EP3939952A1 - Fast burning solid propellant comprising an oxidizer, an energetic binder and a metallic burn-off modifier and method for its preparation - Google Patents

Abstract

A fast-burning solid propellant of the composite propellant type, in particular for rockets, is proposed, which contains the following components: (a) an oxidizer in the form of ammonium dinitramide (ADN); (b) an energetic binder from the group of glycidyl azide polymers (GAP), poly(3,3-bis-azidomethyl-oxetanes) (poly-BAMO), poly(glycidyl)-nitrates (poly-GLYN), poly(3-nitratomethyl-3-methyl-oxetanes). ) (poly-NIMMO) and the poly(3-acidomethyl-3-methyl-oxe-tane (poly-AMMO) including their derivatives and mixtures; and (c) a combustion modifier from the group of metals and semi-metals including their alloys and hydrides In order to increase the combustion rate of such a solid propellant, the invention provides that the combustion modifier is present in the form of fibers.The invention also relates to a method for producing such a solid propellant based on ADN.

Description

1. (a) wenigstens einen Oxidator in Form von Ammoniumdinitramid (ADN);
2. (b) wenigstens einen energetischen Binder aus der Gruppe der Glycidyl-Azidpolymere (GAP), der Poly(3,3-bis-azidomethyl-oxetane) (poly-BAMO), der Poly(glycidyl)-nitrate (poly-GLYN), der Poly(3-nitratomethyl-3-methyl-oxetane) (poly-NIMMO) und der Poly(3-acidomethyl-3-methyl-oxetane (poly-AMMO) einschließlich deren Derivaten und Mischungen; und
3. (c) wenigstens einen Abbrandmodifikator aus der Gruppe der Metalle und Halbmetalle einschließlich deren Legierungen und Hydriden,

sowie ein Verfahren zu dessen Herstellung.The invention relates to a solid propellant containing

1. (a) at least one oxidizer in the form of ammonium dinitramide (ADN);
2. (b) at least one energetic binder from the group of glycidyl azide polymers (GAP), poly(3,3-bisazidomethyloxetanes) (poly-BAMO), poly(glycidyl) nitrates (poly-GLYN), poly(3-nitratomethyl-3-methyl-oxetanes) (poly-NIMMO) and poly(3-acidomethyl-3-methyl-oxetanes (poly-AMMO) including their derivatives and mixtures; and
3. (c) at least one erosion modifier from the group of metals and semi-metals including their alloys and hydrides,

and a method for its production.

Fast-burning solid propellants with an oxidizer and an energetic binder of the aforementioned type are known and are also referred to as composite propellants. In contrast to propellant charges that burn off relatively slowly and especially at the lowest possible temperatures, such as those primarily used in are used in gas generators for airbags and to which coolants are often added, generic fast-burning solid propellants are characterized in that when they are ignited as a result of their combustion, a large volume of gas is released spontaneously. Generic solid propellants are used in a variety of ways in both the civil and military sectors, in particular as solid propellants for spacecraft (rockets) and strategic weapon systems, as propellants for barrel weapons or as explosive systems. While primarily nitrogen-rich and low-carbon fuels have proven to be effective as energetic binders, most of which release non-toxic gases, especially nitrogen, the oxidizers used are primarily oxidizer salts such as ammonium dinitramide (ADN), but also ammonium nitrate (AN), ammonium perchlorate (AP), potassium dinitramide (KDN ), potassium nitrate (KN) and hydroxylammonium nitrate (HAN).

Generic solid propellants are usually produced by introducing the powdered or particulate oxidizers into a liquid or viscous reaction mixture that can be cured to form the energetic binder matrix, after which the reaction mixture is poured, for example, and cured to form the binder, such as using di- or depending on the desired degree of crosslinking of the binder - tri- and/or polyisocyanates. Merely as an example in this context for an energetic binder in the form of glycidyl azide polymers (GAP) should be mentioned that, for example, the corresponding GAP diol (HO-(CH ₂ -CH(CH ₂ N ₃ )O) _n -H) with corresponding Di- or polyisocyanates can be cured to the GAP. Compared to pressing, which enables a binder content of up to about 10% by mass, this proves to be an increased one Part of the binder, in particular, casting the binder matrix mixed with the solid oxidizers is advantageous, especially since the oxidizers are relatively sensitive to friction and impact and thus pose a safety risk during processing.

In order to ensure a high combustion rate in so-called "high-velocity applications", such as in solid propellants for rocket propulsion systems, but at the same time ensure that the solid propellant is as environmentally friendly and low-smoke as possible, it is known to add combustion modifiers to the solid propellant in the form of fine metal and/or or add semi-metal powders, such as in the form of aluminum, magnesium, beryllium, boron, copper, lead, etc. ( U.S. 5,498,303 A , U.S. 2005/0115651 A1 , RU 2 516 711 C or RU 2 582 712 C ).

the U.S. 2018/0179119 A1 describes a solid propellant with an oxidizer dispersed in a binder with an anion from the group of nitrates, perchlorates, chlorates, permanganates or peroxides and mixtures thereof. The cation of the oxidizer is selected in particular from the group consisting of the alkali metals such as lithium, sodium, potassium, rubidium and cesium, the alkaline earth metals such as beryllium, magnesium, calcium, strontium and barium, the transition metals, ammonium and the quaternary amines, the oxidizer for example in the form of ammonium perchlorate (AP), potassium nitrate (KN) and ammonium nitrate (AN). The binder can be, inter alia, an energetic binder, for example one from the group of glycidyl azide polymers (GAP). In addition, the known solid propellant can contain a metal, for example from the group of alkali metals, alkaline earth metals and transition metals. The metal, which can be added in a proportion of up to 20% by mass and serves as an electron donor and/or oxygen acceptor for the oxidation reaction, can have any geometric shape, such as spherical, rounded, cylindrical, cubic, platelets - or flaky particles or in the form of metal structures such as metal threads, rods or networks, where the surface of the metal particles is considered to be decisive for the burning rate.

On the one hand, however, it has proven to be disadvantageous that such combustion modifiers based on metals or semimetals have a high mass both compared to the oxidizer and compared to the binder, whereas the propellant weight is kept as low as possible, especially when the solid propellant is used for rockets or other missiles should. On the other hand, after the solid propellant has burned off, the combustion modifiers occur as a solid residue - be it in the form of (semi)metal oxides or be it in the form of at least partially elementary (semi)metals - while the other fuel components are converted into gaseous and thus volatile components be able. In addition, the effect of (semi)metals as a combustion modifier is limited, especially in the case of ammonium dinitramide (ADN) as the oxidizer, which is advantageous as an oxidizer for solid rocket propellants due to its good oxygen balance and high enthalpy of formation and not least because of its higher environmental compatibility, e.g. compared to perchlorates .

