EP0013850B1 - Granular propellants based on nitrocellulose, nitrated oil and polyvinyl nitrate and process for producing them - Google Patents
Granular propellants based on nitrocellulose, nitrated oil and polyvinyl nitrate and process for producing them Download PDFInfo
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- EP0013850B1 EP0013850B1 EP79401002A EP79401002A EP0013850B1 EP 0013850 B1 EP0013850 B1 EP 0013850B1 EP 79401002 A EP79401002 A EP 79401002A EP 79401002 A EP79401002 A EP 79401002A EP 0013850 B1 EP0013850 B1 EP 0013850B1
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- Prior art keywords
- nitrocellulose
- parts
- polyvinyl nitrate
- weight
- powder
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Classifications
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- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B21/00—Apparatus or methods for working-up explosives, e.g. forming, cutting, drying
- C06B21/0033—Shaping the mixture
- C06B21/0066—Shaping the mixture by granulation, e.g. flaking
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- 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
- C06B25/24—Compositions containing a nitrated organic compound the compound being nitrocellulose present as 10% or more by weight of the total composition with nitroglycerine
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- 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 present invention relates to the field of homogeneous propellant powders in grains for weapons and more particularly to that of gun powders for battle tanks.
- the invention relates to propellants based on nitrocellulose, nitrated oil and polyvinyl nitrate, as well as a process for their production.
- the basic material for the manufacture of current propellant powders is nitrocellulose, which gelatinized by a suitable solvent such as an ethyl ether-ethyl alcohol mixture and mixed with the usual additives known to those skilled in the art, such as stabilizers and moderators. combustion, provides the powders commonly known by the general name of "smokeless powders". These powders are well suited for most conventional weapons. They are, for example, described in the book “Les Poudres et Explosifs”, by MM. L. VENNIN, E. BURLOT, H. LECORCHE, Librairie Polytechnique ch. BERANGER, page 578 et seq., (1932).
- nitrocellulose propellant powders by incorporating an explosive nitrated oil such as nitroglycerin therein.
- This type of powders is for example described in French patents 1 311 647, 1 456 283, 2153 039.
- These powders generally called double base powders, have the force required to be used in tank guns and mortars but have two major drawbacks.
- the nitroglycerin in a large quantity tends to migrate towards the outside of the powder grain and to form droplets at the periphery of the grain, this phenomenon, also called exudation, causes a variation in time of the ballistic properties of the powder not to mention the danger caused by the presence of free nitroglycerin on the surface of the powder grains.
- these powders have a very high combustion temperature and therefore cause too rapid erosion of the weapon by excessive heating of the inner surface of the barrel tube.
- the present invention relates to a new homogeneous propellant powder in grains, based on nitrocellulose, an explosive nitrated oil and polyvinyl nitrate, which has sufficient strength to be used in tank guns while not having the disadvantages of double base powders and in particular by being less erosive than the latter.
- the powders according to the invention are characterized in that they contain between 50 and 75 parts by weight of nitrocellulose, between 5 and 25 parts by weight of polyvinyl nitrate and between 5 and 25 parts by weight of a nitrated oil per 100 parts by weight of energy base.
- the powders according to the invention have a force comparable to that developed, under the same firing conditions, by conventional gun powders based on nitrocellulose and nitroglycerine, but they have a lower combustion temperature than the latter and are therefore less erosive for weapons.
- the Applicant has moreover observed that the powders according to the invention have a lower tendency to exudate than conventional powders based on nitrocellulose and on a nitrated oil, and that, surprisingly, their temperature coefficient is significantly lower than that of conventional gun powders.
- the temperature coefficient measures the variations in the ballistic properties of a powder (pressure in the chamber and velocity of the projectile at the exit of the weapon) as a function of the temperature, the lower this coefficient is the less the ballistic properties of the powder are dependent on temperature.
- the powder grains according to the invention contain, as was said above, between 50 and 75 parts of nitrocellulose, between 5 and 25 parts of nitrated oil and between 5 and 25 parts of polyvinyl nitrate per 100 parts of base energetic.
- the Applicant has observed that apart from these ranges of composition, no homogeneous powder is obtained having sufficient ballistic and mechanical properties to be able to be used as gun powders.
- An oil chosen from the group consisting of nitroglycerin, trimethylol methane trinitrate and trimethylol ethane trinitrate can be used as the nitrated oil. According to a preferred embodiment of the invention, nitroglycerin is used.
- the invention also relates to a method for manufacturing powders according to the invention.
- This process is a process with solvents which consists in kneading the energy bases in the presence of said solvents until a homogeneous paste is obtained which is spun in the press, in the form of strands which are wrung out and cut into grains. powder are then soaked and dried. Obtaining a homogeneous paste from nitrocellulose, a nitrated oil and polyvinyl nitrate is very delicate.
- a solvent acetone / light aliphatic alcohol is used as solvent in proportions such that the content of the acetone paste on mixing is between 30 and 36% by weight relative to the weight of dry nitrocellulose and polyvinyl nitrate. and in that the acetone / alcohol weight ratio is between 1.10 and 1.50.
- As light aliphatic alcohol ethyl alcohol is preferred.
- the kneading must be carried out as follows. The selected quantities of nitrocellulose, generally impregnated with alcohol, and nitrated oil, generally already dissolved in acetone, are introduced into the mixer, and the mixture is supplemented with acetone and alcohol.
- Spinning takes place at a temperature below 30 ° C so as not to alter the mechanical properties of the strands.
