A multi-scale approach to shaping carbon nanotube structures for hollow microneedles

The concept of a carbon nanotube microneedle array is explored in this thesis from multiple perspectives including microneedle fabrication, physical aspects of transdermal delivery, and in vivo transdermal drug delivery experiments. Starting with standard techniques in carbon nanotube (CNT) fabrication, including catalyst patterning and chemical vapor deposition, vertically-aligned carbon nanotubes are utilized as a scaffold to define the shape of the hollow microneedle. Passive, scalable techniques based on capillary action and unique photolithographic methods are utilized to produce a CNT-polymer composite microneedle. Specific examples of CNT-polyimide and CNT-epoxy microneedles are investigated. Further analysis of the transport properties of polymer resins reveals general requirements for applying arbitrary polymers to the fabrication process.

The bottom-up fabrication approach embodied by vertically-aligned carbon nanotubes allows for more direct construction of complex high-aspect ratio features than standard top-down fabrication approaches, making microneedles an ideal application for CNTs. However, current vertically-aligned CNT fabrication techniques only allow for the production of extruded geometries with a constant cross-sectional area, such as cylinders. To rectify this limitation, isotropic oxygen etching is introduced as a novel fabrication technique to create true 3D CNT geometry. Oxygen etching is utilized to create a conical geometry from a cylindrical CNT structure as well as create complex shape transformations in other CNT geometries.

CNT-polymer composite microneedles are anchored onto a common polymer base less than 50 µm thick, which allows for the microneedles to be incorporated into multiple drug delivery platforms, including modified hypodermic syringes and silicone skin patches. Cylindrical microneedles are fabricated with 100 µm outer diameter and height of 200-250 µm with a central cavity, or lumen, diameter of 30 µm to facilitate liquid drug flow. In vitro delivery experiments in swine skin demonstrate the ability of the microneedles to successfully penetrate the skin and deliver aqueous solutions.

An in vivo study was performed to assess the ability of the CNT-polymer microneedles to deliver drugs transdermally. CNT-polymer microneedles are attached to a hand actuated silicone skin patch that holds a liquid reservoir of drugs. Fentanyl, a potent analgesic, was administered to New Zealand White Rabbits through 3 routes of delivery: topical patch, CNT-polymer microneedles, and subcutaneous hypodermic injection. Results demonstrate that the CNT-polymer microneedles have a similar onset of action as the topical patch. CNT-polymer microneedles were also vetted as a painless delivery approach compared to hypodermic injection. Comparative analysis with contemporary microneedle designs demonstrates that the delivery achieved through CNT-polymer microneedles is akin to current hollow microneedle architectures. The inherent advantage of applying a bottom-up fabrication approach alongside similar delivery performance to contemporary microneedle designs demonstrates that the CNT-polymer composite microneedle is a viable architecture in the emerging field of painless transdermal delivery.

Topics in vortex motion

Six topics in incompressible, inviscid fluid flow involving vortex motion are presented. The stability of the unsteady flow field due to the vortex filament expanding under the influence of an axial compression is examined in the first chapter as a possible model of the vortex bursting observed in aircraft contrails. The filament with a stagnant core is found to be unstable to axisymmetric disturbances. For initial disturbances with the form of axisymmetric Kelvin waves, the filament with a uniformly rotating core is neutrally stable, but the compression causes the disturbance to undergo a rapid increase in amplitude. The time at which the increase occurs is, however, later than the observed bursting times, indicating the bursting phenomenon is not caused by this type of instability.

In the second and third chapters the stability of a steady vortex filament deformed by two-dimensional strain and shear flows, respectively, is examined. The steady deformations are in the plane of the vortex cross-section. Disturbances which deform the filament centerline into a wave which does not propagate along the filament are shown to be unstable and a method is described to calculate the wave number and corresponding growth rate of the amplified waves for a general distribution of vorticity in the vortex core.

In Chapter Four exact solutions are constructed for two-dimensional potential flow over a wing with a free ideal vortex standing over the wing. The loci of positions of the free vortex are found and the lift is calculated. It is found that the lift on the wing can be significantly increased by the free vortex.

The two-dimensional trajectories of an ideal vortex pair near an orifice are calculated in Chapter Five. Three geometries are examined, and the criteria for the vortices to travel away from the orifice are determined.

Finally, Chapter Six reproduces completely the paper, "Structure of a linear array of hollow vortices of finite cross-section," co-authored with G. R. Baker and P. G. Saffman. Free streamline theory is employed to construct an exact steady solution for a linear array of hollow, or stagnant cored vortices. If each vortex has area A and the separation is L, then there are two possible shapes if A^(1/2)/L is less than 0.38 and none if it is larger. The stability of the shapes to two-dimensional, periodic and symmetric disturbances is considered for hollow vortices. The more deformed of the two possible shapes is found to be unstable, while the less deformed shape is stable.

Studies in vortex motion

This thesis covers four different problems in the understanding of vortex sheets, and these are presented in four chapters.

In Chapter 1, free streamline theory is used to determine the steady solutions of an array of identical, hollow or stagnant core vortices in an inviscid, incompressible fluid. Assuming the array is symmetric to rotation through π radians about an axis through any vortex centre, there are two solutions or no solutions depending on whether A^(1/2)/L is less than or greater than 0.38 where A is the area of the vortex and L is the separation distance. Stability analysis shows that the more deformed shape is unstable to infinitesimal symmetric disturbances which leave the centres of the vortices undisplaced.

