EP0711263B1 - Application of an additive to stabilize an explosive composition based on a water-in-oil emulsion - Google Patents

Application of an additive to stabilize an explosive composition based on a water-in-oil emulsion Download PDF

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EP0711263B1
EP0711263B1 EP94921010A EP94921010A EP0711263B1 EP 0711263 B1 EP0711263 B1 EP 0711263B1 EP 94921010 A EP94921010 A EP 94921010A EP 94921010 A EP94921010 A EP 94921010A EP 0711263 B1 EP0711263 B1 EP 0711263B1
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additive
phase
emulsion
droplets
phases
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German (de)
French (fr)
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EP0711263A1 (en
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Gilles Jauffret
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Societe dExplosifs et Produits Chimiques SA
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Societe dExplosifs et Produits Chimiques SA
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    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B47/00—Compositions in which the components are separately stored until the moment of burning or explosion, e.g. "Sprengel"-type explosives; Suspensions of solid component in a normally non-explosive liquid phase, including a thickened aqueous phase
    • C06B47/14—Compositions in which the components are separately stored until the moment of burning or explosion, e.g. "Sprengel"-type explosives; Suspensions of solid component in a normally non-explosive liquid phase, including a thickened aqueous phase comprising a solid component and an aqueous phase
    • C06B47/145—Water in oil emulsion type explosives in which a carbonaceous fuel forms the continuous phase

Definitions

  • the subject of the present invention is the application of additives for stabilize a water in oil emulsion.
  • the technical sector of the invention is the field of manufacture of explosive compositions comprising a water emulsion in oil.
  • One of the main applications of the invention is improving the stability over time of explosive emulsions which are sealed, sensitive to initiating explosives and / or detonators, anti-gassy, pumpable, pourable, as well as those of any other mixture containing a part of emulsion.
  • composition is in fact made up of a solution oxidant obtained from at least one mineral salt dissolved in water and a combustible phase containing at least one liquid hydrocarbon and an emulsifier; this last phase known as the oil phase being immiscible with the discontinuous phase known as the water phase.
  • Agents of lightenings and / or possibly one or more salts can be associated so as to obtain the various characteristics desired pyrotechnics.
  • water in oil emulsion means that the oxidizing solution is dispersed as fines droplets in a continuous organic phase.
  • compositions are described, for example, in patents such as US 3,447,978,3 674 578 or 4 149 917 or even more recently in the US patents 4 356 044 and 4 322 258.
  • water rate contained in the oxidative phase can be eliminated or reduced to a level low, for example less than 4% by weight of the emulsion.
  • Such compositions called “Melt in Oil”, explosive emulsion, are described for example in US Patent No. 4,248,644.
  • Manufacturing explosive emulsions is usually performed in the presence of a surfactant which has the essential functions of allowing the setting emulsion and stabilize said emulsion over time in an attempt to solve the main difficulty mentioned above to maintain long-term pyrotechnic characteristics of the emulsion explosive.
  • the major difficulty consists in maintaining this dispersion stable during a long storage time of the order of at least one year.
  • the emulsion will inevitably evolve over time in due to the thermodynamic instability of the phase dispersion supersaturated in the continuous organic phase. This evolution will lead to a bringing together, called flocculation, of the droplets of dispersed phase, then to the fusion, called coalescence, of several droplets into one. This coalescence eventually leads to crystallization of the oxidative phase, which causes a decrease or a loss of the partial or total sensitivity characteristics of the explosive emulsion. So in the case of an explosive emulsion it may happen that the emulsion is no longer sensitive to detonator usually used for initiation.
  • the active component is dissolved in a diluent organic. This solution is exposed in US Patent 4,784,706 deposited by the company IRECO Inc on December 03, 1987.
  • compositions explosives comprising a water-in-oil emulsion having optimum pyrotechnic performance thanks to the use of a small quantity of additives, but also having said stability two-phase emulsion which is greater than at least one year.
  • an additive in an explosive composition of the water in oil type consisting of a mixture of two immiscible phases one inside the other, one continuous called oil phase (2) comprising organic combustible components, the other discontinuous so-called aqueous phase (1) being an oxidizing solution dispersed in the form of droplets (4) in the continuous phase, which emulsion is stabilized by the presence of both a surfactant mixed at least in one of said phases in which it is soluble and of said additive improving the effect of this surfactant: according to the invention, with the aim of increasing the stabilization of the emulsion, this additive which is chosen liquid and insoluble in each of the two phases, and whose molecules are chosen in such a way that the droplets they are much smaller than the average size of droplets (4) of the dispersed oxidizing solution (1), constitutes a third discontinuous phase (3) in said emulsion located between the droplets of the discontinuous phase (1) with the effect of keeping them separate.
  • Said two-phase emulsion can be prepared by kneading known from mixing of said organic combustible components of the oil phase with said oxidizing solution of the aqueous phase dispersed in the form droplets in the continuous phase and said surfactant, and during the preparation of this emulsion, a liquid additive insoluble in each of said phases, which additive, also dispersed in the form of droplets in the phase continuous, separates those from the aqueous phase and constitutes an emulsion with three liquid phases.
  • said additive itself has surfactant characteristics and is in an amount less than that of the surfactant.
  • the additive is a polyorganosiloxane which is in proportion of constituents less than 5% of the composition and preferably 2%.
  • German patent DE 3,712 488 entitled “Use of silicone oil in emulsions water-in-oil explosives, "so that this oil silicone allows to obtain a less sticky surface, the oil of silicone being the other name for polyorganosiloxane.
  • the inventor of this German patent specifies that this additive modifies the texture of the explosive emulsion: by reducing the stickiness, thus ensuring better packaging: the problem raised by the patent above deals with the downside of explosive emulsions which are usually sticky and capable of being worked this fact very reduced, because they are only injected hot in forms prepared by means of, for example, worms or pumps, and the known packaging for plastic explosives using "Rollex" type machines is therefore not possible.
  • the emulsifiers and silicone oils, used for their non-sticky effect by viscosity reduction are mixed in the organic phase continuous, thus constituting with the discontinuous phase a composition with two phases, the stability of which is the same as in the others explosives of this known type: in fact the coalescence of the droplets of the discontinuous phase is not slowed down because these are dispersed in the only other continuous phase, but can therefore touch and merge.
  • the use according to the present invention solves the problem of stability of emulsions, which is therefore different from the above problem; it is new and constitutes an innovation by creating a third liquid phase through incorporation, unlike what was used until now and recalled previously, of a liquid additive which is not soluble in either of the two main phases emulsion, water in oil, base, and can be dispersed in the phase continues to be between the droplets of the phase and separate them: the additive chosen must therefore allow result in an emulsion with three liquid phases, the third phase that it constitutes in fact serving as a physical barrier between droplets of the aqueous phase which thus remain separated others longer; the choice as a silicone additive complies with the previous conditions, while in the request for patent cited above, this solution and this particularity of use and arrangement of the silicone in the composition is not mentioned and the application in this application is therefore good new and innovative in the conditions of its use. Observation under the electron microscope clearly highlights this third phase and the droplet size of each phase discontinuous as in the attached figure.
  • the pyrotechnic performance of the emulsion may decrease despite the theoretical increase in its stability over time.
  • a small enough additive improving performance pyrotechnics, by choosing of course a characteristic additive surfactant by itself as can be silicone.
  • This additive also reduces the quantity of surfactants thus lowering the cost price of the whole composition and improving performance pyrotechnics while improving stability over time.
  • the emulsion may no longer form; there is thus a compromise optimal between the size of the molecule of said additive in the emulsion and its quantity introduced into the emulsion; so it is necessary on the one hand, that the concentration of said additive, such as silicone, is less than 5% and preferably less than 2% and that the molecules of this additive are small in size allowing the droplets that they are better inserted between the droplets of dispersed aqueous phase of the emulsion; an example of dimensions respectively is given below.
  • concentration of said additive such as silicone
  • the alkaline salt is present in the discontinuous phase, which can contain very little or no water.
  • This discontinuous phase can also include ammonium nitrate in solution with or without a other compound; the presence of another compound makes it possible to obtain a mixture whose melting point is lower than a solution of pure ammonium nitrate.
  • oxidizing salts listed above by family one can mention for example inorganic salts such as nitrate of lithium, silver nitrate, lead nitrate, sodium nitrate, calcium nitrate, potassium nitrate or mixtures thereof.
  • the compound which, in addition to the nitrate ammonium, can form by heating a solution having a point of lower melting than ammonium nitrate can be an alcohol such as methyl alcohol, ethylene glycol, glycerol, monitol, sorbitol, pentaerythritol, or mixtures thereof.
  • Other compounds which can replace or be added to ammonium nitrate in order to make a solution with the nitrate ammonium, can be carbohydrates such as sugars, extrins, carboxylic acids and their salts such as acid formic, acetic acid, ammonium formate, formate sodium, sodium acetate, ammonium acetate.
  • ammonium nitrate compounds which can replace or be added to ammonium nitrate include chloroacetic acid, acid glycolic, succinic acid, tartaric acid, adipic acid, and short chain aliphatic amines such as formamide, acetamide and urea.
  • Urea can be used as some can nitrogenous substances such as nitroguanidine, nitrate of guamidine, methylamine, methylamine nitrate and dinitrate ethylene diamine.
  • Each of the substances listed above can be used alone with ammonium nitrate, or mixtures thereof can be used as a mixture with ammonium nitrate in such a way the melting point of the final mixture obtained has a melting point low enough.
  • the substances chosen to form a solution with ammonium nitrate are chosen in addition to the price criterion, so as to form a pyrotechnic mixture without major risks having a melting point between 70 ° C and 130 ° C, although these values do not constitute insurmountable limits.
  • the oil phase which is insoluble and immiscible in water is preferably a non-explosive organic fuel of its own and can include at least one member of the petroleum group, halogenated hydrocarbons and nitrogenous hydrocarbons.
  • the oil phase includes one or more paraffins and / or microcrystalline waxes and / or flexible paraffins and can also include one or more members of the group making up the mineral oils, fuels oils, liquid paraffins, xylene, toluene, petrolatum and dinitrotoluene.
  • the oil phase of the emulsion comprises at least one emulsifier or surfactant selected from the group including among others sorbitan oleate, sorbitan sesquioleate, stearate sorbitan, sorbitan palmitate, sodium monostearate, sodium tristearate, mono and diglycerides of fatty acids, soy lecithin, lanolin derivatives, benzene alkyls sulfonates, oleic acid phosphate, laurylamine acetate, decaglycerol decaoleate, decaglycerol decastearate, 2oleyl4-4'bis (hydroxymethyl) 2oxazoline, and surfactants polymers containing double polyethylene glycol chains with fatty acid chains as well as anhydride derivatives succinic and polyisobutethylene.
  • emulsifier or surfactant selected from the group including among others sorbitan oleate, sorbitan sesquioleate, stearate sorbitan
  • the above process like the previous one can preferably use an additive whose molecules are chosen in such a way that the droplets they form in the emulsion are large much smaller than the average droplet size of the solution dispersed oxidant, said additive itself having characteristics surfactants and being in a quantity lower than that of the agent surfactant.
  • the above process like the previous one can also use and preferably an additive such as polyorganosiloxane, mentioned above as being silicone oil.
  • the additive has a viscosity of between 5 and 30,000 Mpas.
  • a polydimethylsiloxane of preferential viscosity between 5 and 10,000 Mpas and at best between 5 and 1,000 Mpas.
  • this additive of a type such as silicone, depends on its quantity and the size of its molecule. Indeed, the viscosity is a function of the size of the molecule.
  • the third liquid phase which it constitutes is dispersed in the continuous phase in the form of droplets, which are interposed between those of the aqueous phase, make it possible to slow down even more the coalescence then flocculation and therefore the destabilization of the emulsion.
  • this three-phase additive it can be also optionally used as previously indicated in the first stability solution the addition of thickening agents such as waxes, paraffins, bentonites, polymers for thicken the continuous phase.
  • thickening agents such as waxes, paraffins, bentonites, polymers for thicken the continuous phase.
  • the attached figure is a simplified schematic view of an image microscopic of an explosive composition according to the invention: this composition comprising a water-in-oil emulsion, consists, as already described several times previously and such as this is well known to date, of a mixture of two immiscible phases one inside the other, one of which continues known as the oil phase 2 comprises organic fuel components, and the other so-called discontinuous aqueous phase 1 is a dispersed oxidizing solution; this one is formed of medium-sized droplets 4, pressed against each other the others, and whose space they leave between them is filled by the continuous phase 2.
  • said emulsion is stabilized, on the one hand, by the presence of at least one known surfactant, mixed at least in one of said phases, in which it is soluble, and of a liquid additive improving the effect of this surfactant; this is chosen to be insoluble in each of the two said phases 1 and 2, then constitutes a third liquid phase 3 of said composition, in the form of droplets 5, which located in the continuous phase 2 are interposed between those 4 of the aqueous phase and separate them.
  • This third phase thus imposes a separation distance between the droplets 4, thanks to the choice of an additive which is insoluble in the two said phases and which disperses in the continuous phase in the form of droplets 5.
  • said droplets 5 form a screen between the droplets of discontinuous phase 1, and further delay the effect of coalescence and fusion of said droplets between them.

