EP3221283B1 - Thin composite explosive products and preparation thereof - Google Patents
Thin composite explosive products and preparation thereof Download PDFInfo
- 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
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- 239000002360 explosive Substances 0.000 title claims description 46
- 239000002131 composite material Substances 0.000 title claims description 32
- 238000002360 preparation method Methods 0.000 title description 2
- 239000000203 mixture Substances 0.000 claims description 59
- XTFIVUDBNACUBN-UHFFFAOYSA-N 1,3,5-trinitro-1,3,5-triazinane Chemical compound [O-][N+](=O)N1CN([N+]([O-])=O)CN([N+]([O-])=O)C1 XTFIVUDBNACUBN-UHFFFAOYSA-N 0.000 claims description 28
- 239000004014 plasticizer Substances 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 27
- 229920000728 polyester Polymers 0.000 claims description 19
- 239000000028 HMX Substances 0.000 claims description 12
- TZRXHJWUDPFEEY-UHFFFAOYSA-N Pentaerythritol Tetranitrate Chemical compound [O-][N+](=O)OCC(CO[N+]([O-])=O)(CO[N+]([O-])=O)CO[N+]([O-])=O TZRXHJWUDPFEEY-UHFFFAOYSA-N 0.000 claims description 12
- UZGLIIJVICEWHF-UHFFFAOYSA-N octogen Chemical compound [O-][N+](=O)N1CN([N+]([O-])=O)CN([N+]([O-])=O)CN([N+]([O-])=O)C1 UZGLIIJVICEWHF-UHFFFAOYSA-N 0.000 claims description 12
- NDYLCHGXSQOGMS-UHFFFAOYSA-N CL-20 Chemical compound [O-][N+](=O)N1C2N([N+]([O-])=O)C3N([N+](=O)[O-])C2N([N+]([O-])=O)C2N([N+]([O-])=O)C3N([N+]([O-])=O)C21 NDYLCHGXSQOGMS-UHFFFAOYSA-N 0.000 claims description 11
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 11
- 238000005520 cutting process Methods 0.000 claims description 11
- 229920000570 polyether Polymers 0.000 claims description 11
- 238000009826 distribution Methods 0.000 claims description 9
- 238000003490 calendering Methods 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 7
- 230000000996 additive effect Effects 0.000 claims description 7
- 230000000977 initiatory effect Effects 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims 3
- 239000000047 product Substances 0.000 description 58
- 239000011230 binding agent Substances 0.000 description 34
- 238000005474 detonation Methods 0.000 description 28
- 239000002245 particle Substances 0.000 description 13
- 239000000945 filler Substances 0.000 description 12
- 229920001971 elastomer Polymers 0.000 description 6
- 238000000227 grinding Methods 0.000 description 6
- 238000010348 incorporation Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 241001441571 Hiodontidae Species 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 238000001033 granulometry Methods 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 238000005096 rolling process Methods 0.000 description 5
- AGCQZYRSTIRJFM-UHFFFAOYSA-N triethylene glycol dinitrate Chemical compound [O-][N+](=O)OCCOCCOCCO[N+]([O-])=O AGCQZYRSTIRJFM-UHFFFAOYSA-N 0.000 description 5
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Chemical compound CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- 239000005060 rubber Substances 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- POCJOGNVFHPZNS-ZJUUUORDSA-N (6S,7R)-2-azaspiro[5.5]undecan-7-ol Chemical compound O[C@@H]1CCCC[C@]11CNCCC1 POCJOGNVFHPZNS-ZJUUUORDSA-N 0.000 description 3
- BSPUVYFGURDFHE-UHFFFAOYSA-N Nitramine Natural products CC1C(O)CCC2CCCNC12 BSPUVYFGURDFHE-UHFFFAOYSA-N 0.000 description 3
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical group CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- POCJOGNVFHPZNS-UHFFFAOYSA-N isonitramine Natural products OC1CCCCC11CNCCC1 POCJOGNVFHPZNS-UHFFFAOYSA-N 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 235000015927 pasta Nutrition 0.000 description 3
- 229920001169 thermoplastic Polymers 0.000 description 3
- 239000004416 thermosoftening plastic Substances 0.000 description 3
- QUAMCNNWODGSJA-UHFFFAOYSA-N 1,1-dinitrooxybutyl nitrate Chemical compound CCCC(O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QUAMCNNWODGSJA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- LYAGTVMJGHTIDH-UHFFFAOYSA-N diethylene glycol dinitrate Chemical compound [O-][N+](=O)OCCOCCO[N+]([O-])=O LYAGTVMJGHTIDH-UHFFFAOYSA-N 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- VJHINFRRDQUWOJ-UHFFFAOYSA-N dioctyl sebacate Chemical compound CCCCC(CC)COC(=O)CCCCCCCCC(=O)OCC(CC)CCCC VJHINFRRDQUWOJ-UHFFFAOYSA-N 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- JQCXWCOOWVGKMT-UHFFFAOYSA-N phthalic acid diheptyl ester Natural products CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC JQCXWCOOWVGKMT-UHFFFAOYSA-N 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical compound CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 description 2
- IPPYBNCEPZCLNI-UHFFFAOYSA-N trimethylolethane trinitrate Chemical compound [O-][N+](=O)OCC(C)(CO[N+]([O-])=O)CO[N+]([O-])=O IPPYBNCEPZCLNI-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 description 1
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- VAALVBPLSFRYMJ-XXMNONFOSA-N O=C1OC(=O)[C@@H]([C@@H](C23)C4)[C@H]1[C@@H]4C3[C@@H]1C[C@H]2[C@H]2C(=O)OC(=O)[C@@H]12 Chemical compound O=C1OC(=O)[C@@H]([C@@H](C23)C4)[C@H]1[C@@H]4C3[C@@H]1C[C@H]2[C@H]2C(=O)OC(=O)[C@@H]12 VAALVBPLSFRYMJ-XXMNONFOSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- ZDWGXBPVPXVXMQ-UHFFFAOYSA-N bis(2-ethylhexyl) nonanedioate Chemical compound CCCCC(CC)COC(=O)CCCCCCCC(=O)OCC(CC)CCCC ZDWGXBPVPXVXMQ-UHFFFAOYSA-N 0.000 description 1
