EP3221283B1 - Dünne zusammengesetzte explosive produkte und herstellung davon - Google Patents

Dünne zusammengesetzte explosive produkte und herstellung davon Download PDF

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Publication number
EP3221283B1
EP3221283B1 EP15804911.4A EP15804911A EP3221283B1 EP 3221283 B1 EP3221283 B1 EP 3221283B1 EP 15804911 A EP15804911 A EP 15804911A EP 3221283 B1 EP3221283 B1 EP 3221283B1
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EP
European Patent Office
Prior art keywords
charges
advantageously
sheet
product according
gum
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP15804911.4A
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English (en)
French (fr)
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EP3221283A1 (de
Inventor
Philippe Ragon
Karol WOIRIN
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eurenco SA
ArianeGroup SAS
Original Assignee
Eurenco SA
ArianeGroup SAS
Eurenco France SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Eurenco SA, ArianeGroup SAS, Eurenco France SA filed Critical Eurenco SA
Publication of EP3221283A1 publication Critical patent/EP3221283A1/de
Application granted granted Critical
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B21/00—Apparatus or methods for working-up explosives, e.g. forming, cutting, drying
    • C06B21/0008—Compounding the ingredient
    • C06B21/0025—Compounding the ingredient the ingredient being a polymer bonded explosive or thermic component
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B25/00—Compositions containing a nitrated organic compound
    • C06B25/32—Compositions containing a nitrated organic compound the compound being nitrated pentaerythritol
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B25/00—Compositions containing a nitrated organic compound
    • C06B25/34—Compositions containing a nitrated organic compound the compound being a nitrated acyclic, alicyclic or heterocyclic amine
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B45/00—Compositions or products which are defined by structure or arrangement of component of product
    • C06B45/04—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive
    • C06B45/06—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component
    • C06B45/10—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component the organic component containing a resin
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B45/00—Compositions or products which are defined by structure or arrangement of component of product
    • C06B45/12—Compositions or products which are defined by structure or arrangement of component of product having contiguous layers or zones

