Fabrication of high-aspect-ratio polymer microstructures and hierarchical textures using carbon nanotube composite master molds

Scalable and cost effective patterning of polymer structures and their surface textures is essential to engineer material properties such as liquid wetting and dry adhesion, and to design artificial biological interfaces. Further, fabrication of high-aspect-ratio microstructures often requires controlled deep-etching methods or high-intensity exposure. We demonstrate that carbon nanotube (CNT) composites can be used as master molds for fabrication of high-aspect-ratio polymer microstructures having anisotropic nanoscale textures. The master molds are made by growth of vertically aligned CNT patterns, capillary densification of the CNTs using organic solvents, and capillary-driven infiltration of the CNT structures with SU-8. The composite master structures are then replicated in SU-8 using standard PDMS transfer molding methods. By this process, we fabricated a library of replicas including vertical micro-pillars, honeycomb lattices with sub-micron wall thickness and aspect ratios exceeding 50:1, and microwells with sloped sidewalls. This process enables batch manufacturing of polymer features that capture complex nanoscale shapes and textures, while requiring only optical lithography and conventional thermal processing. © 2011 The Royal Society of Chemistry.

Non-destructive characterization of structural hierarchy within aligned carbon nanotube assemblies

Understanding and controlling the hierarchical self-assembly of carbon nanotubes (CNTs) is vital for designing materials such as transparent conductors, chemical sensors, high-performance composites, and microelectronic interconnects. In particular, many applications require high-density CNT assemblies that cannot currently be made directly by low-density CNT growth, and therefore require post-processing by methods such as elastocapillary densification. We characterize the hierarchical structure of pristine and densified vertically aligned multi-wall CNT forests, by combining small-angle and ultra-small-angle x-ray scattering (USAXS) techniques. This enables the nondestructive measurement of both the individual CNT diameter and CNT bundle diameter within CNT forests, which are otherwise quantified only by delicate and often destructive microscopy techniques. Our measurements show that multi-wall CNT forests grown by chemical vapor deposition consist of isolated and bundled CNTs, with an average bundle diameter of 16 nm. After capillary densification of the CNT forest, USAXS reveals bundles with a diameter 4 m, in addition to the small bundles observed in the as-grown forests. Combining these characterization methods with new CNT processing methods could enable the engineering of macro-scale CNT assemblies that exhibit significantly improved bulk properties. © 2011 American Institute of Physics.

Fabrication and electrical integration of robust carbon nanotube micropillars by self-directed elastocapillary densification

Vertically aligned carbon nanotube (CNT) 'forest' microstructures fabricated by chemical vapor deposition (CVD) using patterned catalyst films typically have a low CNT density per unit area. As a result, CNT forests have poor bulk properties and are too fragile for integration with microfabrication processing. We introduce a new self-directed capillary densification method where a liquid is controllably condensed onto and evaporated from the CNT forests. Compared to prior approaches, where the substrate with CNTs is immersed in a liquid, our condensation approach gives significantly more uniform structures and enables precise control of the CNT packing density. We present a set of design rules and parametric studies of CNT micropillar densification by self-directed capillary action, and show that self-directed capillary densification enhances Young's modulus and electrical conductivity of CNT micropillars by more than three orders of magnitude. Owing to the outstanding properties of CNTs, this scalable process will be useful for the integration of CNTs as a functional material in microfabricated devices for mechanical, electrical, thermal and biomedical applications. © 2011 IOP Publishing Ltd.

A temperature sensor from a self-assembled carbon nanotube microbridge

Recent studies show that carbon nanotubes (CNTs) can be used as temperature sensors, and offer great opportunities towards extreme miniaturization, high sensitivity, low power consumption, and rapid response. Previous CNT based temperature sensors are fabricated by either dielectrophoresis or piece-wise alignment of read-out electronics around randomly dispersed CNTs. We introduce a new deterministic and parallel microsensor fabrication method based on the self-assembly of CNTs into three-dimensional microbridges. We fabricated prototype microbridge sensors on patterned electrodes, and found their sensitivity to be better than -0.1 %/K at temperatures between 300K and 420K. This performance is comparable to previously published CNT based temperature sensors. Importantly, however, our research shows how unique sensor architectures can be made by self-assembly, which can be achieved using batch processing rather than piecewise assembly. ©2010 IEEE.

