Selective synthesis of monoclinic and tetragonal phase LaVO<Subscript>4</Subscript> nanorods via oxides-hydrothermal route

Pure monoclinic (m-) and tetragonal (t-) LaVO₄ nanorods are successfully obtained via a facile oxides-hydrothermal method, in which V₂O₅ and La₂O₃ bulk powders are directly utilized as precursors without pretreatment. It is found that ethylenediamine tetraacetic disodium salt (EDTA) is a key factor for synthesizing t-LaVO₄. The as-obtained products are characterized by X-ray powder diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution TEM (HRTEM), and selected area electron diffraction (SAED). The FTIR spectra of VO₄ around 800 cm⁻¹ are suggested as an effective auxiliary means to identify the crystal phase of LaVO₄. UV–Visible spectra of LaVO₄ nanomaterials are obvious blue shift compared with the bulk m-LaVO₄ materials. The different photoluminescent properties of Eu³⁺ doped m- and t-LaVO₄ are demonstrated. A dissolution–precipitation mechanism is mainly responsible for the anisotropic morphology and phase control evolution of the LaVO₄ nanocrystals. The oxides-hydrothermal system is also applicable to prepare other pure LnVO₄ (Ln³⁺: Nd³⁺, Y³⁺, Sm³⁺) and doped LnVO₄ nanomaterials.     

Thermal conductance of nanofluids: is the controversy over?

Over the last decade nanofluids (colloidal suspensions of solid nanoparticles) sparked excitement as well as controversy. In particular, a number of researches reported dramatic increases of thermal conductivity with small nanoparticle loading, while others showed moderate increases consistent with the effective medium theories on well-dispersed conductive spheres. Accordingly, the mechanism of thermal conductivity enhancement is a hotly debated topic. We present a critical analysis of the experimental data in terms of the potential mechanisms and show that, by accounting for linear particle aggregation, the well established effective medium theories for composite materials are capable of explaining the vast majority of the reported data without resorting to novel mechanisms such as Brownian motion induced nanoconvection, liquid layering at the interface, or near-field radiation. However, particle aggregation required to significantly enhance thermal conductivity, also increases fluid viscosity rendering the benefit of nanofluids to flow based cooling applications questionable.     

The effect of solvent on the crystal structure and size distribution of cadmium sulfide nanocrystals

CdS nanocrystals with different structures were synthesized by the method of solution precipitation using thiourea and cadmium acetate as starting materials in different solvents: water, methanol and N,N-dimethylformamide (DMF). Our results show that the solvent has direct effect on the structure and size of the final nanoparticles. It was found that using DMF, as a solvent, results in producing smaller nanoparticles with the cubic structures, while using the other solvents gives rise to larger nanoparticles with the hexagonal structure. It was also found that using heat during washing the precipitate results in a more homogenous size distribution of CdS nanocrystals. On the basis of our experimental results we also suggest a critical structure transformation size.     

Thermal conductivity of nanofluids and size distribution of nanoparticles by Monte Carlo simulations

Nanofluids, a class of solid–liquid suspensions, have received an increasing attention and studied intensively because of their anomalously high thermal conductivites at low nanoparticle concentration. Based on the fractal character of nanoparticles in nanofluids, the probability model for nanoparticle’s sizes and the effective thermal conductivity model are derived, in which the effect of the microconvection due to the Brownian motion of nanoparticles in the fluids is taken into account. The proposed model is expressed as a function of the thermal conductivities of the base fluid and the nanoparticles, the volume fraction, fractal dimension for particles, the size of nanoparticles, and the temperature, as well as random number. This model has the characters of both analytical and numerical solutions. The Monte Carlo simulations combined with the fractal geometry theory are performed. The predictions by the present Monte Carlo simulations are shown in good accord with the existing experimental data.     

Application of SAXS to the study of particle-size-dependent thermal conductivity in silica nanofluids

Knowledge of the size and distribution of nanoparticles in solution is critical to understanding the observed enhancements in thermal conductivity and heat transfer of nanofluids. We have applied small-angle X-ray scattering (SAXS) to the characterization of SiO₂ nanoparticles (10–30 nm) uniformly dispersed in a water-based fluid using the Advanced Photon Source at Argonne National Laboratory. Size distributions for the suspended nanoparticles were derived by fitting experimental data to an established model. Thermal conductivity of the SiO₂ nanofluids was also measured, and the relation between the average particle size and the thermal conductivity enhancement was established. The experimental data contradict models based on fluid interfacial layers or Brownian motion but support the concept of thermal resistance at the liquid–particle interface.     

