WO1995004017A1 - Application of an additive to stabilize a water-in-oil emulsion, explosive composition and corresponding method of preparation - Google Patents

Application of an additive to stabilize a water-in-oil emulsion, explosive composition and corresponding method of preparation Download PDF

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Publication number
WO1995004017A1
WO1995004017A1 PCT/FR1994/000811 FR9400811W WO9504017A1 WO 1995004017 A1 WO1995004017 A1 WO 1995004017A1 FR 9400811 W FR9400811 W FR 9400811W WO 9504017 A1 WO9504017 A1 WO 9504017A1
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phase
emulsion
additive
droplets
phases
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PCT/FR1994/000811
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French (fr)
Inventor
Gilles Jauffret
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Explosifs Et Produits Chimiques S.A.
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Application filed by Explosifs Et Produits Chimiques S.A. filed Critical Explosifs Et Produits Chimiques S.A.
Priority to DE69416519T priority Critical patent/DE69416519T2/en
Priority to EP94921010A priority patent/EP0711263B1/en
Priority to AU71895/94A priority patent/AU7189594A/en
Publication of WO1995004017A1 publication Critical patent/WO1995004017A1/en

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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 to stabilize a water-in-oil emulsion, and explosive compositions and corresponding preparation methods.
  • the technical sector of the invention is the field of manufacturing explosive compositions comprising a water in oil emulsion.
  • One of the main applications of the invention is the improvement of the stability over time of explosive emulsions which are cartridge-sealed, sensitive to priming explosives and / or detonators, anti-gassy, pumpable, pourable, as well as those of any another mixture containing a part of emulsion.
  • various explosive compositions of the water-in-oil emulsion type are known which can be manufactured in different ways: the main difficulty of these manufactures lies in the long-term maintenance of the pyrotechnic characteristics of these explosive emulsions.
  • This type of composition is in fact made up of an oxidizing solution 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.
  • Lightening agents and / or possibly one or more salts can be combined so as to obtain the various desired pyrotechnic characteristics.
  • water in oil emulsion means that the oxidizing solution is dispersed in the form of fine droplets in a continuous organic phase.
  • compositions are described, for example, in patents such as US 3,477,978, 3,67-4,578 or 4 14 17 or even more recently in US patents 4,356 04 * 4 and 4,322,258.
  • water content in the oxidizing phase can be eliminated or reduced to a low level, 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.
  • the manufacture of explosive emulsions is generally carried out in the presence of a surfactant which has the essential functions of allowing emulsification and of stabilizing said emulsion over time in an attempt to resolve the main difficulty mentioned above of maintaining the pyrotechnic characteristics of the explosive emulsion in the long term.
  • the major difficulty consists in keeping this dispersion stable during a long storage time of the order of at least one year. Indeed, the emulsion will inevitably evolve over time due to the thermodynamic instability of the dispersion of the supersaturated phase in the continuous organic phase. This development 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 oxidizing phase, which causes a decrease or loss of the characteristics of partial or total sensitivity of the explosive emulsion. Thus in the case of an explosive cartridge-containing emulsion it may happen that the emulsion is no longer sensitive to the detonator usually used for priming.
  • 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.
  • 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 as a function of the components of the emulsion basic explosive.
  • 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.
  • This solution involves carrying out chemical reactions between the various raw materials used in the composition of the surfactant, which involves additional work and equipment compared to a more widely used product.
  • an additive in an emulsion known as water in oil, consisting of a mixture of two immiscible phases one inside the other, one continuous known as oil phase comprising components organic fuels, the other discontinuous in the form of droplets being an oxidizing solution dispersed in the continuous phase and called the aqueous phase, which emulsion is stabilized by the presence therefore known both of 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, this additive is chosen to be liquid and insoluble in each of the two phases: it is used to constitute a third discontinuous phase in said emulsion and dispersed in the continuous phase, which third phase is located between the droplets of the discontinuous phase of the oxidizing solution, separates them, and increases the stabilization of the emulsion.
  • an explosive composition comprising a water-in-oil emulsion consisting of, and defined above, of a mixture of two phases which are immiscible in one another and according to the invention, of an additive liquid insoluble in each of the two said phases, constituting a third liquid phase of said composition in the form of droplets, which located between the droplets of the discontinuous aqueous phase separate them.
  • the objective of the present invention is also obtained by a process for the preparation of an explosive composition as defined above and comprising a water-in-oil emulsion consisting of a mixture of two phases which are immiscible one in the other, l 'one continuous known as oil phase the other discontinuous known as aqueous phase; which emulsion is stabilized by the known presence of at least one surfactant mixed in at least one of said phases in which it is soluble; a process according to the present invention is then such that:
  • said two-phase emulsion is prepared by known kneading of the mixture of said organic combustible components of the oil phase with said oxidizing solution of the aqueous phase dispersed in the form of droplets in the continuous phase and said surfactant,
  • a liquid additive insoluble in each of the said phases is added, which additive, also dispersed in the form of droplets in the continuous phase, separates those from the aqueous phase and constitutes an emulsion with three liquid phases.
  • the droplets of said additive in the emulsion are of average size much smaller than the average size of the droplets of the dispersed oxidizing solution, said additive itself having surfactant characteristics and being in an amount less than that of l surfactant.
  • the additive is a polyorganosiloxane which is in proportion of constituents less than ⁇ 3% of the composition and preferably 2%.
  • the emulsifiers and silicone oils used for their non-sticky effect by reduction of viscosity, are mixed in the continuous organic phase, thus constituting with the discontinuous phase a two-phase composition, the stability is the same as in other explosives of this known type: in fact the coalescence of the droplets of the discontinuous phase is not slowed down because they are dispersed in the only other continuous phase, but can therefore touch and merge.
