Conformal oxide coating of carbon nanotubes

The International Roadmap for Ferroelectric Memories requires three-dimensional integration of high-dielectric materials onto metal interconnects or bottom electrodes by 2010. Here, we demonstrate the possibility of conformally coating carbon nanotubes with high-dielectric oxide as a first step toward ultrahigh integration density of three-dimensional ferroelectric random access memories.

Structure, Morphology, and Electrochemical Properties of Transition Metal Oxide, Hydroxide, and Phosphate Nanomaterials for Energy Storage

Energy storage technologies are crucial for efficient utilization of electricity. Supercapacitors and rechargeable batteries are of currently available energy storage systems. Transition metal oxides, hydroxides, and phosphates are the most intensely investigated electrode materials for supercapacitors and rechargeable batteries due to their high theoretical charge storage capacities resulted from reversible electrochemical reactions. Their insulating nature, however, causes sluggish electron transport kinetics within these electrode materials, hindering them from reaching the theoretical maximum. The conductivity of these transition metal based-electrode materials can be improved through three main approaches; nanostructuring, chemical substitution, and introducing carbon matrices. These approaches often lead to unique electrochemical properties when combined and balanced.

Ethanol-mediated solvothermal synthesis we developed is found to be highly effective for controlling size and morphology of transition metal-based electrode materials for both pseudocapacitors and batteries. The morphology and the degree of crystallinity of nickel hydroxide are systematically changed by adding various amounts glucose to the solvothermal synthesis. Nickel hydroxide produced in this manner exhibited increased pseudocapacitance, which is partially attributed to the increased surface area. Interestingly, this morphology effect on cobalt doped-nickel hydroxide is found to be more effective at low cobalt contents than at high cobalt contents in terms of improving the electrochemical performance.

Moreover, a thin layer of densely packed nickel oxide flakes on carbon paper substrate was successfully prepared via the glucose-assisted solvothermal synthesis, resulting in the improved electrode conductivity. When reduced graphene oxide was used for conductive coating on as-prepared nickel oxide electrode, the electrode conductivity was only slightly improved. This finding reveals that the influence of reduced graphene oxide coating, increasing the electrode conductivity, is not that obvious when the electrode is already highly conductive to begin with.

We were able to successfully control the interlayer spacing and reduce the particle size of layered titanium hydrogeno phosphate material using our ethanol-mediated solvothermal reaction. In layered structure, interlayer spacing is the key parameter for fast ion diffusion kinetics. The nanosized layered structure prepared via our method, however, exhibited high sodium-ion storage capacity regardless of the interlayer spacing, implying that interlayer space may not be the primary factor for sodium-ion diffusion in nanostructured materials, where many interstitials are available for sodium-ion diffusion.

Our ethanol-mediated solvothermal reaction was also effective for synthesis of NaTi2(PO4)3 nanoparticles with uniform size and morphology, well connected by a carbon nanotube network. This composite electrode exhibited high capacity, which is comparable to that in aqueous electrolyte, probably due to the uniform morphology and size where the preferable surface for sodium-ion diffusion is always available in all individual particles.

Fundamental understandings of the relationship between electrode microstructures and electrochemical properties discussed in this dissertation will be important to design high performance energy storage system applications.

High-resolution TEM characterization of ZnO core-shell nanowires for dye-sensitized solar cells

Recently ZnO nanowire films have been used in very promising and inexpensive dye-sensitized solar cells (DSSC). It was found that the performance of the devices can be enhanced by functionalising the nanowires with a thin metal oxide coating. This nm-scale shell is believed to tailor the electronic structure of the nanowire, and help the absorption of the dye. Core-shell ZnO nanowire structures are synthesised at low temperature (below 120°C) by consecutive hydrothermal growth steps. Different materials are investigated for the coating, including Mg, Al, Cs and Zr oxides. High resolution TEM is used to characterise the quality of both the nanowire core and the shell, and to monitor the thickness and the degree of crystallisation of the oxide coating. The interface between the nanowire core and the outer shell is investigated in order to understand the adhesion of the coating, and give valuable feedback for the synthesis process. Nanowire films are packaged into dye-sensitised solar cell prototypes; samples coated with ZrO2 and MgO show the largest enhancement in the photocurrent and open-circuit voltage and look very promising for further improvement. © 2010 IOP Publishing Ltd.