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Description

La présente invention a pour objet l'application d'additifs pour stabiliser une émulsion eau dans huile.The subject of the present invention is the application of additives for stabilize a water in oil emulsion.

Le secteur technique de l'invention est le domaine de la fabrication de compositions explosives comprenant une émulsion eau dans huile.The technical sector of the invention is the field of manufacture of explosive compositions comprising a water emulsion in oil.

Une des applications principales de l'invention est l'amélioration de la stabilité dans le temps des émulsions explosives quelles soient encartouchées, sensibles aux explosifs d'amorçage et/ou aux détonateurs, anti-grisouteuses, pompables, versables, ainsi que celles de tout autre mélange contenant une partie d'émulsion.One of the main applications of the invention is improving the stability over time of explosive emulsions which are sealed, sensitive to initiating explosives and / or detonators, anti-gassy, pumpable, pourable, as well as those of any other mixture containing a part of emulsion.

On connaít en effet différentes compositions explosives du type émulsion eau dans huile que l'on peut fabriquer de différentes manières : la principale difficulté de ces fabrications réside dans le maintien à long terme des caractéristiques pyrotechniques de ces émulsions explosives.We know indeed different explosive compositions of the type water-in-oil emulsion that can be made from different manners: the main difficulty of these manufactures lies in the long-term maintenance of the pyrotechnic characteristics of these explosive emulsions.