- the strands are cut into grains.
- the grains after having optionally undergone a first hot drying, are then soaked in water and dried in a conventional manner.
- the grains of powder are generally not smoothed, but they can be graphitized according to the intended use.
- the invention thus makes it possible to have grains of homogeneous powder based on nitrocellulose, nitrated oil and polyvinyl nitrate which are in particular usable in the tanks of battle tanks, these grains of powder having a force comparable to that developed in the same conditions by conventional grains of powder based on nitrocellulose and nitroglycerin.
- the powder grains according to the invention also have the double advantage of having a lower combustion temperature than these conventional powder grains and of having a lower temperature coefficient.
- the powder according to the invention gives, depending on the projectile temperatures, a speed at least equal to or greater than that given by a conventional simple base powder and that, between - 40 ° C and + 51 ° C the speed of the projectile varies only by 49 m / s with the powder according to the invention whereas '' it varies from 88 m / s with a conventional powder.
- the pressures developed in the chamber during ignition are the same applies to the pressures developed in the chamber during ignition.
- the combustion temperature of the powder according to the invention calculated from the energy balance is 3600 K ° whereas for a conventional double base powder of the same strength it is close to 3780 K °, so that the thanks to the invention, there is a sufficiently strong powder to be able to be advantageously used in tank guns, while being less hot than the usual double base powders used in this type of weapon.
- Example 1 Take the powder from Example 1 and graphite it in a bezel with 0.2% by weight of graphite.
- the powder thus obtained is fired at room temperature in a smooth 120 ° barrel.
- the projectile weighs 6.2 kg and 8.2 kg of powder are used.
- the velocity of the projectile 40 meters from the muzzle of the gun is 1,675.5 m / s and the maximum pressure developed in the combustion chamber of 4,068 bars.
- This example is intended to show the importance of compliance with the operating conditions in the manufacture of the powder and more particularly the importance of compliance with the conditions relating to the quantities of solvents used.
- Example 2 The procedure is exactly as described in Example 1 with the only difference that a total of 18.1 kg of alcohol and 23.6 kg of acetone are used.
- the dough content of acetone in kneading is therefore only 28% relative to the weight of dry nitrocellulose and polyvinyl nitrate.
- the acetone / alcohol weight ratio is 1.3 and is therefore found to be correct.
Description
La présente invention se rapporte au domaine des poudres propulsives homogènes en grains pour armes et plus spécialement à celui des poudres à canon pour chars de combat. L'invention concerne des poudres propulsives à base de nitrocellulose, d'huile nitrée et de nitrate de polyvinyle ainsi que leur procédé de fabrication.The present invention relates to the field of homogeneous propellant powders in grains for weapons and more particularly to that of gun powders for battle tanks. The invention relates to propellants based on nitrocellulose, nitrated oil and polyvinyl nitrate, as well as a process for their production.
La matière de base pour la fabrication des poudres propulsives actuelles est la nitrocellulose, qui gélatinisée par un solvant approprié telle qu'un mélange éther éthylique-alcool éthylique et mélangée aux additifs usuels connus de l'homme de métier, tels que stabilisants et modérateurs de combustion, fournit les poudres communément désignées sous l'appellation générale de «poudres sans fumées ». Ces poudres conviennent bien pour la plupart des armes conventionnelles. Elles sont par exemple décrites dans l'ouvrage « Les Poudres et Explosifs », de MM. L. VENNIN, E. BURLOT, H. LECORCHE, Librairie Polytechnique ch. BERANGER, page 578 et suivantes, (1932). Par contre, elles ne sont pas assez « fortes » pour être avantageusement utilisées dans les canons de chars de combat. Il faut entendre par là que l'énergie développée dans la culasse de l'arme par les gaz de combustion de la poudre n'est pas suffisante pour donner la quantité de mouvement désirée au projectile. En effet, dans le cas particulier des canons de chars de combat on accepte de sacrifier la durée de vie du tube pour obtenir les performances maximales au niveau de la vitesse d'éjection du projectile et on est amené à utiliser les poudres les plus fortes possibles.The basic material for the manufacture of current propellant powders is nitrocellulose, which gelatinized by a suitable solvent such as an ethyl ether-ethyl alcohol mixture and mixed with the usual additives known to those skilled in the art, such as stabilizers and moderators. combustion, provides the powders commonly known by the general name of "smokeless powders". These powders are well suited for most conventional weapons. They are, for example, described in the book “Les Poudres et Explosifs”, by MM. L. VENNIN, E. BURLOT, H. LECORCHE, Librairie Polytechnique ch. BERANGER, page 578 et seq., (1932). On the other hand, they are not "strong" enough to be advantageously used in the tanks of combat tanks. This means that the energy developed in the breech of the weapon by the combustion gases of the powder is not sufficient to give the desired amount of movement to the projectile. Indeed, in the particular case of battle tank guns, we agree to sacrifice the life of the tube to obtain maximum performance in terms of the projectile's ejection speed and we are led to use the strongest powders possible. .
