Adsorption-mediated self-assembly of nanoparticles at fluid interfaces, driven by reduction in interfacial energy, leads to stabilization of emulsions and foams and can be used for the bottom-up fabrication of functional nanostructured materials. Improved understanding of the parameters that control the self-assembly, the structure of nanoparticles at the interface, the barrier properties of the assembly and the rate of particle attachment and exchange is needed if such nanoparticle assemblies are to be employed for the design and fabrication of novel materials and devices. Here, I report on the use of dynamic surface tension (DST) measurements to probe the kinetics of irreversible adsorption and self-assembly of hydrophobic ethyl-cellulose (EC) nanoparticles at the air-water interface. Using thermodynamic arguments, I make a direct connection between the DST and the time-dependent surface coverage. I show that adsorption models appropriate for surfactants (e.g., Ward and Tordai model) break down for irreversible adsorption of nanoparticles, when the adsorption energy far exceeds the mean energy of thermal fluctuations (kBT) and surface blocking effects give rise to a steric barrier to adsorption. I show instead that irreversible adsorption kinetics are unequivocally characterized in terms of the adsorption rate constant and the maximum (jamming) coverage, both of which are determined on the basis of DST data using the generalized random sequential adsorption theory (RSA) for the first time. Novel accurate estimates of the adsorption energy of 42 nm and 89 nm EC nanoparticles are also provided. Coverage of the interface to the jamming limit of 91%, corresponding to a triangular lattice in 2D, is experimentally demonstrated. Colloidal solutions of EC nanoparticles are stabilized at neutral pH by electrostatic repulsive forces. Strong adsorption of these particles at an interface of like charge suggests the parallel action of attractive hydrophobic forces.

Adsorption-mediated self-assembly of nanoparticles at fluid interfaces, driven by reduction in interfacial energy, leads to stabilization of emulsions and foams and can be used for the bottom-up fabrication of functional nanostructured materials. Improved understanding of the parameters that control the self-assembly, the structure of nanoparticles at the interface, the barrier properties of the assembly and the rate of particle attachment and exchange is needed if such nanoparticle assemblies are to be employed for the design and fabrication of novel materials and devices. Here, I report on the use of dynamic surface tension (DST) measurements to probe the kinetics of irreversible adsorption and self-assembly of hydrophobic ethyl-cellulose (EC) nanoparticles at the air-water interface. Using thermodynamic arguments, I make a direct connection between the DST and the time-dependent surface coverage. I show that adsorption models appropriate for surfactants (e.g., Ward and Tordai model) break down for irreversible adsorption of nanoparticles, when the adsorption energy far exceeds the mean energy of thermal fluctuations (kBT) and surface blocking effects give rise to a steric barrier to adsorption. I show instead that irreversible adsorption kinetics are unequivocally characterized in terms of the adsorption rate constant and the maximum (jamming) coverage, both of which are determined on the basis of DST data using the generalized random sequential adsorption theory (RSA) for the first time. Novel accurate estimates of the adsorption energy of 42 nm and 89 nm EC nanoparticles are also provided. Coverage of the interface to the jamming limit of 91%, corresponding to a triangular lattice in 2D, is experimentally demonstrated. Colloidal solutions of EC nanoparticles are stabilized at neutral pH by electrostatic repulsive forces. Strong adsorption of these particles at an interface of like charge suggests the parallel action of attractive hydrophobic forces.

In this thesis, we report the development of two types of optical sensors, one for high temperature pressure measurements and the other for real-time particle detection. With a high melting temperature (over 2000°C), low optical loss, and excellent corrosion resistance, sapphire (α-Al₂O₃) is ideal for high temperature sensing applications. Fabry-Perot (FP) cavity with optical interrogation of pressure response. The prototype is based on an extrinsic FP interferometer design and is constructed by combining reactive ion etching (RIE) with direct wafer bonding. Long-term testing proves that the adhesive-free wafer bond is sufficient to create a sealed Fabry-Perot cavity as a pressure transducer. Pressure measurement over a range of 6 to 200 psi has been demonstrated at room temperature using white-light interferometry. For the other sensor, the goal is to detect the presence of micro- and nanoparticles in real time. The sensor is based on a silica fiber taper, and we aim to detect particle presence by measuring optical scattering and absorption induced by particles attached to the taper surface. To establish the relationship between particle density and optical transmission loss, we first consider a model where Au nanospheres are self-assembled on taper surface through electrostatic interaction. An analytical model is established to describe the adsorption of gold nanospheres onto cylindrical and spherical silica surfaces from quiescent aqueous particle suspensions. The curved surfaces of the fiber taper and microspheres are coated with nm-thick layer of a polycation, enabling irreversible adsorption of the negatively charged spheres. Our results fit well with theory, which predicts that the rates of particle adsorption will depend strongly on the surface geometry. In particular, adsorption is significantly faster on curved than on planar surfaces at times long enough that the particle diffusion length is large compared to the surface curvature. This is of particular importance for plasmonic sensors and other devices where particles are deposited from a suspension onto surfaces which may have non-trivial geometries. We have established a theoretical model that can describe optical loss generated by particles on taper surface. This theory is validated by measuring, in real time, optical loss during the self-assembly of gold nanoparticles. We find that the measured optical loss can be quantitatively explained by the presence of multiple guided modes within the fiber taper region. Based on this work, we incorporate a fiber taper into a cascade impactor and show that welding aerosols attached to the fiber taper surface can induce measurable transmission loss during the welding process. / Ph. D.