Isolating chemically-reactive sites into nanosized compartments is an important mode of control used by Nature to perform chemical transformations with extremely high yields and selectivity. Biological systems are fundamentally organized as bounded and isolated nano- and micro-sized environments featuring distinct localized properties, such as steric crowding, polarity, hydrophobicity, potential for molecular recognition, or pH. Through this compartmentalization, reaction substrates are sequestered away from interfering factors and competing substrates, or are physically prevented from forming alternative products or favoring specific pathways. Inspired by Nature, chemists have explored the rational design and application of various nanocompartments. This work explores three types of nanoconfinement systems capable of catalysis and specific transport: surfactant micelles, block-copolymer micelles, and hollow inorganic nanoparticles. The surfactant micelles are designed as part of a system of self-replicating micelles and are used to show how the chirality of the confinement system effects reaction kinetics. Simple click chemistry between a hydrophilic chiral head and a hydrophobic tail is used to produce an amphiphile under biphasic conditions. Once the product achieves critical micelle concentration, stable micelles can form. These micelles subsequently compartmentalize and pre-concentrate hydrophobic substrates, increasing the reaction rate and resulting in the self-propagation of the micellar structures and their chiralities. The next system explores block-copolymer micelles that are made up of a hydrophobic saturated fluorocarbon block and a hydrophilic block. The amphiphilic copolymers can form aggregates in water and, because of properties unique to the hydrophobic block, this system also increases oxygen solubility in water. Different fluorocarbon monomers are discussed and it was found that the structure of the fluorinated monomer, temperature, and pH effect aggregation behavior and the concentration of dissolved oxygen. Additionally, varying the pH of the system could be used to trigger oxygen release. Similar to the block-copolymer micelles, the hollow inorganic nanoparticles were designed to transport oxygen. Here, hollow silica nanoparticles were designed with a fluorinated interior surface and a hydrophilic exterior. This design allows for highly dispersible nanoparticles in water and facilitates the uptake of saturated fluorocarbon liquids into their cores. Once the saturated fluorocarbon is incorporated, the system can les to increases in oxygen solubility.

Nanocomposites consist of graphene dispersed in matrices of soft materials are promising thermal management materials. A fundamental understanding of the thermal transport at graphene-soft material interfaces is essential for developing these nanocomposites. In this dissertation, thermal transport at graphene-octane interfaces was investigated using molecular dynamics simulations, and the results revealed several important characteristics of such thermal transport. The interfacial thermal conductance of graphene-octane interfaces were studied first. It was found that the interfacial thermal conductance exhibits a distinct duality: if heat enters graphene from one side of its basal plane and leaves it through the other side, the corresponding interfacial thermal conductance, Gacross, is large; if heat enters graphene from both sides of its basal plane and leaves it at a position far away on its basal plane, the corresponding interfacial thermal conductance, Gnon-across, is small. Gacross is ~30 times larger than Gnon-across for a single-layer graphene immersed in liquid octane. Additional analysis showed that this duality originates partially from the strong, positive correlations between the heat fluxes at the two surfaces of a graphene layer. The interfacial thermal conductance of the graphene-soft material interfaces in presence of defects in the graphene was then studied. The results showed that the heat transfer at the interfaces is enhanced by defects. Estimations based on effective medium theories showed that the effective thermal conductivity of the graphene-based composites could even be enhanced with defects in graphene when heat transfer at the graphene-soft material interface is the bottleneck for the thermal transport in these composites. To describe the interfacial thermal transport at graphene interfaces uniformly, a nonlocal constitutive model was proposed and validated to replace the classical Kapitza model. By characterizing the thermal transport properties of graphene interfaces using a pair of thermal conductance, the model affords a uniform description of the thermal transport at graphene interfaces for different thermal transport modes. Using this model, the data interpretation in time domain thermalreflectance (TDTR) measurements was investigated, and the results showed that the interfacial thermal conductance measured in typical TDTR tests is that of the across mode for thin-layered materials. / Ph. D.

