EP3018112B1 - Gas generator fuel based on ammonium dinitramide (adn) and method for producing the same - Google Patents

Gas generator fuel based on ammonium dinitramide (adn) and method for producing the same Download PDF

Info

Publication number
EP3018112B1
EP3018112B1 EP15003111.0A EP15003111A EP3018112B1 EP 3018112 B1 EP3018112 B1 EP 3018112B1 EP 15003111 A EP15003111 A EP 15003111A EP 3018112 B1 EP3018112 B1 EP 3018112B1
Authority
EP
European Patent Office
Prior art keywords
mass
adn
gas generator
fuel
ammonia
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP15003111.0A
Other languages
German (de)
French (fr)
Other versions
EP3018112A1 (en
Inventor
Uwe Schaller
Jürgen HÜRTTLEN
Horst Krause
Volker Weiser
Stefan Schlechtriem
Helmut Konrad Ciezki
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Deutsches Zentrum fuer Luft und Raumfahrt eV
Original Assignee
Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Deutsches Zentrum fuer Luft und Raumfahrt eV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV, Deutsches Zentrum fuer Luft und Raumfahrt eV filed Critical Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Publication of EP3018112A1 publication Critical patent/EP3018112A1/en
Application granted granted Critical
Publication of EP3018112B1 publication Critical patent/EP3018112B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06D—MEANS FOR GENERATING SMOKE OR MIST; GAS-ATTACK COMPOSITIONS; GENERATION OF GAS FOR BLASTING OR PROPULSION (CHEMICAL PART)
    • C06D5/00—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B31/00—Compositions containing an inorganic nitrogen-oxygen salt
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B47/00—Compositions in which the components are separately stored until the moment of burning or explosion, e.g. "Sprengel"-type explosives; Suspensions of solid component in a normally non-explosive liquid phase, including a thickened aqueous phase

Definitions

  • the invention relates to a gas generator fuel containing a monergolene fuel based on ammonium dinitramide (ADN) and at least one solvent, and a process for its preparation.
  • ADN ammonium dinitramide
  • Such gas generator fuels are used in liquid form, in particular for rocket and satellite propellants in aerospace, but also for military purposes, including military missiles and for torpedo fuels, for aircraft and submarine aircraft fuels, etc.
  • conventional monergol gas generator propellants such as those based on hydrogen peroxide or hydrazine
  • ammonium dinitramide has in particular a relatively good long-term stability (eg compared with hydrogen peroxide) and usefulness at relatively low temperatures below -20 ° C and a much lower health hazard (eg in comparison with hydrazine).
  • Liquid gas generator fuels based on ADN, water and fuel additives were developed as early as the end of the last century as a substitute for hydrazine-based fuels ( Per Sjöberg: "A stable liquid mono-propellant based on ADN", IMEM Arlington, USA, May 11-14, 2009 ).
  • the DE 600 03 428 T2 describes a gas generator propellant based on ADN with water and / or hydrogen peroxide as a solvent, the latter, however, has a low durability and water from an energetic point of view is an unnecessary ballast, which causes weight problems especially in an application of the fuel in space.
  • the WO 2012/166046 A1 describes another liquid gas generator fuel based on ADN, which with a total content of 55 wt .-% and 62 wt .-% dissolved in a solvent mixture of 4 wt .-% to 12 wt .-% ammonia and otherwise water and which may further contain up to 22% by mass of methanol.
  • WO 2012/166046 A1 proposed further solvents methanol in particular for applications of such gas generator fuel in aerospace to that extent is a disadvantage, as it necessarily requires an oxidizer, otherwise there is an incomplete implementation of the carbon contained herein, which in particular can result in the formation of carbon monoxide in the exhaust gas.
  • ADN has limited solubility in methanol (about 87 g of ADN in 100 g of methanol), which limits the maximum possible level of ADN in a corresponding fuel composition.
  • the gas generator fuel contains, on the one hand, a first component of the general formula XD, referred to as "oxidizer”, where "X” is any cation and may be formed, inter alia, by an ammonium cation, while “D” is a dinitramide anion, on the other hand a second component referred to as "fuel” and optionally a solvent as a third component.
  • oxidizer any component of the general formula XD
  • fuel referred to as "fuel”
  • fuel optionally a solvent as a third component.
  • the second component referred to as "fuel” may likewise be a solvent, wherein, inter alia, aqueous ammonia solutions are proposed.
  • ballast water content is also the disadvantage of a need to improve low temperature stability, which is especially for applications in the space sector, such as rocket and satellite fuel, of crucial importance to the already very limited available and To use energy to be entrained at startup to the lowest possible extent for preheating the fuel in order to prevent any crystallization of the fuel in the supply lines of the drive units.
  • the RU 2012 144 167 A describes a solid propellant propellant propellant fuel propellant and an oxidizer containing 44.61 mass% (+/- 10 mass%) beryllium borohydride, 35.75 mass% (+/- 10 % By mass) ADN and 19.63 mass% (+/- 5 mass%) of ammonia.
  • the added as an oxidizer beryllium-borohydride serves to increase the specific momentum of the Fuel and should improve the recoil of the hereby supplied rocket motor.
  • the US 5 714 714 A discloses a process for producing ADN by nitrating a compound having the chemical formula Z-NH 2 to form Z-NHNO 2 , then reacting the resulting compound Z-NHNO 2 with ammonia in anhydrous medium to form a salt having the chemical formula Z -NNO 2 - NH 4 + and then nitrating this salt and treating the reaction mixture with ammonia to obtain crystalline ADN and ammonium nitrate and to recover the starting compound Z-NH 2 .
  • the invention has the object of providing a liquid at room temperature gas generator fuel on the basis of ammonium dinitramide (ADN) of the type mentioned in that it has at least largely avoiding the aforementioned disadvantages improved low temperature resistance at an increased mass-specific performance. It is further directed to a method of making such gas generator fuel.
  • ADN ammonium dinitramide
  • the gas generator fuel according to the invention which is in the liquid phase up to a temperature in the range of at least -30 ° C, has a high mass-specific performance due to its high proportion of ADN, in particular to the Fig. 1 on the one hand, the mass-specific pulse "I sp (frz equilibrium 70: 1)" in [Ns / kg] (left ordinate), on the other hand, the volume-specific pulse "I sp vol (frz equilibrium 70: 1)” in [Ns / dm 3 ] (right ordinate) of a liquid gas generator fuel according to the invention, which consists exclusively of ammonium dinitramide (ADN) dissolved in ammonia, with different proportions of ADN between about 66 mass% and about 84 mass% on the one hand compared with the mass specific momentum of conventional hydrazine, on the other hand, as compared to the mass specific momentum of a known gas generator propellant with 63.0 mass% ADN, 18.4 mass% methanol, 4.6 mass% ammonia
  • the liquid gas generator fuel Due to the excellent solubility of ADN in ammonia and the possibly very small proportion of water, the liquid gas generator fuel, even at room temperature, has a low volatility and in particular outstanding low-temperature properties.
  • Fig. 2 which shows a differential scanning calorimetry (DSC) graph to illustrate the low temperature behavior of one consisting exclusively of about 75 mass% ADN and about 25 mass% ammonia ( ⁇ 3 mass%) , Gas generator propellant according to the invention in the second heating in dependence of the supplied amount of heat "heat flow" in [W / g] shows.
  • the melting peak of such a gas generator fuel is about -31.4 ° C, while the extrapolated onset temperature is about -35.7 ° C.
  • the melting point of pure ADN is about + 95.2 ° C and the extrapolated onset temperature is about + 94.5 ° C.
  • the 3 and 4 it can be seen that pure ADN has a decomposition temperature (onset temperature) of about 143.9 ° C, while the gas generator fuel according to the invention has a decomposition temperature (onset temperature) of about 173.8 ° C.
  • the gas generator fuel according to the invention proves to be stable even with repeated cooling / heating between about -90 ° C and about + 100 ° C.
  • the gas generator fuel according to the invention depending on the selection of any additives (see below) substantially free of carcinogenic ingredients and in particular also be substantially free of carbon, so that when it burns no toxic carbon monoxide or hydrogen cyanide can be formed , The same applies to a formation of solid burn-off products, as they can arise in the prior art.
  • the gas generator fuel according to the invention depending on the selection of any additives and in particular in additives free form offers the opportunity to abandon the existing primarily nitrogen, hydrogen and water combustion products of a hydrogen fuel cell as fuel, so that the gas generator fuel can additionally be used as a hydrogen generator, which does not require separation of any carbon monoxide or dioxide.
  • the ratio according to the invention of at least 65% by mass of ADN to the mixture of ADN and all solvents present (ie in particular ammonia, including the optionally present, maximum 5% proportion of water and optionally additional solvent present) corresponding to a mass ratio of at least about 1.85: 1 of ADN to solvent.
  • the inventive method for producing the liquid gas generator fuel which is a dissolution of ADN in liquid ammonia, a condensation of ammonia on the ADN, such as a condensation of gaseous ammonia at about -30 ° C to solid ADN under atmospheric pressure, and / or a concentration of an ammoniacal
  • ADN solution allows a very simple and inexpensive preparation of the same, and it is of course also possible for economic reasons to synthesize the ADN in such a known manner from guanyl urea dinitramide (GUDN, FOX 12).
  • the gas generator fuel contains at most about 4% by weight of water, in particular at most about 3% by mass of water, preferably at most about 2% by mass.
  • % Water in each case based on the mixture of ADN and solvent, wherein it most preferably contains at most about 1 wt .-% water and in particular may be substantially free of water.
  • the gas generator fuel is substantially free of carbonaceous solvents, in particular at least 15% by mass, preferably at least 20% by mass, most preferably at least 20% by mass. %, in each case based on the mixture of ADN and solvent, of ammonia and preferably contains substantially exclusively ammonia as the solvent and any further solvents, for example in an amount of at most about 5 mass%, preferably at most about 4 mass%, in particular at most about 3 mass%, most preferably at most about 2 mass%, and most preferably at most about 1 mass .-% or in particular to 0 Mass .-%, are present.
  • the gas generator fuel contains at least about 70% by mass, in particular at least about 75% by mass, of ADN, for example between about 75% by mass. % and about 80 to about 85% by mass of ADN, based in each case on the mixture of ADN and solvent.
  • the ADN is dissolved in a proportion of at least 70% by weight, in particular of at least 75% by weight, preferably largely pure and anhydrous, ammonia, or is preferably substantially pure and anhydrous - ammonia is condensed with a corresponding proportion of the ADN or "pressed" is.
  • preferred levels of ADN for such applications may be on the order of at least about 65 mass% to about 78 mass% or preferably to about 77 mass%, more preferably at least about 70 mass% to about 78 mass % or preferably to about 77 mass%, most preferably between at least about 75 mass% to about 78 mass% or preferably to about 77 mass%.
  • gas generator propellant according to the invention may in principle be in the liquid phase, according to an advantageous development it can also be provided that it is present as a gelatinous propellant and contains at least one gelling agent, which is expediently contained in a proportion of about 0.1 mass % to about 10% by mass, in particular from about 0.5% by mass to about 10% by mass, in each case based on the total mixture (ie on the total mixture of ADN, solvent, gelling agent and optionally present additives ( see also below)), may be present.
  • gelling agent which is expediently contained in a proportion of about 0.1 mass % to about 10% by mass, in particular from about 0.5% by mass to about 10% by mass, in each case based on the total mixture (ie on the total mixture of ADN, solvent, gelling agent and optionally present additives ( see also below)
  • Suitable gelling agents include carbon nanotubes including functionalized carbon nanotubes, in particular having functional groups from the group of amino groups, alkylamino groups and other functional groups having a base strength greater than ammonia, and / or doped carbon nanotubes, in particular nitrogen-doped carbon nanotubes, such as CN 2 nanotubes.
  • the carbon nanotubes can be used as single-walled, double-walled or multi-walled nanotubes and / or in the form of modified side-group carbon nanotubes.
  • n is a number between 0 and 6 and R 1 , R 2 are selected from the group consisting of hydrogen (-H), alkyl groups having 1 to 6 carbon atoms, allyl, vinyl, hydroxyalkyl, ether, cyanoalkyl, azidoalkyl and Nitromethyl groups are selected.
  • advantageous gelling agents include powdered metals, semimetals, metal oxides and / or semi-metal oxides, in particular based on silicon, such as, for example, available under the trade name "Aerosil” ( Evonik Industries ) fumed silica.
  • the particle size of such powdered metals or metal oxides is preferably between about 1 nm and about 10 ⁇ m, in particular between about 1 nm and about 1 ⁇ m.
  • advantageous gel formers include OH-functionalized, in particular alcoholic gelling agents, in particular based on energetic di- and / or triols, such as glycidyl azide polymer diols (GAP diols), as well as polymeric gelling agents, especially with nitrogen-containing functional groups, such as isocyanate and / or urea-based, including triazine polymers and polymeric urea urethanes.
  • suitable urea-urethane are eg from the DE 199 19 482 A1 such as DE 102 41 853 A1 known.
  • urea-urethane which by reacting mono-, di- and / or polyalcohols, especially of energetic monoalcohols and / or diols, such as nitro alcohols, GAP-diols or the like, with diisocyanates and subsequent reaction with mono - And / or diamines or mono- and / or dinitramines including mixtures thereof have been obtained with ionic liquids (IL), in particular with energetic ionic liquids (EIL), as a solvent.
  • IL ionic liquids
  • EIL energetic ionic liquids
  • the gas generator fuel is gelled with the addition of a suitable gelling agent or gelling agent, in particular of the aforementioned type, wherein the gelling agent should expediently be dispersed as finely as possible into the mixture of ADN and solvent, for example by means of ultrasound and / or entry of shear forces, eg using appropriate homogenizers, Scheibenrlochern (dissolvers) and the like.
  • ionic liquids with dinitramide anions prove to be particularly preferred additives for melting point reduction, whereby suitable cations of such ionic liquids can be obtained for example by N-quaternization of corresponding nitrogen compounds. This can be done, for example, by protonation and / or alkylation of the aforementioned nitrogen-containing heterocyclic compounds to produce a cation therefrom.
  • Particularly advantageous ionic liquids are, for example, 1,4,5-trimethyltetrazolium dinitramide, 1- (2-hydroxyethyl) -4,5-dimethyltetrazolium dinitramide, 1- (2-hydroxyethyl) -4-methyl-5-aminotetrazolium dinitramide and 1- (2-hydroxyethyl) -3-methyl-1,2,3-triazolium dinitramide, including isomeric mixtures of the foregoing ionic liquids, diamino urea dinitramide, oxalhydrazine dinitramide, 2-hydroxyethyl hydrazinium dinitramide, 2-hydroxydiethylammonium dinitramide, 2
  • EIL energetic ionic liquids
  • ethylammonium dinitramide with an oxygen balance of -42.1%.
  • protic ionic liquids based on a more basic amine than the solvent for The ADN used ammonia moreover, also offers the possibility of adding the corresponding free amine directly to the gas generator fuel mixture and to generate the respective (energetic) ionic liquid in this way in situ:
  • HEHDN 2-hydroxyethylhydrazinium dinitramide
  • a monergous gas generator propellant of about 75% by weight of ADN and about 23% by weight of ammonia ( ⁇ 3% by weight) according to Fig. 2 causes, for example, a reduction in its melting or freezing point by 5 ° C from about -31 ° C to about -36 ° C.
  • ionic liquids or salts with anions other than dinitramide to lower the melting point is possible in principle, in particular oxygen-rich anions are in view of the oxygen balance of advantage, which have a high solubility in the novel ammonia used as a solvent, such as Anions from the group of nitrates, perchlorates, formates and azolates, in particular with nitro and / or nitramine substituents, such as 3,5-dinitro-1,2,4-triazolate, 5-nitro-1,2,3, 4-tetrazolate, 3,4,5-trinitropyrazolate, 5,5'-dinitramine-3,3'-bis (1,2,4-triazole), 1,2,4-triazolate including their N-oxide derivatives and like.
  • Other examples of advantageous heterocyclic anions of suitable ionic liquids or salts include Embodiments of monergolic gas generator propellants according to the present invention having various proportions of ammonium dinitramide are shown below.
  • the burnup temperature is 2377 ° K at a combustion chamber pressure of 70 bar (expansion against ambient pressure); the exhaust gas composition is about 44 mass% water (H 2 O), about 54 mass% nitrogen (N 2 ) and about 2 mass% hydrogen (H 2 ).
  • the exhaust gas composition may be fed directly to a hydrogen fuel cell as a fuel.
  • the burnup temperature is 1985 ° K at a combustion chamber pressure of 70 bar (expansion against ambient pressure); the exhaust gas composition is about 40 mass% water (H 2 O), about 56 mass% nitrogen (N 2 ) and about 4 mass% hydrogen (H 2 ).
  • the exhaust gas composition may also be fed directly to a hydrogen fuel cell as a fuel.
  • Example 5 (not according to the invention):

