Primary and rechargeable zinc-air batteries using ceramic and highly stable TiCN as an oxygen reduction reaction electrocatalyst

Primary and secondary zinc-air batteries based on ceramic, stable, one dimensional titanium carbonitride (TiCN) nanostructures are reported. The optimized titanium carbonitride composition by density functional theory reveals their good activity towards the oxygen reduction reaction (ORR). Electrochemical measurements show their superior performance for the ORR in alkaline media coupled with favourable kinetics. The nanostructured TiCN lends itself amenable to be used as an air cathode material in primary and rechargeable zinc-air batteries. The battery performance and cyclability are found to be good. Further, we have demonstrated a gel-based electrolyte for rechargeable zinc-air batteries based on a TiCN cathode under ambient, atmospheric conditions without any oxygen supply from a cylinder. The present cell can work at current densities of 10-20 mA cm(2) (app. 10 000 mA g(-1) of TiCN) for several hours (63 h in the case of 10 mA cm(-2)) with a charge retention of 98%. The low cost, noble metal-free, mechanically stable and corrosion resistant TiCN is a very good alternative to Pt for metal-air battery chemistry.

Structural and Mechanical Properties of the Organic Matrix Layers of Nacre

The type of nanostructure referred to in biomineralization as a mineral bridge has been directly observed and measured in the organic matrix layers of nacre by transmission electron microscopy and scanning electron microscopy. Statistical analysis provides the geometric characteristics and a distribution law of the mineral bridges in the organic matrix layers. Experiments reveal that the nanostructures significantly influences the mechanical properties of the organic matrix layers. In addition, the mechanical analysis illustrates the effects of the nanostructures on the behaviors of the organic matrix layers, and the analytical results explain the corresponding experimental phenomena fairly well. The present study shows that the mineral bridges play a key role in the mechanical performances of the organic matrix layers of nacre. The results obtained provide a guide to the interfacial design of synthetic materials.

Influence of cluster-assembly parameters on the field emission properties of nanostructured carbon films

Supersonic cluster beam deposition has been used to produce films with different nanostructures by controlling the deposition parameters such as the film thickness, substrate temperature and cluster mass distribution. The field emission properties of cluster-assembled carbon films have been characterized and correlated to the evolution of the film nanostructure. Threshold fields ranging between 4 and 10 V/mum and saturation current densities as high as 0.7 mA have been measured for samples heated during deposition. A series of voltage ramps, i.e., a conditioning process, was found to initiate more stable and reproducible emission. It was found that the presence of graphitic particles (onions, nanotube embryos) in the films substantially enhances the field emission performance. Films patterned on a micrometer scale have been conditioned spot by spot by a ball-tip anode, showing that a relatively high emission site density can be achieved from the cluster-assembled material. (C) 2002 American Institute of Physics.

Surface attachment of protein fibrils via covalent modification strategies.

Chemical control of surface functionality and topography is an essential requirement for many technological purposes. In particular, the covalent attachment of monomeric proteins to surfaces has been the object of intense studies in recent years, for applications as varied as electrochemistry, immuno-sensing, and the production of biocompatible coatings. Little is known, however, about the characteristics and requirements underlying surface attachment of supramolecular protein nanostructures. Amyloid fibrils formed by the self-assembly of peptide and protein molecules represent one important class of such structures. These highly organized beta-sheet-rich assemblies are a hallmark of a range of neurodegenerative disorders, including Alzheimer's disease and type II diabetes, but recent findings suggest that they have much broader significance, potentially representing the global free energy minima of the energy landscapes of proteins and having potential applications in material science. In this paper, we describe strategies for attaching amyloid fibrils formed from different proteins to gold surfaces under different solution conditions. Our methods involve the reaction of sulfur containing small molecules (cystamine and 2-iminothiolane) with the amyloid fibrils, enabling their covalent linkage to gold surfaces. We demonstrate that irreversible attachment using these approaches makes possible quantitative analysis of experiments using biosensor techniques, such as quartz crystal microbalance (QCM) assays that are revolutionizing our understanding of the mechanisms of amyloid growth and the factors that determine its kinetic behavior. Moreover, our results shed light on the nature and relative importance of covalent versus noncovalent forces acting on protein superstructures at metal surfaces.

