In situ scanning tunneling microscopy studies of nanometer size palladium particles on highly oriented pyrolytic graphite

A special electrodeposition process of palladium was studied by cyclic voltammetry, X-ray photoelectron spectroscopy (XPS) and in situ scanning tunneling microscopy (STM). A kind of palladium(IV) complex was attached to the highly oriented pyrolytic graphite (HOPG) electrode surface by electro-oxidation of palladium(II) complex first, and was then reduced to palladium particles. The surface complexes and particles of palladium were both characterized by in situ STM and XPS. The Pd particles are in the nanometer range of size and exhibit electrocatalytic activity towards the oxidation of hydrazine and hydroxylamine.

Nanometer-size anisotropy of injection-molded polymer micro-cantilever arrays

Understanding and controlling the structural anisotropies of injection-molded polymers is vital for designing products such as cantilever-based sensors. Such micro-cantilevers are considered as cost-effective alternatives to single-crystalline silicon-based sensors. In order to achieve similar sensing characteristics,structure and morphology have to be controlled by means of processing parameters including mold temperature and injection speed. Synchrotron radiation-based scanning small- (SAXS) and wide-angle x-ray scattering techniques were used to quantify crystallinity and anisotropy in polymer micro-cantilevers with micrometer resolution in real space. SAXS measurements confirmed the lamellar nature of the injection-molded semi-crystalline micro-cantilevers. The homogenous cantilever material exhibits a lamellar periodicity increasing with mold temperature but not with injection speed. We demonstrate that micro-cantilevers made of semi-crystalline polymers such as polyvinylidenefluoride, polyoxymethylene, and polypropylene show the expected strong degree of anisotropy along the injection direction.

Size dependent microstructure for Ag-Ni nanoparticles

The Ag-Ni system is characterized by large differences in atomic sizes (14%) and a positive heat of mixing (+23 kJ mol(-1)). The binary equilibrium diagram for this system therefore exhibits a large miscibility gap in both solid and liquid state. This paper explores the size-dependent changes in microstructure and the suppression of the miscibility gap which occurs when free alloy particles of nanometer size are synthesized by co-reduction of Ag and Ni metal precursors. The paper reports that complete mixing between Ag and Ni atoms could be achieved for smaller nanoparticles (<7 nm). These particles exhibit a single-phase solid solution with face-centered cubic (fcc) structure. With increase in size, the nanoparticles revealed two distinct regions. One of the regions is composed of pure Ag. This region partially surrounds a region of fcc solid solution at an early stage of decomposition. Experimental observations were compared with the results obtained from the thermodynamic calculations, which compared the free energies corresponding to a physical mixture of pure Ag and Ni phases and a fcc Ag-Ni solid solution for different particle sizes. Results from the theoretical calculations revealed that, for the Ag-Ni system, solid solution was energetically preferred over the physical mixture configuration for particle sizes of 7 nm and below. The experimentally observed two-phase microstructure for larger particles was thus primarily due to the growth of Ag-rich regions epitaxially on initially formed small fcc Ag-Ni nanoparticles. (C) 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Size-induced diffuse behavior in Pb0.89La0.11Zr0.40Ti0.60O3 nanocrystalline ferroelectric ceramics

The Pb1-xLaxZryTi1-yO3 system is a perovskite ABO(3) structured material which presents ferroelectric properties and has been used as capacitors, actuators, transducers and electro-optic devices. In this paper, we describe the synthesis and the characterization of Pb0.89La0.11Zr0.40Ti0.60O3 (PLZT11) nanostructured material. The precursor polymeric method and the spark plasma sintering technique were respectively used to prepare ceramic samples. In order to compare the effect of grain size, microcrystalline PLZT11 ceramic samples were also prepared. PLZT11 samples were characterized by X-ray diffraction technique which results show a reduction on the degree of tetragonality as the average grain size decreases. Moreover, the grain size decrease to a nanometer range induces a diffuse behavior on the dielectric permittivity curves as a function of the temperature and a reduction on the dielectric permittivity magnitude. Furthermore, the large number of grain boundaries due to the nanometer size gives rise to a dielectric anomaly. (C) 2012 Elsevier Masson SAS. All rights reserved.

