Kinetics of thermal degradation of vinyl polyperoxides in solution

The thermal degradation of vinyl polyperoxides, poly(styrene peroxide, (PSP), poly(alpha-methylstyrene peroxide) (PAMSP) and poly(alpha-phenylstyrene pet-oxide) (PAPSP), was carried out at different temperatures in toluene. The time evolution of molecular weight distributions (MWDs) was determined by gel permeation chromatography (GPC). A continuous distribution model was used to evaluate the random chain degradation rate coefficients. The activation energies, determined from the temperature dependence of the rate coefficients, suggest that thermal degradation of polyperoxides is controlled by the dissociation of the O-O bonds in the backbone of the polymer chain. Among the three polyperoxides investigated, the thermal stability is the highest for PAPSP and the lowest for PAMSP. (C) 2002 Elsevier Science Ltd. All rights reserved.

Morphology and thermal characteristics of nano-sized Pb-Sn inclusions in Al

Nanoembedded aluminum alloys with bimetallic dispersoids of Sn and Pb of compositions Sn-82-Pb-18,Pb- Sn-64-Pb-36, and Sn-54-Pb-46 were synthesized by rapid solidification. The two phases, face-centered-cubic Pb and tetragonal Sn solid-solution, coexist in all the particles. The crystallographic relation between the two phases and the matrix depends upon the solidification pathways adopted by the particles. For Al-(Sn-82-Pb-18), we report a new orientation relation given by [011]Al//[010]Sn and (011)Al//(101)Sn. Pb exhibits a cube-on-cube orientation with Al in few particles, while in others no orientation relationship could be observed. In contrast, Pb in Sn-64-Pb-36 and Sn-54-Pb-46 particles always exhibits cube-on-cube orientation with the matrix. Sn does not show any orientation relationship with Al or Pb in these cases. Differential scanning calorimetry studies revealed melting at eutectic temperature for all compositions, although solidification pathways are different. Attempts were made to correlate these with the melting and heterogeneous nucleation. characteristics.

Synthesis and thermal expansion hysteresis of Ca1-xSrxZr4P6O24

The low thermal expansion ceramic system, Ca1-xSrxZr4P6O24, for the compositions with x = 0, 0.25, 0.50, 0.75 and 1 was synthesized by solid-state reaction. The sintering characteristics were ascertained by bulk density measurements. The fracture surface microstructure examined by scanning electron microscopy showed the average grain size of 2.47 mum for all the compositions. The thermal expansion data for these ceramic systems over the temperature range 25-800degreesC is reported. The sinterability of various solid solutions and the hysteresis in dilatometric behaviour are shown to be related to the crystallographic thermal expansion anisotropy. A steady increase in the amount of porosity and critical grain size with increase in x is suggested to explain the observed decrease in the hysteresis.

Thermal degradation processes in polysulfide copolymers investigated by direct pyrolysis mass spectrometry and flash pyrolysis-gas chromatography/mass spectrometry

This is the first report on the analysis of random block polysulfide copolymers containing different amounts of repeating units in the copolymer backbone, which has been studied by direct pyrolysis mass spectrometry (DPMS) and by pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). The homopolymers such as poly(ethylene sulfide) (PES), poly(styrene sulfide) (PSS), and two random copolymers, viz., poly(ethylene sulfide(x)-co-styrene sulfide(y)) [copolymer I (x = y = 0.5) and copolymer II (x = 0.74, y = 0.26)] were investigated by both DPMS and Py-GC/MS (except copolymer II) techniques. In the case of copolymer I, the thermal degradation products of SE1, SE2, S-2, and S2E (S = styrene sulfide, E = ethylene sulfide) were detected in DPMS, whereas the formation of SE1 and SE2 were observed by Py-GC/MS technique. However, for copolymer II, SE3 was also found along with SE1, SE2, S-2, and S2E in DPMS. The formation of additional product (SE3) observed in copolymer II could be due to an increase in the block length formed during copolymerization. Further, a comparative study on thermal degradation of PES, poly(ethylene disulfide) (PEDS), and poly(ethylene tetrasulfide) (PETS) were investigated by Py-GC/MS. The pyrolysis products detected by both DPMS and Py-GC/MS indicates that the thermal decomposition of these polymers yield cyclic sulfides through an intramolecular exchange or by backbiting processes. The linear products with thiol and vinyl groups were also observed by Py-GC/MS along with the cyclic products via carbon hydrogen transfer reaction.

Thermal degradation studies of para-substituted poly(styrene peroxide)s

The thermal degradation of a series of para-substituted poly(styrene peroxide)s with electron-donating [CH3, C(CH3)(3)] and electron-attracting (Br) substitutents are investigated by thermogravimetric analysis (TGA). The results indicate that the Hammett relationship can describe quantitatively the trends in maximum rate of polymer decomposition (T-max) observed in TGA and thus thermostability of substituted poly(styrene peroxide)s depends only on the electronic nature of substituents and their ability to stabilize macroradicals formed during chain scission. The experimental results are also substantiated by thermochemical calculations. (C) 2002 Elsevier Science Ltd. All rights reserved.

