Mechanistic studies on the effect of ferrocene bonding agents in composite solid propellents

Five compounds, viz. 1,1'-ferrocenediyldiethylidene bis(thiocarbonohydrazide) (DAFT), 1,1-diacetylferrocene disemicarbazone (DAFS), 1,1-diacetylferrocenebenzoyl hydrazone (FDBAH), 1,1-diacetylferrocene-p-nitrobenzoyl hydrazone (FDNBAH), and p-toluenesulfonic acid 1,1'-ferrocenediyldiethylidene dihydrazide (TFDD) were found to be bonding agents as well as burning-rate modifiers for the ammonium perchlorate + hydroxy-terminated polybutadiene system. The tensile strength and percentage elongation significantly increased in the presence of these bonding agents (except FDBAH). The bonding agents generally did not adversely affect the slurry viscosity during processing. The bonding sites were located by infrared spectroscopy, supported by determination of the dissolution kinetics of the bonding agents and scanning electron microscopy. The bonding agents did not undergo any side-reactions with the curing agents.

Mechanistic studies on the effect of ferrocene bonding agents in composite solid propellents

Five compounds, viz. 1,1'-ferrocenediyldiethylidene bis(thiocarbonohydrazide) (DAFT), 1,1-diacetylferrocene disemicarbazone (DAFS), 1,1-diacetylferrocenebenzoyl hydrazone (FDBAH), 1,1-diacetylferrocene-p-nitrobenzoyl hydrazone (FDNBAH), and p-tolenesulfonic acid, 1,1'-ferrocenediyldiethylidene dihydrazide (TFDD) were found to be bonding agents as well as burning-rate modifiers for the ammonium perchlorate + hydroxy-terminated polybutadiene system. The tensile strength and percentage elongation significantly increased in the presence of these bonding agents (except FDBAH). The bonding agents generally did not adversely affect the slurry viscosity during processing. The bonding sites were located by infrared spectroscopy, supported by determination of the dissolution kinetics of the bonding agents and scanning electron microscopy. The bonding agents did not undergo any side-reactions with the curing agents.

Combustion synthesis and properties of the NASICON family of materials

The fine-particle NASICON family of materials, MZr2P3O12(where M = Na, K, ½Ca and ¼Zr) and NbZrP3O12, have been prepared by the combustion of aqueous heterogeneous mixtures of stoichiometric amounts of metal nitrate, zirconyl nitrate, niobium phosphate, diammonium hydrogen phosphate, ammonium perchlorate and carbohydrazide (CH) at 400 °C. The formation of NASICON materials was confirmed by powder X-ray diffraction (XRD), IR, solid-state (31P) NMR spectroscopy and thermal expansion coefficient measurements. The combustion-synthesized NASICON powders have an average agglomerate size of 9�13 µm with a specific surface area varying from 8 to 28 m2 g�1. The powders pelletized and sintered in the range 1100�1200 °C for 5 h achieved 95�97% theoretical density and showed fine-grain microstructure. The coefficient of thermal expansion of a sintered compact was measured up to 500 °C and ranged from �1.5 × 10�6°C�1 to 1.0 × 10�6°C�1 depending on the composition.

Reactivities of aluminium and aluminium-magnesium alloy powders in polymeric composites

Polymeric compositions containing Al-Mg alloys show higher reactivities, in comparison with similar compositions containing aluminium. This is observed irrespective of the amount of oxidizer, type of oxidizer used, type of polymeric binder, and over a range of the particle sizes of the metal additive. This is evident from the higher calorimetric values obtained for compositions containing the alloy, in comparison to samples containing aluminium. Analysis of the combustion residue shows the increase in calorimetric value to be due to the greater extent of oxidation of the alloy. The interaction between the polymeric binder and the alloy was studied by coating the metal particles with the polymer by a coacervation technique. On ageing in the presence of ammonium perchlorate, cracking of the polymer coating on the alloy was noticed. This was deduced from differential thermal analysis experiments, and confirmed by scanning electron microscopic observations. The increase in stiffness of the coating, leading to cracking, has been traced to the cross-linking of the polymer by magnesium.