Ce type de composition est en effet constitué d'une solution oxydante obtenue à partir d'au moins un sel minéral dissous dans l'eau et d'une phase combustible contenant au moins un hydrocarbure liquide et un émulsifiant ; cette dernière phase dite phase huile étant immiscible avec la phase discontinue dite phase eau. Des agents d'allégements et/ou éventuellement un ou plusieurs sels peuvent être associés de façon à obtenir les diverses caractéristiques pyrotechniques souhaitées. Le terme émulsion "eau dans huile" signifie que la solution oxydante est dispersée sous forme de fines gouttelettes dans une phase continue organique. De telles compositions sont décrites, par exemple, dans les brevets tels que US 3 447 978, 3 674 578 ou 4 149 917 ou encore plus récemment dans les brevets US 4 356 044 et 4 322 258. Pour certaines applications le taux d'eau contenu dans la phase oxydante peut être éliminé ou réduit à un niveau bas, par exemple moins de 4 % en poids de l'émulsion. De telles compositions, appelées "Melt in Oil", émulsion explosive, sont décrites par exemple dans le brevet US n° 4 248 644. La fabrication des émulsions explosives est généralement effectuée en présence d'un tensioactif qui a pour fonctions essentielles de permettre la mise en émulsion et de stabiliser dans le temps ladite émulsion pour tenter de résoudre la principale difficulté évoquée précédemment de maintenir à long terme les caractéristiques pyrotechniques de l'émulsion explosive.This type of composition is in fact made up of a solution oxidant obtained from at least one mineral salt dissolved in water and a combustible phase containing at least one liquid hydrocarbon and an emulsifier; this last phase known as the oil phase being immiscible with the discontinuous phase known as the water phase. Agents of lightenings and / or possibly one or more salts can be associated so as to obtain the various characteristics desired pyrotechnics. The term "water in oil" emulsion means that the oxidizing solution is dispersed as fines droplets in a continuous organic phase. Such compositions are described, for example, in patents such as US 3,447,978,3 674 578 or 4 149 917 or even more recently in the US patents 4 356 044 and 4 322 258. For certain applications the water rate contained in the oxidative phase can be eliminated or reduced to a level low, for example less than 4% by weight of the emulsion. Such compositions, called "Melt in Oil", explosive emulsion, are described for example in US Patent No. 4,248,644. Manufacturing explosive emulsions is usually performed in the presence of a surfactant which has the essential functions of allowing the setting emulsion and stabilize said emulsion over time in an attempt to solve the main difficulty mentioned above to maintain long-term pyrotechnic characteristics of the emulsion explosive.

En effet, nous venons de voir que les émulsions explosives dites "eau dans huile" dans lesquelles se situe la présente invention, était un mélange de deux phases non miscibles l'une dans l'autre et dont celle aqueuse sursaturée en produits oxydants se présente sous forme de gouttelettes dispersées dans l'autre phase huile.Indeed, we have just seen that the so-called explosive emulsions "water in oil" in which the present invention is located, was a mixture of two immiscible phases one inside the other and of which that aqueous supersaturated with oxidizing products is in the form droplets dispersed in the other oil phase.

La difficulté majeure consiste à maintenir cette dispersion stable durant un long temps de stockage de l'ordre d'au moins une année. En effet, l'émulsion va inévitablement évoluer dans le temps en raison de l'instabilité thermodynamique de la dispersion de la phase sursaturée dans la phase organique continue. Cette évolution va conduire à un rapprochement, appelé floculation, des gouttelettes de phase dispersée, puis à la fusion, appelée coalescence, de plusieurs gouttelettes en une seule. Cette coalescence entraíne à terme une cristallisation de la phase oxydante, ce qui provoque une baisse ou une perte des caractéristiques de sensibilité partielle ou totale de l'émulsion explosive. Ainsi dans le cas d'une émulsion explosive encartouchée il peut arriver que l'émulsion ne soit plus sensible au détonateur habituellement utilisé pour l'amorçage.The major difficulty consists in maintaining this dispersion stable during a long storage time of the order of at least one year. Indeed, the emulsion will inevitably evolve over time in due to the thermodynamic instability of the phase dispersion supersaturated in the continuous organic phase. This evolution will lead to a bringing together, called flocculation, of the droplets of dispersed phase, then to the fusion, called coalescence, of several droplets into one. This coalescence eventually leads to crystallization of the oxidative phase, which causes a decrease or a loss of the partial or total sensitivity characteristics of the explosive emulsion. So in the case of an explosive emulsion it may happen that the emulsion is no longer sensitive to detonator usually used for initiation.

Pour retarder ce phénomène et donc tenter d'améliorer la stabilité de l'émulsion diphasique dans le temps, on rajoute généralement d'une manière connue et dans tous les cas à ce jour, un produit tensioactif que l'on peut qualifier de standard, dont la molécule est composée, pour faciliter sa solubilité dans chacune des deux phases, de deux parties dont l'une est compatible avec la phase aqueuse dispersée et l'autre avec la phase organique continue. Cependant, ce rajout de produit tensioactif standard, s'il est économiquement acceptable n'est pas suffisant pour améliorer durablement la stabilité de l'émulsion, pour laquelle trois autres solutions ont été développées par divers fabricants :

  • la première solution consiste à augmenter la viscosité de la phase huile de façon à ralentir le phénomène de coalescence : pour cela il a été proposé comme dans la demande de brevet US 4 908 079 d'ajouter dans la phase continue des agents épaississants telles que des cires, des paraffines, des polymères ; il pourrait être ajouté également des bentonites. On retrouve également ce type de solution dans la demande de brevet n° FR 2 645 144 déposée le 3 mars 1990 sous priorité norvégienne par la société NORSK HYDRO et intitulée "explosif brisant stabilisé de type de nitrate ammonium mazout et son procédé de fabrication" comportant essentiellement le rajout d'un élastomère soluble dans les huiles.
To delay this phenomenon and therefore try to improve the stability of the two-phase emulsion over time, a surfactant which can be described as standard is generally added in a known manner and in all cases to date. whose molecule is composed, to facilitate its solubility in each of the two phases, of two parts, one of which is compatible with the dispersed aqueous phase and the other with the continuous organic phase. However, this addition of standard surfactant, if it is economically acceptable is not sufficient to durably improve the stability of the emulsion, for which three other solutions have been developed by various manufacturers:
  • the first solution consists in increasing the viscosity of the oil phase so as to slow down the coalescence phenomenon: for this it has been proposed, as in patent application US Pat. No. 4,908,079, to add thickening agents such as waxes, paraffins, polymers; bentonites could also be added. This type of solution is also found in patent application No. FR 2 645 144 filed on March 3, 1990 under Norwegian priority by the company NORSK HYDRO and entitled "stabilized breaking explosive of the type of ammonium nitrate fuel oil and its manufacturing process" comprising essentially the addition of an elastomer soluble in oils.

Cependant cette solution, qui est du reste toujours possible en option dans les solutions suivantes et même dans la présente invention, pose des problèmes de fabrication car la viscosité des mélanges et des produits est très élevée, gênant les pompages ; la manipulation est très difficile et donc plus coûteuse.

  • la deuxième solution porte essentiellement sur les phénomènes chimiques alors que la solution précédente joue sur un phénomène physique: elle consiste à améliorer la stabilisation de l'émulsion par l'utilisation d'un tensioactif optimisé choisi spécifiquement en fonction des composants de l'émulsion explosive de base. Ce tensioactif est choisi de façon à pouvoir être soluble dans chacune des deux phases constituant l'émulsion, et ainsi grâce à ces interactions entre chacune de ces phases il parvient à augmenter la stabilité dans le temps de celle-ci. Son utilisation permet de ralentir le phénomène de coalescence et stabilise donc l'émulsion. Le problème de cette solution est que ces produits tensioactifs sont d'un coût très élevé. Cette solution peut mettre en oeuvre notamment des dérivés phénoliques du type polybutène polymérisé avec une amine à chaíne carbonée polyéthylène comportant un radical phénolique.
However, this solution, which is moreover always possible as an option in the following solutions and even in the present invention, poses manufacturing problems because the viscosity of the mixtures and of the products is very high, hampering pumping; handling is very difficult and therefore more expensive.
  • the second solution relates essentially to chemical phenomena whereas the preceding solution plays on a physical phenomenon: it consists in improving the stabilization of the emulsion by the use of an optimized surfactant chosen specifically according to the components of the explosive emulsion basic. This surfactant is chosen so as to be able to be soluble in each of the two phases constituting the emulsion, and thus thanks to these interactions between each of these phases it succeeds in increasing the stability over time thereof. Its use makes it possible to slow down the phenomenon of coalescence and therefore stabilizes the emulsion. The problem with this solution is that these surfactants are very expensive. This solution can use in particular phenolic derivatives of the polybutene type polymerized with an amine with a polyethylene carbon chain comprising a phenolic radical.

