Domains in Ferroelectric Nanodots

Almost free-standing single crystal mesoscale and nanoscale dots of ferroelectric BaTiO3 have been made by direct focused ion beam patterning of bulk single crystal material. The domain structures which appear in these single crystal dots, after cooling through the Curie temperature, were observed to form into quadrants, with each quadrant consisting of fine 90° stripe domains. The reason that these rather complex domain configurations form is uncertain, but we consider and discuss three possibilities for their genesis: first, that the quadrant features initially form to facilitate field-closure, but then develop 90° shape compensating stripe domains in order to accommodate disclination stresses; second, that they are the result of the impingement of domain packets which nucleate at the sidewalls of the dots forming “Forsbergh” patterns (essentially the result of phase transition kinetics); and third, that 90° domains form to conserve the shape of the nanodot as it is cooled through the Curie temperature but arrange into quadrant packets in order to minimize the energy associated with uncompensated surface charges (thus representing an equilibrium state). While the third model is the preferred one, we note that the second and third models are not mutually exclusive.

Polarization Closure in PbZr(0.42)Ti(0.58)O3 Nanodots

Domain states in PbZr(0.42)Ti(0.58)O3 single-crystal ferroelectric nanodots, formed on cooling through the Curie temperature, were imaged by transmission electron microscopy. In the majority of cases, 90o stripe domains were found to form into four distinct “bundles” or quadrants. Detailed analysis of the dipole orientations in the system was undertaken, using both dark-field imaging and an assumption that charged domain walls were energetically unfavorable in comparison to uncharged walls. On this basis, we conclude that the dipoles in these nanodots are arranged such that the resultant polarizations, associated with the four quadrant domain bundles, form into a closed loop. This “polarization closure” pattern is reminiscent of the flux-closure already commonly observed in soft ferromagnetic microdots but to date unseen in analogous ferroelectric dots.

Controlling Subnanometer Gaps in Plasmonic Dimers Using Graphene

Graphene is used as the thinnest possible spacer between gold nanoparticles and a gold substrate. This creates a robust, repeatable, and stable subnanometer gap for massive plasmonic field enhancements. White light spectroscopy of single 80 nm gold nanoparticles reveals plasmonic coupling between the particle and its image within the gold substrate. While for a single graphene layer, spectral doublets from coupled dimer modes are observed shifted into the near-infrared, these disappear for increasing numbers of layers. These doublets arise from charger-transfer-sensitive gap plasmons, allowing optical measurement to access out-of-plane conductivity in such layered systems. Gating the graphene can thus directly produce plasmon tuning.

Low loading platinum nanoparticles on reduced graphene oxide-supported tungsten carbide crystallites as a highly active electrocatalyst for methanol oxidation

In this study, low loading platinum nanoparticles (Pt NPs) have been highly dispersed on reduced graphene oxide-supported WC nanocrystallites (Pt-WC/RGO) via program-controlled reduction-carburization technique and microwave-assisted method. The scanning electron microscopy and transmission electron microscopy results show that WC nanocrystallites are homogeneously decorated on RGO, and Pt NPs with a size of ca. 3 nm are dispersed on both RGO and WC. The prepared Pt-WC/RGO is used as an electrocatalyst for methanol oxidation reaction (MOR). Compared with the Pt/RGO, commercial carbon-supported Pt (Pt/C) and PtRu alloy (PtRu/C) electrocatalysts, the Pt-WC/RGO composites demonstrate higher electrochemical active surface area and excellent electrocatalytic activity toward the methanol oxidation, such as better tolerance toward CO, higher peak current density, lower onset potential and long-term stability, which could be attributed to the characterized RGO support, highly dispersed Pt NPs and WC nanocrystallites and the valid synergistic effect resulted from the increased interface between WC and Pt. The present work proves that Pt-WC/RGO composites could be a promising alternative catalyst for direct methanol fuel cells where WC plays the important role as a functional additive in preparing Pt-based catalysts because of its CO tolerance and lower price. 

Graphene Nanoribbons as a Drug Delivery Agent for Lucanthone Mediated Therapy of Glioblastoma Multiforme

We report use of PEG-DSPE coated oxidized graphene nanoribbons (O-GNR-PEG-DSPE) as agent for delivery of anti-tumor drug Lucanthone (Luc) into Glioblastoma Multiformae (GBM) cells targeting base excision repair enzyme APE-1 (Apurinic endonuclease-1). Lucanthone, an endonuclease inhibitor of APE-1, was loaded onto O-GNR-PEG-DSPEs using a simple non-covalent method. We found its uptake by GBM cell line U251 exceeding 67% and 60% in APE-1-overexpressing U251, post 24 h. However, their uptake was ~ 38% and 29% by MCF-7 and rat glial progenitor cells (CG-4), respectively. TEM analysis of U251 showed large aggregates of O-GNR-PEG-DSPE in vesicles. Luc-O-GNR-PEG-DSPE was significantly toxic to U251 but showed little/no toxicity when exposed to MCF-7/CG-4 cells. This differential uptake effect can be exploited to use O-GNR-PEG-DSPEs as a vehicle for Luc delivery to GBM, while reducing nonspecific cytotoxicity to the surrounding healthy tissue. Cell death in U251 was necrotic, probably due to oxidative degradation of APE-1.