Definitions

  • the present invention relates to composite explosive products of small thickness (small thickness perfectly controlled), conformable (i.e. deformable, by action of temperature, with shape retention) and efficient. They contain a high rate of energy charges in a binder of a specific nature. They consist in particular of sheets or products obtained by cutting such sheets, such as miniaturized multi-point initiation networks of explosive charges, for example explosive military heads.
  • the present invention also relates to a process for preparing said composite explosive products. Said method is particularly easy to implement: at temperatures perfectly compatible with the sensitivity of the energy charges present, without the use of a solvent and including only one type of operation.
  • This critical detonation dimension is determined from degressive-sized samples (stepped cylindrical rods, degressive section, for example), the detonation being initiated on the side of the sample with the largest dimension (on the bar side presenting the largest section).
  • explosives with critical dimensions of detonation as low as possible are sought to constitute the channels of said networks (having a section as small as possible but capable of ensuring the propagation of the detonation, including in the angles).
  • the patent US 3,354,010 describes explosive products, in the form of flexible sheets (typically 6.3 mm thick), the composition of which contains hexogenic (HMX) and / or octogen (RDX) organic energy charges in a binder ( nitrocellulose) plasticized (tributyl acetyl citrate).
  • HMX hexogenic
  • RDX octogen
  • the demand EP 0 406 190 describes a process for the production of explosive substances, in the form of sheets, the composition of which contains at least one binder which may consist of a thermally crosslinkable plastic, a thermoplastic or a thermoelastic.
  • Elastomers (gums, "raw” (non-crosslinked) rubbers) of the polyurethane-polyester type (ie of polyurethane type with flexible segments of polyester type) and / or polyurethane-polyether (ie of polyurethane type with flexible segments of polyether type), have also been marketed for some years, particularly under the trademark UREPAN® by RheinChemie and under the Millathane® brand by TSE Industries.
  • the present invention provides an original outlet for this type of elastomer.
  • the composite explosive products of the invention therefore contain a high level of charges, "highly” energetic ("sensitive”) organic charges and fine granulometry in a binder of a new type.
  • the composite explosive products of the invention contain from 85 to 92%, advantageously from 88 to 90% (% by weight), of specific organic energy charges.
  • the charges in question are "highly" energetic (“sensitive") charges. These are octogen (HMX) charges, hexogen (RDX) charges, hexaazaisowurtzitane (CL20) charges, pentrite (PETN) charges or a mixture of such charges.
  • HMX octogen
  • RDX hexogen
  • CL20 hexaazaisowurtzitane
  • PETN pentrite
  • these are charges of hexogen (RDX), charges of hexanitrohexaazaisowurtzitane (CL20) or a mixture of these two types of charges (the most energetic).
  • the charges in question are not present in the form of large and small crystals, they are present only in the form of small crystals.
  • the value of D 10 is not specified as it is in no way critical. It was understood that the more the charges are fine (ie the lower the value of the D 10 (for example a value of 100 nm or even less)), the more the products in question are interesting.
  • granulometric data (D 90 , D 50 (and D 10 )) are measured by means of a photon correlation optical particle size analyzer (PCS-DLS: Photons Correlation Spectroscopy-Diffusion Light Scattering), according to a procedure defined by the standard NF 11-666. They correspond respectively to the diameter for which the cumulative volume percentage (of the particles of charges) is equal to 90%, 50% (median diameter) (and 10%).
  • PCS-DLS Photons Correlation Spectroscopy-Diffusion Light Scattering
  • Such fine fillers are generally obtained by grinding "large" crystals.
  • Those skilled in the art know many grinding processes, adapted to the sensitivity of the loads in question. We can in no way limit mention the possible use of SWECO® crushers.
  • the Applicant has also described in the patent application FR 14 00669 , published under No. 3,018,807 (September 25, 2015), an original grinding process for obtaining CL20 charges of submicron monomodal particle size.
  • Said method comprises the continuous grinding of a charge of CL20 crystals, of particle size beyond the micron (D 50 > 1 ⁇ m), in suspension in a liquid; said grinding being carried out, with cooling, by multi-passage of the suspension in a circulation mill, horizontal axis, attrition with agitated grinding media.
  • organic energy charges (whose presence rate, nature and particle size have been specified above) are therefore found in the composition of the composite explosive products of the invention, within an original binder.
  • the binder of the products of the invention generally consists of a polyurethane-polyester gum or a polyurethane-polyether gum, but mixtures of at least two gums (at least two polyurethane-polyester gums, at least two polyurethane-polyether gums or at least two gums). less a polyurethane-polyester gum and at least one polyurethane-polyether gum, such mixtures of gums (gums within the meaning of the invention) constituting a gum within the meaning of the invention) having the required properties (referred to above) can be used.
  • Said binder advantageously consists of a polyurethane-polyester gum.
  • composition of the composite pyrotechnic products of the invention is capable of containing at least one plasticizer chosen from energetic plasticizers, non-energetic plasticizers and mixtures thereof; it may also contain in general up to 4% by weight of at least one such plasticizer.
  • Said at least one plasticizer is therefore chosen from non-energetic plasticizers (for example, di-octyl azelate (DOZ), di-2-ethylhexyl sebacate (DOS), di-n-octyl phthalate (DOP), triacetin and mixtures thereof), energetic plasticizers (advantageously of the type nitrate or nitramine, for example, diethylene glycol dinitrate (DEGDN), triethylene glycol dinitrate (TEGDN), butanetriol trinitrate (BTTN), trimethylolethane trinitrate (TMETN), a mixture of 2,4-dinitrogen 2,4-diaza-pentane, 2,4-dinitro-2,4-diaza-hexane and 3,5-dinitro-3,5-diaza-heptane (and especially DNDA 5.7), nitrates ethyl nitramines (and especially methyl-2-nitratomethyl