Sandwich propellant combustion: Modeling and experimental comparison

This paper reports reacting fluid dynamics calculations for an ammonium percholrate binder sandwich and extracts experimentally observed features including surface profiles and maximum regression rates as a function of pressure and binder thickness. These studies have been carried out by solving the two-dimensional unsteady Navier-Stokes equations with energy and species conservation equations and a kinetic model of three reaction steps (ammonium perchlorate decomposition flame, primary diffusion flame, and final diffusion flame) in the gas phase. The unsteady two-dimensional conduction equation is solved in the condensed phase. The regressing surface is unsteady and two dimensional. Computations have been carried out for a binder thickness range of 25-125 mum and a pressure range of 1.4 to 6.9 MPa. Good comparisons at several levels of detail are used to demonstrate the need for condensed-phase two-dimensional unsteady conduction and three-step gas-phase reactions. The choice of kinetic and thermodynamic parameters is crucial to good comparison with experiments. The choice of activation energy parameters for ammonium percholrate combustion has been made with stability of combustion in addition to experimentally determined values reported in literature. The choice of gas-phase parameters for the diffusion flames are made considering that (a) primary diffusion flame affects the low-pressure behavior and (b) final diffusion flame affects high-pressure behavior. The predictions include the low-pressure deflagration limit of the sandwich apart from others noted above. Finally, this study demonstrates the possibility of making meaningful comparisons with experimental observations on sandwich propellant combustion.

Thermal degradation of a composite solid propellant examined by DSC - Kinetic study

The thermal decomposition of ammonium perchlorate (AP)/hydroxyl-terminated-polybutadiene (HTPB), the AP/HTPB solid propellant, was studied at different heating rates in dynamic nitrogen atmosphere. The exothermic reaction kinetics was studied by differential scanning calorimetry (DSC) in non-isothermal conditions. The Arrhenius Parameters were estimated according to the Ozawa method. The calculated activation energy was 134.5 W mol(-1), the pre-exponential factor, A, was 2.04.10(10) min(-1) and the reaction order for the global composite decomposition was estimated in 0.7 by the kinetic Shimadzu software based on the Ozawa method. The Kissinger method for obtaining the activation energy value was also used for comparison. These results are discussed here.

TG studies of a composite solid rocket propellant based on HTPB-binder

Thermal decomposition kinetics of solid rocket propellants based on hydroxyl-terminated polybutadiene-HTPB binder was studied by applying the Arrhenius and Flynn-Wall-Ozawa's methods. The thermal decomposition data of the propellant samples were analyzed by thermogravimetric analysis (TG/DTG) at different heating rates in the temperature range of 300-1200 K. TG curves showed that the thermal degradation occurred in three main stages regardless of the plasticizer (DOA) raw material, the partial HTPB/IPDI binder and the total ammonium perchlorate decompositions. The kinetic parameters E-a (activation energy) and A (pre-exponential factor) and the compensation parameter (S-p) were determined. The apparent activation energies obtained from different methods showed a very good agreement.

Managing crises in defense industry : the PEPCON and Avtex cases /

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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.

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.

Oxygen reduction reaction on a Pt/carbon fuel cell catalyst in the presence of trace quantities of ammonium ions: An RRDE study

The effect of trace quantities of ammonia on oxygen reduction reaction (ORR) on carbon-supported platinum catalysts in perchloric acid solutions is assessed using rotating ring disk electrode (RRDE) technique. The study demonstrates that ammonia has detrimental effects on ORR. The most significant effect takes place in the potential region above 0.7 V vs RHE. The effect is explained by the electrochemical oxidation of ammonia, which blocks Pt active sites and increases the formation of H2O2. This leads to losses in the disk currents and increments in the ring currents. The apparent losses in ORR currents may occur in two ways, namely, through the blocking of the active sites for ORR as well as by generating a small anodic current, which is believed to have a lower contribution. In addition, a detrimental effect of sodium cations in the potential range below 0.75 V vs RHE was demonstrated. This effect is most likely due to the co-adsorption of sodium cations and perchlorate anions on the Pt surface. Copyright (C) 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