On a cherché à augmenter la force des poudres propulsives à la nitrocellulose en y incorporant une huile explosive nitrée telle que la nitroglycérine. Ce type de poudres est par exemple décrit dans les brevets français 1 311 647, 1 456 283, 2153 039. Ces poudres, généralement appelées poudres à double base, possèdent la force requise pour être utilisées dans les canons de chars et les mortiers mais présentent deux inconvénients majeurs. D'une part la nitroglycérine en quantité importante a tendance à migrer vers l'extérieur du grain de poudre et à former des gouttelettes à la périphérie du grain, ce phénomène, encore appelé exsudation, entraîne une variation dans le temps des propriétés balistiques de la poudre sans parler du danger occasionné par la présence de nitroglycérine libre en surface des grains de poudre. D'autre part, ces poudres ont une température de combustion très élevée et de ce fait provoquent une érosion trop rapide de l'arme par un échauffement excessif de la surface intérieure du tube du canon.Attempts have been made to increase the strength of the nitrocellulose propellant powders by incorporating an explosive nitrated oil such as nitroglycerin therein. This type of powders is for example described in French patents 1 311 647, 1 456 283, 2153 039. These powders, generally called double base powders, have the force required to be used in tank guns and mortars but have two major drawbacks. On the one hand, the nitroglycerin in a large quantity tends to migrate towards the outside of the powder grain and to form droplets at the periphery of the grain, this phenomenon, also called exudation, causes a variation in time of the ballistic properties of the powder not to mention the danger caused by the presence of free nitroglycerin on the surface of the powder grains. On the other hand, these powders have a very high combustion temperature and therefore cause too rapid erosion of the weapon by excessive heating of the inner surface of the barrel tube.
De manière à obtenir des poudres propulsives fortes mais présentant une température de combustion moins élevée on a proposé des poudres hétérogènes à base de nitrocellulose et de nitroglycérine et d'une charge comme la nitroguanidine. On dit que ces poudres sont hétérogènes et non homogènes car, vues en coupe au microscope, on observe que la charge ne se fond pas aux autres bases propulsives, mais conserve son identité propre. Ces poudres présentent effectivement une force intéressante pour une température de combustion inférieure à celle des poudres à double base précédemment mentionnées mais ont une tenue mécanique médiocre notamment à froid, et ce notamment en raison de leur hétérogénéité. De telles poudres sont par exemple décrites dans le brevet français 2 295 932.In order to obtain strong propellant powders but having a lower combustion temperature, heterogeneous powders based on nitrocellulose and nitroglycerin and of a filler such as nitroguanidine have been proposed. It is said that these powders are heterogeneous and non-homogeneous because, seen in section under a microscope, we observe that the charge does not melt with other propellant bases, but retains its own identity. These powders do indeed have an advantageous force for a combustion temperature lower than that of the previously mentioned double-base powders but have poor mechanical strength, especially when cold, and this in particular because of their heterogeneity. Such powders are for example described in French patent 2,295,932.
Il a également été proposé d'utiliser d'autres bases pour les poudres propulsives et notamment le nitrate de polyvinyle décrit dans le brevet français 911 759. Le nitrate de polyvinyle ne peut cependant pas être utilisé seul car sa tenue mécanique n'est pas suffisante. En mélange avec la nitrocellulose le nitrate de polyvinyle permet d'obtenir de bonnes poudres propulsives. De telles poudres sont par exemple décrites dans le brevet français 2 210 589. Cependant ces poudres ne sont pas assez fortes pour pouvolr être avantageusement utilisées dans les canons de chars, par ailleurs on n'a jamais réussi jusqu'à présent à ajouter à ce type de poudre une huile nitrée explosive et les essais de mélange des trois constituants nitrocellulose, nitrate de polyvinyle et huile explosive, ont conduit jusqu'à présent à une pâte non homogène, qu'ii est pratiquement impossible de filer et de découper en grains. Pour ces raisons on ne connaît pas à l'heure actuelle de poudres pour canons de chars à base de nitrocellulose, de nitrate de polyvinyle et d'huile nitrée.It has also been proposed to use other bases for propellant powders and in particular polyvinyl nitrate described in French patent 911,759. Polyvinyl nitrate cannot however be used alone because its mechanical strength is not sufficient . When mixed with nitrocellulose, polyvinyl nitrate provides good propellant powders. Such powders are for example described in French patent 2,210,589. However, these powders are not strong enough to be advantageously used in tank guns, moreover we have never managed to add to this powder type an explosive nitrated oil and attempts to mix the three constituents nitrocellulose, polyvinyl nitrate and explosive oil, have so far resulted in a non-homogeneous paste, which is practically impossible to spin and cut into grains. For these reasons, powders for tank guns based on nitrocellulose, polyvinyl nitrate and nitrated oil are not known at the present time.
On a également cherché à fabriquer des poudres à base de nitrocellulose, de nitrate de polyvinyle et de nitroguanidine. Ces poudres sont fabriquées selon le procédé conventionnel dit « avec solvant et sont par exemple décrites dans le brevet français 2 294 998. De telles poudres présentent des performances comparables à celles des poudres à base de nitrocellulose, de nitroglycérine et de nitroguanidine tout en étant plus « froides » que ces dernières, mais, comme ces dernières, ce sont des poudres hétérogènes qui pnésentent l'inconvénient de la tenue mécanique médiocre à froid.Attempts have also been made to manufacture powders based on nitrocellulose, polyvinyl nitrate and nitroguanidine. These powders are produced according to the conventional process known as “with solvent and are for example described in French patent 2,294,998. Such powders have performances comparable to those of powders based on nitrocellulose, nitroglycerine and nitroguanidine while being more “Cold” than the latter, but, like the latter, it is heterogeneous powders which have the disadvantage of poor mechanical strength when cold.
