Mechanically-activated delivery systems harness existing physiological and/or externally-applied forces to provide spatiotemporal control over the release of active agents. The presence and necessity of these forces in the human body and in the increasing use of mechanically-driven medical devices (e.g., stents, balloon catheters, gastric bands, tissue expanders) can serve as functional dynamic triggers. Therefore, this dissertation investigates the use of applied tensile strain and cyclic loading to control release of entrapped agents, and further translates the concept towards clinical applications by integrating the system with commercial medical devices that provide precise forces to trigger release. As an initial proof-of-concept, mechanoresponsive composites, consisting of highly-textured superhydrophobic barrier coatings over a hydrophilic substrate, are fabricated. The release of entrapped agents, controlled by the magnitude of applied strain, results in a graded response due to water infiltration through propagating patterned cracks in the coating. The strain-dependent delivery of anticancer agents with in vitro efficacy as well as the ex vivo delivery to esophageal tissue with an integrated stent system are demonstrated. Release is further modulated by barrier coating properties. Thicker coatings afford slower release rates with preserved in vitro activity for both a chemotherapeutic and an enzyme. Localizing coating crack patterns based on different geometric stress concentration factors further controls the selective sequential release of multiple agents. Finally, the development of a reversible mechanoresponsive system is investigated to provide cycle-mediated pulsatile release. Optimization of mechanical parameters results in delivery of multiple doses. To translate this concept towards the clinic, the system is integrated with commercial balloon catheters to provide multidose delivery of small molecules to ex vivo vessels. Using the inherent inflation and deflation of the catheter to trigger release, the system enhances existing capabilities to treat cardiovascular and peripheral artery diseases. In summary, the development of mechanoresponsive systems that respond to tensile strain and cycle number are described for the delivery of a wide-range of active agents (hydrophilic and hydrophobic small molecules as well as an enzyme), and their integration with existing medical devices. Furthermore, the comprehensive range of specific kinetic profiles, including triggered release, pulsatile delivery, and the sequential delivery of multiple agents, showcases the capabilities and versatility of these dynamic mechanoresponsive systems to modulate release for the treatment of various clinical diseases. / 2019-02-20T00:00:00Z

abstract: Durable, cost-effective, and environmentally friendly anti-icing methods are desired to reduce the icing hazard in many different industrial areas including transportation systems, power plants, power transmission, as well as offshore oil and gas production. In contrast to traditional passive anti-icing surfaces, this thesis work introduces an anti-icing coating that responds to different icing conditions by releasing an antifreeze liquid. It consists of an outer porous superhydrophobic epidermis and a wick-like underlying dermis that is infused with the antifreeze liquid. This bi-layer coating prevents accumulation of frost, freezing fog, and freezing rain, while conventional anti-icing surfaces typically work only in one of these conditions. The bi-layer coating also delays condensation on the exterior surface at least ten times longer than identical system without antifreeze. It is demonstrated that the significant delay in condensation onset is due to the integral humidity sink effect posed by the hygroscopic antifreeze liquid infused in the porous structure. This effect significantly alters the water vapor concentration field at the coating surface, which delays nucleation of drops and ice. It was demonstrated that with a proper design of the environmental chamber the size of the region of inhibited condensation and condensation frosting around an isolated pore, as well as periodically spaced pores, filled by propylene glycol can be quantitatively predicted from quasi-steady state water vapor concentration field. Theoretical analysis and experiments revealed that the inhibition of nucleation is governed by only two non-dimensional geometrical parameters: the pore size relative to the unit cell size and the ratio of the unit cell size to the thickness of the boundary layer. It is demonstrated that by switching the size of the pores from millimeters to nanometers, a dramatic depression of the nucleation onset temperature, as well as significantly greater delay in nucleation onset can be achieved. / Dissertation/Thesis / Doctoral Dissertation Mechanical Engineering 2017