- 229940073532 candelilla wax Drugs 0.000 description 1
- 235000013868 candelilla wax Nutrition 0.000 description 1
- 239000004204 candelilla wax Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 229940082150 encore Drugs 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- -1 for example Chemical compound 0.000 description 1
- 239000001087 glyceryl triacetate Substances 0.000 description 1
- 235000013773 glyceryl triacetate Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- IUJAMGNYPWYUPM-UHFFFAOYSA-N hentriacontane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC IUJAMGNYPWYUPM-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000013528 metallic particle Substances 0.000 description 1
- HKQRKLJWAQVSBC-UHFFFAOYSA-N n,n'-dimethylmethanediamine Chemical compound CNCNC HKQRKLJWAQVSBC-UHFFFAOYSA-N 0.000 description 1
- KUNXCAIGAVGORW-UHFFFAOYSA-N n-ethyl-n-[[ethyl(nitro)amino]methyl]nitramide Chemical compound CCN([N+]([O-])=O)CN(CC)[N+]([O-])=O KUNXCAIGAVGORW-UHFFFAOYSA-N 0.000 description 1
- NQPFICHAHMRTNV-UHFFFAOYSA-N n-ethyl-n-[[methyl(nitro)amino]methyl]nitramide Chemical compound CCN([N+]([O-])=O)CN(C)[N+]([O-])=O NQPFICHAHMRTNV-UHFFFAOYSA-N 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 229960002622 triacetin Drugs 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
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)
Description
La présente invention concerne des produits explosifs composites de faible épaisseur (faible épaisseur parfaitement maîtrisée), conformables (i.e. déformables, par action de la température, avec conservation de forme) et performants. Ils renferment un fort taux de charges énergétiques dans un liant de nature spécifique. Ils consistent notamment en des feuilles ou en des produits obtenus par découpage de telles feuilles, tels des réseaux miniaturisés d'amorçage multipoints de charges explosives, par exemple de têtes militaires explosives.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.
La présente invention a également pour objet un procédé de préparation desdits produits explosifs composites. Ledit procédé est d'une mise en oeuvre particulièrement aisée : à des températures parfaitement compatibles avec la sensibilité des charges énergétiques présentes, sans utilisation de solvant et n'incluant qu'un seul type d'opération.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.
Pour les explosifs en forme de feuille ou de barreau (généralement de section circulaire, carrée ou rectangulaire), il existe une valeur de dimension, respectivement d'épaisseur ou de section, en dessous de laquelle la détonation amorcée en un point subit un affaiblissement puis cesse après un certain parcours, laissant une partie de l'explosif intacte. Cette dimension (épaisseur ou section) minimale, en dessous de laquelle il n'y a pas de propagation de la détonation stable, est appelée épaisseur ou section critique de détonation. On parle aussi de diamètre critique de détonation pour un barreau cylindrique.For explosives in the shape of a sheet or bar (generally of circular, square or rectangular section), there is a dimension value, respectively of thickness or of section, below which the detonation initiated at a point undergoes a weakening then stops after a certain route, leaving part of the explosive intact. This minimum dimension (thickness or section), below which there is no propagation of the stable detonation, is called the critical thickness or section of detonation. We also speak of critical diameter of detonation for a cylindrical bar.
Cette dimension critique de détonation est déterminée à partir d'échantillons de dimension dégressive (de barreaux cylindriques à gradins, à section dégressive, par exemple), la détonation étant amorcée du côté de l'échantillon présentant la plus grande dimension (du côté du barreau présentant la plus grande section).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).
Pour certaines applications, on recherche des explosifs performants à faible épaisseur. Il est toutefois évidemment impératif que cette faible épaisseur demeure supérieure à leur dimension critique de détonation. On recherche donc des explosifs à dimension critique de détonation aussi faible que possible. Une telle faible dimension critique de détonation est opportunément inférieure ou égale à 5 mm, voire inférieure ou égale à 1,5 mm, voire même inférieure ou égale à 1 mm. Ainsi, dans le contexte des réseaux miniaturisés d'amorçage multipoints de charges explosives (un tel réseau présente par exemple la géométrie montrée sur la figure 5 de la demande de brevet
Selon l'art antérieur, on s'est donc déjà intéressé aux explosifs performants de faible épaisseur et à leur obtention.According to the prior art, we have already been interested in performing thin explosives and obtaining them.
Le brevet
La demande
Le brevet
Des élastomères (gommes, caoutchoucs « crus » (non réticulés)) de type polyuréthane-polyester (i.e. de nature polyuréthane à segments souples de type polyester) et/ou polyuréthane-polyéther (i.e. de nature polyuréthane à segments souples de type polyéther), sont par ailleurs commercialisés, depuis quelques années, notamment sous la marque UREPAN® par la société RheinChemie et sous la marque Millathane® par la société TSE Industries. La présente invention offre un débouché original à ce type d'élastomères.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.
