EP3939952A1 - Combustible solide à combustion rapide comportant un oxydant, un liant énergétique et un modificateur de combustion métallique, ainsi que son procédé de production - Google Patents

Combustible solide à combustion rapide comportant un oxydant, un liant énergétique et un modificateur de combustion métallique, ainsi que son procédé de production Download PDF

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Publication number
EP3939952A1
EP3939952A1 EP21180751.6A EP21180751A EP3939952A1 EP 3939952 A1 EP3939952 A1 EP 3939952A1 EP 21180751 A EP21180751 A EP 21180751A EP 3939952 A1 EP3939952 A1 EP 3939952A1
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EP
European Patent Office
Prior art keywords
mass
poly
solid propellant
oxidizer
adn
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.)
Pending
Application number
EP21180751.6A
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German (de)
English (en)
Inventor
Sebastian Fischer
Stefan Sims
Claudio Tagliabue
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
Original Assignee
Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
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Publication date
Application filed by Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV filed Critical Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Publication of EP3939952A1 publication Critical patent/EP3939952A1/fr
Pending legal-status Critical Current

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    • 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
    • C06D5/06—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets by reaction of two or more solids
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
    • C06B23/007—Ballistic modifiers, burning rate catalysts, burning rate depressing agents, e.g. for gas generating
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B45/00—Compositions or products which are defined by structure or arrangement of component of product
    • C06B45/04—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive
    • C06B45/06—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component
    • C06B45/10—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component the organic component containing a resin
    • C06B45/105—The resin being a polymer bearing energetic groups or containing a soluble organic explosive