La présente invention a pour objet une nouvelle poudre propulsive homogène en grains, à base de nitrocellulose, d'une huile nitrée explosive et de nitrate de polyvinyle, qui présente une force suffisante pour pouvoir être employée dans les canons de chars tout en ne présentant pas les inconvénients des poudres à double base et notamment en étant moins érosive que ces dernières. Les poudres selon t'invention se caractérisent en ce qu'elles contiennent entre 50 et 75 parties en poids de nitrocellulose, entre 5 et 25 parties en poids de nitrate de polyvinyle et entre 5 et 25 parties en poids d'une huile nitrée pour 100 parties en poids de base énergétique.The present invention relates to a new homogeneous propellant powder in grains, based on nitrocellulose, an explosive nitrated oil and polyvinyl nitrate, which has sufficient strength to be used in tank guns while not having the disadvantages of double base powders and in particular by being less erosive than the latter. The powders according to the invention are characterized in that they contain between 50 and 75 parts by weight of nitrocellulose, between 5 and 25 parts by weight of polyvinyl nitrate and between 5 and 25 parts by weight of a nitrated oil per 100 parts by weight of energy base.
La présente invention a également pour objet un procédé d'obtention des poudres selon l'invention. Le procédé selon l'invention consiste à malaxer les bases énergétiques en présence d'un mélange acétone/alcool jusqu'à l'obtention d'une pâte homogène qui est filée à la presse, essorée, découpée, trempée et séchée, ce procédé se caractérise en ce que :
- (i) la teneur de la pâte en acétone au malaxage est comprise entre 30 et 36 % en poids par rapport au poids de nitrocellulose et de nitrate de polyvinyle secs, et en ce que le rapport pondéral acétone/alcool est compris entre 1,10 et 1,50,
- (ii) on commence par mélanger la nitrocellulose avec l'huile nitrée en présence des solvants puis l'on rajoute le nitrate de polyvinyle sec par fraction au mélange nitrocellulose-huile nitrée-solvants,
- (iii) l'essorage avant découpage est effectué à une température inférieure à 30 °C.
- (i) the content of the acetone in the kneading during the mixing is between 30 and 36% by weight relative to the weight of dry nitrocellulose and polyvinyl nitrate, and in that the acetone / alcohol weight ratio is between 1.10 and 1.50,
- (ii) firstly mixing the nitrocellulose with the nitrated oil in the presence of the solvents, then adding the dry polyvinyl nitrate by fraction to the nitrocellulose-nitrated oil-solvents mixture,
- (iii) the spin before cutting is carried out at a temperature below 30 ° C.
Les poudres selon l'invention présentent une force comparable à celle développée, dans les mêmes conditions de tir, par les poudres à canon classiques à base de nitrocellulose et de nitroglycérine, mais elles ont une température de combustion plus faible que ces dernières et sont donc moins érosives pour les armes. La demanderesse a par ailleurs observé, que les poudres selon l'invention présentent une tendance à l'exsudation plus faible que les poudres classiques à base de nitrocellulose et d'une huile nitrée, et que, de façon surprenante, leur coefficient de température est nettement plus faible que celui des poudres à canon classiques. Le coefficient de température mesure les variations des propriétés balistiques d'une poudre (pression dans la chambre et vitesse de projectile à la sortie de l'arme) en fonction de la température, plus ce coefficient est faible et moins les propriétés balistiques de la poudre sont dépendantes de la température.The powders according to the invention have a force comparable to that developed, under the same firing conditions, by conventional gun powders based on nitrocellulose and nitroglycerine, but they have a lower combustion temperature than the latter and are therefore less erosive for weapons. The Applicant has moreover observed that the powders according to the invention have a lower tendency to exudate than conventional powders based on nitrocellulose and on a nitrated oil, and that, surprisingly, their temperature coefficient is significantly lower than that of conventional gun powders. The temperature coefficient measures the variations in the ballistic properties of a powder (pressure in the chamber and velocity of the projectile at the exit of the weapon) as a function of the temperature, the lower this coefficient is the less the ballistic properties of the powder are dependent on temperature.
Comme il a été dit dans l'état de la technique on n'a pas su obtenir jusqu'à présent une pâte homogène à partir des trois constituants nitrocellulose-nitrate de polyvinyle-huile nitrée. La demanderesse a observé que le respect scrupuleux des conditions opératoires énoncées ci-dessus permet d'obtenir une pâte homogène qui se file bien à la presse et qui après découpage et trempage conduit à des grains de poudre ayant une géométrie définie et une bonne tenue mécanique.As has been said in the state of the art, it has not hitherto been possible to obtain a homogeneous paste from the three constituents nitrocellulose-polyvinyl nitrate-nitrated oil. The Applicant has observed that scrupulous compliance with the operating conditions set out above makes it possible to obtain a homogeneous paste which spins well with the press and which after cutting and soaking leads to grains of powder having a defined geometry and good mechanical strength. .
Les grains de poudre selon l'invention contiennent, comme il a été dit plus haut, entre 50 et 75 parties de nitrocellulose, entre 5 et 25 parties d'huile nitrée et entre 5 et 25 parties de nitrate de polyvinyle pour 100 parties de base énergétique. La demanderesse a observé qu'en dehors de ces fourchettes de composition on n'obtenait pas de poudre homogène présentant les propriétés balistiques et mécaniques suffisantes pour pouvoir être employées comme poudres à canon. On peut employer comme huile nitrée une huile choisie dans le groupe constitué par la nitroglycérine, le trinitrate de triméthylol méthane et le trinitrate de triméthylol éthane. Selon une réalisation préférée de l'invention on utilise la nitroglycérine.The powder grains according to the invention contain, as was said above, between 50 and 75 parts of nitrocellulose, between 5 and 25 parts of nitrated oil and between 5 and 25 parts of polyvinyl nitrate per 100 parts of base energetic. The Applicant has observed that apart from these ranges of composition, no homogeneous powder is obtained having sufficient ballistic and mechanical properties to be able to be used as gun powders. An oil chosen from the group consisting of nitroglycerin, trimethylol methane trinitrate and trimethylol ethane trinitrate can be used as the nitrated oil. According to a preferred embodiment of the invention, nitroglycerin is used.
