Resistance of nanocrystalline vis-à-vis microcrystalline Fe–Cr alloys to environmental degradation and challenges to their synthesis

This paper presents a hypothesis and its experimental validation that a nanostructure can bring about dramatic improvements in the oxidation/corrosion resistance of iron–chromium alloys. More specifically, a nanocrystalline Fe–10 wt% Cr alloy was found to undergo oxidation at a rate that was an order of magnitude lower than its microcrystalline counterpart. Importantly, the oxidation resistance of nanocrystalline Fe–10 wt% Cr alloy was comparable with that of the common corrosion-resistant microcrystalline stainless steels (having 18–20 wt% chromium). The findings have the potential of leading to the next generation of oxidation-resistant alloys. However, due to poor thermal stability of nanocrystalline structure, synthesis/processing of such alloys is a challenge. Discs of nanocrystalline Fe–10% Cr alloy were produced by ball-milling of Fe and Cr powders and compaction of the powder without considerable grain growth by processing within a suitable time–temperature window. The paper also presents a theoretical treatise to arrive at the minimum chromium content required for establishing a protective layer of chromium oxide in an Fe–Cr alloy of a given nanometric grain size.

Recyclable textiles functionalized with reduced graphene Oxide@ZnO for removal of oil spills and dye pollutants

A novel recyclable and flexible membrane was prepared for the removal of oil spills and organic dye pollutants, by functionalizing polyester textiles with reduced graphene oxide@ZnO nanocomposites using a layer-by-layer technique. The membrane showed efficient water/oil separation, and the amount of oil adsorbed by the membrane could be up to 23 times its own weight. The adsorption capacity was largely retained during many adsorption recycling cycles. The membrane also displayed highly efficient removal of a dye pollutant from water under simulated sunlight. The membrane maintained a near-original removal efficiency after five cycles of dye removal. This new type of membrane may find practical applications in the large-scale separation of organic pollutants from water, particularly in the field of oil spills clean-up and dye removal from industrial effluent.

Mixing layer oscillations for a submerged horizontal wall-jet

Measurements of the horizontal velocity component were made for a horizontal wall-jet emanating from a submerged sluice gate forming one side of a large flow compartment. The existence of large-scale vortex structures was quantified by spectral analysis of the velocity measurements taken at various distances from the floor of the flow compartment, for different measurement stations from the jet exit. Close to the jet exit, the spectra of the velocity measurements within the potential core exhibit multiple peaks. Further downstream, the spectra are more defined and peak at the same frequency, irrespective of whether the measurements were made within the potential core or the mixing layer. The spectral peak corresponds to the passage frequency of large-scale vortex structures. Downstream of the potential core, the peak frequencies of the velocity spectra increase as the measurement location was moved towards the floor of the flow compartment. The increase in peak frequencies is attributed to fluctuations associated with the wall boundary layer. Predictions of the mixing layer instabilities were made using linear stability analysis. The predictions are in good agreement with the observed vortex shedding frequencies in the mixing layer

Sulfur-doped porous reduced graphene oxide hollow nanosphere frameworks as metal-free electrocatalysts for oxygen reduction reaction and as supercapacitor electrode materials.

Chemical doping with foreign atoms is an effective approach to significantly enhance the electrochemical performance of the carbon materials. Herein, sulfur-doped three-dimensional (3D) porous reduced graphene oxide (RGO) hollow nanosphere frameworks (S-PGHS) are fabricated by directly annealing graphene oxide (GO)-encapsulated amino-modified SiO2 nanoparticles with dibenzyl disulfide (DBDS), followed by hydrofluoric acid etching. The XPS and Raman spectra confirmed that sulfur atoms were successfully introduced into the PGHS framework via covalent bonds. The as-prepared S-PGHS has been demonstrated to be an efficient metal-free electrocatalyst for oxygen reduction reaction (ORR) with the activity comparable to that of commercial Pt/C (40%) and much better methanol tolerance and durability, and to be a supercapacitor electrode material with a high specific capacitance of 343 F g(-1), good rate capability and excellent cycling stability in aqueous electrolytes. The impressive performance for ORR and supercapacitors is believed to be due to the synergistic effect caused by sulfur-doping enhancing the electrochemical activity and 3D porous hollow nanosphere framework structures facilitating ion diffusion and electronic transfer.

