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 process 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). For some applications, it seeks high performance explosives thin. However, it is obviously imperative that this small thickness remains greater than their critical dimension of detonation. Explosives with critical dimensions of detonation as low as possible are therefore sought. Such a small critical dimension of detonation is suitably less than or equal to 5 mm, even less than or equal to 1.5 mm, or even less than or equal to 1 mm. Thus, in the context of miniaturized networks for multipoint ignition of explosive charges (such a network has for example the geometry shown in FIG.
• explosives with a critical dimension of detonation are also sought. as small as possible 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).
• US Pat. No. 3,354,010 discloses explosive products, in the form of flexible sheets (typically of a thickness of 6.3 mm), the composition of which contains organic energy charges of hexogen (HMX) and / or octogenous (RDX) type. ), in a binder (nitrocellulose) plasticized (tributyl acetyl citrate).
• HMX hexogen
• RDX octogenous
• 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), are by elsewhere marketed, in recent 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 present invention therefore relates to new composite explosive products.
• Said products having a small critical dimension of detonation in view of their specific composition (composition containing a high level of charges, charges “highly” energy (“sensitive”) and fine particle size), therefore associate, with said specific composition, a thin (but obviously greater than or equal to their small critical dimension detonation).
• the composite explosive products of the invention exhibit:
• composition expressed in percentages by weight, which contains:
• organic energy charges being selected from octogen (HMX), hexogen (RDX), hexanitrohexaazaisowurtzitane (CL20), pentrite (PETN) and mixtures thereof and b) having a particle size distribution with a value of of D 90 less than 15 ⁇ m and a value of D 50 less than or equal to 5 ⁇ m; and
• a polymeric gum chosen from polyurethane-polyester gums, polyurethane-polyether gums and mixtures thereof, the number-average molecular mass of which is greater than 20,000 g / mol and whose Mooney viscosity is between 20 and 70 ML (5 + 4) at 100 ° C; and
• the composite explosive products of the invention thus contain a high level of "Strongly" energetic ("sensitive”) organic 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 (H MX) charges, hexogen (RDX) charges, hexaazaisowurtzitane (CL20) charges, pentrite charges ( ⁇ ) or a mixture of such charges.
• H MX octogen
• RDX hexogen
• CL20 hexaazaisowurtzitane
• pentrite charges ⁇
• 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 i0 (for example a value of 100 nm or less)), the more interesting the products in question are.
• Such fine fillers are generally obtained by grinding "large" crystals.
• the skilled person knows 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 moreover described in the patent application FR 14 00669, published under No. 3,018,807 (September 25, 2015), an original grinding process for obtaining charges of CL20 submicron monomodal particle size.
• Said method comprises the continuous grinding of a charge of CL20 crystals, with a granulometry beyond the micron (D 50 > 1 ⁇ ), in suspension in a liquid; said grinding being carried out, with cooling, by multi-pass 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.
• Said binder is a polymeric gum:
• polyurethane-polyester gums i.e. of polyurethane type with flexible segments of polyester type
• polyurethane-polyether gums i.e. of polyurethane type with flexible segments of polyether type
• 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 a 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) may 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 nitrate or nitramine type, for example, diethylene glycol dinitrate (DEGDN), triethylene glycol dinitrate (TEGDN), butanetriol trinitrate (BTTN), trimethylolethane trinitrate ( TMETN), a mixture of 2,4-dinitro-2,4-diaza-pentane, 2,4-dinitro-2,4-diaza-hexane and 3,5-dinitro-3,5-diaza-heptane ( and most particularly DNDA 5,7), nitrato ethyl nitramines (and especially methyl-2-nitratomethyl n
• the 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 of the composite explosive products of the invention thus comprises:
• organic energy charges a) being selected from octogen (HMX), hexogen (RDX), hexanitrohexaazaisowurtzitane (CL20), pentrite (PETN) and mixtures thereof and b) having a particle size distribution with a value of of D 90 less than 15 ⁇ and a value of D 5 o less than or equal to 5 ⁇ m;
• a polymeric gum chosen from polyurethane-polyester gums, polyurethane-polyether gums and mixtures thereof, the number-average molecular mass of which is greater than 20,000 g / mol (advantageously greater than 35,000) g / mol, most preferably greater than 75,000 g / mol) and whose Mooney viscosity is between 20 and 70 ML (5 + 4) at 100 ° C; + from 1 to 4%, advantageously from 2 to 3%, of a plasticizer chosen from energetic plasticizers, non-energetic plasticizers and mixtures thereof, and
• 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 a adequate process (see below), authorizes the incorporation within it of a high rate of charges ("sensitive”) of fine particle size.