Formation of composite organic thin film transistors with nanotubes and nanowires

Plastic electronics is a rapidly expanding topic, much of which has been focused on organic semiconductors. However, it is also of interest to find viable ways to integrate nanomaterials, such as silicon nanowires (SiNWs) and carbon nanotubes (CNTs), into this technology. Here, we present methods of fabrication of composite devices incorporating such nanostructured materials into an organic matrix. We investigate the formation of polymer/CNT composites, for which we use the semiconducting polymer poly(3,3‴-dialkyl-quaterthiophene) (PQT). We also report a method of fabricating polymer/SiNW TFTs, whereby sparse arrays of parallel oriented SiNWs are initially prepared on silicon dioxide substrates from forests of as-grown gold-catalysed SiNWs. Subsequent ink-jet printing of PQT on these arrays produces a polymer/SiNW composite film. We also present the electrical characterization of all composite devices. © 2007 Elsevier B.V. All rights reserved.

Relationship between prion propensity and the rates of individual molecular steps of fibril assembly.

Peptides and proteins possess an inherent propensity to self-assemble into generic fibrillar nanostructures known as amyloid fibrils, some of which are involved in medical conditions such as Alzheimer disease. In certain cases, such structures can self-propagate in living systems as prions and transmit characteristic traits to the host organism. The mechanisms that allow certain amyloid species but not others to function as prions are not fully understood. Much progress in understanding the prion phenomenon has been achieved through the study of prions in yeast as this system has proved to be experimentally highly tractable; but quantitative understanding of the biophysics and kinetics of the assembly process has remained challenging. Here, we explore the assembly of two closely related homologues of the Ure2p protein from Saccharomyces cerevisiae and Saccharomyces paradoxus, and by using a combination of kinetic theory with solution and biosensor assays, we are able to compare the rates of the individual microscopic steps of prion fibril assembly. We find that for these proteins the fragmentation rate is encoded in the structure of the seed fibrils, whereas the elongation rate is principally determined by the nature of the soluble precursor protein. Our results further reveal that fibrils that elongate faster but fracture less frequently can lose their ability to propagate as prions. These findings illuminate the connections between the in vitro aggregation of proteins and the in vivo proliferation of prions, and provide a framework for the quantitative understanding of the parameters governing the behavior of amyloid fibrils in normal and aberrant biological pathways.

The Stability of a Vertical Single-Walled Carbon Nanotube Under Its Own Weight

It has been reported recently that single carbon nanotubes were attached to AFM tips to act as nanotweezers. In order to investigate its stability, a vertical single-walled carbon nanotube (SWCNT) under its own weight is studied in this paper. The lower end of the carbon nanotube is clamped. Firstly the governing dimensionless numbers are derived by dimensional analysis. Then the theoretical analysis based on an elastic column model is carried out. Two ratios, I.e., the ratio of half wall thickness to radius (t=R) and the ratio of gravity to elastic resilience ($\rho$gR=E), and their influences on the ratio of critical length to radius are discussed. It is found that the relationship between the critical ratio of altitude to radius and ratio of half thickness to radius is approximately linear. As the dimensionless number $\rho$gR=E increases, the compressive force per unit length (weight) becomes larger, thus critical ratio of altitude to radius must become smaller to maintain stability. At last the critical length of SWCNT is calculated. The results of this paper will be helpful for the stability design of nanotweezers-like nanostructures.

Strength of nanotubes, filaments, and nanowires from sonication-onduced scission

A model to describe the cavitation-induced breakage of nanofilaments during their sonication in solution is proposed. The model predicts a limiting length below which scission no longer occurs, and accurately describes experimental results for materials ranging from carbon nanotubes to protein fibrils. Sonication-induced breakage can now be used as a probe for the strength of nanostructures. © 2009 WILEY-VCH Verlag GmbH & Co. KGaA.