Promoted water transport across graphene oxide-poly(amide) thin film composite membranes and their antibacterial activity

Hybrid composite membranes have great potential for desalination applications since water transport can be favorably promoted by selective diffusion at the interface between matrix and reinforcement materials. In this paper, graphene oxide nano-sheets were successfully incorporated across 200nm thick poly(amide) films by interfacial polymerization to form novel thin-film composite membranes. The impact of the graphene oxide on the morphology, chemistry, and surface charge of the ultra-thin poly(amide) layer, and the ability to desalinate seawater was investigated. The graphene oxide nano-sheets were found to be well dispersed across the composite membranes, leading to a lower membrane surface energy and an enhanced hydrophilicity. The iso-electric point of the samples, key to surface charge repulsion during desalination, was found to be consistently shifted to higher pH values with an increasing graphene oxide content. Compared to a pristine poly(amide) membrane, the pure water flux across the composite membranes with 0.12wt.% of graphene oxide was also found to increase by up to 80% from 0.122 to 0.219L·μm·m-2·h-1·bar-1 without significantly affecting salt selectivity. Furthermore, the inhibitory effects of the composite membrane on microbial growth were evaluated and the novel composite membranes exhibited superior anti-microbial activity and may act as a potential anti-fouling membrane material.

Sulfur-impregnated, sandwich-type, hybrid carbon nanosheets with hierarchical porous structure for high-performance lithium-sulfur batteries

Sandwich-type hybrid carbon nanosheets (SCNMM) consisting of graphene and micro/mesoporous carbon layer are fabricated via a double template method using graphene oxide as the shape-directing agent and SiO2 nanoparticles as the mesoporous guide. The polypyrrole synthesized in situ on the graphene oxide sheets is used as a carbon precursor. The micro/mesoporous strcutures of the SCNMM are created by a carbonization process followed by HF solution etching and KOH treatment. Sulfur is impregnated into the hybrid carbon nanosheets to generate S@SCNMM composites for the cathode materials in Li-S secondary batteries. The microstructures and electrochemical performance of the as-prepared samples are investigated in detail. The hybrid carbon nanosheets, which have a thickness of about 10-25 nm, high surface area of 1588 m2 g-1, and broad pore size distribution of 0.8-6.0 nm, are highly interconnected to form a 3D hierarchical structure. The S@SCNMM sample with the sulfur content of 74 wt% exhibits excellent electrochemical performance, including large reversible capacity, good cycling stability and coulombic efficiency, and good rate capability, which is believed to be due to the structure of hybrid carbon materials with hierarchical porous structure, which have large specific surface area and pore volume.

Performance enhancement of single-walled nanotube-microwave exfoliated graphene oxide composite electrodes using a stacked electrode configuration

We report the development of a stacked electrode supercapacitor cell using stainless steel meshes as the current collectors and optimised single walled nanotubes (SWNT)-microwave exfoliated graphene oxide (mw rGO) composites as the electrode material. The introduction of mw rGO into a SWNT matrix creates an intertwined porous structure that enhances the electroactive surface area and capacitive performance due to the 3-D hierarchical structure that is formed. The composite structure was optimised by varying the weight ratio of the SWNTs and mw rGO. The best performing ratio was the 90% SWNT-10% mw rGO electrode which achieved a specific capacitance of 306 F g-1 (3 electrode measurement calculated at 20 mV s-1). The 90% SWNT-10% mw rGO was then fabricated into a stacked electrode configuration (SEC) which significantly enhanced the electrode performance per volume (1.43 mW h cm-3, & 6.25 W cm-3). Device testing showed excellent switching capability up to 10 A g-1, and very good stability over 10000 cycles at 1.0 A g-1 with 93% capacity retention. © the Partner Organisations 2014.

