Interaction of a low-pressure gas flame and heterogeneous catalytic processes on the reactor surface

Conclusions (1) It was shown that the Semenov theory in various modes of chain termination quantitatively describes oxyhydrogen combustion near the first ignition limit with allowance for the interaction between the flame and the catalytic processes on the reactor wall. (2) Numerical modeling of oxyhydrogen ignition in the diffusion-controlled chain-termination mode detected the dependence of the rate “constant” for heterogeneous chain initiation on the model of the reaction in the gas. (3) For the first time, the change in the specific rate of heterogeneous chain initiation during a single ignition was determined. (4) method for controlling the low-pressure flame mode by affecting tubes far from the reactor was proposed and applied. Original Russian Text ? E.N. Aleksandrov, S.N. Kozlov, N.M. Kuznetsov, 2006, published in Doklady Akademii Nauk, 2006, Vol. 407, No. 5, pp. 630–633. Presented by Academician A.E. Shilov October 5, 2005     

Approximate critical conditions in thermal explosion theory for a two-step kinetic model

Approximate critical conditions for a thermal explosion problem is developed for a two-step reactions based on theories of Semenov and Frank-Kamenetskii. The aim is to examine the contributions of the radical termination step and the temperature dependent pre-exponential factor on the critical parameters within the framework of classical stationary and non-stationary theories. In the non-stationary case, a more general expression for the critical Semenov parameter (Ψ _cr ) and critical temperature (θ _cr ) were obtained by asymptotic procedure. In the stationary case, numerical estimates for the critical Frank-Kamenetskii parameter (δ _cr ) and the critical temperature (θ _cr ) were obtained by variational method technique. It was observed that the Semenov and Frank-Kamenetskii parameters are greatly influenced by the termination step and the variable pre-exponential factor. Apart from elucidating hitherto unknown features in the theory of thermal explosion, the results are more general as some known results are easily recovered.     

The chain character of the third self-ignition limit of hydrogen-oxygen mixtures and flame propagation at atmospheric pressure

It is shown that the characteristic time of the hydrogen-oxygen reaction without the participation of reaction chains is thousands of times longer than the characteristic time of heat removal from the reactor under third self-ignition limit conditions. As a result, reaction mixture self-heating does not exceed several degrees and, contrary to commonly accepted views, cannot cause thermal ignition. It is also shown that the reason for self-ignition under these conditions is the excess rate of chain branching compared with chain termination responsible for the formation of chain avalanches. For the same reason, layer-by-layer ignition during laminar flame propagation is also a chain process. Self-heating arises as a result of the development of chain combustion and strengthens chain avalanches. Explosion and detonation inhibition shows that chain avalanches play an important role in these processes.     

The constancy of the concentration of an inhibitor preventing the ignition of gases

Mechanisms of consumption of inhibitors in gas mixtures in different combustion modes—ignition prevention and suppression of flame propagation and detonation—have been revealed. It has been found that no more than a few hundredths of a percent of the initial reagents, including the inhibitor, are consumed for the prevention of ignition. In suppression of flame propagation and detonation, the inhibitor is consumed only in chain termination reactions. Oxygen is additionally consumed only in reactions with the products of incomplete oxidation of the inhibitor. The results have been interpreted in the framework of the theory of nonisothermal chain processes.     

Effect of radiation absorption modes on ignition time of translucent polymers subjected to time-dependent heat flux

Majority of previous solid ignition models, including numerical and analytical ones, considered only surface absorption of incident heat flux for simplification. However, the influence of in-depth absorption on pyrolysis and subsequent ignition cannot be ignored for infrared translucent polymers. This work addresses this problem and focuses on time-dependent heat flux to establish an analytical model for ignition behaviors prediction by means of theoretical analysis. Ignition temperature was utilized as the ignition criterion, and both surface and in-depth absorption scenarios were considered. Thermally thick polymethyl methacrylate and polyamide 6 were selected as reference materials to verify the reliability and applicability of the proposed model by comparing the analysis results with experimental data as well as numerical simulations. A method for determining the approximation parameters of the theoretical analysis was presented to derive the relationship between ignition time and the coefficients in heat flux expressions. The results show that the higher surface temperature owing to surface absorption accelerates the pyrolysis rate and results in a shorter ignition time, while in-depth absorption affects the ignition time inversely. The effect of surface heat loss was also evaluated quantitatively through both analytical and numerical models. The uncertainty of the proposed model is mainly caused by the selection of the approximation parameters. Nevertheless, it provides an alternative approach to estimate the ignition time of translucent polymers besides numerical simulation.

