X-Ray Mapping and Interpretation of Scatter Diagrams

Electron beam induced quantitative X-ray mapping has become a very useful characterisation tool for determining the elemental distribution in materials, whether using energy dispersive spectroscopy or wavelength dispersive spectroscopy. The X-ray intensity distributions of the elements from an X-ray map allow us to generate two dimensional and ternary scatter diagrams thus converting spatial information into concentration dimensions, which is an important tool for displaying the spatial relationships of elements or correlated elements (phases) in materials. To best understand how to use this tool, we need to understand the production and features of the scatter diagram. The type of clustering observed in the scatter diagram, whether oval, linear or spherical, can give the major and trace element distributions within phases as well as qualitative and quantitative phase information. This paper demonstrates the generation of scatter diagrams, properties of scatter diagrams, interpretation of scatter diagrams and the advantages of scatter diagrams through the use of examples.     

Control of the block copolymer morphology in templated epoxy thermosets

It has been found that by the addition of low concentrations of an amphiphilic block copolymer to an epoxy resin, novel disordered morphologies can be formed and preserved through curing. This article will focus on characterizing the influence of the block copolymer and casting solvent on the templated morphology achieved in the thermoset sample. The ultimate goal of this work is to determine the parameters that would control the microphase morphology produced. Epoxy resins blended with a series of amphiphilic block copolymers based on hydrogenated polyisoprene (polyethylene-alt-propylene or PEP) and polyethylene oxide (PEO), specifically, were investigated. In this article, the cure-induced order–order phase transition from the spherical to wormlike micelle morphology will also be discussed. It is proposed that the formation of the wormlike micelle structure from the spherical micelle structure is similar to the phase transition behavior that occurs in dilute block copolymer solutions as a function of the influence of the solvent on micelle morphology. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 3338–3348, 2007     

Numerical Modeling of Solitons in a Low Birefringent Optical Fiber

A numerical investigation, based on the split-step Fourier transform algorithm of all optical switching of solitons in a low birefringent optical fiber is presented. The numerical algorithm is described in detail. This revised version was published online in August 2006 with corrections to the Cover Date.     

Selected-area growth of carbon nanotubes by the combination of focused ion beam and chemical vapor deposition techniques.

In this article, we report a technique for growing carbon nanotubes in a more controllable fashion, which enables us to synthesize nanotubes directly in various forms of designed patterns. This nanofabrication process is based on a combination of focused ion beam (FIB) and chemical vapor deposition (CVD) techniques. In this process, arrays of conductive patterns were first deposited on silicon substrates by directing a gaseous compound (C(9)H(16)Pt) via the capillary needle-sized nozzles within a FIB system. The substrates were then coated with catalyst and further modified by the FIB to localize the position of the catalyst. Finally, the growth of carbon nanotubes on the designed substrates was carried out by CVD of hydrocarbon gases. This fabrication technique has the advantage of positioning carbon nanotubes in selected locations. This may open up opportunities for the direct synthesis of carbon nanotubes onto almost any substrate material, thus allowing fabrication of carbon nanotube-based devices.     

Second Dissociation Constant of Bis-[(2-hydroxyethyl)amino]acetic Acid (BICINE) and pH of Its Buffer Solutions from 5 to 55 °C

The values of the second dissociation constant, K ₂, and related thermodynamic quantities of the ampholyte bis[(2-hydroxyethyl)amino]acetic acid (BICINE) have been determined at temperatures from 5 to 55 ^∘C. The pH values of six equimolal buffer solutions, and four buffer solutions having ionic strengths (I = 0.16 mol⋅kg⁻¹) similar to those in blood plasma, have been evaluated at 12 temperatures from 5 to 55 ^∘C using the Bates–Guggenheim convention. The liquid junction potentials (E _j ) between the buffer solutions of BICINE and saturated KCl solution of the calomel electrode at 25 and 37 ^∘C have been estimated by measurement with a flowing junction cell. These values of E _j have been used to ascertain the operational pH values at 25 and 37 ^∘C. The pK ₂ values at 25 and 37 ^∘C are 8.333 and 8.156, respectively. The thermodynamic quantities associated with the second acid dissociation have been calculated from the values of pK ₂ as a function of temperature. The zwitterionic buffer BICINE was shown to be useful as a pH standard in the region close to that of blood serum.     

Ammonium hexafluorosilicate salts

The preparation and characterization of the ammonium hexafluorosilicate salts, 2[R]⁺ [SiF₆]²⁻ (where R=piperidinium (2), methylammonium (3), quinolinium (4), acridinium (5), 2,2,6,6-tetramethylpiperidinium (6), and propylammonium (7)) is described.The salts were prepared from the reaction of the corresponding alkylammonium fluoride with silica gel. The compounds were characterized by NMR, IR, mass spectrometry and in the case of 1 (piperidinium fluoride), 2-4 by X-ray crystallography. Compounds 1-3 crystallize in the orthorhombic crystal system (space groups Iba2, Fdd2, and Pnnm, respectively), with Z=8, 14, and 4, respectively. Compound 4 crystallizes in the triclinic space group P-1, with Z=2. Compounds 1-4 exhibit hydrogen bonding.     

