Studies using carbon isotopes to understand the global carbon cycle are critical to identify and quantify sources, sinks, and processes and how humans may impact them. 13C and 14C are routinely measured individually; however, there is a need to develop instrumentation that can perform concurrent online analyses that can generate rich data sets conveniently and efficiently. To satisfy these requirements, we coupled an elemental analyzer to a stable isotope mass spectrometer and an accelerator mass spectrometer system fitted with a gas ion source. We first tested the system with standard materials and then reanalyzed a sediment core from the Bay of Bengal that had been analyzed for 14C by conventional methods. The system was able to produce %C, 13C, and 14C data that were accurate and precise, and suitable for the purposes of our biogeochemistry group. The system was compact and convenient and is appropriate for use in a range of fields of research.

Zn-Al layered double hydroxides (LDH), before and after calcination, were tested for the removal of indigo carmine (IC) dye from solution. These LDH photocatalysts were characterized by powder x-ray diffraction (PXRD), Fourier transform infrared (FTIR) spectroscopy, thermogravimetry/differential thermogravimetry (TG/DTG), nitrogen physisorption at −196°C, scanning electron microscopy (SEM) and diffuse reflectance spectrophotometry (DRS). The different photocatalysts were supported on polyacrylonitrile (PAN) nanofibres, so that filtration was unnecessary.

The PXRD and FTIR analyses showed that the IC adsorption on c-Zn-Al-3-500 (LDH calcined at 500°C) was enhanced by construction of the hydrotalcite matrix intercalated with the dye. The intercalation was clearly evidenced by the appearance of a peak at low °2θ values. All of the materials prepared exhibited photocatalytic activity, which for the c-Zn-Al-3-500 was comparable to that of commercial PAN-supported ZnO nanoparticles (100% degradation after 180 min). Kinetic studies showed that the degradation of the IC followed a pseudo-first order rate. The high activity and the ease of both synthesis and separation processes rendered this photocatalyst a promising candidate for environmental remediation.

Thermoelectric (TE) materials have been studied during past decades since they can generate electricity directly from waste heat. Antimony chalcogenides (Sb2M3, M = S, Se, Te) are well known as one of the promising candidates among the inorganic TE materials. We report on the synthesis of Sb2Te3 nanoparticle via thermolysis method. A systematic study was done to investigate the effect of reaction time and ratio between the precursors as well as the method of cooling on the morphology and composition of obtained nanoparticles. The ratio between precursors was varied to study the effect on the morphology. Furthermore, the high purity phase Sb2Te3 was obtained by a rapid cooling process.

The present work investigates the fabrication, thermal conductivity (TC) and rheological properties of water based carbon nanotubes (CNTs) nanofluids (NFs) prepared using a two-step method. As-received (AR) CNTs heated and the effect of heat treatment was studied using X-ray diffraction and thermogravimetric analysis. The AR-CNTs and heat-treated CNTs (HT-CNTs) were dispersed with varying concentration of surface modifiers Gum Arabic (GA) and TritonX-100 (TX) respectively. It was found that heat treatment of CNTs effectively improved the TC and influenced rheological properties of NFs. Scanning electron microscopy analysis revealed TX modified NFs showed better dispersion ability compared to GA. Surface modification of the CNTs was confirmed by Fourier Transformation Infrared (FTIR) analysis. Zeta potential measurement showed the stability region for GA modified NFs in the pH range of 5-11, whereas pH was between 9.5-10 for TX NFs. The concentration of surface modifier plays an extensive role on both TC and rheological behavior of NFs. A maximum TC enhancement of 10% with increases in viscosity around 2% for TX based HT-CNTs NFs was measured. Finally comparison of experimental TC results with the predicted values obtained from a model demonstrated inadequacy of the predictive model for CNT NFs system.

We report on the development and capabilities of two new measurement systems developed at Fraunhofer-IPM. The first measurement system is based on an extension of the Van der Pauw method and is suitable for cube-shaped samples. A mapping of the electrical conductivity tensor of a Skutterudite-SPS samples produced at the Instituto de Microelectrónica de Madrid is presented. The second measurement system is a ZTmeter also developed at the Fraunhofer-IPM. It enables the simultaneous measurement of the electrical conductivity, Seebeck coefficient and thermal conductivity up to 900 K of cubes at least 5x5x5 mm3 in size. The capacity of this measurement system for measuring the anisotropy of the transport properties of a (Bi,Sb)2Te3SPS sample produced by KTH is demonstrated by simply rotating the samples.

