Polymorphic Elastocapillarity: Kinetically Reconfigurable Self-Assembly of Hair Bundles by Varying the Drain Rate

We report various patterns formed by draining liquid from hair bundles. Hair-like fibers arranged in triangular bundles self-assemble into various cross sections when immersed in liquid then removed. The combinations of their length and the kinetics, represented by the drain rate, lead to various polymorphic self-assemblies: concave hexagonal, triangular, circular, or inverted triangular patterns. The equilibrium of these shapes is predicted by elastocapillarity, the balance between the bending strain energy of the hairs and the surface energy of the liquid. Shapes with a larger strain energy, such as the inverted triangular bundles, are obtained at the higher liquid drain rates. This polymorphic self-assembly is fully reversible by rewetting and draining and can have applications in multifunctional dynamic textures

Polymorphic Elastocapillarity: Kinetically Reconfigurable Self-Assembly of Hair Bundles by Varying the Drain Rate

We report various patterns formed by draining liquid from hair bundles. Hair-like fibers arranged in triangular bundles self-assemble into various cross sections when immersed in liquid then removed. The combinations of their length and the kinetics, represented by the drain rate, lead to various polymorphic self-assemblies: concave hexagonal, triangular, circular, or inverted triangular patterns. The equilibrium of these shapes is predicted by elastocapillarity, the balance between the bending strain energy of the hairs and the surface energy of the liquid. Shapes with a larger strain energy, such as the inverted triangular bundles, are obtained at the higher liquid drain rates. This polymorphic self-assembly is fully reversible by rewetting and draining and can have applications in multifunctional dynamic textures

Polymorphic Elastocapillarity: Kinetically Reconfigurable Self-Assembly of Hair Bundles by Varying the Drain Rate

We report various patterns formed by draining liquid from hair bundles. Hair-like fibers arranged in triangular bundles self-assemble into various cross sections when immersed in liquid then removed. The combinations of their length and the kinetics, represented by the drain rate, lead to various polymorphic self-assemblies: concave hexagonal, triangular, circular, or inverted triangular patterns. The equilibrium of these shapes is predicted by elastocapillarity, the balance between the bending strain energy of the hairs and the surface energy of the liquid. Shapes with a larger strain energy, such as the inverted triangular bundles, are obtained at the higher liquid drain rates. This polymorphic self-assembly is fully reversible by rewetting and draining and can have applications in multifunctional dynamic textures

Polymorphic Elastocapillarity: Kinetically Reconfigurable Self-Assembly of Hair Bundles by Varying the Drain Rate

We report various patterns formed by draining liquid from hair bundles. Hair-like fibers arranged in triangular bundles self-assemble into various cross sections when immersed in liquid then removed. The combinations of their length and the kinetics, represented by the drain rate, lead to various polymorphic self-assemblies: concave hexagonal, triangular, circular, or inverted triangular patterns. The equilibrium of these shapes is predicted by elastocapillarity, the balance between the bending strain energy of the hairs and the surface energy of the liquid. Shapes with a larger strain energy, such as the inverted triangular bundles, are obtained at the higher liquid drain rates. This polymorphic self-assembly is fully reversible by rewetting and draining and can have applications in multifunctional dynamic textures

Polymorphic Elastocapillarity: Kinetically Reconfigurable Self-Assembly of Hair Bundles by Varying the Drain Rate

We report various patterns formed by draining liquid from hair bundles. Hair-like fibers arranged in triangular bundles self-assemble into various cross sections when immersed in liquid then removed. The combinations of their length and the kinetics, represented by the drain rate, lead to various polymorphic self-assemblies: concave hexagonal, triangular, circular, or inverted triangular patterns. The equilibrium of these shapes is predicted by elastocapillarity, the balance between the bending strain energy of the hairs and the surface energy of the liquid. Shapes with a larger strain energy, such as the inverted triangular bundles, are obtained at the higher liquid drain rates. This polymorphic self-assembly is fully reversible by rewetting and draining and can have applications in multifunctional dynamic textures

Highly Consistent Atmospheric Pressure Synthesis of Carbon Nanotube Forests by Mitigation of Moisture Transients

Consistent synthesis of carbon nanotubes (CNTs) using laboratory-scale methods is essential to the development of commercial applications, particularly with respect to the verification of recipes that achieve control of CNT diameter, chirality, alignment, and density. Here, we report that transients in the moisture level and carbon concentration during the chemical vapor deposition (CVD) process for vertically aligned CNT “forests” can contribute significantly to run-to-run variation of height and density. Then, we show that highly consistent CNT forest growth can be achieved by physically decoupling the catalyst annealing and hydrocarbon exposure steps, to allow the gas composition to stabilize between the steps. This decoupling is achieved using a magnetically actuated transfer arm to move the substrate rapidly into and out of the CVD reactor. Compared to a reference process where the sample resides in the furnace throughout the process, the decoupled method gives 21% greater CNT forest height, reduces the run-to-run variance of height by 76%, and results in forests with improved vertical alignment (Herman’s orientation parameter of 0.68 compared to 0.50). Building on this foundation, we study the influence of the moisture level during the CNT growth step and find a 30% improvement in growth rate going from the baseline condition (<15 ppm) to 40 ppm. Interestingly, however, the increased moisture concentration does not improve the catalyst lifetime or the CNT forest density, warranting further study of the role of moisture on CNT nucleation versus growth

Statistical Analysis of Variation in Laboratory Growth of Carbon Nanotube Forests and Recommendations for Improved Consistency