西江流域环境河水地球化学研究

River is a major component of the global surface water and CO2 cycles. The chemistry of river waters reveals the nature of weathering on a basin-wide scale and helps us understand the exogenic cycles of elements in the continent-river-ocean system. In particular, geochemical investigation of large river gives important information on the biogeochemical cycles of the elements, chemical weathering rates, physical erosion rates and CO2 consumption during the weathering of the rocks within the drainage basin. Its importance has led to a number of detailed geochemical studies on some of the world's large and medium-size river systems. Flowing in the south of China, the Xijiang River is the second largest river in the China with respect to its discharge, after the Yangtze River. Its headwaters drain the YunGui Plateau, where altitude is approximately 2000 meters. Geologically, the carbonate rocks are widely spread in the river drainage basin, which covers an area of about 0.17xl06 km2, i.e., 39% of the whole drainage basin. This study focuses on the chemistry of the Xijiang river system and constitutes the first geochemical investigation into major and trace elements concentrations for both suspended and dissolved loads of this river and its main tributaries, and Sr isotopic composition of the dissolved load is also investigated, in order to determine both chemical weathering and mechanical erosion rates. As compared with the other large rivers of the world, the Xijiang River is characterized by higher major element concentration. The dissolved major cations average 1.17, 0.33, 0.15, and 0.04 mmol I"1 for Ca, Mg, Na, and K, respectively. The total cation concentrations (TZ+) in these rivers vary between 2.2 and 4.4 meq I'1. The high concentration of Ca and Mg, high (Ca+Mg)/(Na+K) ratio (7.9), enormous alkalinity and low dissolved SiO2/HCO3 ratio (0.05) in river waters reveal the importance of carbonate weathering and relatively weak silicate weathering over the river drainage basin. The major elements in river water, such as the alkalis and alkaline-earths, are of different origins: from rain water, silicate weathering, carbonate and evaporite weathering. A mixing model based on mass budget equation is used in this study, which allows the proportions of each element derived from the different source to be calculated. The carbonate weathering is the main source of these elements in the Xijiang drainage basin. The contribution of rainwater, especially for Na, reaches to approximately 50% in some tributaries. Dissolved elemental concentration of the river waters are corrected for rain inputs (mainly oceanic salts), the elemental concentrations derived from the different rock weathering are calculated. As a consequence, silicate, carbonate and total rock weathering rates, together with the consumption rates of atmospheric CO2 by weathering of each of these lithologies have been estimated. They provide specific chemical erosion rates varying between 5.1~17.8 t/km2/yr for silicate, 95.5~157.2 t/km2/yr for carbonate, and 100.6-169.1 t/km2/yr for total rock, respectively. CO2 consumptions by silicate and carbonate weathering approach 13><109and 270.5x10 mol/yr. Mechanical denudation rates deduced from the multi-year average of suspended load concentrations range from 92-874 t/km2/yr. The high denudation rates are mainly attributable to high relief and heavy rainfall, and acid rain is very frequent in the drainage basin, may exceed 50% and the pH value of rainwater may be <4.0, result from SO2 pollution in the atmosphere, results in the dissolution of carbonates and aluminosilicates and hence accelerates the chemical erosion rate. The compositions of minerals and elements of suspended particulate matter are also investigated. The most soluble elements (e.g. Ca, Na, Sr, Mg) are strongly depleted in the suspended phase with respect to upper continent crust, which reflects the high intensity of rock weathering in the drainage basin. Some elements (e.g. Pb, Cu, Co, Cr) show positive anomalies, Pb/Th ratios in suspended matter approach 7 times (Liu Jiang) to 10 times (Nanpan Jiang) the crustal value. The enrichment of these elements in suspended matter reflects the intensity both of anthropogenic pollution and adsorption processes onto particles. The contents of the soluble fraction of rare earth elements (REE) in the river are low, and REE mainly reside in particulate phase. In dissolved phase, the PAAS-normalized distribution patterns show significant HREE enrichment with (La/Yb) SN=0.26~0.94 and Ce depletion with (Ce/Ce*) SN=0.31-0.98, and the most pronounced negative Ce anomalies occur in rivers of high pH. In the suspended phase, the rivers have LREE-enriched patterns relative to PAAS, with (La/Yb) SN=1 -00-1 .40. The results suggest that pH is a major factor controlling both the absolute abundances of REE in solution and the fractionation of REE of dissolved phase. Ce depletion in river waters with high pH values results probably from both preferential removal of Ce onto Fe-Mn oxide coating of particles and CeC^ sedimentation. This process is known to occur in the marine environment and may also occur in high pH rivers. Positive correlations are also observed between La/Yb ratio and DOC, HCO3", PO4", suggesting that colloids and (or) adsorption processes play an important role in the control of these elements.

