Oxidation of some aliphatic polyols on anodically deposited MnO2

Galvanostatic steady state current potential measurements were carried out for oxidation of a series of aliphatic alcohols having varying number of hydroxyl groups. The anodically deposited layer of MnO₂ on platinum was used as the electrode material. The deposit was characterised by scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDAX) and electrode potential measurements. The catalytic role of MnO₂ in the electro-oxidation of alcohols was indicated by the chronopotentiograms and the cyclic voltammograms. An analysis of the electrochemical data indicated a catalytic EC mechanism in which Mn (V) is generated electrochemically and consumed chemically in succession. Based on this and the hydrogen bonding interaction between alcoholic hydroxyl groups and MnO₂ layer, a mechanism was proposed which accounts for the variation in the observed electrochemical reaction orders. Tafel behaviour was found to be followed only approximately. Current efficiency of the electrochemical oxidation of polyols was studied. Replacement of platinum by carbon as current collector was found to leave the electrocatalytic activity of the MnO₂ deposit practically unaltered.     

NMR studies of poly(2-hydroxy ethyl methacrylate-co-2-vinyl pyridine)

Copolymers of 2-hydroxy ethyl methacrylate-2-vinyl pyridine (H/V) of different composition were synthesized by free radical bulk polymerization using azobisisobutyronitrile (AIBN) as an initiator under nitrogen atmosphere. The copolymer compositions were calculated from ¹H NMR spectra. The reactivity ratios for H/V copolymers obtained from a linear Kelen-Tudos method (KT) and nonlinear error-in-variables method (EVM) are r_H = 0.50 ± 0.10, r_V = 1.04 ± 0.08 and r_H = 0.55, r_V = 1.06 respectively. The complete spectral assignment of methine, methylene, methyl, carbonyl, and aromatic carbon regions in term of compositional and configurational sequences of H/V copolymers were done with the help of ¹³C{¹H} NMR, distortionless enhancement by polarization transfer (DEPT), two-dimensional heteronuclear single quantum coherence (HSQC) along with total correlated spectroscopy (TOCSY). © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Polymer transcrystallinity induced by carbon nanotubes

In this work, we provide the evidence of polymer transcrystallinity in the presence of carbon nanotubes (CNTs). The interfacial morphology of carbon nanotube fiber-polypropylene matrix is investigated by means of polarized optical microscopy (POM), wide-angle X-ray diffraction (WAXD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The supramolecular microstructures of polypropylene transcrystals induced by the nanotube fiber are observed in the range of isothermal crystallization temperatures from 118 °C to 132 °C. The dynamic process of transcrystallization is analyzed by using the theory of heterogeneous nucleation. Microstructure analysis shows that the nanotubes can nucleate the growth of both α- and γ-transcrystal, and α-transcrystals dominate the overall interfacial morphology. Close to the nanotube fiber surface, a cross-hatched lamellar microstructure composed of mother lamellae and daughter lamellae is observed.     

Microstructural effects on the tensile properties and deformation behavior of a Ti-48Al gamma titanium aluminide

The effects of microstructure on the tensile properties and deformation behavior of a binary Ti-48Al gamma titanium aluminide were studied. Tensile-mechanical properties of samples with microstructures ranging from near γ to duplex to fine grained, near- and fully-lamellar were determined at a range of temperatures, and the deformation structures in these characterized by transmission electron microscopy (TEM). Microstructure was observed to exert a strong influence on the tensile properties, with the grain size and lamellar volume fraction playing connected, but complex, roles. Acoustic emission response monitored during the tensile test revealed spikes whose amplitude and frequency increased with an increase in the volume fraction of lamellar grains in the microstructure. Analysis of failed samples suggested that microcracking was the main factor responsible for the spikes, with twinning providing a minor contribution in the near-lamellar materials. The most important factor that controls ductility of these alloys is grain size. The ductility, yield stress, and work-hardening rate of the binary Ti-48Al alloy exhibit maximum values between 0.50 and 0.60 volume fraction of the lamellar constituent. The high work-hardening rate, which is associated with the low mobility of dislocations, is the likely cause of low ductility of these alloys. In the near-γ and duplex structures, slip by motion of 1/2<110] unit dislocations and twinning are the prevalent deformation modes at room temperature (RT), whereas twinning is more common in the near- and fully-lamellar structures. The occurrence of twinning is largely dictated by the Schmid factor. The 1/2<110] unit dislocations are prevalent even for grain orientations for which the Schmid factor is higher for <101] superdislocations, though the latter are observed in favorably oriented grains. The activity of both of these systems is responsible for the higher ductility at ambient temperatures compared with Al-rich single-phase γ alloys. A higher twin density is observed in lamellar grains, but their propagation depends on the orientation and geometry of the individual γ lamellae. The increase in ductility at high temperatures correlates with increased activity of 1/2<110] dislocations (including their climb motion) and twin thickening. The role of microstructural variables on strength, ductility, and fracture are discussed. This article is based on a presentation made in the symposium entitled “Fundamentals of Structural Intermetallics,” presented at the 2002 TMS Annual Meeting, February 21–27, 2002, in Seattle, Washington, under the auspices of the ASM and TMS Joint Committee on Mechanical Behavior of Materials.     

