Control of porosity and pore size of metal reinforced carbon nanotube membranes

Membranes are crucial in modern industry and both new technologies and materials need to be designed to achieve higher selectivity and performance. Exotic materials such as nanoparticles offer promising perspectives, and combining both their very high specific surface area and the possibility to incorporate them into macrostructures have already shown to substantially increase the membrane performance. In this paper we report on the fabrication and engineering of metal-reinforced carbon nanotube (CNT) Bucky-Paper (BP) composites with tuneable porosity and surface pore size. A BP is an entangled mesh non-woven like structure of nanotubes. Pure CNT BPs present both very high porosity (>90%) and specific surface area (>400 m2/g). Furthermore, their pore size is generally between 20–50 nm making them promising candidates for various membrane and separation applications. Both electro-plating and electroless plating techniques were used to plate different series of BPs and offered various degrees of success. Here we will report mainly on electroless plated gold/CNT composites. The benefit of this method resides in the versatility of the plating and the opportunity to tune both average pore size and porosity of the structure with a high degree of reproducibility. The CNT BPs were first oxidized by short UV/O3 treatment, followed by successive immersion in different plating solutions. The morphology and properties of these samples has been investigated and their performance in air permeation and gas adsorption will be reported.

Synthesis of single-crystalline LiFePO4 with rhombus-like morphology

In this investigation, carbon-coated LiFePO4 cathode materials were synthesized with a facile hydrothermal method. The structure and electrochemical properties of the materials were investigated by X-ray diffraction (XRD), Roman, transmission electron microscopy-energy dispersive spectroscopy (TEM-EDS), and electrochemical impedance spectroscopy (EIS). By adjusting the mixing concentration of starting materials, a single-crystalline LiFePO4 with an anisotropic rhombus morphology (Space Group: Pmnb No. 62) were successfully synthesized. In addition, the carbon coated on the surface of LiFePO4 material prepared has a lower ID/IG (0.80), which indicates an optimized carbon structure with an increased amount of sp2-type carbon. Electrochemical performance test shows that the carbon-coated LiFePO4 cathode materials have an initial discharge capacity of 146 mAh g−1 at 0.2C.

Temperature-dependent Raman spectra of bamboo-like boron nitride nanotubes

Phonon properties of boron nitride nanotubes (BNNTs) were investigated using Raman spectroscopy at different temperatures and new sp3- bonded BN vibrations were identified. The Raman peak of the E2g mode of BNNTs is found to be downshifted and broadened compared to that of hexagonal BN at the same temperature. By increasing the temperature, the energy of the E2g mode and the sp3-bonding mode are downshifted, with the temperature coefficients being -0.010 and -0.069cm-1/K, respectively. We attribute this downshifting to anharmonic effects as well as the elongation of the B-N bond in BNNT structures with increasing temperature. © 2014 The Japan Society of Applied Physics.

Improvement of light harvesting and device performance of dye-sensitized solar cells using rod-like nanocrystal TiO2 overlay coating on TiO2 nanoparticle working electrode

Novel TiO2 single crystalline nanorods were synthesized by electrospinning and hydrothermal treatment. The role of the TiO2 nanorods on TiO2 nanoparticle electrode in improvement of light harvesting and photovoltaic properties of dye-sensitized solar cells (DSSCs) was examined. Although the TiO2 nanorods had lower dye loading than TiO2 nanoparticle, they showed higher light utilization behaviour. Electron transfer in TiO2 nanorods received less resistance than that in TiO2 nanoparticle aggregation. By just applying a thin layer of TiO2 nanorods on TiO2 nanoparticle working electrode, the DSSC device light harvesting ability and energy conversion efficiency were improved significantly. The thickness of the nanorod layer in the working electrode played an important role in determining the photovoltaic property of DSSCs. An energy conversion efficiency as high as 6.6% was found on a DSSC device with the working electrode consisting of a 12 μm think TiO2 nanoparticle layer covered with 3 μm thick TiO2 nanorods. The results obtained from this study may benefit further design of highly efficient DSSCs.