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Air Bags (AREA)
  • Liquid Carbonaceous Fuels (AREA)

Description

Die Erfindung betrifft einen Gasgenerator-Treibstoff, enthaltend einen monergolen Treibstoff auf der Basis von Ammoniumdinitramid (ADN) und wenigstens ein Lösungsmittel, sowie ein Verfahren zu seiner Herstellung.The invention relates to a gas generator fuel containing a monergolene fuel based on ammonium dinitramide (ADN) and at least one solvent, and a process for its preparation.

Derartige Gasgenerator-Treibstoffe finden in flüssiger Form insbesondere für Raketen-und Satelliten-Treibstoffe in der Raumfahrt, aber auch für militärische Zwecke einschließlich militärischer Flugkörper und für Torpedo-Treibstoffe, für Nottreibstoffe von Flugzeugen und U-Booten etc. Verwendung. Gegenüber herkömmlichen monergolischen Gasgenerator-Treibstoffen, wie solchen auf der Basis von Wasserstoffperoxid oder Hydrazin, weist Ammoniumdinitramid insbesondere eine relativ gute Langzeitstabilität (z.B. im Vergleich mit Wasserstoffperoxid) und Einsatzfähigkeit bei relativ tiefen Temperaturen unterhalb -20°C sowie ein ungleich geringeres gesundheitliches Gefährdungspotenzial (z.B. im Vergleich mit Hydrazin) auf.Such gas generator fuels are used in liquid form, in particular for rocket and satellite propellants in aerospace, but also for military purposes, including military missiles and for torpedo fuels, for aircraft and submarine aircraft fuels, etc. Compared with conventional monergol gas generator propellants, such as those based on hydrogen peroxide or hydrazine, ammonium dinitramide has in particular a relatively good long-term stability (eg compared with hydrogen peroxide) and usefulness at relatively low temperatures below -20 ° C and a much lower health hazard (eg in comparison with hydrazine).

Flüssige Gasgenerator-Treibstoffe auf der Basis von ADN, Wasser sowie Brennstoff-Additiven wurden bereits gegen Ende des vergangenen Jahrhunderts als Ersatz von Hydrazin-basierte Treibstoffe entwickelt ( Per Sjöberg: "A stable liquid mono-propellant based on ADN", IMEM Tucson, USA, May 11-14, 2009 ). Die DE 600 03 428 T2 beschreibt einen Gasgenerator-Treibstoff auf der Basis von ADN mit Wasser und/oder Wasserstoffperoxid als Lösungsmittel, wobei letzteres allerdings eine nur geringe Haltbarkeit aufweist und Wasser aus energetischer Sicht einen unnötigen Ballast darstellt, welcher insbesondere bei einer Anwendung des Treibstoffes in der Raumfahrt Gewichtsprobleme verursacht.Liquid gas generator fuels based on ADN, water and fuel additives were developed as early as the end of the last century as a substitute for hydrazine-based fuels ( Per Sjöberg: "A stable liquid mono-propellant based on ADN", IMEM Tucson, USA, May 11-14, 2009 ). The DE 600 03 428 T2 describes a gas generator propellant based on ADN with water and / or hydrogen peroxide as a solvent, the latter, however, has a low durability and water from an energetic point of view is an unnecessary ballast, which causes weight problems especially in an application of the fuel in space.

Die WO 2012/166046 A1 beschreibt einen weiteren flüssigen Gasgenerator-Treibstoff auf der Basis von ADN, welcher mit einem Gesamtanteil zwischen 55 Mass.-% und 62 Mass.-% in einer Lösungsmittelmischung aus 4 Mass.-% bis 12 Mass.-% Ammoniak und im Übrigen Wasser gelöst ist und welcher ferner bis zu 22 Mass.-% Methanol enthalten kann. Davon abgesehen, dass auch der aus der WO 2012/166046 A1 bekannte Gasgenerator-Treibstoff einen verhältnismäßig hohen Anteil an lediglich als Ballast anfallendem Wasser enthält und folglich eine relativ geringe massen- bzw. volumenspezifische Leistung aufweist, sind insbesondere die Tieftemperatureigenschaften zwar einem bekannten monergolischen Gasgenerator-Treibstoff auf der Basis von 63,0 Mass.-% ADN in einem Lösungsmittelgemisch aus Methanol, Wasser und Ammoniak ("LMP-103S") überlegen, aber gleichwohl für verschiedene Anwendungen, insbesondere in Form von Raketen- und/oder Satellitentreibstoffen, verbesserungsbedürftig. Die Druckschrift erwähnt diesbezüglich eine mögliche Lagertemperatur von mindestens -30°C, doch hat sich beispielsweise gezeigt, dass beim Abkühlen der dort beschriebenen Mischung auf unterhalb -90°C und anschließendem Erwärmen kein Gefrier- bzw. Schmelzpunkt mehr nachweisbar war. Darüber hinaus vermag die gemäß der WO 2012/166046 A1 durchgeführte Testmethode einer Abkühlung des Gasgenerator-Treibstoffes auf -30°C eine nur sehr bedingte Aussagekraft zu dessen Tieftemperatureigenschaften zur Verfügung zu stellen, weil ADN-Lösungen bekanntlich auch im (stark) unterkühlten Zustand erst bei einer Temperatur deutlich tiefer als ihr eigentlicher Erstarrungspunkt auskristallisieren, sofern sie nicht mit Kristallisationskeimen beaufschlagt, einer äußeren Einwirkung von mechanischer Energie unterworfen werden oder dergleichen. Um die Tieftemperaturstabilität zu ermitteln, ist es daher zwingend erforderlich, die ADN-Lösung bis zu einer Temperatur abzukühlen, bei welcher sie auskristallisiert, wonach sie bis zum Übergang in die flüssige Phase erwärmt werden muss, um den Gefrier- bzw. Schmelzpunkt zu ermitteln. Schließlich stellt das gemäß der WO 2012/166046 A1 vorgeschlagene weitere Lösungsmittel Methanol insbesondere für Anwendungen eines solchen Gasgenerator-Treibstoffes in der Raumfahrt insoweit einen Nachteil dar, als es zwingend einen Oxidator erfordert, andernfalls sich eine unvollständige Umsetzung des hierin enthaltenen Kohlenstoffes ergibt, was insbesondere in einer Entstehung von Kohlenmonoxid im Abgas resultieren kann. Darüber hinaus weist ADN nur eine begrenzte Löslichkeit in Methanol auf (etwa 87 g ADN in 100 g Methanol), was den maximal möglichen Anteil an ADN in einer entsprechenden Treibstoffzusammensetzung beschränkt.The WO 2012/166046 A1 describes another liquid gas generator fuel based on ADN, which with a total content of 55 wt .-% and 62 wt .-% dissolved in a solvent mixture of 4 wt .-% to 12 wt .-% ammonia and otherwise water and which may further contain up to 22% by mass of methanol. Apart from that also from the WO 2012/166046 A1 known gas generator fuel contains a relatively high proportion of water only as ballast and thus has a relatively low mass or volume specific performance, in particular the low temperature properties, although a known monomeric gasoline propellant based on 63.0 Mass .-% ADN in a solvent mixture of methanol, water and ammonia ("LMP-103S") superior, but nevertheless for various applications, in particular in the form of rocket and / or satellite fuels, in need of improvement. The publication mentioned in this regard a possible storage temperature of at least -30 ° C, but it has been found, for example, that when cooling the mixture described therein to below -90 ° C and subsequent heating no freezing or melting point was more detectable. Moreover, according to the WO 2012/166046 A1 carried out test method of cooling the gas generator fuel to -30 ° C to provide a very limited predictive power to its low temperature properties available, because ADN solutions known to crystallize even in the (strongly) supercooled state only at a temperature significantly lower than their actual solidification point, unless they are subjected to nucleation, subjected to an external action of mechanical energy, or the like. Therefore, in order to determine the low-temperature stability, it is imperative to cool the ADN solution to a temperature at which it crystallizes, after which it must be heated to the transition to the liquid phase in order to determine the freezing or melting point. Finally, according to the WO 2012/166046 A1 proposed further solvents methanol in particular for applications of such gas generator fuel in aerospace to that extent is a disadvantage, as it necessarily requires an oxidizer, otherwise there is an incomplete implementation of the carbon contained herein, which in particular can result in the formation of carbon monoxide in the exhaust gas. In addition, ADN has limited solubility in methanol (about 87 g of ADN in 100 g of methanol), which limits the maximum possible level of ADN in a corresponding fuel composition.

