Wear lip formation during dry sliding

A pin-on-disc test configuration has been used to examine the formation of the strain-hardened projection, or wear lips, especially at the trailing edge of the pin during dry sliding of aluminium alloys against steel discs. The mechanism of formation of such wear lips is studied with the aid of optical and electron microscopes. The plastic deformation of the pin, growth and eventual removal of the wear lip as wear debris are elucidated. The size and shape of the wear lips in pins of different shapes, i.e. square, rectangular, triangular and circular cross-sections, are described.

Re-entrant Phase Behavior of a Concentrated Anionic Surfactant System with Strongly Binding Counterions

The phase behavior of the anionic surfactant sodium dodecyl sulfate (SDS) in the presence of the strongly binding counterion p-toluidine hydrochloride (PTHC) has been examined using small-angle X-ray diffraction and polarizing microscopy. A hexagonal-to-lamellar transition on varying the PTHC to SDS molar ratio (alpha) occurs through a nematic phase of rodlike micelles (N-C) -> isotropic (I) -> nematic of disklike micelles (N-D) at a fixed surfactant concentration (phi). The lamellar phase is found to coexist with an isotropic phase (l') over a large region of the phase diagram. Deuterium nuclear magnetic resonance investigations of the phase behavior at phi = 0.4 confirm the transition from N-C to N-D on varying alpha. The viscoelastic and flow behaviors of the different phases were examined. A decrease in the steady shear viscosity across the different phases with increasing alpha suggests a decrease in the aspect ratio of the micellar aggregates. From the transient shear stress response of the N-C and N-D nematic phases in step shear experiments, they were characterized to be tumbling and now aligning, respectively. Our studies reveal that by tuning the morphology of the surfactant micelles strongly binding counterions modify the phase behavior and rheological properties of concentrated surfactant solutions.

Kinetics and mechanism of the transformation in antimony trioxide from orthorhombic valentinite to cubic senarmontite

The kinetics of the polymorphic transformation in antimony trioxide from metastable orthorhombic valentinite to cubic senarmontite has been studied in polycrystalline material between 490 and 530°C. Quantitative analysis of the mixtures was done using infrared spectrophotometry. The kinetic data was analyzed and the activation energy for the process was obtained: (i) On the basis of Avrami's equation, which is derived on the basis of a nucleation and growth mechanism; and (ii) from the time required for a constant fraction of the transformation to take place. The values obtained were 50.8 and 46.0 kcal/mole. Observations have also been made on partly transformed single crystals of valentinite using a polarizing microscope. The latter studies and the value of the activation energy suggest that a better understanding of the transformation could be obtained on the basis of a vapor phase mechanism.

Synthesis of liquid crystalline benzothiazole base derivatives: A study of their optical and electrical properties

Two new donor-acceptor type liquid crystalline semiconductors based on benzothiazole have been synthesized. Their structural, photophysical and electronic properties were investigated using X-ray diffraction, atomic force microscopy, cyclic voltammetry, UV-Vis, photoluminescence, and Raman spectroscopy. The liquid crystalline behaviour of the molecules was thoroughly examined by differential scanning calorimetry (DSC) and optical polarizing microscope. The DSC and thermogravimetric analysis (TGA) show that these materials posses excellent thermal stability and have decomposition temperatures in excess of 300 degrees C. Beyond 160 degrees C both molecules show a smectic A liquid crystalline phase that exists till about 240 degrees C. Field-effect transistors were fabricated by vacuum evaporating the semiconductor layer using standard bottom gate/top contact geometry. The devices exhibit p-channel behaviour with hole mobilities of 10(-2) cm(2)/Vs. (C) 2009 Elsevier B.V. All rights reserved.

Unraveling the packing pattern leading to gelation using SS NMR and X-ray diffraction: direct observation of the evolution of self-assembled fibers

A detailed understanding of the mode of packing patterns that leads to the gelation of low molecular mass gelators derived from bile acid esters was carried out using solid state NMR along with complementary techniques such as powder X-ray diffraction (PXRD), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and polarizing optical microscopy (POM). Solid state C-13{H-1} cross polarization (CP) magic angle spinning (MAS) NMR of the low molecularmass gel in its native state was recorded for the first time. A close resemblance in the packing patterns of the gel, xerogel and bulk solid states was revealed upon comparing their C-13{H-1} CPMAS NMR spectral pattern. A doublet resonance pattern of C-13 signals in C-13{H-1}CPMAS NMR spectra were observed for the gelator molecules, whereas the non-gelators showed simple singlet resonance or resulted inthe formation of inclusion complexes/solvates. PXRD patterns revealed a close isomorphous nature of the gelators indicating the similarity in the mode of the packing pattern in their solid state. Direct imaging of the evolution of nanofibers (sol-gel transition) was carried out using POM, which proved the presence of self-assembled fibrillar networks (SAFINs) in the gel. Finally powder X-ray structure determination revealed the presence of two non-equivalent molecules in an asymmetric unit which is responsible for the doublet resonance pattern in the solid state NMR spectra.