Skutterudites are known to be efficient thermoelectric (TE) materials in the temperature range from 600 K to 900 K. Dimensionless figure of merit (ZT) for filled skutterudite TE materials have been reported as ca. 1 at 800 K. Novel nano- engineering approaches and filling of the skutterudites crystal can further improve the transport properties and ultimately the ZT. Although classified among the promising TE materials, research on their large-scale production via bottom up synthetic routes is rather limited. In this work, large quantity of cobalt antimonide (CoSb3) based skutterudites nanopowder (NP) was fabricated through a room temperature co-precipitation precursor method. Dried precipitates were process by thermo-chemical treatment steps including calcination (in air) and reduction (in hydrogen). CoSb3 NPs were then mixed with silver (Ag) nanoparticles at different weight percentages (1%, 5% and 10% by wt) to form nanocomposites. Skutterudite NP was then consolidated by Spark Plasma Sintering (SPS) technique to produce highly dense compacts while maintaining the nanostructure. Temperature dependent TE characteristics of SPS’d CoSb3 and Ag containing nanocomposite samples were evaluated for transport properties, including thermal conductivity, electrical conductivity and Seebeck coefficient over the temperature range of 300 - 900 K. Physicochemical, structural and microstructural evaluation results are presented in detail.

1,8-Diazabicyclo[5,4,0]undec-7-ene (DBU) was neutralized by a range of Brønsted acids with a wide variation in the ΔpK a values of their constituent acids and base. The salts exhibited properties characteristic of an ionic liquid, such as high thermal stability and liquidity near ambient temperature. Analyses of thermal behaviors and temperature dependencies of density, viscosity (η), and ionic conductivity were made to correlate the physicochemical properties with the ΔpK a value of the obtained protic ionic liquids (PILs). Differential thermal analyses (DTA) revealed that PILs with high ΔpK a values underwent thermal decomposition resembling their aprotic counterparts; however, PILs with a low ΔpK a exhibited the evaporation of neutral species progressively generated from the shifting of the equilibrium toward neutral components during the weight loss process. The ionicity of the PILs, determined from Walden plots utilizing density, conductivity, and viscosity data, was found to decrease as temperature increased, and this effect was more pronounced for low ΔpK a values, possibly because of the shifting of the equilibrium and the imbalance between strong hydrogen bonds and Coulombic interactions. Fragility, estimated from plots of log(η) versus the scaled temperature T g /T was found to be lower for PILs than for DBU owing to neutralization. [DBU]-based PILs exhibit intermediate fragility in nature, but this fragility becomes more prominent for PILs with low ΔpK a values

We present a study on the magnetic behavior of nanosized iron oxide particles coated with different surfactants (sodium oleate, PVA and starch) in a ferrofluid. The effect of the coating material, and different particle concentrations in the ferrofluid have been magnetically investigated to determine the effective magnetic particle size and possible interaction. The superparamagnetic iron oxide particles, synthesized by a controlled co-precipitation technique, are found to contain magnetite (Fe3O4) as a main phase with a narrow physical particle size distribution between 6 and 8 nm. The mean effective magnetic size of the particles in different ferrofluid systems are estimated to be around 4-5 nm which is smaller than the physical particle size. On a 10% dilution in the starch coated ferrofluid we observe a decrease in the blocking temperature.

Ferrofluids containing superparamagnetic Fe3O4 nanoparticles have been prepared by a controlled co-precipitation method.The aggregation of the particles was prevented by using a polymeric starch network as a coating agent. Structural and magnetic measurements reveal a particle size of around 6 nm, with a clear evidence of a uniform particle coating. The ferrofluids have been used as a contrast agent for MR imaging in biological tissue.

The synthesis and characterisation of gold-coated cobalt nanoparticles, as well as their chemically- and magnetically-induced self-organisation have been studied. Metallic core-shell nanoparticles were prepared using two different experimental techniques: bulk reductive precipitation, with average particles size ∼15 nm, and microemulsion confining method, with average particle size of ∼6 nm. The self-assembly of prepared nanoparticles on flat substrates was achieved by derivatising the substrate and particle surfaces with bifunctional organic molecules that attaches to both particles and substrates. Examination of the self-assembled systems was carried out by a number of characterisation techniques including transmission electron microscopy (TEM), UV-visible spectrophotometry (UV-VIS), and atomic force microscopy (AFM).

