EP0711263B1 - Verwendung eines additives zur stabilisierung einer sprengstoffzusammensetzung des typus wasser-in-öl emulsion - Google Patents

Verwendung eines additives zur stabilisierung einer sprengstoffzusammensetzung des typus wasser-in-öl emulsion Download PDF

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Publication number
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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Prior art keywords
additive
phase
emulsion
droplets
phases
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Expired - Lifetime
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EP94921010A
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English (en)
French (fr)
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EP0711263A1 (de
Inventor
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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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Colloid Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Medicinal Preparation (AREA)

Claims (7)

  1. Verwendung eines Zusatzstoffs in einer Explosivzusammensetzung vom Wasser-in-Öl-Emulsionstyp, die aus einem Gemisch von zwei nicht miteinander mischbaren Phasen besteht, wobei die kontinuierliche, als Ölphase (2) bezeichnete Phase brennbare organische Bestandteile enthält und die diskontinuierliche, als wäßrige Phase (1) bezeichnete Phase eine in Form von Tröpfchen (4) dispergierte oxidierende Lösung ist, wobei die Emulsion durch die Gegenwart mindestens eines grenzflächenaktiven Stoffs, der in mindestens eine der obigen Phasen eingemischt ist, in denen er löslich ist, und des Zusatzstoffs, der die Wirkung des grenzflächenaktiven Stoffs verbessert, stabilisiert ist, dadurch gekennzeichnet, daß zur Erhöhung der Stabilität der Emulsion der Zusatzstoff, der flüssig und unlöslich in den beiden Phasen ausgewählt wird und dessen Moleküle so ausgewählt werden, daß die mittlere Größe der Tröpfchen, die sie bilden, sehr viel kleiner ist als die mittlere Größe der Tröpfchen (4) der dispergierten oxidierenden Lösung (1), eine dritte diskontinuierliche Phase (3) dieser Emulsion bildet, die zwischen den Tröpfchen (4) der diskontinuierlichen Phase (1) angeordnet ist mit der Wirkung, daß die Tröpfchen (4) getrennt voneinander bleiben.
  2. Verwendung eines Zusatzstoffs in einer Wasser-in-Öl-Emulsion gemäß Anspruch 1, dadurch gekennzeichnet, daß als Zusatzstoff ein Polyorganosiloxan in einer Konzentration unter 5 %, bezogen auf die Zusammensetzung, verwendet wird.
  3. Verwendung eines Zusatzstoffs nach einem der Ansprüche 1 und 2, dadurch gekennzeichnet, daß der Zusatzstoff selbst grenzflächenaktive Eigenschaften aufweist und in einem geringeren Anteil als der grenzflächenaktive Stoff enthalten ist.
  4. Verwendung eines Zusatzstoffs nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß der Zusatzstoff eine Viskosität von 5 bis 30000 MPa·s aufweist.
  5. Verwendung eines Zusatzstoffs nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß der Zusatzstoff ein Polydimethylsiloxan ist.
  6. Verwendung eines Zusatzstoffs nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß
    die Wasser-in-Öl-Emulsion durch an sich bekanntes Vermischen des Gemischs der brennbaren organischen Bestandteile der Ölphase (2) mit der oxidierenden Lösung der wäßrigen Phase (1) in Form von Tröpfchen (4), die in der kontinuierlichen Phase (2) dispergiert sind, und dem grenzflächenaktiven Stoff hergestellt wird, und daß
    im Laufe der Herstellung dieser Emulsion der in diesen Phasen unlösliche flüssige Zusatzstoff zugegeben wird.
  7. Verwendung eines Zusatzstoffs nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß
    der flüssige, in den beiden Phasen nicht lösliche Zusatzstoff (3) vor dem Vermischen mit der diskontinuierlichen Phase nur zu der kontinuierlichen Phase (2) zugegeben wird, so daß der Zusatzstoff mit der kontinuierlichen Phase eine erste zweiphasige Emulsion bildet und daß
    die diskontinuierliche Phase (1) in diese erste Emulsion eingebracht wird, wonach vermischt wird, um eine dreiphasige Emulsion zu erhalten.
EP94921010A 1993-07-29 1994-07-01 Verwendung eines additives zur stabilisierung einer sprengstoffzusammensetzung des typus wasser-in-öl emulsion Expired - Lifetime EP0711263B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR9309638A FR2708479B1 (fr) 1993-07-29 1993-07-29 Application d'un additif pour stabiliser une émulsion eau dans huile, composition explosive et procédé de préparation correspondant.
FR9309638 1993-07-29
PCT/FR1994/000811 WO1995004017A1 (fr) 1993-07-29 1994-07-01 Application d'un additif pour stabiliser une emulsion eau dans huile, composition explosive et procede de preparation correspondant

Publications (2)

Publication Number Publication Date
EP0711263A1 EP0711263A1 (de) 1996-05-15
EP0711263B1 true EP0711263B1 (de) 1999-02-10

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EP94921010A Expired - Lifetime EP0711263B1 (de) 1993-07-29 1994-07-01 Verwendung eines additives zur stabilisierung einer sprengstoffzusammensetzung des typus wasser-in-öl emulsion

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

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003006402A1 (de) * 2001-07-12 2003-01-23 Dynaenergetics Gmbh & Co. Kg Plattier- und kompaktiersprengstoff

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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 (de) * 1991-02-15 1992-08-20 Dynamit Nobel Ag Schlagwettersichere emulsionssprengstoffe

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

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