Les poudres selon l'invention contiennent d'une façon générale en plus des bases énergétiques un stabilisant tel que la nitro-2 diphénylamine, elles peuvent également contenir des agents anti-lueur comme par exemple la cryolithe de potassium. Les poudres selon l'invention ne sont en général pas lissées mais elles peuvent être graphitées selon l'usage envisagé. Une composition préférée selon l'invention contient :
- -67 parties de nitrocellulose,
- -16,5 parties de nitroglycérine,
- -16,5 parties de nitrate de polyvinyle,
- - 1,5 partie de nitro-2 diphénylamine.
- -67 parts of nitrocellulose,
- -16.5 parts of nitroglycerin,
- -16.5 parts of polyvinyl nitrate,
- - 1.5 parts of 2-nitro-diphenylamine.
Une autre composition préférée contient :
- - 60 parties de nitrocellulose,
- - 20 parties de nitroglycérine,
- - 20 parties de nitrate de polyvinyle,
- - 1,5 partie de nitro-2 diphénylamine.
- - 60 parts of nitrocellulose,
- - 20 parts of nitroglycerin,
- - 20 parts of polyvinyl nitrate,
- - 1.5 parts of 2-nitro-diphenylamine.
L'invention a également pour objet un procédé de fabrication des poudres selon l'invention. Ce procédé est un procédé avec solvants qui consiste à malaxer en présence desdits solvants les bases énergétiques jusqu'à l'obtention d'une pâte homogène qui est filée à la presse, sous forme de brins qui sont essorés et découpés en grains.Les grains de poudre sont alors trempés et séchés. L'obtention d'une pâte homogène à partir de nitrocellulose, d'une huile nitrée et de nitrate de polyvinyle est très délicate.The invention also relates to a method for manufacturing powders according to the invention. This process is a process with solvents which consists in kneading the energy bases in the presence of said solvents until a homogeneous paste is obtained which is spun in the press, in the form of strands which are wrung out and cut into grains. powder are then soaked and dried. Obtaining a homogeneous paste from nitrocellulose, a nitrated oil and polyvinyl nitrate is very delicate.
La demanderesse a découvert que seul le respect de conditions très particulières quant à la nature et aux quantités des solvants utilisés et quant aux conditions opératoires du mélange permettait d'obtenir des pâtes homogènes pouvant être aisément filées et découpées en grains.The Applicant has discovered that only compliance with very specific conditions as to the nature and quantities of the solvents used and as to the operating conditions of the mixture makes it possible to obtain homogeneous doughs which can be easily spun and cut into grains.
Selon l'invention on utilise comme solvant un mélange acétone/alcool aliphatique léger dans des proportions telles que la teneur de la pâte en acétone au malaxage soit comprise entre 30 et 36 % en poids par rapport au poids de nitrocellulose et de nitrate de polyvinyle secs et en ce que le rapport pondéral acétone/alcool soit compris entre 1,10 et 1,50. Comme alcool aliphatique léger on préférera l'alcool éthylique. De manière à obtenir une pâte homogène le malaxage doit s'effectuer de la façon suivante. On introduit dans le malaxeur les quantités choisies de nitrocellulose, en général imprégnée par de l'alcool, et d'huile nitrée, en général déjà en solution dans l'acétone, et on complète avec de l'acétone et de l'alcool de manière à avoir les teneurs requises en solvants telles que précédemment définies. On ajoute alors le stabilisant ainsi que les additifs éventuels et on fait alors tourner le malaxeur. Dès que la pâte nitrocellulose-huile nitrée est formée on ajoute par fractions le nitrate de polyvinyle sec en faisant tourner le malaxeur entre chaque fraction de manière à obtenir à chaque fois l'absorption du nitrate de polyvinyle par la pâte déjà formée. Lorsque la totalité de la quantité de nitrate de polyvinyle a ainsi été rajoutée, on fait tourner le malaxeur pendant plusieurs heures de manière à obtenir une pâte parfaitement homogène. Une durée d'environ cinq heures est en général suffisante. La pâte ainsi obtenue est ensuite filée en brins à la presse. Les brins sont alors essorés avant d'être découpés en grains. L'essorage se fait à une température inférieure à 30°C de manière à ne pas altérer les propriétés mécaniques des brins. Après essorage les brins sont découpés en grains. Les grains, après avoir éventuellement subi un premier séchage à chaud, sont alors trempés à l'eau et séchés de façon classique. Les grains de poudre ne sont en général pas lissés, mais ils peuvent être graphités selon l'usage envisagé.According to the invention, a solvent acetone / light aliphatic alcohol is used as solvent in proportions such that the content of the acetone paste on mixing is between 30 and 36% by weight relative to the weight of dry nitrocellulose and polyvinyl nitrate. and in that the acetone / alcohol weight ratio is between 1.10 and 1.50. As light aliphatic alcohol, ethyl alcohol is preferred. In order to obtain a homogeneous paste, the kneading must be carried out as follows. The selected quantities of nitrocellulose, generally impregnated with alcohol, and nitrated oil, generally already dissolved in acetone, are introduced into the mixer, and the mixture is supplemented with acetone and alcohol. so as to have the required levels of solvents as defined above. We add then the stabilizer and any additives and the mixer is then rotated. As soon as the nitrocellulose-nitrated oil paste is formed, dry polyvinyl nitrate is added in fractions by rotating the kneader between each fraction so as to obtain each time the absorption of polyvinyl nitrate by the paste already formed. When the entire quantity of polyvinyl nitrate has thus been added, the mixer is rotated for several hours so as to obtain a perfectly homogeneous paste. A duration of approximately five hours is generally sufficient. The dough thus obtained is then spun into strands by press. The strands are then wrung before being cut into grains. Spinning takes place at a temperature below 30 ° C so as not to alter the mechanical properties of the strands. After spinning the strands are cut into grains. The grains, after having optionally undergone a first hot drying, are then soaked in water and dried in a conventional manner. The grains of powder are generally not smoothed, but they can be graphitized according to the intended use.