  • the addition of this additive makes it possible to reduce the size of the droplets of the aqueous phase and therefore effectively improves the aging resistance of this type of emulsion: in particular and for example without silicone the average diameter of the droplets was measured on the order of 2 ⁇ m whereas with silicone also in droplets according to the invention the droplets obtained from the discontinuous aqueous phase have an average diameter of the order of 0.5 ⁇ m, which improves well more secure over time and delays the coalescence phenomenon mentioned above.
  • the pyrotechnic performance of the emulsion may decrease despite the theoretical increase in its stability over time.
  • a small amount of additive is sufficient, thereby improving the pyrotechnic performance, by of course choosing an additive with surfactant characteristic by itself as can be silicone.
  • the presence of this additive also makes it possible to reduce the quantity of surfactants, thereby lowering the cost price of the entire composition and improving performance pyrotechnics while improving stability over time.
  • the emulsion may no longer be formed; there is thus an optimal compromise between the size of the molecule of said additive in the emulsion and its quantity introduced into the emulsion; thus it is necessary on the one hand that the concentration of said additive, such as silicone, is less than 5% and preferably at 2% and that the molecules of this additive are of small sizes allowing the droplets that they constitute better s insert between the droplets of aqueous dispersed phase of the emulsion; an example of respective dimensions is given below.
  • concentration of said additive such as silicone
  • the discontinuous phase of said emulsion comprises at least one of the following oxidizing salts:
  • the alkaline salt is present in the discontinuous phase, which may contain very little or no water.
  • This discontinuous phase can also comprise ammonium nitrate in solution with or without another 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.
  • inorganic salts such as lithium nitrate, silver nitrate, lead nitrate, sodium nitrate, calcium nitrate, potassium nitrate or mixtures of these.
  • the compound which, in addition to ammonium nitrate, can form by heating a solution having a melting point lower than that of 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 ammonium nitrate, can be carbohydrates such as sugars, extrins, carboxylic acids and their salts such as formic acid, acetic acid, ammonium formate, sodium formate, sodium acetate, ammonium acetate.
  • Other compounds which can replace or be added to ammonium nitrate include chloroacetic acid, glycolic acid, succinic acid, tartaric acid, adipic acid, and short chain aliphatic amines such as formamide, acetamide and urea.
  • Urea can be used as can certain nitrogenous substances such as nitroguanidine, guamidine nitrate, methylamine, methylamine nitrate and dinitrate ethylene diamine.
  • Each of the substances mentioned above can be used alone with ammonium nitrate, or mixtures of them can be used in mixture with ammonium nitrate so that the melting point of the final mixture obtained has a point sufficiently low.
  • 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 of between 70 ° C and 130 ° C, although these values are not insurmountable limits.
  • the oil phase which is insoluble and immiscible in water is preferably an organic non-explosive fuel of its own and can comprise at least one member from the group of hydrocarbons, halogenated hydrocarbons and nitrogenous hydrocarbons.
  • the oil phase comprises one or more paraffins and / or microcrystalline waxes and / or flexible paraffins and can also include one or more members of the group comprising 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 comprising inter alia sorbitan oleate, sorbitan sesquioleate, sorbitan stearate, sorbitan palmitate, sodium monostearate, tristearate sodium, mono and diglycerides of fatty acids, soy lecithin, lanolin derivatives, alkyl benzene sulfonates, oleic acid phosphate, laurylamine acetate, decaglycerol decaoleate, decaglycerol decastearate, 2oleyl4-4'bis (hydroxymethyl) 2oxazoline, and polymeric surfactants containing double polyethylene glycol chains with fatty acid chains as well as derivatives of succinic anhydride and polyisobutethylene.
  • emulsifier or surfactant selected from the group comprising inter alia sorbitan oleate, sorbitan sesquioleate, sorbitan
  • 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
  • a water emulsion in oil consisting of a mixture of two immiscible phases, one in 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 continuous phase, which emulsion is stabilized by the presence of a mixed surfactant in at least one of said phases in which it is miscible, and in one of which it is previously dissolved:
  • the above process can preferably use an additive, the molecules of which are chosen so that the droplets which they form in the emulsion are much smaller than the average size of the droplets of the dispersed oxidizing solution, said additive itself having surfactant characteristics and being in an amount less than that of the surfactant.
  • the above process like the previous one can also and preferably use 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 the type such as silicone oil, 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 interposed between those of the aqueous phase, make it possible to slow down even more the coalescence then flocculation and therefore destabilization of the emulsion.
  • this three-phase additive can also be used as an option, as indicated previously in the first stability solution, the addition of thickening agents such as waxes, paraffins, bentonites, polymers to thicken the continuous phase.
  • thickening agents such as waxes, paraffins, bentonites, polymers to thicken the continuous phase.
  • the attached figure is a simplified schematic view of a microscopic image of an explosive composition according to the invention: this composition comprising a water-in-oil emulsion, is constituted, as already described several times previously and as it 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 the organic combustible components, and the other discontinuous known as the aqueous phase 1 is an oxidizing solution scattered; the latter is formed of medium-sized droplets 4, placed against one another, and the space of which 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 inserted 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 insoluble in the two said phases and which disperses in the continuous phase in the form of droplets -
  • 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 x 10 ⁇ 2 ⁇ , while the droplets 4 of the discontinuous phase 3 are of external dimensions of the order of 50 x 10 ⁇ 2 ⁇ , which allows such an arrangement according to the attached figure: the distance which separates the droplets 4 is then at least equal to the diameter of these droplets 5- while without the presence of these it would not be than 0.2 x 10 ⁇ 2 ⁇ approximately, which being much lower, causes the effect of coalescence and flocculation noted in the emulsions known to date thus reducing their stability over time. It can be seen in this figure that said droplets 5 form a screen between the droplets 4 of the discontinuous phase 1, and further delay the coalescence and melting effect of said droplets 4 between them.