Definitions

  • Fast-burning solid propellants with an oxidizer and an energetic binder of the aforementioned type are known and are also referred to as composite propellants.
  • composite propellants In contrast to propellant charges that burn off relatively slowly and especially at the lowest possible temperatures, such as those primarily used in are used in gas generators for airbags and to which coolants are often added, generic fast-burning solid propellants are characterized in that when they are ignited as a result of their combustion, a large volume of gas is released spontaneously.
  • Generic solid propellants are used in a variety of ways in both the civil and military sectors, in particular as solid propellants for spacecraft (rockets) and strategic weapon systems, as propellants for barrel weapons or as explosive systems.
  • oxidizers used are primarily oxidizer salts such as ammonium dinitramide (ADN), but also ammonium nitrate (AN), ammonium perchlorate (AP), potassium dinitramide (KDN ), potassium nitrate (KN) and hydroxylammonium nitrate (HAN).
  • ADN ammonium dinitramide
  • AN ammonium nitrate
  • AP ammonium perchlorate
  • KDN potassium dinitramide
  • KN potassium nitrate
  • HAN hydroxylammonium nitrate
  • Generic solid propellants are usually produced by introducing the powdered or particulate oxidizers into a liquid or viscous reaction mixture that can be cured to form the energetic binder matrix, after which the reaction mixture is poured, for example, and cured to form the binder, such as using di- or depending on the desired degree of crosslinking of the binder - tri- and/or polyisocyanates.
  • GAP glycidyl azide polymers
  • combustion modifiers to the solid propellant in the form of fine metal and/or or add semi-metal powders, such as in the form of aluminum, magnesium, beryllium, boron, copper, lead, etc.
  • the U.S. 2018/0179119 A1 describes a solid propellant with an oxidizer dispersed in a binder with an anion from the group of nitrates, perchlorates, chlorates, permanganates or peroxides and mixtures thereof.
  • the cation of the oxidizer is selected in particular from the group consisting of the alkali metals such as lithium, sodium, potassium, rubidium and cesium, the alkaline earth metals such as beryllium, magnesium, calcium, strontium and barium, the transition metals, ammonium and the quaternary amines, the oxidizer for example in the form of ammonium perchlorate (AP), potassium nitrate (KN) and ammonium nitrate (AN).
  • AP ammonium perchlorate
  • KN potassium nitrate
  • AN ammonium nitrate
  • the binder can be, inter alia, an energetic binder, for example one from the group of glycidyl azide polymers (GAP).
  • GAP glycidyl azide polymers
  • the known solid propellant can contain a metal, for example from the group of alkali metals, alkaline earth metals and transition metals.
  • the metal which can be added in a proportion of up to 20% by mass and serves as an electron donor and/or oxygen acceptor for the oxidation reaction, can have any geometric shape, such as spherical, rounded, cylindrical, cubic, platelets - or flaky particles or in the form of metal structures such as metal threads, rods or networks, where the surface of the metal particles is considered to be decisive for the burning rate.
  • combustion modifiers based on metals or semimetals have a high mass both compared to the oxidizer and compared to the binder, whereas the propellant weight is kept as low as possible, especially when the solid propellant is used for rockets or other missiles should.
  • the combustion modifiers occur as a solid residue - be it in the form of (semi)metal oxides or be it in the form of at least partially elementary (semi)metals - while the other fuel components are converted into gaseous and thus volatile components be able.
  • the invention is based on the object of further developing a solid propellant based on ammonium dinitramide (ADN) of the type mentioned at the outset in a simple and cost-effective manner, while at least largely avoiding the aforementioned disadvantages, such that its burning rate is increased. It is also directed to a method for producing such a solid propellant.
  • ADN ammonium dinitramide
  • the first part of this object is achieved according to the invention with a solid propellant based on ammonium dinitramide (ADN) of the type mentioned at the outset in that the at least one combustion modifier is present in the form of fibers.
  • ADN ammonium dinitramide
  • the configuration according to the invention in which the at least one erosion modifier from the group of metals and semimetals including their alloys and hydrides in the form of a plurality of fibers in the matrix of the at least one energetic binder with the incorporated therein, at least one oxidizer is dispersed in the form of ADN, leads to a significantly increased combustion rate compared to the same amount of combustion modifier in the form of essentially spherical, angular, platelet-shaped or other types of particles, it being assumed that on the one hand the high thermal conductivity of the fibrous combustion modifiers plays a role, which are able to quickly transfer the heat generated during the combustion of the solid propellant in the direction of extension of the fibers to adjacent areas of the solid propellant.
  • the (semi)metallic fiber structures have a smaller but still very large surface compared to largely spherical particles the combustion modifiers contribute to the increased combustion rate as a result of pores with an elongated pore shape that are formed during their combustion.
  • the proportion of burn-up modifier can be reduced compared to the prior art, or a higher burn-up rate can be achieved with a corresponding proportion of burn-up modifier, which would otherwise not be achievable with a generic solid propellant based on ADN according to the prior art .
  • the fibers of the at least one combustion modifier can, for example, have a substantially round, e.g.
  • circular or oval, cross section, or the fibers can, for example, also have a flat, e.g. substantially rectangular, cross section. which can lead to an even larger surface and an even better heat conduction to the surrounding energetic binder matrix, which is mixed with the at least one oxidizer in the form of ADN.
  • the fiber geometry of the combustion modifiers has proven to be particularly decisive here, whereby the fibers must not be too “short” to fulfill their function according to the invention, but must not be too “long” to avoid fiber breakage and thus avoiding impairment of the reproducibility and, in particular, ensuring controlled combustion of the fast-burning solid propellant based on ADN.