The invention is based on the object of further developing a solid propellant based on ammonium dinitramide (ADN) of the type mentioned at the outset in a simple and cost-effective manner, while at least largely avoiding the aforementioned disadvantages, such that its burning rate is increased. It is also directed to a method for producing such a solid propellant.

The first part of this object is achieved according to the invention with a solid propellant based on ammonium dinitramide (ADN) of the type mentioned at the outset in that the at least one combustion modifier is present in the form of fibers.

Surprisingly, it was found that the configuration according to the invention, in which the at least one erosion modifier from the group of metals and semimetals including their alloys and hydrides in the form of a plurality of fibers in the matrix of the at least one energetic binder with the incorporated therein, at least one oxidizer is dispersed in the form of ADN, leads to a significantly increased combustion rate compared to the same amount of combustion modifier in the form of essentially spherical, angular, platelet-shaped or other types of particles, it being assumed that on the one hand the high thermal conductivity of the fibrous combustion modifiers plays a role, which are able to quickly transfer the heat generated during the combustion of the solid propellant in the direction of extension of the fibers to adjacent areas of the solid propellant. On the other hand, it is assumed that the (semi)metallic fiber structures have a smaller but still very large surface compared to largely spherical particles the combustion modifiers contribute to the increased combustion rate as a result of pores with an elongated pore shape that are formed during their combustion. In this way, the proportion of burn-up modifier can be reduced compared to the prior art, or a higher burn-up rate can be achieved with a corresponding proportion of burn-up modifier, which would otherwise not be achievable with a generic solid propellant based on ADN according to the prior art . There are no limits to the cross-sectional shape of the fibers of the at least one combustion modifier, in which case the fibers can, for example, have a substantially round, e.g. circular or oval, cross section, or the fibers can, for example, also have a flat, e.g. substantially rectangular, cross section. which can lead to an even larger surface and an even better heat conduction to the surrounding energetic binder matrix, which is mixed with the at least one oxidizer in the form of ADN.

The fiber geometry of the combustion modifiers has proven to be particularly decisive here, whereby the fibers must not be too "short" to fulfill their function according to the invention, but must not be too "long" to avoid fiber breakage and thus avoiding impairment of the reproducibility and, in particular, ensuring controlled combustion of the fast-burning solid propellant based on ADN. In addition, the cross-section of the fibers must not be too "small" for the fibers to be able to fulfill their function according to the invention, while the cross-section of the fibers must not be too "large" either, again for ease of processing of the solid propellant and in particular to ensure a controlled combustion with as few residues as possible.

• ein Verhältnis ihrer mittleren Länge zu ihrem mittleren Querschnitt von wenigstens etwa 5:1, insbesondere von wenigstens etwa 10:1, vorzugsweise von wenigstens etwa 15:1, beispielsweise von wenigstens etwa 20:1; und/oder
• ein Verhältnis ihrer mittleren Länge zu ihrem mittleren Querschnitt von höchstens etwa 600:1, insbesondere von höchstens etwa 550:1, vorzugsweise von höchstens 500:1, beispielsweise von höchstens etwa 450:1,

aufweisen. Als besonders bevorzugt hat sich hierbei ein Bereich des Verhältnisses von mittlerer Faserlänge zu mittlerem Faserquerschnitt von etwa 10:1 bis etwa 500:1, insbesondere von etwa 10:1 bis etwa 450:1, erwiesen.In this connection it was found that the fibers of the at least one combustion modifier expediently

• a ratio of their average length to their average cross section of at least about 5:1, in particular at least about 10:1, preferably at least about 15:1, for example at least about 20:1; and or
• a ratio of their mean length to their mean cross section of at most about 600:1, in particular at most about 550:1, preferably at most 500:1, for example at most about 450:1,

exhibit. A range of the ratio of average fiber length to average fiber cross-section from about 10:1 to about 500:1, in particular from about 10:1 to about 450:1, has proven to be particularly preferred.

• einen mittleren Querschnitt von höchstens etwa 200 pm, insbesondere von höchstens etwa 170 pm, vorzugsweise von höchstens etwa 140 pm, beispielsweise von höchstens etwa 110 pm; und/oder
• einen mittleren Querschnitt von mindestens etwa 1 pm, insbesondere von mindestens etwa 5 pm, vorzugsweise von mindestens etwa 10 pm; und/oder
• eine mittlere Länge von wenigstens etwa 250 pm, insbesondere von wenigstens etwa 500 pm, vorzugsweise von wenigstens etwa 750 pm, beispielsweise von wenigstens etwa 1 mm; und/oder
• eine mittlere Länge von höchstens etwa 10 mm, insbesondere von höchstens etwa 7,5 mm, vorzugsweise von höchstens etwa 5 mm,

aufweisen. Auf diese Weise ergibt sich eine für eine signifikante Erhöhung der Abbrandgeschwindigkeit hinreichende Faserlänge bei gleichwohl homogenem und praktisch vollständigem Abbrand des schnellbrennenden Festtreibstoffes auf der Basis von ADN unter Gewährleistung einer einfachen Verarbeitung. Der Faserquerschnitt in den vorgenannten Intervallen erweist sich dabei einerseits in Bezug auf eine hinreichende Faserstabilität, andererseits in Bezug auf die Möglichkeit eines nur verhältnismäßig geringen Anteils an Abbrandmodifikatoren als vorteilhaft.In addition, it was found in this connection that the fibers of the at least one combustion modifier expediently

• an average cross section of at most about 200 μm, in particular at most about 170 μm, preferably at most about 140 μm, for example at most about 110 μm; and or
• an average cross-section of at least about 1 μm, in particular at least about 5 μm, preferably at least about 10 μm; and or
• an average length of at least about 250 μm, in particular at least about 500 μm, preferably at least about 750 μm, for example at least about 1 mm; and or
• an average length of at most about 10 mm, in particular no more than about 7.5 mm, preferably no more than about 5 mm,

exhibit. This results in a fiber length that is sufficient for a significant increase in the burning rate while the fast-burning solid propellant based on ADN burns homogeneously and practically completely, while ensuring simple processing. The fiber cross-section in the aforementioned intervals proves to be advantageous on the one hand with regard to sufficient fiber stability and on the other hand with regard to the possibility of only a relatively small proportion of combustion modifiers.