Synthesis, structural characterization, thermal studies and chain dynamics of poly(methacrylonitrile peroxide) by NMR spectroscopy

Poly(methacrylonitrile peroxide) (PMNP) has been synthesized from methacrylonitrile by free radical initiated oxidative polymerization and characterized by different spectroscopic methods. NMR spectroscopy confirmed the alternating copolymer structure with labile peroxy bonds in the main chain. The extreme instability of PMNP was noted from FTIR spectroscopy. Thermal degradation studies by using differential scanning calorimetry and thermogravimetry have revealed that PMNP degrades highly exothermically and the heat of degradation, 42.5 kcal mol−1, is of the same order as that reported for other vinyl polyperoxides. Mass spectral fragmentation pattern under electron impact (EI) condition has also been investigated. The mechanism of the primary exothermic degradation has been substantiated by thermochemical calculations. The chain dynamics of the polyperoxide chain has been studied by means of 13C spin–lattice relaxation times (T1) of the main chain as well as the side chain carbons. The temperature dependence of the spin–lattice relaxation times shows that the PMNP is more flexible compared to the analogous poly(styrene peroxide).

Thermal instability in a three-dimensional rigid container with prescribed heat flux at lower boundary

The Bénard–Marangoni convection is studied in a three-dimensional container with thermally insulated lateral walls and prescribed heat flux at lower boundary. The upper surface of the incompressible, viscous fluid is assumed to be flat with temperature dependent surface tension. A Galerkin–Tau method with odd and even trial functions satisfying all the essential boundary conditions except the natural boundary conditions at the free surface has been used to solve the problem. The critical Marangoni and Rayleigh numbers are determined for the onset of steady convection as a function of aspect ratios x0 and y0 for the cases of Bénard–Marangoni, pure Marangoni and pure Bénard convections. It is observed that critical parameters are decreasing with an increase in aspect ratios. The flow structures corresponding to the values of the critical parameters are presented in all the cases. It is observed that the critical parameters are higher for case with heat flux prescribed than those corresponding to the case with prescribed temperature. The critical Marangoni number for pure Marangoni convection is higher than critical Rayleigh number corresponding to pure Bénard convection for a given aspect ratio whereas the reverse was observed for two-dimensional infinite layer.

Thermal Lipid Order−Disorder Transitions in Mixtures of Cationic Cholesteryl Lipid Analogues and Dipalmitoyl Phosphatidylcholine Membranes

Two types of cationic cholesteryl amphiphiles, one where the headgroup is attached to the steroid by an ester linkage and the second by an ether linkage, were synthesized. A third type of cholesteryl lipid bearing an oligoethylene glycol segment was also prepared. Each of these synthetic lipids generated vesicle-like aggregates with closed inner aqueous compartments from their aqueous suspensions. We examined their interaction with L-α-dipalmitoyl phosphatidylcholine (DPPC) membranes using fluorescence anisotropy, transmission electron microscopy (TEM), and differential scanning calorimetry (DSC). When included in membranes, the synthetic cholesteryl lipids were found to quench the chain motion of the acyl chains of DPPC. This suggests that these cationic cholesteryl derivatives act as filler molecules despite modification at the headgroup level from the molecular structure of natural cholesterol. Careful analyses of DSC and fluorescence anisotropy data suggest that the nature of perturbation induced by each of these cationic cholesterol derivatives is dependent on the details of their molecular structure and provides significant information on the nature of interaction of these derivatives with phospholipid molecules. In general, amphiphiles that support structured water at the interfacial region tend to rigidify the fluid phase more than others. Importantly, these cholesteryl amphiphiles behave less like cholesterol in that their incorporation in DPPC not only abolishes the phase transition but also depresses the phase transition temperature.

Vertical thermal structure of the atmosphere during active and weak phases of convection over the north Bay of Bengal: Observation and model results

Owing to the lack of atmospheric vertical profile data with sufficient accuracy and vertical resolution, the response of the deep atmosphere to passage of monsoon systems over the Bay of Bengal. had not been satisfactorily elucidated. Under the Indian Climate Research Programme, a special observational programme called 'Bay of Bengal Monsoon Experiment' (BOBMEX), was conducted during July-August 1999. The present study is based on the high-resolution radiosondes launched during BOBMEX in the north Bay. Clear changes in the vertical thermal structure of the atmosphere between active and weak phases of convection have been observed. The atmosphere cooled below 6 km height and became warmer between 6 and 13 km height. The warmest layer was located between 8 and 10 km height, and the coldest layer was found just below 5 km height. The largest fluctuations in the humidity field occurred in the mid-troposphere. The observed changes between active and weak phases of convection are compared with the results from an atmospheric general circulation model, which is similar to that used at the National Centre for Medium Range Weather Forecasting, New Delhi. The model is not able to capture realistically some important features of the temperature and humidity profiles in the lower troposphere and in the boundary layer during the active and weak spells.

