Mechanism of thermal transport in dilute nanocolloids

Thermal conduction modes in a nanocolloid (nanofluid) are quantitatively assessed by combining linear response theory with molecular dynamics simulations. The microscopic heat flux is decomposed into three additive fluctuation modes, namely, kinetic, potential, and collision. For low volume fractions (<1%) of nanosized platinum clusters which interact strongly with xenon host liquid, a significant thermal conductivity enhancement results from the self correlation in the potential flux. Our findings reveal a molecular-level mechanism for enhanced thermal conductivity in nanocolloids with short-ranged attraction and offer predictions that can be experimentally tested.     

A diffractive optical element for shaping arbitrary beams

A design method is presented for an optical element that shapes an arbitrary collimated beam. The optical element consists of a pair of diffractive optical elements (DOEs). The outgoing beam is also collimated, and can have any desired intensity profile. The phase functions of the DOEs are computed by minimizing an appropriate cost function under an energy conservation constraint.     

pH‐controlled reaction divergence of decarboxylation versus fragmentation in reactions of dihydroxyfumarate with glyoxylate and formaldehyde: parallels to biological pathways

The reactions of dihydroxyfumarate with glyoxylate and formaldehyde exhibit a unique pH‐controlled mechanistic divergence leading to different product suites by two distinct pathways. The divergent reactions proceed via a central intermediate (2,3‐dihydroxy‐oxalosuccinate, 3 , in the reaction with glyoxylate and 2‐hydroxy‐2‐hydroxymethyl‐3‐oxosuccinate, 14 , in the reaction with formaldehyde). At pH 7–8, products ( 7 , 8 , and 15 ) exclusively from a decarboxylation of the intermediate are observed, while at pH 13–14, products ( 9 , 10 , and 16 ) solely derived from a hydroxide‐promoted fragmentation of the intermediate are formed. The decarboxylative and fragmentation pathways are mutually exclusive and do not appear to coexist under the range of pH (7–14) conditions investigated. Herein, we employ a combination of quantitative ¹³C NMR measurements and density functional theory calculations to provide a rationale for this pH‐driven reaction divergence. These rationalizations also hold true for the reactions of dihydroxyfumarate produced in situ by the catalytic cyanide‐mediated dimerization of glyoxylate. In addition, the non‐enzymatic decarboxylation and fragmentation transformations of these central intermediates ( 3 and 14 ) appear to have intriguing parallels to the enzymatic reactions of oxalosuccinate and formation of glyceric acid derivatives in extant metabolism – the high and low pH mimicking the precise control exerted by the enzymes over reaction pathways. Copyright © 2016 John Wiley & Sons, Ltd.     

Design of robust differential microphone arrays with the Jacobi–Anger expansion

Due to their small size, differential microphone arrays (DMAs) are very attractive. Moreover, they have been effective in combating noise and reverberation. Recently, a new class of DMAs of different orders have been developed with the MacLaurin’s series and the frequency-independent patterns. However, the MacLaurin’s series does not approximate well the exponential function, which appears in the general definition of the beampattern, when the intersensor spacing is not small enough. To circumvent this problem, we propose in this paper to approximate the exponential function with the Jacobi–Anger expansion. Based on this approximation and the frequency-independent Chebyshev patterns, we derive first-, second-, and third-order DMAs. Furthermore, in order to improve the robustness of DMAs against white noise amplification, we propose to use more microphones combined with minimum-norm filters. It is also shown that the Jacobi–Anger expansion is optimal from a mean-squared error perspective. Simulations are carried out to evaluate the performance of the proposed DMAs.     

VSM and Mössbauer study of nanostructured hematite

In the present work, we have synthesized nanostructured hematite samples using chemical precipitation method. The crystal structure and the grain size of the samples were studied using XRD. The zero field cooled and field cooled magnetization curves of the samples were recorded in the temperature range from 300 to 10 K. The variations of Morin transition temperature and blocking temperature with the grain size of the samples were investigated. The hysterics curves of the samples were recorded and the samples showed a superparamagnetic nature at room temperature whereas, at 10 K the samples showed open hysteresis curves. The sample with smaller grain size showed higher value of coercivity compared to samples with larger grain size. Mössbauer spectra of the samples were recorded and the grain size dependence on Mössbauer parameters was investigated.     

Interpretation of Polarized Absorption and Emission Spectra of Molecules Incorporated in Stretched Polymer Films

Different methods for the interpretation of linear dichroic spectra of molecules incorporated in uniaxial matrices are discussed. A method based on the combination of both polarized absorption and emission measurements is described for the resolution of absorption and emission spectra into their different polarized components, and for the investigation of molecular distributions in the oriented matrix. The distributions of some planar molecules of different shapes incorporated in stretched polyethylene films are presented.     

Characterization of Al(III) complexes with hematein in artistic alum logwood inks

The complexes between Al(III) and hematein, the main coloring matter in alum logwood inks, were characterized by Raman and ²⁷Al NMR (nuclear magnetic resonance) spectroscopies. Raman spectra of the crystallized complexes and of the compounds applied on a paper substrate are presented and assigned based on published data for the parent compounds. These Raman spectra show that the coordination of the hematein to the Al(III) ions takes place in both cases through the carbonyl and hydroxyl groups in the molecule, and that the aromatic rings are also involved in the interaction. The Raman spectra of the pure hematein–Al(III) complexes were found to be consistent with those recorded for a logwood ink prepared following a late 19th century recipe, using logwood chips instead of pure hematein, and applied on a paper substrate. These spectra can be used as references for the noninvasive identification of the compounds in works of art. ²⁷Al solid‐state NMR showed that the coordination of the Al(III) atoms in the crystallized powder is predominantly octahedral, while when applied on a paper substrate the colorant is present mainly as a tetrahedral complex, with an octahedral coordination also present in a smaller proportion. The fact that the predominant coordinations for the complexes in the crystallized material and for the ones present on the paper substrate are different is relevant for the study of the lightfastness and thermal stability of works of art bearing these media. Copyright © 2009 John Wiley & Sons, Ltd.     

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.