According to one embodiment, it can be provided that the fibers of the at least one combustion modifier are present in the form of a plurality of loose cut fibers, so that - similar to the powdered or particulate oxidizer based on ADN -, preferably largely homogeneously, in the energetic binder matrix are dispersed. Alternatively or additionally, it can be advantageous if the fibers of the at least one combustion modifier are present in the binder matrix in the form of a textile fabric or three-dimensional structure with a plurality of fibers, in particular from the group of fleece, knitted fabrics, scrims, crocheted fabrics or woven fabrics, with the the energetic binder matrix mixed with the powdered or particulate oxidizer based on ADN surrounds the textile fabric or spatial structure or the latter is impregnated with the energetic binder matrix mixed with the powdered or particulate oxidizer based on ADN.

1. (a)
   • wenigstens etwa 40 Mass.-%, insbesondere wenigstens etwa 50 Mass.-%, beispielsweise wenigstens etwa 55 Mass.-%, und/oder
   • höchstens etwa 90 Mass.-%, insbesondere höchstens etwa 80 Mass.-%, vorzugsweise höchstens etwa 75 Mass.-%, des wenigstens einen Oxidators in Form von Ammoniumdinitramid (ADN);
2. (b)
   • wenigstens etwa 5 Mass.-%, insbesondere wenigstens etwa 10 Mass.-%, vorzugsweise wenigstens etwa 15 Mass.-%, und/oder
   • höchstens etwa 40 Mass.-%, insbesondere höchstens etwa 30 Mass.-%, vorzugsweise höchstens etwa 35 Mass.-%,
   des wenigstens einen energetischen Binders; und
3. (c)
   • wenigstens etwa 0,5 Mass.-%, insbesondere wenigstens etwa 1 Mass.-%, vorzugsweise wenigstens etwa 1,5 Mass.-%, und/oder
   • höchstens etwa 12,5 Mass.-%, insbesondere höchstens etwa 10 Mass.-%, vorzugsweise höchstens etwa 7,5 Mass.-%,
   des wenigstens einen Abbrandmodifikators,
   jeweils bezogen auf die Masse des gesamten Festtreibstoffes, enthalten oder im Wesentlichen gänzlich hieraus bestehen.

Depending on the application, the solid propellant according to the invention can advantageously

1. (a)
   • at least about 40% by mass, in particular at least about 50% by mass, for example at least about 55% by mass, and/or
   • at most about 90% by mass, in particular at most about 80% by mass, preferably at most about 75% by mass, of the at least one oxidizer in the form of ammonium dinitramide (ADN);
2. (b)
   • at least about 5% by mass, in particular at least about 10% by mass, preferably at least about 15% by mass, and/or
   • at most about 40% by mass, in particular at most about 30% by mass, preferably at most about 35% by mass,
   the at least one energetic binder; and
3. (c)
   • at least about 0.5% by mass, in particular at least about 1% by mass, preferably at least about 1.5% by mass, and/or
   • at most about 12.5% by mass, in particular at most about 10% by mass, preferably at most about 7.5% by mass,
   the at least one burn-up modifier,
   in each case based on the mass of the entire solid propellant, contain or essentially consist entirely of it.

While any metals and semimetals known as such from the prior art, including their alloys and hydrides, can be used as fibrous combustion modifiers of the solid propellant according to the invention, such as aluminum (Al), magnesium (Mg), copper (Cu), zinc (Zn ), tin (Sn), nickel (Ni), iron (Fe), manganese (Mn), chromium (Cr), titanium (Ti), silicon (Si), lead (Pb) and the like, the solid propellant can be based on of ADN preferably contain at least one erosion modifier from the group aluminum (Al), magnesium (Mg), copper (Cu), zinc (Zn) including their alloys and hydrides.

As also already mentioned, the at least one oxidizer in the form of ammonium dinitramide (ADN) in powder or particle form can be dispersed into the binder matrix of the fast-burning solid propellant, as is known per se from the prior art of composite propellants.

According to a development of the solid propellant according to the invention, it can also be provided that it also contains at least one energetic plasticizer, which can be selected in particular from the group of nitrate esters and azido plasticizers. Advantageous representatives of suitable energetic plasticizers include, for example, alkyl nitratoethyl nitramine (NENA), ethylene glycol dinitrate (EGDN), metriol trinitrate (MTN), butane-1,2,4-triol trinitrate (BTTN), dinitrodiazaalkanes (DNDA), trimethylolethane trinitrate (TMETN), ethylene glycol bis -(azidoacetate) (EGBAA, also referred to as "A17") and 1,2-bis-(2-azidoethoxy)ethane (TEGDA, also referred to as bis-azido-triethylene glycol or BATEG) including their derivatives and mixtures.

Alternatively or additionally, it can be provided that the solid propellant according to the invention contains at least one further oxidizer, for example from the group of ammonium nitrate (AN), ammonium perchlorate (AP), potassium dinitramide (KDN), potassium nitrate (KN), hydroxylammonium nitrate (HAN) and the like. where he instead of such Mixture of ADN with one or more other, expediently also about powdered or particulate, oxidizer salts can of course also contain essentially only ADN as oxidizer.

1. (a) Bereitstellen wenigstens eines Oxidators in Form von Ammoniumdinitramid (ADN);
2. (b) Bereitstellen einer zu einem energetischen Binder aus der Gruppe der Glycidyl-Azidpolymere (GAP), der Poly-(3,3-bis-azidomethyl-oxetane) (poly-BAMO), der Poly-(glycidyl)-nitrate (poly-GLYN), der Poly(3-nitratomethyl-3-methyl-oxetane) (poly-NIMMO) und der Poly(3-acidomethyl-3-methyl-oxetane (poly-AMMO) einschließlich deren Derivaten und Mischungen aushärtbaren, flüssigen oder viskosen Reaktionsmischung;
3. (c) Bereitstellen wenigstens eines Abbrandmodifikators aus der Gruppe der Metalle und Halbmetalle einschließlich deren Legierungen und Hydriden in Form von Fasern;
4. (d) Eindispergieren des wenigstens einen Oxidators in Form von Ammoniumdinitramid (ADN) in Pulver- oder Partikelform in die zu dem energetischen Binder aushärtbare, flüssige oder viskose Reaktionsmischung;
5. (e)
   • Eindispergieren der Fasern des wenigstens einen Abbrandmodifikators in Form loser Schnittfasern in die mit dem wenigstens einen Oxidator in Form von Ammoniumdinitramid (ADN) versetzte, zu dem energetischen Binder aushärtbare, flüssige oder viskose Reaktionsmischung, oder
   • Imprägnieren der Fasern des wenigstens einen Abbrandmodifikators in Form eines textilen Flächen- oder Raumgebildes, insbesondere aus der Gruppe Vlies, Gewirke, Gelege, Gestricke oder Gewebe, mit der mit dem wenigstens einen Oxidator in Form von Ammoniumdinitramid (ADN) versetzten, zu dem energetischen Binder aushärtbaren, flüssigen oder viskosen Reaktionsmischung; und
6. (f) Aushärten der Reaktionsmischung zu dem energetischen Binder unter Erhalt des Festtreibstoffes.

