V. R. Pai Verneker

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.

Synthesis and Characterisation of Metal Hydrazine Nitrate, Azide and Perchlorate Complexes

Metal hydrazine nitrate complexes of the type M(N2H4)Nn (NO3)2 where M = Mg, n = 2; M = Mn, Fe, Co, Ni, Zn and Cd and n = 3; metal dihydrazine azide complexes of the type M(N2H4)2 (N3)2 where M = Mg, Co, Ni and Zn; and Mg(N2H4)2 (C1O4)2 have been prepared by dissolving the respective metal powders in the solution of corresponding ammonium salts (NO3, N3 and C1O4) in hydrazine hydrate. These hydrazine complexes were also prepared by the conventional method involving the addition of alcoholic hydrazine hydrate to the aqueous solution of metal salts. The hydrazine complexes have been characterised by chemical analysis, infrared spectra and differential thermal analysis (DTA). Impact sensitivities of hydrazine complexes were determined by the drop weight method. The reactivity of these hydrazine complexes does not change with the method of preparation.

Effect of prior mechanical and thermal treatment on the thermal decomposition and sublimation of cubic ammonium perchlorate

Abstract The thermal decomposition of ammonium perchlorate (AP) in its cubic modification has been studied in the temperature range 300–390°C. Two distinct regions of temperature dependence are observed for the rate constants of the decomposition. The activation energies in the two regions are found to be 20 ± 2 kcals/mole and 60 ± 2 kcals/mole. Prior mechanical and thermal treatment of the materials is seen to result in a marked increase in the thermal reactivity of AP in the range 300–370°C. Differential thermal analysis of pre-compressed AP shows pronounced changes in the exothermic characteristics of the material. Prior compression of AP in addition enhances the sublimation of the material. The activation energies are not altered by the pretreatment. The results are explained in terms of crystal imperfections and the role of dislocations in the thermal decomposition of AP.

Low temperature ferrite formation using metal oxalate hydrazinate precursor

Magnesium ferrite, MgFe2O4 has been prepared at low temperatures by the thermal decomposition of a new precursor, MgFe2(C2O4)3. 5N2H4. The ferrite has been characterized by X-ray diffraction, infrared and Mossbauer spectra.

Antireflection properties of indium tin oxide (ITO) on silicon for photovoltaic applications

The short‐circuit current density (Jsc) of indium tin oxide (ITO/silicon solar cells has been shown both theoretically and experimentally to be a function of the thickness of the ion beam sputtered ITO layer. These results can be accounted for by computing the optical reflection from the ITO/silicon interface.

Thermoanalytical studies of hydrazidocarbonic acid derivatives

Preparation, thermal analysis and IR spectra of a number of transition metal hydrazidocarbonates have been described. Metal hydrazido carbonates decompose exothermically through oxalate and carbonate intermediates to the respective metal oxides. Reaction of ammonium carbonate with hydrazine hydrate yields hydrazinium derivative of hydrazidocarbonic acid; N2H3COON2H5

Differential scanning calorimetric studies on ammonium perchlorate

Differential scanning calorimetric studies on ammonium perchlorate have been carried out. The enthalpy values for the phase transition endotherm and the two exotherms have been reported in the present communication. A new method has been developed for the estimation of kinetic parameters from DSC the mograms. The values for activation energy as calculated by the above method for low temperature and high temperature exotherms are in close agreement with literature values. The present studies also confirm the presence of small exothermic peaks at the initial stages of high temperature exotherm. Explanation for the same has been given.

Mechanism of ageing of composite solid propellants

Composite propellants mostly consist of two major ingredients: oxidiser and binder. It has almost been established now that propellants undergo slow decomposition during the course of ageing [1-3]. To increase the longevity of the propellants, it is necessary to know the mechanism of the ageing process. Thus it has to be established whether the rate-controlling step lies in the oxidiser decomposition or in the binder decomposition. The objective of the present investigation, therefore, is to identify the constituent responsible for the ageing. It may be noted that contrary to the available literature on the mechanism of the ageing of double-base propellants, very little is known about the mechanism of composite propellant ageing [4-11]. From accelerated ageing studies in the temperature range 40-750C of five cast composite propellants, Kuletz and Pakulak [4] have shown that the primary component altered at the exposed surface is the binder, whereas in the interior it is the oxidiser. However, they found the activation energy (E) for surface, subsurface, and bulk material to be almost similar (23-27 kcal/mole). Schedlbauer [6] observed that polyurethane and carboxy terminated polybutadiene (CTPB)-based propellants harden during ageing, which he attributed to cross-linkage through the double bonds present in the main chain. He suggested that HCIO4 generated due to the interaction of AP and moisture may act as an excellent cross-linkage agent for double bonds. Myers [7] also observed the hardening of the CTPB propellant, which he explained on the basis of cross-linkage reactions due to the oxidative attack of AP on CTPB double bonds. Layton [9-11] correlated the chemical structural changes of CTPB, hydroxy terminated butadiene (HTPB), and terepolymer of butadiene, acrylic acid, and acrylonitrile (PBAN)-based propdlants with the change in their mechanical properties during the ageing process. He proposed that the cross-linkages are formed along the polymer chains at the unsaturated sites, with the maximum percentage at the pendant vinyl group. He estimated energy (E) values (5-7 kcal/mole) for the chemical and mechanical changes during ageing and attributed this to the diffusion process. It may be seen from the works of Kuletz and Pakulak [4] and Layton [9-11 ] that there is controversy over the E values for the ageing process. Another objective of the present work, therefore, is to estimate the E values for changes occurring in the mechanical properties, burning rate (~), and thermal decomposition (TD) during ageing and to see whether there is a correlation between them.

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.

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.