Spectroscopic and Thermal Studies on 2,4,6-trinitro Toluene (TNT)

The kinetics and mechanism of the initial stage of thermal decomposition of 2,4,6-trinitro toluene (TNT), a widely used high explosive, have been studied, together with its morphology and evolved gaseous products using thermogravimetry (TG), differential thermal analysis (DTA), infrared spectroscopy (IR) and hot-stage microscopy. The kinetics of the thermolysis has been followed by IR after suppressing volatilisation by matrixing and by isothermal TG without suppressing volatilisation to simulate actual user conditions. The best linearity was obtained for Avrami-Erofeev equation for n=1 in isothermal IR and also in isothermal TG. The activation energy was found to be 135 kJ mol⁻¹, with logA (in s⁻¹) 12.5 by IR. The effect of additives on the initial thermolysis of TNT has also been studied. Evolved gas analysis by IR showed that CO₂, NO₂, NO and H₂O are more dominant than N₂O, HCN and CO. The decomposition involves the initial rupture of the C-NO₂ bond, weakened by hydrogen bonding with the labile hydrogen atom of the adjacent CH₃ group, followed by the abstraction of the hydrogen atom of the methyl group by NO₂, generated in the initial step. This revised version was published online in August 2006 with corrections to the Cover Date.     

Spectroscopic and thermal studies on the decomposition of l,3,5-triamino-2,4,6-trinitrobenzene (TATB)

The kinetics of the thermal decomposition of 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) in condensed state has been investigated by high temperature infrared spectroscopy (IR) and thermogravimetry (TG) in conjunction with pyrolysis gas analysis, differential thermal analysis (DTA) and hot stage microscopy. The decomposition proceeds in two main stages under isothermal conditions and the initial stage involving about 24% loss in weight obeys Avrami-Erofe'ev equation (n= 1), and is governed by an activation energy (E) of 150.58 kJ·mol^–1 and log(A in s^–1) 12.06. The second stage corresponding to 24 to 90% loss in weight gave best fit for Avrami-Erofe'ev equation,n=2, withE=239.56 kJ·mol^–1 and log(A in s^–1) 19.88 by isothermal TG. The effect of additives, on the initial thermolysis of TATB has also been studied. Evolved gas analysis by IR showed that NH₃, CO₂, NO₂, HCN and H₂O are produced in the initial stage of decomposition. The decomposition in KBr matrix in the temperature range 272 to 311.5°C shows relative preferential loss in the -NH₂ to -NO₂ band intensity which indicates that the rupture of C-NH₂ bond, weakened also by the interaction of the NH₂ with the neighbouring NO₂ group, appears to be the primary step in the thermolysis of TATB.     

Determination of repaglinide in pharmaceutical formulations by HPLC with UV detection.

A simple, precise and rapid RP-HPLC method was developed for the determination of repaglinide in pharmaceutical dosage forms. The method was carried out on a Shim-pack, RP-C18 column using a mixture of methanol: 0.1% v/v triethylamine (pH adjusted to 7 with orthophosphoric acid) and detection was done at 235 nm using nimesulide as internal standard. The linearity range was 0.1 to 0.5 microg/ml. The intra-day and inter-day precision were in the range of 0.48 to 1.01 and 0.15 to 1.15, respectively.     

Stability of electrostatic ion cyclotron waves in a multi-ion plasma

We have studied the stability of the electrostatic ion cyclotron wave in a plasma consisting of isotropic hydrogen ions (H⁺) and temperature-anisotropic positively (O⁺) and negatively (O⁻) charged oxygen ions, with the electrons drifting parallel to the magnetic field. Analytical expressions have been derived for the frequency and growth/damping rate of ion cyclotron waves around the first harmonic of both hydrogen and oxygen ion gyrofrequencies. We find that the frequencies and growth/damping rates are dependent on the densities and temperatures of all species of ions. A detailed numerical study, for parameters relevant to comet Halley, shows that the growth rate is dependent on the magnitude of the frequency. The ion cyclotron waves are driven by the electron drift parallel to the magnetic field; the temperature anisotropy of the oxygen ions only slightly enhance the growth rates for small values of temperature anisotropies. A simple explanation, in terms of wave exponentiation times, is offered for the absence of electrostatic ion cyclotron waves in the multi-ion plasma of comet Halley.     