To solve the problem on which the invention is based, the invention provides, in addition to a fast-burning solid propellant of the type described above, a method for its production, which comprises the following steps:

1. (a) providing at least one oxidizer in the form of ammonium dinitramide (ADN);
2. (B) providing an energetic binder from the group of glycidyl azide polymers (GAP), poly-(3,3-bis-azidomethyl-oxetanes) (poly-BAMO), poly-(glycidyl) nitrates (poly -GLYN), poly(3-nitratomethyl-3-methyl-oxetanes) (poly-NIMMO) and poly(3-acidomethyl-3-methyl-oxetanes (poly-AMMO) including their derivatives and mixtures, curable, liquid or viscous reaction mixture;
3. (c) providing at least one erosion modifier from the group of metals and semimetals including their alloys and hydrides in the form of fibers;
4. (d) dispersing the at least one oxidizer in the form of ammonium dinitramide (ADN) in powder or particle form into the liquid or viscous reaction mixture that can be cured to form the energetic binder;
5. (e)
   • dispersing the fibers of the at least one combustion modifier in the form of loose cut fibers into the liquid or viscous reaction mixture to which the at least one oxidizer in the form of ammonium dinitramide (ADN) has been added and which can be cured to form the energetic binder, or
   • Impregnating the fibers of the at least one combustion modifier in the form of a textile fabric or three-dimensional structure, in particular from the group of non-woven fabrics, knitted fabrics, scrims, crocheted fabrics or woven fabrics, with the at least one oxidizer in the form of ammonium dinitramide (ADN) added to the curable, liquid or viscous reaction mixture to form the energetic binder; and
6. (f) curing the reaction mixture to form the energetic binder while obtaining the solid propellant.

• ein Verhältnis ihrer mittleren Länge zu ihrem mittleren Querschnitt von wenigstens etwa 5:1, insbesondere von wenigstens etwa 10:1, vorzugsweise von wenigstens etwa 15:1, beispielsweise von wenigstens etwa 20:1; und/oder
• ein Verhältnis ihrer mittleren Länge zu ihrem mittleren Querschnitt von höchstens etwa 600:1, insbesondere von höchstens etwa 550:1, vorzugsweise von höchstens etwa 500:1, beispielsweise von höchstens etwa 450:1,

aufweisen.For the reasons mentioned above, it has proven to be expedient here if the fibers of the at least one combustion modifier according to step (c) are provided in such a way that they

• a ratio of their average length to their average cross section of at least about 5:1, in particular at least about 10:1, preferably at least about 15:1, for example at least about 20:1; and or
• a ratio of their mean length to their mean cross section of at most about 600:1, in particular at most about 550:1, preferably at most about 500:1, for example at most about 450:1,

exhibit.

• einen mittleren Querschnitt von höchstens etwa 200 pm, insbesondere von höchstens etwa 170 pm, vorzugsweise von höchstens etwa 140 pm; beispielsweise von höchstens etwa 110 pm, und/oder
• einen mittleren Querschnitt von mindestens etwa 1 pm, insbesondere von mindestens etwa 5 pm, vorzugsweise von mindestens etwa 10 pm; und/oder
• eine mittlere Länge von wenigstens etwa 250 pm, insbesondere von wenigstens etwa 500 pm, vorzugsweise von wenigstens etwa 750 pm, beispielsweise von wenigstens etwa 1 mm; und/oder
• eine mittlere Länge von höchstens etwa 10 mm, insbesondere von höchstens etwa 7,5 mm, vorzugsweise von höchstens etwa 5 mm,

aufweisen.In addition, for the reasons mentioned above, it has proven to be expedient if the fibers of the at least one combustion modifier according to step (c) are provided in such a way that they

• an average cross section of at most about 200 μm, in particular at most about 170 μm, preferably at most about 140 μm; for example at most about 110 pm, and/or
• an average cross-section of at least about 1 μm, especially at least about 5 µm, preferably at least about 10 µm; and or
• an average length of at least about 250 μm, in particular at least about 500 μm, preferably at least about 750 μm, for example at least about 1 mm; and or
• an average length of no more than about 10 mm, in particular no more than about 7.5 mm, preferably no more than about 5 mm,

exhibit.

1. (a) der wenigstens eine Oxidator in Form von Ammoniumdinitramid (ADN) gemäß Schritt (a) mit einem Anteil von
   • wenigstens etwa 40 Mass.-%, insbesondere wenigstens etwa 50 Mass.-%, beispielsweise wenigstens etwa 45 Mass.-%, und/oder
   • höchstens etwa 90 Mass.-%, insbesondere höchstens etwa 80 Mass.-%, beispielsweise höchstens etwa 75 Mass.-%;
2. (b) der wenigstens eine energetische Binder gemäß Schritt (b) mit einem Anteil von
   • wenigstens etwa 5 Mass.-%, insbesondere wenigstens etwa 10 Mass.-%, beispielsweise wenigstens etwa 15 Mass.-%, und/oder
   • höchstens etwa 40 Mass.-%, insbesondere höchstens etwa 30 Mass.-%, beispielsweise höchstens etwa 35 Mass.-%; und
3. (c) der wenigstens eine Abbrandmodifikator gemäß Schritt (c) mit einem Anteil von
   • wenigstens etwa 0,5 Mass.-%, insbesondere wenigstens etwa 1 Mass.-%, beispielsweise wenigstens etwa 1,5 Mass.-%, und/oder
   • höchstens etwa 12,5 Mass.-%, insbesondere höchstens etwa 10 Mass.-%, beispielsweise höchstens etwa 7,5 Mass.-%,
   jeweils bezogen auf die Masse des gesamten Festtreibstoffes, bereitgestellt wird.

