EP0002968A1 - Fragmentable propellant unit charge containing a polyvinylnitrate binder and process for making it - Google Patents

Fragmentable propellant unit charge containing a polyvinylnitrate binder and process for making it Download PDF

Info

Publication number
EP0002968A1
EP0002968A1 EP78400186A EP78400186A EP0002968A1 EP 0002968 A1 EP0002968 A1 EP 0002968A1 EP 78400186 A EP78400186 A EP 78400186A EP 78400186 A EP78400186 A EP 78400186A EP 0002968 A1 EP0002968 A1 EP 0002968A1
Authority
EP
European Patent Office
Prior art keywords
binder
weight
powder
nitrocellulose
fragmentable
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.)
Granted
Application number
EP78400186A
Other languages
German (de)
French (fr)
Other versions
EP0002968B1 (en
Inventor
Louis Leneveu
Didier Treneules
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.)
Societe Nationale des Poudres et Explosifs
Original Assignee
Societe Nationale des Poudres et Explosifs
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 Societe Nationale des Poudres et Explosifs filed Critical Societe Nationale des Poudres et Explosifs
Publication of EP0002968A1 publication Critical patent/EP0002968A1/en
Application granted granted Critical
Publication of EP0002968B1 publication Critical patent/EP0002968B1/en
Expired legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B25/00—Compositions containing a nitrated organic compound
    • C06B25/18—Compositions containing a nitrated organic compound the compound being nitrocellulose present as 10% or more by weight of the total composition
    • C06B25/20—Compositions containing a nitrated organic compound the compound being nitrocellulose present as 10% or more by weight of the total composition with a non-explosive or a non-explosive or a non-thermic component
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B25/00—Compositions containing a nitrated organic compound
    • C06B25/18—Compositions containing a nitrated organic compound the compound being nitrocellulose present as 10% or more by weight of the total composition
    • 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

  • the subject of the present invention is a fragmentable unit charge of propellant powder consisting of grains of nitrocellulose powder, agglomerated together by a solid, thermoplastic energy binder, said unit charge having the ballistic properties of a granular charge.
  • Granular charges of nitrocellulose powder are commonly used in ammunition for small and medium caliber weapons.
  • the pot life at 20 ° C. of the crosslinkable binders after addition of the catalysts is low, which limits their industrial interest.
  • nitroglycerin has a strong tendency to exude from the block, that is to say to migrate from the interior of the block towards the periphery thereof. This exudation not only causes a modification of the composition at certain points of the block, therefore a disturbance of the ballistic performance of this block, but also the tiny droplets of nitroglycerin exuded at the periphery of this block risk detonating at the slightest shock.
  • powders containing nitroglycerin are too strong and too bright and they are too erosive and do not lend themselves to the production of fragmentable charges.
  • the amount of energy binder incorporated must be low and between 3 to 15% by weight relative to the load, and preferably between 5 to 10% by weight.
  • the binder may also contain at least one additive chosen from the group comprising polymers of the ABS (acrylonitrile-butadiene-styrene) type, dinitrotoluene, cellulose acetate, phthalates, heavy esters, heterocyclic ketones (camphor) or ureas (centralite).
  • ABS acrylonitrile-butadiene-styrene
  • dinitrotoluene cellulose acetate
  • phthalates heavy esters
  • heterocyclic ketones camphor
  • ureas centralite
  • the propellant powder is a single base grain nitrocellulose powder obtained by the solvent process, called powder "B".
  • this powder B is a monotubular powder having a potential of 870 to 950 cal / g.
  • Powders with a potential greater than 950 cal / g are too strong (too strong pressure build-up), and the maximum pressures measured in the cylinder head are too strong for conventional weapons.
  • Powders having a potential of less than 870 cal / g are not strong enough (pressure build-up too slow), the maximum pressures measured in the cylinder head are too low.
  • Multitubular grain powders are difficult to compression mold in a homogeneous manner because the grains are too large, and are of no interest given the mode of disintegration of the block.
  • the mold used is a conventional compression mold comprising a mold body provided with a cylindrical axial bore forming the molding cavity, and two movable cylindrical punches, engaged respectively in the upper part and in the lower part of the molding cavity and respectively forming the matrix and the mold ejector.
  • the ejector carries an axial core extended through the molding cavity and engaged in an axial bore provided in the die.
  • the movement of the punches is controlled by jacks.
  • the heating or cooling of the mold is ensured by a circulation circuit of heating or cooling fluid.
  • the mold is prepared by coating the inside of the mold, the punches and the core with a release agent.
  • Molding The mold is heated beforehand to 120 ° C. and the powder-binder mixture produced above is loaded into the molding cavity.
  • the fragmentation of the block is correct. On the same series of 20 strokes there is a satisfactory standard deviation of 20 m / s for speed and 200 bar for pressure. The mechanical strength is good.
  • the propellant powder and the energy binder used are the same as those of Example 1, but the rate of the binder is brought to 10%.
  • the fragmentation of the block is correct and the mechanical strength of the block is good.
  • This example is intended to show the influence of the rate of binder on the ballistic characteristics of the final unit load; with a rate of binder higher than 15% the load breaks up badly and burns like a compact block.
  • the propellant powder and the energy binder used in this example are the same as those of Example 1, but the binder rate is increased to 20%.
  • Example 2 The procedure is as in Example 1, but starting from a mixture of 56 g of BTu 93 powder (0.5) smoothed with 1% centralite and 14 g of binder of composition No. 1.
  • a hollow cylindrical block with a weight of 70 g, a height of 72 mm, a diameter of 30 mm is obtained.
  • This example is intended to show the influence of the potential of the propellant powder on the characteristics of the final block.
  • a powder with a potential lower than 900 cal / g is not sufficiently lively.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Molecular Biology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Powder Metallurgy (AREA)