Superhydrophobic surfaces have gained attention as a potential mechanism for increasing condensation heat transfer rates. Various aspects related to condensation heat transfer are explored. Adiabatic, air-water mixtures are used to explore the influence of hydrophobicity on two-phase flows and the hydrodynamics which might be present in flow condensation environments. Pressure drop measurements in a rectangular channel with one superhydrophobic wall (cross-section approximately 0.37 X 10 mm) are obtained, revealing a reduction in the pressure drop for two-phase flow compared to a control scenario. The observed reduction is approximately 10% greater than the reduction that is observed for single-phase flow (relative to a classical channel). Carbon nanotubes have been used to create superhydrophobic coatings due to their ability to offer a relatively uniform nanostructure. However, as-grown carbon nanotubes often require the addition of a thin-film hydrophobic coating to render them superhydrophobic, and fine control of the overall nanostructure is difficult. This work demonstrates the utility of using carbon infiltration to layer amorphous carbon on multi-walled nanotubes to achieve superhydrophobic behavior with tunable geometry. The native surface can be rendered superhydrophobic with a vacuum pyrolysis treatment, with contact angles as high as 160 degrees and contact angle hysteresis less than 2-3 degrees. Drop-size distribution is an important aspect of heat transfer modeling that is difficult to measure for small drop sizes. The present work uses a numerical simulation of condensation to explore the influence of nucleation site distribution approach, nucleation site density, contact angle, maximum drop size, heat transfer modeling to individual drops, and minimum jumping size on the distribution function and overall heat transfer rate. The simulation incorporates the possibility of coalescence-induced jumping over a range of sizes. Results of the simulation are compared with previous theoretical models and the impact of the assumptions used in those models is explored. Results from the simulation suggest that when the contact angle is large, as on superhydrophobic surfaces, the heat transfer may not be as sensitive to the maximum drop-size as previously supposed. Furthermore, previous drop-size distribution models may under-predict the heat transfer rate at high contact angles. Condensate drop behavior (jumping, non-jumping, and flooding) and size distribution are shown to be dependent on the degree of subcooling and nanostructure size. Drop-size distributions for surfaces experiencing coalescence-induced jumping are obtained experimentally. Understanding the drop-size distribution in the departure region is important since drops in this size are expected to contribute significantly to the overall heat transfer rate.

This dissertation focuses on the effects of superhydrophobic (SHPo) surfaces on thermal transport. The work is divided into two main categories: thermal transport without phase change and thermal transport with phase change. Thermal transport without phase change is the topic of four stand-alone chapters. Three address jet impingement at SHPo surfaces and the fourth considers natural convection at a vertical, SHPo wall. Thermal transport with phase change is the topic of a single stand-alone chapter exploring pool boiling at SHPo surfaces.Two chapters examining jet impingement present analytical models for thermal transport; one considered an isothermal wall and the other considered an isoflux wall. The chapter considering the isothermal scenario has been archivally published. Conclusions are presented for both models. The models indicated that the Nusselt number decreased dramatically as the temperature jump length increased. Further, the influence of radial position, jet Reynolds number, Prandtl number and isoflux versus isothermal heating become negligible as temperature jump length increased. The final chapter concerning jet impingement reports an experimental exploration of jet impingement at post patterned SHPo surfaces with varying microfeature pitch and cavity fraction. The empirical results show a decrease in Nusselt number relative to smooth hydrophobic surfaces for small pitch and cavity fraction and the isoflux model agrees well with this data when the ratio of temperature jump length to slip length is 3.1. At larger pitch and cavity fractions, the empirical results have higher Nusselt numbers than the SHPo surfaces with small pitch and cavity fraction but remain smaller than the smooth hydrophobic surface. We attribute this to the influence of small wetting regions. The chapter addressing natural convection presents an analytical model for buoyant flow at a vertical SHPo surface. The Nusselt number decreased dramatically as temperature jump length increased, with greater decrease occurring near the lower edge and at higher Rayleigh number. Thermal transport with phase change is the topic of the final stand-alone chapter concerning pool boiling, which has been archivally published. Surface heat flux as a function of surface superheat was reported for SHPo surfaces with rib and post patterning at varying microfeature pitch, cavity fraction, and microfeature height. Nucleate boiling is more suppressed on post patterned surfaces than rib patterned surfaces. At rib patterned surfaces, transition superheat decreases as cavity fraction increases. Increasing microfeature height modestly increases the transition superheat. Once stable film boiling is achieved, changes in surface microstructure negligibly influence thermal transport.