Photocatalytic activity of nanostructured anatase coatings obtained by cold gas spray

[EN] This article describes a photocatalytic nanostructured anatase coating deposited by cold gas spray (CGS) supported on titanium sub-oxide (TiO22x) coatings obtained by atmospheric plasma spray (APS) onto stainless steel cylinders. The photocatalytic coating was homogeneous and preserved the composition and nanostructure of the starting powder. The inner titanium sub-oxide coating favored the deposition of anatase particles in the solid state. Agglomerated nano-TiO2 particles fragmented when impacting onto the hard surface of the APS TiO22x bond coat. The rough surface provided by APS provided an ideal scenario for entrapping the nanostructured particles, which may be adhered onto the bond coat due to chemical bonding; a possible bonding mechanism is described. Photocatalytic experiments showed that CGS nano-TiO2 coating was active for photodegrading phenol and formic acid under aqueous conditions. The results were similar to the performance obtained by competitor technologies and materials such as dip-coating P25 photocatalysts. Disparity in the final performance of the photoactive materials may have been caused by differences in grain size and the crystalline composition of titanium dioxide.

Electrolytic Recovery of Copper and Zinc from Brasses

Reclaimed metals, or secondary metals, are becoming of great im­portance in the metal industries of the world. Secondary metals are an important factor in production. The increase in the secondary production of copper is due to many factors. One of these may be its permenance, that is, the metal does not corrode very readily. Another reason for increase in production is the high price paid for it.

An Investigation of the Anodic Oxidation of Aluminum in a Sulfuric Acid Electrolyte

When aluminum is allowed to stand in air or is heated in air, a thin oxide film is produced on the metal. If aluminum is made the anode in a suitable electrolyte and a current applied, a coating is obtained which is similar to that produced in air, but may be effected much quicker. This film is thicker, harder, more resistant to corrosion and abrasion, and more adhesive than the natural oxide. The film is porous and makes an excellent adsorptive for dyes and pigments.

Neodymium and Strontium chemistry of Arctic Ocean sediments

The early oceanographic history of the Arctic Ocean is important in regulating, and responding to, climatic changes. However, constraints on its oceanographic history preceding the Quaternary (the past 1.8 Myr) have become available only recently, because of the difficulties associated with obtaining continuous sediment records in such a hostile setting. Here, we use the neodymium isotope compositions of two sediment cores recovered near the North Pole to reconstruct over the past ~5 Myr the sources contributing to Arctic Intermediate Water, a water mass found today at depths of 200 to 1,500 m. We interpret high neodymium ratios for the period between 15 and 2 Myr ago, and for the glacial periods thereafter, as indicative of weathering input from the Siberian Putoranan basalts into the Arctic Ocean. Arctic Intermediate Water was then derived from brine formation in the Eurasian shelf regions, with only a limited contribution of intermediate water from the North Atlantic. In contrast, the modern circulation pattern, with relatively high contributions of North Atlantic Intermediate Water and negligible input from brine formation, exhibits low neodymium isotope ratios and is typical for the interglacial periods of the past 2 Myr. We suggest that changes in climatic conditions and the tectonic setting were responsible for switches between these two modes.

Madrepora oculata and Lophelia pertusa mass and 210Pb-226Ra chronology, Røst Reef, Norway, 2011

