Influence of the electric field on the low-temperature thermal decomposition of ammonium perchlorate/polystyrene propellant

An electric field (100 V/cm at 230°C and 150°C) has been applied to ammonium perchlorate (AP)/polystyrene (PS) propellant mixtures in order to understand the low temperature decomposition behavior of the propellant. The charge-carrying species is anionic in nature at 230°C, which could be ClO4−, but is cationic at 150°C, which could be either NH4+ or H+. These results are parallel to that observed for pure ammonium perchlorate (AP) pellets [1]. The burning rate (r' ) of the propellant was found to follow the same trend as that for the thermal decomposition of the propellant on application of an electric field. At 150°C Image was higher at the −ve electrode than at the +ve electrode, but at 230°C just the opposite was observed. Kinetic studies have confirmed that the decomposition of the orthorhombic AP follows two mechanism corresponding to E = 30 kcal mol−1 (180–230°C) and E = 15 kcal mol−1 (150–180°C).

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.

Impression creep of zinc and the rate-controlling dislocation mechanism of plastic flow at high temperatures

The impression creep behaviour of zinc is studied in the range 300 to 500 K and the results are compared with the data from conventional creep tests. The steady-state impression velocity is found to exhibit the same stress and temperature dependence as in conventional tensile creep with the same power law stress exponent. Also studied is the effect of indenter size on the impression velocity. The thermal activation parameters for plastic flow at high temperatures derived from a number of testing techniques agree reasonably well. Grain boundary sliding is shown to be unimportant in controlling the rate of plastic flow at high temperatures. It is observed that the Cottrell-Stokes law is obeyed during high-temperature deformation of zinc. It is concluded that a mechanism such as forest intersection involving attractive trees controls the high-temperature flow rather than a diffusion mechanism.

Role of alloys in the thermal decomposition and combustion of ammonium perchlorate

The participation of aluminum in the decomposition reaction of ammonium perchlorate (AP) is enhanced if magnesium is added—either as a mixture of Al and Mg powders or as an alloy of Mg in Al. The differential thermal analyses of the compositions show a sensitization in the temperatures of decomposition, as well as increase in the heat of reaction. The AP-Mg and Ap-(Mg---Li) alloy pellets also show increased reactivity. The burning rates of AP-(Al-10% Mg) alloy pellets increase with increase in the alloy content, while calorimetric values peak at 40% alloy content. The combustion product gases of AP-40% (Al-10% Mg) alloy contain large quantities of hydrogen.

Chemical changes during the aging and decomposition of composite solid propellants

During the thermal decomposition of orthorhombic ammonium perchlorate (AP) at 230°C, where the decomposition is only up to 30 wt %, there is an accumulation in the solid of acids, the concentration of which increases up to 15% decomposition, after which it decreases till it reaches the original value. Similar observations have been made in the polystyrene (PS)/AP propellant systems. Aging studies of PS/AP propellants have been carried out earlier [1], where it has been shown that for the aged propellants the thermal decomposition (TD) rate at 230°C and 260°C and ambient pressure burning rate (Image ) both increase and this increase is due to the formation of reactive intermediate “polystyrene peroxide (PSP).” In the present studies it has been observed that during the aging of the propellant at 150°C, the acid is formed and gets accumulated in the propellant, which may also be responsible for the increase in TD rate and perhaps may be more effective than PSP.

Fractional power dependence of rate on activation energy for reactions with very low internal barriers

The dynamics of reactions with low internal barriers are studied both analytically and numerically for two different models. Exact expressions for the average rate,kI, are obtained by solving the associated first passage time problems. Both the average rate constant, kI, and the numerically calculated long-time rate constant, kL, show a fractional power law dependence on the barrier height for very low barriers. The crossover of the reaction dynamics from low to high barrier is investigated.

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.

Electrochemical phase formation (ECPF) and macrogrowth Part II. Two-rate models

A general theory is evolved for a class of macrogrowth models which possess two independent growth-rates. Relations connecting growth-rates to growth geometry are established and some new growth forms are shown to result for models with passivation or diffusion-controlled rates. The corresponding potentiostatic responses, their small and large time behaviours and peak characteristics are obtained. Numerical transients are also presented. An empirical equation is derived as a special case and an earlier equation is corrected. An interesting stochastic result pertaining to nucleation events in the successive layers is proved.