Abstract

Chargement unitaire fragmentable de poudre propulsive ayant les propriétés balistiques d'un chargement granulaire. Un tel chargement est constitué de: - 85 à 97% de grains de poudre propulsive à la nitrocellulose, - 15 à 3% d'un liant énergétique, thermoplastique, se présentant sous forme de petits grains solides dans les conditions normales et ayant la composition suivante: (a) 30 à 60% de nitrate de polyvinyle, (b) 70 à 40% de nitrocellulose à faible taux d'azote, ou d'acétate de polyvinyle ou un mélange des deux, (c) éventuellement un stabilisant. L'emploi d'un liant solide permet de réaliser instantanément le mélange homogène de la poudre propulsive avec ledit liant, la mise en moule de quantités précises du mélange ainsi obtenu, et de simplifier les opérations de moulage.Fragmentable unit charge of propellant powder having the ballistic properties of a granular charge. Such a load consists of: - 85 to 97% grains of nitrocellulose propellant powder, - 15 to 3% of an energetic binder, thermoplastic, in the form of small solid grains under normal conditions and having the composition following: (a) 30 to 60% of polyvinyl nitrate, (b) 70 to 40% of nitrocellulose with low nitrogen content, or polyvinyl acetate or a mixture of the two, (c) optionally a stabilizer. The use of a solid binder enables instantaneous homogeneous mixing of the propellant powder with said binder, the molding of precise quantities of the mixture thus obtained, and simplification of the molding operations.

Description

La présente invention a pour objet un chargement unitaire fragmentable de poudre propulsive constitué de grains de poudre à la nitrocellulose, agglomérés ensemble par un liant énergétique solide, thermoplastique, ledit chargement unitaire ayant les propriétés balistiques d'un chargement granulaire.The subject of the present invention is a fragmentable unit charge of propellant powder consisting of grains of nitrocellulose powder, agglomerated together by a solid, thermoplastic energy binder, said unit charge having the ballistic properties of a granular charge.

Les chargements granulaires de poudre à la nitrocellulose sont couramment utilisés dans les munitions pour armes de petits et moyens calibres.Granular charges of nitrocellulose powder are commonly used in ammunition for small and medium caliber weapons.

On a déjà proposé d'agglomérer par compression les grains de poudre à la nitrocellulose en petits blocs à l'aide d'un liant liquide non énergétique, réticulable, tel que le polyuréthanne, en vue d'augmenter la quantité de matière énergétique incorporée dans un volume donné du chargement et, éventuellement, de permettre la suppression de la douille ou de la cartouche de la munition, nécessaire dans le cas des chargements granulaires en vrac.It has already been proposed to agglomerate by compression the grains of nitrocellulose powder into small blocks using a non-energetic, crosslinkable liquid binder, such as polyurethane, in order to increase the amount of energetic material incorporated in a given volume of the load and, possibly, to allow the removal of the cartridge case or cartridge of the ammunition, necessary in the case of granular bulk loads.

Toutefois, l'emploi d'un liant réticulable pose des problèmes de fabrication et de conservation :

  • - il faut introduire dans le moule une masse constante de matière pâteuse gluante constituée par le mélange de poudre et de liant et le moindre écart de poids conduit à une variation des performances balistiques obtenues avec le bloc final ;
  • - les caractéristiques de stabilité dimensionnelle du bloc se révèlent insuffisantes dans les conditions thermiques sévères dans lesquelles ont lieu l'emploi et le stockage du bloc ; or, les caractéristiques dimensionnelles ont une influence importante sur les propriétés balistiques, et avec le liant réticulable, la stabilité dimensionnelle est mauvaise.
However, the use of a crosslinkable binder poses manufacturing and storage problems:
  • - It is necessary to introduce into the mold a constant mass of sticky pasty material consisting of the mixture of powder and binder and the slightest difference in weight leads to a variation in ballistic performance obtained with the final block;
  • - the dimensional stability characteristics of the block are revealed insufficient under the severe thermal conditions in which the use and storage of the block takes place; however, the dimensional characteristics have an important influence on the ballistic properties, and with the crosslinkable binder, the dimensional stability is poor.

Par ailleurs, dans le cas où l'on désire un cycle de compression court, la vie en pot à 20°C des liants réticulables après addition des catalyseurs est faible, ce qui limite leur intérêt industriel.Furthermore, in the case where a short compression cycle is desired, the pot life at 20 ° C. of the crosslinkable binders after addition of the catalysts is low, which limits their industrial interest.

On a également proposé d'agglomérer les grains de poudre à la nitrocellulose par de la nitroglycérine qui est un agent gélatinisant énergétique liquide de la nitrocellulose.It has also been proposed to agglomerate the grains of powder with nitrocellulose with nitroglycerin which is a liquid energizing gelatinizing agent for nitrocellulose.

Or, on sait que la nitroglycérine présente une forte tendance à s'exsuder du bloc, c'est à dire à migrer de l'intérieur du bloc vers la périphérie de celui-ci. Cette exsudation entraine non seulement une modification de la composition en certains points du bloc donc une perturbation des performances balistiques de ce bloc, mais encore les minuscules gouttelettes de nitroglycérine exsudée à la périphérie de ce bloc risquent de détoner au moindre choc. De plus, les poudres contenant de la nitroglycérine sont trop fortes et trop vives et elles sont trop érosives et ne se prêtent pas à la fabrication des chargements fragmentables.However, it is known that nitroglycerin has a strong tendency to exude from the block, that is to say to migrate from the interior of the block towards the periphery thereof. This exudation not only causes a modification of the composition at certain points of the block, therefore a disturbance of the ballistic performance of this block, but also the tiny droplets of nitroglycerin exuded at the periphery of this block risk detonating at the slightest shock. In addition, powders containing nitroglycerin are too strong and too bright and they are too erosive and do not lend themselves to the production of fragmentable charges.