The properties of small clusters Fe3 and Fe5, in which the non-collinearity of magnetic density is expected to be important, and of larger nanoparticles (consisting of up to 62 atoms) are studied from first principles making use of density functional theory, norm-conserving pseudopotential and numerical local orbitals method, as implemented in the SIESTA code. We concentrate on the interplay of lattice relaxation, mostly pronounced near the surface of particles, and the particles' magnetic characteristics. Previously obtained theoretical findings of enhanced magnetic moments in outer shells of nanoparticles are confirmed. These results are refined by taking structure relaxation into account and by considering more representative bcc- and fcc-related particles; moreover, we allowed antiferromagnetic ordering along with ferromagnetic one.

Electrochemical deposition of metals and alloys onto metallic substrates plays an important role in many modern technologies. Usually, a photolithographic patterning process is used to produce the desired feature on the substrate surface. An alternative method to patterned metal deposition on semiconductors is presented here: it is based on changing the electrochemical properties of the semiconductor by controlled surface defect creation. A focused ion beam (FIB) was used to introduce defects into p-Si, followed by a selective electrochemical reaction to produce metal structures in the sub-micrometer range.

In this work we study the selective deposition behavior of Cu on FIB sensitized surface locations and show that crystallite growth follows a three- dimensional growth law. Crystallites grow very rapidly in a first phase and reach a size of roughly 200nm after 5s. Factors determining nucleation, growth, and coalescence of metal clusters are identified and investigated.

The experimental analysis of dry laser cleaning efficiency is done for certified spherical particle (SiO2, 5.0, 2.5, 1.0 and 0.5 μm) from different substrates (Si, Ge and NiP). The influence of different options (laser wavelength, incident angle, substrate properties, i.e. type of material, surface roughness, etc.) on the cleaning efficiency is presented in addition to commonly analyzed options (cleaning efficiency versus laser fluence and particle size). Found laser cleaning efficiency demonstrates a great sensitivity to some of these options (e.g. laser wavelength, angle of incidence, etc.). Partially these effects can be explained within the frame of the Mie theory of scattering. Other effects (e.g. influence of roughness) can be explained along the more complex line, related to examination of the problem “particle on the surface” beyond the Mie theory. 0.5 μm spherical silica particles were placed on Silicon (100) substrate. After laser irradiation with a 248 nm KrF excimer laser, hillocks with size of about 100 nm were obtained at the original position of the particles. Mechanism of the formation of the sub-wavelength structures were investigated and found to be the near-field optical resonance effect induced by particles on surface. Theoretical prediction of the near-field light intensity distribution was presented, which was in agreement with the experimental result.

SiO2 nanospheres have been produced via a high temperature evaporation process and they have been Ni or Ag plated using electroless plating solutions. These samples were examined by Atomic Force Microscopy (AFM) and Magnetic Resonance (MR). The initial SiO2 nanospheres were about 30 nm in diameter, and the Ni plating layer resulted in a 25nm thick metallic Ni coverage, while the Ag coverage was estimated to be in the 150 nm range. In the case of the Ni/SiO2 nanosphere composites, the MR signals show the presence of Ni+2 and Ni+3 paramagnetic centers, seen below 40K, and ferromagnetic metallic Ni, which is seen above 40K. The dried Ni plating solution (with no SiO2) shows only the presence of paramagnetic Ni+3. These results suggest that an interfacial reaction at the surface of the SiO2 nanospheres leads to the formation of ferromagnetic Ni, which deposits onto the spheres and forms a ferromagnetic Ni/SiO2 nanosphere composite. In the case of the Ag/SiO2 nanosphere composites, no MR signal is seen from the non-magnetic Ag, but strong paramagnetic behavior has been noted for Co+2, which originates from the plating solution.