While many promising applications have been demonstrated for vertically aligned carbon nanotube (CNT) forests, lack of consistency in results (<i>e</i>.<i>g</i>., CNT quality, height, and density) continues to hinder knowledge transfer and commercialization. For example, it is well known that CNT growth can be influenced by small concentrations of water vapor, carbon deposits on the reactor wall, and experiment-to-experiment variations in pressure within the reaction chamber. However, even when these parameters are controlled during synthesis, we found that variations in ambient lab conditions can overwhelm attempts to perform parametric optimization studies. We established a standard growth procedure, including the chemical vapor deposition (CVD) recipe, while we varied other variables related to the furnace configuration and experimental procedure. Statistical analysis of 280 samples showed that ambient humidity, barometric pressure, and sample position in the CVD furnace contribute significantly to experiment-to-experiment variation. We investigated how these factors lead to CNT growth variation and recommend practices to improve process repeatability. Initial results using this approach reduced run-to-run variation in CNT forest height and density by more than 50%

Mechanics of Capillary Forming of Aligned Carbon Nanotube Assemblies

Elastocapillary self-assembly is emerging as a versatile technique to manufacture three-dimensional (3D) microstructures and complex surface textures from arrangements of micro- and nanoscale filaments. Understanding the mechanics of capillary self-assembly is essential to engineering of properties such as shape-directed actuation, anisotropic wetting and adhesion, and mechanical energy transfer and dissipation. We study elastocapillary self-assembly (herein called “capillary forming”) of carbon nanotube (CNT) microstructures, combining <i>in situ</i> optical imaging, micromechanical testing, and finite element modeling. By imaging, we identify sequential stages of liquid infiltration, evaporation, and solid shrinkage, whose kinetics relate to the size and shape of the CNT microstructure. We couple these observations with measurements of the orthotropic elastic moduli of CNT forests to understand how the dynamic of shrinkage of the vapor–liquid interface is coupled to the compression of the forest. We compare the kinetics of shrinkage to the rate of evporation from liquid droplets having the same size and geometry. Moreover, we show that the amount of shrinkage during evaporation is governed by the ability of the CNTs to slip against one another, which can be manipulated by the deposition of thin conformal coatings on the CNTs by atomic layer deposition (ALD). This insight is confirmed by finite element modeling of pairs of CNTs as corrugated beams in contact and highlights the coupled role of elasticity and friction in shrinkage and stability of nanoporous solids. Overall, this study shows that nanoscale porosity can be tailored via the filament density and adhesion at contact points, which is important to the development of lightweight multifunctional materials

Mechanics of Capillary Forming of Aligned Carbon Nanotube Assemblies

Elastocapillary self-assembly is emerging as a versatile technique to manufacture three-dimensional (3D) microstructures and complex surface textures from arrangements of micro- and nanoscale filaments. Understanding the mechanics of capillary self-assembly is essential to engineering of properties such as shape-directed actuation, anisotropic wetting and adhesion, and mechanical energy transfer and dissipation. We study elastocapillary self-assembly (herein called “capillary forming”) of carbon nanotube (CNT) microstructures, combining <i>in situ</i> optical imaging, micromechanical testing, and finite element modeling. By imaging, we identify sequential stages of liquid infiltration, evaporation, and solid shrinkage, whose kinetics relate to the size and shape of the CNT microstructure. We couple these observations with measurements of the orthotropic elastic moduli of CNT forests to understand how the dynamic of shrinkage of the vapor–liquid interface is coupled to the compression of the forest. We compare the kinetics of shrinkage to the rate of evporation from liquid droplets having the same size and geometry. Moreover, we show that the amount of shrinkage during evaporation is governed by the ability of the CNTs to slip against one another, which can be manipulated by the deposition of thin conformal coatings on the CNTs by atomic layer deposition (ALD). This insight is confirmed by finite element modeling of pairs of CNTs as corrugated beams in contact and highlights the coupled role of elasticity and friction in shrinkage and stability of nanoporous solids. Overall, this study shows that nanoscale porosity can be tailored via the filament density and adhesion at contact points, which is important to the development of lightweight multifunctional materials

High-Speed <i>in Situ</i> X-ray Scattering of Carbon Nanotube Film Nucleation and Self-Organization

The production of high-performance carbon nanotube (CNT) materials demands understanding of the growth behavior of individual CNTs as well as collective effects among CNTs. We demonstrate the first use of grazing incidence small-angle X-ray scattering to monitor in real time the synthesis of CNT films by chemical vapor deposition. We use a custom-built cold-wall reactor along with a high-speed pixel array detector resulting in a time resolution of 10 msec. Quantitative models applied to time-resolved X-ray scattering patterns reveal that the Fe catalyst film first rapidly dewets into well-defined hemispherical particles during heating in a reducing atmosphere, and then the particles coarsen slowly upon continued annealing. After introduction of the carbon source, the initial CNT diameter distribution closely matches that of the catalyst particles. However, significant changes in CNT diameter can occur quickly during the subsequent CNT self-organization process. Correlation of time-resolved orientation data to X-ray scattering intensity and height kinetics suggests that the rate of self-organization is driven by both the CNT growth rate and density, and vertical CNT growth begins abruptly when CNT alignment reaches a critical threshold. The dynamics of CNT size evolution and self-organization vary according to the catalyst annealing conditions and substrate temperature. Knowledge of these intrinsically rapid processes is vital to improve control of CNT structure and to enable efficient manufacturing of high-density arrays of long, straight CNTs