High Shear Thin Film Synthesis of Partially Oxidized Gallium and Indium Composite 2D Sheets.

Reducing resistance in silicon-based devices is important as they get miniaturized further. 2D materials offer an opportunity to increase conductivity whilst reducing size. A scalable, environmentally benign method is developed for preparing partially oxidized gallium/indium sheets down to 10 nm thick from a eutectic melt of the two metals. Exfoliation of the planar/corrugated oxide skin of the melt is achieved using the vortex fluidic device with a variation in composition across the sheets determined using Auger spectroscopy. From an application perspective, the oxidized gallium indium sheets reduce the contact resistance between metals such as platinum and silicon (Si) as a semiconductor. Current-voltage measurements between a platinum atomic force microscopy tip and a Si-H substrate show that the current switches from being a rectifier to a highly conducting ohmic contact. These characteristics offer new opportunities for controlling Si surface properties at the nanoscale and enable the integration of new materials with Si platforms.

Surfactant-free Fabrication of Fullerene C60 Nanotubules Under Shear.

A method for controlling the self-assembly of fullerene C60 molecules into nanotubules in the fcc phase, devoid of entrapped solvent, has been established in a thin film microfluidic device. The micron length C60 nanotubules, with individual hollow diameters of 100 to 400 nm, are formed under continuous flow processing during high shear micromixing of water and a toluene solution of the fullerene, in the absence of surfactant, and without the need for further down-stream processing. TEM revealed pores on the surface of the nanotubes, and the isolated material has a much higher response to small molecule sensing than that for analogous material formed using multistep batch processing.

Vortex fluidic high shear induced crystallisation of fullerene C70 into nanotubules.

Hollow C70 nanotubules are formed under high shear within the thin film of a vortex fluidic device (VFD) without the need for using auxiliary reagents, high temperatures and pressures, and/or requiring downstream processing. This novel bottom-up crystallisation process involves intense micro mixing of two liquids (toluene solution of C70 and anti-solvent, isopropyl alcohol) within a thin film in the VFD to precisely control the hierarchical assembly of C70 molecules into hollow nanotubules. The mechanism of self-assembly was consistent with them being a mould of the high shear double helical topological flow from Faraday waves coupled with Coriolis forces generated within the thin film.

Printable Hydrogel Arrays for Portable and High-Throughput Shear-Mediated Assays.

Hydrogels have been widely used to entrap biomolecules for various biocatalytic reactions. However, solute diffusion in these matrices to initiate such reactions can be a very slow process. Conventional mixing remains a challenge as it can cause irreversible distortion or fragmentation of the hydrogel itself. To overcome the diffusion-limit, a shear-stress-mediated platform named the portable vortex-fluidic device (P-VFD) is developed. P-VFD is a portable platform which consists of two main components, (i) a plasma oxazoline-coated polyvinyl chloride (POx-PVC) film with polyacrylamide and alginate (PAAm/Alg-Ca2+) tough hydrogel covalently bound to its surface and (ii) a reactor tube (L × D: 90 mm × 20 mm) where the aforementioned POx-PVC film could be readily inserted for reactions. Through a spotting machine, the PAAm/Alg-Ca2+ hydrogel can be readily printed on a POx-PVC film in an array pattern and up to 25.4 J/m2 adhesion energy can be achieved. The hydrogel arrays on the film not only offer a strong matrix for entrapping biomolecules such as streptavidin-horseradish peroxidase but are also shear stress-tolerant in the reactor tube, enabling a >6-fold increase in its reaction rate after adding tetramethylbenzidine, relative to incubation. Through using the tough hydrogel and its stably bonded substrate, this portable platform effectively overcomes the diffusion-limit and achieves fast assay detection without causing appreciable hydrogel array deformation or dislocation on the substrate film.

Continuous flow fabrication of green graphene oxide in aqueous hydrogen peroxide.

Highly processible graphene oxide (GO) has a diversity of applications as a material readily dispersed in aqueous media. However, methods for preparing such free-standing GO use hazardous and toxic reagents and generate significant waste streams. This is an impediment for uptake of GO in any application, for developing sustainable technologies and industries, and overcoming this remains a major challenge. We have developed a robust scalable continuous flow method for fabricating GO directly from graphite in 30% aqueous hydrogen peroxide which dramatically minimises the generation of waste. The process features the continuous flow thin film microfluidic vortex fluidic device (VFD), operating at specific conditions while irradiated sequentially by UV LED than a NIR pulsed laser. The resulting 'green' graphene oxide (gGO) has unique properties, possessing highly oxidized edges with large intact sp2 domains which gives rise to exceptional electrical and optical properties, including purple to deep blue emission of narrow full width at half maximum (<35 nm). Colloidally stable gGO exhibits cytotoxicity owing to the oxidised surface groups while solid-state films of gGO are biocompatible. The continuous flow method of generating gGO also provides unprecedented control of the level of oxidation and its location in the exfoliated graphene sheets by harnessing the high shear topological fluid flows in the liquid, and varying the wavelength, power and pulse frequency of the light source.