Graphical abstract

We used O-GNR-PEG-DSPE as a reliable, non-toxic vehicle for delivery of APE-1 inhibiting Lucanthone into GBM tumor cell lines. LUC-O-GNR-PEG-DSPE particles showed 60% or more uptake by CMV/U251 and A1-5/CMV/U251 where as the uptake by MCF7 and normal CG4 glial cells was much lower (38% and 29% respectively). Different concentrations of Luc (5–80 μM) loaded onto O-GNR-PEG-DSPE showed lower toxicity in the exposed cells compared to the free drug, due to possible slow release of the drug from this particle, which ensures minimum non-specific release of the drug from the particle once it is injected in vivo.
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Nanoscale reinforced orthopaedic bone cement with graphene oxide - a possible solution to aseptic loosening of cemented hip implants? Preliminary results of an ongoing study

Hip replacement surgery is amongst the most common orthopaedic operations performed in the UK. Aseptic loosening is responsible for 40% of hip revision procedures. Aseptic loosening is a result of cement mantle fatigue. The aim of the current study is to analyse the effect of nanoscale Graphene Oxide (GO) on the mechanical properties of orthopaedic bone cement. Study Design A experimental thermal and mechanical analysis was conducted in a laboratory set up conforming to international standards for bone cement testing according to ISO 5583. Testing was performed on control cement samples of Colacryl bone cement, and additional samples reinforced with variable wt% of Graphene Oxide containing composites – 0.1%, 0.25%, 0.5% and 1.0% GO loading. Pilot Data Porosity demonstrated a linear relationship with increasing wt% loading compared to control (p<0.001). Thermal characterisation demonstrated maximal temperature during polymerization, and generated exotherm were inversely proportional to w%t loading (p<0.05) Fatigue strength performed on the control and 0.1 and 0.25%wt loadings of GO demonstrate increased average cycles to failure compared to control specimens. A right shift of the Weibull curve was demonstrated for both wt% available currently. Logistic regression analysis for failure demonstrated significant increases in number of cycles to failure for both specimens compared to a control (p<0.001). Forward Plan Early results convey positive benefits at low wt% loadings of GO containing bone cement. Study completion and further analysis is required in order to elude to the optimum w%t of GO which conveys the greatest mechanical advantage.

Melt Processing and Properties of Polyamide 6/Graphene Nanoplatelet Composites

Graphene, due to its outstanding properties, has become the topic of much research activity in recent years. Much of that work has been on a laboratory scale however, if we are to introduce graphene into real product applications it is necessary to examine how the material behaves under industrial processing conditions. In this paper the melt processing of polyamide 6/graphene nanoplatelet composites via twin screw extrusion is investigated and structure–property relationships are examined for mechanical and electrical properties. Graphene nanoplatelets (GNPs) with two aspect ratios (700 and 1000) were used in order to examine the influence of particle dimensions on composite properties. It was found that the introduction of GNPs had a nucleating effect on polyamide 6 (PA6) crystallization and substantially increased crystallinity by up to 120% for a 20% loading in PA6. A small increase in crystallinity was observed when extruder screw speed increased from 50 rpm to 200 rpm which could be attributed to better dispersion and more nucleation sites for crystallization. A maximum enhancement of 412% in Young's modulus was achieved at 20 wt% loading of GNPs. This is the highest reported enhancement in modulus achieved to date for a melt mixed thermoplastic/GNPs composite. A further result of importance here is that the modulus continued to increase as the loading of GNPs increased even at 20 wt% loading and results are in excellent agreement with theoretical predictions for modulus enhancement. Electrical percolation was achieved between 10–15 wt% loading for both aspect ratios of GNPs with an increase in conductivity of approximately 6 orders of magnitude compared to the unfilled PA6.

Oxygen reduction reaction mechanism on nitrogen-doped graphene:A density functional theory study

Nitrogen-doped graphene (N-graphene) was reported to exhibit a good activity experimentally as an electrocatalyst of oxygen reduction reaction (ORR) on the cathode of fuel cells under the condition of electropotential of similar to 0.04 V (vs. NNE) and pH of 14. This material is promising to replace or partially replace the conventionally used Pt. In order to understand the experimental results. ORR catalyzed by N-graphene is studied using density functional theory (DFT) calculations under experimental conditions taking the solvent, surface adsorbates, and coverages into consideration. Two mechanisms, i.e., dissociative and associative mechanisms, over different N-doping configurations are investigated. The results show that N-graphene surface is covered by O with 1/6 monolayer, which is used for reactions in this work. The transition state of each elementary step was identified using four different approaches, which give rise to a similar chemistry. A full energy profile including all the reaction barriers shows that the associative mechanism is more energetically favored than the dissociative one and the removal of O species from the surface is the rate-determining step. (C) 2011 Elsevier Inc. All rights reserved.