Subject to a sufficiently large compression, materials may undergo mechanical instabilities of various types. When the material is homogeneous, creases set in. When the material is a bilayer consisting of a stiff thin film on a thick compliant substrate, wrinkles set in. Creases are localized self-contact regions with large strain deviating from the smooth state, while wrinkles are undulations finite in space with infinitesimal strain deviating from the smooth state. After the formation of wrinkles, if the compression further increases, wrinkles double their period and form localized folds. If the substrate is subject to a sufficiently large pre-tension, wrinkles transit to ridges. This thesis explores different types of mechanical instabilities: creases, wrinkles, folds, and ridges. We start with studying creases in different materials. Soft tissues growing under constraint often form creases. We adopt the model of growth that factors the deformation gradient into a growth tensor and an elastic deformation tensor, and show that the critical conditions for the onset of creases take a remarkably simple form. We then perform simulations to explore creases in strain-stiffening materials. For a solid that stiffens steeply at large strains, as the compression increases, the surface is initially smooth, then forms creases, and finally becomes smooth again. For a solid that stiffens steeply at small strains, creases never form for all levels of compression. In order to better control the formation and disappearance of creases, we design a soft elastic bilayer with same moduli of the film and substrate but the substrate pre-compressed, and show that the bilayer can snap between the flat and creased states reproducibly with tunable hysteresis in a large strain range. We also show that an interface between two soft materials can form creases under compression. We then investigate the critical conditions for the onset of wrinkles and creases in bilayers with arbitrary thicknesses and moduli of the two layers, and show several new types of bifurcation behavior when the film and substrate have comparable moduli and thicknesses. We study the effect of substrate pre-stretch on post-wrinkling bifurcations, and show that pre-tension stabilizes wrinkles while pre-compression destabilizes wrinkles. When the pre-compression is sufficiently large, `chaotic' morphologies emerge. When the pre-tension is sufficiently large, we realize ridge localizations and networks under an equi-biaxial compression, and study the mechanics of ridge formation and propagation. / Engineering and Applied Sciences

<p>  </p> <p>Adhesives are becoming more widely used for applications that previously relied on mechanical methods to secure the interface of two materials due to their cost effectiveness, lower weight, and ease of use. Examples of these new adhesive spaces include functional adhesives for robotic or manufacturing applications, composite materials in automotives and aircrafts, and wearable medical devices. As adhesives continue to push into new spaces, new methods must be developed to control their adhesive properties. Furthermore, understanding how the adhesive properties of these materials change due to deformation is critical in order to select or design new adhesives for specific applications. </p> <p>In this work we develop a material with pressure tunable adhesion by utilizing surface patterning. A simple and scalable fabrication method, polymer thin film dewetting, is used to pattern the surface of a soft elastomer with stiff, microscopic, and axisymmetric asperities. Patterning of the surface with these asperities leads to pressure tunable adhesion where adhesion strength increases with increasing applied pressure. Additionally, it is shown that changes to the relationship between adhesion strength and applied pressure by altering the pattern geometry are investigated.</p> <p>The surface properties of amorphous elastomers have long been assumed to be independent of deformation. However, experimental studies within the last 15 years have shown this to be false for very soft solids and gels with moduli on the order of 10s-100s KPa when deformation of the material is below a critical length scale. The surface stress of these materials differs from the bulk and are dependent on the degree of deformation of the solid. Theoretical works have also shown this to be true for stiffer materials, however it is difficult to use the same experimental techniques to probe the surface stress of elastomers with moduli on the order of MPa. In this work, a new experimental technique is proposed to investigate the deformation dependent surface properties of elastomers. Additionally, this same technique allows us to probe the deformation-dependent adhesion properties of elastomers. We show that the shape of contact between a uniaxially stretched elastomer and rigid spherical probe provides insight into changes in surface stress. Furthermore, our results indicate that material composition, specifically filler composition and loading, affects the adhesion hysteresis of these elastomers. </p>

"Recently, hydrogel have found to be promising biomaterials since their porous structure and hydrophilicity enables them to absorb a large amount of water. In this study the role of water on the mechanical properties of hydrogel are studied using ab-initio molecular dynamics (MD) and coarse-grained simulations. Condensed-Phased Optimized Molecular Potential (COMPASS) and MARTINI force fields are used in the all-atom atomistic models and coarse-grained simulations, respectively. The crosslinking process is modeled using a novel approach by cyclic NPT and NVT simulations starting from a high temperature, cooling down to a lower temperature to model the curing process. Radial distribution functions for different water contents (20%, 40%, 60% and 80%) have shown the crosslinks atoms are more hydrophilic than the other atoms. Diffusion coefficients are quantified in different water contents and the effect of crosslinking density on the water diffusion is studied. Elasticity parameters are computed by constant strain energy minimization in mechanical deformation simulations. It is shown that an increase in the water content results in a decrease in the elastic. Finally, continuum hyper elastic model of contact lens is studied for three different loading scenarios using Finite Element Model. "

Polydimethylsiloxane (PDMS) mechanical properties were measured using custom-built compression test device. PDMS elastic modulus can be varied with the elastomer base to the curing agent ratio, i.e. by changing the cross-linking density. PDMS samples with different crosslink density in terms of their elastic modulus were measured. In this project the PDMS samples with the base/curing agent ratio ranging from 5:1 to 20:1 were tested. The elastic modulus varied with the amount of the crosslinker, and ranged from 0.8 MPa to 4.44 MPa. The compression device was modified by adding digital displacement gauges to measure the lateral strain of the sample, which allowed obtaining the true stress-strain data. Since the unloading behavior was different than the loading behavior of the viscoelastic PDMS, it was utilized to asses viscoelastic properties of the polymer. The thesis describes a simple method for measuring mechanical properties of soft polymeric materials.