Chapter 2 is concerned with the roll-up of vortex sheets in homogeneous fluid. The flow over conventional and ring wings is used to test the method of Fink and Soh (1974). Despite modifications which improve the accuracy of the method, unphysical results occur. A possible explanation for this is that small scales are important and an alternate method based on "Cloud-in-Cell" techniques is introduced. The results show small scale growth and amalgamation into larger structures.

The motion of a buoyant pair of line vortices of opposite circulation is considered in Chapter 3. The density difference between the fluid carried by the vortices and the fluid outside is considered small, so that the Boussinesq approximation may be used. A macroscopic model is developed which shows the formation of a detrainment filament and this is included as a modification to the model. The results agree well with the numerical solution as developed by Hill (1975b) and show that after an initial slowdown, the vortices begin to accelerate downwards.

Chapter 4 reproduces completely a paper that has already been published (Baker, Barker, Bofah and Saffman (1974)) on the effect of "vortex wandering" on the measurement of velocity profiles of the trailing vortices behind a wing.

Fabrication, Characterization, And Deformation of 3D Structural Meta-Materials

Current technological advances in fabrication methods have provided pathways to creating architected structural meta-materials similar to those found in natural organisms that are structurally robust and lightweight, such as diatoms. Structural meta-materials are materials with mechanical properties that are determined by material properties at various length scales, which range from the material microstructure (nm) to the macro-scale architecture (μm – mm). It is now possible to exploit material size effect, which emerge at the nanometer length scale, as well as structural effects to tune the material properties and failure mechanisms of small-scale cellular solids, such as nanolattices. This work demonstrates the fabrication and mechanical properties of 3-dimensional hollow nanolattices in both tension and compression. Hollow gold nanolattices loaded in uniaxial compression demonstrate that strength and stiffness vary as a function of geometry and tube wall thickness. Structural effects were explored by increasing the unit cell angle from 30° to 60° while keeping all other parameters constant; material size effects were probed by varying the tube wall thickness, t, from 200nm to 635nm, at a constant relative density and grain size. In-situ uniaxial compression experiments reveal an order-of-magnitude increase in yield stress and modulus in nanolattices with greater lattice angles, and a 150% increase in the yield strength without a concomitant change in modulus in thicker-walled nanolattices for fixed lattice angles. These results imply that independent control of structural and material size effects enables tunability of mechanical properties of 3-dimensional architected meta-materials and highlight the importance of material, geometric, and microstructural effects in small-scale mechanics. This work also explores the flaw tolerance of 3D hollow-tube alumina kagome nanolattices with and without pre-fabricated notches, both in experiment and simulation. Experiments demonstrate that the hollow kagome nanolattices in uniaxial tension always fail at the same load when the ratio of notch length (a) to sample width (w) is no greater than 1/3, with no correlation between failure occurring at or away from the notch. For notches with (a/w) > 1/3, the samples fail at lower peak loads and this is attributed to the increased compliance as fewer unit cells span the un-notched region. Finite element simulations of the kagome tension samples show that the failure is governed by tensile loading for (a/w) < 1/3 but as (a/w) increases, bending begins to play a significant role in the failure. This work explores the flaw sensitivity of hollow alumina kagome nanolattices in tension, using experiments and simulations, and demonstrates that the discrete-continuum duality of architected structural meta-materials gives rise to their flaw insensitivity even when made entirely of intrinsically brittle materials.

Design, Fabrication, and Mechanical Property Analysis of 3D Nanoarchitected Materials

Recent developments in micro- and nanoscale 3D fabrication techniques have enabled the creation of materials with a controllable nanoarchitecture that can have structural features spanning 5 orders of magnitude from tens of nanometers to millimeters. These fabrication methods in conjunction with nanomaterial processing techniques permit a nearly unbounded design space through which new combinations of nanomaterials and architecture can be realized. In the course of this work, we designed, fabricated, and mechanically analyzed a wide range of nanoarchitected materials in the form of nanolattices made from polymer, composite, and hollow ceramic beams. Using a combination of two-photon lithography and atomic layer deposition, we fabricated samples with periodic and hierarchical architectures spanning densities over 4 orders of magnitude from ρ=0.3-300kg/m³ and with features as small as 5nm. Uniaxial compression and cyclic loading tests performed on different nanolattice topologies revealed a range of novel mechanical properties: the constituent nanoceramics used here have size-enhanced strengths that approach the theoretical limit of materials strength; hollow aluminum oxide (Al₂O₃) nanolattices exhibited ductile-like deformation and recovered nearly completely after compression to 50% strain when their wall thicknesses were reduced below 20nm due to the activation of shell buckling; hierarchical nanolattices exhibited enhanced recoverability and a near linear scaling of strength and stiffness with relative density, with E∝ρ^1.04 and σy∝ρ^1.17 for hollow Al₂O₃ samples; periodic rigid and non-rigid nanolattice topologies were tested and showed a nearly uniform scaling of strength and stiffness with relative density, marking a significant deviation from traditional theories on “bending” and “stretching” dominated cellular solids; and the mechanical behavior across all topologies was highly tunable and was observed to strongly correlate with the slenderness λ and the wall thickness-to-radius ratio t/a of the beams. These results demonstrate the potential of nanoarchitected materials to create new highly tunable mechanical metamaterials with previously unattainable properties.