Reduced graphene oxide directed self-assembly of phospholipid monolayers in liquid and gel phases

The response of cell membranes to the local physical environment significantly determines many biological processes and the practical applications of biomaterials. A better understanding of the dynamic assembly and environmental response of lipid membranes can help understand these processes and design novel nanomaterials for biomedical applications. The present work demonstrates the directed assembly of lipid monolayers, in both liquid and gel phases, on the surface of a monolayered reduced graphene oxide (rGO). The results from atomic force microscopy indicate that the hydrophobic aromatic plane and the defect holes due to reduction of GO sheets, along with the phase state and planar surface pressure of lipids, corporately determine the morphology and lateral structure of the assembled lipid monolayers. The DOPC molecules, in liquid phase, probably spread over the rGO surface with their tails associating closely with the hydrophobic aromatic plane, and accumulate to form circles of high area surrounding the defect holes on rGO sheets. However, the DPPC molecules, in gel phase, prefer to form a layer of continuous membrane covering the whole rGO sheet including defect holes. The strong association between rGO sheets and lipid tails further influences the melting behavior of lipids. This work reveals a dramatic effect of the local structure and surface property of rGO sheets on the substrate-directed assembly and subsequent phase behavior of the supported lipid membranes.

Improved efficiency and stability of flexible dye sensitized solar cells on ITO/PEN substrates using an ionic liquid electrolyte

Flexible dye-sensitized solar cells (DSSCs) built on plastic substrates have attracted great interest as they are lightweight and can be roll-to-roll printed to accelerate production and reduce cost. However, plastic substrates such as PEN and PET are permeable to water, oxygen and volatile electrolyte solvents, which is detrimental to the cell stability. Therefore, to address this problem, in this work, an ionic liquid (IL) electrolyte is used to replace the volatile solvent electrolyte. The initial IL-based devices only achieved around 50% of the photovoltaic conversion efficiency of the cells using the solvent electrolyte. Current-voltage and electrochemical impedance spectroscopy (EIS) analysis of the cells in the dark indicated that this lower efficiency mainly originated from (i) a lack of blocking layer to reduce recombination, and (ii) a lower charge collection efficiency. To combat these problems, cells were developed using a 12 nm thick blocking layer, produced by atomic layer deposition, and 1 μm thick P25 TiO2 film sensitized with the hydrophobic MK-2 dye. These flexible DSSCs utilizing an IL electrolyte exhibit significantly improved efficiencies and a <10% drop in performance after 1000 h aging at 60°C under continuous light illumination.

A highly conductive porous graphene electrode prepared via in situ reduction of graphene oxide using Cu nanoparticles for the fabrication of high performance supercapacitors

Herein, a new graphene/Cu nanoparticle composite was prepared via the in situ reduction of GO in the presence of Cu nanoparticles which was then utilized as a sacrificing template for the formation of flexible and porous graphene capacitor electrodes by the dissolution of the intercalated Cu nanoparticle in a mixed solution of FeCl3 and HCl. The porous RGO electrode was characterized by atomic force microscopy (AFM), Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and thermogravimetric analysis (TGA). The as-prepared graphene/Cu nanoparticle composite and the pure graphene film after removal of Cu nanoparticles possessed high conductivity of 3.1 × 10³ S m^-1 and 436 S m^-1 respectively. The porous RGO can be used as the electrode for the fabrication of supercapacitors with high gravimetric specific capacitances up to 146 F g^-1, good rate capability and satisfactory electrochemical stability. This environmentally friendly and efficient approach to fabricating porous graphene nanostructures could have enormous potential applications in the field of energy storage and nanotechnology.

An acetylcholinesterase inhibition biosensor based on a reduced graphene oxide/silver nanocluster/chitosan nanocomposite for detection of organophosphorus pesticides

A sensitive electrochemical acetylcholinesterase (AChE) biosensor based on a reduced graphene oxide (rGO) and silver nanocluster (AgNC) modified glassy carbon electrode (GCE) was developed. rGO and AgNC nanomaterials with excellent conductivity, catalytic activity and biocompatibility offered an extremely hydrophilic surface, which facilitated the immobilization of AChE to fabricate the organophosphorus pesticide biosensor. Carboxylic chitosan (CChit) was used as a cross-linker to immobilize AChE on a rGO and AgNC modified GCE. The AChE biosensor showed favorable affinity to acetylthiocholine chloride (ATCl) and could catalyze the hydrolysis of ATCl. Based on the inhibition effect of organophosphorus pesticides on the AChE activity, using phoxim as a model compound, the inhibition effect of phoxim was proportional to its concentration ranging from 0.2 to 250 nM with a detection limit of 81 pM estimated at a signal-to-noise ratio of 3. The developed biosensor exhibited good sensitivity, stability and reproducibility, thus providing a promising tool for analysis of enzyme inhibitors and direct analysis of practical samples.