Depending on the intended use of the solid propellant according to the invention, it can advantageously be provided that

1. (a) the at least one oxidizer in the form of ammonium dinitramide (ADN) according to step (a) with a proportion of
   • at least about 40% by mass, in particular at least about 50% by mass, for example at least about 45% by mass, and/or
   • at most about 90% by mass, in particular at most about 80% by mass, for example at most about 75% by mass;
2. (b) the at least one energetic binder according to step (b) with a proportion of
   • at least about 5% by mass, in particular at least about 10% by mass, for example at least about 15% by mass, and/or
   • at most about 40% by mass, in particular at most about 30% by mass, for example at most about 35% by mass; and
3. (c) the at least one combustion modifier according to step (c) with a proportion of
   • at least about 0.5% by mass, in particular at least about 1% by mass, for example at least about 1.5% by mass, and/or
   • at most about 12.5% by mass, in particular at most about 10% by mass, for example at most about 7.5% by mass,
   in each case based on the mass of the entire solid propellant.

While basically any metals and semimetals including their alloys and hydrides can be used as fibrous combustion modifiers of the solid propellant according to the invention based on ADN, such as those of the type mentioned above, preferably at least one combustion modifier according to step (c) from the group aluminum ( Al), magnesium (Mg), copper (Cu), zinc (Zn) and their alloys and hydrides are provided.

According to one development, it can also be provided that the reaction mixture that can be cured to form the energetic binder also contains at least one energetic plasticizer, in particular from the group of alkyl nitratoethyl nitramine (NENA), ethylene glycol dinitrate (EGDN), metriol trinitrate (MTN), butane-1, 2,4-trioltrinitrates (BTTN), dinitrodiazaalkanes (DNDA), trimethylolethane trinitrates (TMETN), ethylene glycol bis-(azidoacetates) (EGBAA, also referred to as "A17") and 1,2-bis-( 2-azidoethoxy)ethane (TEGDA, also referred to as bis-azido-triethylene glycols or BATEG) including derivatives and mixtures thereof, is added.

While according to step (a) essentially only ADN can be used as the oxidizer, it can also be provided that at least one further oxidizer, expediently also in powder or particle form, the at least one further oxidizer being, for example, ammonium nitrate (AN), ammonium perchlorate (AP), potassium dinitramide (KDN), potassium nitrate (KN) and hydroxylammonium nitrate (HAN) and the like.

Fig. 1

ein Schaubild der Abbrandgeschwindigkeit (r_b) über den Druck (p) verschiedener Zusammensetzungen eines Festtreibstoffes mit einerseits - 70 Mass.-% des Oxidators Ammoniumdinitramid (ADN) und 30 Mass.-% eines energetischen Binders auf der Basis eines Glycidyl-Azidpolymers (GAP), erhalten durch Aushärten von GAP-Diol mit einem Diisocyanat, ohne Abbrandmodifikator als Referenz (untere Kurve: "

"), andererseits - jeweils 67 Mass.-% des Oxidators ADN und jeweils 30 Mass.-% desselben energetischen Binders auf der Basis des GAP, mit jeweils 3 Mass.-% eines erfindungsgemäßen Abbrandmodifikators in Form von Schnittfasern mit einem mittleren Faserquerschnitt von 90 µm und einer mittleren Faserlänge von 1 mm aus Kupfer (Cu; zweitunterste Kurve: "-◆-"), einer Messinglegierung aus 66 bis 68 Mass.-% Kupfer (Cu) und 31 bis 35 Mass.-% Zink (Zn; zweitoberste Kurve: "

") und einer Aluminium-/Magnesiumlegierung mit 93 Mass.-% Aluminium (Al) und 5 Mass.-% Magnesium (Mg) sowie Spuren an Silicium (Si), Eisen (Fe) und Kupfer (Cu; obere Kurve: "-●-");

Fig. 2

ein Schaubild der Abbrandgeschwindigkeit (r_b) über den Druck (p) verschiedener Zusammensetzungen eines erfindungsgemäßen Festtreibstoffes mit jeweils 67 Mass.-% des Oxidators ADN, jeweils 30 Mass.-% des energetischen Binders auf der Basis des GAP gemäß Fig. 1 sowie jeweils 3 Mass.-% eines erfindungsgemäßen Abbrandmodifikators in Form einer Aluminium-/Magnesiumlegierung mit 93 Mass.-% Aluminium (Al) und 5 Mass.-% Magnesium (Mg) sowie Spuren an Silicium (Si), Eisen (Fe) und Kupfer (Cu), jeweils in Form von Schnittfasern mit einem mittleren Faserquerschnitt von 90 µm und einer mittleren Faserlänge von - 0,5 mm (untere Kurve: "-●-"), - 1,0 mm (mittlere Kurve: "-■-") und - 3,0 mm (obere Kurve: "-▲-") ;

Fig. 3

ein Schaubild der Abbrandgeschwindigkeit (r_b) über den Druck (p) verschiedener Zusammensetzungen eines Festtreibstoffes mit einerseits - jeweils 67 Mass.-% des Oxidators ADN und jeweils 30 Mass.-% des energetischen Binders auf der Basis des GAP gemäß Fig. 1 und 2 sowie jeweils 3 Mass.-% eines Abbrandmodifikators in Pulverform mit einem mittleren Partikeldurchmesser von 20 µm aus Aluminium (Al; untere Kurve: "-◆-") sowie aus einer Aluminium-/Magnesiumlegierung mit 93 Mass.-% Aluminium (Al) und 5 Mass.-% Magnesium (Mg) sowie Spuren an Silicium (Si), Eisen (Fe) und Kupfer (Cu; mittlere Kurve: "

"), andererseits - 67 Mass.-% des Oxidators ADN und 30 Mass.-% desselben energetischen Binders auf der Basis des GAP sowie jeweils 3 Mass.-% eines erfindungsgemäßen Abbrandmodifikators aus derselben Aluminium-/Magnesiumlegierung mit 93 Mass.-% Aluminium (Al) und 5 Mass.-% Magnesium (Mg) sowie Spuren an Silicium (Si), Eisen (Fe) und Kupfer (Cu), aber in Form von Schnittfasern mit einem mittleren Faserquerschnitt von 90 µm und einer mittleren Faserlänge von 1,0 mm (obere Kurve: "-●-"); und

Fig. 4

eine rasterelektronenmikroskopische (REM) Aufnahme der in den Ausführungsbeispielen gemäß den Fig. 1 (obere Kurve: "-●-"), 2 und 3 (obere Kurve: "-●-") eingesetzten Schnittfasern der Aluminium-/Magnesiumlegierung mit 93 Mass.-% Aluminium (Al) und 5 Mass.-% Magnesium (Mg) sowie Spuren an Silicium (Si), Eisen (Fe) und Kupfer (Cu) mit einem mittleren Faserquerschnitt von 90 pm.