Metallurgical Investigation of a Prematurely Failed Concentric Reducer Tube Used in a Hot-Rolling Mill

A concentric reducer tube, which was a part of the top exit roughing hydraulic descaler in a hot strip mill failed prematurely under working pressure. A detailed metallurgical investigation comprising physical examination, optical microscopy, scanning electron microscopy, and electron probe microanalysis was carried out to find out the genesis of the failure. Physical examination revealed cracks located symmetrically around the circumference of the tube that ran along its full length, up to the weld beads at both ends. Optical microscopy of etched samples revealed a banded ferrite-pearlite structure and the existence of forging folds near the change-in-section(160° fillets). Cracks were found to initiate from these forging folds. No structural abnormalities were found in the weld beads and heat-affected zones.     

Corrosion failure of Zn–Al detonator housing

Some batches of detonator housings made up of Chromium plated Zn–Al alloy were found in an extensively cracked condition after few months of storage at room temperature. An analysis of the failure showed that the cracks were due to intergranular corrosion facilitated by segregation of lead at the grain boundaries. Improper chromium plating further aggravated the corrosion problem. This failure case emphasises the need for strict control of chemical composition for components made from Zn–Al alloy and the process of Cr plating of the components.     

Synthesis and characterization of acidic properties of Al-SBA-15 materials with varying Si/Al ratios

Al-SBA-15 of varying Si/Al ratios in the range 11.4–78.4 was synthesized using tri-block copolymer P123. The calcined materials were examined by XRD, pore size distribution, surface area, ²⁷Al NMR spectroscopy. The acidity and acid strength distribution were studied using microcalorimetric adsorption of NH₃. The acidic properties were also examined by cumene cracking reaction as a function of Si/Al ratios. Systematic variation of acidity and activity was observed as a function of Si/Al ratio. The initial heats of NH₃ adsorption correlated well with activity indicate that acid sites with ΔH > 100 kJ/mole is responsible for cumene cracking activity. Linear correlations were obtained with total acidity and cumene cracking activities. The tetrahedral aluminum was found to be responsible for the observed acidities and catalytic activities.     

Flavor Fade in Peanuts During Short-term Storage

ABSTRACT: Flavor characteristics of roasted peanuts over short-term storage were explored through sensory and chemical analyses. The volatiles from freshly roasted peanuts were evaluated over short-time (21 d) storage using gas chromatography, chemosensory techniques, and a sensory panel to quantify and identify pyrazines and hexanal over a 21-d storage period. A significant decrease ( P < 0.05) was noted in 2,3-diethylpyrazine, 2-methoxypyrazine, 2,3-dimethylpyrazine, 2-ethyl-3-methylpyrazine, and 2,3,5-trimethylpyrazine concentrations over a 21-d period. No significant difference ( P > 0.05) was noted in the 2-methylpyrazine and 2-ethylpyrazine concentrations. The hexanal concentration significantly increased ( P < 0.05) over the 21-d period. The peroxide values and sensory analysis agreed with these results. A significant increase ( P < 0.05) in peroxide value was seen at days 14 and 21, and a significant decrease ( P < 0.05) in fresh roasted peanuty flavor from day 0 to 21 and significant increases ( P < 0.05) in painty, cardboardy, and bitter flavors from day 7 to 21 with the sensory analysis. The electronic nose successfully separated day 0 and 21 samples from day 7 and 14 samples, which were also separated but with some overlap.