Size effect of graphene on electrocatalytic activation of oxygen

Crystals of graphite nanosheets, achieved via a simple ball milling approach, show a significant size effect in electrocatalytic activation of oxygen.

Melt Processing and Properties of Polyamide 6/Graphene Nanoplatelet Composites

In this paper, the processing and characterization of Polyamide 6 (PA6) / graphite nanoplatelets
(GNPs) composites is reported. PA6/GNPs composites were prepared by melt-mixing using an
industrial, co-rotating, intermeshing, twin-screw extruder. A bespoke screw configuration was used
that was designed in-house to enhance nanoparticle dispersion into a polymer matrix. The effects of
GNPs type (xGnP® M-5 and xGnP® C-500), GNPs content, and extruder screw speed on the bulk
properties of the PA6/GNPs nanocomposites were investigated. Results show a considerable
improvement in the thermal and mechanical properties of PA6/GNPs composites, as compared with
the unfilled PA6 polymer. An increase in crystallinity (%Xc) with increasing GNPs content, and a
change in shape of the crystallization exotherms (broadening) and melting endotherms, both suggest a
change in the crystal type and perfection. An increase in tensile modulus of as much as 376% and
412% was observed for PA6/M-5 xGnP® and PA6/C-500 xGnP® composites, respectively, at filler
contents of 20wt%. The enhancement of Young’s modulus and yield stress can be attributed to the
reinforcing effect of GNPs and their uniform dispersion in the PA6 matrix. The rheological response
of the composite resembles that of a ‘pseudo-solid’, rather than a molten liquid, and analysis of the
rheological data indicates that a percolation threshold was reached at GNPs contents of between 10–
15wt%. The electrical conductivity of the composite also increased with increasing GNPs content,
with an addition of 15wt% GNPs resulting in a 6 order-of-magnitude increase in conductivity. The
electrical percolation thresholds of all composites were between 10–15wt%.

Sandwich nanoarchitecture of LiV3O8/graphene multilayer nanomembranes via layer-by-layer self-assembly for long-cycle-life lithium-ion battery cathodes

A lack of suitable high-performance cathode materials has become the major barrier to their applications in future advanced communication equipment and electric vehicle power systems. In this paper, we have developed a layer-by-layer self-assembly approach for fabricating a novel sandwich nanoarchitecture of multilayered LiV₃O₈ nanoparticle/graphene nanosheet (M-nLVO/GN) hybrid electrodes for potential use in high performance lithium ion batteries by using a porous Ni foam as a substrate. The prepared sandwich nanoarchitecture of M-nLVO/GN hybrid electrodes exhibited high performance as a cathode material for lithium-ion batteries, such as high reversible specific capacity (235 mA h g^-1 at a current density of 0.3 A g^-1), high coulombic efficiency (over 98%), fast rate capability (up to a current density of 10 A g^-1), and superior capacity retention during cycling (90% capacity retention with a current density of 0.3 A g^-1 after 300 cycles). Very significantly, this novel insight into the design and synthesis of sandwich nanoarchitecture would extend their application to various electrochemical energy storage devices, such as fuel cells and supercapacitors.

In situ preparation of 3D graphene aerogels@hierarchical Fe3O4 nanoclusters as high rate and long cycle anode materials for lithium ion batteries

We describe a novel strategy for in situ fabrication of hierarchical Fe₃O₄ nanoclusters-GAs. Fe₃O₄ NCs-GAs deliver excellent rate capability (the reversible capacities obtained were 1442, 392 and 118 mA h g^-1 at 0.1C, 12C and 35C rates), and a high reversible capacity of 577 mA h g^-1 over 300 cycles at the current density of 5.2 A g^-1 (6C).

Three-dimensional graphene-Co3O4 cathodes for rechargeable Li-O2 batteries

A three-dimensional (3D) graphene-Co₃O₄ electrode was prepared by a two-step method in which graphene was initially deposited on a Ni foam with Co₃O₄ then grown on the resulting graphene structure. Cross-linked Co₃O₄ nanosheets with an open pore structure were fully and vertically distributed throughout the graphene skeleton. The free-standing and binder-free monolithic electrode was used directly as a cathode in a Li-O₂ battery. This composite structure exhibited enhanced performance with a specific capacity of 2453 mA h g^-1 at 0.1 mA cm^-2 and 62 stable cycles with 583 mA h g^-1 (1000 mA h g_carbon^-1). The excellent electrochemical performance is associated with the unique architecture and superior catalytic activity of the 3D electrode.