Le composant actif est mis en solution dans un diluant organique. Cette solution est exposé dans le brevet US 4 784 706 déposé par la société IRECO Inc le 03 Décembre 1987.The active component is dissolved in a diluent organic. This solution is exposed in US Patent 4,784,706 deposited by the company IRECO Inc on December 03, 1987.

Des variantes voisines sont exposées dans de nombreux brevets.Similar variants are exposed in numerous patents.

Cette solution implique de réaliser des réactions chimiques entre les différentes matières premières entrant dans la composition du tensioactif ce qui implique un surcroít de travail et d'équipement par rapport à un produit commercialement plus répandu.

  • une troisième solution qui est en fait une sous solution de la précédente est l'utilisation d'un additif rajouté au tensioactif soit standard, soit tel que défini dans la solution précédente, et qui est soluble dans l'une des deux phases : son choix permet d'améliorer les propriétés du tensioactif et donc de diminuer la quantité de celui-ci, facilitant la mise en oeuvre précédente, réduisant les coûts tout en maintenant une stabilité considérée comme optimisée dans les solutions de fabrications actuelles. Cette solution a fait l'objet de nombreuses demandes de brevets, notamment celles déposées par la voie européenne sous les n°EP 0107368 le 26 Septembre 1983 par la société Imperial Chemical Industries PLC, et EP 0018085 du 18 Mars 1980 par la société CIL Inc. Cependant, malgré ces combinaisons d'additifs et de tensioactifs en fonction des objectifs et des procédés précédents, il est difficile d'obtenir des compositions explosives d'émulsions eau dans huile permettant d'avoir une stabilité de qualité explosive supérieure à une année. De plus, quand on augmente la quantité d'additifs, on diminue les performances pyrotechniques : on se trouve ainsi devant le dilemme d'avoir à augmenter la stabilité du mélange mais au détriment des performances pyrotechniques ou d'améliorer ces performances en diminuant la quantité d'additif mais au détriment de la stabilité.
This solution involves carrying out chemical reactions between the different raw materials used in the composition of the surfactant, which involves additional work and equipment compared to a commercially more widespread product.
  • a third solution which is in fact a sub-solution of the previous one is the use of an additive added to the surfactant either standard or as defined in the previous solution, and which is soluble in one of the two phases: its choice makes it possible to improve the properties of the surfactant and therefore to reduce the quantity of it, facilitating the previous implementation, reducing the costs while maintaining a stability considered to be optimized in current manufacturing solutions. This solution has been the subject of numerous patent applications, in particular those filed by the European channel under the number EP 0107368 on September 26, 1983 by the company Imperial Chemical Industries PLC, and EP 0018085 of March 18, 1980 by the company CIL Inc However, despite these combinations of additives and surfactants depending on the objectives and the previous methods, it is difficult to obtain explosive compositions of water-in-oil emulsions making it possible to have an explosive quality stability greater than one year. In addition, when the quantity of additives is increased, the pyrotechnic performances are reduced: we are thus faced with the dilemma of having to increase the stability of the mixture but at the expense of pyrotechnic performances or of improving these performances by reducing the quantity additive but at the expense of stability.

Le problème posé est donc de pouvoir réaliser des compositions explosives comprenant une émulsion eau dans huile ayant des performances pyrotechniques optimum grâce à l'utilisation d'une petite quantité d'additifs, mais ayant par ailleurs une stabilité de ladite émulsion diphasique qui soit supérieure à au moins une année.The problem is therefore to be able to make compositions explosives comprising a water-in-oil emulsion having optimum pyrotechnic performance thanks to the use of a small quantity of additives, but also having said stability two-phase emulsion which is greater than at least one year.

Selon l'invention le problème est résolu par l'application d'un additif dans une composition explosive du type eau dans huile, constituée d'un mélange de deux phases non miscibles l'une dans l'autre, l'une continue dite phase huile (2) comprenant des composants combustibles organiques, l'autre discontinue dite phase aqueuse (1) étant une solution oxydante dispersée sous forme de gouttelettes (4) dans la phase continue, laquelle émulsion est stabilisée par la présence à la fois d'un agent tensioactif mélangé au moins dans une desdites phases dans lesquelles il est soluble et dudit additif améliorant l'effet de cet agent tensioactif : suivant l'invention, dans le but d'augmenter la stabilisation de l'emulsion, cet additif qui est choisi liquide et insoluble dans chacune des deux phases, et dont les molécules sont choisies de telle façon que les gouttelettes qu'elles forment sont de taille très inférieure à la taille moyenne des gouttelettes (4) de la solution oxydante dispersée (1), constitue une troisième phase discontinue (3) dans ladite émulsion située entre les gouttelettes de la phase discontinue (1) avec pour effet de les maintenir séparées.According to the invention the problem is solved by the application of an additive in an explosive composition of the water in oil type, consisting of a mixture of two immiscible phases one inside the other, one continuous called oil phase (2) comprising organic combustible components, the other discontinuous so-called aqueous phase (1) being an oxidizing solution dispersed in the form of droplets (4) in the continuous phase, which emulsion is stabilized by the presence of both a surfactant mixed at least in one of said phases in which it is soluble and of said additive improving the effect of this surfactant: according to the invention, with the aim of increasing the stabilization of the emulsion, this additive which is chosen liquid and insoluble in each of the two phases, and whose molecules are chosen in such a way that the droplets they are much smaller than the average size of droplets (4) of the dispersed oxidizing solution (1), constitutes a third discontinuous phase (3) in said emulsion located between the droplets of the discontinuous phase (1) with the effect of keeping them separate.

On peut préparer ladite émulsion diphasique par malaxage connu du mélange desdits composants combustibles organiques de la phase huile avec ladite solution oxydante de la phase aqueuse dispersée sous forme de gouttelettes dans la phase continue et ledit agent tensioactif, et on rajoute en cours de préparation de cette émulsion un additif liquide insoluble dans chacune desdites phases, lequel additif, également dispersé sous forme de gouttelettes dans la phase continue, sépare celles de la phase aqueuse et constitue une émulsion à trois phases liquides.Said two-phase emulsion can be prepared by kneading known from mixing of said organic combustible components of the oil phase with said oxidizing solution of the aqueous phase dispersed in the form droplets in the continuous phase and said surfactant, and during the preparation of this emulsion, a liquid additive insoluble in each of said phases, which additive, also dispersed in the form of droplets in the phase continuous, separates those from the aqueous phase and constitutes an emulsion with three liquid phases.

Dans un mode préférentiel de réalisation ledit additif a lui-même des caractéristiques tensioactives et est en quantité inférieure à celle de l'agent tensioactif.In a preferred embodiment said additive itself has surfactant characteristics and is in an amount less than that of the surfactant.

De préférence, l'additif est un polyorganosiloxane qui est en proportion de constituants inférieure à 5% de la composition et préférentiellement 2%.Preferably, the additive is a polyorganosiloxane which is in proportion of constituents less than 5% of the composition and preferably 2%.

Ce dernier additif est enseigné dans le brevet allemand DE 3 712 488 intitulé "utilisation d'huile de silicone dans les émulsions explosives du type eau dans huile", de telle façon que cette huile de silicone permette d'obtenir une surface moins collante, l'huile de silicone étant l'autre nom du polyorganosiloxane. L'inventeur de ce brevet allemand précise que cet additif modifie la texture de l'émulsion explosive : en diminuant le pouvoir collant, assurant ainsi un meilleur encartouchage : le problème soulevé en effet par le brevet ci-dessus porte sur l'inconvénient des émulsions explosives qui sont habituellement collantes et dont la capacité à être travaillées est de ce fait très réduite, car elles ne se laissent injecter qu'à chaud dans des formes préparées au moyen par exemple de vis sans fin ou pompes, et l'encartouchage connu pour les explosifs plastiques au moyen de machines de type "Rollex", n'est alors pas possible.The latter additive is taught in German patent DE 3,712 488 entitled "Use of silicone oil in emulsions water-in-oil explosives, "so that this oil silicone allows to obtain a less sticky surface, the oil of silicone being the other name for polyorganosiloxane. The inventor of this German patent specifies that this additive modifies the texture of the explosive emulsion: by reducing the stickiness, thus ensuring better packaging: the problem raised by the patent above deals with the downside of explosive emulsions which are usually sticky and capable of being worked this fact very reduced, because they are only injected hot in forms prepared by means of, for example, worms or pumps, and the known packaging for plastic explosives using "Rollex" type machines is therefore not possible.

