The manufacture of tailored carbon‐based adsorbent structures with exceptionally low‐pressure drops and improved kinetics using stereolithographic 3D printing is presented. Adsorbent structures are printed from commercial resins with square, circular, and hexagonal cross‐sectional microchannels. These structures can reduce energy use by 50–95% compared to conventional carbon‐packed beds. The activated 3D printed carbon achieves Brunauer–Emmett–Teller surface areas over 1000 m2 g−1 and shows outstanding butane adsorption capacities, over twice the capacity of a commercial carbon and a comparable capacity to phenolic‐based carbons. The structures also show excellent uptakes of cyclohexane, up to 0.62 g g−1 in a saturated feed. The introduction of complex axial geometries including spirals and chevrons enable superior adsorption kinetics and premature breakthrough of contaminants at high gas flow rates. These results demonstrate the success of intelligent manufacturing of low‐pressure drop, high‐capacity micro‐structured adsorbents, allowing for the development of gas separation technologies for applications such as greenhouse gas removal and respiratory protection.
The formation of non-equilibrium and transient phases in metastable beta titanium alloys during low temperature thermal treatments is currently of great interest, as they provide a potential method of controlling the size and distribution of the equilibrium alpha phase and, hence, the resulting mechanical properties. Here, for the first time, we report on the formation of a new, B2 structured phase in the Ti-Mo system. The phase was observed in electron transparent material during in situ, and following ex situ, heat treatment at 300 degrees C. The B2 phase was enriched in Mo compared to the surrounding matrix material and formed in regular arrays of approximately square cross-section particles interspersed by thin beta channels. Electron diffraction indicated that the lattice parameter of this new phase was smaller than that of the parent phase, leading to significant strain in the beta channels. Critically, the B2 phase was only observed in material that had been electro-polished prior to heat treatment, and, therefore, it is hypothesised that this phase forms as a result of the preparation method and thin foil effects.
We investigate the impact of a fluorine plasma treatment used to obtain enhancement-mode operation on the structure and chemistry at the nanometer and atomic scales of an InAlN/GaN field effect transistor. The fluorine plasma treatment is successful in that enhancement mode operation is achieved with a +2.8 V threshold voltage. However, the InAlN barrier layers are observed to have been damaged by the fluorine treatment with their thickness being reduced by up to 50%. The treatment also led to oxygen incorporation within the InAlN barrier layers. Furthermore, even in the as-grown structure, Ga was unintentionally incorporated during the growth of the InAlN barrier. The impact of both the reduced barrier thickness and the incorporated Ga within the barrier on the transistor properties has been evaluated theoretically and compared to the experimentally determined two-dimensional electron gas density and threshold voltage of the transistor. For devices without fluorine treatment, the two-dimensional electron gas density is better predicted if the quaternary nature of the barrier is taken into account. For the fluorine treated device, not only the changes to the barrier layer thickness and composition, but also the fluorine doping needs to be considered to predict device performance. These studies reveal the factors influencing the performance of these specific transistor structures and highlight the strengths of the applied nanoscale characterisation techniques in revealing information relevant to device performance.
Raman spectroscopy's D:G ratio is a well-known indicator of graphitic crystallinity in single-wall carbon nanotubes (SWCNTs) with widespread qualitative application to macroscopic CNT assemblies. Here, we show how the D:G ratio yields quantitative characteristic crystal length features that is remarkably independent of SWCNT chirality when purified SWCNTs are in a high density, heavily bundled textile form. Purified, unaligned, SWCNT films of enriched length distributions and controlled chirality responded in ways consistent with power law behaviour, where the D:G ratio is proportional to the fourth power of excitation wavelength, inversely proportional to SWCNT length, and fits to a master curve independent of electronic species concentration. This behaviour, matching the established response of graphite and graphene, unexpectedly persists despite complications from chirality-dependent resonances unique to SWCNTs. We also show that textiles comprising of aligned, long length CNTs defy these simple power laws until defective multiwall CNTs and impurities are removed post-process, and only if sample heating under the Raman laser is minimized. Adjusting the Raman laser beam diameter up to 6 mm, which is well beyond the average CNT length, we propose that the CNT textile's characteristic crystal length is the CNT length or, with point defects, the distance between point defects. (C) 2017 Elsevier Ltd. All rights reserved.
An isothermal section of the Fe-Mo-Ti ternary system at 1000°C has been constructed using data acquired from a series of seven alloys. The limit of solubility of Fe in the continuous A2 phase field between Ti and Mo has been determined, as have the extents to which Mo may be accommodated in the B2 TiFe phase, and Ti in the D85 Fe7Mo6 phase. The B2, D85 and C14 Fe2 (Ti, Mo) intermetallics were found to have limited tolerance for non-stoichiometric compositions. The positions of the A2+B2+C14 and A2+C14+D85 three-phase fields were determined, along with the extents of the A2+B2, A2+D85, A2+C14, C14+B2 and C14+D85 two-phase fields. No ternary phases were observed in any of the alloys studied.
A polycrystalline L1(2)-hardened Co-base superalloy was creep deformed at 750 degrees C. The investigation of the deformed microstructure in the transmission electron microscope revealed microtwinning to be the prevailing deformation mechanism. The detected twins spanned the entire grain and cut through both, gamma and gamma'. Detailed high-resolution transmission electron microscopy investigations indicated that twin growth takes place by the slip of single a/6 (112) partial dislocations along the twin boundary. Further analysis of the twin boundaries in the gamma' phase revealed segregation of elements known to decrease the stacking fault energy and a local depletion of gamma' forming elements. We propose that this segregation behavior enables subsequent a/6 < 112 > dislocations to easily slip along the twin boundary and further thicken the twins in the process. (C) 2016 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
Reactions inside the pores of metal-organic frameworks (MOFs) offer potential for controlling polymer structures with regularity to sub-nanometre scales. We report a wet-chemistry route to poly3,4-ethylenedioxythiophene (PEDOT)-MOF composites. After a two-step removal of the MOF template we obtain unique and stable macroscale structures of this conductive polymer with some nano-scale regularity.