Atomic scale engineering of carbon nanotubes

Carbon nanotubes, seamless cylinders made from carbon atoms, have outstanding characteristics: inherent nano-size, record-high Young’s modulus, high thermal stability and chemical inertness. They also have extraordinary electronic properties: in addition to extremely high conductance, they can be both metals and semiconductors without any external doping, just due to minute changes in the arrangements of atoms. As traditional silicon-based devices are reaching the level of miniaturisation where leakage currents become a problem, these properties make nanotubes a promising material for applications in nanoelectronics. However, several obstacles must be overcome for the development of nanotube-based nanoelectronics. One of them is the ability to modify locally the electronic structure of carbon nanotubes and create reliable interconnects between nanotubes and metal contacts which likely can be used for integration of the nanotubes in macroscopic electronic devices. In this thesis, the possibility of using ion and electron irradiation as a tool to introduce defects in nanotubes in a controllable manner and to achieve these goals is explored. Defects are known to modify the electronic properties of carbon nanotubes. Some defects are always present in pristine nanotubes, and naturally are introduced during irradiation. Obviously, their density can be controlled by irradiation dose. Since different types of defects have very different effects on the conductivity, knowledge of their abundance as induced by ion irradiation is central for controlling the conductivity. In this thesis, the response of single walled carbon nanotubes to ion irradiation is studied. It is shown that, indeed, by energy selective irradiation the conductance can be controlled. Not only the conductivity, but the local electronic structure of single walled carbon nanotubes can be changed by the defects. The presented studies show a variety of changes in the electronic structures of semiconducting single walled nanotubes, varying from individual new states in the band gap to changes in the band gap width. The extensive simulation results for various types of defect make it possible to unequivocally identify defects in single walled carbon nanotubes by combining electronic structure calculations and scanning tunneling spectroscopy, offering a reference data for a wide scientific community of researchers studying nanotubes with surface probe microscopy methods. In electronics applications, carbon nanotubes have to be interconnected to the macroscopic world via metal contacts. Interactions between the nanotubes and metal particles are also essential for nanotube synthesis, as single walled nanotubes are always grown from metal catalyst particles. In this thesis, both growth and creation of nanotube-metal nanoparticle interconnects driven by electron irradiation is studied. Surface curvature and the size of metal nanoparticles is demonstrated to determine the local carbon solubility in these particles. As for nanotube-metal contacts, previous experiments have proved the possibility to create junctions between carbon nanotubes and metal nanoparticles under irradiation in a transmission electron microscope. In this thesis, the microscopic mechanism of junction formation is studied by atomistic simulations carried out at various levels of sophistication. It is shown that structural defects created by the electron beam and efficient reconstruction of the nanotube atomic network, inherently related to the nanometer size and quasi-one dimensional structure of nanotubes, are the driving force for junction formation. Thus, the results of this thesis not only address practical aspects of irradiation-mediated engineering of nanosystems, but also contribute to our understanding of the behaviour of point defects in low-dimensional nanoscale materials.

Novel Approaches to the Sampling of Atmospheric Aerosols and Determination of Chemical Composition

The Earth s climate is a highly dynamic and complex system in which atmospheric aerosols have been increasingly recognized to play a key role. Aerosol particles affect the climate through a multitude of processes, directly by absorbing and reflecting radiation and indirectly by changing the properties of clouds. Because of the complexity, quantification of the effects of aerosols continues to be a highly uncertain science. Better understanding of the effects of aerosols requires more information on aerosol chemistry. Before the determination of aerosol chemical composition by the various available analytical techniques, aerosol particles must be reliably sampled and prepared. Indeed, sampling is one of the most challenging steps in aerosol studies, since all available sampling techniques harbor drawbacks. In this study, novel methodologies were developed for sampling and determination of the chemical composition of atmospheric aerosols. In the particle-into-liquid sampler (PILS), aerosol particles grow in saturated water vapor with further impaction and dissolution in liquid water. Once in water, the aerosol sample can then be transported and analyzed by various off-line or on-line techniques. In this study, PILS was modified and the sampling procedure was optimized to obtain less altered aerosol samples with good time resolution. A combination of denuders with different coatings was tested to adsorb gas phase compounds before PILS. Mixtures of water with alcohols were introduced to increase the solubility of aerosols. Minimum sampling time required was determined by collecting samples off-line every hour and proceeding with liquid-liquid extraction (LLE) and analysis by gas chromatography-mass spectrometry (GC-MS). The laboriousness of LLE followed by GC-MS analysis next prompted an evaluation of solid-phase extraction (SPE) for the extraction of aldehydes and acids in aerosol samples. These two compound groups are thought to be key for aerosol growth. Octadecylsilica, hydrophilic-lipophilic balance (HLB), and mixed phase anion exchange (MAX) were tested as extraction materials. MAX proved to be efficient for acids, but no tested material offered sufficient adsorption for aldehydes. Thus, PILS samples were extracted only with MAX to guarantee good results for organic acids determined by liquid chromatography-mass spectrometry (HPLC-MS). On-line coupling of SPE with HPLC-MS is relatively easy, and here on-line coupling of PILS with HPLC-MS through the SPE trap produced some interesting data on relevant acids in atmospheric aerosol samples. A completely different approach to aerosol sampling, namely, differential mobility analyzer (DMA)-assisted filter sampling, was employed in this study to provide information about the size dependent chemical composition of aerosols and understanding of the processes driving aerosol growth from nano-size clusters to climatically relevant particles (>40 nm). The DMA was set to sample particles with diameters of 50, 40, and 30 nm and aerosols were collected on teflon or quartz fiber filters. To clarify the gas-phase contribution, zero gas-phase samples were collected by switching off the DMA every other 15 minutes. Gas-phase compounds were adsorbed equally well on both types of filter, and were found to contribute significantly to the total compound mass. Gas-phase adsorption is especially significant during the collection of nanometer-size aerosols and needs always to be taken into account. Other aims of this study were to determine the oxidation products of β-caryophyllene (the major sesquiterpene in boreal forest) in aerosol particles. Since reference compounds are needed for verification of the accuracy of analytical measurements, three oxidation products of β-caryophyllene were synthesized: β-caryophyllene aldehyde, β-nocaryophyllene aldehyde, and β-caryophyllinic acid. All three were identified for the first time in ambient aerosol samples, at relatively high concentrations, and their contribution to the aerosol mass (and probably growth) was concluded to be significant. Methodological and instrumental developments presented in this work enable fuller understanding of the processes behind biogenic aerosol formation and provide new tools for more precise determination of biosphere-atmosphere interactions.

