S.R. Jain

A new approach to thermochemical calculations of condensed fuel-oxidizer mixtures

A simple method of calculating the elemental stoichiometric coefficient, φe has been developed, which can easily be applied to multicomponent fuel-oxidizer compositions. The method correctly predicts whether a mixture is fuel lean, fuel rich, or stoichiometrically balanced. The total composition of oxidizing (or reducing) elements of the mixture appears to be related to the thermochemistry of the system. For the reaction of ammonium perchlorate and an organic fuel the heat of reaction varies linearly with the total composition of oxidizing elements. The physical significance of such a correlation based on thermochemical reasoning is highlighted in the paper.

Kinetics of copolyurethane network formation

Cure kinetics for the formation of copolyurethane networks of various compositions based on hydroxy-terminated polybutadiene(HTPB), poly(12-hydroxy stearic acid-co-TMP) ester polyol(PEP), and different isocyanates has been studied through viscosity build up during the cure reaction. The viscosity (N)-time (t) plots conform to the equation N = ae(bt), where a and b are empirical constants, dependent on the composition and the nature of the polyols and the isocyanates. The rate constants (b) for viscosity build up, evaluated from the slopes of dN/dt versus N plots at different temperatures, were found to vary significantly from 0.0073 to 0.25 min(-1); and the activation energies for gelation were found to be in the range 20 to 40 kJ mol(-1). The results have been interpreted in terms of the dependence of the rate constants on structural characteristics of the prepolymers

Phase Modification of Ammonium Nitrate by Potassium Salts

Modification of the room temperature phase (IV-III) of ammonium nitrate (AN) has been attempted using a variety of potassium salts namely, KF, KCl, KI, KNO3, K2CO3, K2SO4, KSCN and K2Cr2O7. No phase transition was observed when AN containing 1–2% by mass of these potassium salts is heated from room temperature (25°C) onwards in DTA and DSC scans, but the linear expansion due to phase transition was still observable in TMA measurements. Complete arrest of the linear expansion occurs only when a higher concentration of the additive is used. Similarly, in thermal cycling experiments, complete phase modification in the temperature range -80 to 100°C occurs only with a higher percentage of the potassium salt. The extent of modification, however, is found to be dependent both on the concentration, and the type of the anion. Potassium dichromate when used as an additive modifies the phase as well as the decomposition pattern of AN.

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.

Thermal decomposition studies on copolyurethanes based on hydroxyl terminated polybutadiene and poly(12-hydroxy stearic acid-co-TMP) ester polyol

Thermal degradation of copolyurethanes based on hydroxyl terminated polybutadiene (HTPB) and poly(12-hydroxy stearic acid-co-TMP) ester polyol (PEP) with varying compositions has been studied by thermo-gravimetric and pyrolysis-GC techniques. The copolyurethanes were found to decompose in multiple stages and the kinetic parameters were found to be dependent on the method of their evaluation. The activation energy for the initial stage of decomposition was found to increase, and for the main stage decreases with the increase in PEP content. The pyrolysis-GC studies on the ammonium perchlorate filled copolyurethanes (solid propellants) showed that the major products during the pyrolysis were C-2, C-3 hydrocarbons and butadiene. The amount of C-2 fraction in the pyrolyslate increased with solid loading, as well as with the HTPB content in the copolyurethanes. A linear relationship apparently exists between the amount of C-2 fraction and the burn rates of the solid propellants

Chemical aspects of the hypergolic preignition reactions of some hybrid hypergols

A new class of solid compounds, viz., bisthiocarbonohydrazones and thiosemicarbazones, have been found to be hypergolic with fuming nitric acid. The observed ignition delays of these hypergols have been compared with those of the monothiocarbonohydrazones-nitric acid systems and explained in terms of the chemical reactions-neutralization, oxidation, and nitration-occurring in the preignition stage. p-Nitrobenzoic acid, benzoic acid, benzaldehyde, sulfur trioxide, nitrogen dioxide, and nitrogen have been isolated as preignition reaction intermediates in the mono- and bisbenzaldehydethiocarbonohydrazone-nitric acid systems. A scheme of reactions occurring in the preignition stage is proposed based on the formation of these products.