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Abstract

The technical field of the invention is that of the manufacture of explosive compositions comprising a water-in-oil emulsion containing of a mixture of two phases immiscible in one another, a continuous phase (2) comprising organic combustible components, and a discontinuous phase (1) in a dispersed oxidizing solution. The emulsion is stabilized by the presence of at least one surface-active agent mixed at least in one of said phases, wherein it is soluble, and of a surface-active agent reinforcing additive. According to the invention, the additive selected is insoluble in each of the two phases, and is used to form a third phase (3) in said emulsion, the third phase (3) being situated between the droplets (4) of the discontinuous phase (1). The third phase acts as a barrier between the droplets and increases emulsion stabilization.

Description

Application d'un additif pour stabiliser une émulsion eau dans huile, composition explosive et procédé de préparation correspondant. Application of an additive to stabilize a water in oil emulsion, explosive composition and corresponding preparation process.
La présente invention a pour objet l'application d'additifs pour stabiliser une émulsion eau dans huile, et des compositions explosives et des procédés de préparation correspondants.The subject of the present invention is the application of additives to stabilize a water-in-oil emulsion, and explosive compositions and corresponding preparation methods.
Le secteur technique de l'invention est le domaine de la fabrication de compositions explosives comprenant une émulsion eau dans huile. 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. On connaît 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. 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 47 978, 3 67-4 578 ou 4 14 17 ou encore plus récemment dans les brevets US 4 356 04*4 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.The technical sector of the invention is the field of manufacturing explosive compositions comprising a water in oil emulsion. One of the main applications of the invention is the improvement of the stability over time of explosive emulsions which are cartridge-sealed, sensitive to priming explosives and / or detonators, anti-gassy, pumpable, pourable, as well as those of any another mixture containing a part of emulsion. In fact, various explosive compositions of the water-in-oil emulsion type are known which can be manufactured in different ways: the main difficulty of these manufactures lies in the long-term maintenance of the pyrotechnic characteristics of these explosive emulsions. This type of composition is in fact made up of an oxidizing solution 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. Lightening agents and / or possibly one or more salts can be combined so as to obtain the various desired pyrotechnic characteristics. The term "water in oil" emulsion means that the oxidizing solution is dispersed in the form of fine droplets in a continuous organic phase. Such compositions are described, for example, in patents such as US 3,477,978, 3,67-4,578 or 4 14 17 or even more recently in US patents 4,356 04 * 4 and 4,322,258. For certain applications the water content in the oxidizing phase can be eliminated or reduced to a low level, 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. The manufacture of explosive emulsions is generally carried out in the presence of a surfactant which has the essential functions of allowing emulsification and of stabilizing said emulsion over time in an attempt to resolve the main difficulty mentioned above of maintaining the pyrotechnic characteristics of the explosive emulsion in the long term.
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 1'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 explosive emulsions called "water in oil" in which the present invention is located, was a mixture of two phases immiscible one in the other and of which the aqueous one supersaturated in oxidizing products occurs in the form of 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 entraîne à terme une cristallisation de la phase oxydante, ce qui provoque une baisse ou une perte des caractéristiques de sensibilité partielle ou totale de 1'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 keeping this dispersion stable during a long storage time of the order of at least one year. Indeed, the emulsion will inevitably evolve over time due to the thermodynamic instability of the dispersion of the supersaturated phase in the continuous organic phase. This development 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 oxidizing phase, which causes a decrease or loss of the characteristics of partial or total sensitivity of the explosive emulsion. Thus in the case of an explosive cartridge-containing emulsion it may happen that the emulsion is no longer sensitive to the detonator usually used for priming.
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 US patent application 4,908,079 adding in the continuous phase 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.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.
- 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 aminé à chaîne carbonée polyéthylène comportant un radical phénolique.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 as a function of the components of the emulsion basic explosive. 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 IREC0 Inc le 03 Décembre 1987-The active component is dissolved in an organic diluent. This solution is exposed in US patent 4,784,706 filed by the company IREC0 Inc on December 03, 1987-
Des variantes voisines sont exposées dans de nombreux brevets. Cette solution implique de réaliser des réactions chimiques entre les différentes matières premières entrant dans la composition du tensioactif ce qui implique un surcroît de travail et d'équipement par rapport à un produit commercialement plus répandu.Similar variants are exposed in numerous patents. This solution involves carrying out chemical reactions between the various raw materials used in the composition of the surfactant, which involves additional work and equipment compared to a more widely used product.