Nonlinear aspects of supersonic flow past a cavity

Study of supersonic flow over wall-mounted cavities for two different length/depth (L/D) ratios is carried out experimentally. Unsteady pressure measurements were made on the front and aft walls of the cavity. Data analysis was performed on the experimental results so obtained. Spectra of the unsteady pressure data exhibit multiple tones. Higher-order spectral technique is implemented on the unsteady pressure data to ascertain whether these multiple tones are due to possible nonlinear interactions between the primary cavity modes (Rossiter modes) or not. Significant nonlinear interactions in the form of both sum and difference frequencies between the cavity modes are observed in both the cavities. The spectra of the cavity with L/D ratio 2 show distinct peaks due to nonlinear interactions while the cavity with L/D ratio 3 does not exhibit observable peaks in the spectra. The spectra of both the cavities show presence of low-frequency peaks of significant amplitudes. These low-frequency modes interact with the primary cavity modes to produce significant bicoherence values. The reasons for their existence could not be predicted. It is identified that the dominant mode in the spectra of the cavities is critical for most of the interactions observed.     

Acoustic and velocity field over 3D cavities

Effects of wall mounted cavity on a Mach 1.7 freestream flow over it are investigated experimentally and numerically. Three different three dimensional (3D) cavity configurations have been used in the study. The results are compared with those of a two dimensional (2D) cavity. Flow field over the cavity is observed to depend intensely on the cavity width and on the allied aerodynamic flow structure in the vicinity of the cavity. Pressure oscillations generated by presence of wall mounted cavity in supersonic freestream was also observed to affect the fluid motion over cavities.     

Chaos in the solar wind flow near Earth

We have done a time series analysis of daily average data of solar wind velocity, density and temperature at 1 AU measured by ACE spacecraft for a period of nine years. We have used the raw data without filtering to give a faithful representation of the nonlinear behaviour of the solar wind flow which is a novel one. The sensitivity of the results on filtering is highlighted. The attractor dimension is estimated for every parameter of the solar wind and it is found that they differ substantially. Hence a chaotic picture for the problem from different angles have been obtained. The calculated Kolmogorov entropies and Lyapunov exponents are positive showing evidences that the complex solar wind near the Earth is most likely a deterministic chaotic system.      

Laser reflection method for determination of shear stress in low density transitional flows

The details of laser reflection method (LRM) for the determination of shear stress in low density transitional flows are presented. The method is employed to determine the shear stress due to impingement of a low density supersonic free jet issuing out from a convergent divergent nozzle on a flat plate. The plate is smeared with a thin oil film and kept parallel to the nozzle axis. For a thin oil film moving under the action of aerodynamic boundary layer, the shear stress at the air–oil interface is equal to the shear stress between the surface and air. A direct and dynamic measurement of the oil film slope generated by the shear force is done using a position sensing detector (PSD). The thinning rate of the oil film is directly measured which is the major advantage of the LRM. From the oil film slope history, calculation of the shear stress is done using a three-point formula. The range of Knudsen numbers investigated is from 0.028 to 0.516. Pressure ratio across the nozzle varied from 3,500 to 8,500 giving highly under expanded free jets. The measured values of shear, in the overlapping region of experimental parameters, show fair agreement with those obtained by force balance method and laser interferometric method.     

Synthesis and characterization of novel amphiphilic block copolymers di‐, tri‐, multi‐, and star blocks of PEG and PIB

A simple but efficient strategy has been developed for the synthesis of novel di‐, tri‐, multi‐, and star‐block copolymers comprising poly(ethylene glycol) (PEG) and polyisobutylene (PIB) blocks. The synthesis principle involves the coupling of appropriately terminally functionalized PEG and PIB sequences, specifically the hydrosilation of mono‐, di‐, and tetra‐allyl‐telechelic PEGs (PEG‐allyl, allyl‐PEG‐allyl, and C(‐PEG‐allyl)₄ by mono‐ and di‐Si(CH₃)₂H telechelic PIBs (PIB‐SiH and HiS‐PIB‐SiH). Representative block copolymers, for example, PEG‐PIB, PIB‐PEG‐PIB, (‐PIB‐PEG‐)_n, and C(‐PEG‐PIB)₄ have been assembled and their structures determined by ¹H and ¹³C NMR spectroscopy. The bulk and surface morphology of select triblocks have been investigated by DSC and AFM and the findings interpreted in terms of phase‐separated PEG and PIB microdomains. The swelling behavior in water of various block copolymers also has been studied. Block copolymers containing 50–70 wt % PIB produce hydrogels, the integrity of which is maintained by physical crosslinks by PIB segments. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3200–3209, 2000