Dans un tel contexte, l'homme du métier est toujours à la recherche d'un produit explosif de faible épaisseur (parfaitement maîtrisée), conformable, performant (i.e. de dimension critique de détonation faible (en référence à sa faible épaisseur (voir ci-dessus)) et de fabrication aisée.In such a context, the person skilled in the art is always looking for an explosive product of small thickness (perfectly controlled), conformable, efficient (ie critical dimension of weak detonation (in reference to its small thickness (see below). above)) and easy to manufacture.
Il est du mérite des inventeurs de proposer un tel produit constitué essentiellement de charges énergétiques spécifiques (lesdites charges « fortement » énergétiques (« sensibles ») étant présentes, sous une granulométrie fine (micronique), à un taux « maximal » (≥ à 85 % en masse)) et d'un liant d'un type nouveau, ledit liant permettant l'obtention dudit produit par un procédé particulièrement aisé à mettre en oeuvre (ne nécessitant pas l'intervention d'un solvant, n'exigeant pas une température élevée (dangereuse au vu de la sensibilité des charges) en référence à la viscosité du liant, ne nécessitant qu'un unique type d'opération, dans un unique type de dispositif (mélangeur(s) à cylindres), voire dans un unique dispositif (mélangeur à cylindres) (voir ci-après)). Il n'était pas évident d'obtenir des produits explosifs fortement chargés en charges de fine granulométrie, encore moins évident d'obtenir de tels produits par un procédé d'une mise en oeuvre aisée.It is the merit of the inventors to propose such a product consisting essentially of specific energy charges (said "high" energy ("sensitive") charges being present, under a fine granulometry (micron), at a "maximum" rate (≥ 85 % by weight)) and a binder of a new type, said binder making it possible to obtain said product by a process that is particularly easy to implement (which does not require the use of a solvent, not requiring a high temperature (dangerous in view of the sensitivity of the charges) with reference to the viscosity of the binder, requiring only a single type of operation, in a single type of device (mixer (s) with cylinders), or even in a single device (roller mixer) (see below). It was not obvious to obtain explosive products heavily loaded with thin granulometry charges, even less obvious to obtain such products by a process of easy implementation.
Selon son premier objet, la présente invention concerne donc de nouveaux produits explosifs composites. Lesdits produits, présentant une faible dimension critique de détonation au vu de leur composition spécifique (composition renfermant un fort taux de charges, charges « fortement » énergétiques (« sensibles ») et de fine granulométrie), associent donc, à ladite composition spécifique, une faible épaisseur (toutefois évidemment supérieure ou égale à leur faible dimension critique de détonation). De façon caractéristique, les produits explosifs composites de l'invention présentent :
- une composition, exprimée en pourcentages massiques, qui renferme :
- + de 85 à 92 %, avantageusement de 88 à 90 %, de charges énergétiques organiques ; lesdites charges énergétiques organiques a) étant choisies parmi des charges d'octogène (HMX), d'hexogène (RDX), d'hexanitrohexaazaisowurtzitane (CL20), de pentrite (PETN) et leurs mélanges et b) présentant une distribution granulométrique avec une valeur de D90 inférieure à 15 µm et une valeur de D50 inférieure ou égale à 5 µm ; et
- + de 7 à 12 %, avantageusement de 8 à 10 %, d'une gomme polymérique choisie parmi les gommes polyuréthane-polyester, les gommes polyuréthane-polyéther et leurs mélanges, dont la masse moléculaire moyenne en nombre est supérieure à 20 000 g/mol et dont la viscosité Mooney est comprise entre 20 et 70 ML (5 + 4) à 100°C ; et
- une épaisseur de 0,4 à 5 mm, avantageusement de 1 à 2 mm.
- a composition, expressed in percentages by weight, which contains:
- + from 85 to 92%, advantageously from 88 to 90%, of organic energy charges; said organic energy charges a) being chosen from octogen (HMX), hexogen (RDX), hexanitrohexaazaisowurtzitane (CL20), pentrite (PETN) and their mixtures and b) having a particle size distribution with a value of D 90 less than 15 μm and a value of D 50 less than or equal to 5 μm; and
- + from 7 to 12%, advantageously from 8 to 10%, of 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
- a thickness of 0.4 to 5 mm, advantageously 1 to 2 mm.
On peut d'ores et déjà relever que les plages indiquées pour les teneurs en charges et en liant sont des plages étroites. C'est avec de telles teneurs de charges (de la nature précisée et de la (fine) granulométrie précisée) et de liant (de la nature précisée) que les résultats recherchés ont été obtenus. Les propriétés mécaniques des produits « obtenus » (à supposer que lesdits produits puissent être obtenus) avec plus de charges ne sont pas satisfaisantes ; les performances énergétiques (et notamment les dimensions critiques de détonation) des produits obtenus avec moins de charges ne sont pas satisfaisantes (on rappelle que l'on vise des dimensions critiques de détonation inférieures ou égales à 5 mm, voire inférieures ou égales à 1,5 mm, voire même inférieures ou égales à 1 mm).It can already be noted that the ranges indicated for the contents of charges and binding are narrow ranges. It is with such contents (of the specified nature and the (fine) granulometry specified) and binder (of the specified nature) that the desired results were obtained. The mechanical properties of products "obtained" (assuming that the said products can be obtained) with more charges are not satisfactory; the energetic performances (and in particular the critical dimensions of detonation) of the products obtained with less loads are not satisfactory (one recalls that one targets critical dimensions of detonation lower or equal to 5 mm, even lower or equal to 1, 5 mm, or even less than or equal to 1 mm).