- 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 1'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 Impérial Chemical Industries PLC, et EP OOI8O85 du 18 Mars I98O 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 d1émulsions 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. 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. Une solution au problème posé est l'application d'un additif dans une émulsion, dite 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 sous forme de gouttelettes étant une solution oxydante dispersée dans la phase continue et dite phase aqueuse, laquelle émulsion est stabilisée par la présence donc connue 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, cet additif est choisi liquide et insoluble dans chacune des deux phases : il est utilisé pour constituer une troisième phase discontinue dans ladite émulsion et dispersée dans la phase continue, laquelle troisième phase est située entre les gouttelettes de la phase discontinue de la solution oxydante, les sépare, et augmente la stabilisation de l'émulsion.- 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 preceding implementation , reducing costs while maintaining stability considered as 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 Impérial Chemical Industries PLC, and EP OOI8O85 of March 18, I98O by the company CIL Inc . However, despite these combinations of additives and surfactants based on the objectives and previous methods, it is difficult to obtain explosive compositions 1 water in oil emulsions to have an explosive quality stability than a 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. The problem is therefore to be able to produce explosive compositions comprising a water in oil emulsion having optimum pyrotechnic performance thanks to the use of a small amount of additives, but also having a stability of said two-phase emulsion which is greater than at least a year. One solution to the problem posed is the application of an additive in an emulsion, known as water in oil, consisting of a mixture of two immiscible phases one inside the other, one continuous known as oil phase comprising components organic fuels, the other discontinuous in the form of droplets being an oxidizing solution dispersed in the continuous phase and called the aqueous phase, which emulsion is stabilized by the presence therefore known both of 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, this additive is chosen to be liquid and insoluble in each of the two phases: it is used to constitute a third discontinuous phase in said emulsion and dispersed in the continuous phase, which third phase is located between the droplets of the discontinuous phase of the oxidizing solution, separates them, and increases the stabilization of the emulsion.
Une autre solution au problème posé est une composition explosive comprenant une émulsion eau dans huile constituée, et définie ci-dessus, d'un mélange de deux phases non miscibles l'une dans l'autre et suivant l'invention, d'un additif liquide insoluble dans chacune des deux dites phases, constituant une troisième phase liquide de ladite composition sous forme de gouttelettes, qui situées entre les gouttelettes de la phase discontinue aqueuse les séparent. L'objectif de la présente invention est également obtenu par un procédé de préparation d'une composition explosive telle que définie précédemment et 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 1'autre discontinue dite phase aqueuse ; laquelle émulsion est stabilisée par la présence connue d'au moins un agent tensioactif mélangé dans au moins une desdites phases dans lesquelles il est soluble ; un procédé suivant la présente invention est alors tel que :Another solution to the problem posed is an explosive composition comprising a water-in-oil emulsion consisting of, and defined above, of a mixture of two phases which are immiscible in one another and according to the invention, of an additive liquid insoluble in each of the two said phases, constituting a third liquid phase of said composition in the form of droplets, which located between the droplets of the discontinuous aqueous phase separate them. The objective of the present invention is also obtained by a process for the preparation of an explosive composition as defined above and comprising a water-in-oil emulsion consisting of a mixture of two phases which are immiscible one in the other, l 'one continuous known as oil phase the other discontinuous known as aqueous phase; which emulsion is stabilized by the known presence of at least one surfactant mixed in at least one of said phases in which it is soluble; a process according to the present invention is then such that:
- on prépare 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,said two-phase emulsion is prepared by known kneading of the mixture of said organic combustible components of the oil phase with said oxidizing solution of the aqueous phase dispersed in the form of droplets in the continuous phase and said surfactant,
- 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.- during the preparation of this emulsion, a liquid additive insoluble in each of the said phases is added, which additive, also dispersed in the form of droplets in the continuous phase, separates those from the aqueous phase and constitutes an emulsion with three liquid phases.
Dans un mode préférentiel de réalisation les gouttelettes dudit additif dans l'émulsion sont de taille moyenne 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.In a preferred embodiment, the droplets of said additive in the emulsion are of average size much smaller than the average size of the droplets of the dispersed oxidizing solution, said additive itself having surfactant characteristics and being in an amount less than that of l surfactant.
De préférence, l'additif est un polyorganosiloxane qui est en proportion de constituants inférieure à →3% de la composition et préférentiellement 2% .Preferably, the additive is a polyorganosiloxane which is in proportion of constituents less than → 3% 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 siïicone 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 1'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 1'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 explosives of the water-in-oil type ", in such a way that this silicone oil makes it possible to obtain a less sticky surface, the silicone oil being the other name of the polyorganosiloxane. The inventor of this German patent specifies that this additive modifies the texture of the explosive emulsion: by reducing the tackiness, thus ensuring better sealing: the problem raised in fact by the above patent relates to the disadvantage of explosive emulsions which are usually sticky and whose ability to be worked is therefore very reduced, because they can only be injected hot in forms prepared by means of, for example, worms or pumps, and the known cartridge filling for plastic explosives by means of "Rollex" type machines , is then 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 reduction of viscosity, are mixed in the continuous organic phase, thus constituting with the discontinuous phase a two-phase composition, the stability is the same as in other explosives of this known type: in fact the coalescence of the droplets of the discontinuous phase is not slowed down because they are dispersed in the only other continuous phase, but can therefore touch and merge.