Epoxy nanocomposites containing magnetite-carbon nanofibers aligned using a weak magnetic field

Abstract Novel magnetite-carbon nanofiber hybrids (denoted by Fe3O4@CNFs) have been developed by coating carbon nanofibers (CNFs) with magnetite nanoparticles in order to align CNFs in epoxy using a relatively weak magnetic field. Experimental results have shown that a weak magnetic field (∼mT) can align these newly-developed nanofiber hybrids to form a chain-like structure in the epoxy resin. Upon curing, the epoxy nanocomposites containing the aligned Fe3O4@CNFs show (i) greatly improved electrical conductivity in the alignment direction and (ii) significantly higher fracture toughness when the Fe3O4@CNFs are aligned normal to the crack surface, compared to the nanocomposites containing randomly-oriented Fe3O4@CNFs. The mechanisms underpinning the significant improvements in the fracture toughness have been identified, including interfacial debonding, pull-out, crack bridging and rupture of the Fe3O4@CNFs, and plastic void growth in the polymer matrix.

Improving the toughness and electrical conductivity of epoxy nanocomposites by using aligned carbon nanofibres

There is an increasing demand for high performance composites with enhanced mechanical and electrical properties. Carbon nanofibres offer a promising solution but their effectiveness has been limited by difficulty in achieving directional alignment. Here we report the use of an alternating current (AC) electric field to align carbon nanofibres in an epoxy. During the cure process of an epoxy resin, carbon nanofibres (CNFs) are observed to rotate and align with the applied electric field, forming a chain-like structure. The fracture energies of the resultant epoxy nanocomposites containing different concentrations of CNFs (up to 1.6wt%) are measured using double cantilever beam specimens. The results show that the addition of 1.6wt% of aligned CNFs increases the electrical conductivity of such nanocomposites by about seven orders of magnitudes to 10^-2S/m and increases the fracture energy, G<inf>Ic</inf>, by about 1600% from 134 to 2345J/m². A modelling technique is presented to quantify this major increase in the fracture energy with aligned CNFs. The results of this research open up new opportunities to create multi-scale composites with greatly enhanced multifunctional properties.

Raman microscopic analysis of internal stress in boron-doped diamond

Analysis of the induced stress on undoped and boron-doped diamond (BDD) thin films by confocal Raman microscopy is performed in this study to investigate its correlation with sample chemical composition and the substrate used during fabrication. Knowledge of this nature is very important to the issue of long-term stability of BDD coated neurosurgical electrodes that will be used in fast-scan cyclic voltammetry, as potential occurrence of film delaminations and dislocations during their surgical implantation can have unwanted consequences for the reliability of BDD-based biosensing electrodes. To achieve a more uniform deposition of the films on cylindrically-shaped tungsten rods, substrate rotation was employed in a custom-built chemical vapor deposition reactor. In addition to visibly preferential boron incorporation into the diamond lattice and columnar growth, the results also reveal a direct correlation between regions of pure diamond and enhanced stress. Definite stress release throughout entire film thicknesses was found in the OPEN ACCESS current Raman mapping images for higher amounts of boron addition. There is also a possible contribution to the high values of compressive stress from sp2 type carbon impurities, besides that of the expected lattice mismatch between film and substrate.

Fabrication of graphene foam supported carbon nanotube/polyaniline hybrids for high-performance supercapacitor applications

A large-scale, high-powered energy storage system is crucial for addressing the energy problem. The development of high-performance materials is a key issue in realizing the grid-scale applications of energy-storage devices. In this work, we describe a simple and scalable method for fabricating hybrids (graphenepyrrole/ carbon nanotube-polyaniline (GPCP)) using graphene foam as the supporting template. Graphene-pyrrole (G-Py) aerogels are prepared via a green hydrothermal route from two-dimensional materials such as graphene sheets, while a carbon nanotube/polyaniline (CNT/PANI) composite dispersion is obtained via the in situ polymerization method. The functional nanohybrid materials of GPCP can be assembled by simply dipping the prepared G-py aerogels into the CNT/PANI dispersion. The morphology of the obtained GPCP is investigated by scanning electron microscopy (SEM) and transmission electron microscopy (TEM), which revealed that the CNT/PANI was uniformly deposited onto the surfaces of the graphene. The as-synthesized GPCP maintains its original three-dimensional hierarchical porous architecture, which favors the diffusion of the electrolyte ions into the inner region of the active materials. Such hybrid materials exhibit significant specific capacitance of up to 350 F g^-1, making them promising in large-scale energy-storage device applications.