La présente invention permet de remédier aux inconvénients précités. A cet effet, elle a pour objet un chargement unitaire fragmentable de poudre propulsive constitué par des grains de poudre propulsive à la nitrocellulose agglomérés ensemble par un liant énergétique, thermoplastique, se présentant sous forme de petits grains, solides dans les conditions normales de température et de pression et ayant la composition suivante :

  • (a) 30 à 60% en poids (par rapport au liant) de nitrate de polyvinyle,
  • (b) 70 à 40% en poids (par rapport au liant) de nitrocellulose ayant un taux d'azote faible, inférieur à 12,8%, ou d'acétate de polyvinyle ou un mélange des deux,
  • (c) éventuellement un stabilisant. Le stabilisant peut être avantageuse-ment la nitro-2 diphénylamine ajoutée en quantité pouvant atteindre 3% en poids par rapport au liant.
The present invention overcomes the aforementioned drawbacks. To this end, it relates to a unitary load of propellant powder which can be fragmented and consists of grains of nitrocellulose propellant powder agglomerated together by an energetic, thermoplastic binder, in the form of small grains, solid under normal temperature conditions and pressure and having the following composition:
  • (a) 30 to 60% by weight (relative to the binder) of polyvinyl nitrate,
  • (b) 70 to 40% by weight (relative to the binder) of nitrocellulose having a low nitrogen level, less than 12.8%, or of polyvinyl acetate or a mixture of the two,
  • (c) optionally a stabilizer. The stabilizer can be advantageous- ment 2-nitro diphenylamine added in an amount up to 3% by weight relative to the binder.

La quantité de liant énergétique incorporée doit être faible et comprise entre 3 à 15% en poids par rapport au chargement, et de préférence entre 5 à 10% en poids.The amount of energy binder incorporated must be low and between 3 to 15% by weight relative to the load, and preferably between 5 to 10% by weight.

C'est dans cet intervalle que l'on obtient à la fois une bonne tenue mécanique du bloc entre - 54°C et + 74°C et une bonne fragmentation du chargement au moment du tir.It is in this interval that we obtain both good mechanical strength of the block between - 54 ° C and + 74 ° C and good fragmentation of the load when fired.

Avec un taux de liant supérieur à 15%, la tenue mécanique sera bonne, mais le chargement obtenu se fragmentera mal et commencera à brûler comme un bloc compact et non plus comme un chargement en vrac.With a binder rate greater than 15%, the mechanical strength will be good, but the load obtained will fragment badly and start to burn as a compact block and no longer as a bulk load.

Avec un taux de liant inférieur à 3%, le chargement aura une mauvaise tenue mécanique à froid.With a binder rate of less than 3%, the load will have poor mechanical strength when cold.

Eventuellement, le liant peut contenir également au moins un additif choisi dans le groupe comprenant les polymères du type A B S (acrylonitrile-butadiène-styrène), le dinitrotoluène, l'acétate de cellulose, les phtalates, les esters lourds, les cétones hétéro-cycliques(camphre) ou les urées (centralite).Optionally, the binder may also contain at least one additive chosen from the group comprising polymers of the ABS (acrylonitrile-butadiene-styrene) type, dinitrotoluene, cellulose acetate, phthalates, heavy esters, heterocyclic ketones (camphor) or ureas (centralite).

Ces additifs sont destinés notamment à conférer au chargement de bonnes propriétés mécaniques.These additives are intended in particular to give the load good mechanical properties.

Selon un mode particulier de réalisation, le liant présente la composition suivante :

  • - 40 à 60 parties en poids de nitrate de polyvinyle fortement nitré (taux d'azote pouvant atteindre 15,4%),
  • - 60 à 40 parties en poids de nitrocellulose à faible taux d'azote de 11% à 12,6%,
  • - et 2 à 3 parties en poids de nitro-2 diphényl-amine.
According to a particular embodiment, the binder has the following composition:
  • - 40 to 60 parts by weight of highly nitrated polyvinyl nitrate (nitrogen content up to 15.4%),
  • - 60 to 40 parts by weight of nitrocellulose with a low nitrogen content of 11% to 12.6%,
  • - And 2 to 3 parts by weight of 2-nitro-diphenylamine.

Par ailleurs, la poudre propulsive est une poudre à la nitrocellulose en grains à simple base obtenue par le procédé avec solvant, dite poudre "B".Furthermore, the propellant powder is a single base grain nitrocellulose powder obtained by the solvent process, called powder "B".

De préférence, cette poudre B est une poudre monotubulaire ayant un potentiel de 870 à 950 cal/g.Preferably, this powder B is a monotubular powder having a potential of 870 to 950 cal / g.

Les poudres ayant un potentiel supérieur à 950 cal/g sont trop vives (trop forte montée en pression), et les pressions maximales mesurées dans la culasse sont trop fortes pour les armes usuelles.Powders with a potential greater than 950 cal / g are too strong (too strong pressure build-up), and the maximum pressures measured in the cylinder head are too strong for conventional weapons.

Les poudres ayant un potentiel inférieur à 870 cal/g ne sont pas assez vives (montée en pression trop lente), les pressions maximales mesurées dans la culasse sont trop faibles.Powders having a potential of less than 870 cal / g are not strong enough (pressure build-up too slow), the maximum pressures measured in the cylinder head are too low.

Les poudres à grains multitubulaires sont difficiles à mouler par compression d'une manière homogène car les grains sont trop gros, et ne présentent pas d'intérêt compte tenu du mode de désagrégation du bloc.Multitubular grain powders are difficult to compression mold in a homogeneous manner because the grains are too large, and are of no interest given the mode of disintegration of the block.

