Overview of the Development of Hydrazinium Nitroformate-Based Propellants

Schöyer, H.F.R.; Welland-Veltmans, W.H.M.; Louwers, J.; Korting, P.A.O.G.; Heijden, A.E.D.M. van der; Keizers, H.L.J.; Berg, R.P. van den

doi:10.2514/2.5909

Cited by 31 publications

(4 citation statements)

References 7 publications

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“…Trinitromethane (nitroform, 7 ) appears as the intermediate in the hydrazine nitroformate decomposition, which is a promising chlorine-free oxidant for the solid rocket fuel. – Thermodynamic characteristics of nitroform and intermediates of its decomposition as well as the rate constants of elementary reactions are crucial for modeling the complex process of the hydrazine nitroformate combustion. , …”

Section: Introductionmentioning

confidence: 99%

“…18,20,21 Trinitromethane (nitroform, 7) appears as the intermediate in the hydrazine nitroformate decomposition, which is a promising chlorine-free oxidant for the solid rocket fuel. [23][24][25][26][27] Thermodynamic characteristics of nitroform and intermediates of its decomposition as well as the rate constants of elementary reactions are crucial for modeling the complex process of the hydrazine nitroformate combustion. 27,28 Although the nitroalkanes have been studied extensively, there is still some disagreement among the existing experimental thermodynamic data, especially on the formation enthalpy of these species.…”

Section: Introductionmentioning

confidence: 99%

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Theoretical Study of the Nitroalkane Thermolysis. 1. Computation of the Formation Enthalpy of the Nitroalkanes, Their Isomers and Radical Products

Kiselev

Gritsan

2008

J. Phys. Chem. A

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The gas phase enthalpies of formation of mono-, di-, tri-, tetranitromethane and nitroethane, as well as of their nitrite and aci-form isomers were calculated using different multilevel (G2, G3, G2M(CC5)) and density functional theory (DFT)-based (B3LYP, MPW1B95 and MPWB1K) techniques. The enthalpies of the C-N bond dissociation and isomerization of these nitroalkanes were also calculated. The calculated values of the formation and reaction enthalpies were compared with the experimental data when these data were available. It was found that only the G3 procedure gave accurate (within 1 kcal/mol) results for the formation enthalpy of nitroalkanes, their isomers, and radical products. The G3 procedure and two new hybrid meta DFT methods proposed by Truhlar's group (Zhao, Y.; Truhlar, D. J. Phys. Chem. A 2004, 108, 6908) showed good results for the reaction enthalpies of the nitromethane isomerization and the C-N bond dissociation. Our calculation results were used to analyze thermodynamics of the dissociation and isomerization reactions of the poly nitro-substituted methanes.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Theoretical Study of the Nitroalkane Thermolysis. 1. Computation of the Formation Enthalpy of the Nitroalkanes, Their Isomers and Radical Products

Kiselev

Gritsan

2008

J. Phys. Chem. A

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“…The main criteria in the demand for an energetic oxidizer are high density, high enthalpy of formation, and high positive oxygen balance. − Ammonium perchlorate (AP) is the most widely used oxidizer in composite (CP) and composite-modified double base (CMDB) rocket propellants. However, as the most popular oxidizer, AP has its own inherent disadvantage in the production of chlorine-rich combustion products (30%), which will cause environmental problems such as ozone depletion and acid rain. − Energetic eco-friendly oxidizers ammonium dinitramide (ADN) and hydrazinium nitroformate (HNF) have entered in the domain of advanced propellant systems because they offer halogen-free propellant formulations. − In comparison with ADN, HNF has certain advantages such as its simple synthetic route, higher melting point (b.p.) and lower hygroscopicity. , The synthesis of HNF involves a two-step process comprising the preparation of nitroform (NF) and its neutralization with hydrazine to form HNF (Scheme ).…”

Section: Introductionmentioning

confidence: 99%

Studies on Synthetic Technology and Reduced Sensitivity Technology of Hydrazinium Nitroformate

Ding

Wang

Wen

et al. 2014

Ind. Eng. Chem. Res.

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A practical synthetic route of hydrazinium nitroformate (HNF) was reported in this paper. The preparation of intermediate nitroform (NF) from isopropyl alcohol was investigated by utilizing anhydrous nitric acid (HNO3) as a nitrating system. The influence of various factors such as reaction temperature, time, and amount of anhydrous HNO3 on yield of NF, as well as the effect of temperature on the extraction efficiency was demonstrated. NF was obtained with an optimal yield of 53.6%, far beyond that reported in the literature (25%). The synthesis of HNF was followed by the neutralization reaction of NF with equal molar hydrazine hydrate (80%) instead of hydrazine anhydrous. With the purpose of decreasing the sensitivity, the crystal morphology of HNF was adjusted through varied crystallization methods such as antisolvent crystallization, sono-crystallization and sequential cooling crystallization. HNF crystals obtained from sequential cooling crystallization displayed excellent morphology with a length/diameter ratio (L/D) approximate to 1:1. Corresponding sensitivity performance toward external impulse, especially friction and electrostatic discharge, was improved greatly in comparison with that of crude HNF without the crystallization process. The synthetic route in this paper would provide a basis to promote the industrial production of NF and HNF.

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“…For the first time, the HNF-based propellants were investigated in some detail in the 1960s, − but the research program was terminated, primarily because of the low stability of this compound and hazardous methods of its synthesis. The interest in HNF was revived in the late 1970s − when safe synthetic procedures and efficient stabilizers and binders were found. ,,,, …”

Section: Introductionmentioning

confidence: 99%

Theoretical Study of the Primary Processes in the Thermal Decomposition of Hydrazinium Nitroformate

Kiselev

Gritsan

2009

J. Phys. Chem. A

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The primary reactions of the thermal decomposition of hydrazinium nitroformate (HNF) as well as ammonium nitroformate (ANF) were investigated theoretically using the G3 multilevel procedure. Calculations were performed for the reactions in the gas phase and in the melt using a simplified model of the latter. The influence of the melt on the reaction barriers was taken into account by calculation of the solvation free energies using a PCM model. In contrast with many other energetic salts, the ionic salt structures of the HNF and ANF were found to be minima on the PES. However, the most energetically favorable structures of the HNF and ANF in the gas phase are H-bonded complexes. In the melt, on the contrary, the ionic structure is lowest in free energy because of solvation effects. In both the gas phase and melt, the HNF decomposes preferably to nitroform and hydrazine. This fact agrees well with the experimentally observed absence of HNF among the gas-phase decomposition products. Thermolysis of HNF occurs mainly through the intermediacy of nitroform; computations do not support the suggestion that the aci-nitroform is an important intermediate of HNF thermolysis. The primary dissociation reactions of ANF resemble those of the HNF.

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Overview of the Development of Hydrazinium Nitroformate-Based Propellants

Cited by 31 publications

References 7 publications

Theoretical Study of the Nitroalkane Thermolysis. 1. Computation of the Formation Enthalpy of the Nitroalkanes, Their Isomers and Radical Products

Theoretical Study of the Nitroalkane Thermolysis. 1. Computation of the Formation Enthalpy of the Nitroalkanes, Their Isomers and Radical Products

Studies on Synthetic Technology and Reduced Sensitivity Technology of Hydrazinium Nitroformate

Theoretical Study of the Primary Processes in the Thermal Decomposition of Hydrazinium Nitroformate

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