Raman Spectrum of silicon nanowires

We measure the effects of phonon confinement on the Raman spectra of silicon nanowires (SiNWs). We show how previous reports of phonon confinement in SiNWs and nanostructures are actually inconsistent with phonon confinement, but are due to the intense local heating caused by the laser power used for Raman measurements. This is peculiar to nanostructures, and would require orders of magnitude higher power in bulk Si. By varying the temperature, power and excitation energy, we identify the contributions of pure confinement, heating and carrier photo-excitation. After eliminating laser-related effects, the Raman spectra show confinement signatures typical of quantum wires. © 2003 Elsevier B.V. All rights reserved.

Raman spectroscopy of silicon nanowires

We measure the effects of phonon confinement on the Raman spectra of silicon nanowires. We show how previous spectra were inconsistent with phonon confinement, but were due to intense local heating caused by the laser. This is peculiar to nanostructures, and would require orders of magnitude more power in bulk Si. By working at very low laser powers, we identify the contribution of pure confinement typical of quantum wires.

Tolman Effect On Fluid Dynamics In Carbon Nanotubes

The numerical solutions of or(R) given by two different methods (Samsonov et al., 2003; and Lu et al., 2005) are compared with the result that they are coincident closely (the difference is within 4%). We conclude that it is necessary to consider the Tolman correction in the calculation of fluid dynamics in carbon nanotubes. Although our conclusion is the same as that of Prylutskyy et al. (2005), the sign of our Tolman correction is opposite to theirs, and the difference can be attributed to the errors appeared in the paper of Prylutskyy et al.

Effect Of A Negative Poisson Ratio In The Tension Of Ceramics

The effect of a negative Poisson ratio is experimentally revealed in the tension deformation of a natural layered ceramic. This effect can increase the volume strain energy per unit volume by 1100% and, simultaneously, decrease the deformation strain energy per unit volume by about 44%, so that it effectively enhances the deformation capacity by about 1 order of magnitude in the tension of the material. The present study also shows that the physical mechanisms producing the effect are attributed to the climbing on one another of the nanostructures in the natural material, which provides a guide to the design of synthetic toughening composites.

Size effects on the melting of nickel nanowires: a molecular dynamics study

The melting process of nickel nanowires are simulated by using molecular dynamics with the quantum Sutten-Chen many-body force field. The wires studied were approximately cylindrical in cross-section and periodic boundary conditions were applied along their length; the atoms were arranged initially in a face-centred cubic structure with the [0 0 1] direction parallel to the long axis of the wire. The size effects of the nanowires on the melting temperatures are investigated. We find that for the nanoscale regime, the melting temperatures of Ni nanowires are much lower than that of the bulk and are linear with the reciprocal of the diameter of the nanowire. When a nanowire is heated up above the melting temperature, the neck of the nanowire begins to arise and the diameter of neck decreases rapidly with the equilibrated running time. Finally, the breaking of nanowire arises, which leads to the formation of the spherical clusters. (C) 2004 Elsevier B.V. All rights reserved.

On the formation of well-aligned ZnO nanowall networks by catalyst-free thermal evaporation method

Two-dimensional ZnO nanowall networks were grown on ZnO-coated silicon by thermal evaporation at low temperature without catalysts or additives. All of the results from scanning electronic spectroscope, X-ray diffraction and Raman scattering confirmed that the ZnO nanowalls were vertically aligned and c-axis oriented. The room-temperature photoluminescence spectra showed a dominated UV peak at 378 nm, and a much suppressed orange emission centered at similar to 590 nm. This demonstrates fairly good crystal quality and optical properties of the product. A possible three-step, zinc vapor-controlled process was proposed to explain the growth of well-aligned ZnO nanowall networks. The pre-coated ZnO template layer plays a key role during the synthesis process, which guides the growth direction of the synthesized products. (C) 2007 Elsevier B.V. All rights reserved.