High shear spheroidal topological fluid flow induced coating of polystyrene beads with C60 spicules.

Spheroidal spicular like topological fluid flow in an angled vortex fluidic device (VFD) housing a 20 mm diameter tube with a hemispherical base rotating at 4k rpm and tilted at 45° is effective in reducing the thermodynamic equilibrium concentration of fullerene C60 in toluene, with the formation of spicules of the material under continuous flow processing. Under the same operational conditions in the presence of polystyrene beads 2 to 6 µm in diameter, spicules of C60ca. 150 nm in length grow on their surfaces. This establishes that the spheroidal topological fluid flow in the VFD prevails while enveloping spheroidal like particles of such size.

High shear in situ exfoliation of 2D gallium oxide sheets from centrifugally derived thin films of liquid gallium.

A diversity of two-dimensional nanomaterials has recently emerged with recent attention turning to the post-transition metal elements, in particular material derived from liquid metals and eutectic melts below 330 °C where processing is more flexible and in the temperature regime suitable for industry. This has been explored for liquid gallium using an angled vortex fluidic device (VFD) to fabricate ultrathin gallium oxide (Ga2O3) sheets under continuous flow conditions. We have established the nanosheets to form highly insulating material and have electrocatalytic activity for hydrogen evolution, with a Tafel slope of 39 mV dec-1 revealing promoting effects of the surface oxidation (passivation layer).

Sub-micron moulding topological mass transport regimes in angled vortex fluidic flow.

Shear stress in dynamic thin films, as in vortex fluidics, can be harnessed for generating non-equilibrium conditions, but the nature of the fluid flow is not understood. A rapidly rotating inclined tube in the vortex fluidic device (VFD) imparts shear stress (mechanical energy) into a thin film of liquid, depending on the physical characteristics of the liquid and rotational speed, ω, tilt angle, θ, and diameter of the tube. Through understanding that the fluid exhibits resonance behaviours from the confining boundaries of the glass surface and the meniscus that determines the liquid film thickness, we have established specific topological mass transport regimes. These topologies have been established through materials processing, as spinning top flow normal to the surface of the tube, double-helical flow across the thin film, and spicular flow, a transitional region where both effects contribute. The manifestation of mass transport patterns within the film have been observed by monitoring the mixing time, temperature profile, and film thickness against increasing rotational speed, ω. In addition, these flow patterns have unique signatures that enable the morphology of nanomaterials processed in the VFD to be predicted, for example in reversible scrolling and crumbling graphene oxide sheets. Shear-stress induced recrystallisation, crystallisation and polymerisation, at different rotational speeds, provide moulds of high-shear topologies, as 'positive' and 'negative' spicular flow behaviour. 'Molecular drilling' of holes in a thin film of polysulfone demonstrate spatial arrangement of double-helices. The grand sum of the different behavioural regimes is a general fluid flow model that accounts for all processing in the VFD at an optimal tilt angle of 45°, and provides a new concept in the fabrication of novel nanomaterials and controlling the organisation of matter.

Vertically aligned laser sliced MWCNTs.

Applications of multi-walled carbon nanotubes (MWCNTs) benefit from the availability of specific lengths of the material while keeping the outer walls pristine, for example, for applications requiring vertically aligned tubes. To this end, a simple and effective continuous flow 'top down' process to control the length of sliced MWCNTs has been developed using a vortex fluidic device (VFD) coupled with a 1064 nm pulse laser, with the process in the absence of chemicals and any auxiliary substances. Three different length distributions of the sliced MWCNTs, centered at 75 ± 2.1 nm, 300 ± 1.8 nm and 550 ± 1.4 nm, have been generated with the length depending on the VFD operating parameters and laser energy, with the processing resulting in a decrease in side wall defects of the material. We also show the ability to vertically self assemble short MWCNTs on a silicon substrate with control of the surface density coverage using a simple dipping and rinsing method.

Continuous flow photolytic reduction of graphene oxide.