This thesis presents a microfluidic strategy for the in-flow definition of a 3D soft material with a tunable and perfusable microstructure. The strategy was enabled by a microfluidic device containing up to fifteen layers that were individually patterned in polydimethylsiloxane (PDMS). Each layer contained an array of ten to thirty equidistantly spaced microchannels. Two miscible fluids (aqueous solutions of alginate and CaCl2) were used as working fluids and were introduced into the device via separate inlets and distributed on chip to form a complex fluid at the exit. The fluid microstructure was tuned by altering the flow rates of the working fluids. Upon solidification of alginate in the presence of calcium chloride, the created microstructure was retained and a soft material with a tunable microstructure was formed. The produced material was subsequently perfused using the same microfluidic architecture. The demonstrated strategy potentially offers applications in materials science and regenerative medicine.

This thesis presents a microfluidic strategy for the in-flow definition of a 3D soft material with a tunable and perfusable microstructure. The strategy was enabled by a microfluidic device containing up to fifteen layers that were individually patterned in polydimethylsiloxane (PDMS). Each layer contained an array of ten to thirty equidistantly spaced microchannels. Two miscible fluids (aqueous solutions of alginate and CaCl2) were used as working fluids and were introduced into the device via separate inlets and distributed on chip to form a complex fluid at the exit. The fluid microstructure was tuned by altering the flow rates of the working fluids. Upon solidification of alginate in the presence of calcium chloride, the created microstructure was retained and a soft material with a tunable microstructure was formed. The produced material was subsequently perfused using the same microfluidic architecture. The demonstrated strategy potentially offers applications in materials science and regenerative medicine.

abstract: Deformable heat exchangers could provide a multitude of previously untapped advantages ranging from adaptable performance via macroscale, dynamic shape change (akin to dilation/constriction seen in blood vessels) to enhanced heat transfer at thermal interfaces through microscale, surface deformations. So far, making deformable, ‘soft heat exchangers’ (SHXs) has been limited by the low thermal conductivity of materials with suitable mechanical properties. The recent introduction of liquid-metal embedded elastomers by Bartlett et al1 has addressed this need. Specifically, by remaining soft and stretchable despite the addition of filler, these thermally conductive composites provide an ideal material for the new class of “soft thermal systems”, which is introduced in this work. Understanding such thermal systems will be a key element in enabling technology that require high levels of stretchability, such as thermoregulatory garments, soft electronics, wearable electronics, and high-powered robotics. Shape change inherent to SHX operation has the potential to violate many conventional assumptions used in HX design and thus requires the development of new theoretical approaches to predict performance. To create a basis for understanding these devices, this work highlights two sequential studies. First, the effects of transitioning to a surface deformable, SHX under steady state static conditions in the setting of a liquid cooling device for thermoregulation, electronics and robotics applications was explored. In this study, a thermomechanical model was built and validated to predict the thermal performance and a system wide analysis to optimize such devices was carried out. Second, from a more fundamental perspective, the effects of SHXs undergoing transient shape deformation during operation was explored. A phase shift phenomenon in cooling performance dependent on stretch rate, stretch extent and thermal diffusivity was discovered and explained. With the use of a time scale analysis, the extent of quasi-static assumption viability in modeling such systems was quantified and multiple shape modulation regime limits were defined. Finally, nuance considerations and future work of using liquid metal-silicone composites in SHXs were discussed. / Dissertation/Thesis / Doctoral Dissertation Engineering 2020

The commercial exoskeletons are often heavy and bulky, thus reducing the weight and simplifying the form factor becomes a critical task. This thesis details the process of designing and making a low-profile, cable-driven arm exoskeleton. Many advanced methods are explored: 3D scanning, generative design, soft material, compliant joint, additive manufacturing, and 3D latticing. The experiments on TPU kerf cut found that the stress-strain curve of the sample can be modified by changing the cut pattern, it is even possible to control the linear region. The TPU TPMS test showed that given the same volume, changing the lattice parameters can result in different bending stress-strain curves. This thesis also provides many prototypes, test data, and samples for future reference. / Master of Science / Wearing an exoskeleton should be easy and stress-free, but many of the available models are not ergonomic nor user-friendly. To make an exoskeleton that is inviting and comfortable to wear, various nontraditional methods are used. The arm exoskeleton prototype has a lightweight and ergonomic frame, the joints are soft and compact, the cable-driven system is safe and low-profile. This design also brings aesthetics to the exoskeleton which closes the gap between engineering and design.