Ähnliches gilt für einen aus der WO 00/50363 A1 bekannten Gasgenerator-Treibstoff auf der Basis von Dinitramiden, welcher sowohl für Airbags als auch für Raketenantriebe zum Einsatz gelangen soll. Der Gasgenerator-Treibstoff enthält einerseits eine als "Oxidator" bezeichnete erste Komponente der allgemeinen Formel XD, wobei "X" ein beliebiges Kation ist und unter anderem von einem Ammonium-Kation gebildet sein kann, während "D" ein Dinitramid-Anion ist, andererseits eine als "Treibstoff" bezeichnete zweite Komponente sowie gegebenenfalls ein Lösungsmittel als dritte Komponente. Bei der mit "Treibstoff" bezeichneten zweiten Komponente kann es sich gleichfalls um ein Lösungsmittel handeln, wobei unter anderem wässrige Ammoniaklösungen vorgeschlagen werden. Abgesehen von dem relativ hohen, als Ballast anfallenden Wasseranteil besteht auch hier insbesondere der Nachteil einer verbesserungsbedürftigen Tieftemperaturstabilität, welche insbesondere für Einsatzfelder im Raumfahrtbereich, wie für Raketen- bzw. Satellitentreibstoffe, von entscheidender Bedeutung ist, um die ohnehin nur sehr begrenzt zur Verfügung stehende und bereits beim Start mitzuführende Energie in einem nur geringstmöglichen Umfang zur Vorheizung des Treibstoffes verwenden zu müssen, um jegliche Kristallisation des Treibstoffes in den Zuführleitungen der Antriebsaggregate zu verhindern.The same applies to one of the WO 00/50363 A1 known gas generator fuel based on dinitramides, which is to be used for both airbags and rocket engines used. The gas generator fuel contains, on the one hand, a first component of the general formula XD, referred to as "oxidizer", where "X" is any cation and may be formed, inter alia, by an ammonium cation, while "D" is a dinitramide anion, on the other hand a second component referred to as "fuel" and optionally a solvent as a third component. The second component referred to as "fuel" may likewise be a solvent, wherein, inter alia, aqueous ammonia solutions are proposed. Apart from the relatively high, accumulating as ballast water content here is also the disadvantage of a need to improve low temperature stability, which is especially for applications in the space sector, such as rocket and satellite fuel, of crucial importance to the already very limited available and To use energy to be entrained at startup to the lowest possible extent for preheating the fuel in order to prevent any crystallization of the fuel in the supply lines of the drive units.

Die RU 2012 144 167 A beschreibt einen für Raketenantriebe vorgesehenen festen Gasgenerator-Treibstoff mit einem Treibstoff und einem Oxidator, welcher 44,61 Mass.-% (+/- 10 Mass.-%) Beryllium-Borhydrid, 35,75 Mass.-% (+/- 10 Mass.-%) ADN und 19,63 Mass.-% (+/- 5 Mass.-%) Ammoniak enthält. Das als Oxidator zugesetzte Beryllium-Borhydrid dient zur Erhöhung des spezifischen Impulses des Treibstoffes und soll den Rückstoß des hiermit versorgten Raketenmotors verbessern.The RU 2012 144 167 A describes a solid propellant propellant propellant fuel propellant and an oxidizer containing 44.61 mass% (+/- 10 mass%) beryllium borohydride, 35.75 mass% (+/- 10 % By mass) ADN and 19.63 mass% (+/- 5 mass%) of ammonia. The added as an oxidizer beryllium-borohydride serves to increase the specific momentum of the Fuel and should improve the recoil of the hereby supplied rocket motor.

Die US 5 714 714 A offenbart ein Verfahren zur Herstellung von ADN durch Nitrieren einer Verbindung mit der chemischen Formel Z-NH2 unter Bildung von Z-NHNO2, anschließende Reaktion der erhaltenen Verbindung Z-NHNO2 mit Ammoniak in wasserfreiem Medium unter Bildung eines Salzes mit der chemischen Formel Z-NNO2 -NH4 + sowie anschließendes Nitrieren dieses Salzes und Behandlung der Reaktionsmischung mit Ammoniak, um kristallines ADN und Ammoniumnitrat zu erhalten und die Ausgangsverbindung Z-NH2 zurückzugewinnen.The US 5 714 714 A discloses a process for producing ADN by nitrating a compound having the chemical formula Z-NH 2 to form Z-NHNO 2 , then reacting the resulting compound Z-NHNO 2 with ammonia in anhydrous medium to form a salt having the chemical formula Z -NNO 2 - NH 4 + and then nitrating this salt and treating the reaction mixture with ammonia to obtain crystalline ADN and ammonium nitrate and to recover the starting compound Z-NH 2 .

In der EP 2 662 350 A1 geht es allgemein um einen monergolen, kohlenstoffbasierten Gasgenerator-Treibstoff, wie insbesondere auf der Basis von Nitromethan und Nitroethan, welchem Kohlenstoff-Nanoröhren als Gelbildner zugesetzt sein können.In the EP 2 662 350 A1 It is generally a monergolen, carbon-based gas generator fuel, in particular on the basis of nitromethane and nitroethane, which carbon nanotubes may be added as a gelling agent.

Der Erfindung liegt die Aufgabe zugrunde, einen bei Raumtemperatur flüssigen Gasgenerator-Treibstoff auf der Basis von Ammoniumdinitramid (ADN) der eingangs genannten Art dahingehend weiterzubilden, dass er unter zumindest weitestgehender Vermeidung der vorgenannten Nachteile eine verbesserte Tieftemperaturbeständigkeit bei einer erhöhten massenspezifischen Leistung aufweist. Sie ist ferner auf ein Verfahren zur Herstellung eines solchen Gasgenerator-Treibstoffes gerichtet.The invention has the object of providing a liquid at room temperature gas generator fuel on the basis of ammonium dinitramide (ADN) of the type mentioned in that it has at least largely avoiding the aforementioned disadvantages improved low temperature resistance at an increased mass-specific performance. It is further directed to a method of making such gas generator fuel.

Der erste Teil dieser Aufgabe wird erfindungsgemäß mit einem flüssigen oder gelförmigen Gasgenerator-Treibstoff der eingangs genannten Art gelöst, bestehend aus

  • einem monergolen Treibstoff auf der Basis von Ammoniumdinitramid (ADN);
  • wenigstens einem Lösungsmittel, wobei wenigstens ein Lösungsmittel von Ammoniak (NH3) gebildet ist,
wobei der Gasgenerator-Treibstoff wenigstens 65 Mass.-% ADN und höchstens 5 Mass.-% Wasser, jeweils bezogen auf die Mischung aus ADN und Lösungsmittel, enthält; und
  • gegebenenfalls wenigstens einem Gelbildner mit einem Anteil von bis 10 Mass.-%, bezogen auf die Gesamtmischung; und
  • gegebenenfalls wenigstens einem Additiv zur Verbesserung seiner Tieftemperatureigenschaften.
The first part of this object is achieved with a liquid or gelatinous gas generator fuel of the type mentioned, consisting of
  • a monergous fuel based on ammonium dinitramide (ADN);
  • at least one solvent, wherein at least one solvent is formed by ammonia (NH 3 ),
the gas generator fuel containing at least 65% by weight of ADN and not more than 5% by weight of water, based in each case on the mixture of ADN and solvent; and
  • optionally at least one gelling agent with a proportion of up to 10% by mass, based on the total mixture; and
  • optionally at least one additive for improving its low-temperature properties.

In verfahrenstechnischer Hinsicht sieht die Erfindung zur Lösung dieser Aufgabe ein Verfahren zur Herstellung eines flüssigen oder gelförmigen Gasgenerator-Treibstoffes der eingangs genannten Art vor, bestehend aus

  • einem monergolen Treibstoff auf der Basis von Ammoniumdinitramid (ADN);
  • wenigstens einem Lösungsmittel, wobei wenigstens ein Lösungsmittel von Ammoniak (NH3) gebildet ist, wobei der Gasgenerator-Treibstoff wenigstens 65 Mass.-% ADN und höchstens 5 Mass.-% Wasser, jeweils bezogen auf die Mischung aus ADN und Lösungsmittel, enthält;
  • gegebenenfalls wenigstens einem Gelbildner; und
  • gegebenenfalls wenigstens einem Additiv zur Verbesserung seiner Tieftemperatureigenschaften,
wobei das Verfahren wenigstens einen Verfahrensschritt aus der Gruppe
  • Lösen von ADN in Ammoniak mit einem Anteil an ADN von wenigstens 65 Mass.-% ADN;
  • Aufkondensieren von Ammoniak auf ADN mit einem Anteil an ADN von wenigstens 65 Mass.-%; und
  • Aufkonzentrieren einer Mischung aus ADN und Ammoniak auf einen Anteil an ADN von wenigstens 65 Mass.-%,
jeweils bezogen auf die Mischung aus ADN und Ammoniak, umfasst; und wobei
  • der Gasgenerator-Treibstoff gegebenenfalls geliert wird, indem ihm das wenigstens eine Gelierungsmittel mit einem Anteil von bis 10 Mass.-%, bezogen auf die Gesamtmischung, zugesetzt wird; und
  • dem Gasgenerator-Treibstoff gegebenenfalls das wenigstens eine Additiv zur Verbesserung seiner Tieftemperatureigenschaften zugesetzt wird.
In procedural terms, the invention provides for solving this problem, a method for producing a liquid or gelatinous gas generator fuel of the type mentioned, consisting of
  • a monergous fuel based on ammonium dinitramide (ADN);
  • at least one solvent, wherein at least one solvent of ammonia (NH 3 ) is formed, wherein the gas generator fuel contains at least 65% by mass of ADN and at most 5% by mass of water, based in each case on the mixture of ADN and solvent;
  • optionally at least one gelling agent; and
  • optionally at least one additive for improving its low-temperature properties,
wherein the method at least one method step from the group
  • Dissolving ADN in ammonia with an amount of ADN of at least 65 mass% of ADN;
  • Condensing ammonia to ADN with an amount of ADN of at least 65 mass%; and
  • Concentrating a mixture of ADN and ammonia to a proportion of ADN of at least 65% by mass,
each based on the mixture of ADN and ammonia comprises; and where
  • the gas generator fuel is optionally gelled by adding to it the at least one gelling agent at a level of up to 10 mass%, based on the total mixture; and
  • the at least one additive for improving its low-temperature properties is optionally added to the gas generator fuel.

