DSC combined with chemiluminescence for studying polymer oxidation

The oxidation of (Ti,W)C ceramics have been studied as a part of the program to investigate of properties of powder materials. Thermogravimetry, derivative thermogravimetry (TG-DTG), and differential thermal analysis DSC have been used in the non-isothermal study of powder oxidation (Ti,W)C in dry air atmosphere. The powder of crystalline carbide cermets with a ratio of W:Ti equals 0.3 was used in this study. The diagrams were recorded on a sample mass 3.42 mg on the Setaram apparatus in temperatures ranging from 25 to 1000°C. Seven different heating rates were used. The analytical techniques SEM, WDX, EDX and XRD were used in the research. The kinetics of the oxidation process was followed by the integral method by applying the Coats-Redfern's approximation. The kinetic models of particular stages of (Ti,W)C oxidation were evaluated from the dynamic mass losses data. The values of apparent activation energy E and the pre-exponential factor A of each stage of the oxidation were calculated. This revised version was published online in July 2006 with corrections to the Cover Date.     

Preparation and (13C)NMR spectroscopy of stereoregular poly(methacrylic acid)

Several procedures for synthesis of stereoregular poly(methacrylic acid) have been examined and the polymer characterized by (¹³C)NMR. Using d⁶ DMSO as solvent for spectroscopy gives better spectra than those previously obtained using aqueous solutions and stereochemical splittings can be resolved in the methyl signals. Free-radical polymerization in toluene solution is a Bernouilli process giving mainly heterotactic/syndiotactic polymer. Polymers produced with free-radical initiation in aqueous solution have a higher, and pH dependent, content of syndiotactic triads. A previously described procedure for producing regular polymers by hydrolysis of poly(trimethylsilyl methacrylate) requires modification to produce isotactic contents of above 90% and does not give truly syndiotactic polymer. In contrast, polymerization with γ-radiation can produce polymers with close to 90% of syndiotactic triads.     

Numerical solutions of a model for the propagation of a surface-catalysed flame in a tube

Numerical simulations of a surface-catalysed flame in a tubeare performed, corresponding to an experiment where a premixedfuel is fed into a tube whose inner surface is coated with acatalyst. In these experiments, subsequent to ignition, a reactionwave can be seen as a red-hot region which propagates back alongthe tube towards the inlet, and is due to low temperature combustionoccurring only on the inner surface of the tube where the catalystis present. The solutions of a mathematical model for this behaviourshow that initial-value problems do indeed result in such steadilypropagating waves. The numerically obtained wave speeds andsteady solution are compared to a previous large Damköhlernumber (D_a) asymptotic analysis using a simple reaction ratemodel, and agreement is very good even for moderately largevalues of D_a. However, for such Damköhler numbers, thewave speeds are found to be much larger than observed experimentally.Indeed, the simulations show that O(1) values of D_a are requiredto obtain the lower experimental wave speeds. Nevertheless,the wave speeds as a function of flow rate through the tubedo not agree well with the preliminary experimental resultsfor any choice of the parameters. A more realistic, Arrheniusreaction rate model is then considered. The Arrhenius modelpredicts a rapid change in temperature at the wave front, inmuch better agreement with the experiments than for the simplerreaction model.     

A simple photon counter using the BBC micro-computer for measurements of oxyluminescence from polymers

A simple photon counter is described, capable of measuring the luminescence associated with the oxidative degradation of a polymer down to count rates of a few Hertz. The control of sample environment, counting of pulses and subsequent collection and analysis of data are all controlled by a simple and inexpensive micro-computer. Typical luminescence results for Nylon 6,6 are described.     