Further features and advantages of the invention result from the following description of exemplary embodiments with reference to the drawings. show:

1

a graph of the burning rate (r _b ) versus the pressure (p) of different compositions of a solid propellant with on the one hand - 70% by mass of the oxidizer ammonium dinitramide (ADN) and 30% by mass of an energetic binder based on a glycidyl azide polymer (GAP ), obtained by curing GAP-diol with a diisocyanate, without burn-off modifier as a reference (lower curve: "

"), on the other hand - 67% by mass of the oxidizer ADN and 30% by mass of the same energetic binder based on the GAP, each with 3% by mass of a combustion modifier according to the invention in the form of cut fibers with an average fiber cross-section of 90 µm and an average fiber length of 1 mm made of copper (Cu; second lowest curve: "-◆-"), a brass alloy of 66 to 68% by weight copper (Cu) and 31 to 35% by weight zinc (Zn; second highest Curve: "

") and an aluminum/magnesium alloy with 93% by mass aluminum (Al) and 5% by mass Magnesium (Mg) and traces of silicon (Si), iron (Fe) and copper (Cu; upper curve: "-●-");

2

a graph of the combustion rate (r _b ) over the pressure (p) of various compositions of a solid propellant according to the invention, each with 67% by mass of the oxidizer ADN, each with 30% by mass of the energetic binder based on the GAP 1 and in each case 3% by mass of a combustion modifier according to the invention in the form of an aluminum/magnesium alloy with 93% by mass of aluminum (Al) and 5% by mass of magnesium (Mg) and traces of silicon (Si), iron (Fe) and Copper (Cu), each in the form of chopped fibers with an average fiber cross-section of 90 µm and an average fiber length of - 0.5 mm (lower curve: "-●-"), - 1.0 mm (middle curve: "-■ -") and - 3.0 mm (upper curve: "-▲-") ;

3

a diagram of the combustion rate (r _b ) over the pressure (p) of various compositions of a solid propellant with on the one hand - 67% by mass of the oxidizer ADN and 30% by mass of the energetic binder based on the GAP Figures 1 and 2 and in each case 3% by mass of a combustion modifier in powder form with an average particle diameter of 20 µm made of aluminum (Al; lower curve: "-◆-") and of an aluminum/magnesium alloy with 93% by mass of aluminum (Al) and 5% by mass magnesium (Mg) and traces of silicon (Si), iron (Fe) and copper (Cu; middle curve: "

"), on the other hand - 67% by mass of the oxidizer ADN and 30% by mass of the same energetic binder based on the GAP and 3% by mass of a combustion modifier according to the invention from the same aluminum/magnesium alloy with 93% by mass aluminum (Al) and 5 wt. 0 mm (upper curve: "-●-"); and

4

a scanning electron microscopic (SEM) recording of the in the embodiments according to 1 (upper curve: "-●-"), 2 and 3 (upper curve: "-●-") used cut fibers of the aluminum/magnesium alloy with 93% by mass of aluminum (Al) and 5% by mass of magnesium (Mg ) as well as traces of silicon (Si), iron (Fe) and copper (Cu) with a mean fiber cross-section of 90 pm.

Examples:

For the production of the solid propellants, whose combustion rates (r _b ) have been determined at a pressure (p) of 7 MPa, 10 MPa, 13 MPa, 18 MPa and 25 MPa, as in the Figures 1 to 3 is documented, particles of ammonium dinitramide (ADN) were dispersed into a liquid GAP diol resin, after which the mixture was poured and formed into the energetic binder in the presence of a diisocyanate onto which a glycidyl azide polymer (GAP) base has been cured.

" und einer Aluminium-/Magnesiumlegierung mit 93 Mass.-% Aluminium (Al) und 5 Mass.-% Magnesium (Mg) sowie Spuren an Silicium (Si), Eisen (Fe) und Kupfer (Cu; obere Kurve: "-●-")While in the reference example without burnup modifiers according to the 1 70% by mass of ADN and 30% by mass of GAP have been used (lower curve: "-·-"), in all other exemplary embodiments it is 67% by mass of ADN and 30% by mass of GAP for the purpose of comparability and 3% by mass of a metallic erosion modifier of different types and geometries have been used, as in the case of 1 geometrically identical chopped fibers with an average fiber cross-section of 90 µm and an average fiber length of 1 mm made of copper (Cu; second lowest curve: "-◆-"), a brass alloy of 66 to 68% by mass copper (Cu) and 31 to 35 Mass % Zinc (Zn; second top curve: "

" and an aluminium/magnesium alloy with 93% by mass aluminum (Al) and 5% by mass magnesium (Mg) as well as traces of silicon (Si), iron (Fe) and copper (Cu; upper curve: "-● -")

") bei 7 bar um etwa 30% erhöht wird, im Falle der Messinglegierung bei zunehmendem Druck aber stärker ansteigt.the 1 It can be seen that the metallic combustion modifiers used in identical fibrous form increase the combustion rate, as is qualitatively known as such with powdered, but otherwise identical combustion modifiers, whereby in the case of the ADN used as an oxidizer with the fibrous aluminum/magnesium alloy, a almost double the charring rate compared to the pure mixture of GAP with ADN (upper curve: "-●-"), while the charring rate for fibrous copper (second-lowest curve: "-◆-") and for fibrous brass (second-top curve: "

") at 7 bar is increased by about 30% in the case of the Brass alloy but increases more with increasing pressure.

• 0,5 mm, entsprechend einem Verhältnis ihrer mittleren Länge zu ihrem mittleren Querschnitt von etwa 5,6 (untere Kurve: "-●-"),
• 1,0 mm, entsprechend einem Verhältnis ihrer mittleren Länge zu ihrem mittleren Querschnitt von etwa 11,1 (mittlere Kurve: "-■-"), und
• 3,0 mm, entsprechend einem Verhältnis ihrer mittleren Länge zu ihrem mittleren Querschnitt von etwa 33,3 (obere Kurve: "-▲-")

dem Festtreibstoff zugesetzt worden sind. Letzteres kann durch Eindispergieren der Schnittfasern in das GAP-Diolharz gemeinsam mit den ADN-Partikeln und/oder auch separat, vor oder nach dem Eindispergieren der ADN-Partikel geschehen.In the 2 the influence of the length of otherwise identical fibers from a metallic erosion modifier in the form of the aluminium/magnesium alloy with 93% by mass of aluminum (Al) and 5% by mass of magnesium (Mg) and traces of silicon (Si), iron ( Fe) and copper (Cu), each with an average fiber cross-section of 90 pm, examined for the combustion rate of the solid propellant, the cut fibers with an average fiber length of

• 0.5 mm, corresponding to a ratio of their mean length to their mean cross-section of about 5.6 (lower curve: "-●-"),
• 1.0 mm, corresponding to a ratio of their average length to their average cross-section of about 11.1 (middle curve: "-■-"), and
• 3.0 mm, corresponding to a ratio of their mean length to their mean cross-section of about 33.3 (upper curve: "-▲-")

have been added to the solid propellant. The latter can be done by dispersing the cut fibers into the GAP diol resin together with the ADN particles and/or separately, before or after dispersing the ADN particles.