Der erfindungsgemäße Gasgenerator-Treibstoff, welcher bis zu einer Temperatur im Bereich von zumindest -30°C in flüssiger Phase vorliegt, weist aufgrund seines hohen Anteils an ADN eine hohe massenspezifische Leistung auf, wobei insbesondere auf die Fig. 1 verwiesen sei, welche einerseits den massenspezifischen Impuls "Isp (frz equilibrium 70:1)" in [Ns/kg] (linke Ordinate), andererseits den volumenspezifischen Impuls "Isp vol (frz equilibrium 70:1)" in [Ns/dm3] (rechte Ordinate) eines erfindungsgemäßen flüssigen Gasgenerator-Treibstoffes zeigt, welcher ausschließlich aus in Ammoniak gelöstem Ammoniumdinitramid (ADN) besteht, mit verschiedenen Anteilen an ADN zwischen etwa 66 Mass.-% und etwa 84 Mass.-% einerseits im Vergleich mit dem massenspezifischen Impuls von herkömmlichem Hydrazin, andererseits im Vergleich mit dem massenspezifischen Impuls eines bekannten Gasgenerator-Treibstoffes mit 63,0 Mass.-% ADN, 18,4 Mass.-% Methanol, 4,6 Mass.-% Ammoniak und 14,0 Mass.-% Wasser ("LMP-103S").The gas generator fuel according to the invention, which is in the liquid phase up to a temperature in the range of at least -30 ° C, has a high mass-specific performance due to its high proportion of ADN, in particular to the Fig. 1 on the one hand, the mass-specific pulse "I sp (frz equilibrium 70: 1)" in [Ns / kg] (left ordinate), on the other hand, the volume-specific pulse "I sp vol (frz equilibrium 70: 1)" in [Ns / dm 3 ] (right ordinate) of a liquid gas generator fuel according to the invention, which consists exclusively of ammonium dinitramide (ADN) dissolved in ammonia, with different proportions of ADN between about 66 mass% and about 84 mass% on the one hand compared with the mass specific momentum of conventional hydrazine, on the other hand, as compared to the mass specific momentum of a known gas generator propellant with 63.0 mass% ADN, 18.4 mass% methanol, 4.6 mass% ammonia and 14.0 Mass .-% water ("LMP-103S").

Aufgrund der hervorragenden Löslichkeit von ADN in Ammoniak und des allenfalls sehr geringen Anteils an Wasser weist der flüssige Gasgenerator-Treibstoff auch bei Raumtemperatur eine geringe Flüchtigkeit sowie insbesondere hervorragende Tieftemperatureigenschaften auf. In diesem Zusammenhang sei zunächst auf die Fig. 2 verwiesen, welche ein mittels Diffential-Scanning-Kalorimetrie (Differential Scanning Calorimetry, DSC) erhaltenes Schaubild zur Veranschaulichung des Tieftemperaturverhaltens eines ausschließlich aus etwa 75 Mass.-% ADN und etwa 25 Mass.-% Ammoniak (± 3 Mass.-%) bestehenden, erfindungsgemäßen Gasgenerator-Treibstoffes bei der zweiten Erwärmung in Abhängigkeit der zugeführten Wärmemenge "heat flow" in [W/g] zeigt. Wie aus der Fig. 2 ersichtlich, liegt der Schmelzpeak eines solchen Gasgenerator-Treibstoffes bei etwa -31,4°C, während die extrapolierte Onset-Temperatur etwa -35,7°C beträgt. Wie ferner aus den DSC-Diagrammen gemäß Fig. 3 (derselbe Gasgenerator-Treibstoff, bestehend aus etwa 75 Mass.-% ADN und etwa 25 Mass.-% Ammoniak ± 3 Mass.-%) und Fig. 4 (reines ADN) hervorgeht, liegt der Schmelzpunkt von reinem ADN demgegenüber bei etwa +95,2°C und die extrapolierte Onset-Temperatur bei etwa +94,5°C. Darüber hinaus ist den Fig. 3 und 4 zu entnehmen, dass reines ADN eine Zersetzungstemperatur (Onset-Temperatur) von etwa 143,9°C besitzt, während der erfindungsgemäße Gasgenerator-Treibstoff eine Zersetzungstemperatur (Onset-Temperatur) von etwa 173.8°C aufweist. Darüber hinaus erweist sich der erfindungsgemäße Gasgenerator-Treibstoff auch bei mehrmaligem Abkühlen/Erwärmen zwischen etwa -90°C und etwa +100°C als stabil.Due to the excellent solubility of ADN in ammonia and the possibly very small proportion of water, the liquid gas generator fuel, even at room temperature, has a low volatility and in particular outstanding low-temperature properties. In this context be first on the Fig. 2 which shows a differential scanning calorimetry (DSC) graph to illustrate the low temperature behavior of one consisting exclusively of about 75 mass% ADN and about 25 mass% ammonia (± 3 mass%) , Gas generator propellant according to the invention in the second heating in dependence of the supplied amount of heat "heat flow" in [W / g] shows. Like from the Fig. 2 As can be seen, the melting peak of such a gas generator fuel is about -31.4 ° C, while the extrapolated onset temperature is about -35.7 ° C. Further, from the DSC diagrams according to Fig. 3 (the same gas generator fuel consisting of about 75 mass% ADN and about 25 mass% ammonia ± 3 mass%) and Fig. 4 (pure ADN), the melting point of pure ADN is about + 95.2 ° C and the extrapolated onset temperature is about + 94.5 ° C. In addition, the 3 and 4 it can be seen that pure ADN has a decomposition temperature (onset temperature) of about 143.9 ° C, while the gas generator fuel according to the invention has a decomposition temperature (onset temperature) of about 173.8 ° C. In addition, the gas generator fuel according to the invention proves to be stable even with repeated cooling / heating between about -90 ° C and about + 100 ° C.

Während in Fig. 5 überdies die temperaturabhängige Viskosität eines Gasgenerator-Treibstoffes mit derselben Zusammensetzung zwischen -20°C und +25°C gezeigt ist, welche sich über den gesamten Temperaturbereich als niedrig erweist, ist in der Fig. 6 dessen Dichte im Bereich zwischen 10°C und +35°C dargestellt.While in Fig. 5 In addition, the temperature-dependent viscosity of a gas generator fuel having the same composition between -20 ° C and + 25 ° C is shown, which proves to be low over the entire temperature range, is in the Fig. 6 its density is shown in the range between 10 ° C and + 35 ° C.

Darüber hinaus kann der erfindungsgemäße Gasgenerator-Treibstoff je nach Auswahl der etwaigen Additive (siehe hierzu auch weiter unten) im Wesentlichen frei von kanzerogenen Inhaltsstoffen sowie insbesondere auch im Wesentlichen frei von Kohlenstoff sein, so dass bei seinem Abbrand kein toxisches Kohlenmonoxid oder Blausäure gebildet werden kann. Entsprechendes gilt für eine Bildung fester Abbrandprodukte, wie sie beim Stand der Technik entstehen können. Ferner sei erwähnt, dass der erfindungsgemäße Gasgenerator-Treibstoff je nach Auswahl etwaiger Additive sowie insbesondere in von Additiven freier Form die Möglichkeit bietet, die vornehmlich aus Stickstoff, Wasserstoff und Wasser bestehenden Verbrennungsprodukte einer Wasserstoff-Brennstoffzelle als Brennstoff aufzugeben, so dass der Gasgenerator-Treibstoff zusätzlich als Wasserstoffgenerator genutzt werden kann, welcher keine Abtrennung von etwaigem Kohlenmonoxid oder -dioxid erfordert.In addition, the gas generator fuel according to the invention depending on the selection of any additives (see below) substantially free of carcinogenic ingredients and in particular also be substantially free of carbon, so that when it burns no toxic carbon monoxide or hydrogen cyanide can be formed , The same applies to a formation of solid burn-off products, as they can arise in the prior art. It should also be mentioned that the gas generator fuel according to the invention, depending on the selection of any additives and in particular in additives free form offers the opportunity to abandon the existing primarily nitrogen, hydrogen and water combustion products of a hydrogen fuel cell as fuel, so that the gas generator fuel can additionally be used as a hydrogen generator, which does not require separation of any carbon monoxide or dioxide.

Im Übrigen sei an dieser Stelle darauf hingewiesen, dass sich das erfindungsgemäße Verhältnis von wenigstens 65 Mass.-% ADN auf die Mischung aus ADN und allen vorhandenen Lösungsmitteln (also insbesondere Ammoniak einschließlich des gegebenenfalls vorhandenen, maximal 5%-igen Anteils an Wasser sowie gegebenenfalls vorhandenen weiteren Lösungsmitteln) bezieht, was einem Massenverhältnis von wenigstens etwa 1,85:1 von ADN zu Lösungsmittel entspricht.Incidentally, it should be noted at this point that the ratio according to the invention of at least 65% by mass of ADN to the mixture of ADN and all solvents present (ie in particular ammonia, including the optionally present, maximum 5% proportion of water and optionally additional solvent present) corresponding to a mass ratio of at least about 1.85: 1 of ADN to solvent.

Das erfindungsgemäße Verfahren zur Herstellung des flüssigen Gasgenerator-Treibstoffes, welches ein Lösen von ADN in flüssigem Ammoniak, ein Aufkondensieren von Ammoniak auf das ADN, wie beispielsweise ein Aufkondensieren von gasförmigem Ammoniak bei etwa -30°C auf festes ADN unter Atmosphärendruck, und/oder ein Aufkonzentrieren einer ammoniakalischen ADN-Lösung vorsieht, erlaubt schließlich eine sehr einfache und kostengünstige Herstellung desselben, wobei es aus wirtschaftlichen Gründen selbstverständlich auch möglich ist, das ADN in als solcher bekannter Weise aus Guanylharnstoffdinitramid (GUDN, FOX 12) zu synthetisieren.The inventive method for producing the liquid gas generator fuel, which is a dissolution of ADN in liquid ammonia, a condensation of ammonia on the ADN, such as a condensation of gaseous ammonia at about -30 ° C to solid ADN under atmospheric pressure, and / or a concentration of an ammoniacal Finally, ADN solution allows a very simple and inexpensive preparation of the same, and it is of course also possible for economic reasons to synthesize the ADN in such a known manner from guanyl urea dinitramide (GUDN, FOX 12).

In vorteilhafter Ausgestaltung kann aus den vorgenannten Gründen, insbesondere in Bezug auf die vorteilhaften Tieftemperatureigenschaften, vorgesehen sein, dass der Gasgenerator-Treibstoff höchstens etwa 4 Mass.-% Wasser, insbesondere höchstens etwa 3 Mass.-% Wasser, vorzugsweise höchstens etwa 2 Mass.-% Wasser, jeweils bezogen auf die Mischung aus ADN und Lösungsmittel, enthält, wobei er höchst vorzugsweise höchstens etwa 1 Mass.-% Wasser enthält und insbesondere im Wesentlichen frei von Wasser sein kann.In an advantageous embodiment, for the aforementioned reasons, in particular with regard to the advantageous low-temperature properties, it can be provided that the gas generator fuel contains at most about 4% by weight of water, in particular at most about 3% by mass of water, preferably at most about 2% by mass. % Water, in each case based on the mixture of ADN and solvent, wherein it most preferably contains at most about 1 wt .-% water and in particular may be substantially free of water.