Nonlinear Transport in Hybrid Polypyrrole-Gold Nanostructures

We have studied charge transport in nanometer scale films of polypyrrole (PPy) that were grown electrochemically onto discontinuous ultrathin films of gold. The gold films consisted of 100 nm size islands, separated from each other by nanometer-size gaps. The thickness of PPy can be varied from 30 to 200 nm. The I-V characteristics of these hybrid PPy-Au nanostructures show strong non-linearity at low temperatures, and in particular for the more insulating samples. The hopping transport is further verified from the log / versus V-1/4 plots. Furthermore, the I-V data follow an empirical relation dlog//dV(1/4) similar to T-1/2.

Wet chemical formation of nanoparticles of binary perovskites through isothermal gel to crystallite conversion

Coarse BO2·xH2O (2 < x < 80) gels, free of anion contaminants react with A(OH)2 under refluxing conditions at 70�100°C giving rise to crystallites of single phased, nanometer size powders of ABO3 perovskites (A = Ba, Sr, Ca, Mg, Pb; B = Zr, Ti, Sn). Solid solutions of perovskites could be prepared from compositionally modified gels or mixtures of A(OH)2. Donor doped perovskites could also be prepared from the same method so that the products after processing are often semiconducting. Faster interfacial diffusion of A2+ ions into the gel generates the crystalline regions whose composition is controllable by the A/B ratio as well as the A(OH)2 concentration.

Evidence of nanoscale structural phase separation in large bandwidth La0.2Sr0.8MnO3

We have investigated the structural evolution of La0.2Sr0.8MnO3 using temperature dependent high resolution synchrotron x-ray diffraction technique. In a wide temperature range, La0.2Sr0.8MnO3 reveals nanoscale structural inhomogeneity consisting of cubic and tetragonal phases. The present results suggest that domains of nanometer size of the tetragonal (low temperature) phase start nucleating in the cubic (high temperature) phase even above the Neel temperature (T-N). The tetragonal phase fraction increases substantially below T-N. Detailed analysis suggests that the twinned phase is tetragonal, orbital ordered, and insulating. At temperatures below 170 K, a small amount of the cubic phase is retained. The present results reveal the significance of the connectivity between the nanoscale structural phase separation with the physical properties.

Flow Stress of Biomorphous Metal-Matrix Composites

For metal-matrix composites (MMCs), interfacial debonding between the ductile matrix and the reinforcing hard inclusions is an important failure mode. A fundamental approach to improving the properties of MMCs is to optimize their microstructure to achieve maximum strength and toughness. Here, we investigate the flow stress of a MMC with a nanoscale microstructure similar to that of bone. Such a 'biomorphous' MMC would be made of staggered hard and slender nanoparticles embedded in a ductile matrix. We show that the large aspect ratio and the nanometer size of inclusions in the biomorphous MMC lead to significantly improved properties with increased tolerance of interfacial damage. In this case, the partially debonded inclusions continue to carry mechanical load transferred via longitudinal shearing of the matrix material between neighboring inclusions. The larger the inclusion aspect ratio, the larger is the flow stress and work hardening rate for the composite. Increasing the volume concentration of inclusion also makes the biomorphous MMC more tolerant of interfacial damage.