L'invention permet ainsi de disposer de grains de poudre homogène à base de nitrocellulose, d'huile nitrée et de nitrate de polyvinyle qui sont notamment utilisables dans les canons de chars de combat, ces grains de poudre ayant une force comparable à celle développée dans les mêmes conditions par des grains de poudre classiques à base de nitrocellulose et de nitroglycérine. Les grains de poudre selon l'invention présentent par ailleurs le double avantage d'avoir une température de combustion moins élevée que ces grains de poudre classiques et d'avoir un coefficient de température plus faible.The invention thus makes it possible to have grains of homogeneous powder based on nitrocellulose, nitrated oil and polyvinyl nitrate which are in particular usable in the tanks of battle tanks, these grains of powder having a force comparable to that developed in the same conditions by conventional grains of powder based on nitrocellulose and nitroglycerin. The powder grains according to the invention also have the double advantage of having a lower combustion temperature than these conventional powder grains and of having a lower temperature coefficient.
L'invention sera mieux comprise à l'aide des exemples de mise en oeuvre, donnés à titre non limitatif, qui suivent.The invention will be better understood with the aid of the examples of implementation, given without implied limitation, which follow.
On introduit dans un malaxeur 67 kg de nitrocellulose (taux d'azote 13,2 %) imprégnée d'alcool éthylique et 16,6 kg de nitroglycérine en solution dans de l'acétone et 1,5 kg de nitro-2 diphénylamine. On rajoute de l'alcool et de l'acétone de manière à avoir au total 23,4 kg d'alcool et 28,4 kg d'acétone dans le malaxeur. On fait tourner le malaxeur et quand la pâte nitrocellulose-nitroglycérine s'est formée on ajoute le nitrate de polyvinyle sec par fraction d'environ 2 kg en faisant tourner le malaxeur entre chaque ajout jusqu'à ce que l'on ait introduit 16,5 kg de nitrate de polyvinyle. On fait alors tourner le malaxeur pendant cinq heures. Après malaxage la pâte obtenue est filée à la presse sous une pression de 170 bars à travers une filière à sept broches. Les brins de poudre ainsi obtenus sont essorés à température ambiante pendant 6 heures. Après essorage les brins de poudre sont découpés en grains et trempés à l'eau à 55 °C pendant 96 heures. Les grains de poudre sont ensuite séchés. Les grains de poudre présentent alors les dimensions suivantes :
- - longueur : 15,5 mm
- -diamètre du grain : 7,5 mm
- -diamètre des trous (7 trous au total) : 0,82 mm
- - web moyen : 1,29 mm.
- - length: 15.5 mm
- - grain diameter: 7.5 mm
- - hole diameter (7 holes in total): 0.82 mm
- - medium web: 1.29 mm.
On a tiré ces grains de poudre dans un canon lisse de 120. Le projectile pesait 6,2 kg et la quantité de poudre employée pesait 7,850 kg. Les tirs ont été effectués à - 40 °C, à + 15 °C et + 51 °C. A titre comparatif on a tiré dans les mêmes conditions des grains de poudre à simple base analogues aux précédents, mais constitués principalement par de la nitrocellulose ayant un taux d'azote de 13,2 %.These grains of powder were fired in a smooth barrel of 120. The projectile weighed 6.2 kg and the quantity of powder used weighed 7.850 kg. The shots were taken at -40 ° C, + 15 ° C and + 51 ° C. By way of comparison, single-base powder grains similar to the previous ones, but mainly constituted by nitrocellulose having a nitrogen content of 13.2%, were drawn up under the same conditions.