Stochastic elastohydrodynamics of a microcantilever oscillating near a wall

We consider the thermally driven motion of a microcantilever in a fluid environment near a wall, a configuration characteristic of the atomic force microscope. A theoretical model is presented which accounts for hydrodynamic interactions between the cantilever and wall over a wide range of frequencies and which exploits the fluctuation-dissipation theorem to capture the Brownian dynamics of the coupled fluid-cantilever system. Model predictions are tested against experimental thermal spectra for a cantilever in air and water. The model shows how, in a liquid environment, the effects of non-delta-correlated Brownian forcing appear in the power spectrum, particularly at low frequencies. The model also predicts accurately changes in the spectrum in liquid arising through hydrodynamic wall effects, which we show are strongly mediated by the angle at which the cantilever is tilted relative to the wall.     

Water-soluble ABC triblock copolymers based on vinyl ethers: Synthesis by living cationic polymerization and solution characterization

Water-soluble ABC triblock copolymers of methyl vinyl ether (MVE), ethyl vinyl ether (EVE), and methyl tri(ethylene glycol) vinyl ether (MTEGVE) of various block sequences and carrying 20 monomer units in each block were synthesized by living cationic polymerization. In addition to the triblocks, one AB diblock, one BA diblock, and one statistical copolymer of MVE and MTEGVE carrying 20 units of each type of monomer were synthesized as controls. Moreover, three homopolymers each carrying 20 units of MVE and end groups of varying hydrophobicity were synthesized using three different initiators. The molecular weights and molecular weight distributions of all the polymers were determined by gel permeation chromatography (GPC) in tetrahydrofuran (THF). The number average degrees of polymerization (DP_ns) and composition of all the polymers were calculated by proton nuclear magnetic resonance (¹H-NMR) spectroscopy. The molecular weights and degrees of polymerization corresponded to the values expected from the monomer/initiator ratios. The calculated polydispersities were reasonably narrow at 1.3. Aqueous GPC studies at room temperature on the triblock copolymers showed that the polymers exist as isolated chains (unimers) in solution but they tend to assemble and form micelles in the presence of a sufficiently high salt concentration apparently due to the insolubility of the EVE units under the latter conditions. Triblocks with a different block sequence exhibited a different susceptibility to salt-induced micellization, as indicated by the retention volume of the micelles and the relative micelle/unimer peak areas. Similarly, the cloud points of the triblock copolymers covered a relatively wide temperature range from 56 to 72°C. These differences in micellization and cloud points suggest a profound effect of the location of the hydrophilic MTEGVE block on copolymer association. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 1181–1195, 1997     

The initiation of polymerization by organometallic compounds—V. The termination mechanism in the polymerization of acrylonitrile initiated by tetrakis(dimethylamido)titanium(IV)

A simple method is described for the preparation of pure, dry alcohols, tritiated in the hydroxyl group. The polymerization of acrylonitrile initiated by tetrakis(dimethylamido)titanium(IV) has been terminated by quenching with tritiated isopropanol at varying reaction times, and the radioactivity of the polymer has been determined, in order to measure the concentration of metal-polymer bonds present in the reaction. The results indicate that about 97 per cent of the polymer present has been terminated by a reaction leading to detachment of the polymer chain from the metal centre. A very small fraction of the total polymer is terminated by a reaction which does not lead to detachment of the polymer. Possible reaction mechanisms are discussed.     

The development of slugging in two-layer hydraulic flows

In this paper, we develop a hydraulic theory to describe theoccurrence and structure of slugging in a confined two-layergas–liquid flow generated by prescribed, constant, upstreamvolumetric flow rates in each layer. A linearized theory forthe uniform flow is established, after which we use bifurcationtheory to study fully non-linear periodic travelling wave structures.We find that a two-parameter family of such travelling wavesolutions exists. Under given conditions, the volumetric flowrate constraint provides a relation between these two parameters.To select a unique periodic travelling wave solution, we requirea further relation. We first investigate the conjecture thatthe periodic travelling wave solution selected in the initialvalue problem has the same wavelength as the linearly most temporallyunstable mode. To do this, we solve the initial value problemnumerically on a periodic domain. We find that the separationof the liquid slugs that form is much longer than the wavelengthof the most unstable temporal mode. We then develop a differentconjecture based on the convective instability of the long ‘tails’of the available periodic travelling wave solutions, which leadsto a better understanding of the wavelength selection process.