Luminescence characteristics of Yb3+, La3+ codoped yttrium oxide nanopowders

Luminescence characteristics of Yb3+, La3+ codoped yttrium oxide nanopowders were investigated. The grain size and the crystallinity of (Yb0.05Y0.90La0.05)(2)O-3 nanopowders increase with the increase of calcination temperature. The average grain size of the nanopowders calcined at 1100 degrees C is 66 nm and its cooperative up-conversion luminescence centered at 498 nm was detected due to nanometer size effect and perfect crystallinity. However, the cooperative up-conversion luminescence of (Yb0.05Y0.90La0.05)(2)O-3 transparent ceramics was not detected. (c) 2008 Elsevier B.V. All rights reserved.

Measurement of the elastic constants of nanometric films

Carbon coatings of thickness down to 2 nanometers are needed to increase the storage density in magnetic hard disks and reach the 100 Gbit/in2 target. Methods to measure the properties of these ultrathin hard films still have to be developed. We show that combining Surface Brillouin Scattering (SBS) andX-ray reflectivity measurements the elastic constants of such films are accessible. Tetrahedral amorphous carbofilms of thickness down to about 2 nm were deposited on Si by an S bend filtered cathodic vacuum arc, achieving a continuous coverage on large areas free of macroparticles. Film thickness and mass density are measured by X-ray reflectivity: densities above 3 g/cm3 are found, indicating a significant sp3 content. The dispersion relations of surface acoustic waves are measured by SBS. We show that for thicknesses above ∼4 nm these waves can be described by a continuum elastic model based on a single homogeneous equivalent film. The elastic constants can then be obtained by fitting the dispersion relations, computed for given film properties, to the measured dispersion relations. For thicknesses of 3 nm or less qualitative differences among films are well measurable, but quantitative results are less reliable. We have thus shown that we can grow and characterise nanometer size tetrahedral amorphous carbon film, which maintain their high density and peculiar mechanical properties down to around 4 nm thickness, satisfying the requirements set for the hard disk coating material.

Parameters determining crystallinity in beta-SiC thin films prepared by catalytic chemical vapor deposition

The effects of deposition gas pressure and H-2 dilution ratio (H-2/SiH4+CH4+H-2), generally considered two of dominant parameters determining crystallinity in beta-SiC thin films prepared by catalytic chemical vapor deposition (Cat-CVD), often called hot-wire CVD method, on the films properties have been systematically studied. As deposition gas pressure increase from 40 to 1000 Pa, the crystallinity of the films is improved. From the study of H-2 dilution ratio, it is considered that H-2 plays a role as etching gas and modulating the phases in beta-SiC thin films. On the basis of the study on the parameters, nanocrystalline beta-SiC films were successfully synthesized on Si substrate at a low temperature of 300degreesC. The Fourier Transform Infrared Spectroscopy (FTIR) and X-ray diffraction (XRD) spectra show formation of beta-SiC. Moreover, according to Sherrer equation, the average grain size of the films estimated is in nanometer-size. (C) 2003 Elsevier B.V. All rights reserved.

Nanocrystalline SnO2 synthesised by means of hydrothermal precipitation

Nanocrystalline SnO2 with different particle sizes has been prepared by means of hydrothermal precipitation. The resulting SnO2 nanometer size powders, which are basically spherical in shape according to TEM, are tetragonal in structure with space group P4/mnm. Calculation shows that the crystallite size of SnO2 increases with increase of the calcination temperature, but that the average crystal lattice distortion rate decreases with increase of crystallite size. The smaller the particle, the bigger the crystal lattice distortion and the slower the crystal growth rate. Weight loss analysis indicates the prepared SnO2 is very slightly impure.

Studies on the nature of the macromolecular condensed state of "nascent" ultra high molar mass polyethylene

Ultra high molar mass polyethylene (UHPE) powder as polymerized in a slurry process has been studied, in its nascent state, after recrystallization on rapid cooling from the melt and after hot compression molding to a film, by DSC, effect of annealing the recrystallized specimen at 120 similar to 130 degreesC, morphology by polarizing optical microscopy and small angle X-ray scattering. Based on the experimental results obtained the macromolecular condensed state of the nascent UHPE powder is a rare case of a multi-chain condensed state of non-interpenetrating chains, involving interlaced extended chain crystalline layers and relaxed parallel chain amorphous layers. On melting, a nematic rubbery state of nanometer size domain resulted. The nematic-isotropic transition temperature was judged from literature data to be at least 220 degreesC, possibly higher than 300 degreesC, the exact temperature is however not sue because of chain degradation at such high temperatures. The recrystallization process from the melt is a crystallization from a nematic rubbery state. The drop of remelting peak temperature by 10 K of the specimen recrystallized from its melt as compared to the nascent state has its origin in the decrease both of the crystalline chain stem length and of the degree of crystallinity. The remelting peak temperature could be returned close to that of the nascent state by annealing at 120 similar to 130 degreesC.