This work discusses the effects of alloying on the coarsening behaviour of the L1(2) ordered gamma' phase and the structure of the gamma/gamma' interfaces in three Co-Al-W base superalloys aged at similar to 90 degrees C below the respective solvus temperatures: Co-7Al-7W, Co-10Al-5W-2Ta and Co-7Al-7W-20Ni (at.%). The coarsening kinetics are adequately characterised by the classical Lifshitz-Slyozov-Wagner model for Ostwald ripening. Co-7Al-7W exhibited much slower coarsening than its quaternary derivatives. Alloying can be exploited to modify the coarsening kinetics either by increasing the solvus temperature by adding tantalum, or by adding nickel to shift the rate controlling mechanism towards dependence on the diffusion of aluminium rather than tungsten. Lattice resolution STEM imaging was used to measure the widths of the order disorder (structural) and Z-contrast (compositional) gradients across the gamma/gamma' interfaces. Similarly to nickel base superalloys, the compositional gradient was found to be wider than the structural. Co-7Al-7W-20Ni had much wider interface gradients than Co-7Al-7W and Co-10Al-5W-2Ta, which suggests that its gamma' phase stoichiometry is less constrained. A possible correlation between temperature and misfit normalised r vs. t(1/3) coarsening rate coefficients and the structural gradient width has also been identified, whereby alloys with wider interfaces exhibit faster coarsening rates. (C) 2016 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
Methods are presented for aligning the pivot point of a precessing electron probe in the scanning transmission electron microscope (STEM) and for assessing the spatial resolution in scanning precession electron diffraction (SPED) experiments. The alignment procedure is performed entirely in diffraction mode, minimising probe wander within the bright-field (BF) convergent beam electron diffraction (CBED) disk and is used to obtain high spatial resolution SPED maps. Through analysis of the power spectra of virtual bright-field images extracted from the SPED data, the precession-induced blur was measured as a function of precession angle. At low precession angles, SPED spatial resolution was limited by electronic noise in the scan coils; whereas at high precession angles SPED spatial resolution was limited by tilt-induced two-fold astigmatism caused by the positive spherical aberration of the probe-forming lens.
The selective laser melting of high temperature alloys is of great interest to the aerospace industry as it offers the prospect of producing more complex geometries than can be achieved with other manufacturing methods. In this study, the microstructure of the nickel-based superalloy, CM247LC, has been characterised following selective laser melting and after a post deposition heat treatment below the γʹ solvus temperature. In the as-deposited state, scanning electron microscopy with electron backscatter diffraction revealed a fine, cellular microstructure with preferential alignment of 〈001〉 along the build direction. A high dislocation density was seen at the periphery of the cells, indicating substantial localised deformation of the material. Fine primary MC carbides were also observed in the inter-cellular regions. High-resolution transmission electron microscopy identified the occurrence of very fine γʹ precipitates, approximately 5nm in diameter, dispersed within the gamma phase. After heat treatment, the elongated cell colonies were observed to partially coalesce, accompanied by a decrease in dislocation density, producing columnar grains along the build direction. Cuboidal γʹ precipitates approximately 500nm in diameter were observed to form in the recrystallised grains, accompanied by larger γʹ precipitates on the grain boundaries.
We have studied the influence of different carbon precursors (methane, ethanol and toluene) on the type, diameter and chiral angle distributions of carbon nanotubes (CNTs) grown with the floating catalyst technique in a horizontal gas-flow reactor. Using electron diffraction to study their atomic structures, we found that ethanol and toluene precursors gave high single-wall CNT yields (92% and 89% respectively), with narrow diameter distributions: 1.1 nm to 1.7 nm (ethanol); 1.3 nm to 2.1 nm (toluene), with a propensity for armchair-type chiral angles. In contrast, methane-grown CNTs gave high double-wall CNT yields (75%) with broader diameter populations: 1.2 to 4.6 nm (inner CNT) and 2.2 to 5.3 nm (outer CNT) with a more uniform spread of chiral angles, but weakly peaked around 15 to 20 degrees. These observations agree with known growth models. However, double-wall CNTs grown with toluene showed an unusually narrow interlayer spacing of 0.286 ± 0.003 nm with suggestions of large, 20° to 25°, differences between inner and outer CNT chiral angles. Methane gave a large interlayer spacing (0.385 ± 0.002 nm) with suggestions of small 5° to 10° inter-tube chirality correlations.
A non-polar m-plane structure consisting of five InGaN/GaN quantum wells (QWs) was grown on ammonothermal bulk GaN by metal-organic vapor phase epitaxy. Surface step bunches propagating through the QW stack were found to accommodate the 2° substrate miscut towards the -c direction. Both large steps with heights of a few tens of nanometres and small steps between one and a few atomic layers in height are observed, the former of which exhibit cathodoluminescence at longer wavelengths than the adjacent m-plane terraces. This is attributed to the formation of semi-polar facets at the steps on which the QWs are shown to be thicker and have higher Indium contents than those in the adjacent m-plane regions. Discrete basal-plane stacking faults (BSFs) were occasionally initiated from the QWs on the main m-plane terraces, but groups of BSFs were frequently observed to initiate from those on the large steps, probably related to the increased strain associated with the locally higher indium content and thickness.