Wie bereits angedeutet, kann in weiterhin vorteilhafter Ausgestaltung vorgesehen sein, dass der Gasgenerator-Treibstoff im Wesentlichen frei von kohlenstoffhaltigen Lösungsmitteln ist, wobei er insbesondere wenigstens 15 Mass.-%, vorzugsweise wenigstens 20 Mass.-%, höchst vorzugsweise wenigstens 20 Mass.-%, jeweils bezogen auf die Mischung aus ADN und Lösungsmittel, an Ammoniak enthält und vorzugsweise im Wesentlichen ausschließlich Ammoniak als Lösungsmittel enthält und etwaige weitere Lösungsmittel z.B. in einem Anteil von höchstens etwa 5 Mass.-%, vorzugsweise von höchstens etwa 4 Mass.-%, insbesondere von höchstens etwa 3 Mass.-%, höchst vorzugsweise von höchstens etwa 2 Mass.-% und besonders bevorzugt von höchstens etwa 1 Mass.-% oder insbesondere zu 0 Mass.-%, vorhanden sind.As already indicated, it can be provided in a further advantageous embodiment that the gas generator fuel is substantially free of carbonaceous solvents, in particular at least 15% by mass, preferably at least 20% by mass, most preferably at least 20% by mass. %, in each case based on the mixture of ADN and solvent, of ammonia and preferably contains substantially exclusively ammonia as the solvent and any further solvents, for example in an amount of at most about 5 mass%, preferably at most about 4 mass%, in particular at most about 3 mass%, most preferably at most about 2 mass%, and most preferably at most about 1 mass .-% or in particular to 0 Mass .-%, are present.

Die Herstellung eines solchen Gasgenerator-Treibstoffes kann beispielsweise dadurch geschehen, dass

  • das ADN in im Wesentlichen wasserfreiem Ammoniak gelöst; und/oder
  • im Wesentlichen wasserfreier Ammoniak auf das ADN aufkondensiert; und/oder
  • eine Mischung aus ADN und im Wesentlichen wasserfreiem Ammoniak aufkonzentriert
wird, wobei insbesondere jeweils weitestgehend reiner Ammoniak eingesetzt und/oder die Erzeugung der ammoniakalischen ADN-Lösung beispielsweise unter Schutzgasatmosphäre durchgeführt werden kann, so dass keine Luftfeuchtigkeit von dem hygroskopischen Ammoniak aufgenommen werden kann.The production of such a gas generator fuel can be done, for example, that
  • the ADN dissolved in essentially anhydrous ammonia; and or
  • substantially anhydrous ammonia condensed on the ADN; and or
  • a mixture of ADN and substantially anhydrous ammonia concentrated
is used, in particular, in each case largely pure ammonia used and / or the generation of the ammoniacal ADN solution, for example, under a protective gas atmosphere can be performed so that no humidity can be absorbed by the hygroscopic ammonia.

Um für einen möglichst hohen spezifischen Impuls des Gasgenerator-Treibstoffes zu sorgen, kann in weiterhin vorteilhafter Ausgestaltung vorgesehen sein, dass er wenigstens etwa 70 Mass.-%, insbesondere wenigstens etwa 75 Mass.-%, ADN, beispielsweise zwischen etwa 75 Mass.-% und etwa 80 bis etwa 85 Mass.-% ADN, jeweils bezogen auf die Mischung aus ADN und Lösungsmittel, enthält. Zur Herstellung eines solchen Gasgenerator-Treibstoffes kann beispielsweise vorgesehen sein, dass das ADN mit einem Anteil von wenigstens 70 Mass.-%, insbesondere von wenigstens 75 Mass.-%, in - vorzugweise weitestgehend reinem und wasserfreiem - Ammoniak gelöst oder - vorzugweise weitestgehend reiner und wasserfreier - Ammoniak mit einem entsprechenden Anteil auf das ADN aufkondensiert bzw. "aufgepresst" wird. Es sei an dieser Stelle allerdings darauf hingewiesen, dass sich für einige Anwendungen des erfindungsgemäßen Gasgenerator-Treibstoffes, wie insbesondere für Satelliten- und Raketentreibstoffe oder für andere in der Raumfahrt Anwendung findende Treibstoffe ein maximaler Anteil an ADN von etwa 78 Mass.-%, vorzugsweise von etwa 77 Mass.-%, als günstig erweisen kann, um für moderate Abbrandtemperaturen, aber gleichwohl für eine sehr hohe Leistung zu sorgen. Bevorzugte Anteile an ADN für solche Anwendungen können folglich in der Größenordnung zwischen wenigstens etwa 65 Mass.-% bis etwa 78 Mass.-% oder vorzugsweise bis etwa 77 Mass.-%, insbesondere zwischen wenigstens etwa 70 Mass.-% bis etwa 78 Mass.-% oder vorzugsweise bis etwa 77 Mass.-%, höchst vorzugsweise zwischen wenigstens etwa 75 Mass.-% bis etwa 78 Mass.-% oder vorzugsweise bis etwa 77 Mass.-%, betragen.In order to ensure the highest possible specific impulse of the gas generator fuel, it can be provided in a further advantageous embodiment that it contains at least about 70% by mass, in particular at least about 75% by mass, of ADN, for example between about 75% by mass. % and about 80 to about 85% by mass of ADN, based in each case on the mixture of ADN and solvent. To produce such a gas generator fuel, it may be provided, for example, that the ADN is dissolved in a proportion of at least 70% by weight, in particular of at least 75% by weight, preferably largely pure and anhydrous, ammonia, or is preferably substantially pure and anhydrous - ammonia is condensed with a corresponding proportion of the ADN or "pressed" is. It should be noted at this point, however, that for some applications of the gas generator propellant of the invention, such as in particular for satellite and rocket propellants or for other aerospace application applying fuels, a maximum proportion of ADN of about 78 Mass .-%, preferably from about 77% by mass, as may prove beneficial, for moderate burning temperatures, however nevertheless to ensure a very high performance. Thus, preferred levels of ADN for such applications may be on the order of at least about 65 mass% to about 78 mass% or preferably to about 77 mass%, more preferably at least about 70 mass% to about 78 mass % or preferably to about 77 mass%, most preferably between at least about 75 mass% to about 78 mass% or preferably to about 77 mass%.

Während der erfindungsgemäße Gasgenerator-Treibstoff, wie bereits erwähnt, grundsätzlich in flüssiger Phase vorliegen kann, kann gemäß einer vorteilhaften Weiterbildung auch vorgesehen sein, dass er als gelförmiger Treibstoff vorliegt und wenigstens einen Gelbildner enthält, welcher zweckmäßigerweise in einem Anteil von etwa 0,1 Mass.-% bis etwa 10 Mass.-%, insbesondere von etwa 0,5 Mass.-% bis etwa 10 Mass.-%, jeweils bezogen auf die Gesamtmischung (d.h. auf die Gesamtmischung aus ADN, Lösungsmittel, Gelbildner und gegebenenfalls vorhandenen Additiven (siehe hierzu auch weiter unten)), vorhanden sein kann.While the gas generator propellant according to the invention, as already mentioned, may in principle be in the liquid phase, according to an advantageous development it can also be provided that it is present as a gelatinous propellant and contains at least one gelling agent, which is expediently contained in a proportion of about 0.1 mass % to about 10% by mass, in particular from about 0.5% by mass to about 10% by mass, in each case based on the total mixture (ie on the total mixture of ADN, solvent, gelling agent and optionally present additives ( see also below)), may be present.

Vorteilhafte Vertreter von geeigneten Gelbildnern umfassen Kohlenstoff-Nanoröhren einschließlich funktionalisierter Kohlenstoff-Nanoröhren, insbesondere mit funktionellen Gruppen aus der Gruppe Aminogruppen, Alkylaminogruppen und anderen funktionellen Gruppen mit einer Basenstärke größer als Ammoniak, und/oder dotierter Kohlenstoff-Nanoröhren, insbesondere stickstoffdotierte Kohlenstoff-Nanoröhren, wie beispielsweise CN2-Nanoröhren. Die Kohlenstoff-Nanoröhren ("carbon nanotubes") können als einwandige (single wall), doppelwandige (double wall) oder mehrwandige (multi wall) Nanoröhren und/oder in Form von modifizierten, Seitengruppen aufweisenden Kohlenstoff-Nanoröhren eingesetzt werden.Advantageous representatives of suitable gelling agents include carbon nanotubes including functionalized carbon nanotubes, in particular having functional groups from the group of amino groups, alkylamino groups and other functional groups having a base strength greater than ammonia, and / or doped carbon nanotubes, in particular nitrogen-doped carbon nanotubes, such as CN 2 nanotubes. The carbon nanotubes can be used as single-walled, double-walled or multi-walled nanotubes and / or in the form of modified side-group carbon nanotubes.

Die vorgenannten funktionellen Gruppen solcher Kohlenstoff-Nanoröhren können sich in dem Gasgenerator-Treibstoff zu energetischen ionischen Flüssigkeiten (EIL, energetic ionic liquids) umsetzen:

Figure imgb0001
wobei z.B. n eine Zahl zwischen 0 und 6 ist und R1, R2 aus der Gruppe Wasserstoff (-H), Alkylgruppen mit 1 bis 6 Kohlenstoffatomen, Allyl-, Vinyl-, Hydroxyalkyl-, Ether-, Cyanoalkyl-, Azidoalkyl- und Nitromethylgruppen gewählt sind.The above-mentioned functional groups of such carbon nanotubes can be converted into energetic ionic liquids (EIL) in the gas generator fuel:
Figure imgb0001
 where, for example, n is a number between 0 and 6 and R 1 , R 2 are selected from the group consisting of hydrogen (-H), alkyl groups having 1 to 6 carbon atoms, allyl, vinyl, hydroxyalkyl, ether, cyanoalkyl, azidoalkyl and Nitromethyl groups are selected.

Weitere Vertreter von vorteilhaften Gelbildnern umfassen pulverförmige Metalle, Halbmetalle, Metalloxide und/oder Halbmetalloxide, insbesondere auf der Basis von Silicium, wie beispielsweise unter dem Handelsnamen "Aerosil" (Evonik Industries) erhältliche pyrogene Kieselsäure. Die Partikelgröße derartiger pulverförmiger Metalle oder Metalloxide beträgt vorzugsweise zwischen etwa 1 nm und etwa 10 µm, insbesondere zwischen etwa 1 nm und etwa 1 µm.Further representatives of advantageous gelling agents include powdered metals, semimetals, metal oxides and / or semi-metal oxides, in particular based on silicon, such as, for example, available under the trade name "Aerosil" ( Evonik Industries ) fumed silica. The particle size of such powdered metals or metal oxides is preferably between about 1 nm and about 10 μm, in particular between about 1 nm and about 1 μm.

Weitere Vertreter von vorteilhaften Gelbildnern umfassen OH-funktionalisierte, wie insbesondere alkoholische Gelbildner, insbesondere auf der Basis von energetischen Di- und/oder Triolen, wie beispielsweise Glycidyl-Azid-Polymer-Diole (GAP-Diole), sowie polymere Gelbildner, insbesondere mit Stickstoff enthaltenden funktionellen Gruppen, wie auf Isocyanat- und/oder Harnstoffbasis, einschließlich Triazin-Polymeren und polymeren Harnstoffurethanen. Vertreter von geeigneten Harnstoffurethanen sind z.B. aus der DE 199 19 482 A1 sowie DE 102 41 853 A1 bekannt.Further representatives of advantageous gel formers include OH-functionalized, in particular alcoholic gelling agents, in particular based on energetic di- and / or triols, such as glycidyl azide polymer diols (GAP diols), as well as polymeric gelling agents, especially with nitrogen-containing functional groups, such as isocyanate and / or urea-based, including triazine polymers and polymeric urea urethanes. Representatives of suitable urea-urethane are eg from the DE 199 19 482 A1 such as DE 102 41 853 A1 known.