Reduced graphene oxide (rGO) is generated from GO dispersed in water under continuous flow in the absence of harsh reducing agents, in a vortex fluidic device, such that the processing is scalable with uniformity of the product. This involves simultaneously UV irradiating (λ = 254 nm, 20 W) the dynamic thin film in the rapidly rotating glass tube in the microfluidic platform. The rGO is comparable to that formed using waste generating chemical based processing, with a film of the material having a resistance of 2.2 × 105 Ω and a remarkably high conductivity of 2 × 104 S cm-1.

Vortex fluidic mediated transformation of graphite into highly conducting graphene scrolls.

Two-dimensional graphene has remarkable properties that are revolutionary in many applications. Scrolling monolayer graphene with precise tunability would create further potential for niche applications but this has proved challenging. We have now established the ability to fabricate monolayer graphene scrolls in high yield directly from graphite flakes under non-equilibrium conditions at room temperature in dynamic thin films of liquid. Using conductive atomic force microscopy we demonstrate that the graphene scrolls form highly conducting electrical contacts to highly oriented pyrolytic graphite (HOPG). These highly conducting graphite-graphene contacts are attractive for the fabrication of interconnects in microcircuits and align with the increasing interest in building all sp2-carbon circuits. Above a temperature of 450 °C the scrolls unravel into buckled graphene sheets, and this process is understood on a theoretical basis. These findings augur well for new applications, in particular for incorporating the scrolls into miniaturized electronic devices.

Fluid dynamic lateral slicing of high tensile strength carbon nanotubes.

Lateral slicing of micron length carbon nanotubes (CNTs) is effective on laser irradiation of the materials suspended within dynamic liquid thin films in a microfluidic vortex fluidic device (VFD). The method produces sliced CNTs with minimal defects in the absence of any chemical stabilizers, having broad length distributions centred at ca 190, 160 nm and 171 nm for single, double and multi walled CNTs respectively, as established using atomic force microscopy and supported by small angle neutron scattering solution data. Molecular dynamics simulations on a bent single walled carbon nanotube (SWCNT) with a radius of curvature of order 10 nm results in tearing across the tube upon heating, highlighting the role of shear forces which bend the tube forming strained bonds which are ruptured by the laser irradiation. CNT slicing occurs with the VFD operating in both the confined mode for a finite volume of liquid and continuous flow for scalability purposes.

Aqueous based synthesis of antimicrobial-decorated graphene.

Ramizol® (1,3,5-tris[(1E)-2'-(4'-benzoic acid)vinyl]benzene) is a potent amphiphilic anti-microbial agent. It is essentially a planar molecule and can interact with the surface of graphene via extended π-π interactions. Herein we demonstrate the utility of Ramizol® in potentially acting as a molecular 'wedge' to exfoliate graphene and stabilise it in water. The non-covalent attachment of Ramizol® on the graphene surface enables release of Ramizol® by altering the pH of the solution. Furthermore, the stabilised composite material demonstrates antibacterial activity against Staphylococcus aureus which leads to potential in biomedical applications with graphene acting as a drug carrier as well as enhancing the structural strength of the composite material.

Shear induced fabrication of intertwined single walled carbon nanotube rings.

Thin film microfluidic shearing of a mixture of toluene dispersed single walled carbon nanotubes (SWCNTs) and water in a vortex fluidic device results in SWCNT nanorings (and related structures), diameters 100 to 200 nm or 300 to 700 nm, for respectively 10 mm or 20 mm diameter rotating tubes.

Self-assembled calixarene aligned patterning of noble metal nanoparticles on graphene.

Patterns of noble metal nanoparticles (NMNPs) of ruthenium and platinum are formed on p-phosphonic acid calix[8]arene stabilised graphene in water. This involves hydrogen gas induced reduction of metal ions absorbed on the stabilised graphene, with TEM revealing the patterns being comprised of domains of parallel arrays of NMNPs ∼7 nm apart. The domains are orientated in three directions on each graphene sheet at an angle of ∼60° or ∼120° with respect to each other. AFM of self-assembled p-phosphonic acid calix[8]arene on the surface of a highly ordered pyrolytic graphite (HOPG) revealed a similar pattern, implying that the orientation of the assembly of p-phosphonic acid calix[8]arene is governed by the hexagonal motif of graphite/graphene.

A versatile approach for decorating 2D nanomaterials with Pd or Pt nanoparticles.

Bubbling H(2) into colloidal suspensions of 2D sheets of graphene or h-BN stabilised in water with p-phosphonic acid calix[8]arene, and pre-treated to bind Pd(II) or Pt(IV) species to their surfaces, is effective in decorating the material with nanoparticles of the noble metals approximately 5 nm in diameter.