From the 2 it becomes clear that the fiber geometry of the burn-up modifier has a significant influence on the burn-up rate over the entire pressure range from 7 MPa to 25 MPa, with the burn-up rate increasing with increasing fiber length or with an increasing ratio of mean fiber length to mean fiber cross-section.

• der Aluminium-/Magnesiumlegierung mit 93 Mass.-% Aluminium (Al) und 5 Mass.-% Magnesium (Mg) sowie Spuren an Silicium (Si), Eisen (Fe) und Kupfer (Cu; mittlere Kurve: "
  
  "), sowie aus
• im Wesentlichen reinem Aluminium (Al; untere Kurve: "-◆-")

in der obigen Weise hergestellt. In der Fig. 3 ist erkennbar, dass die Abbrandgeschwindigkeit des Festtreibstoffes im Falle von pulver- bzw. partikelförmigem Aluminium als Abbrandmodifikator mit der pulver- bzw. partikelförmigen Aluminium-/ Magnesiumlegierung vergleichbar ist, wobei sie bei geringen Drücken im Bereich von 7 MPa im Falle von Aluminium etwas geringer ist als im Falle der Aluminium-/Magnesiumlegierung, bei höheren Drücken ab etwa 25 MPa aufgrund stärkeren Anstieges bei zunehmendem Druck im Falle von Aluminium aber weitgehend identisch ist.In the 3 Finally, to illustrate the influence of the fiber geometry of metallic combustion modifiers compared to particulate, but otherwise identical combustion modifiers of the solid propellant on the combustion rate, solid propellants made of 67% by mass of ADN, 30% by mass of GAP and on the one hand 3% by mass of one particulate combustion modifier each were used with an average particle size of 20 µm

• the aluminium/magnesium alloy with 93% by mass of aluminum (Al) and 5% by mass of magnesium (Mg) and traces of silicon (Si), iron (Fe) and copper (Cu; middle curve: "
  
  "), as well as from
• essentially pure aluminum (Al; lower curve: "-◆-")

made in the above manner. In the 3 it can be seen that the combustion rate of the solid propellant in the case of powdered or particulate aluminum as a combustion modifier is comparable to the powdered or particulate aluminum/magnesium alloy, although it is somewhat lower at low pressures in the range of 7 MPa in the case of aluminum than in the case of the aluminium/magnesium alloy, but is largely identical at higher pressures from around 25 MPa due to the greater increase with increasing pressure in the case of aluminium.

") in Partikelform eingesetzt worden ist, wobei der Abbrandmodifikator jedoch in Form von Schnittfasern mit einem mittleren Faserquerschnitt von 90 µm und einer mittleren Faserlänge von 1 mm, entsprechend einem Verhältnis der mittleren Faserlänge zum mittleren Faserquerschnitt von etwa 11,1, eingesetzt worden sind (obere Kurve der Fig. 3: "-●-").On the other hand, a solid propellant was produced in the above manner from again 67% by mass of ADN, 30% by mass of GAP and 3% by mass of a combustion modifier from the same aluminum/magnesium alloy as is shown in the middle curve of FIG 3 ("

") has been used in particle form, but the combustion modifier in the form of chopped fibers with an average fiber cross-section of 90 µm and an average fiber length of 1 mm, corresponding to a ratio the average fiber length to the average fiber cross-section of about 11.1, have been used (upper curve of the 3 : "-●-").

In the 3 it can be seen that the combustion rate of the solid propellant in the case of the fibrous combustion modifier compared to the same proportion of the same particulate combustion modifier over the entire pressure range from here 7 MPa to 25 MPa kant - here approximately doubled - and this is already at a relatively small Average fiber length to average fiber cross-section ratio of about 11.1.

Consequently, the proportion of (semi)metallic combustion modifiers in the solid propellant according to the invention can be significantly reduced purely due to the geometry of its fiber shape compared to particulate combustion modifiers of the prior art, which is accompanied by a corresponding weight saving and a reduction in solid combustion residues, or it can be corresponding proportion of fibrous combustion modifier compared to the same particulate combustion modifier of the prior art, a significantly higher combustion rate can be achieved, which would otherwise not be achievable with a generic solid propellant according to the prior art. A significant increase in the burning rate of the solid propellant already occurs at a ratio of average fiber length to average fiber cross section or diameter of about 5:1, with the burning rate increasing with an increasing ratio of average fiber length to average fiber cross section or with increasing fiber length.

In the 4 Finally, an SEM micrograph of the fibrous aluminium/magnesium alloy as described in the above Figures 1 to 3 is used, the cut fibers having an approximately rectangular/oval cross-sectional shape, but in principle also having any other cross-section, for example round etc. can be.

Claims (14)