Aggregation and mesomorphic properties of 'double-headed' carbohydrate amphiphiles

Sugar-based amphiphiles, consisting of two sugar head groups and an alkylene chain within the molecules, are synthesized and their aggregation and mesomorphic properties are evaluated. The hydrophilic sugar head groups, constituted with beta-D-glucopyranoside units, and the lyophilic alkylene units, are coupled to a glycerol backbone to afford the 'double-headed' sugar amphiphiles. Aggregation studies in aqueous solutions provided their critical micellar concentrations and the aggregation numbers. Mesophase characterizations by polarizing optical microscopy and differential scanning calorimetry (DSC) revealed the phase-transition behaviour of these new 'double-headed' glycolipids.

Phase behavior of concentrated aqueous solutions of cetyltrimethylammonium bromide (CTAB) and sodium hydroxy naphthoate (SHN)

We have characterized the phase behavior of mixtures of the cationic surfactant cetyltrimethylammonium bromide (CTAB) and the organic salt 3-sodium-2-hydroxy naphthoate (SHN) over a wide range of surfactant concentrations using polarizing optical microscopy and X-ray diffraction. A variety of liquid crystalline phases, such as hexagonal, lamellar with and without curvature defects, and nematic, are observed in these mixtures. At high temperatures the curvature defects in the lamellar phase are annealed gradually on decreasing the water content. However, at lower temperatures these two lamellar structures are separated by an intermediate phase, where the bilayer defects appear to order into a lattice. The ternary phase diagram shows a high degree of symmetry about the line corresponding to equimolar CTAB/SHN composition, as in the case of mixtures of cationic and anionic surfactants.

Role of hydroxyl group on the mesomorphism of alkyl glycosides:synthesis and thermal behavior of alkyl 6-deoxy-beta-D-glucopyranosides

A homologous series of alkyl 6-deoxy-beta-D-glucopyranoside amphiphiles was prepared,in an effort to identify the role of hydroxyl group in the mesomorphic behavior of alkyl glycosides. Synthesis was performed by a chlorination of the sugar moiety in alkyl-beta-D-glucopyranosides with methylsulfonyl chloride in DMF, followed by a metal mediated dehalogenation to secure alkyl 6-deoxy-beta-D-glucopyranosides, wherein the alkyl chain length varied from C-9 to C-16. The mesomorphic behavior of these 6-deoxy alkyl glycosides was assessed using polarizing optical microscopy, differential scanning calorimetry and X-ray diffraction method. Whereas the lower homologues exhibited a monotropic SmA phase till sub-ambient temperatures, the higher homologues formed a plastic phase. A partial interdigitized bilaye structure of SmA phase is inferred from experimental d-spacing and computationally derived lengths of the molecules. The results were compared with those of normal alkyl glucopyranosides, retained with hydroxyl groups at C-2-C-6 carbons, and alkyl 2-deoxy-glucopyranosides, devoid of a hydroxyl group at C-2 and the comparison showed important differences in the mesomorphic behavior.(C)2010 Elsevier Ireland Ltd. All rights reserved.

Src Homology 3-interacting Domain of Rv1917c of Mycobacterium tuberculosis Induces Selective Maturation of Human Dendritic Cells by Regulating PI3K-MAPK-NF-kappa B Signaling and Drives Th2 Immune Responses

Mycobacterium tuberculosis, an etiological agent of pulmonary tuberculosis, causes significant morbidity and mortality worldwide. Pathogenic mycobacteria survive in the host by subverting host innate immunity. Dendritic cells (DCs) are professional antigen-presenting cells that are vital for eliciting immune responses to infectious agents, including pathogenic mycobacteria. DCs orchestrate distinct Th responses based on the signals they receive. In this perspective, deciphering the interactions of the proline-glutamic acid/proline-proline-glutamic acid (PE/PPE) family of proteins of M. tuberculosis with DCs assumes significant pathophysiological attributes. In this study, we demonstrate that Rv1917c (PPE34), a representative member of the proline-proline-glutamic-major polymorphic tandem repeat family, interacts with TLR2 and triggers functional maturation of human DCs. Signaling perturbations implicated a critical role for integrated cross-talk among PI3K-MAPK and NF-kappa B signaling cascades in Rv1917c-induced maturation of DCs. However, this maturation of DCs was associated with a secretion of high amounts of anti-inflammatory cytokine IL-10, whereas Th1-polarizing cytokine IL-12 was not induced. Consistent with these results, Rv1917c-matured DCs favored secretion of IL-4, IL-5, and IL-10 from CD4(+) T cells and contributed to Th2-skewed cytokine balance ex vivo in healthy individuals and in patients with pulmonary tuberculosis. Interestingly, the Rv1917c-skewed Th2 immune response involved induced expression of cyclooxygenase-2 (COX-2) in DCs. Taken together, these results indicate that Rv1917c facilitates a shift in the ensuing immunity toward the Th2 phenotype and could aid in immune evasion by mycobacteria.