Les avantages que présente le liant selon l'invention sont multiples :

  • - d'une part, les ingrédients du liant sont hautement énergétiques et ne provoquent pas une baisse d'énergie comme le ferait un liant non énergétique, lors de la mise à feu du chargement ; ainsi,
  • - le nitrate de polyvinyle a un potentiel de 990 cal/g (pour une masse moléculaire moyenne de 89 et un taux d'azote de 15,4%),
  • - la nitrocellulose a un potentiel de 940 cal/g (pour un taux d'azote de 12,5%),
  • - l'acétate de polyvinyle a un potentiel de - 1088 cal/g.
  • - d'autre part, les ingrédients du liant sont à l'état solide dans les conditions normales de température et de pression, et deviennent plastiques à chaud ; ainsi, on peut réaliser instantanément le mélange homogène des grains de liant à l'état solide avec les grains de poudre propulsive et la mise en moule de quantité précises du mélange ainsi obtenu, et éviter les opération fastidieuses nécessaires dans le cas d'un liant liquide, à savoir les opérations d'imprégnation des grains de poudre propulsive à l'aide dudit liant liquide, de séchage et de stabilisation des grains imprégnés, De plus, le moulage du chargement selon l'invention peut consister en une simple compression du mélange poudre propulsive-liant en moule, à chaud, de courte durée (1 minute à la température de 120°C, sous une pression de 115 kg/cm2) et le chargement ainsi moulé peut être démoulé, aussitôt après la compression ; aucune polymérisation sous pression n'est nécessaire.
The advantages of the binder according to the invention are manifold:
  • - On the one hand, the ingredients of the binder are highly energetic and do not cause a drop in energy as would a non-energetic binder, when igniting the load; so,
  • - polyvinyl nitrate has a potential of 990 cal / g (for an average molecular weight of 89 and a nitrogen content of 15.4%),
  • - nitrocellulose has a potential of 940 cal / g (for a nitrogen content of 12.5%),
  • - polyvinyl acetate has a potential of - 1088 cal / g.
  • - on the other hand, the ingredients of the binder are in the solid state under normal conditions of temperature and pressure, and become hot plastic; thus, the homogeneous mixing of the grains of binder in the solid state with the grains of propellant powder and the molding of precise quantities of the mixture thus obtained can be carried out instantly, and the tedious operations necessary in the case of a binder can be avoided. liquid, namely the operations of impregnating the grains of propellant powder using said liquid binder, drying and stabilization of the impregnated grains, In addition, the molding of the load according to the invention may consist of a simple compression of the propellant powder-binder mixture in the mold, hot, of short duration (1 minute at a temperature of 120 ° C., under a pressure of 115 kg / cm2) and the load thus molded can be removed from the mold immediately after compression; no pressure polymerization is necessary.

La présente invention concerne également un procédé de fabrication des chargements unitaires fragmentables de poudre propulsive, comprenant les étapes suivantes :

  • - mélangeage des grains de poudre à la nitrocellulose dans la proportion de 85 à 97% en poids avec un liant énergétique solide, thermoplastique, tel que défini ci-dessus, dans la proportion de 15 à 3% en poids,
  • - chargement du mélange obtenu dans un moule,
  • - mise à température du moule et dudit mélange à une température à laquelle le liant devient plastique, de préférence à une température de 105°C à 130°C,
  • - compression du mélange à cette température, à une pression de 100 à 150 bars, pendant une courte durée, d'environ une minute,
  • - démoulage du chargement unitaire ainsi obtenu immédiatement après compression.
The present invention also relates to a process for manufacturing fragmentable unit charges of propellant powder, comprising the following steps:
  • mixing of the grains of powder with nitrocellulose in the proportion of 85 to 97% by weight with a solid energetic binder, thermoplastic, as defined above, in the proportion of 15 to 3% by weight,
  • - loading of the mixture obtained in a mold,
  • - bringing the mold and said mixture to temperature at a temperature at which the binder becomes plastic, preferably at a temperature of 105 ° C to 130 ° C,
  • - compression of the mixture at this temperature, at a pressure of 100 to 150 bars, for a short time, of about one minute,
  • - demoulding of the unit load thus obtained immediately after compression.

A titre d'exemple de liant énergétique, on peut utiliser notamment les compositions suivantes :

Figure imgb0001
A titre d'exemple de poudre propulsive à la nitrocellulose, on peut utiliser notamment les poudres B suivantes :

  • . BTu 90 (0,4) = poudre B en grains monotubulaires de potentiel 900 cal/g, d'épaisseur de paroi 0,4 mm
  • . BTu 93 (0,4) = poudre B en grains monotubulaires de potentiel 930 cal/g, d'épaisseur de paroi 0,4 mm
  • . BTu 93 (0,5) = poudre B en grains monotubulaires de potentiel 930 cal/g, d'épaisseur de paroi 0,5 mm.
As an example of an energy binder, the following compositions can be used in particular:
Figure imgb0001
 As an example of a nitrocellulose propellant powder, the following powders B can be used in particular:
  • . BTu 90 (0.4) = powder B in monotubular grains of potential 900 cal / g, wall thickness 0.4 mm
  • . BTu 93 (0.4) = powder B in monotubular grains of potential 930 cal / g, wall thickness 0.4 mm
  • . BTu 93 (0.5) = powder B in monotubular grains of potential 930 cal / g, with wall thickness 0.5 mm.

On illustre l'invention par les exemples non mimitatifs qui suivent :The invention is illustrated by the following non-mimicking examples:

Exemple 1 :Example 1:

La poudre propulsive utilisée dans cet exemple est une poudre en grains à la nitrocellulose du type BTu 93 (0,5) lissée par 1% de centralite. Le liant énergétique utilisé est la composition n° 1 indiquée ci-dessus :

  • - nitrate de polyvinyle 40 parties en poids (masse moléculaire moyenne 89, taux d'azote 14,7%, potentiel 990 cal/g)
  • - nitrocellulose à 12,5% d'azote 60 parties en poids
  • - nitro-2 diphénylamine 2 parties en poids.
The propellant powder used in this example is a powder in nitrocellulose grains of the BTu 93 (0.5) type smoothed with 1% centralite. The energy binder used is composition n ° 1 indicated above:
  • - polyvinyl nitrate 40 parts by weight (average molecular weight 89, nitrogen content 14.7%, potential 990 cal / g)
  • - nitrocellulose with 12.5% nitrogen 60 parts by weight
  • - 2-nitro-diphenylamine 2 parts by weight.