Thermal ignition studies on metallized fuel-oxidizer systems

The thermal ignition behaviour of various mixtures of organic fuels, magnesium and ammonium nitrate (AN) has been examined by differential thermal analysis technique. It has been observed that the thermal decomposition/ignition of organic fuel-AN mixtures is modified significantly in the presence of magnesium metal. The decomposition characteristics of the binary mixtures of AN with various metals indicate the specific action of magnesium and zinc in lowering the decomposition temperature. A possible explanation for the low temperature decomposition is given in terms of the solid state reaction causing the fusion of AN which further reacts with the metal resulting in a highly exothermic reaction.ZusammenfassungMittels DTA wurde das thermische Initiierungsverhalten verschiedener Gemische aus organischen Brennstoffen, Magnesium und Ammoniumnitrat (AN) untersucht. Es wurde festgestellt, daß die thermische Zersetzung/Initiierung von Gemischen aus organischen Brennstoffen und AN durch die Gegenwart von metallischem Magnesium bedeutsam beeinflußt wird. Die Zersetzungscharakteristiken binären Gemische aus AN und verschiedener Metalle zeigen eine spezielle Wirkung von Magnesium und Zink bei der Herabsetzung der Zersetzungstemperatur. Eine mögliche Erklärung für die Zersetzung bei niedrigerer Temperatur kann in Bezug auf die Festkörperreaktion gesehen werden, die das Schmelzen von AN verursacht, welches dann mit dem Metall stark exotherm reagiert.РезюмеМетодом дифференциа льного термического анализа изучено тер мическое воспламен ие различных смесей ор ганических топлив, м агния и нитрата аммония (НА). Установлено, что термическое разложе ние/воспламенение с месей органическое топли во — НА значительно меняется в присутст вии металлического магния. Характеристики ра зложения бинарных с месей НА с различными мет аллами показали спе цифическое влияние магния и цин ка в понижении температуры разло жения. Возможное об ъяснение такого низкотемпературно го разложения дано, исходя из твердо тельной реакции прив одящей к плавлению нитрата ам мония, вступающего затем в с ильно экзотермическ ую реакцию с металлом.

Thermal analysis of monothiocarbonohydrazones

Abstract Thermal analysis of monothiocarbonohydrazones carried out using DTA and TG techniques show that they all decompose exothermally soon after melting. The exothermal decomposition is attributed to the presence of a hydrazino (NN) bond. The decomposition process has been studied by examining the products of decomposition of benzaldehydethio-carbonohydrazone. Nitrogen, ammonia, hydrogen sulphide, benzonitrile, thiobenzaldehyde, 2,4,6-triphenyl-s-triazine and complex condensation products containing CN linkages, have been found to be the main products of decomposition. A probable mechanism of decomposition is proposed based on the formation of these products, assuming the homolytic cleavage of the NN bond as a primary step.

Structure and explosive sensitivity relation in ring-substituted arylammonium perchlorates

The thermal and explosive characteristics of ring-substituted arylammonium perchlorates have been studied by differential thermal analysis, explosion delay, and impact-sensitivity measurements. The decomposition and dissociation temperatures, as well as activiation energy for explosion, increase with increasing basicity of the corresponding arylamine. These parameters, when plotted against σ, the Hammett substituent constant, show a linear relationship in the case of meta- and para-substituted derivatives. The results indicate that a proton transfer from arylammonium ion to perchlorate ion is involved in the decompostion and also in the explosion process of these arylammonium perchlorates.

Studies on the synergistic hypergolic ignition of hybrid systems

A variety of solid organic compounds, such as Schiff bases, azines, hydrazones, thiocarbonohydrazones, thiosemicarbazones, and hydroxy compounds, on mixing with metal powders, especially with magnesium, become synergistically hypergolic with white fuming nitric acid (WFNA). In the absence of magnesium powder, these compounds are either nonhypergolic or have longer ignition delays, when WFNA is used as oxidizer. The synergistic ignition behavior has been explained in terms of increased exothermicity of the system, primarily due to the heat evolving chemical reactions occurring between the fuels (organic compound and magnesium) and the oxidizer in the preignition stage.