Thermoanalytical studies of natural potassium, sodium and ammonium alunites

Dynamic and controlled rate thermal analysis (CRTA) has been used to characterise alunites of formula [M(Al)3(SO4)2(OH)6 ] where M+ is the cations K+, Na+ or NH4+. Thermal decomposition occurs in a series of steps. (a) dehydration, (b) well defined dehydroxylation and (c) desulphation. CRTA offers a better resolution and a more detailed interpretation of water formation processes via approaching equilibrium conditions of decomposition through the elimination of the slow transfer of heat to the sample as a controlling parameter on the process of decomposition. Constant-rate decomposition processes of water formation reveal the subtle nature of dehydration and dehydroxylation.

rac-Ammonium cis-2-carboxycyclohexane-1-carboxylate

In the structure of the title compound, cis NH4+ C8H11O4-, the carboxylic acid and carboxyl groups of the cation adopt C-C-C-O torsion angles of 174.9(2) and -145.4(2)deg. respecticely with the alicyclic ring. The ammonium H atoms of the cations give a total of five hydrogen-bonding associations with carboxyl O-atom acceptors of the anion which, together with a carboxylic acid O-H...O(carboxyl) interaction give two-dimensional sheet structures which lie in the (101) planes in the unit cell.

Recovery and reuse of ammonium from wastewater treatment plants : an application for agriculture

In wastewater treatment plants based on anaerobic digestion, supernatant and outflows from sludge dewatering systems contain significantly high amount of ammonium. Generally, these waters are returned to the head of wastewater treatment plant (WWTP), thereby increasing the total nitrogen load of the influent flow. Ammonium from these waters can be recovered and commercially utilised using novel ion-exchange materials. Mackinnon et al. have described an approach for removal and recovery of ammonium from side stream centrate returns obtained from anaerobic digester of a typical WWTP. Most of the ammonium from side streams can potentially be removed, which significantly reduces overall inlet demand at a WWTP. However, the extent of reduction achieved depends on the level of ammonium and flow-rate in the side stream. The exchange efficiency of the ion-exchange material, MesoLite, used in the ammonium recovery process deteriorates with long-term use due to mechanical degradation and use of regenerant. To ensure that a sustainable process is utilised a range of potential applications for this “spent” MesoLite have been evaluated. The primary focus of evaluations has been use of ammonium-loaded MesoLite as a source of nitrogen and growth medium for plants. A MesoLite fertiliser has advantage over soluble fertilisers in that N is held on an insoluble matrix and is gradually released according to exchange equilibria. Many conventional N fertilisers are water-soluble and thus, instantly release all applied N into the soil solution. Loss of nutrient commonly occurs through volatilisation and/or leaching. On average, up to half of the N delivered by a typical soluble fertiliser can be lost through these processes. In this context, use of ammonium-loaded MesoLite as a fertiliser has been evaluated using standard greenhouse and field-based experiments for low fertility soils. Rye grass, a suitable test species for greenhouse trials, was grown in 1kg pots over a period of several weeks with regular irrigation. Nitrogen was applied at a range of rates using a chemical fertiliser as a control and using two MesoLite fertilisers. All other nutrients were applied in adequate amounts. All treatments were replicated three times. Plants were harvested after four weeks, and dry plant mass and N concentrations were determined. At all nitrogen application rates, ammonium-loaded MesoLite produced higher plant mass than plants fertilised by the chemical fertiliser. The lower fertiliser effectiveness of the chemical fertliser is attributed to possible loss of some N through volatilisation. The MesoLite fertilisers did not show any adverse effect on availability of macro and trace nutrients, as shown by lack of deficiency symptoms, dry matter yield and plant analyses. Nitrogen loaded on to MesoLite in the form of exchanged ammonium is readily available to plants while remaining protected from losses via leaching and volatilisation. Spent MesoLite appears to be a suitable and effective fertiliser for a wide range of soils, particularly sandy soils with poor nutrient holding capacity.