Growth and characterization of single crystal cored fibers of organic nonlinear optical materials

The recent development of several organic materials with large nonlinear susceptibilities, high damage threshold and low melting points encouraged researchers to employ these materials in fiber form to efficiently couple diode laser pumps and obtain enhanced second harmonic generation (SHG). In this paper we report the growth of single crystal cored fibers of 4-nitro-4'-methylbenzylidene aniline, ethoxy methoxy chalcone and (-)2-((alpha) -methylbenzylamino)-5- nitropyridine by inverted Bridgman-Stockbarger technique. The fibers were grown in glass capillaries with varying internal diameters and lengths and were characterized using x-ray and polarizing microscope techniques. The propagation loss at 632.8 nm and 1300 nm were measured and SHG was studied using 1064 nm pump.

2-Halooxyethylene ethers of cholesterol as novel single component, room temperature cholesteric LC materials

A series of 2-haloethoxyethyl cholesteryl ethers has been synthesized. Each material shows attractive liquid-crystalline properties as revealed by differential scanning calorimetry, polarizing microscopy, and temperature-dependence of selective reflection characteristic of the cholesteric mesophase. These are interesting examples of simple, nonpolymeric, single component systems that show the cholesteric mesophase at room temperature.

Relationship Between Physical Structure and Tribology of Single Soot Particles Generated by Burning Ethylene

Ethylene gas is burnt and the soot generated is sampled thermophoretically at different heights along the flame axis starting from a region close to the root of the flame. The morphology and crystallinity of the particle are recorded using high resolution transmission electron microscopes. The hardness of a single particle is measured using a nanoindenter. The frictional resistance and material removal of a particle are measured using an atomic force microscope. The particles present in the mid-flame region are found to have a crystalline shell. The ones at the flame root are found to be highly disordered and the ones at the flame tip and above have randomly distributed pockets of short range order. The physical state of a particle is found to relate, but not very strongly, with the mechanical and tribological properties of the particles.

Phase Characterization and Study of Molecular Order of a Three-Ring Mesogen by (13)C NMR in Smectic C and Nematic Phases

Molecules exhibiting a thermotropic liquid-crystalline property have acquired significant importance due to their sensitivity to external stimuli such as temperature, mechanical forces, and electric and magnetic fields. As a result, several novel mesogens have been synthesized by the introduction of various functional groups in the vicinity of the aromatic core as well as in the side chains and their properties have been studied. In the present study, we report three-ring mesogens with hydroxyl groups at one terminal. These mesogens were synthesized by a multistep route, and structural characterization was accomplished by spectral techniques. The mesophase properties were studied by hot-stage optical polarizing microscopy, differential scanning calorimetry, and small-angle X-ray scattering. An enantiotropic nematic phase was noticed for lower homologues, while an additional smectic C phase was found for higher homologues. Solid-state high-resolution natural abundance (13)C NMR studies of a typical mesogen in the solid phase and in the mesophases have been carried out. The (13)C NMR spectrum of the mesogen in the smectic C and nematic phases indicated spontaneous alignment of the molecule in the magnetic field. By utilizing the two-dimensional separated local field (SLF) NMR experiment known as SAMPI4, (13)C-(1)H dipolar couplings have been obtained, which were utilized to determine the orientational order parameters of the mesogen.

A solid-state probe for SO2/SO3 based on Na2SO4 I electrolyte

Conductivity measurements as a function of temperature and partial pressures of SOs, SO2, and O2, and transference experiments indicate that the transport number of Na + ions is unity in Na2SO4-I. A concentration cell based on this electrolyte Pt, O2' + SO2' + SOs'/Na2SO4-I/SOa" + SO~" + O~", Pt produces emf's that are in agreement with those calculated from the Nernst equation when equilibrium is assumed between the gas species at the electrodes. The cell can be used for monitoring the SO#SOs pollution in air, and in combination with an oxygen probe can be used for the determination of SO=/SOs concentrations in coal combustion reactors, for the evaluation of the partial pressure of $2 in coal gasification systems, and for emission control in nonferrous smelters using sulfide ores. The probe is similar to that developed recently by Gauthier et aL (4, 5) using K=SO4 as the electrolyte, but can operate at higher pressures of SO3. Because of the greater polarizing power of the Na+ ion compared to the K + ion, Na2S207 is less stable and can be formed only at a considerably higher pressure of S03 than that required for K~20~.

Aggregation and mesomorphic properties of 'double-headed' carbohydrate amphiphiles

Sugar-based amphiphiles, consisting of two sugar head groups and an alkylene chain within the molecules, are synthesized and their aggregation and mesomorphic properties are evaluated. The hydrophilic sugar head groups, constituted with β-D-glucopyranoside units, and the lyophilic alkylene units, are coupled to a glycerol backbone to afford the ‘double-headed’ sugar amphiphiles. Aggregation studies in aqueous solutions provided their critical micellar concentrations and the aggregation numbers. Mesophase characterizations by polarizing optical microscopy and differential scanning calorimetry (DSC) revealed the phase-transition behaviour of these new ‘double-headed’ glycolipids.