Self-similar organization of arrays of individual carbon nanotubes and carbon nanotube micropillars

It is well-known that carbon nanotube (CNT) growth from a dense arrangement of catalyst nanoparticles creates a vertically aligned CNT forest. CNT forests offer attractive anisotropic mechanical, thermal, and electrical properties, and their anisotropic structure is enabled by the self-organization of a large number of CNTs. This process is governed by individual CNT diameter, spacing, and the CNT-to-CNT interaction. However, little information is known about the self-organization of CNTs within a forest. Insight into the self-organization is, however, essential for tailoring the properties of the CNT forests for applications such as electrical interconnects, thermal interfaces, dry adhesives and energy storage. We demonstrate that arrays of CNT micropillars having micron-scale diameters organize in a similar manner as individual CNTs within a forest. For example, as previously demonstrated for individual CNTs within a forest, entanglement of small-diameter CNT micropillars during the initial stage of growth creates a film of entwined pillars. This layer enables coordinated subsequent growth of the pillars in the vertical direction, in a case where isolated pillars would not grow in a self-supporting fashion. Finally, we provide a detailed overview of the self-organization as a function of the diameter, length and spacing of the CNT pillars. This study, which is applicable to many one-dimensional nanostructured films, demonstrates guidelines for tailoring the self-organization which can enable control of the collective mechanical, electrical and interfacial properties of the films. © 2009 Elsevier B.V. All rights reserved.

Controlled growth orientation of carbon nanotube pillars by catalyst patterning in microtrenches

We present a novel method for controlling the growth orientation of individual carbon nanotube (CNT) microstructures on a silicon wafer substrate. Our method controls the CNT forest orientation by patterning the catalyst layer used in the CNTs growth on slanted KOH edges. The overlap of catalyst area on the horizontal bottom and sloped sidewall surfaces of the KOH-etched substrate enables precise variation of the growth direction. These inclined structures can profit from the outstanding mechanical, electrical, thermal, and optical properties of CNTs and can therefore improve the performance of several MEMS devices. Inclined CNT microstructures could for instance be used as cantilever springs in probe card arrays, as tips in dip-pen lithography, and as sensing element in advanced transducers. ©2009 IEEE.

Self-assembled multilayer graphene oxide membrane and carbon nanotubes synthesized using a rare form of natural graphite

The fabrication of flexible multilayer graphene oxide (GO) membrane and carbon nanotubes (CNTs) using a rare form of high-purity natural graphite, vein graphite, is reported for the first time. Graphite oxide is synthesized using vein graphite following Hummer's method. By facilitating functionalized graphene sheets in graphite oxide to self-assemble, a multilayer GO membrane is fabricated. Electric arc discharge is used to synthesis CNTs from vein graphite. Both multilayer GO membrane and CNTs are investigated using microscopy and spectroscopy experiments, i.e., scanning electron microscopy (SEM), atomic force microscopy (AFM), high-resolution transmission electron microscopy (HRTEM), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), thermogravimetric analysis (TGA), core level photoelectron spectroscopy, and C K-edge X-ray absorption spectroscopy (NEXAFS), to characterize their structural and topographical properties. Characterization of vein graphite using different techniques reveals that it has a large number of crystallites, hence the large number of graphene sheets per crystallite, preferentially oriented along the (002) plane. NEXAFS and core level spectra confirm that vein graphite is highly crystalline and pure. Fourier transform infrared (FT-IR) and C 1s core level spectra show that oxygen functionalities (-C-OH, -CO,-C-O-C-) are introduced into the basal plane of graphite following chemical oxidation. Carbon nanotubes are produced from vein graphite through arc discharge without the use of any catalyst. HRTEM confirm that multiwalled carbon nanotube (MWNTs) are produced with the presence of some structure in the central pipe. A small percentage of single-walled nanotubes (SWNTs) are also produced simultaneously with MWNTs. Spectroscopic and microscopic data are further discussed here with a view to using vein graphite as the source material for the synthesis of carbon nanomaterials. © 2013 American Chemical Society.