Weitere Vertreter von vorteilhaften Gelbildnern umfassen Lösungen von Harnstoffurethanen, welche durch Umsetzung von Mono-, Di- und/oder Polyalkoholen, insbesondere von energetischen Monoalkoholen und/oder Diolen, wie beispielsweise Nitroalkoholen, GAP-Diolen oder dergleichen, mit Diisocyanaten und anschließender Reaktion mit Mono- und/oder Diaminen bzw. Mono- und/oder Dinitraminen einschließlich Mischungen derselben erhalten worden sind, mit ionischen Flüssigkeiten (ionic liquids, IL), insbesondere mit energetischen ionischen Flüssigkeiten (energetic ionic liquids, EIL), als Lösungsmittel.Other representatives of advantageous gelling agents include solutions of urea-urethane, which by reacting mono-, di- and / or polyalcohols, especially of energetic monoalcohols and / or diols, such as nitro alcohols, GAP-diols or the like, with diisocyanates and subsequent reaction with mono - And / or diamines or mono- and / or dinitramines including mixtures thereof have been obtained with ionic liquids (IL), in particular with energetic ionic liquids (EIL), as a solvent.

Zur Herstellung eines solchen Geltreibstoffes wird der Gasgenerator-Treibstoff unter Zusatz eines geeigneten Gelierungsmittels bzw. Gelbildners, insbesondere der vorgenannten Art, geliert, wobei das Gelierungsmittels zweckmäßigerweise möglichst feindispers in die Mischung aus ADN und Lösungsmittel eindispergiert werden sollte, beispielsweise mittels Ultraschall und/oder Eintrag von Scherkräften, z.B. unter Einsatz entsprechender Homogenisatoren, Scheibenrührern (Dissolvern) und dergleichen.To produce such a natural fuel, the gas generator fuel is gelled with the addition of a suitable gelling agent or gelling agent, in particular of the aforementioned type, wherein the gelling agent should expediently be dispersed as finely as possible into the mixture of ADN and solvent, for example by means of ultrasound and / or entry of shear forces, eg using appropriate homogenizers, Scheibenrührern (dissolvers) and the like.

Alternativ oder zusätzlich zu einem Einsatz von Gelierungsmitteln kann vorgesehen sein, dass der Gasgenerator-Treibstoff zur weiteren Verbesserung seiner Tieftemperatureigen-Schäften, wie insbesondere zur Erniedrigung seines Schmelz- bzw. Erstarrungspunktes, wenigstens ein Additiv aus der Gruppe der

  • Diaminoharnstoffe,
  • Oxalhydrazine,
  • Acetamide,
  • N-Guanylharnstoffsalze,
  • Hydrazodicarbonamide,
  • Amine, insbesondere mit einer höheren Basenstärke als Ammoniak (d.h. mit einem pKb-Wert kleiner als der von Ammoniak),
  • stickstoffhaltigen Heterocyclen, insbesondere aus der Gruppe der Pyrazole, Imidazole, Triazole, Tetrazine und Oxadiazole, mit wenigstens einer der Strukturformeln
    Figure imgb0002
    Figure imgb0003
     enthält, wobei R, R1, R2, R3, R4 aus der Gruppe der Alkylreste mit einem bis sechs Kohlenstoffatomen, Allyl-, Vinyl-, Hydroxyalkyl-, Ether-, Cyanoalkyl-, Azidoalkyl-, Nitromethyl-, Amino-, Aminoalkylgruppen und Wasserstoff gewählt ist, einschließlich Pyridin, Pyrrol und deren Derivate,
  • ionischen Flüssigkeiten (IL), insbesondere mit einem Dinitramid-Anion,
enthält. Geeignete Anteile derartiger Additive zur Schmelzpunktverringerung betragen zwischen etwa 0,05 Mass.-% bis etwa 10 Mass.-%, insbesondere von etwa 0,1 Mass.-% bis etwa 5 Mass.-%, jeweils bezogen auf die Gesamtmischung, (d.h. auf die Gesamtmischung aus ADN, Lösungsmittel, dem Additiv zur Verbesserung der Tieftemperatureigenschaften sowie gegebenenfalls vorhandenem Gelbildner (siehe hierzu weiter oben)).Alternatively or in addition to the use of gelling agents, it may be provided that the gas generator fuel is used to further improve its low-temperature shafts, as in particular for lowering its melting or solidification point, at least one additive from the group of
  • Diaminoharnstoffe,
  • Oxalhydrazine,
  • acetamides
  • N-Guanylharnstoffsalze,
  • Hydrazodicarbonamide,
  • Amines, in particular having a higher base strength than ammonia (ie having a pK b value less than that of ammonia),
  • nitrogen-containing heterocycles, in particular from the group of the pyrazoles, imidazoles, triazoles, tetrazines and oxadiazoles, having at least one of the structural formulas
    Figure imgb0002
    Figure imgb0003
     where R, R 1 , R 2 , R 3 , R 4 is selected from the group of alkyl radicals having one to six carbon atoms, allyl, vinyl, hydroxyalkyl, ether, cyanoalkyl, azidoalkyl, nitromethyl, amino, , Aminoalkyl groups and hydrogen, including pyridine, pyrrole and their derivatives,
  • ionic liquids (IL), in particular with a dinitramide anion,
contains. Suitable proportions of such additives for melting point reduction are between about 0.05 mass% to about 10 mass%, in particular from about 0.1 mass% to about 5 mass%, in each case based on the total mixture, (ie on the total mixture of ADN, solvent, the additive for improving the low temperature properties and optionally present Gelling agent (see above)).

Aufgrund ihrer hervorragenden Löslichkeit mit in Ammoniak gelöstem ADN erweisen sich insbesondere ionische Flüssigkeiten mit Dinitramid-Anionen als besonders bevorzugte Additive zur Schmelzpunktverringerung, wobei geeignete Kationen solcher ionischer Flüssigkeiten beispielsweise durch N-Quarternisierung entsprechender Stickstoffverbindungen erhalten werden können. Dies kann beispielsweise durch Protonierung und/oder Alkylierung der vorgenannten stickstoffhaltigen heterocyclischen Verbindungen geschehen, um hieraus ein Kation zu erzeugen. Besonders vorteilhafte ionische Flüssigkeiten stellen dabei beispielsweise 1,4,5-Trimethyltetrazolium-Dinitramid, 1-(2-Hydroxyethyl)-4,5-dimethyltetrazolium-Dinitramid, 1-(2-Hydroxyethyl)-4-methyl-5-aminotetrazolium-Dinitramid und 1-(2-Hydroxyethyl)-3-methyl-1,2,3-triazolium-Dinitramid einschließlich Isomerengemischen der vorgenannten ionischen Flüssigkeiten, Diaminoharnstoff-Dinitramid, Oxalhydrazinium-Dinitramid, 2-Hydroxyethylhydrazinium-Dinitramid, 2-Hyxdroxyethylammonium-Dinitramid, 2-Azidoethylammonium-Dinitramid, Ethylammonium-Dinitramid und dergleichen dar. Hierunter erweisen sich aufgrund ihrer vorteilhaften Sauerstoffbilanz insbesondere energetische ionische Flüssigkeiten (EIL) als besonders geeignet, wie beispielsweise Ethylammonium-Dinitramid mit einer Sauerstoffbilanz von -42,1%. Der Einsatz von protischen ionischen Flüssigkeiten, welche auf einem basischeren Amin basieren als der als Lösungsmittel für das ADN verwendete Ammoniak, bietet im Übrigen ferner die Möglichkeit, das entsprechende freie Amin direkt der Gasgenerator-Treibstoffmischung zuzusetzen und die jeweilige (energetische) ionische Flüssigkeit auf diese Weise in situ zu erzeugen:

Figure imgb0004
Due to their excellent solubility with dissolved in ammonia ADN, ionic liquids with dinitramide anions prove to be particularly preferred additives for melting point reduction, whereby suitable cations of such ionic liquids can be obtained for example by N-quaternization of corresponding nitrogen compounds. This can be done, for example, by protonation and / or alkylation of the aforementioned nitrogen-containing heterocyclic compounds to produce a cation therefrom. Particularly advantageous ionic liquids are, for example, 1,4,5-trimethyltetrazolium dinitramide, 1- (2-hydroxyethyl) -4,5-dimethyltetrazolium dinitramide, 1- (2-hydroxyethyl) -4-methyl-5-aminotetrazolium dinitramide and 1- (2-hydroxyethyl) -3-methyl-1,2,3-triazolium dinitramide, including isomeric mixtures of the foregoing ionic liquids, diamino urea dinitramide, oxalhydrazine dinitramide, 2-hydroxyethyl hydrazinium dinitramide, 2-hydroxydiethylammonium dinitramide, 2 These include, on the basis of their advantageous oxygen balance, especially energetic ionic liquids (EIL), such as ethylammonium dinitramide with an oxygen balance of -42.1%. The use of protic ionic liquids based on a more basic amine than the solvent for The ADN used ammonia, moreover, also offers the possibility of adding the corresponding free amine directly to the gas generator fuel mixture and to generate the respective (energetic) ionic liquid in this way in situ:
Figure imgb0004

Der Zusatz von 1,4 Mass.-% 2-Hydroxyethylhydrazinium-Dinitramid (HEHDN) zu einem monergolischen Gasgenerator-Treibstoff aus etwa 75 Mass.-% ADN und etwa 23 Mass.-% Ammoniak (± 3 Mass.-%) gemäß Fig. 2 bewirkt beispielsweise eine Verringerung seines Schmelz- bzw. Erstarrungspunktes um 5°C von etwa -31°C auf etwa -36°C.The addition of 1.4% by weight of 2-hydroxyethylhydrazinium dinitramide (HEHDN) to a monergous gas generator propellant of about 75% by weight of ADN and about 23% by weight of ammonia (± 3% by weight) according to Fig. 2 causes, for example, a reduction in its melting or freezing point by 5 ° C from about -31 ° C to about -36 ° C.

Darüber hinaus ist grundsätzlich auch die Zugabe von ionischen Flüssigkeiten bzw. Salzen mit anderen Anionen als Dinitramid zur Schmelzpunkterniedrigung möglich, wobei im Hinblick auf die Sauerstoffbilanz insbesondere sauerstoffreiche Anionen von Vorteil sind, welche eine hohe Löslichkeit in dem erfindungsgemäße als Lösungsmittel eingesetzten Ammoniak besitzen, wie beispielsweise Anionen aus der Gruppe der Nitrate, Perchlorate, Formiate und Azolate, insbesondere mit Nitro- und/oder Nitramin-Substituenten, wie beispielsweise 3,5-Dinitro-1,2,4-triazolat, 5-Nitro-1,2,3,4-tetrazolat, 3,4,5-Trinitropyrazolat, 5,5'-Dinitramin-3,3'-bis(1,2,4-triazol), 1,2,4-Triazolat einschließlich deren N-Oxid-Derivaten und dergleichen. Weitere Beispiele für vorteilhafte heterocyclische Anionen von geeigneten ionischen Flüssigkeiten bzw. Salzen umfassen

Figure imgb0005
Nachstehend sind Ausführungsbeispiele von erfindungsgemäßen monergolischen Gasgenerator-Treibstoffen mit verschiedenen Anteilen an Ammoniumdinitramid wiedergegeben.In addition, the addition of ionic liquids or salts with anions other than dinitramide to lower the melting point is possible in principle, in particular oxygen-rich anions are in view of the oxygen balance of advantage, which have a high solubility in the novel ammonia used as a solvent, such as Anions from the group of nitrates, perchlorates, formates and azolates, in particular with nitro and / or nitramine substituents, such as 3,5-dinitro-1,2,4-triazolate, 5-nitro-1,2,3, 4-tetrazolate, 3,4,5-trinitropyrazolate, 5,5'-dinitramine-3,3'-bis (1,2,4-triazole), 1,2,4-triazolate including their N-oxide derivatives and like. Other examples of advantageous heterocyclic anions of suitable ionic liquids or salts include
Figure imgb0005
 Embodiments of monergolic gas generator propellants according to the present invention having various proportions of ammonium dinitramide are shown below.