Solid propellant containing (a) at least one oxidizer in the form of ammonium dinitramide (ADN); (b) at least one energetic binder from the group of glycidyl azide polymers (GAP), poly(3,3-bisazidomethyloxetanes) (poly-BAMO), poly(glycidyl) nitrates (poly-GLYN), poly(3-nitratomethyl-3-methyl-oxetanes) (poly-NIMMO) and poly(3-acidomethyl-3-methyl-oxetanes (poly-AMMO) including their derivatives and mixtures; and (c) at least one erosion modifier from the group of metals and semi-metals including their alloys and hydrides, characterized in that the at least one combustion modifier is in the form of fibers. Solid propellant according to Claim 1, characterized in that the fibers of the at least one combustion modifier - a ratio of their average length to their average cross-section of at least 5:1, in particular at least 10:1, preferably at least 15:1; and or - a ratio of their average length to their average cross section of at most 600:1, in particular at most 550:1, preferably at most 500:1, exhibit. Solid propellant according to Claim 1 or 2, characterized in that the fibers of the at least one combustion modifier - an average cross-section of at most 200 μm, in particular at most 170 μm, preferably at most 140 μm; and or - an average cross-section of at least 1 μm, in particular at least 5 μm, preferably at least 10 μm; and or - an average length of at least 250 μm, in particular at least 500 μm, preferably at least 750 μm; and or - an average length of no more than 10 mm, in particular no more than 7.5 mm, preferably no more than 5 mm, exhibit. Solid propellant according to one of Claims 1 to 3, characterized in that the fibers of the at least one combustion modifier are in the form of loose cut fibers or in the form of a textile fabric or three-dimensional structure, in particular from the group of fleece, knitted fabrics, scrims, crocheted fabrics or woven fabrics, in the binder matrix present. Solid propellant according to any one of claims 1 to 4, characterized in that it (a) - at least 40% by mass, in particular at least 50% by mass, and/or - at most 90% by mass, in particular at most 80% by mass, the at least one oxidizer in the form of ammonium dinitramide (ADN); (b) - at least 5% by mass, in particular at least 10% by mass, and/or - no more than 40% by mass, in particular no more than 30% by mass, the at least one energetic binder; and (c) - at least 0.5% by mass, in particular at least 1% by mass, and/or - at most 12.5% by mass, in particular at most 10% by mass, the at least one combustion modifier present in the form of fibers, in each case based on the mass of the entire solid propellant. Solid propellant according to one of Claims 1 to 5, characterized in that it contains at least one combustion modifier from the group consisting of aluminum (Al), magnesium (Mg), copper (Cu), zinc (Zn) including their alloys and hydrides. Solid propellant according to one of Claims 1 to 6, characterized in that the at least one oxidizer in the form of ammonium dinitramide (ADN) is dispersed in the binder matrix in powder or particle form. Solid propellant according to any one of claims 1 to 7, characterized in that it further - at least one energetic plasticizer, in particular from the group of alkyl nitratoethyl nitramines (NENA), ethylene glycol dinitrates (EGDN), metriol trinitrates (MTN), butane-1,2,4-triol trinitrates (BTTN), dinitrodiazaalkanes (DNDA), trimethylolethane trinitrates (TMETN ), ethylene glycol bis(azidoacetate) (EGBAA) and 1,2-bis(2-azidoethoxy)ethane (TEGDA) including their derivatives and mixtures, and/or - at least one further oxidizer, in particular from the group of ammonium nitrate (AN), ammonium perchlorate (AP), potassium dinitramide (KDN), potassium nitrate (KN) and hydroxylammonium nitrate (HAN), contains. Process for the production of a solid propellant according to one of Claims 1 to 8, comprising the following steps: (a) providing at least one oxidizer in the form of ammonium dinitramide (ADN); (b) Providing an energetic binder from the group of glycidyl azide polymers (GAP), poly(3,3-bis-azidomethyl-oxetanes) (poly-BAMO), poly(glycidyl) nitrates (poly-GLYN ), the poly(3-nitratomethyl-3-methyl-oxetanes) (poly-NIMMO) and the poly(3-acidomethyl-3-methyl-oxetanes (poly-AMMO) including their derivatives and mixtures curable, liquid or viscous reaction mixture; (c) providing at least one erosion modifier from the group of metals and semimetals including their alloys and hydrides in the form of fibers; (d) dispersing the at least one oxidizer in Form of ammonium dinitramide (ADN) in powder or particle form into the energetic binder curable, liquid or viscous reaction mixture; (e) - dispersing the fibers of the at least one combustion modifier in the form of loose cut fibers into the liquid or viscous reaction mixture to which the at least one oxidizer in the form of ammonium dinitramide (ADN) has been added and which can be cured to form the energetic binder, or - Impregnation of the fibers of the at least one combustion modifier in the form of a textile fabric or spatial structure, in particular from the group of fleece, knitted fabrics, scrims, crocheted fabrics or woven fabrics, with the at least one oxidizer in the form of ammonium dinitramide (ADN) added to the energetic binder curable, liquid or viscous reaction mixture; and (f) curing the reaction mixture to form the energetic binder while obtaining the solid propellant. The method according to claim 9, characterized in that the fibers of the at least one combustion modifier according to step (c) are provided in such a way that they - a ratio of their average length to their average cross-section of at least 5:1, in particular at least 10:1, preferably at least 15:1; and or - have a ratio of their average length to their average cross-section of at most 600:1, in particular at most 550:1, preferably at most 500:1. The method according to claim 9 or 10, characterized in that the fibers of the at least one combustion modifier according to step (c) are provided in such a way that they - an average cross-section of at most 200 μm, in particular at most 170 μm, preferably at most 140 μm; and or - an average cross-section of at least 1 μm, in particular at least 5 μm, preferably at least 10 μm; and or - an average length of at least 250 μm, in particular at least 500 μm, preferably at least 750 μm; and or - an average length of no more than 10 mm, in particular no more than 7.5 mm, preferably no more than 5 mm, exhibit. The method according to any one of claims 9 to 11, characterized in that (a) the at least one oxidizer in the form of ammonium dinitramide (ADN) according to step (a) with a proportion of - at least 40% by mass, in particular at least 50% by mass, and/or - at most 90% by mass, in particular at most 80% by mass; (b) the at least one energetic binder according to step (b) with a proportion of - at least 5% by mass, in particular at least 10% by mass, and/or - at most 40% by mass, in particular at most 30% by mass; and (c) the at least one combustion modifier according to step (c) with a proportion of - at least 0.5% by mass, in particular at least 1% by mass, and/or - at most 12.5% by mass, in particular at most 10% by mass, in each case based on the mass of the entire solid propellant. Method according to one of Claims 9 to 12, characterized in that according to step (c) at least one erosion modifier from the group aluminum (Al), magnesium (Mg), copper (Cu), zinc (Zn) including their alloys and hydrides is provided . Method according to one of Claims 9 to 13, characterized in that the reaction mixture which can be cured to form the energetic binder also - at least one energetic plasticizer, in particular from the group of alkyl nitratoethyl nitramines (NENA), ethylene glycol dinitrates (EGDN), metriol trinitrates (MTN), butane-1,2,4-triol trinitrates (BTTN), dinitrodiazaalkanes (DNDA), trimethylolethane trinitrates (TMETN), ethylene glycol bis(azidoacetates) (EGBAA) and 1,2-bis(2azidoethoxy)ethanes (TEGDA) including their derivatives and mixtures, and/or - at least one further oxidizer in powder or particle form, in particular from the group of ammonium nitrate (AN), ammonium perchlorate (AP), potassium dinitramide (KDN), potassium nitrate (KN) and hydroxylammonium nitrate (HAN), is added.

Images