Making Progress Towards «Green» Propellants

Dejeaifve, Alain; Fantin, André; Monseur, Lara; Dobson, Rowan

doi:10.1002/prep.201800026

Cited by 28 publications

(22 citation statements)

References 28 publications

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“…New, non-toxic, environmentally friendly compounds (such as tocopherol or ionone derivatives) have also been offered as stabilizers [10][11][12]. Derivatives of these substances have been determined as being non-toxic and having stabilizing properties of nitrocellulose propellants [13].…”

Section: Introductionmentioning

confidence: 99%

Effect of stabilizers and nitrogen content on thermal properties of nitrocellulose granules

Cieślak

Gańczyk-Specjalska

Drożdżewska-Szymańska

et al. 2020

J Therm Anal Calorim

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The granules containing nitrogen of various content (12.2-13.3%) and stabilizers (centralite I, centralite II, akardite II, triphenylamine) were obtained in laboratory scale, and the study of their physicochemical and thermal properties was conducted. It has been observed that the helium density of granules depends on the degree of gelling of nitrocellulose by the stabilizer as well as the lack of effect of the stabilizer type on the heat of combustion value. In turn, the heat of combustion depends on the content of nitrogen in nitrocellulose. Granules of 13.3% N nitrocellulose were characterized by a more rapidly developing thermal decomposition than the granules containing 12.2 and 12.9% N nitrocellulose. The maximum temperature of decomposition shifts toward higher temperatures (from 207.6 to 209.8 °C) with decreasing nitrogen content in nitrocellulose for granules containing triphenylamine as a stabilizer. All values of heat generation rate obtained for granules with triphenylamine were lower than the respective rates for granules with centralite I. Thermal properties and chemical stability of granules containing triphenylamine have better properties, when compared to other examined stabilizers. On the basis of differential scanning calorimetry and thermogravimetry, kinetic parameters were calculated by means of Ozawa-Flynn-Wall analysis. The effect of stabilizers and nitrogen content on kinetic parameters was determined. The kinetic model of thermal decomposition of granules was adjusted-the best fit was nth-order reaction with autocatalysis. The activation energy of thermal decomposition process according to the adopted chemical reaction model increases from 190 to 239 kJ mol −1 with increasing nitrogen content in the granulate.

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Section: Introductionmentioning

confidence: 99%

Effect of stabilizers and nitrogen content on thermal properties of nitrocellulose granules

Cieślak

Gańczyk-Specjalska

Drożdżewska-Szymańska

et al. 2020

J Therm Anal Calorim

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“…Table 5 presents the above values from Eq. (11). Granules signed as G(TPA + AkaII)1 were characterized by the highest n value-this reaction order was about 0.5 higher than remaining granules.…”

Section: Thermal Properties Of Granules and Determination Of Decomposition Kinetic Parametersmentioning

confidence: 90%

“…For this reason, the extensive research has been conducted in recent years on novel, environmentally friendly stabilizers for nitrocellulose. The proposed alternative sources of nitrocellulose stabilizers include, among others, triphenylamine, various types of fullerene derivatives, ionone, tocopherol, clinoptilolite or natural compounds, such as lignin, curcumin and guaiacol [6][7][8][9][10][11][12][13][14][15][16]. Efficient stabilizers should be characterized by high-performance reactivity with nitrogen oxides and acids, fine adsorptive properties of nitrogen oxides as well as compatibility with other ingredients used in nitrocellulose powders [8,17,18].…”

Section: Introductionmentioning

confidence: 99%

Physicochemical properties and thermal behavior of nitrocellulose granules with eutectic mixtures of stabilizers

Cieślak

Gańczyk-Specjalska

Drożdżewska-Szymańska

et al. 2021

J Therm Anal Calorim

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Examinations of two-component mixtures, namely: triphenylamine + centralite I (TPA + CI) and triphenylamine + akardite II (TPA + AkaII) were carried out using differential scanning calorimetry (DSC), which served to determine phase diagrams. Experimental data were described with NRTL model and eutectic points for both systems were determined. For TPA + CI system, they were equal to xEu,TPA = 0.2899, TEu = 62.9 °C, whereas for TPA + AkaII system they amounted to xEu,TPA = 0.7868, TEu = 117.5 °C. Granules contain mixtures of eutectic composition were obtained. The physicochemical and thermal properties of resultant single base granules were studied. The helium density of both granules was approx. 1.47 g cm−3, the average dynamic force amounted to 0.55–0.60 bar−1 s−1, and the calorific value ranged from 3060 to 3095 J g−1. Both granules should be chemically stable for 10 years of storage at 25 °C; they meet the requirements of STANAG 4582 standard. DSC analysis of decomposition processes was used to determine kinetic parameters and to adjust the chemical reaction model of nth order with autocatalysis (CnB). Reaction order ranged from 2.6 to 3.0, while the activation energy was similar (197–198 kJ mol−1). Based on examination of thermal properties, it was observed that both eutectic mixtures of stabilizers prevent the decomposition reaction more efficiently than the use of individual compounds as stabilizers.

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“…This last criterion is essential in the light of the current REACh regu-lation, which requires that old stabilisers be replaced by "greener" products [14,[26][27][28]. Dejeaifve et al demonstrate that stabiliser such as 2,3,5-trimethylphenol, 1,2,3-trimethoxybenzene, α-ionone, curcumin and α-tocopherol are able to stabiliser nitrate esters [2,26,29]. These stabilisers are efficient for all nitrate ester-based propellants, and so mainly gun propellants, however also rocket propellants containing nitrocellulose.…”

Section: Introductionmentioning

confidence: 99%

Identification of the Degradation Products from α‐Ionone Used as Stabiliser in “Green” Propellants through its Lifetime

Damseaux

Scholl

Damblon

et al. 2021

Propellants Explo Pyrotec

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A stabiliser is added to gun and rocket propellants to react with species responsible for degradation during decomposition. Propellant powder manufacturers and army personnel are confronted with toxicity during powder degradation and must replace current stabilisers with nontoxic molecules. According to the STANAG 4582 (North Atlantic Treaty Organization (NATO) Standardisation Agreement [1]), propellant powders must remain chemically stable for a minimum of ten years when stored at temperatures equivalent to an isothermal storage (25 °C). Single and double base smokeless powders with α-ionone as a "green" stabiliser are tested and the results show that the heat flow is stable over time and that the autocatalysis occurs 2 to 3 times later than in powders with conventional stabilisers. This stabiliser is efficient for all nitrate esterbased propellants. In the present paper, we identify and monitor the evolution of the main degradation products over time by nuclear magnetic resonance (NMR), mass spectrometry (MS) to unravel the stabilisation mechanism under accelerated aging conditions. A time-related fluctuation of their respective amounts (increasing then decreasing, then re-increasing, …) is observed, which indicates that the daughter products have also a stabilisation effect. The three major α-ionone daughter products are identified as: 3-oxo-α-ionone, 4-oxo-β-ionone and 4,5-epoxy-α-ionone.

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Making Progress Towards «Green» Propellants

Cited by 28 publications

References 28 publications

Effect of stabilizers and nitrogen content on thermal properties of nitrocellulose granules

Effect of stabilizers and nitrogen content on thermal properties of nitrocellulose granules

Physicochemical properties and thermal behavior of nitrocellulose granules with eutectic mixtures of stabilizers

Identification of the Degradation Products from α‐Ionone Used as Stabiliser in “Green” Propellants through its Lifetime

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