     

Thermal ignition behaviour of ammonium perchlorate in presence of fuel-rich compounds

The thermal ignition behaviour of ammonium perchlorate has been investigated in the presence of fuel-rich compounds such as tetramethylammonium perchlorate, trimethylammonium nitrate, carbon and cellulose. The ignition characteristics, as studied by differential thermal analysis, have been found to be strongly influenced by self-decomposition and other physicochemical properties of the additives. For a simple system, an analytical model proposed on the basis of the coupling of two exothermic decomposition reaction kinetics and a heat-balance equation, appears to explain to some extent the observed trend in peak ignition temperature when the composition is varied. The salient features of the analysis, as regards its application to fuel-oxidizer interactions in general, have been pointed out.     

Modeling and calculation of thermal explosion time to ignition of cylindrical fireworks and crackers

To analyze the thermal safety of cylindrical fireworks and crackers in storage and transportation, this article establishes a physical model and a mathematical model of thermal explosion time to ignition of finite cylindrical fireworks and crackers. And in order to simplify the thermal explosion model, effective Biot number about boundary condition is deduced according to the theory of heat transfer. The partial differential equation of thermal explosion model are calculated with difference method in Matlab program, to obtain the time to ignition as well as the temperature–time history before explosion system explodes. The rationality of effective Biot number and calculation method is proved through comparison of calculation solution and literature solution. Being the first to solve the problem of two-dimensional thermal explosion unsteady-state model of fireworks and crackers, where the upper surface, lower surface, and side surface have different heat dissipation conditions. Meanwhile, calculation steps were shown about a type of fireworks.     

Fire behaviour of hybrid filament-wound single and adhesively bonded composites tubes under static pressure

The present work aims to experimentally investigate the fire behaviour of water-filled E glass reinforced thermoset resin hybrid filament-wound composites tubes under static pressure. Heretofore, fire endurance tests have been conducted on single and adhesively bonded tubes manufactured by CTRA Company. Furthermore, internal pressure tests until failure have been performed on the burnt single and burnt joined tubes in order to quantify their abilities to contain the fluid after being exposed to heat flux. A comparison between the pressure behaviour of exposed to fire (burnt) and non-exposed tubes (single and joined) was also inspected. The identification of the fire-induced damage mechanisms of the tubes was performed through optical microscopy, Scanning Electron Microscopy (SEM) and X-ray tomographic observations. Finally, the thermal analysis was carried-out on burnt specimens in order to better understand the multiphysical phenomenon taking place during the fire endurance tests. The experimental results have revealed that the combustion process of both single and joined tubes was described in four steps namely tube heating, resin degradation, ignition and flame decay. Moreover, it was found that no leakage was witnessed on the tubes (single and joined) outer surfaces during the fire endurance tests. The comparison between the pressure behaviour of the burnt single tube and the burnt joined one has proved that the single tube is much resistant under internal pressure loading than the burnt joined tube. Finally, the fire-induced damage included matrix cracking and delamination between the tube plies which was noticed from microscopic observations.     

The relative contributions of self-heating and chain branching to the kinetics of hydrogen oxidation outside the ignition region close to the third limit

It is shown that, in hydrogen-oxygen mixtures, under the conditions when the rate of reaction chain termination is higher than the rate of chain branching, the characteristic reaction time is hundreds of seconds even in the immediate vicinity of the third ignition limit. The self-heating of the mixtures therefore does not exceed several degrees and, contrary to the accepted views, cannot result in thermal combustion. Ignition observed in the third limit region is caused by a higher rate of chain branching compared with chain termination; that is, it is a chain reaction. Self-heating only becomes substantial during the development of chain combustion.     