• the composite pyrotechnic products of the invention may have any type of shape and may be in particular:
• said elements consist of pieces of sheets, such as (strips, bars, for example) or possibly worked on a part (only part) of their thickness), or
• the cuttings in question are conventional cuttings, implemented with conventional mechanical means (advantageously cutting by jet (s) of water, with two parallel blades or die cutter).
• the composite pyrotechnic products of the invention can thus notably consist of:
• V-groove usable as part of a detonating cutting line, said V-groove being intended to be covered with a metallic coating or a coating loaded with metallic particles
• a miniaturized multi-point explosive charge initiation network see (c) above.
• 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).
• the invention relates to a method for preparing (obtaining) composite pyrotechnic products of the invention, as described above.
• Said method is based, typically, on the use of at least one roll mill. It typically comprises incorporating the charges into the binder in a roll mill. It includes, more precisely:
• the incorporation of the fillers into the eraser raised to a temperature of at least 50 ° C., generally at a temperature between 60 and 80 ° C .; said incorporation being carried out in a roll mill, and
• the roller mixer is a known Persian device. Its use has made it possible to obtain the products of the invention (it has made it possible to incorporate the high level of small charges into the gum), it has made it possible to obtain the said advantageously (without using a solvent (this is very advantageous compared to certain processes of the prior art) at temperatures compatible with the sensitivity of the charges, mixing and rolling being provided in a single step, at the same station (this is very advantageous compared to some processes of the prior art)).
• 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. It is generally carried out beforehand a mixture fillers + ingredient (s), when at least one such ingredient is involved, and then introducing said mixture.
• 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 to a lower value because two phenomena are likely to occur: the material may force the spacing of the rolls and there may 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 advantageously by jet (s) of water, with two parallel blades or punch, the calendered filled sheet.
• This produces cut elements as specified above. We have seen that said cut elements can further be worked.
• the cutting of the leaves, more particularly with blades, can be facilitated by previously heating said sheets between 40 and 50 ° C.
• UREPAN ® G 643 sold by RheinChemie company (polyaddition product of diphenyl-methane diisocyanate and a polyester). It has the following characteristics:
• UREPAN ® 600 sold by RheinChemie company (polyaddition product of toluene diisocyanate and a polyester). It has the following characteristics:
• RDX hexogen
• Step a of the process pasty mixtures were obtained in a roll mill, in a known Persian manner.
• 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.
• a coating of one of the cylinders was then obtained. Finally, the rotation of the rolls was stopped and the coating was cut in its width in order to recover it in the form of a sheet (dimensions: 250 mm ⁇ 150 mm).
• the sheets obtained had, according to the spacing of the rolls, 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. 3) Results
• 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 rate logically leads to a decrease in the critical detonation section (the charge rate of the composition of Example 6 is
• Binder PBHT (marketed by the company CRAY VALLEY under the name: R45HT) with a number-average molecular weight of 2800 g / mol (binder conventionally used in the context of composite energy products).
• Pastes very viscous have been obtained by kneading, from said binder (20% by weight) and RDX charges (80% by mass), reference M3c from EURENCO, whose particle size distribution had a value of Dm of 1 ⁇ , a value of D 50 of 4 pm and a D 90 value of 9 pm (see above).
• This binder very liquid, allowed the incorporation of a high rate of small charges within it. However, it must be cross-linked.

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• 2014
  • 2014-11-21 FR FR1402626A patent/FR3028852B1/fr not_active Expired - Fee Related
• 2015
  • 2015-11-20 US US15/527,932 patent/US20180346393A1/en not_active Abandoned
  • 2015-11-20 CA CA2968255A patent/CA2968255A1/fr not_active Abandoned
  • 2015-11-20 WO PCT/FR2015/053158 patent/WO2016079453A1/fr active Application Filing
  • 2015-11-20 EP EP15804911.4A patent/EP3221283B1/de active Active
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  • 2017-05-18 IL IL252369A patent/IL252369B/en active IP Right Grant

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