Graphene reflux: improving the yield of liquid-exfoliated nanosheets through repeated separation techniques.

Scalable production of graphene through liquid-phase exfoliation has been plagued by low yields. Although several recent studies have attempted to improve graphene exfoliation technology, the problem of separating colloidal nanosheets from unexfoliated parent material has received far less attention. Here we demonstrate a scalable method for improving nanosheet yield through a facile washing process. By probing the sedimentation of liquid-phase exfoliated slurries of graphene nanosheets and parent material, we found that a portion of exfoliated graphene is entrapped in the sediment, but can be recovered by repeatedly washing the slurry of nanosheet and parent material with additional solvent. We found this process to significantly increase the overall yield of graphene (graphene/parent material) and recover a roughly constant proportion of graphene with each wash. The cumulative amount of graphene recovered is only a function of total solvent volume. Moreover, we found this technique to be applicable to other types of nanosheets such as boron nitride nanosheets.

Radio Frequency Heating of Carbon Nanotube Composite Materials.

Here, we give the first-ever report of radio frequency (RF) electromagnetic heating of polymer nanocomposite materials via direct-contact and capacitively coupled electric field applicators. Notably, RF heating allows nanocomposite materials to be resistively heated with electric fields. We highlight our novel RF heating technique for multiwalled carbon nanotube (MWCNT) thermoplastic composites and measure their broadband dielectric properties. We also demonstrate three different electric field applicator configurations and discuss their practical use in an industrial setting. We demonstrate the use of RF heating to cure an automotive-grade epoxy loaded with MWCNTs. Our results show that lap shear joints cured faster with the RF method compared with control samples cured in an oven because of the heat-transfer advantages of directly heating the epoxy composite. Finally, we implement our RF curing technique to assemble an automotive structure by locally curing an epoxy adhesive applied to a truck chassis.

Welding of 3D-printed carbon nanotube-polymer composites by locally induced microwave heating.

Additive manufacturing through material extrusion, often termed three-dimensional (3D) printing, is a burgeoning method for manufacturing thermoplastic components. However, a key obstacle facing 3D-printed plastic parts in engineering applications is the weak weld between successive filament traces, which often leads to delamination and mechanical failure. This is the chief obstacle to the use of thermoplastic additive manufacturing. We report a novel concept for welding 3D-printed thermoplastic interfaces using intense localized heating of carbon nanotubes (CNTs) by microwave irradiation. The microwave heating of the CNT-polymer composites is a function of CNT percolation, as shown through in situ infrared imaging and simulation. We apply CNT-loaded coatings to a 3D printer filament; after printing, microwave irradiation is shown to improve the weld fracture strength by 275%. These remarkable results open up entirely new design spaces for additive manufacturing and also yield new insight into the coupling between dielectric properties and radio frequency field response for nanomaterial networks.

Photodegradation of dispersants in colloidal suspensions of pristine graphene.

We demonstrate that UV degradation can remove polymeric dispersants from the surface of colloidal pristine graphene. In particular, we investigated the irradiation of polyvinylpyrrolidone (PVP)-dispersed graphene in water; this polymer has been established as a versatile nanosheet dispersant for a range of solvents, and it undergoes photo-oxidative degradation when exposed to UV light. We find that the molecular weight of PVP decreases with irradiation time and subsequently desorbs from the graphene surface. This causes gradual destabilization of graphene and agglomeration in water. The amount of adsorbed PVP decreases by approximately 45% after 4 h of irradiation in comparison with the non-irradiated dispersion. At this point, the majority of the stable graphene nanosheets flocculate, likely because of insufficient surface coverage as indicated by thermogravimetric analysis. Graphene aggregates were characterized as a function of irradiation time by optical microscopy, UV-vis spectroscopy, Raman spectroscopy, and conductivity measurements; the data suggest that the agglomerates maintain a graphene-like (rather than graphite-like) structure. The effect is also observed for another graphene dispersant (sapogenin), which suggests that our findings can be generalized to the broader class of photodegradable dispersants.

Challenges in Liquid-Phase Exfoliation, Processing, and Assembly of Pristine Graphene.

Recent developments in the exfoliation, dispersion, and processing of pristine graphene (i.e., non-oxidized graphene) are described. General metrics are outlined that can be used to assess the quality and processability of various "graphene" products, as well as metrics that determine the potential for industrial scale-up. The pristine graphene production process is categorized from a chemical engineering point of view with three key steps: i) pretreatment, ii) exfoliation, and iii) separation. How pristine graphene colloidal stability is distinct from the exfoliation step and is dependent upon graphene interactions with solvents and dispersants are extensively reviewed. Finally, the challenges and opportunities of using pristine graphene as nanofillers in polymer composites, as well as as building blocks for macrostructure assemblies are summarized in the context of large-scale production.