Les résultats des tirs sont résumés dans le tableau 1 ci-dessous
II ressort du tableau que la poudre selon l'invention donne selon les températures au projectile une vitesse au moins égale ou supérieure à celle donnée par une poudre classique à simple base et que, entre - 40 °C et + 51 °C la vitesse du projectile ne varie que de 49 m/s avec la poudre selon l'invention alors qu'elle varie de 88 m/s avec une poudre classique. Il en va de même au niveau des pressions développées dans la chambre lors de la mise à feu. Par ailleurs, la température de combustion de la poudre selon l'invention calculée à partir du bilan énergétique est de 3600 K° alors que pour une poudre classique à double base de même force elle est voisine de 3 780 K°, de sorte que l'on dispose grâce à l'invention d'une poudre suffisamment forte pour pouvoir être avantageusement utilisée dans les canons de chars, tout en étant moins chaude que les poudres usuelles à double base utilisées dans ce type d'arme.It emerges from the table that the powder according to the invention gives, depending on the projectile temperatures, a speed at least equal to or greater than that given by a conventional simple base powder and that, between - 40 ° C and + 51 ° C the speed of the projectile varies only by 49 m / s with the powder according to the invention whereas '' it varies from 88 m / s with a conventional powder. The same applies to the pressures developed in the chamber during ignition. Furthermore, the combustion temperature of the powder according to the invention calculated from the energy balance is 3600 K ° whereas for a conventional double base powder of the same strength it is close to 3780 K °, so that the thanks to the invention, there is a sufficiently strong powder to be able to be advantageously used in tank guns, while being less hot than the usual double base powders used in this type of weapon.
On prend la poudre de l'exemple 1 et on la graphite dans un drageoir avec 0,2 % en poids de graphite. La poudre ainsi obtenue est tirée à température ambiante dans un canon lisse de 120. Le projectile pèse 6,2 kg et on emploie 8,2 kg de poudre. La vitesse du projectile à 40 mètres de la bouche du canon est de 1 675,5 m/s et la pression maximum développée dans la chambre de combustion de 4 068 bars.Take the powder from Example 1 and graphite it in a bezel with 0.2% by weight of graphite. The powder thus obtained is fired at room temperature in a smooth 120 ° barrel. The projectile weighs 6.2 kg and 8.2 kg of powder are used. The velocity of the projectile 40 meters from the muzzle of the gun is 1,675.5 m / s and the maximum pressure developed in the combustion chamber of 4,068 bars.
On introduit dans un malaxeur 50 kg de nitrocellulose (taux d'azote 13,2) imprégnée d'alcool éthylique et 25 kg de nitroglycérine en solution dans l'acétone ainsi que 1,5 kg de nitro-2 diphénylamine. On rajoute de l'alcool et de l'acétone de manière à avoir au total 22,5 kg d'alcool et 26,3 kg d'acétone dans le malaxeur. On fait tourner le malaxeur et quand la pâte nitrocellulose-nitroglycérine s'est formée on ajoute le nitrate de polyvinyle sec par fraction d'environ 2 kg en faisant tourner le malaxeur entre chaque ajout jusqu'à ce que l'on ait introduit au total 25 kg de nitrate de polyvinyle. On procède alors comme décrit dans l'exemple 1 de manière à obtenir des grains de poudre présentant les dimensions suivantes :
- - longueur : 18,94 mm
- - diamètre du grain : 8,44 mm
- - diamètre des trous (sept trous au total) : 1,21 mm
- - web moyen : 1,25 mm.
- - length: 18.94 mm
- - grain diameter: 8.44 mm
- - hole diameter (seven holes in total): 1.21 mm
- - medium web: 1.25 mm.
On a tiré ces grains de poudre dans un canon lisse de 120. Le projectile pesait 6,2 kg et la quantité de poudre employée pesait 6,2 kg. Le tir a été effectué à 15 °C. La vitesse de l'obus à 40 mètres de la bouche du canon était de 1 538 m/s tandis que la pression maximale dans la chambre de combustion était de 3 504 bars. A titre de comparaison le même obus tiré avec 6,5 kg de poudre à simple base telle qu'utilisée dans l'exemple 1 avait une vitesse à 40 mètres de la bouche du canon de 1 480 m/s pour une pression maximale dans la chambre de 3 250 bars.These grains of powder were fired in a smooth barrel of 120. The projectile weighed 6.2 kg and the quantity of powder used weighed 6.2 kg. The shooting was carried out at 15 ° C. The speed of the shell 40 meters from the muzzle was 1,538 m / s while the maximum pressure in the combustion chamber was 3,504 bars. By way of comparison, the same shell fired with 6.5 kg of simple base powder as used in Example 1 had a speed 40 meters from the muzzle of the gun of 1480 m / s for maximum pressure in the 3,250 bar chamber.
Cet exemple est destiné à montrer l'importance du respect des conditions opératoires dans la fabrication de la poudre et plus particulièrement l'importance du respect des conditions relatives aux quantités de solvants utilisées.This example is intended to show the importance of compliance with the operating conditions in the manufacture of the powder and more particularly the importance of compliance with the conditions relating to the quantities of solvents used.
On opère exactement comme décrit dans l'exemple 1 à la seule différence que l'on utilise au total 18,1 kg d'alcool et 23,6 kg d'acétone. La teneur de la pâte en acétone au malaxage est donc de 28 % seulement par rapport au poids de nitrocellulose et de nitrate de polyvinyle secs. Par contre, le rapport pondéral acétone/alcool est de 1,3 et se trouve donc correct.The procedure is exactly as described in Example 1 with the only difference that a total of 18.1 kg of alcohol and 23.6 kg of acetone are used. The dough content of acetone in kneading is therefore only 28% relative to the weight of dry nitrocellulose and polyvinyl nitrate. On the other hand, the acetone / alcohol weight ratio is 1.3 and is therefore found to be correct.
Dès la sortie de la filière on observe sur les brins un gonflement de l'ordre de 5 à 6 % sur le diamètre. Après trempage et séchage les grains de poudre obtenus sont déformés et on observe une très grande dispersion des dimensions rendant tout usage industriel de ces grains impossible.As soon as they leave the die, a swelling of the order of 5 to 6% on the diameter is observed on the strands. After soaking and drying the grains of powder obtained are deformed and a very large dispersion of dimensions is observed, making any industrial use of these grains impossible.