Les solutions de la présente invention au problème de la stabilité des émulsions, qui est donc différent du problème ci-dessus, sont nouvelles et constituent une innovation en créant une troisième phase liquide grâce à l'utilisation, 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 solutions of the present invention to the problem of the stability of emulsions, which is therefore different from the above problem, are new and constitute an innovation by creating a third liquid phase through use, unlike what was used until now. now and recalled above, of a liquid additive which is not soluble in either of the two main phases of the emulsion, water in oil, of base, and can be dispersed in the continuous phase to be between the droplets of the aqueous phase and separate them: the additive chosen must thus allow an emulsion with three liquid phases to be obtained, the third phase which it constitutes serving in fact as a physical barrier between the droplets of the aqueous phase which thus remain separated each other longer; the choice as a silicone additive complies with the preceding conditions, whereas in the patent application cited above, this solution and this particularity of use and arrangement of the silicone in the composition is not not mentioned and the application in this application is therefore very new and innovative in the conditions of its use. Observation with an electron microscope clearly highlights this third phase and the size of the droplets of each of the discontinuous phases 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, it has been possible to measure that the addition of this additive makes it possible to reduce the size of the droplets of the aqueous phase and therefore effectively improves the aging resistance of this type of emulsion: in particular and for example without silicone the average diameter of the droplets was measured on the order of 2 μm whereas with silicone also in droplets according to the invention the droplets obtained from the discontinuous aqueous phase have an average diameter of the order of 0.5 μm, which improves well more secure over time and delays the coalescence phenomenon mentioned above.
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 uni de diamètre pour une taille moyenne de 0,5 μm des gouttelettes de la phase discontinue aqueuse comme indiqué ci-dessus.Likewise, it has also been possible to measure, to illustrate the preferential characteristic of the average size of the droplets of the additive in the emulsion that is much smaller than that of the oxidizing solution that, those of silicone in particular have an average size of 0, 03 plain in diameter for an average size of 0.5 μm of the 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 droplet size reduction which constitutes a first effect of this additive creating this third phase, the latter, creating an additional discontinuity in the continuous phase, as previously indicated, delays the flocculation phenomenon, preventing crystallization and therefore preserves all the longer the sensitivity of the emulsions over time.
Par ailleurs, comme nous l'avons déjà cité précédemment, au delà d'une certaine quantité d'additif, les performances pyrotechniques de 1'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. La présence de cet additif permet également de diminuer la quantité de produits tensioactifs abaissant ainsi le prix de revient de 1'ensemble de la composition et améliorant les performances pyrotechniques tout en améliorant la stabilité dans le temps.Furthermore, as we have already mentioned above, beyond 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 amount of additive is sufficient, thereby improving the pyrotechnic performance, by of course choosing an additive with surfactant characteristic by itself as can be silicone. The presence of this additive also makes it possible to reduce the quantity of surfactants, thereby lowering the cost price of the entire 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 be formed; there is thus an optimal compromise between the size of the molecule of said additive in the emulsion and its quantity introduced into the emulsion; thus it is necessary on the one hand that the concentration of said additive, such as silicone, is less than 5% and preferably at 2% and that the molecules of this additive are of small sizes allowing the droplets that they constitute better s insert between the droplets of aqueous dispersed phase of the emulsion; an example of respective dimensions 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 the stability is effectively much improved: in particular with silicone, emulsion lifetimes have been measured, all conditions being equal, with sufficient pyrotechnic performances, greater 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 sensitization of these emulsions is obtained to the desired priming mode. Reference is made here in particular to the possibilities of reducing the density of said emulsions in various ways and in particular by mechanical incorporation of gas, chemical evolution of gas, or mechanical incorporation of light materials such as hollow glass microbeads, phenolic resins, perlites, expanded polystyrene. or others and, 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 mentioned above already show enough to demonstrate its 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. Habituellement la phase discontinue de ladite émulsion comprend au moins un des sels oxydants suivants :The present description includes examples of embodiments of the invention but are in no way limiting: other embodiments are possible in particular by using other additives: other embodiments are indeed possible from the claims which specify the scope and extent of this invention and make it possible to find other possible compositions having the characteristics mentioned. Usually the discontinuous phase of said emulsion comprises at least one of the following oxidizing salts:
- nitrate ammonium- ammonium nitrate
- nitrate de métaux alcalins - nitrate de métaux alcalins-terreux- alkali metal nitrate - alkaline earth metal nitrate
- perchlorate d'ammonium- ammonium perchlorate
- perchlorate de métaux alcalins- alkali metal perchlorate
- perchlorate de métaux alcalins-terreux.- perchlorate of alkaline earth metals.
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. 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.The alkaline salt is present in the discontinuous phase, which may contain very little or no water. This discontinuous phase can also comprise ammonium nitrate in solution with or without another 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. Among the oxidizing salts listed above by family, there may be mentioned for example inorganic salts such as lithium nitrate, silver nitrate, lead nitrate, sodium nitrate, calcium nitrate, potassium nitrate or mixtures of these.