Dans ce document, il est précisé également que les émulsifiants et les huiles de silicone, utilisées pour leur effet non collant par réduction de viscosité, sont mélangés dans la phase organique continue, constituant donc avec la phase discontinue une composition à deux phases, dont la stabilité est la même que dans les autres explosifs de ce type connu : en effet la coalescence des gouttelettes de la phase discontinue n'est pas ralentie car celles-ci sont dispersées dans la seule autre phase continue, mais peuvent donc se toucher et fusionner.In this document, it is also specified that the emulsifiers and silicone oils, used for their non-sticky effect by viscosity reduction, are mixed in the organic phase continuous, thus constituting with the discontinuous phase a composition with two phases, the stability of which is the same as in the others explosives of this known type: in fact the coalescence of the droplets of the discontinuous phase is not slowed down because these are dispersed in the only other continuous phase, but can therefore touch and merge.

L'utilisation selon la présente invention résoud le problème de la stabilité des émulsions, qui est donc différent du problème ci-dessus; elle est nouvelle et constitue une innovation en créant une troisième phase liquide grâce à l'incorporation, contrairement à ce qui était utilisé jusqu'à présent et rappelé précédemment, d'un additif liquide qui à la fois ne soit soluble dans aucune des deux phases principales de l'émulsion, eau dans huile, de base, et puisse être dispersé dans la phase continue pour se situer entre les gouttelettes de la phase aqueuse et les séparer : l'additif choisi doit ainsi permettre d'aboutir à une émulsion à trois phases liquides, la troisième phase qu'il constitue servant en fait de barrière physique entre les gouttelettes de la phase aqueuse qui restent ainsi séparées les unes des autres plus longtemps ; le choix comme additif du silicone respecte les conditions précédentes, alors que dans la demande de brevet citée ci-dessus, cette solution et cette particularité d'utilisation et de disposition du silicone dans la composition n'est pas évoquée et l'application dans la présente demande est donc bien nouvelle et innovatrice dans les conditions de son utilisation. L'observation au microscope électronique met bien en évidence cette troisième phase et la taille des gouttelettes de chacune des phases discontinues telle que dans la figure jointe.The use according to the present invention solves the problem of stability of emulsions, which is therefore different from the above problem; it is new and constitutes an innovation by creating a third liquid phase through incorporation, unlike what was used until now and recalled previously, of a liquid additive which is not soluble in either of the two main phases emulsion, water in oil, base, and can be dispersed in the phase continues to be between the droplets of the phase and separate them: the additive chosen must therefore allow result in an emulsion with three liquid phases, the third phase that it constitutes in fact serving as a physical barrier between droplets of the aqueous phase which thus remain separated others longer; the choice as a silicone additive complies with the previous conditions, while in the request for patent cited above, this solution and this particularity of use and arrangement of the silicone in the composition is not mentioned and the application in this application is therefore good new and innovative in the conditions of its use. Observation under the electron microscope clearly highlights this third phase and the droplet size of each phase discontinuous as in the attached figure.

De plus, on a pu mesurer que le rajout de cet additif permet de diminuer la taille des gouttelettes de la phase aqueuse et donc améliore effectivement la tenue au vieillissement de ce type d'émulsion : en particulier et par exemple sans silicone le diamètre moyen des gouttelettes a été mesuré de l'ordre de 2 µm alors qu'avec du silicone également en gouttelettes suivant l'invention les gouttelettes obtenues de la phase aqueuse discontinue ont un diamètre moyen de l'ordre de 0,5 µm, ce qui améliore bien sûr d'autant plus la tenue dans le temps et retarde le phénomène de coalescence cité précédemment.In addition, we were able to measure that the addition of this additive makes it possible to decrease the size of the droplets of the aqueous phase and therefore effectively improves aging resistance of this type emulsion: in particular and without silicone, the diameter mean of the droplets was measured in the order of 2 µm whereas with silicone also in droplets according to the invention droplets obtained from the discontinuous aqueous phase have a diameter 0.5 µm, which of course improves the held over time and delays the phenomenon of coalescence cited previously.

De même, on a pu mesurer également, pour illustrer la caractéristique préférentielle de la taille moyenne des gouttelettes de l'additif dans l'émulsion très inférieure à celle de la solution oxydante que, celles du silicone en particulier ont une taille moyenne de 0,03 µm de diamètre pour une taille moyenne de 0,5 µm des gouttelettes de la phase discontinue aqueuse comme indiqué ci-dessus.Similarly, we were also able to measure, to illustrate the preferred characteristic of the average droplet size of the additive in the emulsion much lower than that of the solution oxidizing that those of silicone in particular have an average size 0.03 µm in diameter for an average size of 0.5 µm of droplets of the discontinuous aqueous phase as indicated above.

De plus, au delà de cette diminution de taille des gouttelettes qui constitue un premier effet de cet additif créant cette troisième phase, cette dernière, créant une discontinuité supplémentaire dans la phase continue, retarde comme indiqué précédemment le phénomène de floculation, empêchant une cristallisation et donc préserve d'autant plus longtemps la sensibilité des émulsions dans le temps.In addition, beyond this reduction in droplet size which constitutes a first effect of this additive creating this third phase, the latter, creating an additional discontinuity in the continuous phase, delays the phenomenon of flocculation, preventing crystallization and therefore preserves as much the longer the sensitivity of emulsions over time.

Par ailleurs, comme nous l'avons déjà cité précédemment, au delà d'une certaine quantité d'additif, les performances pyrotechniques de l'émulsion risquent de diminuer malgré l'augmentation théorique de sa stabilité dans le temps. Dans la présente invention, une petite quantité d'additif suffit, améliorant ainsi les performances pyrotechniques, en choisissant bien sûr un additif à caractéristique tensioactive par lui-même tel que peut l'être le silicone.Furthermore, as we have already mentioned above, beyond of a certain amount of additive, the pyrotechnic performance of the emulsion may decrease despite the theoretical increase in its stability over time. In the present invention, a small enough additive, improving performance pyrotechnics, by choosing of course a characteristic additive surfactant by itself as can be silicone.

La présence de cet additif permet également de diminuer la quantité de produits tensioactifs abaissant ainsi le prix de revient de l'ensemble de la composition et améliorant les performances pyrotechniques tout en améliorant la stabilité dans le temps.The presence of this additive also reduces the quantity of surfactants thus lowering the cost price of the whole composition and improving performance pyrotechnics while improving stability over time.

Par contre, au delà d'une certaine quantité d'additif créant une troisième phase telle que décrit dans la présente invention, l'émulsion risque de ne plus se former ; il existe ainsi un compromis optimal entre la taille de la molécule dudit additif dans l'émulsion et sa quantité introduite dans l'émulsion ; ainsi il est nécessaire d'une part que la concentration dudit additif, tel que le silicone, soit inférieure à 5% et préférentiellement à 2% et que les molécules de cet additif soient de petites tailles permettant aux gouttelettes qu'elles constituent de mieux s'insérer entre les gouttelettes de phase dispersée aqueuse de l'émulsion ; un exemple de dimensions respectives est donné ci-après.By cons, beyond a certain amount of additive creating a third phase as described in the present invention, the emulsion may no longer form; there is thus a compromise optimal between the size of the molecule of said additive in the emulsion and its quantity introduced into the emulsion; so it is necessary on the one hand, that the concentration of said additive, such as silicone, is less than 5% and preferably less than 2% and that the molecules of this additive are small in size allowing the droplets that they are better inserted between the droplets of dispersed aqueous phase of the emulsion; an example of dimensions respectively is given below.