Le moule utilisé est un moule à compression classique comprenant un corps de moule muni d'un alésage axial cyclindrique formant la cavité de moulage, et deux poinçons cylindriques mobiles, engagés respectivement dans la partie supérieure et dans la partie inférieure de la cavité de moulage et formant respectivement la matrice et l'éjecteur du moule. L'éjecteur porte un noyau axial prolongé à travers la cavité de moulage et engagé dans un alésage axial prévu dans la matrice. Le déplacement des poinçons est commandé par des vérins. La mise en température ou le refroidissement du moule est assuré par un circuit à circulation de fluide de chauffage ou de refroidissement.The mold used is a conventional compression mold comprising a mold body provided with a cylindrical axial bore forming the molding cavity, and two movable cylindrical punches, engaged respectively in the upper part and in the lower part of the molding cavity and respectively forming the matrix and the mold ejector. The ejector carries an axial core extended through the molding cavity and engaged in an axial bore provided in the die. The movement of the punches is controlled by jacks. The heating or cooling of the mold is ensured by a circulation circuit of heating or cooling fluid.

On prépare le moule en enduisant l'intérieur du moule, les poinçons et le noyau d'un agent de démoulage.The mold is prepared by coating the inside of the mold, the punches and the core with a release agent.

Mélange : On mélange 66 g de poudre propulsive avec 4 g de liant dans un mélangeur (taux de liant 5,7%).Mixing: 66 g of propellant powder are mixed with 4 g of binder in a mixer (binder rate 5.7%).

Moulage : On chauffe au préalable le moule à 120°C et on charge dans la cavité de moulage le mélange poudre-liant réalisé ci-dessus.Molding: The mold is heated beforehand to 120 ° C. and the powder-binder mixture produced above is loaded into the molding cavity.

On laisse ledit mélange se réchauffer à 120°C puis on le comprime à cette température sous une pression de 800 kg/cm2 pendant une minute, puis on démoule à chaud le chargement obtenu. On obtient ainsi un bloc cylindrique creux d'un poids de 70 g, d'une hauteur de 72,5mm et d'un diamètre de 30 mm.Said mixture is allowed to warm to 120 ° C and then it is compressed at this temperature under a pressure of 800 kg / cm 2 for one minute, then the load obtained is demolded hot. A hollow cylindrical block with a weight of 70 g, a height of 72.5 mm and a diameter of 30 mm is thus obtained.

Ce bloc,monté dans une douille métallique avec un obus, et tiré à l'aide d'une amorce électrique, et 0,7 g d'une poudre d'appoint dans le canal central du bloc servant à allumer le bloc,et à initier sa fragmentation, a donné les résultats suivants :

  • - pression maximale moyenne (Pm) : 2818 bars,
  • - vitesse mesurée à 25 m de la bouche de l'arme (V25) : 850 m/s.
This block, mounted in a metal casing with a shell, and fired using an electric primer, and 0.7 g of an auxiliary powder in the central channel of the block used to light the block, and to initiating its fragmentation, gave the following results:
  • - average maximum pressure (Pm): 2818 bars,
  • - speed measured 25 m from the muzzle of the weapon (V 25 ): 850 m / s.

La fragmentation du bloc est correcte. Sur une même série de 20 coups on note un écart type satisfaisant de 20 m/s pour la vitesse et de 200 bars pour la pression. La tenue mécanique est bonne.The fragmentation of the block is correct. On the same series of 20 strokes there is a satisfactory standard deviation of 20 m / s for speed and 200 bar for pressure. The mechanical strength is good.

Exemple 2 :Example 2:

La poudre propulsive et le liant énergétique utilisés sont les mêmes que ceux de l'exemple 1, mais le taux du liant est porté à 10%.The propellant powder and the energy binder used are the same as those of Example 1, but the rate of the binder is brought to 10%.

A cet effet, on mélange 63 g de poudre propulsive BTu 93 (0,5)lissée par 1% de centralite avec 7 g de liant de composition n° 1, puis on moule comme décrit à l'exemple 1. On obtient un bloc cylindrique creux d'un poids de 70 g, d'une hauteur de 71,8 mm et d'un diamètre de 30 mm. Le bloc monté dans une douille métallique avec un obus et tiré à l'aide d'une amorce électrique et 2 g d'une poudre d'appoint dans le canal du bloc a donné les résultats suivants :

  • - pression maximale moyenne : 2180 bars,
  • - vitesse mesurée à 25 m de la bouche de l'arme : 840 m/s.
To this end, 63 g of propellant powder BTu 93 (0.5) smoothed with 1% centralite are mixed with 7 g of binder of composition No. 1, then molded as described in Example 1. A block is obtained hollow cylindrical with a weight of 70 g, a height of 71.8 mm and a diameter of 30 mm. The block mounted in a metal casing with a shell and fired using an electric primer and 2 g of an auxiliary powder in the block channel gave the following results:
  • - average maximum pressure: 2180 bars,
  • - speed measured at 25 m from the muzzle of the weapon: 840 m / s.

La fragmentation du bloc est correcte et la tenue mécanique de celui-ci est bonne.The fragmentation of the block is correct and the mechanical strength of the block is good.

Exemple 3 :Example 3:

Cet exemple est destiné à montrer l'influence du taux de liant sur les caractéristiques balistiques du chargement unitaire final ; avec un taux de liant supérieur à 15% le chargement se fragmente mal et brûle comme un bloc compact.This example is intended to show the influence of the rate of binder on the ballistic characteristics of the final unit load; with a rate of binder higher than 15% the load breaks up badly and burns like a compact block.

La poudre propulsive et le liant énergétique utilisés dans cet exemple sont les mêmes que ceux de l'exemple 1 mais le taux de liant est porté à 20%.The propellant powder and the energy binder used in this example are the same as those of Example 1, but the binder rate is increased to 20%.

On procède comme à l'exemple 1, mais en partant d'un mélange de 56 g de poudre BTu 93 (0,5) lissée par 1% de centralite et 14 g de liant de composition n° 1.The procedure is as in Example 1, but starting from a mixture of 56 g of BTu 93 powder (0.5) smoothed with 1% centralite and 14 g of binder of composition No. 1.

On obtient un bloc cylindrique creux d'un poids de 70 g, d'une hauteur de 72 mm, d'un diamètre de 30 mm.A hollow cylindrical block with a weight of 70 g, a height of 72 mm, a diameter of 30 mm is obtained.