Liquid jet impingement is a technique ubiquitously used to rapidly remove large amounts of heat from a surface. Several different regions of heat transfer spanning from forced convection to nucleate, transition, and film boiling can occur very near to one other both temporally and spatially in quenching or high wall heat flux scenarios. Heat transfer involving jet impingement has previously shown dependency both on jet characteristics such as flow rate and temperature as well as surface material properties. Water droplets are known to bead up upon contact with superhydrophobic (SH) surfaces. This is due to reduced surface attraction caused by micro- or nanostructures that, combined with a natively hydrophobic surface chemistry, reduce liquid-solid contact area and attraction, promoting droplet mobility. This remarkable capability possessed by SH surfaces has been studied in depth due to its potential for self-cleaning and shear reduction, but previous research regarding heat transfer on such surfaces shows that it has varying effects on thermal transport. This thesis investigates the effect that quenching initially hot SH surfaces by water jet impingement has on heat transfer, particularly regarding phase change. Two comparative studies are presented. The first examines differences in transient heat transfer from hydrophilic, hydrophobic, and SH surfaces over a range of initial surface temperatures and with jets of varying Reynolds number (ReD), modified by adjusting flow rate. Comparisons of instantaneous local heat flux from the surfaces are made by performing an energy balance over differential control volumes across the surfaces. General trends show increased heat flux, jet spreading velocity and maximum jet spread radius when ReD is increased. An increase in inital surface temperature resulted in increased heat flux across all surfaces, but slowed jet spreading. The local heat flux, average heat rate, and total thermal energy transfer from the surface all confirmed that SH surfaces allow significantly less heat to transfer to the jet compared to hydrophilic surfaces, due to the enhanced Leidenfrost condition and reduced liquid-solid contact on SH surfaces which augments thermal resistance. The second study compares jet impingement heat transfer from SH surfaces of varying microstructures. Similar thermal effects due to modified jet ReD and initial surface temperature were observed. Modifying geometric pattern from microposts to microholes, altering cavity fraction, and changing feature pitch and width had little impact on heat transfer. However, reducing feature height on the post surfaces facilitated water penetration within the microstructure, slightly enhancing thermal transport.

In this study, the associated dynamic of water droplets at low impact velocity on the Superhydrophobic surface have been investigated. The experiment is conducted on superhydrophobic surface (SH), (Contact Angel > 1500) while varying the impact velocity (V0). When the drop hits the surface, large oscillation starts, and the capillary waves travel up to the upper of the drop where a cylindrical cavity can be formed inside the drop. The cavity closes up in a self-similar way until collapse, followed by a violent singular jet which can reach up to 35 m/s. The study showed that during drop receding, the cavity can collapse in different scenarios based on the impact velocity and the surface wettability. More importantly, the collapse is observed for the first time at very high-speed video, up to 5 million fps. Furthermore, we correct the optical distortion of the cavity due to the curvature of the drop surface. This study classifies all of the 5 encountered behaviors of the cavity collapse. The jet formation and speed are strongly dependent on the specific cavity configuration. Very fast jetting behavior is observed when the collapse is pinch-off singularity which reaches zero value in the middle of the drop. Other behaviors of the collapse such the unsymmetrical closing of the cavity or bubble entrapment is discussed. The optical distortion factor is calculated through 3 different approaches. The first one is an experimental calibration technique where a small cylinder is inserted into the drop. While the other two approaches are indirect implantations of theoretical models presented in the literature to fit the instantaneous geometrical shape of the cavity inside the drop. The distortion factor (DF) gives in all cases a similar value. Therefore, the averaged distortion value is calculated, and it is a magnification of 33% increase of the actual size. The experiment results of the cavity radius are compared with power-laws and the modified Rayleigh-Plesset equation for free cylindrical flow and good agreement is shown.