Des tests de vieillissement ont montré que la stabilité est effectivement de beaucoup améliorée : en particulier avec du silicone il a été mesuré des durées de vies d'émulsion, toutes conditions égales par ailleurs, avec des performances pyrotechniques suffisantes, supérieure à 24 mois alors que sans silicone la durée de vie est de l'ordre de 9 mois.Aging tests have shown that stability is actually much improved: especially with silicone emulsion lifetimes were measured, all conditions also equal, with sufficient pyrotechnic performance, more than 24 months whereas without silicone the lifespan is around 9 months.

Il est à noter que les améliorations citées précédemment sont valables de quelle manière que soit obtenue la sensibilisation de ces émulsions au mode d'amorçage désiré. Il est fait ici notamment allusion aux possibilités de réduire la densité desdites émulsions de différentes façons et notamment par incorporation mécanique de gaz, dégagement chimique de gaz, ou incorporation mécanique de matériaux légers tels que microbilles de verre creuses, résines phénoliques, perlites, polystyrène expansé ou autres et, tels que certaines demandes de brevets en revendiquent des caractéristiques spécifiques.It should be noted that the improvements mentioned above are valid in whatever way the awareness of these emulsions in the desired priming mode. It is made here in particular allusion to the possibilities of reducing the density of said emulsions of different ways and in particular by mechanical incorporation of gas, chemical release of gas, or mechanical incorporation of materials light such as hollow glass microbeads, phenolic resins, perlites, expanded polystyrene or others and, such as certain patent applications claim specific characteristics.

On pourrait citer d'autres avantages de la présente invention, mais ceux cités ci-dessus en montrent déjà suffisamment pour en démontrer la nouveauté et l'intérêt.We could cite other advantages of the present invention, but those cited above already show enough to demonstrate novelty and interest.

La présente description inclut des exemples de réalisations de l'invention mais n'ont aucun caractère limitatif : d'autres réalisations sont possibles en particulier en utilisant d'autres additifs : d'autres réalisations sont en effet possibles à partir des revendications qui précisent la portée et l'étendue de cette invention et permettent de trouver d'autres compositions possibles ayant les caractéristiques citées. This description includes examples of realizations of the invention but have no limiting character: others achievements are possible especially using other additives: other realizations are indeed possible from claims which specify the scope and extent of this invention and allow to find other possible compositions having the features cited.

Habituellement la phase discontinue de ladite émulsion comprend au moins un des sels oxydants suivants :

  • nitrate ammonium
  • nitrate de métaux alcalins
  • nitrate de métaux alcalins-terreux
  • perchlorate d'ammonium
  • perchlorate de métaux alcalins
  • perchlorate de métaux alcalins-terreux.
Usually the discontinuous phase of said emulsion comprises at least one of the following oxidizing salts:
  • ammonium nitrate
  • alkali metal nitrate
  • alkaline earth metal nitrate
  • ammonium perchlorate
  • alkali metal perchlorate
  • alkaline earth metal perchlorate.

Le sel alcalin est présent dans la phase discontinue, qui peut contenir très peu d'eau ou pas d'eau. Cette phase discontinue peut comprendre également du nitrate d'ammonium en solution avec ou sans un autre composé ; la présence d'un autre composé permet d'obtenir un mélange dont le point de fusion est inférieur à une solution de nitrate d'ammonium pur.The alkaline salt is present in the discontinuous phase, which can contain very little or no water. This discontinuous phase can also include ammonium nitrate in solution with or without a other compound; the presence of another compound makes it possible to obtain a mixture whose melting point is lower than a solution of pure ammonium nitrate.

Parmi les sels oxydants listés ci-dessus par famille, on peut citer par exemple des sels inorganiques tels que du nitrate de lithium, nitrate d'argent, nitrate de plomb, nitrate de sodium, nitrate de calcium, nitrate de potassium ou des mélanges de ceux-ci.Among the oxidizing salts listed above by family, one can mention for example inorganic salts such as nitrate of lithium, silver nitrate, lead nitrate, sodium nitrate, calcium nitrate, potassium nitrate or mixtures thereof.

De même ou de plus, le composé qui, en addition avec le nitrate d'ammonium, peut former en chauffant une solution ayant un point de fusion inférieure à celui du nitrate d'ammonium, peut être un alcool tel que l'alcool méthylique, l'éthylène glycol, le glycérol, le monitol, le sorbitol, le pentaérythritol, ou des mélanges de ceux-ci.Likewise or in addition, the compound which, in addition to the nitrate ammonium, can form by heating a solution having a point of lower melting than ammonium nitrate, can be an alcohol such as methyl alcohol, ethylene glycol, glycerol, monitol, sorbitol, pentaerythritol, or mixtures thereof.

D'autres composés, qui peuvent remplacer ou être ajoutés au nitrate d'ammonium afin de faire une solution avec le nitrate d'ammonium, peuvent être des carbohydrates tels que des sucres, des extrines, des acides carboxyliques et leurs sels tels que l'acide formique, l'acide acétique, le formate d'ammonium, le formate de sodium, l'acétate de sodium, l'acétate d'ammonium.Other compounds, which can replace or be added to ammonium nitrate in order to make a solution with the nitrate ammonium, can be carbohydrates such as sugars, extrins, carboxylic acids and their salts such as acid formic, acetic acid, ammonium formate, formate sodium, sodium acetate, ammonium acetate.

D'autres composés qui peuvent remplacer ou être ajoutés au nitrate d'ammonium incluent l'acide chloroacétique, l'acide glycolique, l'acide succinique, l'acide tartrique, l'acide adipique, et des amines aliphatiques à chaíne courte telles que la formamide, l'acétamide et l'urée.Other compounds which can replace or be added to ammonium nitrate include chloroacetic acid, acid glycolic, succinic acid, tartaric acid, adipic acid, and short chain aliphatic amines such as formamide, acetamide and urea.

L'urée peut être utilisée comme peuvent l'être certaines substances azotées telles que la nitroguanidine, le nitrate de guamidine, la méthylamine, le nitrate de méthylamine et le dinitrate d'éthylène diamine.Urea can be used as some can nitrogenous substances such as nitroguanidine, nitrate of guamidine, methylamine, methylamine nitrate and dinitrate ethylene diamine.

Chacune des substances citées ci-dessus peuvent être utilisées seules avec le nitrate d'ammonium, ou des mélanges d'entre elles peuvent être utilisées en mélange au nitrate d'ammonium de telle façon que le point de fusion du mélange final obtenu ait un point de fusion suffisamment bas.Each of the substances listed above can be used alone with ammonium nitrate, or mixtures thereof can be used as a mixture with ammonium nitrate in such a way the melting point of the final mixture obtained has a melting point low enough.

En général, les substances choisies pour former une solution avec le nitrate d'ammonium sont choisies en plus du critère du prix, de façon à former un mélange pyrotechnique sans risques majeurs ayant un point de fusion compris entre 70°C et 130°C, bien que ces valeurs ne constituent pas des limites infranchissables.In general, the substances chosen to form a solution with ammonium nitrate are chosen in addition to the price criterion, so as to form a pyrotechnic mixture without major risks having a melting point between 70 ° C and 130 ° C, although these values do not constitute insurmountable limits.

La phase huile qui est insoluble et immiscible dans l'eau est de préférence un combustible organique non explosif de lui-même et peut comprendre au moins un membre du groupe des hydrocarbures, des hydrocarbures halogénés et des hydrocarbures azotés.The oil phase which is insoluble and immiscible in water is preferably a non-explosive organic fuel of its own and can include at least one member of the petroleum group, halogenated hydrocarbons and nitrogenous hydrocarbons.