Comme indiqué ci-dessus, les produits explosifs composites de l'invention renferment donc un fort taux de charges, de charges « fortement » énergétiques (« sensibles ») organiques et de fine granulométrie dans un liant d'un type nouveau.As indicated above, 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.
Les produits explosifs composites de l'invention renferment de 85 à 92 %, avantageusement de 88 à 90 % (% massiques), de charges énergétiques organiques spécifiques.The composite explosive products of the invention contain from 85 to 92%, advantageously from 88 to 90% (% by weight), of specific organic energy charges.
Les charges en cause sont des charges « fortement » énergétiques (« sensibles »). Il s'agit de charges d'octogène (HMX), de charges d'hexogène (RDX), de charges d'hexaazaisowurtzitane (CL20), de charges de pentrite (PETN) ou d'un mélange de telles charges. Avantageusement, il s'agit de charges d'hexogène (RDX), de charges d'hexanitrohexaazaisowurtzitane (CL20) ou d'un mélange de ces deux types de charges (les plus énergétiques).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. Advantageously, these are charges of hexogen (RDX), charges of hexanitrohexaazaisowurtzitane (CL20) or a mixture of these two types of charges (the most energetic).
Les charges en cause ne sont pas présentes sous la forme de gros et de petits cristaux, elles ne sont présentes que sous la forme de petits cristaux. Il s'agit de charges (fines) qui présentent une distribution granulométrique avec une valeur de D90 inférieure à 15 µm et une valeur de D50 inférieure ou égale à 5 µm (la notion de charges « fines », de « petits » cristaux est ainsi précisée). La valeur de D10 n'est pas précisée dans la mesure où elle est en rien critique. On a compris que plus les charges sont fines (i.e. plus la valeur du D10 est faible (par exemple une valeur de 100 nm ou encore moins)), plus les produits en cause sont intéressants. Ces données granulométriques (D90, D50 (et D10)) se mesurent au moyen d'un granulométre optique à corrélation de photons (PCS-DLS : Photons Corrélation Spectroscopy-Diffusion Light Scattering), selon un mode opératoire défini par la norme NF 11-666. Elles correspondent respectivement au diamètre pour lequel le pourcentage volumique cumulé (des particules de charges) est égal à 90 %, 50 % (diamètre médian) (et 10 %).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. These are (fine) fillers that have a particle size distribution with a D 90 value of less than 15 μm and a D 50 value of less than or equal to 5 μm (the notion of "fine" fillers, "small" crystals is thus specified). 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. These 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%).
De telles charges fines sont généralement obtenues par broyage de « gros » cristaux. L'homme du métier connaît de nombreux procédés de broyage, adaptés à la sensibilité des charges en cause. On peut de façon nullement limitative mentionner l'utilisation possible de broyeurs SWECO®. La Demanderesse a par ailleurs décrit dans la demande de brevet
Les charges énergétiques organiques (dont le taux de présence, la nature et la granulométrie ont été précisés ci-dessus) se trouvent donc, dans la composition des produits explosifs composites de l'invention, au sein d'un liant original.The 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.
Ledit liant est une gomme polymérique :
- choisie parmi les gommes polyuréthane-polyester (i.e. de nature polyuréthane à segments souples de type polyester), les gommes polyuréthane-polyéther (i.e. de nature polyuréthane à segments souples de type polyéther) et leurs mélanges,
- qui présente une masse moléculaire moyenne en nombre supérieure à 20 000 g/mol (avantageusement supérieure à 35 000 g/mol, très avantageusement supérieure à 75 000 g/mol (tout particulièrement en référence à la résistance au vieillissement du produit final)), et
- qui présente une viscosité Mooney comprise entre 20 et 70 ML (5 + 4) à 100°C. Ce paramètre est très utilisé dans l'industrie du caoutchouc. « x ML (5 + 4) à 100°C » se lit « x M égal à la viscosité en unités (ou points) Mooney ; L ou S (ici L) correspondant à la taille du rotor, 5 indiquant le temps de préchauffage du produit et 4, le temps en minutes après le démarrage du moteur auquel lecture est prise, 100°C étant la température de la mesure ». La valeur « x » est généralement donnée à « +/- y » ; c'est ladite valeur « x » qui doit être dans la plage 20-70 (valeurs d'extrémités comprises).
- chosen from polyurethane-polyester gums (ie of polyurethane type with flexible segments of polyester type), polyurethane-polyether gums (ie of polyurethane type with flexible segments of polyether type) and their mixtures,
- which has a number average molecular weight greater than 20 000 g / mol (advantageously greater than 35 000 g / mol, very advantageously greater than 75 000 g / mol (especially with reference to the aging resistance of the final product)), and
- which has a Mooney viscosity of 20 to 70 ML (5 + 4) at 100 ° C. This parameter is widely used in the rubber industry. "X ML (5 + 4) at 100 ° C" reads "x M equal to the viscosity in units (or points) Mooney; L or S (here L) corresponding to the size of the rotor, 5 indicating the preheating time of the product and 4, the time in minutes after starting the engine to which reading is taken, 100 ° C being the temperature of the measurement ". The value "x" is usually given to "+/- y"; it is said value "x" that must be in the range 20-70 (including end values).
