On Coloration of Polyacrylonitrile: A Nuclear Magnetic Resonance Study

Coloration in polyacrylonitrile can be induced in three distinct ways: by heat treatment, by treatment with base, or during synthesis of the polymer itself using ionic initiators at relatively higher temperatures. The present investigation employing 'H and NMR spectroscopy has revealed some common features in colored polyacrylonitrile irrespective of ita mode of coloration. All colored polyacrylonitriles give an additional peak around S 2.7 in 'H NMR spectra and, except for heat-treated polyacrylonitrile, one extra group of peaks in the region 8 12-16 in 13C NMR spectra. The former peak has been attributed to methine and/or methylene protons in branched and/or cyclized structures, while the latter peak has been attributed to methylene carbon atoms in the branched structure. Colorless polyacrylonitriles have been found to be predominantly heterotactic, while colored polyacrylonitriles have been found to have appreciable isotactic contribution.

Indian developments in ultrasonics and acoustic emission methods

Fundamental investigations in ultrasonics in India date back to the early 20th century. But, fundamental and applied research in the field of nondestructive evaluation (NDE) came much later. In the last four decades it has grown steadily in academic institutions, national laboratories and industry. Currently, commensurate with rapid industrial growth and realisation of the benefits of NDE, the activity is becoming much stronger, deeper, broader and very wide spread. Acoustic Emission (AE) is a recent entry into the field of nondestructive evaluation. Pioneering efforts in India in AE were carried out at the Indian Institute of Science in the early 1970s. The nuclear industry was the first to utilise it. Current activity in AE in the country spans materials research, incipient failure detection, integrity evaluation of structures, fracture mechanics studies and rock mechanics. In this paper, we attempt to project the current scenario in ultrasonics and acoustic emission research in India.

Dipole ordering in dilute solutions of ferroelectrics in antiferroelectric materials

The coefficients of thermal expansion reported by Worlton et al. [6] in the case of zircon are given in Table II along with the present data. Although Oql > or• in both cases, the anisotropy is more marked in the case of DyV04. From Table II, it is clear that the coefficient of volume expansion (,6) is almost the same for both compounds.

A nuclear magnetic resonance study of tetramethylammonium tribromocadmate

Proton spin lattice relaxation (T1) in (CH3)4NCdBr3 at different Larmor frequencies (10, 20 and 30 MHz) has been studied in the temperature range 77 to 400 K. The variations in T1 at high temperature are independent of frequency and show a maximum due to spin rotation- interaction. The other features are interpreted as being due to isotropic tumbling of the tetramethylammonium ion and random reorientation of the CH3 group. The CW spectrum remained narrow up to 77 K and develops a wing structure at low temperatures. This observation is attributed to a possible tunnelling motion of the CH3 group, which has rather low activation energy as demonstrated by the study of T1.

Pressure sensitive flow and constraint factor in amorphous materials below glass transition

The constraint factor, C (given by the hardness-yield strength ratio H/Y in the fully lastic regime of indentation), in metallic glasses, is greater than three, a reflection of the sensitivity of their plastic flow to pressure. Furthermore, C increases with increasing temperature. In this work, we examine if this is true in amorphous polymers as well, through experiments on amorphous poly(methyl methacrylate) (PMMA). Uniaxial compression as well as spherical indentation tests were conducted in the 248-348 K range to construct H/Y versus indentation strain plots at each temperature and obtain the C-values. Results show that C increases with temperature in PMMA as well. Good correlation between the loss factors, measured using a dynamic mechanical analyzer, and C, suggest that the enhanced sensitivity to pressure is possibly due to beta-relaxation. We offer possible mechanistic reasons for the observed trends in amorphous materials in terms of relaxation processes.

Analysis of flange joints with elastic bolt

The contact zone and pressure distribution between two elastic plates joined by an elastic bolt and nut are estimated using finite element analysis. Smooth interfacial conditions are assumed in all the regions of contact. Eight node axisymmetric ring elements are used to model the structure. The matrix solution is obtained through frontal technique and this solution technique is shown to be very efficient for the iterative scheme adopted to determine the extent of contact. A parametric study is conducted varying the elastic properties of bolt and plate materials, bolt head diameter and thickness of the plates. The method of approach presented in this paper provides a solution with a realistic idealization of tension flange joints.

Performance of graphic aluminium particulate composite materials

Friction characteristics of journal bearings made from cast graphic aluminum particulate composite alloy were determined under mixed lubrication and compared with those of the base alloy (without graphite) and leaded phosphor bronze. All three materials ran without seizure while the performance of the particulate composite and leaded phosphor bronze improved with running. Temperature rise in the journal bearing under mixed/boundary lubrication was also measured. It was found that with 0.3D/1000 to 1.5D/1000 clearance and a low lubrication rate (typical value for a bearing of diameter 35 mm × length 35 mm is 80 mm3/min) and at a PV value of 73 × 106 Nm m−2 min−1 graphitic aluminium alloy journal bearings operate satisfactorily without seizure and excessive temperature rise. In comparison, the bronze bearings, with all the other parameters remaining the same, could not run without excessive temperature rise at clearances below D/1000 at lubrication rates lower than 200 mm3/min

A simulation study of the mixing, atomic flow and velocity profiles of crystalline materials during sliding

Self-contained Non-Equilibrium Molecular Dynamics (NEMD) simulations using Lennard-Jones potentials were performed to identify the origin and mechanisms of atomic scale interfacial behavior between sliding metals. The mixing sequence and velocity profiles were compared via MD simulations for three cases, viz.: sell-mated, similar and hard-softvcrystal pairs. The results showed shear instability, atomic scale mixing, and generation of eddies at the sliding interface. Vorticity at the interface suggests that atomic flow during sliding is similar to fluid flow under Kelvin-Helmholtz instability and this is supported by velocity profiles from the simulations. The initial step-function velocity profile spreads during sliding. However the velocity profile does not change much at later stages of the simulation and it eventually stops spreading. The steady state friction coefficient during simulation was monitored as a function of sliding velocity. Frictional behavior can be explained on the basis of plastic deformation and adiabatic effects. The mixing layer growth kinetics was also investigated.