  • the cross-section of the fibers must not be too “small” for the fibers to be able to fulfill their function according to the invention, while the cross-section of the fibers must not be too “large” either, again for ease of processing of the solid propellant and in particular to ensure a controlled combustion with as few residues as possible.
  • the fibers of the at least one combustion modifier are present in the form of a plurality of loose cut fibers, so that - similar to the powdered or particulate oxidizer based on ADN -, preferably largely homogeneously, in the energetic binder matrix are dispersed.
  • the fibers of the at least one combustion modifier are present in the binder matrix in the form of a textile fabric or three-dimensional structure with a plurality of fibers, in particular from the group of fleece, knitted fabrics, scrims, crocheted fabrics or woven fabrics, with the the energetic binder matrix mixed with the powdered or particulate oxidizer based on ADN surrounds the textile fabric or spatial structure or the latter is impregnated with the energetic binder matrix mixed with the powdered or particulate oxidizer based on ADN.
  • the solid propellant can be based on of ADN preferably contain at least one erosion modifier from the group aluminum (Al), magnesium (Mg), copper (Cu), zinc (Zn) including their alloys and hydrides.
  • the at least one oxidizer in the form of ammonium dinitramide (ADN) in powder or particle form can be dispersed into the binder matrix of the fast-burning solid propellant, as is known per se from the prior art of composite propellants.
  • ADN ammonium dinitramide
  • the solid propellant according to the invention it can also be provided that it also contains at least one energetic plasticizer, which can be selected in particular from the group of nitrate esters and azido plasticizers.
  • suitable energetic plasticizers include, for example, alkyl nitratoethyl nitramine (NENA), ethylene glycol dinitrate (EGDN), metriol trinitrate (MTN), butane-1,2,4-triol trinitrate (BTTN), dinitrodiazaalkanes (DNDA), trimethylolethane trinitrate (TMETN), ethylene glycol bis -(azidoacetate) (EGBAA, also referred to as "A17”) and 1,2-bis-(2-azidoethoxy)ethane (TEGDA, also referred to as bis-azido-triethylene glycol or BATEG) including their derivatives and mixtures.
  • NENA alkyl nitratoethyl nitramine
  • the solid propellant according to the invention contains at least one further oxidizer, for example from the group of ammonium nitrate (AN), ammonium perchlorate (AP), potassium dinitramide (KDN), potassium nitrate (KN), hydroxylammonium nitrate (HAN) and the like.
  • oxidizer salts can of course also contain essentially only ADN as oxidizer.
  • At least one combustion modifier according to step (c) from the group aluminum ( Al), magnesium (Mg), copper (Cu), zinc (Zn) and their alloys and hydrides are provided.
  • the reaction mixture that can be cured to form the energetic binder also contains at least one energetic plasticizer, in particular from the group of alkyl nitratoethyl nitramine (NENA), ethylene glycol dinitrate (EGDN), metriol trinitrate (MTN), butane-1, 2,4-trioltrinitrates (BTTN), dinitrodiazaalkanes (DNDA), trimethylolethane trinitrates (TMETN), ethylene glycol bis-(azidoacetates) (EGBAA, also referred to as "A17") and 1,2-bis-( 2-azidoethoxy)ethane (TEGDA, also referred to as bis-azido-triethylene glycols or BATEG) including derivatives and mixtures thereof, is added.
  • NENA alkyl nitratoethyl nitramine
  • EGDN ethylene glycol dinitrate
  • MTN metriol trinitrate
  • BTTN but
  • step (a) essentially only ADN can be used as the oxidizer, it can also be provided that at least one further oxidizer, expediently also in powder or particle form, the at least one further oxidizer being, for example, ammonium nitrate (AN), ammonium perchlorate (AP), potassium dinitramide (KDN), potassium nitrate (KN) and hydroxylammonium nitrate (HAN) and the like.
  • AN ammonium nitrate
  • AP ammonium perchlorate
  • KDN potassium dinitramide
  • KN potassium nitrate
  • HAN hydroxylammonium nitrate
  • the metallic combustion modifiers used in identical fibrous form increase the combustion rate, as is qualitatively known as such with powdered, but otherwise identical combustion modifiers, whereby in the case of the ADN used as an oxidizer with the fibrous aluminum/magnesium alloy, a almost double the charring rate compared to the pure mixture of GAP with ADN (upper curve: "- ⁇ -”), while the charring rate for fibrous copper (second-lowest curve: "- ⁇ -”) and for fibrous brass (second-top curve: " ”) at 7 bar is increased by about 30% in the case of the Brass alloy but increases more with increasing pressure.
  • a solid propellant was produced in the above manner from again 67% by mass of ADN, 30% by mass of GAP and 3% by mass of a combustion modifier from the same aluminum/magnesium alloy as is shown in the middle curve of FIG 3 (" ") has been used in particle form, but the combustion modifier in the form of chopped fibers with an average fiber cross-section of 90 ⁇ m and an average fiber length of 1 mm, corresponding to a ratio the average fiber length to the average fiber cross-section of about 11.1, have been used (upper curve of the 3 : "- ⁇ -").
  • the proportion of (semi)metallic combustion modifiers in the solid propellant according to the invention can be significantly reduced purely due to the geometry of its fiber shape compared to particulate combustion modifiers of the prior art, which is accompanied by a corresponding weight saving and a reduction in solid combustion residues, or it can be corresponding proportion of fibrous combustion modifier compared to the same particulate combustion modifier of the prior art, a significantly higher combustion rate can be achieved, which would otherwise not be achievable with a generic solid propellant according to the prior art.
  • a significant increase in the burning rate of the solid propellant already occurs at a ratio of average fiber length to average fiber cross section or diameter of about 5:1, with the burning rate increasing with an increasing ratio of average fiber length to average fiber cross section or with increasing fiber length.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Molecular Biology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP21180751.6A 2020-07-17 2021-06-22 Combustible solide à combustion rapide comportant un oxydant, un liant énergétique et un modificateur de combustion métallique, ainsi que son procédé de production Pending EP3939952A1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE102020118962.1A DE102020118962A1 (de) 2020-07-17 2020-07-17 Schnellbrennender Festtreibstoff mit einem Oxidator, einem energetischen Binder und einem metallischen Abbrandmodifikator sowie Verfahren zu dessen Herstellung

