WO1995004017A1 - Application d'un additif pour stabiliser une emulsion eau dans huile, composition explosive et procede de preparation correspondant - Google Patents
Application d'un additif pour stabiliser une emulsion eau dans huile, composition explosive et procede de preparation correspondant Download PDFInfo
- 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
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- phase
- emulsion
- additive
- droplets
- phases
- Prior art date
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Classifications
-
- 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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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
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- Compositions Of Macromolecular Compounds (AREA)
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Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
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 |
EP94921010A EP0711263B1 (fr) | 1993-07-29 | 1994-07-01 | Application d'un additif pour stabiliser une composition explosive du type emulsion eau dans huile |
DE69416519T DE69416519T2 (de) | 1993-07-29 | 1994-07-01 | Verwendung eines additives zur stabilisierung einer sprengstoffzusammensetzung des typus wasser-in-öl emulsion |
Applications Claiming Priority (2)
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. |
FR93/09638 | 1993-07-29 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1995004017A1 true WO1995004017A1 (fr) | 1995-02-09 |
Family
ID=9449958
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
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 |
Country Status (7)
Country | Link |
---|---|
EP (1) | EP0711263B1 (fr) |
AU (1) | AU7189594A (fr) |
DE (1) | DE69416519T2 (fr) |
ES (1) | ES2127933T3 (fr) |
FR (1) | FR2708479B1 (fr) |
MA (1) | MA23283A1 (fr) |
WO (1) | WO1995004017A1 (fr) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2003006402A1 (fr) * | 2001-07-12 | 2003-01-23 | Dynaenergetics Gmbh & Co. Kg | Explosif de placage et de compactage |
Citations (4)
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 |
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 |
WO1990003111A1 (fr) * | 1987-03-30 | 1990-04-05 | Nc Development, Inc. | Formulations chimiques |
DE4204175A1 (de) * | 1991-02-15 | 1992-08-20 | Dynamit Nobel Ag | Schlagwettersichere emulsionssprengstoffe |
-
1993
- 1993-07-29 FR FR9309638A patent/FR2708479B1/fr not_active Expired - Fee Related
-
1994
- 1994-07-01 WO PCT/FR1994/000811 patent/WO1995004017A1/fr active IP Right Grant
- 1994-07-01 AU AU71895/94A patent/AU7189594A/en not_active Abandoned
- 1994-07-01 DE DE69416519T patent/DE69416519T2/de not_active Expired - Fee Related
- 1994-07-01 EP EP94921010A patent/EP0711263B1/fr not_active Expired - Lifetime
- 1994-07-01 ES ES94921010T patent/ES2127933T3/es not_active Expired - Lifetime
- 1994-07-25 MA MA23598A patent/MA23283A1/fr unknown
Patent Citations (4)
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 |
WO1990003111A1 (fr) * | 1987-03-30 | 1990-04-05 | Nc Development, Inc. | Formulations chimiques |
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 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2003006402A1 (fr) * | 2001-07-12 | 2003-01-23 | Dynaenergetics Gmbh & Co. Kg | Explosif de placage et de compactage |
Also Published As
Publication number | Publication date |
---|---|
DE69416519D1 (de) | 1999-03-25 |
EP0711263A1 (fr) | 1996-05-15 |
DE69416519T2 (de) | 1999-09-16 |
FR2708479A1 (fr) | 1995-02-10 |
AU7189594A (en) | 1995-02-28 |
EP0711263B1 (fr) | 1999-02-10 |
FR2708479B1 (fr) | 1995-10-27 |
MA23283A1 (fr) | 1995-04-01 |
ES2127933T3 (es) | 1999-05-01 |
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