Claims (6)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR7836103A FR2444651A1 (en) | 1978-12-22 | 1978-12-22 | NOVEL PROPULSIVE GRAIN POWDERS BASED ON NITROCELLULOSE, NITRATE OIL AND POLYVINYL NITRATE AND THEIR MANUFACTURING PROCESS |
| FR7836103 | 1978-12-22 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0013850A2 EP0013850A2 (en) | 1980-08-06 |
| EP0013850A3 EP0013850A3 (en) | 1980-08-20 |
| EP0013850B1 true EP0013850B1 (en) | 1982-07-21 |
Family
ID=9216447
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP79401002A Expired EP0013850B1 (en) | 1978-12-22 | 1979-12-11 | Granular propellants based on nitrocellulose, nitrated oil and polyvinyl nitrate and process for producing them |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US4347087A (en) |
| EP (1) | EP0013850B1 (en) |
| AU (1) | AU526506B2 (en) |
| CA (1) | CA1143165A (en) |
| DE (1) | DE2963381D1 (en) |
| FR (1) | FR2444651A1 (en) |
| IL (1) | IL58818A (en) |
| NO (1) | NO148413C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5174837A (en) * | 1990-02-21 | 1992-12-29 | Societe Nationale Des Poudres Et Explosifs | Temperature-resistant, fragmentable propellent charges |
| FR2746054B1 (en) * | 1996-03-13 | 1998-06-12 | COMPACTION METHOD, MEANS AND DEVICE, SUITABLE FOR COMPACTING MATERIALS WITH PYROPHORIC TRENDS | |
| US7842144B1 (en) * | 2007-06-01 | 2010-11-30 | The United States Of America As Represented By The Secretary Of The Navy | Methods of making double base casting powder |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE977704C (en) * | 1958-03-07 | 1968-07-11 | Bundesrep Deutschland | Rocket propellants |
| GB1190001A (en) * | 1963-03-20 | 1970-04-29 | Nitrochemie Gmbh | Improvements in or relating to Solid Propellant Charges |
| CH504482A (en) * | 1968-09-19 | 1971-03-15 | Oerlikon Buehrle Ag | Process for stabilizing polyvinyl nitrate |
| FR2163816A5 (en) * | 1971-12-02 | 1973-07-27 | Poudres & Explosifs Ste Nale | Double-base explosive - of improved plasticity |
| FR2166614A5 (en) * | 1971-12-31 | 1973-08-17 | Poudres & Explosifs Ste Nale | Explosive compsn - with nitrated binder |
| FR2210589B1 (en) * | 1972-12-14 | 1976-08-20 | Poudres & Explosifs Ste Nale | |
| DE2329558C3 (en) * | 1973-06-09 | 1978-10-05 | Fraunhofer-Gesellschaft Zur Foerderung Der Angewandten Forschung E.V., 8000 Muenchen | Pourable gas generator propellants |
| FR2240258A1 (en) * | 1973-08-09 | 1975-03-07 | Poudres & Explosifs Ste Nale | Combustible moulding material for shell cartridges - contg. polyvinylnitrate, nitrocellulose and nitro-2-diphenyl methane as stabiliser |
| US4023996A (en) * | 1973-08-09 | 1977-05-17 | Societe Nationale Des Poudres Et Explosifs | Moldable compositions comprising polyvinyl nitrate |
| FR2294998A1 (en) * | 1974-12-17 | 1976-07-16 | Poudres & Explosifs Ste Nale | Tertiary powder for large calibre weapons= - comprising nitrocellulose, polyvinyl nitrate and nitro-guanidine (BE170676) |
| FR2411817A1 (en) * | 1977-12-15 | 1979-07-13 | Poudres & Explosifs Ste Nale | FRAGMENTABLE UNIT LOADING OF PROPELLANT POWDER CONTAINING A BINDER OF POLYVINYL NITRATE |
-
1978
- 1978-12-22 FR FR7836103A patent/FR2444651A1/en active Granted
-
1979
- 1979-11-27 IL IL58818A patent/IL58818A/en unknown
- 1979-12-05 US US06/100,646 patent/US4347087A/en not_active Expired - Lifetime
- 1979-12-06 CA CA000341336A patent/CA1143165A/en not_active Expired
- 1979-12-11 EP EP79401002A patent/EP0013850B1/en not_active Expired
- 1979-12-11 DE DE7979401002T patent/DE2963381D1/en not_active Expired
- 1979-12-18 NO NO794131A patent/NO148413C/en unknown
- 1979-12-21 AU AU54151/79A patent/AU526506B2/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| EP0013850A2 (en) | 1980-08-06 |
| EP0013850A3 (en) | 1980-08-20 |
| IL58818A (en) | 1982-12-31 |
| CA1143165A (en) | 1983-03-22 |
| AU5415179A (en) | 1980-06-26 |
| FR2444651A1 (en) | 1980-07-18 |
| NO148413B (en) | 1983-06-27 |
| AU526506B2 (en) | 1983-01-13 |
| DE2963381D1 (en) | 1982-09-09 |
| US4347087A (en) | 1982-08-31 |
| FR2444651B1 (en) | 1982-04-23 |
| NO794131L (en) | 1980-06-24 |
| NO148413C (en) | 1983-10-05 |
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