Thermoelectric Properties of Co4Sb12 Skutterudite Materials with Partial In Filling and Excess In Additions

The properties of Co4Sb12 with various In additions were studied. X-ray diffraction revealed the presence of the pure δ-phase of In0.16Co4Sb12, whereas impurity phases (γ-CoSb2 and InSb) appeared for x = 0.25, 0.40, 0.80, and 1.20. The homogeneity and morphology of the samples were observed by Seebeck microprobe and scanning electron microscopy, respectively. All the quenched ingots from which the studied samples were cut were inhomogeneous in the axial direction. The temperature dependence of the Seebeck coefficient (S), electrical conductivity (σ), and thermal conductivity (κ) was measured from room temperature up to 673 K. The Seebeck coefficient of all In-added Co4Sb12 materials was negative. When the filler concentration increases, the Seebeck coefficient decreases. The samples with In additions above the filling limit (x = 0.22) show an even lower Seebeck coefficient due to the formation of secondary phases: InSb and CoSb2. The temperature variation of the electrical conductivity is semiconductor-like. The thermal conductivity of all the samples decreases with temperature. The central region of the In0.4Co4Sb12 ingot shows the lowest thermal conductivity, probably due to the combined effect of (a) rattling due to maximum filling and (b) the presence of a small amount of fine-dispersed secondary phases at the grain boundaries. Thus, regardless of the non-single-phase morphology, a promising ZT (S 2 σT/κ) value of 0.96 at 673 K has been obtained with an In addition above the filling limit.

Circular dichroism and nuclear magnetic resonance studies on the complexation of valinomycin with calcium

Complexation of valinomycin (VM) with the divalent cation Ca2+ in a lipophilic solvent, acetonitrile (CH3-CN), has been studied by using circular dichroism and proton and carbon- 13 nuclear magnetic resonance (‘H NMR and I3C NMR). From analyses of the spectral data, it is concluded that VM forms a 2:l (peptideion-peptide) sandwich complex with Ca2+, at low concentration of VM. At moderate conocentrations of the salt, in addition to the sandwich complex, an equimolar (1:l) complex different from those observed for potassium and sodium is also observed. At very large concentrations of the calcium salt, the data suggested a complex with a conformation similar to that of the free VM in polar solvents. Possible conformations for the sandwich and the equimolar VM-calcium complexes are proposed.

Heat pipes-concepts, materials and applications

The heat pipe is an innovative engineering structure characterized by its capacity to transfer large quantities of heat through relatively small cross-sectional areas with very small temperature differences; it also possesses high thermal conductance and low thermal impedance. In recent times, heat pipes in various forms and designs have found a wide variety of applications. This paper briefly presents the basic concepts of heat pipes, recent innovations in design and their applications.

Penetration Rate Effect on Miniature Cone Tip Resistance for Different Cohesionless Materials

Cone penetrometer tests were carried out in a 140 mm diameter triaxial chamber by using a miniature cone of diameter 19.5 mm. The rate of cone penetration was varied from 0.01 mm/s to 0.1 mm/s. Tests were performed in (i) clean sand, (ii) silty sand, and (iii) sand added with fly ash. Two different effective vertical pressures (sigma(nu)), 100 kPa and 300 kPa, were employed. It was noted that for clean and silty sand, the effect of penetration rate on the ultimate tip resistance (q(cu)) of the cone was found to remain only marginal. On the other hand, for sand added with 30% fly ash, the variation in q(cu) values with penetration rate was found to become quite significant. The effect of penetratio rate on q(cu) in all the cases was found to increase with a decrease in the rate of cone penetration. It was noted that with an increase in sigma(nu), the effect of penetration rate on q(cu) was found to become smaller. The effect of the cone penetration rate on q(cu) generally reduces with an increase in the relative density of the material.

Nuclear magnetic resonance spectra of oriented bicyclic systems containing heteroatom(s):the spectrum of 2-thiocoumarin

From the proton nmr studies of 2-thiocoumarin and coumarin, it is concluded that the relative interproton distances in the two oxygen heteroatom bicyclic systems are similar. The values for the phenyl ring protons do not deviate significantly from the regular hexagonal geometry, unlike bicyclic systems with nitrogens as the heteroatoms, such as diazanaphthalenes. Larger values of the indirect spin-spin couplings within the protons of the ring containing the oxygen heteroatom, compared to the values between the ortho protons in the phenyl rings in coumarin and 2-thiocoumarin, correspond to the olefinic nature of these protons. This is in contrast to results for the nitrogen heterocycles where both the rings are aromatic.

A novel combustion process for the synthesis of fine particle α-alumina and related oxide materials

Synthesis of fine particle α-alumina and related oxide materials such as MgAl2O4, CaAl2O4, Y3Al5O12 (YAG), Image , β′-alumina, LaAlO3 and ruby powder (Image ) has been achieved at low temperatures (500°C) by the combustion of corresponding metal nitrate-urea mixtures. Solid combustion products have been identified by their characteristic X-ray diffraction patterns. The fine particle nature of α-alumina and related oxide materials has been investigated using SEM, TEM, particle size analysis and surface area measurements.