Beispiel 1:Example 1:

  • 75,0 Mass.-% ADN,75.0% by mass of ADN,
  • 25,0 Mass.-% NH3.25.0 mass% NH 3 .
  • Sauerstoffbilanz: -15,88%
    Massenspez. Impuls (I sp , frz equilibrium 70:1): 2464 Ns/kg Vol.spez. Impuls (I sp vol, frz equilibrium 70:1): 3195 Ns/dm3 Spez. Impuls Vakuum (I sp vac, frz equilibrium 70:0): 2641 Ns/kg     Oxygen balance : -15.88%
    Massenspez. Pulse (I sp , frz equilibrium 70: 1): 2464 Ns / kg Vol.spez. Pulse (I sp vol, fast equilibrium 70: 1): 3195 Ns / dm 3 spec. Pulse vacuum (I sp vac, frz equilibrium 70: 0): 2641 Ns / kg

Die Abbrandtemperatur beträgt 2377°K bei einem Brennkammerdruck von 70 bar (Expansion gegen Umgebungsdruck); die Abgaszusammensetzung beträgt etwa 44 Mass.-% Wasser (H2O), etwa 54 Mass.-% Stickstoff (N2) und etwa 2 Mass.-% Wasserstoff (H2). Die Abgaszusammensetzung kann z.B. direkt einer Wasserstoff-Brennstoffzelle als Brennstoff aufgegeben werden.The burnup temperature is 2377 ° K at a combustion chamber pressure of 70 bar (expansion against ambient pressure); the exhaust gas composition is about 44 mass% water (H 2 O), about 54 mass% nitrogen (N 2 ) and about 2 mass% hydrogen (H 2 ). For example, the exhaust gas composition may be fed directly to a hydrogen fuel cell as a fuel.

Beispiel 2:Example 2:

  • 68,0 Mass.-% ADN,68.0% by mass of ADN,
  • 32,0 Mass.-% NH3.32.0 mass% NH 3 .
  • Sauerstoffbilanz: -27,55%
    Massenspez. Impuls (I sp , frz equilibrium 70:1): 2339 Ns/kg Vol.spez. Impuls (I sp vol, frz equilibrium 70:1): 2810 Ns/dm3 Spez. Impuls Vakuum (I sp vac, frz equilibrium 70:0): 2500 Ns/kg     Oxygen balance : -27.55%
    Massenspez. Pulse (I sp , frz equilibrium 70: 1): 2339 Ns / kg Vol.spez. Pulse (I sp vol, frz equilibrium 70: 1): 2810 Ns / dm 3 spec. Pulse vacuum (I sp vac, frz equilibrium 70: 0): 2500 Ns / kg

Die Abbrandtemperatur beträgt 1985°K bei einem Brennkammerdruck von 70 bar (Expansion gegen Umgebungsdruck); die Abgaszusammensetzung beträgt etwa 40 Mass.-% Wasser (H2O), etwa 56 Mass.-% Stickstoff (N2) und etwa 4 Mass.-% Wasserstoff (H2). Die Abgaszusammensetzung kann z.B. gleichfalls direkt einer Wasserstoff-Brennstoffzelle als Brennstoff aufgegeben werden.The burnup temperature is 1985 ° K at a combustion chamber pressure of 70 bar (expansion against ambient pressure); the exhaust gas composition is about 40 mass% water (H 2 O), about 56 mass% nitrogen (N 2 ) and about 4 mass% hydrogen (H 2 ). For example, the exhaust gas composition may also be fed directly to a hydrogen fuel cell as a fuel.

Beispiel 3 (nicht erfindungsgemäß) :Example 3 (not according to the invention):

64,0 Mass.-%64.0 mass% ADN,ADN, 16,5 Mass.-%16.5 mass% NH3 (entsprechend einem Anteil von 79,5 Mass.-% ADN bezogen auf die Mischung bzw. den Mischungsanteil aus ADN und Ammoniak als einzigem Lösungsmittel),NH 3 (corresponding to a proportion of 79.5% by mass of ADN based on the mixture or the mixing ratio of ADN and ammonia as sole solvent), 3,0 Mass.-%3.0% by mass 1,4,5-Trimethyltetrazolium-Dinitramid als Additiv zur Absenkung des Erstarrungspunktes,1,4,5-trimethyltetrazolium dinitramide as an additive for lowering the solidification point, 0,5 Mass.-%0.5 mass% multi wall Kohlenstoff-Nanoröhren (MWCNT) als Gelierungsmittel,multi wall carbon nanotubes (MWCNT) as gelling agent, 2,0 Mass.-%2.0 mass% GAP-Diol als weiteres Gelierungsmittel undGAP-diol as a further gelling agent and 14,0 Mass.-%14.0 mass% Aluminiumpulver mit PTFE gecoatet (anteilig: 12,9 Mass.-% Al und 1,1 Mass.-% PTFE).Aluminum powder coated with PTFE (proportional: 12.9 mass% Al and 1.1 mass% PTFE).

  • Sauerstoffbilanz: -24,19% Oxygen balance : -24.19%
  • Massenspez. Impuls (I sp , frz equilibrium 70:1): 2679 Ns/kg Vol.spez. Impuls (I sp vol, frz equilibrium 70:1): 3938 Ns/dm3 Spez. Impuls Vakuum (I sp vac, frz equilibrium 70:0): 2879 Ns/kg Abbrandtemperatur: 3103°K bei einem Brennkammerdruck von 70 bar (Expansion gegen Umgebungsdruck). Massenspez. Pulse (I sp , frz equilibrium 70: 1): 2679 Ns / kg Vol.spez. Pulse (I sp vol, frz equilibrium 70: 1): 3938 Ns / dm 3 spec. Pulse vacuum (I sp vac, frz equilibrium 70: 0): 2879 Ns / kg burning temperature: 3103 ° K at a combustion chamber pressure of 70 bar ( Expansion against ambient pressure).
Beispiel 4 (nicht erfindungsgemäß) : Example 4 (not according to the invention) :

58,0 Mass.-%58.0 mass% ADN,ADN, 15,0 Mass.-%15.0 mass% NH3 (entsprechend einem Anteil von 79,5 Mass.-% ADN bezogen auf die Mischung bzw. den Mischungsanteil aus ADN und Ammoniak als einzigem Lösungsmittel),NH 3 (corresponding to a proportion of 79.5% by mass of ADN based on the mixture or the mixing ratio of ADN and ammonia as sole solvent), 3,0 Mass.-%3.0% by mass 1,4,5-Trimethyltetrazolium-Dinitramid als Additiv zur Absenkung des Erstarrungspunktes,1,4,5-trimethyltetrazolium dinitramide as an additive for lowering the solidification point, 0,5 Mass.-%0.5 mass% multi wall Kohlenstoff-Nanoröhren (MWCNT) als Gelierungsmittel,multi wall carbon nanotubes (MWCNT) as gelling agent, 2,0 Mass.-%2.0 mass% GAP-Diol als weiteres Gelierungsmittel undGAP-diol as a further gelling agent and 21,5 Mass.-%21.5 mass% Aluminiumpulver mit PTFE gecoatet (anteilig: 19,8 Mass.-% Al und 1,7 Mass.-% PTFE).Aluminum powder coated with PTFE (proportional: 19.8 mass% Al and 1.7 mass% PTFE).

  • Sauerstoffbilanz: -29,95% Oxygen balance : -29.95%
  • Massenspez. Impuls (I sp , frz equilibrium 70:1): 2722 Ns/kg Vol.spez. Impuls (I sp vol, frz equilibrium 70:1): 4162 Ns/dm3 Spez. Impuls Vakuum (I sp vac, frz equilibrium 70:0): 2958 Ns/kg Abbrandtemperatur: 3349°K bei einem Brennkammerdruck von 70 bar (Expansion gegen Umgebungsdruck). Massenspez. Pulse (I sp , frz equilibrium 70: 1): 2722 Ns / kg Vol.spez. Pulse (I sp vol, frz equilibrium 70: 1): 4162 Ns / dm 3 spec. Pulse vacuum (I sp vac, frz equilibrium 70: 0): 2958 Ns / kg burning temperature: 3349 ° K at a combustion chamber pressure of 70 bar ( Expansion against ambient pressure).
Beispiel 5 (nicht erfindungsgemäß) : Example 5 (not according to the invention) :

63,0 Mass.-%63.0 mass% ADN,ADN, 15,5 Mass.-%15.5 mass% NH3 (entsprechend einem Anteil von ca. 80 Mass.-% ADN bezogen auf die Mischung bzw. den Mischungsanteil aus ADN und Ammoniak als einzigem Lösungsmittel),NH 3 (corresponding to a proportion of about 80% by mass of ADN based on the mixture or the mixing ratio of ADN and ammonia as sole solvent), 2,5 Mass.-%2.5 mass% Ethanolamin zur in situ Erzeugung von Ethanolammonium-Dinitramid (entsprechend der Gleichgewichtsreaktion mit Dinitramid-Anionen im Überschuss) als Additiv zur Absenkung des Erstarrungspunktes,Ethanolamine for in situ production of ethanolammonium dinitramide (corresponding to the equilibrium reaction with dinitramide anions in excess) as an additive for lowering the solidification point, 0,5 Mass.-%0.5 mass% multi wall Kohlenstoff-Nanoröhren (MWCNT) als Gelierungsmittel,multi wall carbon nanotubes (MWCNT) as gelling agent, 2,0 Mass.-%2.0 mass% GAP-Diol als weiteres Gelierungsmittel undGAP-diol as a further gelling agent and 16,5 Mass.-%16.5 mass% Aluminiumpulver mit PTFE gecoatet (anteilig: 15,2 Mass.-% Al und 1,3 Mass.-% PTFE).Aluminum powder coated with PTFE (proportional: 15.2 mass% Al and 1.3 mass% PTFE).

  • Sauerstoffbilanz: -27,54% Oxygen balance : -27.54%
  • Massenspez. Impuls (I sp , frz equilibrium 70:1): 2685 Ns/kg Vol.spez. Impuls (I sp vol, frz equilibrium 70:1): 3986 Ns/dm3 Spez. Impuls Vakuum (I sp vac, frz equilibrium 70:0): 2907 Ns/kg Abbrandtemperatur: 3126°K bei einem Brennkammerdruck von 70 bar (Expansion gegen Umgebungsdruck). Massenspez. Pulse (I sp , frz equilibrium 70: 1): 2685 Ns / kg Vol.spez. Pulse (I sp vol, fast equilibrium 70: 1): 3986 Ns / dm 3 spec. Pulse vacuum (I sp vac, frz equilibrium 70: 0): 2907 Ns / kg burning temperature: 3126 ° K at a combustion chamber pressure of 70 bar ( Expansion against ambient pressure).