Thermal studies on beryllium,magnesium and calcium hafnyl oxalates

Beryllium hafnyl oxalate tetrahydrate, magnesium hafnyl oxalate tetrahydrate and calcium hafnyl oxalate tetrahydrate abbreviated as BHO, MHO and CHO, respectively, have been prepared in an aqueous medium and characterized by elemental analysis, magnetic susceptibility measurements and infrared spectral data. The thermal behaviour of these compounds in non-isothermal conditions have been investigated by employing TG, DTG and DSC techniques. The intermediates obtained at the end of various thermal decomposition steps were identified on the basis of elemental analysis and infrared spectral studies. The graphical method of Coats and Redfern has been employed to evaluate the kinetic parameters such as apparent activation energy and order of reaction. Heat of reaction for different decomposition steps have been calculated from the DSC curves.     

Kinetic aspects of chemical control over flame propagation in combustible gases

Kinetic aspects of controlling ignition and flame propagation parameters in the gas phase by chemical methods are considered. The efficiency of the chemical methods is due to the branched chain character of gas-phase combustion reactions and the dominant role of the competition between chain branching and chain termination in these processes.     

Curing studies of epoxy resin with nadic endcapped phosphorylated amines

Polyimides have aromatic moieties in the backbone structure which are responsible for their increased thermal stability. If phosphorus is introduced in the main chain structure of polyimides, there is further improvement in the thermal stability. This has been proved by the work carried out in our group. The polyimide having amine termination can be used for crosslinking of epoxy resins.In the present study amine terminated phosphorus containing nadicimide were taken as curing agent for DGEBA resins. The curing characteristics of DGEBA resin were studied by DSC using different amounts of nadic endcapped phosphorylated amines. DSC thermogram showed the heat of polymerization was lower as compared to system cured with aromatic amines.     

Synergism in combustion processes

The effect of CF₃H, CF₄, and N₂ on the ignition of methane–air mixtures has been investigated. The effect of trifluoromethane is due to its being involved in reaction chain termination. A nonadditive effect of trifluoromethane and nitrogen on the concentration limits of ignition and flame propagation in methane–air mixtures has been predicted and revealed. The synergistic effect arises from the exponential dependence of the rate of the chain process on the concentrations of the initial components.     

Thermal behaviour and non-isothermal decomposition kinetics of some Nd(III) coordination compounds

The authors present the results concerning the thermal behaviour of three polynuclear coordination compounds of Nd(III) and Co(II) or Fe(III) with triptophan. For the dehydration steps the values of the non-isothermal kinetic parameters have been determined.     

Pyrolysis-gas-liquid-chromatography utilised for a kinetic study of the mechanisms of initiation and termination in the thermal degradation of polystyrene

Pyrolysis-gas-liquid-chromatography (“thermocouple feedback” technique) has been used to study the thermal degradation kinetics of ionically-initiated and free-radical-initiated samples of polystyrene. Although mass-spectrometric measurements confirm that the pyrolysis products from large samples (1 mg) contain oligomers up to at least hexamer in addition to monomer, only monomer is detected when small thin samples (0.1 μg, 10²–10⁵ Å) are used. This effect is not due to a sensitivity problem in detecting oligomers, nor to the incapacity of such compounds of limited volatility to elute from the GLC apparatus. In studying the kinetics of monomer evolution from thin films, initial work was concerned with the effect of film thickness and the limits of first-order behaviour. Then the specific rate of monomer evolution (k_obs) was measured as a function of molecular weight for both types of sample at 723 K and 753 K; the results indicate that the pyrolysis mechanism involves both initiation at the chain-ends and initiation by random scission. Kinetic schemes involving mixed initiation have been proposed, and on this basis the results have been analysed to yield activation energies for scission and end-initiation for both types of sample. Comparison of the activation energies obtained with the quoted value for scission of a CC bond has shown that the depolymerization chain termination process cannot be second order and must be first order in the concentration of long chain radicals. The experimental results also indicate that the ionically-initiated polystyrenes are more stable than free-radical-initiated samples of comparable molecular weight. Possible initiation sites have been discussed with reference to the samples examined and to previous published studies. Several mechanisms leading to first order termination have been proposed; it is suggested that the most probable process involves intramolecular transfer with subsequent scission to give an oligomer radical which is small enough to diffuse readily from the system without further reaction.     