Superhydrophobic surfaces are a class of surfaces that have a microscale roughness imposed on an already hydrophobic surface, akin to a lotus leaf. These surfaces have been shown to produce significant drag reduction for both laminar and turbulent flows of water through large and small-scale channels. The goal of this thesis was to explore how these surfaces alter the vortex shedding dynamics of a cylindrical body when coated on its surface, thus leading to an alteration in drag and lift on these surfaces. A cylindrical body was chosen as it is a very nice representative bluff body and sets the stage for predicting the behavior of hydrofoils and other bluff bodies under flow with a slip boundary condition. In this work, a series of experiments were performed which investigated the effect of superhydrophobic-induced slip on the flow past a circular cylinder. In these experiments, circular cylinders were coated with a series of superhydrophobic surfaces fabricated from PDMS with well-defined micron-sized patterns of surface roughness or random slip surfaces fabricated by sanding Teflon cylinders or spray painting superhydrophobic paint on a smooth cylinder. The presence of the superhydrophobic surface was found to have a significant effect on the vortex shedding dynamics in the wake of the circular cylinder. When compared to a smooth, no-slip cylinder, cylinders coated with superhydrophobic surfaces were found to delay the onset of vortex shedding and increase the length of the recirculation region in the wake of the cylinder. For superhydrophobic surfaces with ridges aligned in the flow direction the separation point was found to move further upstream towards the front stagnation point of the cylinder and the vortex shedding frequency was found to increase. For superhydrophobic surfaces with ridges running normal to the flow direction, the separation point and shedding frequency trends were reversed. The vortices shed from these surfaces were found to be weaker and less interlaced leading to reduced circulation and lift forces on these cylinders. The effect of slip on bluff bodies and separating flow was dealt with in detail in this thesis and the results could be used to predict the impact of these surfaces on the flow past hydrofoils which combine skin friction dominated flow with separating flow.

This thesis examines the time resolved heat transfer to drops rolling or sliding along inclined, subcritical heated non-wetting surfaces. Results were experimentally obtained using IR imaging for a smooth hydrophobic surface and post as well as rib structured superhydrophobic surfaces of varying solid fraction (f_s = 0.06 - 0.5). Tests were performed at varying inclination angle (α = 10, 15, 20, and 25°), drop volume (12, 20, 30, and 40 μL), and surface temperature (T_w = 50, 65, and 80 °C). Rib structured superhydrophobic surfaces were explored for drops moving parallel and perpendicular to the rib structures. The findings indicate that transient heat transfer is predominantly influenced by the surface’s solid fraction and the velocity of the drops, with a secondary dependence on drop volume. Surfaces with low solid fraction show a significant reduction in initial heating rate (up to 80% reduction) to the drop, when compared with that of the smooth surface. The drop velocity depends on surface solid fraction and inclination angle, with drop volume exerting smaller influence. Rib structured surfaces impact heat transfer by enhancing heat transfer rate for drops that move along the rib direction compared with drops that move perpendicular to the ribs. The difference is likely due to increased drop velocity that exists for the parallel rib orientation.