Claims (15)

  1. Liquid or gel-like gas generator fuel, consisting of
    - a monergolic fuel based on ammonium dinitramide (ADN);
    - at least one solvent, wherein at least one solvent is formed by ammonia (NH3),
    wherein the gas generator fuel contains at least 65% by mass of ADN and not more than 5% by mass of water, in each case based on the mixture of ADN and solvent; and
    - optionally at least one gelling agent in a content of up to 10% by mass based on the total mixture; and
    - optionally at least one additive for improving the low temperature properties of said fuel.
  2. Gas generator fuel according to claim 1, characterized in that it contains not more than 4% by mass of water, in particular not more than 3% by mass of water, preferably not more than 2% by mass of water, in each case based on the mixture of ADN and solvent.
  3. Gas generator fuel according to claim 1 or 2, characterized in that it is substantially free from carbon-containing solvents.
  4. Gas generator fuel according to any of claims 1 to 3, characterized in that it contains substantially exclusively ammonia as a solvent.
  5. Gas generator fuel according to any of claims 1 to 4, characterized in that it contains at least 70% by mass, in particular at least 75% by mass, of AND, in each case based on the mixture of ADN and solvent.
  6. Gas generator fuel according to any of claims 1 to 5, characterized in that it is in the form of a gel-like fuel and the at least one gelling agent is selected from the group of
    - carbon nanotubes including functionalized and/or doped carbon nanotubes,
    - pulverulent metals, metalloids, metal oxides and/or metalloid oxides, in particular based on silicon,
    - OH-functional gelling agents, in particular based on energetic di- and/or triols, such as glycidyl azide polymer diols (GAP diols),
    - polymeric gelling agents, in particular comprising nitrogen-containing functional groups, such as isocyanate-based and/or urea-based functional groups, including triazine polymers and polymeric urea urethanes, and
    - solutions of urea urethanes obtained by reaction of mono-, di- and/or polyalcohols, in particular of energetic monoalcohols and/or diols, with diisocyanates and subsequent reaction with mono- and/or diamines or mono- and/or dinitramines including mixtures thereof, with ionic liquids (IL), in particular with energetic ionic liquids (EIL), as solvent.
  7. Gas generator fuel according to claim 6, characterized in that it contains as gelling agent
    - functionalized carbon nanotubes comprising functional groups selected from the group of amino groups, alkylamino groups and other functional groups having a basicity greater than ammonia and/or
    - nitrogen-doped carbon nanotubes.
  8. Gas generator fuel according to any of claims 1 to 7, characterized in that the at least one additive for improving the low temperature properties of said fuel is selected from the group of
    - diaminoureas,
    - oxalhydrazines,
    - acetamides,
    - N-guanylurea salts,
    - hydrazodicarbonamides
    - amines, in particular having a higher basicity than ammonia,
    - nitrogen-containing heterocycles, in particular selected from the group of pyrazoles, imidazoles, triazoles, tetrazines and oxadiazoles, having at least one of the structural formulae
    Figure imgb0008
    Figure imgb0009
     wherein R, R1, R2, R3, R4 are selected from the group of alkyl radicals comprising one to six carbon atoms, allyl, vinyl, hydroxyalkyl, ether, cyanoalkyl, azidoalkyl, nitromethyl, amino and aminoalkyl groups and hydrogen, including pyridine, pyrrole and derivatives thereof,
    - ionic liquids (IL), in particular comprising a dinitramide anion.
  9. Gas generator fuel according to claim 8, characterized in that the contents of the additives for improving the low temperature properties of said fuel are between 0.05% by mass and 10% by mass, in particular between 0.1% by mass and 5% by mass, in each case based on the total mixture.
  10. Process for producing a liquid or gel-like gas generator fuel consisting of
    - a monergolic fuel based on ammonium dinitramide (ADN);
    - at least one solvent, wherein at least one solvent is formed by ammonia (NH3);
    - optionally at least one gelling agent; and
    - optionally at least one additive for improving the low temperature properties of said fuel,
    according to any of claims 1 to 9, wherein the process comprises at least one of the process steps from the group of
    - dissolving ADN in ammonia with a content of ADN of at least 65% by mass of ADN;
    - condensing ammonia onto ADN with a content of ADN of at least 65% by mass; and
    - concentrating a mixture of ADN and ammonia to a content of ADN of at least 65% by mass,
    in each case based on the mixture of ADN and ammonia; and wherein
    - the gas generator fuel is optionally gelled by adding to it the at least one gelling agent in a content of up to 10% by mass based on the total mixture; and
    - the gas generator fuel is optionally admixed with the at least one additive for improving the low temperature properties of said fuel.
  11. Process according to claim 10, characterized in that
    - the ADN is dissolved in substantially anhydrous ammonia; and/or
    - substantially anhydrous ammonia is condensed onto the ADN; and/or
    - a mixture of ADN and substantially anhydrous ammonia is concentrated.
  12. Process according to claim 10 or 11, characterized in that the ADN is employed in a content of at least 70% by mass, in particular of at least 75% by mass, based on the mixture of ADN and ammonia.
  13. Process according to any of claims 10 to 12, characterized in that the gas generator fuel is gelled, wherein at least one gelling agent according to claim 6 or 7 is employed to it.
  14. Process according to any of claims 10 to 13, characterized in that the gas generator fuel is admixed with at least one additive for improving the low temperature properties of said fuel according to claim 8.
  15. Process according to claim 14, characterized in that the gas generator fuel is admixed with contents of the additives for improving the low temperature properties of said fuel according to Claim 8 between 0.05% by mass and 10% by mass, in particular between 0.1% by mass and 5% by mass, in each case based on the total mixture.
EP15003111.0A 2014-11-06 2015-10-30 Gas generator fuel based on ammonium dinitramide (adn) and method for producing the same Active EP3018112B1 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE102014016299.0A DE102014016299A1 (en) 2014-11-06 2014-11-06 Ammonium dinitramide based gas generator fuel (ADN) and process for its preparation

Publications (2)

Publication Number Publication Date
EP3018112A1 EP3018112A1 (en) 2016-05-11
EP3018112B1 true EP3018112B1 (en) 2019-07-03

Family

ID=54557197

Family Applications (1)

Application Number Title Priority Date Filing Date
EP15003111.0A Active EP3018112B1 (en) 2014-11-06 2015-10-30 Gas generator fuel based on ammonium dinitramide (adn) and method for producing the same

Country Status (2)

Country Link
EP (1) EP3018112B1 (en)
DE (1) DE102014016299A1 (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB201908786D0 (en) * 2019-06-19 2019-07-31 Spex Oil & Gas Ltd Downhole tool with fuel system
DE102020122337A1 (en) 2020-08-26 2022-03-03 LabOrbital GmbH Hot gas generating device with monergolic ionic fuel and low voltage ignition
CN114768873A (en) * 2022-04-15 2022-07-22 西北大学 Application of Fe-based metal organic framework material as combustion catalyst
CN116947576A (en) * 2022-04-20 2023-10-27 北京理工大学 Simple preparation method of polyhedral oligomeric silsesquioxane coated dinitramide ammonium

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3024595A (en) * 1959-01-07 1962-03-13 Pittsburgh Plate Glass Co Method of rocket propulsion using liquid ammonia and ammonium perchlorate
US5714714A (en) * 1992-10-15 1998-02-03 The United States Of America As Represented By The Secretary Of The Navy Process for preparing ammonium dinitramide
US6254705B1 (en) * 1999-02-26 2001-07-03 Svenska Rymdaktiebolaget Liquid propellant
DE19919482C2 (en) 1999-04-29 2001-04-26 Byk Chemie Gmbh Process for the preparation of a thixotropic agent and its use
WO2001083305A1 (en) 2000-05-04 2001-11-08 Neato (Uk) Limited Cd labeler fixture
DE10241853B3 (en) 2002-09-09 2004-01-22 Byk-Chemie Gmbh Polymeric urea urethane as a rheology control agent and manufacturing process
WO2012166046A2 (en) 2011-06-01 2012-12-06 Ecaps Ab Low-temperature operational and storable ammonium dinitramide based liquid monopropellant blends
DE102012104087A1 (en) * 2012-05-09 2013-11-14 Bayern-Chemie Gesellschaft Für Flugchemische Antriebe Mbh Gas generator fuel
RU2516711C1 (en) * 2012-10-16 2014-05-20 Николай Евгеньевич Староверов Staroverov's rocket propellant - 15 (versions)

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number Publication date
EP3018112A1 (en) 2016-05-11
DE102014016299A1 (en) 2016-05-12

Similar Documents

Publication Publication Date Title
EP3018112B1 (en) Gas generator fuel based on ammonium dinitramide (adn) and method for producing the same
DE60003429T2 (en) FUEL COMPOSITION CONTAINING DINITRAMIDE
EP0949225B1 (en) Non-azide gas generating composition
DE69729881T2 (en) AZIDFREE GAS-CREATING COMPOSITIONS
EP2744796B1 (en) Energetic active composition comprising a dihydroxylammonium salt or diammonium salt of a bistetrazolediol
DE112005000806T5 (en) Gas generant and process for its preparation
DE112005000805T5 (en) Gas generation system
DE2350200A1 (en) EXPLOSIVE MATERIALS
DE10163978B4 (en) Gel fuel, process for its preparation and its use
DE3131445A1 (en) IMPROVED DRIVING AGENTS CONTAINING TRIAMINOGUANIDINE NITRATE
CN105601457A (en) ETN-DNT eutecticevaporate energetic material and preparation method thereof
EP1932817A1 (en) Nitratoethyl nitroamine propellant for automobile safety systems
DE19840993A1 (en) Use of a mixture of non-hygroscopic organic fuel and inorganic nitrate, chlorate or perchlorate oxidizing agent as the igniter for gas generators in safety devices, especially vehicle air-bag systems
DE112007001437T5 (en) Thermally initiated pyrotechnic compositions, use
DE102020001204A1 (en) Binder for an explosive
DE2601162C2 (en) Explosives mixture
DE112005002728T5 (en) Gas generating compositions
DE2126921C3 (en) Energy-supplying eutectic mixture suitable for the production of explosives with a low solidification point and its use
DE1771480B1 (en) Water-based explosives mixture
DE102011081254B4 (en) Energetic active material comprising a dihydroxylammonium salt or diammonium salt of a Bistetrazoldiols and processes for their preparation and use
DE202004009449U1 (en) Gas generating composition
DE102008045192A1 (en) explosive
DE977699C (en) Fuel combination for hybrid missiles
DE102012005759A1 (en) GAS-CREATING COMPOSITION
DE977941C (en) Semi-solid and solid rocket propellant

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

17P Request for examination filed

Effective date: 20160909

RBV Designated contracting states (corrected)

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20180328

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20190311

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

Ref country code: AT

Ref legal event code: REF

Ref document number: 1150810

Country of ref document: AT

Kind code of ref document: T

Effective date: 20190715

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 502015009483

Country of ref document: DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: FP

REG Reference to a national code

Ref country code: SE

Ref legal event code: TRGR

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191104

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190703

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190703

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190703

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190703

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191003

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191003

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191103

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190703

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190703

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190703

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190703

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191004

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190703

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190703

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190703

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190703

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190703

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190703

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200224

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190703

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190703

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 502015009483

Country of ref document: DE

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG2D Information on lapse in contracting state deleted

Ref country code: IS

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20191031

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20191030

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20191031

26N No opposition filed

Effective date: 20200603

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20191031

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190703

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20191031

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20191030

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190703

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190703

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20151030

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 1150810

Country of ref document: AT

Kind code of ref document: T

Effective date: 20201030

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20201030

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190703

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20231023

Year of fee payment: 9

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20231213

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20231025

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 20231025

Year of fee payment: 9

Ref country code: IT

Payment date: 20231031

Year of fee payment: 9

Ref country code: FR

Payment date: 20231023

Year of fee payment: 9

Ref country code: DE

Payment date: 20231010

Year of fee payment: 9