Une telle gomme convient parfaitement aux fins de l'invention, dans la mesure où, en les proportions indiquées (de 7 à 12 % (avantageusement de 8 à 10 %) seulement, on rappelle que des produits à fort taux de charge sont en cause) :
- 1) elle permet d'incorporer le fort taux de charges fines et de travailler mécaniquement le mélange (charges + liant) à basse température, i.e. à une température inférieure à 120°C, généralement inférieure à 100°C (avantageusement entre 60 à 80°C) (température tout à fait compatible avec la stabilité des charges présentes), et ce, sans utilisation de solvant ; et
- 2) elle confère au produit final (de faible épaisseur) les propriétés mécaniques requises : tenue mécanique, cohésion, conformabilité. Les produits de l'invention sont conformables dans la mesure où ladite gomme est conformable. Portée à une température adéquate, elle peut être mise en forme et conserver ensuite la forme en cause. Cette forme ne peut être modifiée que par une nouvelle action de la température.
- 1) it makes it possible to incorporate the high level of fine charges and to mechanically work the mixture (charges + binder) at low temperature, ie at a temperature below 120 ° C., generally below 100 ° C. (advantageously between 60 to 80 ° C. ° C) (temperature completely compatible with the stability of the present charges), and this, without use of solvent; and
- 2) it gives the final product (thin) the required mechanical properties: mechanical strength, cohesion, conformability. The products of the invention are conformable to the extent that said rubber is conformable. Reached at an adequate temperature, it can be shaped and then keep the shape in question. This form can only be modified by a new action of the temperature.
Il est du mérite des inventeurs d'avoir identifié (sélectionné) ce type de liant, convenant parfaitement aux fins de l'invention. D'autres types de liant ont été testés et n'ont pas donné de résultats satisfaisants (quant à la possibilité d'obtenir le mélange, de le travailler à basse température et/ou quant aux propriétés du produit final de faible épaisseur).It is the merit of the inventors to have identified (selected) this type of binder, perfectly suitable for the purposes of the invention. Other types of binder have been tested and have not given satisfactory results (as to the possibility of obtaining the mixture, of working it at low temperature and / or as to the properties of the thin final product).
Le liant des produits de l'invention consiste généralement en une gomme polyuréthane-polyester ou une gomme polyuréthane-polyéther, mais des mélanges d'au moins deux gommes (au moins deux gommes polyuréthane-polyester, au moins deux gommes polyuréthane-polyéther ou au moins une gomme polyuréthane-polyester et au moins une gomme polyuréthane-polyéther ; de tels mélanges de gommes (gommes au sens de l'invention) constituant une gomme au sens de l'invention) présentant les propriétés requises (rappelées ci-dessus)) peuvent être utilisés. Ledit liant consiste avantageusement en une gomme polyuréthane-polyester.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.
La composition des produits pyrotechniques composites de l'invention est susceptible de renfermer en outre au moins un plastifiant, choisi parmi les plastifiants énergétiques, les plastifiants non énergétiques et leurs mélanges ; elle est susceptible de renfermer en outre généralement jusqu'à 4 % en masse d'au moins un tel plastifiant. Un tel au moins un plastifiant (= au moins un plastifiant énergétique, au moins un plastifiant non énergétique ou au moins un plastifiant énergétique et au moins un plastifiant non énergétique), avantageusement présent (en référence à l'obtention du produit et à ses propriétés), l'est généralement à raison de 1 à 4 % en masse, avantageusement de 2 à 3 % en masse.The 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. Such at least one plasticizer (= at least one energetic plasticizer, at least one non-energetic plasticizer or at least one energetic plasticizer and at least one non-energetic plasticizer), advantageously present (with reference to obtaining the product and its properties ), is generally at 1 to 4% by weight, preferably 2 to 3% by weight.
Ledit au moins un plastifiant est donc choisi parmi les plastifiants non énergétiques (par exemple, le di-octyl azélate (DOZ), le di-2-éthylhexyl sébacate (DOS), le di-n-octyl phtalate (DOP), la triacétine et leurs mélanges), les plastifiants énergétiques (avantageusement de type nitrate ou nitramine, par exemple, le dinitrate de diéthylène glycol (DEGDN), le dinitrate de triéthylène glycol (TEGDN), le trinitrate de butanetriol (BTTN), le trinitrate de triméthyloléthane (TMETN), un mélange de 2,4-dinitro-2,4-diaza-pentane, de 2,4-dinitro-2,4-diaza-hexane et de 3,5-dinitro-3,5-diaza-heptane (et tout particulièrement le DNDA 5,7), les nitrato éthyl nitramines (et notamment le méthyl-2-nitratométhyl nitramine (méthylNENA) et l'éthyl-2-nitratoéthyl nitramine (éthylNENA)) et leurs mélanges.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 nitramine (methylNENA) and ethyl-2-nitratoethyl nitramine (ethylNENA)) and mixtures thereof.
La composition des produits pyrotechniques composites de l'invention renferme, selon une variante préférée, comme plastifiant, du dinitrate de triéthylène glycol (TEGDN).The composition of the composite pyrotechnic products of the invention contains, according to a preferred variant, as a plasticizer, triethylene glycol dinitrate (TEGDN).