Here we show the use of the 210Pb-226Ra excess method to determine the growth rate of corals from one of the world's largest known cold-water coral reef, the Røst Reef off Norway. Two large branching framework-forming cold-water coral specimens, one Lophelia pertusa and one Madrepora oculata were collected alive at 350 m water depth from the Røst Reef at ~67° N and ~9° E. Pb and Ra isotopes were measured along the major growth axis of both specimens using low level alpha and gamma spectrometry and the corals trace element compositions were studied using ICP-QMS. Due to the different chemical behaviors of Pb and Ra in the marine environment, 210Pb and 226Ra were not incorporated the same way into the aragonite skeleton of those two cold-water corals. Thus to assess of the growth rates of both specimens we have here taken in consideration the exponential decrease of initially incorporated 210Pb as well as the ingrowth of 210Pb from the decay of 226Ra. Moreover a~post-depositional 210Pb incorporation is found in relation to the Mn-Fe coatings that could not be entirely removed from the oldest parts of the skeletons. The 226Ra activities in both corals were fairly constant, then assuming constant uptake of 210Pb through time the 210Pb-226Ra chronology can be applied to calculate linear growth rate. The 45.5 cm long branch of M. oculata reveals an age of 31 yr and a~linear growth rate of 14.4 ± 1.1 mm yr-1, i.e. 2.6 polyps per year. However, a correction regarding a remaining post-depositional Mn-Fe oxide coating is needed for the base of the specimen. The corrected age tend to confirm the radiocarbon derived basal age of 40 yr (using 14C bomb peak) with a mean growth rate of 2 polyps yr-1. This rate is similar to the one obtained in Aquaria experiments under optimal growth conditions. For the 80 cm-long specimen of L. pertusa a remaining contamination of metal-oxides is observed for the middle and basal part of the coral skeleton, inhibiting similar accurate age and growth rate estimates. However, the youngest branch was free of Mn enrichment and this 15 cm section reveals a growth rate of 8 mm yr-1 (~1 polyp every two to three years). However, the 210Pb growth rate estimate is within the lowermost ranges of previous growth rate estimates and may thus reflect that the coral was not developing at optimal growth conditions. Overall, 210Pb-226Ra dating can be successfully applied to determine the age and growth rate of framework-forming cold-water corals, however, removal of post-depositional Mn-Fe oxide deposits is a prerequisite. If successful, large branching M. oculata and L. pertusa coral skeletons provide unique oceanographic archive for studies of intermediate water environmentals with an up to annual time resolution and spanning over many decades.

Metal oxide nanofibres membranes assembled by spin-coating method

Ceramic membranes are of particular interest in many industrial processes due to their ability to function under extreme conditions while maintaining their chemical and thermal stability. Major structural deficiencies under conventional fabrication approach are pin-holes and cracks, and the dramatic losses of flux when pore sizes are reduced to enhance selectivity. We overcome these structural deficiencies by constructing hierarchically structured separation layer on a porous substrate using larger titanate nanofibres and smaller boehmite nanofibres. This yields a radical change in membrane texture. The differences in the porous supports have no substantial influences on the texture of resulting membranes. The membranes with top layer of nanofibres coated on different porous supports by spin-coating method have similar size of the filtration pores, which is in a range of 10–100 nm. These membranes are able to effectively filter out species larger than 60 nm at flow rates orders of magnitude greater than conventional membranes. The retention can attain more than 95%, while maintaining a high flux rate about 900 L m-2 h. The calcination after spin-coating creates solid linkages between the fibres and between fibres and substrate, in addition to convert boehmite into -alumina nanofibres. This reveals a new direction in membrane fabrication.

Gold coating of silica and zinc oxide nanoparticles by the surface reduction of gold(I) chloride

The possibility of a surface inner sphere electron transfer mechanism leading to the coating of gold via the surface reduction of gold(I) chloride on metal and semi-metal oxide nanoparticles was investigated. Silica and zinc oxide nanoparticles are known to have very different surface chemistry, potentially leading to a new class of gold coated nanoparticles. Monodisperse silica nanoparticles were synthesised by the well known Stöber protocol in conjunction with sonication. The nanoparticle size was regulated solely by varying the amount of ammonia solution added. The presence of surface hydroxyl groups was investigated by liquid proton NMR. The resultant nanoparticle size was directly measured by the use of TEM. The synthesised silica nanoparticles were dispersed in acetonitrile (MeCN) and added to a bis acetonitrile gold(I) co-ordination complex [Au(MeCN)2]+ in MeCN. The silica hydroxyl groups were deprotonated in the presence of MeCN generating a formal negative charge on the siloxy groups. This allowed the [Au(MeCN)2]+ complex to undergo ligand exchange with the silica nanoparticles, which formed a surface co-ordination complex with reduction to gold(0), that proceeded by a surface inner sphere electron transfer mechanism. The residual [Au(MeCN)2]+ complex was allowed to react with water, disproportionating into gold(0) and gold(III) respectively, with gold(0) being added to the reduced gold already bound on the silica surface. The so-formed metallic gold seed surface was found to be suitable for the conventional reduction of gold(III) to gold(0) by ascorbic acid. This process generated a thin and uniform gold coating on the silica nanoparticles. This process was modified to include uniformly gold coated composite zinc oxide nanoparticles (Au@ZnO NPs) using surface co-ordination chemistry. AuCl dissolved in acetonitrile (MeCN) supplied chloride ions which were adsorbed onto ZnO NPs. The co-ordinated gold(I) was reduced on the ZnO surface to gold(0) by the inner sphere electron transfer mechanism. Addition of water disproportionated the remaining gold(I) to gold(0) and gold(III). Gold(0) bonded to gold(0) on the NP surface with gold(III) was reduced to gold(0) by ascorbic acid (ASC), which completed the gold coating process. This gold coating process of Au@ZnO NPs was modified to incorporate iodide instead of chloride. ZnO NPs were synthesised by the use of sodium oxide, zinc iodide and potassium iodide in refluxing basic ethanol with iodide controlling the presence of chemisorbed oxygen. These ZnO NPs were treated by the addition of gold(I) chloride dissolved in acetonitrile leaving chloride anions co-ordinated on the ZnO NP surface. This allowed acetonitrile ligands in the added [Au(MeCN)2]+ complex to surface exchange with adsorbed chloride from the dissolved AuCl on the ZnO NP surface. Gold(I) was then reduced by the surface inner sphere electron transfer mechanism. The presence of the reduced gold on the ZnO NPs allowed adsorption of iodide to generate a uniform deposition of gold onto the ZnO NP surface without the use of additional reducing agents or heat.