  • composition of the composite pyrotechnic products of the invention contains, according to a preferred variant, as a plasticizer, triethylene glycol dinitrate (TEGDN).
  • TAGDN triethylene glycol dinitrate
  • composition generally consists of what is specified.
  • a product of the invention has a thickness (e), a thickness (e) uniform, constant (controlled): 0.4 mm ⁇ e ⁇ 5 mm, preferably 1 mm ⁇ e ⁇ 2 mm. Very advantageously, e ⁇ 1.5 mm.
  • the person skilled in the art understands all the It is up to the inventors to propose such high-performance composite explosive products (the explosive in question must therefore necessarily have a critical dimension of detonation below these low values) and the appropriate mechanical properties (mechanical strength, cohesion, conformability).
  • the good results obtained are essentially based on the binder (the nature of the binder) which, combined with an adequate process (see below), allows the incorporation within it of a high rate of ("sensitive") fines. granulometry.
  • the cuttings in question are conventional cuttings, implemented with conventional mechanical means (advantageously splitting with water jet (s), with two parallel blades or die cutter).
  • the channels of the miniaturized network obviously have a minimum section equal to the critical dimension of detonation of the composition in question. They may exhibit directional changes with high angles up to 90 ° (in view of the low values of said critical dimensions). They generally have a square or rectangular section.
  • Such networks according to the invention are particularly interesting. Their conformability (inherent to the nature of the binder present in their composition and their small thickness) allows their use both on flat surfaces (one can conventionally initiate a cylindrical shaped load with such a network positioned on one of the bases of the load) only on curved surfaces (such unconventional positioning may be particularly interesting for increasing the speed of flashes in one direction).
  • plasticizer and intervening additive is also incorporated into the gum in the roll mill.
  • the roll mill is a device known per se.
  • the present invention is based on the selection of the binder associated with the selection of the process, this dual selection making it not only possible to obtain the products of the invention (products heavily loaded with fine sensitive fillers) possible (the feasibility of said process was not acquired in advance) but possible under simple implementation conditions.
  • the formation of the mixture in the roll mixer is conventionally carried out with the rolls rotated in opposite directions at different speeds.
  • the gum when it is in the form of granules, is first of all roughly shaped to the mill to obtain a thin strip (1 mm to a few mm).
  • Said gum is generally first introduced into the roll mixer, the rolls of which are brought to a temperature (T) of at least 50 ° C. (below 120 ° C., generally below 100 ° C.), advantageously between 60 and 80 ° C (60 ° C ⁇ T ⁇ 80 ° C), for example 70 ° C.
  • T temperature
  • the fillers and any other ingredient (s) are then introduced separately or as a mixture.
  • a charge + ingredient (s) mixture is generally prepared beforehand, when at least one such ingredient is involved, and then said mixture is introduced.
  • the introduction of the charges can conveniently be carried out in several sequences after a setting of the spacing of the rolls.
  • the coating formed around the fastest rotating cylinder can be recovered (cut with a cutter), folded and reintroduced between the cylinders (in order to homogenize the distribution of charges), according to the usual methods applied to this process.
  • a sheet (a film) of small thickness (corresponding to the spacing between the rolls) is thus obtained.
  • said sheet is calendered in a roll mill (the rolls of said roll mixer then rotating in the same direction, at the same speed, and their spacing being set to the value of desired thickness, or even a lower value because two phenomena are likely to manifest: the material can force the spacing of the rolls and there can be a relaxation of the product after rolling).
  • the method of the invention may therefore comprise, in addition, the cutting, advantageously by jet (s) of water, with two parallel blades or punch, the calendered filled sheet.
  • the cutting of the leaves, more particularly with blades, can be facilitated by previously heating said sheets between 40 and 50 ° C.
  • RDX hexogen
  • Step a of the process pasty mixtures were obtained with the roll mill, in a known manner per se.
  • the gum concerned was first introduced between the rolls, brought to a temperature of 70 ° C. It has been softened.
  • a mixture + plasticizer charges previously made in a container, was added. According to Example 8, only the charges were added. When all the charges were incorporated into the gum, the mixture was continued for about 15 minutes.
  • the sheets obtained had, according to the spacing of the rolls, "a" thickness of about 2 mm, 1.5 mm or 1 mm.
  • Step b of the process a calendering was implemented for an adjustment and / or a uniformization of the thickness of the sheets obtained. Said sheets were passed between the two cylinders of the same cylinder mixer, set to the desired spacing, rotating in the same direction at the same speed. This time, there was no winding of leaves around a cylinder. There was implemented a calendering. Once the calender phase was complete, the product obtained in sheet form was homogeneous and had a constant thickness (of 2 mm, 1.5 mm or 1 mm).
  • Step c of the process the cutting into channels of different sections was achieved through a specific tool, consisting essentially of two parallel blades whose spacing is guaranteed by washers of calibrated thicknesses. The leaves were cut after being heated to 45 ° C.
  • compositions of Examples 1, 2 and 3, containing RDX fillers are particularly interesting in that they have a critical detonation section less than or equal to 1 mm 2 .
  • compositions of Examples 6 and 7, containing charges of CL20 have higher critical detonation sections (the critical detonation section of the composition of Example 6 is greater than 1.5 mm 2 and the critical detonation section of the composition of Example 7 is between 1 and 1.5 mm 2 ) than those of Examples 1, 2 and 3 containing RDX fillers.
  • the increase in the charge ratio logically leads to a decrease in the critical detonation section (the charge rate of the composition of Example 6 is 86% whereas the charge ratio of the composition of Example 7 is 87%).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Molecular Biology (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Claims (11)