La composition des produits pyrotechniques composites de l'invention est donc essentiellement constituée, voire constituée, des charges énergétiques, du liant et éventuellement d'au moins un plastifiant (avantageusement présent (voir ci-dessus)). Elle peut être constituée à 100 % en masse desdites charges énergétiques, dudit liant et dudit éventuel au moins un plastifiant (charges + liant = 100 % ou charges + liant + plastifiant = 100 %). Elle l'est généralement à au moins 99 % en masse. Il ne saurait en effet être exclu qu'elle renferme, en sus desdits charges, liant et éventuel(s) plastifiant(s), au moins un additif. Un tel au moins un additif, lorsqu'il est présent, l'est généralement à raison de 0,1 à 1 % en masse. Il peut notamment s'agir d'au moins un agent de mise en oeuvre (cire de candellila et/ou paraffine, par exemple).The composition of the composite pyrotechnic products of the invention is therefore essentially constituted, or even constituted, of energetic charges, binder and optionally at least one plasticizer (advantageously present (see above)). It can consist of 100% by weight of said energy charges, said binder and said optional at least one plasticizer (charges + binder = 100% or charges + binder + plasticizer = 100%). It is generally at least 99% by weight. It can not be ruled out that it contains, in addition to the said charges, binding and optionally plasticizer (s), at least one additive. Such at least one additive, when present, is generally at 0.1 to 1% by weight. It may especially be at least one processing agent (candellila wax and / or paraffin, for example).
Les variantes avantageuses des taux de charges, de liant et de plastifiants indiquées ci-dessus se lisent de façon indépendante ou de façon combinée.The advantageous variants of the levels of fillers, binder and plasticizers indicated above are read independently or in combination.
Selon une variante, la composition des produits explosifs composites de l'invention renferme ainsi :
- + de 88 à 90 %, de charges énergétiques organiques ; lesdites charges énergétiques organiques a) étant choisies parmi des charges d'octogène (HMX), d'hexogène (RDX), d'hexanitrohexaazaisowurtzitane (CL20), de pentrite (PETN) et leurs mélanges et b) présentant une distribution granulométrique avec une valeur de D90 inférieure à 15 µm et une valeur de D50 inférieure ou égale à 5 µm ;
- + de 8 à 10 %, d'une gomme polymérique choisie parmi les gommes polyuréthane-polyester, les gommes polyuréthane-polyéther et leurs mélanges, dont la masse moléculaire moyenne en nombre est supérieure à 20 000 g/mol (avantageusement supérieure à 35 000 g/mol, très avantageusement supérieure à 75 000 g/mol) et dont la viscosité Mooney est comprise entre 20 et 70 ML (5 + 4) à 100°C ;
- + de 1 à 4 %, avantageusement de 2 à 3 %, d'un plastifiant, choisi parmi les plastifiants énergétiques, les plastifiants non énergétiques et leurs mélanges, et
- + de 0 à 1 % d'au moins un additif.
- + from 88 to 90% of organic energy charges; said organic energy charges a) being selected from among octogen charges (HMX), hexogen (RDX), hexanitrohexaazaisowurtzitane (CL20), pentrite (PETN) and mixtures thereof and b) having a particle size distribution with a D 90 value of less than 15 μm and a lower D 50 value or equal to 5 μm;
- + from 8 to 10%, of 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
- + from 0 to 1% of at least one additive.
Dans le cadre de cette variante, ladite composition consiste généralement en ce qui est précisé.In the context of this variant, said composition generally consists of what is specified.
A leur composition caractéristique précisée ci-dessus, les produits explosifs composites de l'invention associent une faible épaisseur. On a compris qu'un produit de l'invention présente une épaisseur (e), une épaisseur (e) uniforme, constante (maîtrisée) : 0,4 mm ≤ e ≤ 5 mm, avantageusement 1 mm ≤ e ≤ 2 mm. Très avantageusement, on a e ≤ 1,5 mm.With their characteristic composition specified above, the composite explosive products of the invention combine a small thickness. It is understood that 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.
L'obtention de produits présentant une épaisseur inférieure à 0,4 mm est quasi impossible, encore faudrait-il que de tels produits puissent être performants (i.e. présentent une dimension critique de détonation en deçà de 0,4 mm).Obtaining products having a thickness of less than 0.4 mm is almost impossible, it would be necessary that such products can be effective (i.e. have a critical dimension of detonation below 0.4 mm).
L'obtention de produits présentant une épaisseur supérieure à 5 mm ne présente guère d'intérêt (les produits en cause étant performants à 5 mm, voire à une épaisseur moindre) et pose, en tout état de cause, des problèmes quant à la conformabilité desdits produits, quant à la maîtrise de leur épaisseur supérieure à 5 mm.Obtaining products having a thickness greater than 5 mm is of little interest (the products in question being effective at 5 mm or even at a lesser thickness) and in any case as a result, problems as to the conformability of said products as to the control of their thickness greater than 5 mm.
A la considération des valeurs d'épaisseur indiquées ci-dessus (0,4 mm ≤ e ≤ 5 mm, avantageusement 1 mm ≤ e ≤ 2 mm, très avantageusement e ≤ 1,5 mm), l'homme du métier comprend tout le mérite qui revient aux inventeurs de proposer de tels produits explosifs composites performants (l'explosif en cause devant donc présenter obligatoirement une dimension critique de détonation en deçà de ces faibles valeurs) et aux propriétés mécaniques adéquates (tenue mécanique, cohésion, conformabilité). Les bons résultats obtenus reposent essentiellement sur le liant (la nature du liant) qui, associé à un procédé adéquat (voir ci-après), autorise l'incorporation en son sein d'un fort taux de charges (« sensibles ») de fine granulométrie.Considering the thickness values indicated above (0.4 mm ≤ e ≤ 5 mm, advantageously 1 mm ≤ e ≤ 2 mm, very advantageously ≤ 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.