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 ammonium nitrate, can form by heating a solution having a melting point lower than that of 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, 1'acide acétique, le formate d'ammonium, le formate de sodium, l'acétate de sodium, l'acétate d'ammonium. D'autres composés qui peuvent remplacer ou être ajoutés au nitrate d'ammonium incluent l'acide chloroacétique, l'acide glycolique, 1'acide succinique, 1'acide tartrique, 1'acide adipique, et des aminés aliphatiques à chaîne courte telles que la formamide, l'acétamide et l'urée. 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 diaminé.Other compounds, which can replace or be added to ammonium nitrate in order to make a solution with ammonium nitrate, can be carbohydrates such as sugars, extrins, carboxylic acids and their salts such as formic acid, acetic acid, ammonium formate, sodium formate, sodium acetate, ammonium acetate. Other compounds which can replace or be added to ammonium nitrate include chloroacetic acid, glycolic acid, succinic acid, tartaric acid, adipic acid, and short chain aliphatic amines such as formamide, acetamide and urea. Urea can be used as can certain nitrogenous substances such as nitroguanidine, guamidine nitrate, 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 mentioned above can be used alone with ammonium nitrate, or mixtures of them can be used in mixture with ammonium nitrate so that the melting point of the final mixture obtained has a point sufficiently low.
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 of between 70 ° C and 130 ° C, although these values are not 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 halogènes et des hydrocarbures azotés.The oil phase which is insoluble and immiscible in water is preferably an organic non-explosive fuel of its own and can comprise at least one member from the group of hydrocarbons, 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 comprises one or more paraffins and / or microcrystalline waxes and / or flexible paraffins and can also include one or more members of the group comprising 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 chaînes polyéthylène glycol avec des chaînes d'acides gras ainsi que des dérivés de 1'anhydride succinique et du polyisobuthylène.The oil phase of the emulsion comprises at least one emulsifier or surfactant selected from the group comprising inter alia sorbitan oleate, sorbitan sesquioleate, sorbitan stearate, sorbitan palmitate, sodium monostearate, tristearate sodium, mono and diglycerides of fatty acids, soy lecithin, lanolin derivatives, alkyl benzene sulfonates, oleic acid phosphate, laurylamine acetate, decaglycerol decaoleate, decaglycerol decastearate, 2oleyl4-4'bis (hydroxymethyl) 2oxazoline, and polymeric surfactants containing double polyethylene glycol chains with fatty acid chains as well as derivatives of succinic anhydride 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 :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 in 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 continuous phase, which emulsion is stabilized by the presence of a mixed surfactant in at least one of said phases in which it is miscible, and in one of which it is previously dissolved:
- 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.- then adding in the continuous phase alone, before mixing with the discontinuous phase, a non-soluble liquid additive in these two phases and then constituting with the continuous phase a first two-phase emulsion, incorporating into this first emulsion said discontinuous phase and mixing to obtain an emulsion with three liquid phases, of which that 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, the molecules of which are chosen so that the droplets which they form in the emulsion are much smaller than the average size of the droplets of the dispersed oxidizing solution, said additive itself having surfactant characteristics and being in an amount less than that of the 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 and preferably use 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 10000 Mpas et au mieux entre 5 et 1 000 Mpas.Preferably, which is the case with the preceding oil, the additive has a viscosity of between 5 and 30,000 Mpas. Likewise, it may be advantageous and preferable to use as preferential additive 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. 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 1'émulsion.The performance of this additive, of the type such as silicone oil, 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 interposed between those of the aqueous phase, make it possible to slow down even more the coalescence then flocculation and therefore 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 also be used as an option, as indicated previously in the first stability solution, the addition of thickening agents such as waxes, paraffins, bentonites, polymers to 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 a microscopic image of an explosive composition according to the invention: this composition comprising a water-in-oil emulsion, is constituted, as already described several times previously and as it 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 the organic combustible components, and the other discontinuous known as the aqueous phase 1 is an oxidizing solution scattered; the latter is formed of medium-sized droplets 4, placed against one another, and the space of which 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 - 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. On constate bien sur cette figure que lesdites gouttelettes 5 forment écran entre les gouttelettes 4 de la phase discontinue 1, et retardent d'autant plus l'effet de coalescence et de fusion desdites gouttelettes 4 entre elles. 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 inserted 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 insoluble in the two said phases and which disperses in the continuous phase in the form of droplets - 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 x 10 ~ 2μ, while the droplets 4 of the discontinuous phase 3 are of external dimensions of the order of 50 x 10 ~ 2μ, which allows such an arrangement according to the attached figure: the distance which separates the droplets 4 is then at least equal to the diameter of these droplets 5- while without the presence of these it would not be than 0.2 x 10 ~ 2μ approximately, which being much lower, causes the effect of coalescence and flocculation noted in the emulsions known to date thus reducing their stability over time. It can be seen in this figure that said droplets 5 form a screen between the droplets 4 of the discontinuous phase 1, and further delay the coalescence and melting effect of said droplets 4 between them.