Habituellement, la phase huile comprend une ou plusieurs paraffines et/ou cires microcristallines et/ou paraffines souples et peut aussi inclure un ou plusieurs membres du groupe composant les huiles minérales, les fuels oils, les paraffines liquide, le xylène, le toluène, le pétrolatum et le dinitrotoluène.Usually the oil phase includes one or more paraffins and / or microcrystalline waxes and / or flexible paraffins and can also include one or more members of the group making up the mineral oils, fuels oils, liquid paraffins, xylene, toluene, petrolatum and dinitrotoluene.

La phase huile de l'émulsion comprend au moins un émulsifiant ou tensioactif sélectionné parmi le groupe comprenant entre autres l'oléate de sorbitan, le sesquioléate de sorbitan, le stéarate de sorbitan, le palmitate de sorbitan, le monostéarate de sodium, le tristéarate de sodium, les mono et diglycérides d'acides gras, la lécithine de soja, les dérivés de lanoline, les alkyls benzène sulfonatés, le phosphate d'acide oléique, l'acétate de laurylamine, le décaoléate de décaglycérol, le décastéarate de décaglycérol, le 2oleyl4-4'bis(hydroxyméthyl)2oxazoline, et des tensioactifs polymériques contenant des doubles chaínes polyéthylène glycol avec des chaínes d'acides gras ainsi que des dérivés de l'anhydride succinique et du polyisobuthylène.The oil phase of the emulsion comprises at least one emulsifier or surfactant selected from the group including among others sorbitan oleate, sorbitan sesquioleate, stearate sorbitan, sorbitan palmitate, sodium monostearate, sodium tristearate, mono and diglycerides of fatty acids, soy lecithin, lanolin derivatives, benzene alkyls sulfonates, oleic acid phosphate, laurylamine acetate, decaglycerol decaoleate, decaglycerol decastearate, 2oleyl4-4'bis (hydroxymethyl) 2oxazoline, and surfactants polymers containing double polyethylene glycol chains with fatty acid chains as well as anhydride derivatives succinic and polyisobutethylene.

Plusieurs procédés de préparation de ces compositions, tels que ci-dessus et tels que suivant l'invention, peuvent être envisagés dont l'un est rappelé précédemment et dont un autre peut être un procédé de préparation d'une composition explosive comprenant une émulsion eau dans huile constituée d'un mélange de deux phases non miscibles l'une dans l'autre, l'une continue dite phase huile comprenant des composants combustibles organiques, l'autre discontinue aqueuse étant une solution oxydante dispersée sous forme de gouttelettes dans la phase continue, laquelle émulsion est stabilisée par la présence d'un agent tensioactif mélangé dans au moins une desdites phases dans lesquelles il est miscible, et dans l'une desquelles il est préalablement dissous :

  • on rajoute alors dans la phase continue seule, avant mélange avec la phase discontinue, un additif liquide non soluble dans ces deux phases et constituant alors avec la phase continue une première émulsion diphasique,
  • on incorpore dans cette première émulsion ladite phase discontinue et on malaxe pour obtenir une émulsion à trois phases liquides, dont celle constituée par ledit additif est située entre les gouttelettes de la phase aqueuse et les sépare.
Several methods for preparing these compositions, as above and such as according to the invention, can be envisaged, one of which is mentioned above and another of which can be a method of preparing an explosive composition comprising a water emulsion in oil consisting of a mixture of two immiscible phases one inside the other, one continuous known as the oil phase comprising organic combustible components, the other aqueous discontinuous being an oxidizing solution dispersed in the form of droplets in the phase continuous, which emulsion is stabilized by the presence of a surfactant mixed in at least one of said phases in which it is miscible, and in one of which it is previously dissolved:
  • a liquid additive which is not soluble in these two phases is then added to the continuous phase alone, before mixing with the discontinuous phase, and then constituting with the continuous phase a first two-phase emulsion,
  • this discontinuous phase is incorporated into this first emulsion and kneaded to obtain an emulsion with three liquid phases, of which the one constituted by said additive is located between the droplets of the aqueous phase and separates them.

Le procédé ci-dessus comme le précédent peut de préférence utiliser un additif dont les molécules sont choisies de telle façon que les gouttelettes qu'elles forment dans l'émulsion sont de taille très inférieure à la taille moyenne des gouttelettes de la solution oxydante dispersée, ledit additif ayant lui-même des caractéristiques tensioactives et étant en quantité inférieure à celle de l'agent tensioactif.The above process like the previous one can preferably use an additive whose molecules are chosen in such a way that the droplets they form in the emulsion are large much smaller than the average droplet size of the solution dispersed oxidant, said additive itself having characteristics surfactants and being in a quantity lower than that of the agent surfactant.

Le procédé ci-dessus comme le précédent peut utiliser également et de préférence un additif tel que le polyorganosiloxane, rappelé ci-dessus comme étant l'huile de silicone.The above process like the previous one can also use and preferably an additive such as polyorganosiloxane, mentioned above as being silicone oil.

De préférence, ce qui est le cas de l'huile précédente, l'additif est d'une viscosité comprise entre 5 et 30000 Mpas. De même, il peut être intéressant et préférable d'utiliser comme additif préférentiel un polydiméthylsiloxane de viscosité préférentielle entre 5 et 10 000 Mpas et au mieux entre 5 et 1 000 Mpas.Preferably, which is the case with the previous oil, the additive has a viscosity of between 5 and 30,000 Mpas. Likewise, it can be interesting and preferable to use as an additive preferably a polydimethylsiloxane of preferential viscosity between 5 and 10,000 Mpas and at best between 5 and 1,000 Mpas.

Les performances de cet additif, de type telle que l'huile de silicone, sont fonctions de sa quantité et de la taille de sa molécule. En effet, la viscosité est fonction de la taille de la molécule.The performance of this additive, of a type such as silicone, depends on its quantity and the size of its molecule. Indeed, the viscosity is a function of the size of the molecule.

La troisième phase liquide qu'il constitue est dispersée dans la phase continue sous forme de gouttelettes, qui intercalées entre celles de la phase aqueuse, permettent de ralentir encore plus la coalescence puis la floculation et donc la déstabilisation de l'émulsion.The third liquid phase which it constitutes is dispersed in the continuous phase in the form of droplets, which are interposed between those of the aqueous phase, make it possible to slow down even more the coalescence then flocculation and therefore the destabilization of the emulsion.

Pour compléter l'effet de cet additif triphasique, il peut être également utilisé en option comme indiqué précédemment dans la première solution de stabilité le rajout d'agents épaississants tels que des cires, des paraffines, des bentonites, des polymères pour épaissir la phase continue.To complete the effect of this three-phase additive, it can be also optionally used as previously indicated in the first stability solution the addition of thickening agents such as waxes, paraffins, bentonites, polymers for thicken the continuous phase.

La figure jointe est une vue schématique simplifiée d'une image microscopique d'une composition explosive suivant l'invention : cette composition comprenant une émulsion eau dans l'huile, est constituée, comme déjà décrit à plusieurs reprises précédemment et tel que cela est bien connu à ce jour, d'un mélange de deux phases non miscibles l'une dans l'autre, dont l'une continue dite phase huile 2 comprend les composants combustibles organiques, et l'autre discontinue dite phase aqueuse 1 est une solution oxydante dispersée ; celle-ci est formée de gouttelettes 4 de taille moyenne, accolées les unes contre les autres, et dont l'espace qu'elles laissent entre elles est rempli par la phase continue 2.The attached figure is a simplified schematic view of an image microscopic of an explosive composition according to the invention: this composition comprising a water-in-oil emulsion, consists, as already described several times previously and such as this is well known to date, of a mixture of two immiscible phases one inside the other, one of which continues known as the oil phase 2 comprises organic fuel components, and the other so-called discontinuous aqueous phase 1 is a dispersed oxidizing solution; this one is formed of medium-sized droplets 4, pressed against each other the others, and whose space they leave between them is filled by the continuous phase 2.

