Solid state effects in the NEXAFS spectra of alkane-based van der Waals crystals: Breakdown of molecular model

Experimental data conclusively shows that the weak van der Waals interactions between alkane molecules, <1.5% the strength of covalent bonding on a per carbon atom basis, modify the carbon 1s near edge X-ray absorption fine structure (NEXAFS) spectrum significantly in ordered solids, both in intensity, spectral shape, peak position, and dichroic signature. This constitutes a further breakdown of the ‘building block’ model, or, more precisely, even a molecular model in interpreting NEXAFS spectra. These observations have significant implications for the interpretation and use of NEXAFS spectra from any crystalline or semi-crystalline macromolecules, small molecules, or other weakly interacting systems.     

Role of matrix crystallinity in carbon nanotube dispersion and electrical conductivity of iPP‐based nanocomposites

A homopolymer iPP and a series of propylene‐ethylene random copolymers with a content of ethylene from 7 to 21 mol % were used as matrices to prepare single‐walled carbon nanotube (SWCNT) nanocomposites in a range of SWCNT concentration from 0.15 to 1 wt %. The solution blending and melt‐ compression molding procedures were kept identical for all nanocomposites. The poly(propylenes) have crystallinities ranging from 70 to 10%, and serve to test the role of SWCNTs acting as nucleants to preserve in the nanocomposites the uniform dispersion of SWCNTs after sonication. The major role of polymer crystallinity is to mediate toward a more open and more connected SWCNT network structure. Fast nucleation and growth of high crystalline matrices on multiple sites along the surface of the nanotubes prevents SWCNT clustering, and entraps the SWCNT network between the semicrystalline structure reducing the driving force of nanotubes to curl and twist. Depletion of crystallites in the less crystalline matrices (<35% crystallinity) leads to curled and poorly connected nanotubes. A consequence of the gradual loss of SWCNT connectivity is a decreased electrical conductivity; however, the change with crystallinity is not linear. Conductivity decreases sharply with decreasing crystallinity for SWCNT contents near the percolation region, while for contents approaching the plateau region the electrical conductivity is less sensitive to matrix crystallinity. The percolation threshold decreases rapidly for polymers with <～30% crystallinity and slowly levels off at crystallinities >～40%. At SWCNT concentrations of 0.15 wt %, SEM images of nanocomposites with the highest crystallinity matrix indicate debundled and interconnected nanotubes, whereas more disconnected and curled SWCNTs remain in the lowest crystallinity nanocomposites. Electrical conductivity in the former is relatively high, whereas the latter are insulators. Also discussed is the nucleating effect of nanotubes and restrictions of the filler to polymer chain diffusion in the crystallization of the polymers. SEM images and Raman spectra in the radial breathing modes region (100–400 cm^?1) are complementary tools to extract the quality and details of the SWCNT dispersion in the nanocomposites. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 2084–2096, 2010     

Synthesis of Pyrimidines,Thienopyrimidines and Pyrazolopyrimidine

5‐Ethoxycarbonyl‐4‐methyl‐2‐phenylpyrimidin‐6(1H)‐thione ( 3 ), which was prepared from the reaction of ethyl β‐aminocrotonate 1 with benzoyl isothiocyanate ( 2 ) in refluxing acetone, was reacted with halo compounds to give S‐alkyl derivatives 4a‐h . Treatment of compounds 4a‐c with sod. ethoxide cyclized into thienopyrimidine 10a‐c . Hydrazinolysis of compound 3 gave hydroxypyrazolopyrimidine derivative 6 . Also the latter compound was obtained upon heating compound 4a with hydrazine hydrate under neat conditions, but when compound 4a refluxed with hydrazine hydrate in ethanol the corresponding carbohydrazide 5 was produced.     

Characterization of multicomponent polymer trilayers with resonant soft X‐ray reflectivity

Resonant soft X‐ray reflectivity (RSoXR) has been used to quantify the layer thicknesses and the interfacial widths of a single, complex thin film with three polymeric layers supported on an inorganic substrate. By adjusting the photon energy, the sensitivity to particular interfaces within the trilayer can be selectively enhanced. The results significantly improve and broaden the capabilities of RSoXR, which has previously only been demonstrated and used for bilayers on silicon substrates. The capability of RSoXR to characterize polymer trilayers was not readily predictable from prior bilayer results, as the RSoXR characterization of bilayers benefits from a strong X‐ray reflection from the substrate that serves as a reference beam with which the reflections from the other interfaces interfere with. The impact of having the capability to investigate trilayers is exemplified by discussing the utility of RSoXR to characterize organic electronic light emitting multilayers. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1291–1299, 2009     

Suppression of nonradiative recombination by V-shaped pits in GaInN/GaN quantum wells produces a large increase in the light emission efficiency

Despite the high density of threading dislocations generally found in (AlGaIn)N heterostructures, the light emission efficiency of such structures is exceptionally high. It has become common to attribute the high efficiency to compositional fluctuations or even phase separation in the active GaInN quantum well region. The resulting localization of charge carriers is thought to keep them from recombining nonradiatively at the defects. Here, we show that random disorder is not the key but that under suitable growth conditions hexagonal V-shaped pits decorating the defects exhibit narrow sidewall quantum wells with an effective band gap significantly larger than that of the regular c-plane quantum wells. Thereby nature provides a unique, hitherto unrecognized mechanism generating a potential landscape which effectively screens the defects themselves by providing an energy barrier around every defect.     

The calculation of the distance to a nearby defective matrix

The distance of a matrix to a nearby defective matrix is an important classical problem in numerical linear algebra, as it determines how sensitive or ill‐conditioned an eigenvalue decomposition of a matrix is. The concept has been discussed throughout the history of numerical linear algebra, and the problem of computing the nearest defective matrix first appeared in Wilkinsons famous book on the algebraic eigenvalue problem. In this paper, a new fast algorithm for the computation of the distance of a matrix to a nearby defective matrix is presented. The problem is formulated following Alam and Bora introduced in (2005) and reduces to finding when a parameter‐dependent matrix is singular subject to a constraint. The solution is achieved by an extension of the implicit determinant method introduced by Spence and Poulton in (2005). Numerical results for several examples illustrate the performance of the algorithm. Copyright © 2013 John Wiley & Sons, Ltd.     

Millimeter-Wave Profiled Corrugated Horns for the Quad Cosmic Background Polarization Experiment

In this paper we report on the design and validation process for the profiled corrugated horn antennas, which feed the bolometer array of a cosmology experiment known as QUaD located at the South Pole. This is a cosmic background radiation polarization project, which demands precise knowledge and control of the optical coupling to the signal in order to map the feeble E- and B-polarization mode structure. The system will operate in two millimeter wavelength bands at 100 and 150 GHz. The imaging horn array collects the incoming signal via on-axis front-end optics and a Cassegrain telescope, with a cold stop in front of the array to terminate side-lobe structure at an edge taper of –20dB. The corrugated horn design process was undertaken using in-house analytical software tools, based on modal scattering, specially developed for millimeter -wave profiled horn antennas. An important part of the instrument development was the validation of the horn design, in particular to verify low edge taper levels and the required well-defined band edges. Suitable feed horn designs were measured and were found to be in excellent agreement with theoretical predictions.