Flexible conversion ratio fast reactors: Overview

Conceptual designs of lead-cooled and liquid salt-cooled fast flexible conversion ratio reactors were developed. The performance achievable by the unity conversion ratio cores of these reactors was compared to an existing supercritical carbon dioxide-cooled (S-CO2) fast reactor design and an uprated version of an existing sodium-cooled fast reactor. All concepts have cores rated at 2400 MWt. The cores of the liquid-cooled reactors are placed in a large-pool-type vessel with dual-free level, which also contains four intermediate heat exchangers (IHXs) coupling a primary coolant to a compact and efficient supercritical CO2 Brayton cycle power conversion system. The S-CO2 reactor is directly coupled to the S-CO2 Brayton cycle power conversion system. Decay heat is removed passively using an enhanced reactor vessel auxiliary cooling system (RVACS) and a passive secondary auxiliary cooling system (PSACS). The selection of the water-cooled versus air-cooled heat sink for the PSACS as well as the analysis of the probability that the PSACS may fail to complete its mission was performed using risk-informed methodology. In addition to these features, all reactors were designed to be self-controllable. Further, the liquid-cooled reactors utilized common passive decay heat removal systems whereas the S-CO2 uses reliable battery powered blowers for post-LOCA decay heat removal to provide flow in well defined regimes and to accommodate inadvertent bypass flows. The multiple design limits and challenges which constrained the execution of the four fast reactor concepts are elaborated. These include principally neutronics and materials challenges. The neutronic challenges are the large positive coolant reactivity feedback, small fuel temperature coefficient, small effective delayed neutron fraction, large reactivity swing and the transition between different conversion ratio cores. The burnup, temperature and fluence constraints on fuels, cladding and vessel materials are elaborated for three categories of material - materials currently available, available on a relatively short time scale and available only with significant development effort. The selected fuels are the metallic U-TRU-Zr (10% Zr) for unity conversion ratio and TRU-Zr (75% Zr) for zero conversion ratio. The principal selected cladding and vessel materials are HT-9 and A533 or A508, respectively, for current availability, T-91 and 9Cr-1Mo steel for relatively short-term availability and oxide dispersion strengthened ferritic steel (ODS) available only with significant development. © 2009 Elsevier B.V. All rights reserved.

Flexible conversion ratio lead cooled reactor design

This paper presents the neutronic design of a lead cooled fast reactor with flexible conversion ratio. The main objective of the design is to accommodate interchangeably within the same reactor core a wide range of transuranic actinides management strategies: from pure burning to self-sustainable breeding. Two, the most limiting, core design options with unity and zero conversion ratios are described. Neutronic feasibility of both designs was demonstrated through calculation of reactivity control and fuel loading requirements, fluence limits, power peaking factors, and reactivity feedback coefficients.

Liquid salt cooled flexible conversion ratio fast reactor: Neutronic design

This paper presents the neutronic design of a liquid salt cooled fast reactor with flexible conversion ratio. The main objective of the design is to accommodate interchangeably within the same reactor core alternative transuranic actinides management strategies ranging from pure burning to self-sustainable breeding. Two, the most limiting, core design options with unity and zero conversion ratios are described. Ternary, NaCl-KCl-MgCl2 salt was chosen as a coolant after a rigorous screening process, due to a combination of favourable neutronic and heat transport properties. Large positive coolant temperature reactivity coefficient was identified as the most significant design challenge. A wide range of strategies aiming at the reduction of the coolant temperature coefficient to assure self-controllability of the core in the most limiting unprotected accidents were explored. However, none of the strategies resulted in sufficient reduction of the coolant temperature coefficient without significantly compromising the core performance characteristics such as power density or cycle length. Therefore, reactivity control devices known as lithium thermal expansion modules were employed instead. This allowed achieving all the design goals for both zero and unity conversion ratio cores. The neutronic feasibility of both designs was demonstrated through calculation of reactivity control and fuel loading requirements, fluence limits, power peaking factors, and reactivity feedback coefficients. © 2009 Elsevier B.V. All rights reserved.