Suivant l'invention, ladite émulsion est stabilisée, d'une part, par la présence au moins d'un agent tensioactif connu, mélangé au moins dans une desdites phases, dans lesquelles il est soluble, et d'un additif liquide améliorant l'effet de cet agent tensioactif ; celui-ci est choisi insoluble dans chacune des deux dites phases 1 et 2, constitue alors une troisième phase liquide 3 de ladite composition, sous forme de gouttelettes 5, qui situées dans la phase continue 2 s'intercalent entre celles 4 de la phase aqueuse et les séparent. Cette troisième phase impose ainsi une distance de séparation entre les gouttelettes 4, grâce au choix d'un additif insoluble dans les deux dites phases et qui se disperse dans la phase continue sous forme de gouttelettes 5. Cette distance de séparation est d'autant plus maintenue que ces gouttelettes 5 formées par les molécules de cet additif sont d'un diamètre de l'ordre de 3 x 10-2µ, alors que les gouttelettes 4 de la phase discontinue 3 sont de dimensions extérieures de l'ordre de 50 x 10-2µ, ce qui permet une telle disposition suivant la figure jointe : la distance qui sépare les gouttelettes 4 est alors au minimum égale au diamètre de ces gouttelettes 5, alors que sans la présence de celles-ci elle ne serait que de 0,2 x 10-2µ environ, ce qui étant beaucoup plus faible, provoque l'effet de coalescence et de floculation relevé dans les émulsions connues à ce jour réduisant ainsi leur stabilité dans le temps.According to the invention, said emulsion is stabilized, on the one hand, by the presence of at least one known surfactant, mixed at least in one of said phases, in which it is soluble, and of a liquid additive improving the effect of this surfactant; this is chosen to be insoluble in each of the two said phases 1 and 2, then constitutes a third liquid phase 3 of said composition, in the form of droplets 5, which located in the continuous phase 2 are interposed between those 4 of the aqueous phase and separate them. This third phase thus imposes a separation distance between the droplets 4, thanks to the choice of an additive which is insoluble in the two said phases and which disperses in the continuous phase in the form of droplets 5. This separation distance is all the more maintained that these droplets 5 formed by the molecules of this additive are of a diameter of the order of 3 × 10 -2 μ, while the droplets 4 of the discontinuous phase 3 are of external dimensions of the order of 50 × 10 -2 µ, which allows such an arrangement according to the attached figure: the distance between the droplets 4 is then at least equal to the diameter of these droplets 5, while without the presence of these it would only be 0 , 2 x 10 -2 μm approximately, which being much smaller, causes the coalescence and flocculation effect noted in the emulsions known to date, thus reducing their stability over time.

On constate bien sur cette figure que lesdites gouttelettes 5 forment écran entre les gouttelettes de la phase discontinue 1, et retardent d'autant plus l'effet de coalescence et de fusion desdites gouttelettes entre elles.It can be seen in this figure that said droplets 5 form a screen between the droplets of discontinuous phase 1, and further delay the effect of coalescence and fusion of said droplets between them.

Claims (7)

  1. The use of an additive in an explosive composition of the water-in-oil type, the composition being constituted by a mixture of two phases that are not miscible one in the other, a continuous "oil" phase (2) thereof comprising organic fuel components, and a discontinuous "aqueous" other phase (1) thereof being an oxidizing solution dispersed in the form of droplets (4), which emulsion is stabilized by the presence of at least one surfactant agent mixed in at least one of said phases in which it is soluble and also by the presence of said additive improving the effect of said surfactant agent, said use being characterized in that in order to increase the stability of the emulsion, the additive is selected to be liquid and insoluble in each of said two phases, the molecules of the additive are selected in such a manner as to ensure that the droplets they form are much smaller in size than the mean size of the droplets (4) of the dispersed oxidizing solution (1), and the additive constitutes a discontinuous third phase (3) of said emulsion situated between the droplets (2) of the discontinuous phase (1) with the effect of keeping said droplets apart.
  2. The use of an additive in a water-in-oil emulsion according to claim 1, characterized in that the additive used is a polyorganosiloxane at a concentration of less than 5% of the composition.
  3. The use of an additive according to claim 1 or 2, characterized in that said additive itself has surfactant characteristics and is present in a quantity smaller than that of the surfactant agent.
  4. The use of an additive according to any one of claims 1 to 3, characterized in that the additive is of viscosity lying in the range 5 MPa.s to 30,000 MPa.s.
  5. The use of an additive according to any one of claims 1 to 4, characterized in that the additive is a polydimethylsiloxane.
  6. The use of an additive according to any one of claims 1 to 5, characterized in that:
    said water-in-oil emulsion is prepared by conventional blending of the mixture of said organic fuel components of the oil phase (2) with said oxidizing solution of the aqueous phase (1) in the form of droplets (4) dispersed in the continuous phase (2) and with said surfactant agent: and
    while preparing said emulsion, said liquid additive that is insoluble in each of said phases is added thereto.
  7. The use of an additive according to any one of claims 1 to 6. characterized in that:
    the liquid additive (3) that is not soluble in either of the two phases is added to the continuous phase (2) on its own prior to mixing with the discontinuous phase, thereby constituting a first two-phase emulsion with the continuous phase; and
    said discontinuous phase (1) is incorporated in said first emulsion and blending is performed to obtain a three-phase emulsion.
EP94921010A 1993-07-29 1994-07-01 Application of an additive to stabilize an explosive composition based on a water-in-oil emulsion Expired - Lifetime EP0711263B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR9309638A FR2708479B1 (en) 1993-07-29 1993-07-29 Application of an additive to stabilize a water in oil emulsion, explosive composition and corresponding preparation process.
FR9309638 1993-07-29
PCT/FR1994/000811 WO1995004017A1 (en) 1993-07-29 1994-07-01 Application of an additive to stabilize a water-in-oil emulsion, explosive composition and corresponding method of preparation

Publications (2)

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EP0711263A1 EP0711263A1 (en) 1996-05-15
EP0711263B1 true EP0711263B1 (en) 1999-02-10

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EP (1) EP0711263B1 (en)
AU (1) AU7189594A (en)
DE (1) DE69416519T2 (en)
ES (1) ES2127933T3 (en)
FR (1) FR2708479B1 (en)
MA (1) MA23283A1 (en)
WO (1) WO1995004017A1 (en)

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WO2003006402A1 (en) * 2001-07-12 2003-01-23 Dynaenergetics Gmbh & Co. Kg Cladding and compacting explosive

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US4632714A (en) * 1985-09-19 1986-12-30 Megabar Corporation Microcellular composite energetic materials and method for making same
GB8822937D0 (en) * 1988-09-30 1988-11-09 Nc Dev Inc Chemical formulations
DE3712488C1 (en) * 1987-04-13 1988-05-05 Dynamit Nobel Ag Use of silicone oils in water-in-oil emulsion explosives, and silicone oil-containing water-in-oil emulsion explosives having reduced surface tackiness
DE4204175A1 (en) * 1991-02-15 1992-08-20 Dynamit Nobel Ag Stable, flameproof emulsion explosives - contain combustible organic phase, aq. phase contg. oxidising agent etc., and inert flame-proofing agent coated with waterproofing agent

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DE69416519T2 (en) 1999-09-16
FR2708479A1 (en) 1995-02-10
MA23283A1 (en) 1995-04-01
ES2127933T3 (en) 1999-05-01
FR2708479B1 (en) 1995-10-27
EP0711263A1 (en) 1996-05-15
DE69416519D1 (en) 1999-03-25
WO1995004017A1 (en) 1995-02-09
AU7189594A (en) 1995-02-28

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