  1. Zusammengesetztes explosives Produkt, dadurch gekennzeichnet, dass:
    - seine Zusammensetzung, ausgedrückt in Massenprozent, enthält:
    85 bis 92 %, vorteilhafterweise 88 bis 90 %, von organischen energetischen Ladungen, wobei die organischen energetischen Ladungen a) ausgewählt sind aus Ladungen von Oktogen (HMX), Hexogen (RDX), Hexanitrohexaazaisowurtzitan (CL20), Pentrit (PETN) und ihren Gemischen und b) eine granulometrische Verteilung mit einem Wert von D90, der kleiner als 15 µm ist, und einem Wert von D50, der kleiner oder gleich 5 µm ist, aufweisen, und
    7 bis 12 %, vorteilhafterweise 8 bis 10 %, eines Polymergummis, ausgewählt aus den Polyurethan-Polyester-Gummis, den Polyurethan-Polyether-Gummis und ihren Gemischen, deren mittlere Molekülmasse zahlenmäßig größer als 20 000 g/mol ist und deren Mooney-Viskosität bei 100 °C zwischen 20 und 70 ML (5 + 4) liegt, und
    - es eine Dicke von 0,4 bis 5 mm, vorteilhafterweise von 1 bis 2 mm, aufweist.
  2. Zusammengesetztes explosives Produkt nach Anspruch 1, dadurch gekennzeichnet, dass die energetischen Ladungen ausgewählt sind aus Ladungen von Hexogen (RDX), Hexanitrohexaazaisowurtzitan (CL20) und ihren Gemischen.
  3. Zusammengesetztes explosives Produkt nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass der Polymergummi ein Polyurethan-Polyester-Gummi oder ein Polyurethan-Polyether-Gummi, vorteilhafterweise ein Polyurethan-Polyester-Gummi, ist.
  4. Zusammengesetztes explosives Produkt nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass der Polymergummi eine mittlere Molekülmasse aufweist, die zahlenmäßig größer als 35 000 g/mol, sehr vorteilhafterweise größer als 75 000 g/mol, ist.
  5. Zusammengesetztes explosives Produkt nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass seine Zusammensetzung ferner mindestens einen Weichmacher enthält, ausgewählt aus den energetischen Weichmachern, den nicht energetischen Weichmachern und ihren Gemischen, wobei der mindestens eine Weichmacher im Allgemeinen mit 1 bis 4 Masse-%, vorteilhafterweise mit 2 bis 3 Masse-%, vorliegt.
  6. Zusammengesetztes explosives Produkt nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass seine Zusammensetzung ferner mindestens einen Zusatzstoff enthält, wobei der mindestens eine Zusatzstoff im Allgemeinen mit 0,1 bis 1 Masse-% vorliegt.
  7. Zusammengesetztes explosives Produkt nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass es in Form einer Folie oder eines Elements, das ohne das Schneiden einer Aussparung, welche die Dicke der Folie durchdringt, zu einer Folie geschnitten wurde, oder eines Elements vorliegt, das mit dem Schneiden von (einer) Aussparung(en), welche die Dicke der Folie durchdringt bzw. durchdringen, zu einer Folie geschnitten wurde.
  8. Zusammengesetztes explosives Produkt nach Anspruch 7, dadurch gekennzeichnet, dass es aus einer explosiven Folie, aus einer explosiven Stange mit einer Nut in V-Form oder aus einem Miniaturnetz zur Mehrpunktzündung von explosiven Ladungen besteht.
  9. Zusammengesetztes explosives Produkt nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass es aus einem Miniaturnetz zur Mehrpunktzündung von explosiven Ladungen besteht, das für die Verwendung der explosiven Ladungen auf einer ebenen Fläche oder auf einer gekrümmten Fläche geeignet ist.
  10. Verfahren zum Erhalten eines zusammengesetzten explosiven Produkts nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, dass es umfasst:
    - Einbinden der Ladungen in den Gummi, der auf eine Temperatur von mindestens 50 °C, vorteilhafterweise auf eine Temperatur zwischen 60 und 80 °C gebracht wird, wobei die Einbindung in einem Zylindermischer umgesetzt wird, und
    - Kalandrieren der erhaltenen geladenen Folie in einem Zylindermischer.
  11. Verfahren zum Erhalten nach Anspruch 10, dadurch gekennzeichnet, dass es ferner umfasst:
    - das Schneiden der kalandrierten geladenen Folie, vorteilhafterweise durch (einen) Wasserstrahl(en), mit zwei parallelen Klingen oder mit der Lochzange.
EP15804911.4A 2014-11-21 2015-11-20 Dünne zusammengesetzte explosive produkte und herstellung davon Active EP3221283B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR1402626A FR3028852B1 (fr) 2014-11-21 2014-11-21 Produits explosifs composites de faible epaisseur et leur preparation
PCT/FR2015/053158 WO2016079453A1 (fr) 2014-11-21 2015-11-20 Produits explosifs composites de faible epaisseur et leur preparation