Le bloc monté dans une douille métallique avec un obus et tiré à l'aide d'une amorce électrique et 2 g d'une poudre d'appoint dans le canal central du bloc a donné les résultats suivants :

  • - pression maximale moyenne : 1495 bars,
  • - vitesse à 25 m de la bouche de l'arme : 765 m/s.
The block mounted in a metal casing with a shell and fired with an electric primer and 2 g of an auxiliary powder in the central channel of the block gave the following results:
  • - average maximum pressure: 1495 bars,
  • - speed 25 m from the muzzle: 765 m / s.

La pression maximale moyenne est nettement insuffisante (inférieure à 1800 bars) et la fragmentation est mauvaise dans les conditions de l'expérience.The average maximum pressure is clearly insufficient (less than 1800 bars) and the fragmentation is poor under the conditions of the experiment.

Exemple 4 :Example 4:

Cet exemple est destiné à montrer l'influence du potentiel de la poudre propulsive sur les caractéristiques du bloc final. Une poudre ayant un potentiel inférieur à 900 cal/g n'est pas suffisamment vive.This example is intended to show the influence of the potential of the propellant powder on the characteristics of the final block. A powder with a potential lower than 900 cal / g is not sufficiently lively.

Figure imgb0002
Figure imgb0002

Avec les poudres B en grains monotubulaires de potentiel 930 cal/g /poudre BTu 93 (0,4)] et 900 cal/g `poudre BTu 90 (0,4)], la fragmentation des blocs obtenus est correcte, et la tenue mécanique de ceux-ci est bonne.With the powders B in monotubular grains of potential 930 cal / g / powder BTu 93 (0.4)] and 900 cal / g `powder BTu 90 (0.4)], the fragmentation of the blocks obtained is correct, and the behavior mechanics of these is good.

Par contre, avec la poudre B en grains monotubulaires de potentiel 850 cal/g [poudre BTu 85 (0,4)], la combustion du bloc est incomplète.On the other hand, with powder B in monotubular grains of potential 850 cal / g [powder BTu 85 (0.4)], the combustion of the block is incomplete.

Claims (8)

1. Chargement unitaire fragmentable de poudre propulsive, caractérisé en ce qu'il est constitué de 85 à 97% en poids de grains de poudre propulsive à la nitrocellulose, agglomérés ensemble par 15 à 3% et de préférence 10 à 5% en poids d'un liant énergétique solide, thermoplastique, ayant la composition suivante : (a) 30 à 60% en poids, par rapport au liant, de nitrate de polyvinyle, (b) 70 à 40% en poids, par rapport au liant, de nitrocellulose ayant un taux d'azote faible inférieur à 12,8%, ou d'acétate de polyvinyle ou un mélange des deux, (c) éventuellement un stabilisant. 1. Fragmentable unit charge of propellant powder, characterized in that it consists of 85 to 97% by weight of grains of nitrocellulose propellant powder, agglomerated together by 15 to 3% and preferably 10 to 5% by weight d '' a solid, thermoplastic energy binder having the following composition: (a) 30 to 60% by weight, relative to the binder, of polyvinyl nitrate, (b) 70 to 40% by weight, relative to the binder, of nitrocellulose having a low nitrogen level of less than 12.8%, or of polyvinyl acetate or a mixture of the two, (c) optionally a stabilizer. 2. Chargement unitaire fragmentable selon la revendication 1, caractérisé en ce que le liant énergétique présente la composition suivante : (a) 30 à 60% en poids de nitrate de polyvinyle, (b) 70 à 40% en poids de nitrocellulose à taux d'azote inférieur à 12,8%, (c) éventuellement un stabilisant. 2. Fragmentable unit charge according to claim 1, characterized in that the energy binder has the following composition: (a) 30 to 60% by weight of polyvinyl nitrate, (b) 70 to 40% by weight of nitrocellulose with a nitrogen content of less than 12.8%, (c) optionally a stabilizer. 3. Chargement unitaire fragmentable selon la revendication 1 ou 2, caractérisé en ce que le stabilisant est la nitro-2 diphénylamine ajouté en quantité pouvant atteindre 3% en poids par rapport au liant énergétique.3. Unit load fragmentable according to claim 1 or 2, characterized in that the stabilizer is 2-nitro-diphenylamine added in an amount up to 3% by weight relative to the energy binder. 4. Chargement unitaire fragmentable selon la revendication 1, 2 ou 3, caractérisé en ce que le liant énergétique contient également au moins un additif choisi dans le groupe comprenant le dinitrotoluène, un polymère du type A B S (acrylonitrile-butadiène-styrène), l'acétate de cellulose, les phtalates, les esters lourds, les cétones hétérocycliques, les urées.4. Fragmentable unit charge according to claim 1, 2 or 3, characterized in that the energy binder also contains at least one additive chosen from the group comprising dinitrotoluene, a polymer of the ABS type (acrylonitrile-butadiene-styrene), cellulose acetate, phthalates, heavy esters, heterocyclic ketones, ureas. 5. Chargement unitaire fragmentable selon l'une des revendications 1 à 4, caractérisé en ce que la poudre propulsive est une poudre à la nitrocellulose en grains à simple base, dite "poudre B".5. Fragmentable unit charge according to one of claims 1 to 4, characterized in that the propellant powder is a nitrocellulose powder in single base grains, called "powder B". 6. Chargement unitaire fragmentable selon la revendication 5, caractérisé en ce que la poudre B est une poudre monotubulaire, ayant un potentiel de 870 à 950 cal/g.6. Fragmentable unit load according to claim 5, character risé in that powder B is a monotubular powder, having a potential of 870 to 950 cal / g. 7. Chargement unitaire fragmentable selon la revendication 1, caractérisé en ce que le liant énergétique présente la composition suivante : - 40 à 60 parties en poids de nitrate de polyvinyle fortement nitré, - 60 à 40 parties en poids de nitrocellulose à taux d'azote de 11% à 12,6%, - 2 à 3 parties en poids de nitro-2 diphénylamine. 7. Fragmentable unit load according to claim 1, characterized in that the energy binder has the following composition: - 40 to 60 parts by weight of highly nitrated polyvinyl nitrate, - 60 to 40 parts by weight of nitrocellulose with a nitrogen content of 11% to 12.6%, - 2 to 3 parts by weight of 2-nitro diphenylamine. 8. Procédé de fabrication d'un chargment unitaire fragmentable de poudre propulsive, caractérisé en ce qu'il comporte les étapes suivantes: - mélangeage des grains de poudre à la nitrocellulose dans la proportion de 85 à 97% en poids, avec un liant énergétique solide, thermoplastique dans la proportion de 15 à 3% en poids, ledit liant ayant la composition suivante : (a) 30 à 60% en poids, par rapport au liant, de nitrate de polyvinyle, (b) 70 à 40% en poids, par rapport au liant, de nitrocellulose ayant un taux d'azote faible, inférieur à 12,8%, ou d'acétate de polyvinyle, ou un mélange des deux, (c) éventuellement un stabilisant ; - chargement du mélange obtenu dans un moule à compression, - mise à température du moule dudit mélange à une température à laquelle le liant devient plastique, de préférence à une température de 105 à 130°C ; - compression du mélange à cette température à une pression de 100 à 150 bars, pendant une courte durée, de préférence pendant une minute environ ; - démoulage du chargement unitaire obtenu immédiatement après compression. 8. Method for manufacturing a fragmentable unitary segment of propellant powder, characterized in that it comprises the following stages: mixing of the grains of powder with nitrocellulose in the proportion of 85 to 97% by weight, with a solid energetic binder, thermoplastic in the proportion of 15 to 3% by weight, said binder having the following composition: (a) 30 to 60% by weight, relative to the binder, of polyvinyl nitrate, (b) 70 to 40% by weight, relative to the binder, of nitrocellulose having a low nitrogen level, less than 12.8%, or of polyvinyl acetate, or a mixture of the two, (c) optionally a stabilizer; - loading of the mixture obtained in a compression mold, - bringing the mold temperature of said mixture to a temperature at which the binder becomes plastic, preferably at a temperature of 105 to 130 ° C; - Compression of the mixture at this temperature at a pressure of 100 to 150 bars, for a short time, preferably for about one minute; - demoulding of the unit load obtained immediately after compression.
EP78400186A 1977-12-15 1978-11-17 Fragmentable propellant unit charge containing a polyvinylnitrate binder and process for making it Expired EP0002968B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR7737901A FR2411817A1 (en) 1977-12-15 1977-12-15 FRAGMENTABLE UNIT LOADING OF PROPELLANT POWDER CONTAINING A BINDER OF POLYVINYL NITRATE
FR7737901 1977-12-15

