The thermal behavior of potassium dinitramide. Part 1. Thermal stability

Lei, Ming; Zhang, Zhizhong; Kong, Yali; Liu, Ziru; Zhu, Chunhua; Shao, Ying-Hui; Zhang, Pei

doi:10.1016/s0040-6031(99)00173-2

Cited by 15 publications

(16 citation statements)

References 1 publication

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“…DSC measurements have identified the main decomposition product of KDN to be KNO 3 . X-ray photoelectric spectroscopy has also revealed KNO 3 to be present in ample amounts on the surface of KDN crystals . FT-IR spectroscopy has identified N 2 O as the main gaseous product .…”

Section: Resultsmentioning

confidence: 99%

“…The decomposition rate of nonstabilized KDN is known to increase with grinding of the crystals, that is, decomposition increases with increased surface area. , Furthermore, the dependence on pressure and the stabilizing effect of water vapor further support surface processes. It would appear that a layer of nitrate can pacify the surface and help to stabilize KDN while also giving rise to the anomalous acceleration at the eutectic temperature . For this reason, work is under way to experimentally probe the surface geometry of ADN and KDN and asses the magnitude of surface distortions as well as the presence of nitrate using more sensitive spectroscopic methods.…”

Section: Discussionmentioning

confidence: 99%

“…In its solid state, KDN decomposes into primarily KNO 3 and N 2 O. NO and NO 2 are also seen. , Knowledge of initial product gases is essential for understanding the initial steps of a decomposition mechanisms. Unfortunately, careful studies of such species have been scarce.…”

Section: Introductionmentioning

confidence: 99%

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On the Anomalous Decomposition and Reactivity of Ammonium and Potassium Dinitramide

Rahm

Brinck

2010

J. Phys. Chem. A

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Mechanistic pathways for the thermal decomposition of the solid-state energetic oxidizers ammonium dinitramide (ADN) and potassium dinitramide (KDN) have been deciphered by carefully considering previously performed experimental studies and using state of the art quantum chemical modeling of molecular clusters. Decomposition is governed by surface chemical processes, involving polarized (twisted) dinitramide anions of reduced stability. Under atmospheric and low-pressure conditions, the rate-determining step for the decomposition of these dinitramide salts is the dissociation into NO(2) and NNO(2)(-) radicals. The activation barriers for these steps are estimated to be 30 and 36 kcal/mol for ADN and KDN, respectively. The known stabilizing effect of water is explained by its hydrogen bonding ability, which counteracts polarization of surface dinitramides. The reactivity of ADN toward various chemical environments is likely explained through metastable decomposition radical intermediates. Donation of hydrogen bonds, antioxidant character, and basicity are properties believed to correlate with a compound's ability to act as a stabilizer for dinitramide salts.

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Section: Resultsmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

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On the Anomalous Decomposition and Reactivity of Ammonium and Potassium Dinitramide

Rahm

Brinck

2010

J. Phys. Chem. A

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“…The value of the eutectic m.p. varied from sample to sample as it depends upon the percentage of KN present in the KDN to form an eutectic mixture [21][22][23]. KDN melting was followed by two exothermic decomposition peaks at 172 °C and 220 °C, while fresh KDN shows only one exothermic decomposition at 202 °C.…”

Section: Dsc and Tg-dtg Of An And Kdnmentioning

confidence: 99%

Thermal Decomposition and Kinetics Studies of AN, KDN and Their Mixtures with and without Catalysts

Kumar¹,

Joshi²

2017

Cent. Eur. J. Energ. Mater.

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Potassium dinitramide (KDN) was incorporated in ammonium nitrate (AN) crystals in AN/KDN ratio of 90/10, 75/25 and 50/50 by a co-crystallization method. These mixtures were subjected to thermal decompositional studies (DSC-TG) using a Simultaneous Thermal Analyzer (STA). The catalysts used for the present studies were: i) cupric(II) oxide (CuO) and, ii) copper-cobalt based metal oxide (Cu-Co * ). For all catalytic samples, 2% by weight percent of catalyst was added to the total weight of the samples. Thermal decomposition studies were carried out for all the oxidizer samples prepared. Thermal decompositional studies were carried out at three different heating rates, i.e. 3 K/min, 5 K/min and 10 K/min, and the kinetic parameters were computed using the model free FlynnWall-Ozawa equation. It has been observed that 50% KDN addition resulted in complete suppression of endothermicity indicating total supression of the phase changes of AN in this temperature range. Further, it was noticed that CuO acts as a better phase stabilizer for AN as compared to Cu-Co * . However, Cu-Co * considerably increased the net exothermic decompositional heat release (J/g) of AN.

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“…The main solid-state decomposition product for both ADN and KDN is nitrate (NO 3 À ), 9,11,14,17,19,20 and nitrate has previously been detected on the surface of KDN using X-ray photoelectronic spectroscopy. 18 Analyzing KDN is advantageous, as it exhibits a solid-state behavior similar to ADN, while having a significantly simpler chemical structure and decomposition chemistry (due to the lack of hydrogen). 9 However, despite the simplified chemical picture, the behavior of KDN is still complex.…”

Section: ' Introductionmentioning

confidence: 99%

The Molecular Surface Structure of Ammonium and Potassium Dinitramide: A Vibrational Sum Frequency Spectroscopy and Quantum Chemical Study

Rahm¹,

Tyrode²,

Brinck³

et al. 2011

J. Phys. Chem. C

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Vibrational sum frequency spectroscopy (VSFS) and quantum chemical modeling have been employed to investigate the molecular surface structure of ammonium and potassium dinitramide (ADN and KDN) crystals. Identification of key vibrational modes was made possible by performing density functional theory calculations of molecular clusters. The surface of KDN was found to be partly covered with a thin layer of the decomposition product KNO 3 , which due to its low thickness was not detectable by infrared and Raman spectroscopy. In contrast, ADN exhibited an extremely inhomogeneous surface, on which polarized dinitramide anions were present, possibly together with a thin layer of NH 4 NO 3 . The intertwined use of theoretical and experimental tools proved indispensable in the analysis of these complex surfaces. The experimental verification of polarized and destabilized dinitramide anions stresses the importance of designing surface-active polymer support, stabilizers, and/or coating agents, in order to enable environmentally friendly ADN-based solid-rocket propulsion.

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The thermal behavior of potassium dinitramide. Part 1. Thermal stability

Cited by 15 publications

References 1 publication

On the Anomalous Decomposition and Reactivity of Ammonium and Potassium Dinitramide

On the Anomalous Decomposition and Reactivity of Ammonium and Potassium Dinitramide

Thermal Decomposition and Kinetics Studies of AN, KDN and Their Mixtures with and without Catalysts

The Molecular Surface Structure of Ammonium and Potassium Dinitramide: A Vibrational Sum Frequency Spectroscopy and Quantum Chemical Study

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