Effects of Isothermal and Adiabatic Thermal Loadings on Size and Strain Rate Dependence of Copper Nanowire

In the present paper, the size and strain rate effects on ultra-thin < 100 >/{100} Cu nanowires at an initial temperature of 10 K have been discussed. Extensive molecular dynamics (MD) simulations have been performed using Embedded atom method (EAM) to investigate the structural behaviours and properties under high strain rate. Velocity-Verlet algorithm has been used to solve the equation of motions. Two different thermal loading cases have been considered: (i) Isothermal loading, in which Nose-Hoover thermostat is used to maintain the constant system temperature, and (ii) Adiabatic loading, i.e., without any thermostat. Five different wire cross-sections were considered ranging from 0.723 x 0.723 nm(2) to 2.169 x 2.169 nm(2) The strain rates used in the present study were 1 x 10(9) s(-1), 1 x 10(8) s(-1), and 1 x 10(7) s(-1). The effect of strain rate on the mechanical properties of copper nanowires was analysed, which shows that elastic properties are independent of thermal loading for a given strain rate and cross-sectional dimension of nanowire. It showed a decreasing yield stress and yield strain with decreasing strain rate for a given cross- section. Also, a decreasing yield stress and increasing yield strain were observed for a given strain rate with increasing cross-sectional area. Elastic modulus was found to be similar to 100 GPa, which was independent of processing temperature, strain rate, and size for a given initial temperature. Reorientation of < 100 >/{100} square cross-sectional copper nanowire into a series of stable ultra-thin Pentagon copper nanobridge structures with dia of similar to 1 nm at 10 K was observed under high strain rate tensile loading. The effect of isothermal and adiabatic loading on the formation of such pentagonal nanobridge structure has been discussed.

State Dependent Attempt Rate Modeling of Single Cell IEEE 802.11 WLANs with Homogeneous Nodes and Poisson Arrivals

Analytical models of IEEE 802.11-based WLANs are invariably based on approximations, such as the well-known mean-field approximations proposed by Bianchi for saturated nodes. In this paper, we provide a new approach for modeling the situation when the nodes are not saturated. We study a State Dependent Attempt Rate (SDAR) approximation to model M queues (one queue per node) served by the CSMA/CA protocol as standardized in the IEEE 802.11 DCF. The approximation is that, when n of the M queues are non-empty, the attempt probability of the n non-empty nodes is given by the long-term attempt probability of n saturated nodes as provided by Bianchi's model. This yields a coupled queue system. When packets arrive to the M queues according to independent Poisson processes, we provide an exact model for the coupled queue system with SDAR service. The main contribution of this paper is to provide an analysis of the coupled queue process by studying a lower dimensional process and by introducing a certain conditional independence approximation. We show that the numerical results obtained from our finite buffer analysis are in excellent agreement with the corresponding results obtained from ns-2 simulations. We replace the CSMA/CA protocol as implemented in the ns-2 simulator with the SDAR service model to show that the SDAR approximation provides an accurate model for the CSMA/CA protocol. We also report the simulation speed-ups thus obtained by our model-based simulation.

Laboratory Test Methods For The Evaluation Of Flammability Of Polymers

Combustion is a complex phenomena involving a multiplicity of variables. Some important variables measured in flame tests follow [1]. In order to characterize ignition, such related parameters as ignition time, ease of ignition, flash ignition temperature, and self-ignition temperature are measured. For studying the propagation of the flame, parameters such as distance burned or charred, area of flame spread, time of flame spread, burning rate, charred or melted area, and fire endurance are measured. Smoke characteristics are studied by determining such parameters as specific optical density, maximum specific optical density, time of occurrence of the densities, maximum rate of density increase, visual obscuration time, and smoke obscuration index. In addition to the above variables, there are a number of specific properties of the combustible system which could be measured. These are soot formation, toxicity of combustion gases, heat of combustion, dripping phenomena during the burning of thermoplastics, afterglow, flame intensity, fuel contribution, visual characteristics, limiting oxygen concentration (OI), products of pyrolysis and combustion, and so forth. A multitude of flammability tests measuring one or more of these properties have been developed [2]. Admittedly, no one small scale test is adequate to mimic or assess the performance of a plastic in a real fire situation. The conditions are much too complicated [3, 4]. Some conceptual problems associated with flammability testing of polymers have been reviewed [5, 6].

Thermochemistry and lower combustion limit of ammonium perchlorate in presence of methylammonium perchlorates

The heats of combustion of mono-, di-, tri- and tetramethylammonium perchlorates have been determined by bomb calorimetry. The data have been used to explain why the thermal behavior of ammonium perchlorate (AP) is considerably modified in presence of these compounds as shown by differential thermal analysis. Above a particular concentration of methylammonium perchlorate (MAP), AP ignites in a single step around 290°C. The minimum concentration of a MAP (mono-, di-, tri- or tetra-) needed to cause ignition of AP in a single step depends on intramolecular “elemental stoichiometric coefficient” of the mixtures that has the same value regardless of the MAP. Furthermore, the calorimetric values of these mixtures are the same. The heat evolved on ignition of such a composition appears to determine the lower concentration limit of combustion of its mixture with AP.

Pyrolysis and combustion of alpha-cellulose: effect of dihydrazinium phosphate (N2H5)2HPO4

A strip of Whatman filter paper (α-cellulose) dipped in an aqueous solution of dihydrazinium phosphate, (N2H5)2HPO4(DHP), and dried, carbonized without flame when ignited. The observed flame retardancy of DHP on α-cellulose has been studied using TG, DTA and mass spectrometry. Dihydrazinium phosphate appears to catalyze the dehydration of α-cellulose, minimizing the depolymerization which produces flammable tars, with the formation of water and char. Flame retardancy of DHP is compared with that of diammonium phosphate and phosphoric acid.