Hydrotalcite and nanometric silica as finishing additives to enhance the thermal stability and flame retardancy of cotton

Suspensions of nanoparticles (namely, hydrotalcite and nanometric silica) have been employed during the finishing of cotton in order to improve its thermal stability and/or flame retardancy. The immersion approach has also been coupled to a surface pre-treatment of the textile by cold oxygen plasma in order to load a higher amount of nanoparticles onto fibres. The time of immersion and the resulting distribution of the nanoparticles onto the fibres, evaluated by scanning electron microscopy in combination with elemental analysis, have been thoroughly investigated. The present study has shown that the above parameters are functions of nanoparticle type. Pre-treatment by cold plasma has been found to be more effective than the immersion only. As far as the thermal stability and the combustion behaviour of treated cotton are concerned, the nanoparticles turned out to be able to delay the degradation in air, modifying mechanism and kinetics, and at the same time enhancing the flame retardancy of cotton by increasing the time to ignition and decreasing the heat release rate peak during the combustion. The joint effect of the two nanoparticles has also been evaluated and found more efficient than the effect of single species.     

Evaluate the flammability of a PU foam with double-scale analysis

Two-scale tests, microscale and bench scale, are conducted to analyze the flammability of a flexible polyurethane foam. Microscale tests include simultaneous thermal analysis coupled to Fourier transform infrared spectroscopy, and microscale combustion calorimeter (MCC). Evolved gas components, heat release rate per unit mass, total heat release, derived heat release capacity, and minimum ignition temperature are obtained. Bench scale tests are performed on cone calorimeter. Peak heat release rate per unit area, effective heat of combustion, minimum incident heat flux for ignition, and total heat release per unit area of different incident heat fluxes are obtained. FO-category of the PU foam is estimated by multiple discriminant function analysis based on the results of cone calorimeter test. The relationship between the two-scale tests is analyzed. The minimum ignition temperatures derived from multi heating rate MCC tests are used to predict the time to ignition and compared with the results from cone calorimeter tests. This PU foam is evaluated as a high fire hazard polymer having low heat release capacity, low ignition temperature, and short ignition time.

     

Simulation of the inhibition of hydrogen-air flame propagation

The results of simulation and experimental data presented here demonstrate that the competition between chain branching and chain termination is the key factor in hydrogen-air flame propagation, including the temperature regime of the process and the formation of concentration limits. Self-heating becomes significant in developed combustion. It enhances the chain avalanche and ensures the temperature necessary for layer-by-layer chain ignition. By varying the ratio between the chain branching and termination rates by means of an inhibitor makes it possible to control the flame propagation process.     

Improvement of thermal stability of poly(methyl methacrylate) by incorporation of colloidal TiO2 nanorods

The thermal degradation behaviour of oleic acid-capped colloidal anatase TiO₂ nanorods, poly(methyl methacrylate), and their nanocomposites has been studied. Thermogravimetric and differential thermal analysis have been carried out in nitrogen atmosphere for both nanorods, and nanocomposites with nanorod loading from 5 to 30 wt% relative to the polymer. Our study shows that the degradation of the oleic acid-capped nanorods in nitrogen is mainly endothermic and occurs in two steps. The thermal stability of the nanocomposites is improved on increasing the filler loading in the considered range, as the nanorods prevent rapid heat diffusion and limit further degradation. This effect seems to be favoured by the nanorods increased mobility, leading to enhanced dispersion in the matrix upon heating the samples during the thermal analysis.