Shear-induced coalescence of emulsified oil drops

Crude oil droplets, when suspended in water, possess negative surface charges which give rise to double-layer repulsive forces between the drops. According to conventional DLVO theory, the magnitude of this repulsion (based on the measured zeta potential) is more than sufficient to prevent coalescence of the droplets. Indeed, when two such droplets were brought together on direct (i.e., "head-on") approach, coalescence was rarely observed. Upon oblique approach, however, the same droplets were seen to coalesce readily. An oblique encounter must necessarily give rise to lateral relative motion-or shearing-between the droplet surfaces. It is speculated that, if the charge distributions at the droplet surfaces were heterogeneous, lateral shearing would facilitate many encounters between surface patches of different zeta potentials across the intervening water film. If the repulsion across any local region were sufficiently weak to allow formation of an oil bridge across the water film, coalescence of the drops would follow inevitably. With the hypothesis of surface heterogeneity, it is not necessary to invoke any additional colloidal interactions (such as "hydrophobic forces") to account for the observed droplet-droplet coalescence. This finding may have important implications for the underlying mechanisms of emulsion stability in general and the commercial extraction of bitumen from oil sands in particular.     

Hamaker constants in integrated circuit metalization

A new method for determining Hamaker constants was examined for materials of interest in integrated circuit manufacture. An ultra-high vacuum atomic force microscope and an atomic force microscope operated in a nitrogen environment were used to measure the interaction forces between metals, dielectrics, and barriers used during the metalization portion of integrated circuit manufacturing. The materials studied included copper, silver, titanium nitride, silicon dioxide, poly(tetrafluoroethylene), and parylene-N. Spheres coated with a material of interest were mounted on AFM cantilevers and brought into contact with substrates of interest. The interaction force was measured as the cantilever approached the substrate but before the two surfaces came into contact, and also when the particle was pulled out of contact with the substrate. The Hamaker constant calculation from the contact measurement is based on an adhesion model that quantifies the contribution of geometrical, morphological and mechanical properties of materials to the measured adhesion force. Hamaker constants determined with this new approach were compared with values found by using the Derjaguin approximation for a sphere to describe the interaction force as the cantilever approaches the surface. Both approaches produced similar values for most of the systems studied, with variations of less than 10%.     

Sigma-aromaticity and sigma-antiaromaticity in saturated inorganic rings

The magnetic properties of a series of inorganic saturated rings, (SiH2)n, (GeH2)n, (NH)n, (PH)n, (AsH)n, On, Sn, and Sen (n = 3-6), exhibit zigzag behavior with ring size resembling that of aromatic and antiaromatic Hückel pi-systems and (CH2)n rings. Computed GIAO-SCF nucleus-independent chemical shifts (NICS) and localized (LMO) NICS analysis indicate that the sigma-ring electrons are chiefly responsible for this zigzag behavior. This evidence for sigma-aromaticity is further supported by theoretical strain energy (TSE). The Hückel 4n + 2/4n aromaticity/antiaromaticity rule for pi-electron systems applies well to the smaller saturated rings.     

Bond dissociation energies and radical stabilization energies associated with model peptide-backbone radicals

Bond dissociation energies (BDEs) and radical stabilization energies (RSEs) have been calculated for a series of models that represent a glycine-containing peptide-backbone. High-level methods that have been used include W1, CBS-QB3, U-CBS-QB3, and G3X(MP2)-RAD. Simpler methods used include MP2, B3-LYP, BMK, and MPWB1K in association with the 6-311+G(3df,2p) basis set. We find that the high-level methods produce BDEs and RSEs that are in good agreement with one another. Of the simpler methods, RBMK and RMPWB1K achieve good accuracy for BDEs and RSEs for all the species that were examined. For monosubstituted carbon-centered radicals, we find that the stabilizing effect (as measured by RSEs) of carbonyl substituents (CX=O) ranges from 24.7 to 36.9 kJ mol(-1), with the largest stabilization occurring for the CH=O group. Amino groups (NHY) also stabilize a monosubstituted alpha-carbon radical, with the calculated RSEs ranging from 44.5 to 49.5 kJ mol(-1), the largest stabilization occurring for the NH2 group. In combination, NHY and CX=O substituents on a disubstituted carbon-centered radical produce a large stabilizing effect ranging from 82.0 to 125.8 kJ mol(-1). This translates to a captodative (synergistic) stabilization of 12.8 to 39.4 kJ mol(-1). For monosubstituted nitrogen-centered radicals, we find that the stabilizing effect of methyl and related (CH2Z) substituents ranges from 25.9 to 31.7 kJ mol(-1), the largest stabilization occurring for the CH3 group. Carbonyl substituents (CX=O) destabilize a nitrogen-centered radical relative to the corresponding closed-shell molecule, with the calculated RSEs ranging from -30.8 to -22.3 kJ mol(-1), the largest destabilization occurring for the CH=O group. In combination, CH2Z and CX=O substituents at a nitrogen radical center produce a destabilizing effect ranging from -19.0 to -0.2 kJ mol(-1). This translates to an additional destabilization associated with disubstitution of -18.6 to -7.8 kJ mol(-1).