Publications (2)

Publication Number Publication Date
EP0002968A1 true EP0002968A1 (en) 1979-07-11
EP0002968B1 EP0002968B1 (en) 1981-01-14

Family

ID=9198905

Family Applications (1)

Application Number Title Priority Date Filing Date
EP78400186A Expired EP0002968B1 (en) 1977-12-15 1978-11-17 Fragmentable propellant unit charge containing a polyvinylnitrate binder and process for making it

Country Status (7)

Country Link
US (1) US4279672A (en)
EP (1) EP0002968B1 (en)
AU (1) AU524341B2 (en)
CA (1) CA1127396A (en)
DE (1) DE2860335D1 (en)
FR (1) FR2411817A1 (en)
IL (1) IL56004A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4326901A (en) * 1978-09-21 1982-04-27 Societe Nationale Des Poudres Et Explosifs Fragmentable charges of propelland powder coated with polyvinyl nitrate, and the process for their manufacture
US4347087A (en) * 1978-12-22 1982-08-31 Societe Nationale Des Poudres Et Explosifs Granular propellant powder based on nitrocellulose, oily nitrate ester and polyvinyl nitrate, and process
EP0633236A1 (en) * 1993-06-30 1995-01-11 Alliant Techsystems Inc. Energetic gun propellant coating
US6837164B1 (en) * 2002-11-13 2005-01-04 The United States Of America As Represented By The Secretary Of The Army Propelling charge increment protector for 120mm mortar ammunition

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2518736B1 (en) * 1981-12-17 1986-09-26 Poudres & Explosifs Ste Nale MIXED LOADS FOR AMMUNITION WITH SOCKET CONSISTING OF AGGLOMERATED PROPULSIVE POWDER AND GRAIN PROPULSIVE POWDER
US4839420A (en) * 1984-04-16 1989-06-13 The United States Of America As Represented By The Secretary Of The Army Preparation of polyvinylazides from polyvinylnitrate
US4843121A (en) * 1984-04-16 1989-06-27 The United States Of America As Represented By The Secretary Of The Army Polyvinylazidonitrate
US5174837A (en) * 1990-02-21 1992-12-29 Societe Nationale Des Poudres Et Explosifs Temperature-resistant, fragmentable propellent charges
US5269224A (en) * 1990-08-30 1993-12-14 Olin Corporation Caseless utilized ammunition charge module
US5489349A (en) * 1995-04-06 1996-02-06 Trw Inc. Grains of gas generating material and process for forming the grains

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1040557A (en) * 1949-04-20 1953-10-16 Ministre De La Defense Nationa Heat-insulating, insulating and plastic adhesive composition
US2990263A (en) * 1949-02-03 1961-06-27 William H Avery Process for manufacturing rocket propellants
FR2114142A5 (en) * 1970-11-17 1972-06-30 Remington Arms Co Inc
FR2182662A2 (en) * 1972-05-03 1973-12-14 France Etat Propellant powder - contg ammonium nitrate, nitrocellulose and polyvinyl nitrate
FR2182663A2 (en) * 1972-05-03 1973-12-14 France Etat
FR2210589A1 (en) * 1972-12-14 1974-07-12 Poudres & Explosifs Ste Nale
DE2329558A1 (en) * 1973-06-09 1975-01-23 Messerschmitt Boelkow Blohm Castable non-hygroscopic gas-generating propellant - with good mechanical props and burning with low flame temps
CA968629A (en) * 1970-07-18 1975-06-03 Heinz Gawlick Caseless formed propellant powder charge