Claims

REVENDICATIONS
1. Application d'un additif dans 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 (2) comprenant des composants combustibles organiques, l'autre discontinue dite phase aqueuse (1) étant une solution oxydante dispersée sous forme de gouttelettes (4) , laquelle émulsion est stabilisée par la présence au moins 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, caractérisée en ce que cet additif, choisi liquide et insoluble dans chacune des deux dites phases, est utilisé pour constituer une troisième phase discontinue (3) dans ladite émulsion, laquelle troisième phase est située entre les gouttelettes (4) de la phase discontinue (1) les sépare et augmente la stabilisation de 1'émulsion.1. Application of an additive in a water-in-oil emulsion consisting of a mixture of two immiscible phases one inside the other, one continuous known as the 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), which emulsion is stabilized by the presence of at least one surfactant mixed at least in one of said phases in which it is soluble and of said improving additive the effect of this surfactant, characterized in that this additive, chosen to be liquid and insoluble in each of the two said phases, is used to constitute a third discontinuous phase (3) in said emulsion, which third phase is located between the droplets ( 4) of the discontinuous phase (1) separates them and increases the stabilization of the emulsion.
2. Application d'un additif dans une émulsion eau dans huile suivant la revendication 1, caractérisée en ce qu'on utilise comme additif un polyorganosiloxane en concentration inférieure à 5% de la composition. 2. Application of an additive in a water-in-oil emulsion according to claim 1, characterized in that a polyorganosiloxane is used as an additive in a concentration of less than 5% of the composition.
3- 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 (2) dite phase huile comprenant des composants combustibles organiques, l'autre discontinue (1) dite phase aqueuse étant une solution oxydante dispersée sous forme de gouttelettes (4) dans la phase huile (2) , laquelle émulsion est stabilisée par la présence au moins d'un agent tensioactif mélangé au moins dans une desdites phases dans lesquelles il est soluble et d'un additif améliorant l'effet de cet agent tensioactif, caractérisé en ce que ledit additif est liquide et insoluble dans chacune des deux dites phases, constitue une troisième phase (3) de ladite composition sous forme de gouttelettes (5). qui situées entre les gouttelettes (4) de la phase discontinue aqueuse (1) les séparent.3- Explosive composition comprising a water-in-oil emulsion consisting of a mixture of two immiscible phases one inside the other, one continuous (2) said oil phase comprising organic combustible components, the other discontinuous (1 ) said aqueous phase being an oxidizing solution dispersed in the form of droplets (4) in the oil phase (2), which emulsion is stabilized by the presence of at least one surfactant mixed at least in one of said phases in which it is soluble and an additive improving the effect of this surfactant, characterized in that said additive is liquid and insoluble in each of the two said phases, constitutes a third phase (3) of said composition in the form of droplets (5). which located between the droplets (4) of the discontinuous aqueous phase (1) separate them.
4. Composition explosive selon la revendication 3* caractérisée en ce que les gouttelettes (5) de l'additif dans 1'émulsion sont de taille moyenne très inférieure à la taille moyenne des gouttelettes (4) de la solution oxydante dispersée, ledit additif ayant lui-même des caractéristiques tensioactives et étant en quantité inférieure à celle de l'agent tensioactif.4. Explosive composition according to claim 3 * characterized in that the droplets (5) of the additive in the emulsion are of average size much smaller than the average size of the droplets (4) of the dispersed oxidizing solution, said additive having itself surfactant characteristics and being in quantity lower than that of the surfactant.
5. Composition explosive selon l'une quelconque des revendications 3 et 4, caractérisée en ce que 1'additif est un polyorganosiloxane en concentration inférieure à 5% de la composition. 5. Explosive composition according to any one of claims 3 and 4, characterized in that the additive is a polyorganosiloxane in a concentration of less than 5% of the composition.
6. Composition explosive selon l'une quelconque des revendications 3 à 5. caractérisée en ce que l'additif est d'une viscosité comprise entre 5 et 30000 Mpa.s.6. Explosive composition according to any one of claims 3 to 5. characterized in that the additive has a viscosity between 5 and 30,000 Mpa.s.
7. Composition explosive selon la revendication 3 à 5. caractérisée en ce que l'additif est un polydiméthylsiloxane. 7. Explosive composition according to claim 3 to 5. characterized in that the additive is a polydimethylsiloxane.
8. 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 (2) dite phase huile comprenant des composants combustibles organiques, l'autre discontinue (1) dite phase aqueuse étant une solution oxydante dispersée sous forme de gouttelettes (4) dans la phase continue huile (2), laquelle émulsion est stabilisée par la présence d'au moins un agent tensioactif mélangé au moins dans une desdites phases dans lesquelles il est soluble, caractérisé en ce que :8. Process for the preparation of an explosive composition comprising a water-in-oil emulsion consisting of a mixture of two immiscible phases, one continuous (2) known as the oil phase comprising organic combustible components, the other discontinuous (1) called aqueous phase being an oxidizing solution dispersed in the form of droplets (4) in the continuous oil phase (2), which emulsion is stabilized by the presence of at least one surfactant mixed at least in one said phases in which it is soluble, characterized in that:
- on prépare ladite émulsion diphasique par malaxage connu du mélange desdits composants combustibles organiques de la phase huile- Preparing said two-phase emulsion by known kneading of the mixture of said organic combustible components of the oil phase
(2) avec ladite solution oxydante de la phase aqueuse (1) sous forme de gouttelettes (4) dans la phase continue (2) dispersée et ledit agent tensioactif,(2) with said oxidizing solution of the aqueous phase (1) in the form of droplets (4) in the continuous phase (2) dispersed and said surfactant,
- 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 (5) dans la phase continue (2) sépare celle de la phase aqueuse et constitue une troisième phase (3) de l'émulsion.- a liquid additive insoluble in each of the said phases is added during the preparation of this emulsion, which additive, also dispersed in the form of droplets (5) in the continuous phase (2) separates that of the aqueous phase and constitutes a third phase ( 3) of the emulsion.
9. 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 (2) dite phase huile comprenant des composants combustibles organiques, l'autre discontinue aqueuse (1) étant une solution oxydante dispersée sous forme de gouttelettes (4) dans la phase continue (2), laquelle émulsion est stabilisée par la présence d'au moins un agent tensioactif mélangé au moins dans une desdites phases dans lesquelles il est soluble, et dans l'une desquelles il est préalablement dissous, caractérisé en ce que :9. Process for the preparation of an explosive composition comprising a water-in-oil emulsion consisting of a mixture of two immiscible phases one inside the other, one continuous (2) known as the oil phase comprising organic combustible components, the other aqueous batch (1) being an oxidizing solution dispersed in the form of droplets (4) in the continuous phase (2), which emulsion is stabilized by the presence of at least one surfactant mixed at least in one of said phases in which it is soluble, and in which one it is previously dissolved, characterized in that:
- on rajoute dans la phase continue (2) seule, avant mélange avec la phase discontinue, un additif (3) 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 (1) et on malaxe pour obtenir une émulsion à trois phases, dont celle (3) constituée par ledit additif est située entre les gouttelettes (4) de la phase aqueuse (1) et les sépare. - Add in the continuous phase (2) alone, before mixing with the discontinuous phase, an additive (3) liquid which is not soluble in these two phases and then constituting with the continuous phase a first two-phase emulsion, this said emulsion is incorporated into this first emulsion discontinuous phase (1) and kneading to obtain an emulsion with three phases, of which that (3) constituted by said additive is located between the droplets (4) of the aqueous phase (1) and separates them.
10. Procédé de préparation d'une composition explosive comprenant une émulsion eau dans huile suivant l'une quelconque des revendications 8 et 9 caractérisé en ce que les molécules de l'additif sont choisis de telle façon que les gouttelettes (5) qu'elles forment dans l'émulsion sont de taille très inférieure à la taille moyenne des gouttelettes (4) de la solution oxydante dispersée (1), ledit additif ayant lui-même des caractéristiques tensioactives et étant en quantité inférieure à celle de l'agent tensioactif.10. A method of preparing an explosive composition comprising a water-in-oil emulsion according to any one of claims 8 and 9 characterized in that the molecules of the additive are chosen such that the droplets (5) that they form in the emulsion are much smaller than the average size of the droplets (4) of the dispersed oxidizing solution (1), said additive itself having surfactant characteristics and being in an amount less than that of the surfactant.
11. Procédé de préparation d'une composition explosive comprenant une émulsion eau dans huile suivant l'une quelconque des revendications 8 à 10 caractérisé en ce que 1'additif est un polyorganosiloxane en concentration inférieure à 5% de la composition. 11. A method of preparing an explosive composition comprising a water-in-oil emulsion according to any one of claims 8 to 10 characterized in that the additive is a polyorganosiloxane in a concentration of less than 5% of the composition.
PCT/FR1994/000811 1993-07-29 1994-07-01 Application of an additive to stabilize a water-in-oil emulsion, explosive composition and corresponding method of preparation WO1995004017A1 (en)

Priority Applications (3)

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DE69416519T DE69416519T2 (en) 1993-07-29 1994-07-01 USE OF AN ADDITIVE TO STABILIZE AN EXPLOSIVE COMPOSITION OF THE TYPE WATER-IN-OIL EMULSION
EP94921010A EP0711263B1 (en) 1993-07-29 1994-07-01 Application of an additive to stabilize an explosive composition based on a water-in-oil emulsion
AU71895/94A AU7189594A (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

Applications Claiming Priority (2)

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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.
FR93/09638 1993-07-29

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

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WO1990003111A1 (en) * 1987-03-30 1990-04-05 Nc Development, Inc. Chemical formulations
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WO1990003111A1 (en) * 1987-03-30 1990-04-05 Nc Development, 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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Publication number Priority date Publication date Assignee Title
WO2003006402A1 (en) * 2001-07-12 2003-01-23 Dynaenergetics Gmbh & Co. Kg Cladding and compacting explosive

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DE69416519D1 (en) 1999-03-25
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DE69416519T2 (en) 1999-09-16
MA23283A1 (en) 1995-04-01
ES2127933T3 (en) 1999-05-01
FR2708479A1 (en) 1995-02-10
EP0711263B1 (en) 1999-02-10

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