Les produits pyrotechniques composites de l'invention, tels que décrits ci-dessus (présentant la composition précisée ci-dessus et la faible épaisseur précisée ci-dessus), peuvent avoir tout type de forme et se présenter notamment :
- a) sous la forme de feuilles (on peut parler de films si les feuilles en cause présentent une « grande » longueur),
- b) sous la forme d'éléments découpés dans une feuille sans découpage d'évidement traversant dans l'épaisseur de ladite feuille (lesdits éléments consistent en des morceaux de feuilles, tels que (bandes, barres, par exemple) ou éventuellement travaillés sur une partie (une partie seulement) de leur épaisseur), ou encore
- c) sous la forme d'éléments découpés dans une feuille avec découpage d'évidement(s) traversant(s) dans l'épaisseur de ladite feuille (lesdits éléments étant susceptibles de présenter toute géométrie).
- (a) in the form of leaves (we can speak of films if the leaves in question have a "great" length),
- b) in the form of cut-out elements in a sheet without recess cut-out passing through the thickness of said sheet (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
- c) in the form of cut-out elements in a sheet with recess cut-out (s) passing through the thickness of said sheet (said elements being capable of having any geometry).
Les découpages en cause sont des découpages conventionnels, mis en oeuvre avec des moyens mécaniques classiques (avantageusement des découpages par jet(s) d'eau, avec deux lames parallèles ou à l'emporte-pièce).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).
Les produits pyrotechniques composites de l'invention peuvent ainsi notamment consister :
- a) en une feuille explosive (utilisable notamment comme matériau de démolition, comme matériau de découpe, comme matériau de formage de métal...) (voir le point a) ci-dessus),
- b) en une barre explosive avec rainure en V (utilisable comme élément constitutif d'un cordeau détonant de découpe, ladite rainure en V étant destinée à être recouverte d'un revêtement métallique ou d'un revêtement chargé en particules métalliques) (voir le point b) ci-dessus), ou
- c) en un réseau miniaturisé d'amorçage multipoints de charges explosives (voir le point c) ci-dessus).
- (a) an explosive film (usable in particular as a demolition material, as a cutting material, as a metal-forming material, etc.) (see point (a) above),
- b) into an explosive bar with a 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) (see point (b) above), or
- (c) a miniaturized multi-point explosive charge initiation network (see (c) above).
Ce dernier type de produits de l'invention est particulièrement préféré. Les canaux du réseau miniaturisé ont évidemment une section a minima égale à la dimension critique de détonation de la composition en cause. Ils peuvent présenter des changements de direction avec des angles élevés, jusqu'à 90° (au vu des faibles valeurs desdites dimensions critiques). Ils présentent généralement une section carrée ou rectangulaire.The latter type of products of the invention is particularly preferred. 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.
De tels réseaux selon l'invention sont particulièrement intéressants. Leur conformabilité (inhérente à la nature du liant présent dans leur composition et à leur faible épaisseur) permet leur utilisation aussi bien sur des surfaces planes (on peut initier de façon conventionnelle une charge de forme cylindrique avec un tel réseau positionné sur une des bases de la charge) que sur des surfaces courbes (un tel positionnement, non conventionnel, peut se révéler particulièrement intéressant pour augmenter la vitesse d'éclats dans une direction).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).
Selon son second objet, l'invention concerne un procédé pour la préparation (l'obtention) des produits pyrotechniques composites de l'invention, tels que décrits ci-dessus. Ledit procédé est basé, de façon caractéristique, sur l'utilisation d'au moins un mélangeur à cylindres. Il comprend, de façon caractéristique, l'incorporation des charges dans le liant dans un mélangeur à cylindres. Il comprend, plus précisément :
- l'incorporation des charges dans la gomme portée à une température d'au moins 50°C, généralement à une température entre 60 et 80°C ; ladite incorporation étant mise en oeuvre dans un mélangeur à cylindres, et
- le calandrage de la feuille chargée obtenue, dans un mélangeur à cylindres.
- incorporating the fillers in the gum heated 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 calendering of the resulting filled sheet in a roll mill.
Tout plastifiant et additif intervenant est aussi incorporé à la gomme dans le mélangeur à cylindres.Any plasticizer and intervening additive is also incorporated into the gum in the roll mill.
Le mélangeur à cylindres est un dispositif connu per se. The roll mill is a device known per se.
Son utilisation a permis l'obtention des produits de l'invention (elle a rendu possible l'incorporation du fort taux de petites charges dans la gomme), elle a permis ladite obtention de manière fort avantageuse (sans faire appel à un solvant (ceci est très avantageux par rapport à certains procédés de l'art antérieur), à des températures compatibles avec la sensibilité des charges, le mélange et le laminage étant assuré en une seule étape, à un même poste (ceci est très avantageux par rapport à certains procédés de l'art antérieur)).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)).
On peut considérer que la présente invention repose sur la sélection du liant associée à la sélection du procédé, cette double sélection rendant non seulement l'obtention des produits de l'invention (produits fortement chargés avec des charges sensibles fines) possible (la faisabilité dudit procédé n'était pas acquise par avance) mais possible dans des conditions de mise en oeuvre simples.It can be considered that 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.
La constitution du mélange, dans le mélangeur à cylindres, est réalisée, de façon conventionnelle, les cylindres étant mis en mouvement de rotation, en sens inverse, à des vitesses différentes.The formation of the mixture in the roll mixer is conventionally carried out with the rolls rotated in opposite directions at different speeds.
La gomme, lorsqu'elle se présente sous la forme de granulés, est tout d'abord façonnée sommairement au laminoir pour l'obtention d'une bande mince (1 mm à quelques mm).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).