Multi-wall carbon nanotube coating of fluorine-doped tin oxide as an electrode surface modifier for polymer solar cells

A controlled layer of multi-wall carbon nanotubes (MWCNT) was grown directly on top of fluorine-doped tin oxide (FTO) glass electrodes as a surface modifier for improving the performance of polymer solar cells. By using low-temperature chemical vapor deposition with short synthesis times, very short MWCNTs were grown, these uniformly decorating the FTO surface. The chemical vapor deposition parameters were carefully refined to balance the tube size and density, while minimizing the decrease in conductivity and light harvesting of the electrode. As created FTO/CNT electrodes were applied to bulk-heterojunction polymer solar cells, both in direct and inverted architecture. Thanks to the inclusion of MWCNT and the consequent nano-structuring of the electrode surface, we observe an increase in external quantum efficiency in the wavelength range from 550 to 650 nm. Overall, polymer solar cells realized with these FTO/CNT electrodes attain power conversion efficiency higher than 2%, outclassing reference cells based on standard FTO electrodes.

Studies on the deposition and characterization of silicon oxide films for optical coating applications

Silicon oxide films were deposited by reactive evaporation of SiO. Parameters such as oxygen partial pressure and substrate temperature were varied to get variable and graded index films. Films with a refractive index in the range 1.718 to 1.465 at 550 nm have been successfully deposited. Films deposited using ionized oxygen has the refractive index 1.465 at 550 nm and good UV transmittance like bulk fused quartz. Preparation of graded index films was also investigated by changing the oxygen partial pressure during deposition. A two layer antireflection coating at 1064nm has been designed using both homogeneous and inhomogeneous films and studied their characteristics.

Simple coating technique for 2-dimensional zinc oxide nanostructure

We report a novel and simple solution-based technique for depositing 2-D zinc oxide platelets at low temperature. Nanoplatelets that were mostly a-oriented associated with the Lotgering orientation factor of 0.65 were obtained by locating a glass substrate at a distance of about 5cm over the aqueous vapour of the boiling precursor. Experiments were carried out to optimize the coating parameters by placing the substrate at different positions, durations and the pH of the precursor. The X-ray diffraction studies confirmed the structure associated with the crystallites to be wurzite. The different morphology of the zinc oxide films and blue light emission were observed using scanning electron microscopy and fluorescence spectroscopy respectively.

Thermal barrier coating of lanthanum-zirconium-cerium composite oxide made by electron beam-physical vapor deposition

Lanthanum-zirconium-cerium composite oxide (La-2(Zr0.7Ce0.3)(2)O-7, LZ7C3) as a candidate material for thermal barrier coatings (TBCs) was prepared by electron beam-physical vapor deposition (EB-PVD). The composition, crystal structure, thermophysical properties, surface and cross-sectional morphologies and cyclic oxidation behavior of the LZ7C3 coating were studied. The results indicated that LZ7C3 has a high phase stability between 298 K and 1573 K, and its linear thermal expansion coefficient (TEC) is similar to that of zirconia containing 8 wt% yttria (8YSZ). The thermal conductivity of LZ7C3 is 0.87 W m(-1) K-1 at 1273 K, which is almost 60% lower than that of 8YSZ. The deviation of coating composition from the ingot can be overcome by the addition of excess CeO2 and ZrO2 during ingot preparation or by adjusting the process parameters.