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1811924C3 (en) * 1968-11-30 1973-07-05 Wasagchemie Ag Propellant body for caseless ammunition
US4023996A (en) * 1973-08-09 1977-05-17 Societe Nationale Des Poudres Et Explosifs Moldable compositions comprising polyvinyl nitrate

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2990263A (en) * 1949-02-03 1961-06-27 William H Avery Process for manufacturing rocket propellants
FR1040557A (en) * 1949-04-20 1953-10-16 Ministre De La Defense Nationa Heat-insulating, insulating and plastic adhesive composition
CA968629A (en) * 1970-07-18 1975-06-03 Heinz Gawlick Caseless formed propellant powder charge
FR2114142A5 (en) * 1970-11-17 1972-06-30 Remington Arms Co Inc
FR2182662A2 (en) * 1972-05-03 1973-12-14 France Etat Propellant powder - contg ammonium nitrate, nitrocellulose and polyvinyl nitrate
FR2182663A2 (en) * 1972-05-03 1973-12-14 France Etat
FR2210589A1 (en) * 1972-12-14 1974-07-12 Poudres & Explosifs Ste Nale
DE2329558A1 (en) * 1973-06-09 1975-01-23 Messerschmitt Boelkow Blohm Castable non-hygroscopic gas-generating propellant - with good mechanical props and burning with low flame temps

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4326901A (en) * 1978-09-21 1982-04-27 Societe Nationale Des Poudres Et Explosifs Fragmentable charges of propelland powder coated with polyvinyl nitrate, and the process for their manufacture
US4347087A (en) * 1978-12-22 1982-08-31 Societe Nationale Des Poudres Et Explosifs Granular propellant powder based on nitrocellulose, oily nitrate ester and polyvinyl nitrate, and process
EP0633236A1 (en) * 1993-06-30 1995-01-11 Alliant Techsystems Inc. Energetic gun propellant coating
US6837164B1 (en) * 2002-11-13 2005-01-04 The United States Of America As Represented By The Secretary Of The Army Propelling charge increment protector for 120mm mortar ammunition

Also Published As

Publication number Publication date
IL56004A (en) 1982-07-30
AU524341B2 (en) 1982-09-09
DE2860335D1 (en) 1981-03-12
FR2411817A1 (en) 1979-07-13
EP0002968B1 (en) 1981-01-14
AU4252978A (en) 1979-06-21
US4279672A (en) 1981-07-21
CA1127396A (en) 1982-07-13
FR2411817B1 (en) 1980-08-22

Similar Documents

Publication Publication Date Title
US3545333A (en) Methods of manufacturing caseless ammunition for air ignition systems
KR102451244B1 (en) propellant filling or grain
EP1275930B1 (en) Pyrotechnical ammunition safety igniter acting in case of slow heating of the ammunition
EP0002968B1 (en) Fragmentable propellant unit charge containing a polyvinylnitrate binder and process for making it
FR2867469A1 (en) Reactive composition, useful in military and industrial explosives, comprises a metallic material defining a continuous phase and having an energetic material, which comprises oxidant and/or explosive of class 1.1
US3954062A (en) Caseless propellant charges
US3092525A (en) Method of producing unitary nitrocellulose grains capable of fragmentation under primer blast to original granules
GB1605251A (en) Propellent powder bodies and process for the production thereof
CH625196A5 (en)
US3028274A (en) Extrusion method for manufacturing smokeless powder
US3036939A (en) Cast gas-producing charge containing nitrocellulose and vinyl polymers
FR2680169A1 (en) PROCESS FOR MAKING POROUS PROPELLANT AGENTS FOR AMMUNITION
Setiani et al. The granulation methods of double base propellant for small caliber ammunition: a review
US3628456A (en) Propellant charge for telescoped caseless ammunition having a deterrent-coated aft-end
US20030192632A1 (en) Method for production of nitrocellulose base for consolidated charges and consolidated propellant charge based thereon
TWI772444B (en) Composition for single-base propelling powder for ammunition and ammunition provided with such composition
CA1187705A (en) Fumigant-type flowable pyrotechnical composition having a colored or not colored flame and containing a chlorinated binding agent
EP3969432B1 (en) Propellant powder grain comprising at least partially obturated channels
US3979486A (en) Process for controlling the ballistic characteristics of double-base propellants
RU2528984C2 (en) Modular throwing charge (versions) and method of its fabrication
US3037417A (en) Explosives
AU2014321144B2 (en) Burn rate modifier
US4844845A (en) Dry mixture for production of pre-formed propellant charge
EP0013850A2 (en) Granular propellants based on nitrocellulose, nitrated oil and polyvinyl nitrate and process for producing them
US3068643A (en) Rocket with internal rod

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

Designated state(s): BE CH DE GB SE

17P Request for examination filed
GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Designated state(s): BE CH DE GB SE

REF Corresponds to:

Ref document number: 2860335

Country of ref document: DE

Date of ref document: 19810312

EAL Se: european patent in force in sweden

Ref document number: 78400186.9

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

Ref country code: DE

Payment date: 19970129

Year of fee payment: 19

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

Ref country code: GB

Payment date: 19971110

Year of fee payment: 20

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

Ref country code: SE

Payment date: 19971120

Year of fee payment: 20

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

Ref country code: DE

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

Effective date: 19971130

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

Ref country code: BE

Payment date: 19971212

Year of fee payment: 20

BE20 Be: patent expired

Free format text: 981117 *SOC. NATIONALE DES *POUDRES ET *EXPLOSIFS

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

Ref country code: CH

Payment date: 19980209

Year of fee payment: 20

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

Ref country code: GB

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 19981116

Ref country code: CH

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 19981116

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

Ref country code: SE

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

Effective date: 19981118

REG Reference to a national code

Ref country code: GB

Ref legal event code: PE20

Effective date: 19981116

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

EUG Se: european patent has lapsed

Ref document number: 78400186.9

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