Organization of nanoscale objects via polymer demixing

We present an extremely versatile method for the lateral organization of nano-scale objects (NOs) based on the phenomenon of polymer demixing. NOs are suspended in a solution of two immiscible polymers, which is used to form a thin polymer film by spin coating. During spin coating the two polymers separate to give a microphase structure, whose length scale depends on the experimental conditions. The NOs spontaneously partition into one or other of the polymer phases resulting in their lateral organization. In this work, the organization of CdSe nanoparticles and fluorescent organic dyes was studied by fluorescence microscopy. The NOs were organized in the polymer film in stochastic patterns or in ordered designs on substrates pre-patterned by soft-lithography techniques. Single-particle measurements, using confocal microscopy, showed that at low concentrations there was little aggregation of the particles.     

Copper and copper oxide nanoparticles in a cellulose support studied using anomalous small-angle X-ray scattering

Microcrystalline cellulose is a porous natural material which can be used both as a support for nanoparticles and as a reducer of metal ions. Cellulose supported nanoparticles can act as catalysts in many reactions. Cu, CuO, and Cu₂O particles were prepared in microcrystalline cellulose by adding a solution of copper salt to the insoluble cellulose matrix and by reducing the copper ions with several reducers. The porous nanocomposites were studied using anomalous small angle X-ray scattering (ASAXS), X-ray absorption spectroscopy, and X-ray diffraction. Reduction of Cu²⁺ with cellulose in ammonium hydrate medium yielded crystalline CuO nanoparticles and the crystallite size was about 6–20 nm irrespective of the copper concentration. The size distribution of the CuO particles was determined with ASAXS measurements and coincided with the crystallite sizes. Using sodium borohydrate or hydrazine sulfate as a reducer both metallic Cu and Cu₂O nanoparticles were obtained and the crystallite size and the oxidation state depended on the amount of reducer.     

Nano organic carbon and soot in turbulent non-premixed ethylene flames

Spectral optical techniques are combined to characterise the distribution of large-molecule soot precursors, nanoparticles of organic carbon, and soot in two turbulent non-premixed ethylene flames with differing residence times. Laser-induced fluorescence, laser-induced incandescence and light scattering are used to define distributions across the particle size distribution. From the scattering and laser-induced emission measurements it appears that two classes of particles are formed. The first ones are preferentially formed in the fuel-rich region of the flame closer to the nozzle, have sizes of the order of few nanometers but are not fully solid particles, because the constituent molecules still maintain their individual identity exhibiting strong broadband fluorescence in the UV. The second class of particles constituted by solid particles, with sizes of the order of tens of nanometers are able to absorb a sufficient number of photons to be heated to incandescent temperatures. These larger particles are formed at larger residence times in the flame since they are the result of slow growth processes such as coagulation or carbonization. The flames are also modeled in order to produce mixture fraction maps. A new discovery is that nanoparticles of organic carbon concentration, unlike soot, does correlate well with mixture fraction, independent of position in the flame. This is likely to be a significant benefit to future modelling of soot inception processes in turbulent non-premixed flames.     

Directly writing with nanoparticles at the nanoscale using dip-pen nanolithography

Well-defined nanostructures were written with quantum dots and magnetic nanoparticles on gold and mica surfaces using dip-pen nanolithography at room temperature. The structures with both the nanoparticles were characterised by in situ topography measurements, and the quantum dot structures were mapped by fluorescence mapping. It is demonstrated that structures of various kinds such as dots and lines can be prepared using such nanoparticles on suitably prepared surfaces.     

Nanoparticles size modifications during femtosecond laser ablation of nickel in vacuum

Nanoparticles were synthesized by irradiating a nickel target with femtosecond laser pulses in high vacuum, and subsequently analyzed. The proof-of-principle experiments aim to modify the size characteristics of the produced nanoparticles. For nickel it is found that: (i) ultraviolet laser pulses lead to a remarkable change in the nanoparticles size distribution with respect to visible laser pulses; (ii) irradiation of the femtosecond pulses induced ablation plume with a second, delayed ultraviolet laser pulse can change the size characteristics of the produced nanoparticles.