Silver nanoparticles were prepared by the method of mixing of two microemulsions having similar chemical composition but different reactants in their respective aqueous core. One microemulsion contains silver nitrate in the aqueous core and other contains sodium borohydride. The silver nanoparticles formed were characterized using UV-Visible absorption spectra and TEM micrographs. Effect of chain length of solvent and addition of Arlacel-20 to the AOT/Heptane, AOT/Decane and AOT/Dodecane microemulsion on particle size and absorption spectra of silver nanoparticles was studied. TEM photographs showed agglomerated and bigger particles in case of pure AOT/dodecane whereas addition of Arlacel-20 showed dispersed and smaller particles. Reaction kinetics was observed for silver nanoparticles using UV-visible spectrophotometer. Silver nanoparticles prepared using pure AOT surfactant showed plasmon band (416 nm) immediately after preparation whereas no absorption band of silver nanoparticles was observed for mixed surfactant microemulsion of AOT and Arlacel 20 for few hours indicating the reaction kinetics is slowed down upon addition of Arlacel-20. Growth rate of silver nanoparticles was plotted by monitoring absorption coefficient ratio (ε416/ε475) as a function of time. AOT/heptane system showed slower growth rate as compared to AOT/decane and AOT/dodecane and also larger particle size. Presence of Arlacel-20 significantly decreases the growth rate in all three alkanes and this observation can be explained using the concept of rigidity of surfactant film at the oil/water interface. It is proposed that higher the interfacial viscosity, slower is the coalescence rate of nanodroplets in the microemulsion system, and hence slower the growth rate of particles and smaller is the final particle size.

Cr1-xMnx (x < 6.3 %) alloy in the bulk form is an interesting complex system that behaves in many but not all respects like a spin-glass system. In this study, 14 nm-size CrMn nanoparticles with 5% Mn, were synthesized by ball milling of Cr and Mn particles in Ar atmosphere. After 50 hours of milling, the x-ray diffraction pattern indicated alloying of the two metals Cr and Mn. However XPS data indicated the formation of MnO2 and Cr2O3oxides on the surface of the chromium core in the nanoparticle. These oxides on the surface, like the Cr core, are antiferromagnets. Magnetization (M) measurement at 200 G as a function of temperature (T), after zero-field-cooling, showed that M increased as T increased from 5 K all the way to 330 K, beyond the Neel temperatures of the Cr and the oxides. Even though the magnetization value is in the range of a typical antiferromagnet at all temperatures from 5 to 330 K, the shape of M versus T curve is neither that of an antiferromagnet nor of a spin-glass. It appears that the behavior of the magnetization curve is due to the frustration of the spins by weak fields associated with spin-density-wave and by the existence of the oxides. This frustration should be different from the frustration of the spins due to the ferromagnetic-antiferromagnetic competition in spin-glass systems.

Safe, lightweight, and cost-effective materials are required to practically store hydrogen for use in portable fuel cell applications. Compressed hydrogen and on-board hydrocarbon reforming present certain advantages, but their limitations must ultimately render them insufficient. Storage in hydrides and adsorption systems show promise in models and experimentation, but a practical medium remains unavailable. To study hydrogen storage properties a new volumetric testing apparatus was designed and constructed. Adsorption conditions are evaluated up to pressures exceeding 250 bar and a broad range of temperatures. RF sputtering was used to introduce metals to carbon nanotubes with the aim to enhance hydrogen storage. Here we show a significant improvement in the gravimetric storage density over that of as-prepared single-wall nanotube samples that may be due to the unique interface introduced.

Monodispersed gold coated Superparamagnetic Iron Oxide Nanoparticles (SPION) were prepared in water-in-oil reverse microemulsion (μE) of CTAB (cetyltrimethyl -ammonium bromide)/octane/butanol/water and Brij@97/cyclohexane/water. Gold coated SPION were obtained in the μE system by coprecipitation of magnetite and subsequent reduction of Au on the surface of the magnetite using NaBH4. The SPION were characterized by TEM with EDX, AFM, TGA, ESA, UV-Vis spectroscopy, and SQUID at intermediate and final stages.

Novel metallic capsules containing magnetite with given size in the sub-micron range have been produced. These nanocapsules are prepared in several steps through a colloidal templating approach. The first step is the synthesis of size-selected SiO2 nanospheres. The second step is coating the SiO2nanospheres by electroless deposition with gold, in order to form a porous gold shell around the silica. Electroless deposition is controlled by the concentration of gold in the coating solution. Subsequently, the core (SiO2) was removed to obtain gold capsules. The final step is the inclusion of magnetite nanoparticles inside these nanocapsules and recoating the capsules with gold in order to have continuous encapsulation. The nanocapsule and core-shell structure have been characterized by TEM and DSC