Morphology and thermal characteristics of nano-sized Pb–Sn inclusions in Al

Nanoembedded aluminum alloys with bimetallic dispersoids of Sn and Pb of compositions Sn82–Pb18, Sn64–Pb36, and Sn54–Pb46 were synthesized by rapid solidification. The two phases, face-centered-cubic Pb and tetragonal Sn solid-solution, coexist in all the particles. The crystallographic relation between the two phases and the matrix depends upon the solidification pathways adopted by the particles. For Al–(Sn82–Pb18), we report a new orientation relation given by [011]Al//[010]Sn and (o11)A1//(101)Sn. Pb exhibits a cube-on-cube orientation with Al in few particles, while in others no orientation relationship could be observed. In contrast, Pb in Sn64–Pb36 and Sn54–Pb46 particles always exhibits cube-on-cube orientation with the matrix. Sn does not show any orientation relationship with Al or Pb in these cases. Differential scanning calorimetry studies revealed melting at eutectic temperature for all compositions, although solidification pathways are different. Attempts were made to correlate these with the melting and heterogeneous nucleation characteristics.

Electron Cyclotron Resonance in Strained Si and Si0.94Ge0.06 Channels on Relaxed Si0.62Ge0.38 Buffers Grown by Rapid Thermal Chemical Vapor Deposition

We report the far-infrared measurements of the electron cyclotron resonance absorption in n-type Si/Si0. 62Ge0.38 and Si0.94Ge0.06 /Si0. 62Ge0.38 modulation- doped heterostructures grown by rapid thermal chemical vapor deposition. The strained Si and Si0.94Ge0.06 channels were grown on relaxed Si0.62Ge0.38 buffer layers, which consist of 0.6 μm uniform Si0.62Ge0.38 layers and 0.5 μm compositionally graded relaxed SiGe layers from 0% Ge to 38 % Ge. The buffer layers were annealed at 800 °C for 1 hr to obtain complete relaxation. The samples had 100 Å spacers and 300 Å 2×1019 cm-3 n-type supply layers on the tops of the 75 Å channels. The far-infrared measurements of electron cyclotron resonance were performed at 4K with the magnetic field of 4 – 8 Tesla. The effective masses determined from the slope of center frequency of absorption peak vs applied magnetic field plot are 0.20 mo and 0.19 mo for the two dimensional electron gases in the Si and Si0.94Ge0.06 channels, respectively. The Si effective mass is very close to that of two dimensional electron gas in Si MOSFET (0.198mo). The electron effective mass of Si0.94Ge0.06 is reported for the first time and about 5 % lower than that of pure Si.

Thermal cycling of Mg-MMCs

Creep resistant Mg alloy QE22 reinforced with maftec(R), saffil(R) or supertec(R) short fibres is cycled between room temperature and 308degreesC at different ramp rates in the longitudinal and transverse directions. From the careful analysis of the strain vs. temperature thermal cycling curves true material behaviour and artifacts from the dilatometer are deciphered. From this analysis true coefficient of thermal expansion and relaxation processes are deduced. Hysteresis at higher temperatures is attributed to the relaxation process, whereas hysteresis at low temperatures giving a tilt-ground shape to the thermal cycling curves is again an artifact due to the instrument. The change in ramp rate highlights this effect. Finally, the effect of thermal cycling on microstructure is examined.

Unsteady free convection flow over an infinite vertical porous plate due to the combined effects of thermal and mass diffusion, magnetic field and Hall currents

The unsteady free convection flow over an infinite vertical porous plate, which moves with time-dependent velocity in an ambient fluid, has been studied. The effects of the magnetic field and Hall current are included in the analysis. The buoyancy forces arise due to both the thermal and mass diffusion. The partial differential equations governing the flow have been solved numerically using both the implicit finite difference scheme and the difference-differential method. For the steady case, analytical solutions have also been obtained. The effect of time variation on the skin friction, heat transfer and mass transfer is very significant. Suction increases the skin friction coefficient in the primary flow, and also the Nusselt and Sherwood numbers, but the skin friction coefficient in the secondary flow is reduced. The effect of injection is opposite to that of suction. The buoyancy force, injection and the Hall parameter induce an overshoot in the velocity profiles in the primary flow which changes the velocity gradient from a negative to a positive value, but the magnetic field and suction reduce this velocity overshoot.