A facile method to fabricate carbon nanostructures via the self-assembly of polyacrylonitrile/poly (methyl methacrylate-b-polyacrylonitrile) AB/B' type block copolymer/homopolymer blends

The self-assembly and high temperature behavior of AB/B′ type block copolymer/homopolymer blends containing polyacrylonitrile (PAN) polymers were studied for the first time. Here, microphase separated nanostructures were formed in the poly(methyl methacrylate-b-polyacrylonitrile) (PMMAN) block copolymer and their blends with homopolymer PAN at various blend ratios. Additionally, these nanostructures were transformed into porous carbon nanostructures by sacrificing PMMA blocks via pyrolysis. Spherical and worm like morphologies were observed in both TEM and AFM images at different compositions. The thermal and phase behavior examinations showed good compatibility between the blend components in all studied compositions. The PAN homopolymer (B′) with a comparatively higher molecular weight than the corresponding block (B) of the block copolymer is expected to exhibit ‘dry brush’ behavior in this AB/B′ type system. This study provides a basic understanding of the miscibility and phase separation in the PMMAN/PAN system, which is important in the nanostructure formation of bulk PAN based materials with the help of block copolymers to develop advanced functional materials.

A diamond-based electrode for detection of neurochemicals in the human brain

Deep brain stimulation (DBS), a surgical technique to treat certain neurologic and psychiatric conditions, relies on pre-determined stimulation parameters in an open-loop configuration. The major advancement in DBS devices is a closed-loop system that uses neurophysiologic feedback to dynamically adjust stimulation frequency and amplitude. Stimulation-driven neurochemical release can be measured by fast-scan cyclic voltammetry (FSCV), but existing FSCV electrodes rely on carbon fiber, which degrades quickly during use and is therefore unsuitable for chronic neurochemical recording. To address this issue, we developed durable, synthetic boron-doped diamond-based electrodes capable of measuring neurochemical release in humans. Compared to carbon fiber electrodes, they were more than two orders-of-magnitude more physically-robust and demonstrated longevity in vitro without deterioration. Applied for the first time in humans, diamond electrode recordings from thalamic targets in patients (n = 4) undergoing DBS for tremor produced signals consistent with adenosine release at a sensitivity comparable to carbon fiber electrodes. (Clinical trials # NCT01705301).

Determination of ascorbic acid by a gold–zinc Oxide Nanoparticle-Modified Glassy carbon electrode

.A novel electrochemical sensing platform was developed based on flower-like gold–zinc oxide core–shell nanoparticles and a graphene nanocomposite-modified glassy carbon electrode. The gold–zinc oxide core–shell nanoflowers were synthesized by seed growth and characterized by high-resolution transmission electron microscopy, energy-dispersive X-ray spectroscopy, and ultraviolet-visible absorption spectroscopy. The modified electrode provided good electrocatalytic properties, rapid response, high stability, and favorable reproducibility for determination of ascorbic acid. The performance of the sensor included a linear dynamic range from 1.0 × 10−7 to 6.0 × 10−4 M, a limit of detection of 3.9 × 10−8 M, and a sensitivity of 24.12 µA/mM. The nanocomposite also provided excellent selectivity and lower potential for the oxidation of ascorbic acid. The sensor was used for the determination of ascorbic acid in tablets with satisfactory results. This device provides rapid, simple, and selective determination of ascorbic acid.

The impact of external forces on cartel network dynamics: direct research in the diamond industry

This paper describes the impact of external environmental forces on cartel networks. Using a case research approach, this report examines two leading business networks within one industry, over time. The results suggest that (a) bargaining power of intermediaries increases with the advent of new and powerful actors, (b) process activities that cartels previously controlled are being outsourced to new actors sometimes based in developing countries, (c) other actors are acquiring resources once dominated by a cartel, (d) external forces triggered by the illegal diamond trade, such as international regulatory constraints, no longer favour cartels like De Beers, and (e) over time, these and additional environment factors are forcing actors like De Beers who perform rigid process activities to become more flexible. For example, forces are moving cartels which relied previously on hand-picked intermediaries in highly controlled networks to market their products to adopt a flexible market-focused expansion of operations in retail contexts.