Publications (2)

Publication Number Publication Date
EP3221283A1 EP3221283A1 (de) 2017-09-27
EP3221283B1 true EP3221283B1 (de) 2019-07-24

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Application Number Title Priority Date Filing Date
EP15804911.4A Active EP3221283B1 (de) 2014-11-21 2015-11-20 Dünne zusammengesetzte explosive produkte und herstellung davon

Country Status (6)

Country Link
US (1) US20180346393A1 (de)
EP (1) EP3221283B1 (de)
CA (1) CA2968255A1 (de)
FR (1) FR3028852B1 (de)
IL (1) IL252369B (de)
WO (1) WO2016079453A1 (de)

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US3354010A (en) 1967-01-27 1967-11-21 John D Hopper Flexible explosive containing rdx and/or rmx and process therefor
US4335231A (en) * 1981-04-03 1982-06-15 Uniroyal, Inc. Sulfur curable millable polyurethane gum
SE449527C (sv) * 1985-06-20 1988-12-08 Nobel Kemi Ab Explosiv laddning foer spraengfogning av grova roer, samt saett att framstaella densamma
US5500060A (en) * 1986-07-04 1996-03-19 Royal Ordnance Plc Energetic plasticized propellant
US5248731A (en) * 1989-03-20 1993-09-28 Reeves Bros. Inc. Calenderable thermoplastic compositions containing millable linear polyurethanes
SE465572B (sv) * 1989-06-21 1991-09-30 Nobel Kemi Ab Saett och anordning foer framstaellning av explosiva substanser
FR2723086B1 (fr) * 1994-07-29 1996-09-13 Poudres & Explosifs Ste Nale Procede continu de fabrication sans solvant de produits pyrotechniques composites
US20050267245A1 (en) * 2003-03-18 2005-12-01 Sandusky Donald A Alloy blends of polyurethane and rubber
US8501390B2 (en) * 2006-06-27 2013-08-06 Xiper Innovations, Inc. Laser engravable flexographic printing articles based on millable polyurethanes, and method
FR2939881B1 (fr) 2008-12-12 2011-02-11 Tda Armements Sas Charge pyrotechnique a faible vulnerabilite
US9914734B2 (en) * 2009-04-16 2018-03-13 Aerojet Rocketoyne, Inc. Cyclic energetic nitramines desensitized with linear nitramines
US8172965B2 (en) * 2009-10-14 2012-05-08 Raytheon Company Explosive compositions and methods for fabricating explosive compositions
FR2954309B1 (fr) * 2009-12-21 2012-03-23 Eurenco France Explosif solide malleable et son obtention
FR3013705B1 (fr) * 2013-11-22 2016-07-01 Herakles Produit pyrotechnique composite a liant non reticule et son procede de preparation
FR3018807B1 (fr) 2014-03-20 2016-04-15 Herakles Procede d'obtention de charges de cristaux d'hexanitrohexaazaisowurtzitane (cl20) de granulometrie monomodale submicronique, lesdites charges et leur utilisation comme charges d'ensemencement

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Also Published As

Publication number Publication date
WO2016079453A1 (fr) 2016-05-26
FR3028852A1 (fr) 2016-05-27
CA2968255A1 (fr) 2016-05-26
IL252369B (en) 2020-07-30
EP3221283A1 (de) 2017-09-27
FR3028852B1 (fr) 2017-01-06
IL252369A0 (en) 2017-07-31
US20180346393A1 (en) 2018-12-06

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