. Modeling of the correlations yields the effective stiffness and damping of the molecule. The resolution in stiffness is limited by the stiffness of the cantilever and the frequency by the natural frequency of the cantilevers, but, importantly, the damping resolution is not limited by the damping of the cantilever, which has enabled high-resolution measurements of the internal friction of a polymer. The concept of CFS was originally presented by Roukes' group in Caltech [Arlett et al., Lecture Notes in Physics, 2007]; I developed the first practical versions of CFS for experimentation, and have used it in two applications (1) microrheology of Newtonian fluids and (2) single molecule force spectroscopy. To understand the correlation in thermal fluctuations of two cantilevers I initially validated the theoretical approach for analyzing correlation in terms of deterministic model using the fluctuation-dissipation theorem [Paul and Cross, PRL, 2004]. I have shown that the main advantages of such correlation measurements are a large improvement in the ability to resolve stiffness and damping. Use of CFS as a rheometer was validated by comparison between experimental data and finite element modeling of the deterministic vibrations of the cantilevers using the known viscosity and density of fluids. Work in this thesis shows that the data can also be accurately fitted using a simple harmonic oscillator model, which can be used for rapid rheometric measurements, after calibration. The mechanical properties of biomolecules such as dextran and single stranded DNA (ssDNA) are also described. CFS measurements of single molecule properties of ssDNA reveal the internal friction of the molecule in solution. / Ph. D.

A compact model representing the dynamics between piezoelectric voltage inputs and cantilever probe positioning, including nonlinear surface interaction forces, for atomic force microscopes (AFM) is considered. By considering a relatively large cantilever stiffness, singular perturbation methods reduce complexity in the model and allows for faster responses to Van der Waals interaction forces experienced by the cantilever's tip and measurement sample. In this study, we outline a nonlinear near-optimal feedback control approach for non-contact mode imaging designed to move the cantilever tip laterally about a desired trajectory and maintain the tip vertically about the equilibrium point of the attraction and repulsion forces. We also consider the universal instance when the tip-sample interaction force is unknown, and we construct cascaded high-gain observers to estimate these forces and multiple AFM dynamics for the purpose of output feedback control. Our proposed output feedback controller is used to accomplish the outlined control objective with only the piezotube position available for state feedback. / Master of Science / In this thesis, the idea of an atomic force microscope (AFM), specifically the applications of the non-contact mode, will be discussed. An atomic force microscope (AFM) is a tool that measures the surface height of nanometer sized samples. To improve the speed and precision of the machine under a non-contact mode objective, a controller is designed based on optimality and is applied to the system. The system contains a series of equations designed to steer the system towards a desired trajectory and minimal vibrations. Given the complexity of the system, resulting from nonlinearities, we will apply singular perturbation principles on the system's stiffness property to separate the larger problem into two smaller ones. These two problems are inserted into a near-optimal controller and a series of simulations are conducted to demonstrate performance. Alongside this, we will outline an observer to estimate the unknown dynamics of the system. These estimates are then applied to our controller to demonstrate that only the AFM's piezotube position is to be known in order to estimate and control the remaining dynamics of the system.

Yes / Tattooing has long been practised in various societies all around the world and is becoming increasingly common and widespread in the West. Tattoo ink suspensions unquestionably contain pigments composed of nanoparticles, i.e., particles of sub-100 nm dimensions. It is widely acknowledged that nanoparticles have higher levels of chemical activity than their larger particle equivalents. However, assessment of the toxicity of tattoo inks has been the subject of little research and ink manufacturers are not obliged to disclose the exact composition of their products. This study examines tattoo ink particles in two fundamental skin components at the nanometre level. We use atomic force microscopy and light microscopy to examine cryosections of tattooed skin, exploring the collagen fibril networks in the dermis that contain ink nanoparticles. Further, we culture fibroblasts in diluted tattoo ink to explore both the immediate impact of ink pigment on cell viability and also to observe the interaction between particles and the cells.

Three models for surface stress loading effect on a micromechanical cantilever are proposed as concentrated moment acting at the free end (Model I), concentrated moment plus axial force acting at the free end (Model II), and uniformly distributed surface force acting along the microcantilever (Model III). Solution to Model I loading is based on the Stoney formula, assuming that the microcantilever is subjected to pure bending and deformed with a constant curvature. Model II takes into account the clamping effect in such a way that an additional axial force is introduced. The deflections resulting from Models I and II surface stress loading effect are solved by Euler-Bernoulli beam theory. In Model III, the effect of surface stress is modeled as uniformly distributed surface force that causes both uniformly distributed bending moment and axial force acting along the axis of the microcantilever. The energy method is then used to obtain the governing equation and boundary conditions for Model III displacement. Comparison of the results obtained by the three models with those by the finite element method and experiment indicates that Model III is the most realistic model for surface stress loading effect to obtain the deflection of a microcantilever. Model III for surface stress loading effect is then used to demonstrate the applications of a microcantilever in sensor technology through the measurement of tip deflection under an atomic adsorption as the source of surface stress. Dual attractive or repulsive characteristics of interactions between a pair of mercury atoms are described in terms of Lennard-Jones potential. The force per unit atomic spacing induced by the adjacent free surface atoms of a monolayer is then computed using the potential. The sensitivities of atomic spacing and monolayer thickness to the tip-deflection of a microcantilever are studied in this research. / Master of Science

Yes / The compression stiffness of a phospholipid microbubble was determined using force-spectroscopy as a function of temperature. The stiffness was found to decrease by approximately a factor of three from 0.08 N m 1, at 10 C, down to 0.03 N m 1 at 37 C. This temperature dependence indicates that the surface tension of lipid coating is the dominant contribution to the microbubble stiffness. The timedependent material properties, e.g. creep, increased non-linearly with temperature, showing a factor of two increase in creep-displacement, from 24 nm, at 10 C, to 50 nm, at 37 C. The standard linear solid model was used to extract the visco-elastic parameters and their determination at different temperatures allowed the first determination of the activation energy for creep, for a microbubble, to be determined. / EPSRC