Synthesis of an indium oxide nanoparticle embedded graphene three-dimensional architecture for enhanced lithium-ion storage

Indium oxide nanoparticles were synthesised by using a facile and scalable strategy. The as-prepared nanoparticles (20-40 nm) were in situ and homogeneously distributed in a three-dimensional (3D) graphene architecture subsequently during the fabrication process. The obtained nanocomposite acts as a high capacity anode material for lithium-ion batteries and demonstrates good cycle stability. A drastically enhanced capacity of 750 mA h g^-1 in comparison with that of bare In2O3 nanoparticles can be maintained after 100 cycles, along with an improved high rate performance (210 mA h g^-1 at 1 A g^-1 and 120 mA h g^-1 at 2 A g^-1). The excellent performance is linked with the indium oxide nanoparticles and the unique 3D interconnected porous graphene structure. The highly conductive and porous 3D graphene structure greatly enhances the performance of lithium-ion batteries by protecting the nanoparticles from the electrolyte, stabilizing the nanoparticles during cycles and buffering the volume expansion upon lithium insertion.

Caracterização termo-mecânica de interconectores metálicos recobertos com filmes de LaCrO3

The cells unitaria of the solid oxide fuel cell are separated by means of interconnects, which serve as electrical contact between the cells. Lanthanum Chromite (LaCrO3) has been the most common material used as interconnect in solid oxide fuel cells. Reducing the operating temperature around 800 º C of cells to solid oxide fuel make possibilite the use of metallic interconnects as an alternative to ceramic LaCrO3. Metallic interconnects have advantages over ceramic interconnects such as high thermal conductivity, electricity, good ductility, low cost, good physical and mechanical properties. In this work evaluate the thermo-mechanical properties of the metallic substrate and coated metallic substrate with the ceramic LaCrO3 film via spray-pyrolysis, in order to demonstrate the feasibility of using this material as a component of a fuel cell solid oxide. The materials were characterized by X-ray diffraction, oxidation behavior, mechanical strength, optical microscopy (OM) and scanning electron microscopy (SEM). The X-ray diffraction proved the formation phase of the LaCrO3 on the metallic substrate and the identification of the phases formed after the oxidative test and mechanical strength at high temperature. The oxidation behavior showed the increased oxidation resistance of the coated metallic substrate. It was noted that the mechanical resistance to bending of the coated metallic substrate only increases at room temperature. The optical microscopy (OM) has provided an assessment of both the metallic substrate and the LaCrO3 film deposited on the metal substrate that, in comparison with the micrographs obtained from SEM. The SEM one proved the formation of Cr2O3 layer on the metallic substrate and stability of LaCrO3 film after oxidative test, it can also observe the displacement of the ceramic LaCrO3 film after of mechanical testing and mapping of the main elements as chromium, manganese, oxygen, lanthanum in samples after the thermo-mechanical tests.

Nitric oxide release using natural rubber latex as matrix

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Immobilization of uricase in layer-by-layer films used in amperometric biosensors for uric acid

The layer-by-layer technique was exploited to immobilize the enzyme uricase onto indium tin oxide substrates coated with a layer of Prussian Blue. Uricase layers were alternated with either poly(ethylene imine) or poly(diallyidimethylammoniumchloride), and the resulting films were used as amperometric biosensors for uric acid. Biosensors with optimum perfomance had a limit of detection of 0.15 mu A mu mol 1(-1) cm(-2) with a linear response between 0.1 and 0.6 mu M of uric acid, which is sufficient for use in clinical tests. Bioactivity was preserved for weeks, and there was negligible influence from interferents, as detection was carried out at 0.0 V vs saturated calomel electrode.