Frictional resistance reduction of liquid flow over surfaces has recently become a more important topic of research in the field of fluid dynamics. Scientific and technological progress and continued interest in nano and micro-technology have required new developments and approaches related to reducing frictional resistance, especially in liquid flow through nano and micro-channels. The application of superhydrophobic surfaces could be very effective in achieving the desired flow through such small channels. Superhydrophobic surfaces are created by intentionally creating roughnesses on the surface and applying a uniform hydrophobic coating to the entire surface. Liquid droplet tests have revealed that because of the trapped air within the cavities such surfaces could have contact angles as high as 179°. Such a property gives superhydrophobic surfaces liquid repelling characteristics making them very suitable for frictional resistance reduction in liquid flow through nano or micro-channels, provided wetting of the cavities could be avoided. This study presents 3-D numerical simulation results of liquid laminar flow over post patterned superhydrophobic surfaces. The research was performed in three phases, 1) pressure-driven flow with square micro-posts, 2) Couette flow with square micro-posts, and 3) pressure-driven flow with rectangular micro-posts at various aspect ratios. In phases (1) and (2) the influences of important parameters such as the cavity fraction, in the range of 0.0-0.9998, and the relative module width, from 0.01 to 1.5, on frictional resistance reduction in the creeping flow regime were explored. Phase (1) also addressed the effect of varying Reynolds number from 1 to 2500 on frictional resistance. Phase (3) was conducted for aspect ratios of 1/8, 1/4, 1/2, 2, 4, and 8 also in the creeping flow regime. The obtained results suggest that important parameters such as cavity fraction (relative area of the cavities), relative module width (combined post and cavity width relative to the channel hydraulic diameter), and the Reynolds number have great influence on the frictional resistance reduction. For pressure-driven flow at cavity fraction 0.9998, reductions as high as 97% in the frictional resistance were predicted compared with the classical channel flow. This reduction is directly related to the significant reduction in liquid-solid contact area. With respect to the effect of relative module width on the overall frictional resistance, a reduction of 93% in the frictional resistance was observed as the relative module width was increased from 0.1 to 1.5. This is indicative of the importance of the relative spacing size of the posts/cavities compared to the channel size in micro-channel liquid flow. The overall frictional resistance for post-patterned superhydrophobic surfaces was found to be independent of the Reynolds number up to a value of nominally 40 after which the non-dimensional frictional resistance increased at high values of the Reynolds number. However, at very high cavity fractions the frictional resistance was independent of Reynolds number only up to about 4. When the driving mechanism was a Couette flow, similar to the pressure-driven flow, as the cavity fraction and the relative module width increased the frictional resistance on the superhydrophobic surface decreased. At a cavity fraction of 0.9998 the reduction in the non-dimensional frictional resistance was approximately 96%, which was only 1% different from the similar pressure-driven scenario. However, a more significant difference was observed between the slip velocities for the two flow types, and it was determined that the pressure-driven flow resulted in greater apparent slip velocities than Couette flow. A maximum difference in normalized slip between the two scenarios of approximately 20% was obtained at relative module width 0.1 and Reynolds number 1. Results for superhydrophobic surfaces with rectangular micro-posts approached those reported in the literature for micro-ribs as the aspect ratio of the posts increased. When the flow was perpendicular to the long side of the posts, and as the aspect ratio increased, the frictional resistance approached previously published transverse rib results. Similarly, when the liquid flow direction was parallel to the long side of the posts, the frictional resistance results also approached those of the previously published longitudinal ribs as the aspect ratio increased.

Superhydrophobic (SH) surfaces are characterized by their extraordinary water repellent qualities. When water comes in contact with these surfaces, it beads up and rolls around. This phenomenon is due partially to surface chemistry which promotes weak adhesive forces between liquid and solid. However, micro- and nanoscale surface roughness also plays a crucial role by trapping air beneath the liquid, reducing liquid-solid contact. Many advantages of these surfaces have been identified, including drag reduction and self-cleaning properties, and the body of research regarding them has grown rapidly over the past few decades.This thesis is concerned with water droplets impinging superheated, superhydrophobic surfaces. In these scenarios, boiling is common in the droplet, producing vapor bubbles which burst through the droplet lamella and cause a spray of miniscule water particles known as thermal atomization. The work contained in this thesis uses an image processing technique to quantify trends in thermal atomization intensity during droplet impingement scenarios for a range of surface microstructure configurations, superheat temperatures, and Weber numbers.In one study, droplet impingement on a smooth hydrophobic and three post-patterned SH surfaces of similar solid fraction is considered. In general, as pitch (center-to-center distance between posts) increases, atomization intensity decreases. This is attributed to the enhanced ability for vapor escape beneath the droplet that is present for wider pitch surfaces. Atomization intensity increases with increasing Weber number for each of the surfaces considered. Additionally, the Leidenfrost point is found to increase with increasing Weber number and decreasing pitch.Next, thermal atomization on SH surfaces with two distinct microstructure configurations is considered: square posts (which allow vapor escape between structures) and square holes (which block vapor escape). Tests are done for each configuration with varying microstructure height, and structure spacing and solid fraction are held constant. Comparing the two configurations at each structure height and Weber number, the post-patterned surfaces suppress atomization for a large number of scenarios compared to the hole surfaces, supporting the theory that vapor escape through microstructures suppresses atomization. Microstructure height significantly affects trends in atomization intensity with surface temperature and Weber number. The LFP is seen to decrease with increasing height.