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EP3939952A1 true EP3939952A1 (fr) 2022-01-19

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EP21180751.6A Pending EP3939952A1 (fr) 2020-07-17 2021-06-22 Combustible solide à combustion rapide comportant un oxydant, un liant énergétique et un modificateur de combustion métallique, ainsi que son procédé de production

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EP (1) EP3939952A1 (fr)
DE (1) DE102020118962A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115092422A (zh) * 2022-05-23 2022-09-23 中国人民解放军战略支援部队航天工程大学 一种用于激光微推力器双层靶带的供给盘制备方法及其生产装置

Citations (10)

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Publication number Priority date Publication date Assignee Title
US5498303A (en) 1993-04-21 1996-03-12 Thiokol Corporation Propellant formulations based on dinitramide salts and energetic binders
CA2322096A1 (fr) * 1999-11-08 2001-05-08 Anthony Joseph Cesaroni Compositions d'agent propulsif a base de polymere thermoplastique
US6872266B1 (en) * 2003-05-30 2005-03-29 The United States Of America As Represented By The Secretary Of The Navy Triazole crosslinked polymers in recyclable energetic compositions and method of preparing the same
US20050115651A1 (en) 2003-11-14 2005-06-02 Swift Enterprises, Ltd. High energy solid propellant
GB2504050A (en) * 1995-12-04 2014-01-22 Thiokol Corp High oxygen content explosive compositions
RU2516711C1 (ru) 2012-10-16 2014-05-20 Николай Евгеньевич Староверов Ракетное топливо староверова - 15 (варианты)
US8986473B1 (en) * 2008-09-03 2015-03-24 The United States Of America As Represented By The Secretary Of The Navy High burning rate tactical solid rocket propellant, and related method
RU2582712C2 (ru) 2014-05-13 2016-04-27 Николай Евгеньевич Староверов Ракетное топливо /варианты/
US20180179119A1 (en) 2016-12-23 2018-06-28 Superior Energy Services, Llc High Temperature Energetic Formulations
CN109206287A (zh) * 2018-03-16 2019-01-15 湖北航天化学技术研究所 一种压装型高密度富燃料推进剂及其制备方法

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US3508494A (en) 1965-05-05 1970-04-28 Thiokol Chemical Corp Solid propellants of enhanced burning rates using bimetallic fibers
US4386979A (en) 1979-07-19 1983-06-07 Jackson Jr Charles H Gas generating compositions
US5529647A (en) 1993-12-10 1996-06-25 Morton International, Inc. Gas generant composition for use with aluminum components

Patent Citations (10)

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Publication number Priority date Publication date Assignee Title
US5498303A (en) 1993-04-21 1996-03-12 Thiokol Corporation Propellant formulations based on dinitramide salts and energetic binders
GB2504050A (en) * 1995-12-04 2014-01-22 Thiokol Corp High oxygen content explosive compositions
CA2322096A1 (fr) * 1999-11-08 2001-05-08 Anthony Joseph Cesaroni Compositions d'agent propulsif a base de polymere thermoplastique
US6872266B1 (en) * 2003-05-30 2005-03-29 The United States Of America As Represented By The Secretary Of The Navy Triazole crosslinked polymers in recyclable energetic compositions and method of preparing the same
US20050115651A1 (en) 2003-11-14 2005-06-02 Swift Enterprises, Ltd. High energy solid propellant
US8986473B1 (en) * 2008-09-03 2015-03-24 The United States Of America As Represented By The Secretary Of The Navy High burning rate tactical solid rocket propellant, and related method
RU2516711C1 (ru) 2012-10-16 2014-05-20 Николай Евгеньевич Староверов Ракетное топливо староверова - 15 (варианты)
RU2582712C2 (ru) 2014-05-13 2016-04-27 Николай Евгеньевич Староверов Ракетное топливо /варианты/
US20180179119A1 (en) 2016-12-23 2018-06-28 Superior Energy Services, Llc High Temperature Energetic Formulations
CN109206287A (zh) * 2018-03-16 2019-01-15 湖北航天化学技术研究所 一种压装型高密度富燃料推进剂及其制备方法

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115092422A (zh) * 2022-05-23 2022-09-23 中国人民解放军战略支援部队航天工程大学 一种用于激光微推力器双层靶带的供给盘制备方法及其生产装置
CN115092422B (zh) * 2022-05-23 2023-03-10 中国人民解放军战略支援部队航天工程大学 一种用于激光微推力器双层靶带的供给盘制备方法及其生产装置

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