Ladite gomme est généralement, dans un premier temps, introduite dans le mélangeur à cylindres, dont les cylindres sont portés à une température (T) d'au moins 50°C (inférieure à 120°C, généralement inférieure à 100°C), avantageusement entre 60 et 80°C (60°C≤T≤80°C), par exemple de 70°C. On introduit ensuite les charges et éventuel(s) autre(s) ingrédient(s) (éventuels plastifiant(s) et additif(s)), séparément ou en mélange. On réalise généralement préalablement un mélange charges + ingrédient(s), lorsqu'au moins un tel ingrédient intervient, et on introduit alors ledit mélange. L'introduction des charges peut être opportunément réalisée en plusieurs séquences après un réglage de l'écartement des cylindres. L'enrobage constitué autour du cylindre tournant le plus vite peut être récupéré (découpé au cutter), replié et réintroduit entre les cylindres (afin d'homogénéiser la répartition des charges), selon les méthodes usuelles appliquées à ce procédé.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. The fillers and any other ingredient (s) (possible plasticizer (s) and additive (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.
On obtient ainsi une feuille (un film) de faible épaisseur (correspondant à l'espacement entre les rouleaux). Pour le réglage de ladite épaisseur à la valeur souhaitée (0,4 mm ≤ e ≤ 5 mm, avantageusement 1 mm ≤ e ≤ 2 mm, très avantageusement e ≤ 1,5 mm), voire pour la simple élimination d'irrégularités en épaisseur (on vise une épaisseur constante, uniforme, parfaitement maîtrisée), ladite feuille est calandrée dans un mélangeur à cylindres (les cylindres dudit mélangeur à cylindres tournant alors dans le même sens, à la même vitesse, et leur écartement étant réglé à la valeur d'épaisseur désirée, voire à une valeur inférieure car deux phénomènes sont susceptible de se manifester : la matière peut forcer l'écartement des cylindres et il peut y avoir une relaxation du produit après laminage).A sheet (a film) of small thickness (corresponding to the spacing between the rolls) is thus obtained. For adjusting said thickness to the desired value (0.4 mm ≤ e ≤ 5 mm, advantageously 1 mm ≤ e ≤ 2 mm, very advantageously ≤ 1.5 mm), or even for the simple elimination of unevenness in thickness (It aims a constant thickness, uniform, perfectly controlled), 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).
On conçoit que les étapes successives du procédé de l'invention - obtention du mélange sous la forme d'un produit de faible épaisseur (feuille) et calandrage - sont très avantageusement mises en oeuvre avec le même mélangeur à cylindres. Ainsi, à un même poste, on réalise mélange, laminage et calandrage ; ainsi, à un même poste, on peut obtenir directement un produit de l'invention type feuille (produit souhaité ou susceptible d'être utilisé pour préparer, notamment par découpage, d'autres produits de l'invention souhaités).It will be understood that the successive steps of the process of the invention - obtaining the mixture in the form of a thin product (sheet) and calendering - are very advantageously carried out with the same roll mixer. Thus, at the same station, it performs mixing, rolling and calendering; thus, at the same station, one can directly obtain a product of the invention sheet type (desired product or can be used to prepare, including cutting, other desired products of the invention).
Le procédé de l'invention peut donc comprendre, en outre, le découpage, avantageusement par jet(s) d'eau, avec deux lames parallèles ou à l'emporte-pièce, de la feuille chargée calandrée.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.
On obtient ainsi des éléments découpés tels que précisés ci-dessus. On a vu que lesdits éléments découpés peuvent en outre être travaillés.This produces cut elements as specified above. We have seen that said cut elements can further be worked.
Le découpage des feuilles, plus particulièrement avec des lames, peut être facilité en chauffant préalablement lesdites feuilles entre 40 et 50°C.The cutting of the leaves, more particularly with blades, can be facilitated by previously heating said sheets between 40 and 50 ° C.
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UREPAN® 643 G : commercialisée par la société RheinChemie (produit de polyaddition du diisocyanate de diphényl-méthane et d'un polyester). Elle présente les caractéristiques ci-après :
- Masse moléculaire moyenne en nombre : 80 000 g/mol
- Viscosité Mooney : 40 (+/-10) ML (5 + 4) à 100°C.
- Number average molecular weight: 80,000 g / mol
- Mooney viscosity: 40 (+/- 10) ML (5 + 4) at 100 ° C.
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UREPAN® 600 : commercialisée par la société RheinChemie (produit de polyaddition du diisocyanate de toluène et d'un polyester). Elle présente les caractéristiques ci-après :
- Masse moléculaire moyenne en nombre : 40 000 g/mol
- Viscosité Mooney : 26 (+/-6) ML (5 + 4) à 100°C.
- Number average molecular weight: 40,000 g / mol
- Mooney viscosity: 26 (+/- 6) ML (5 + 4) at 100 ° C.
L'hexogène (RDX) est celui commercialisé par la société EURENCO sous la référence RDX M3c (D10 = 1 µm, D50 = 4 µm et D90 = 9 µm).The hexogen (RDX) is the one sold by the company EURENCO under the reference RDX M3c (D 10 = 1 μm, D 50 = 4 μm and D 90 = 9 μm).
L'hexanitrohexaazaisowurtzitane (CL20) est préparé et finement broyé avant son utilisation. Sa coupe granulométrique est caractérisée comme suit : D10 = 0,5 µm, D50 = 4,7 µm et D90 = 12,2 µm.Hexanitrohexaazaisowurtzitane (CL20) is prepared and finely ground before use. Its particle size cut is characterized as follows: D 10 = 0.5 μm, D 50 = 4.7 μm and D 90 = 12.2 μm.
Des produits pyrotechniques composites de l'invention ont été préparés et testés comme suit.Composite pyrotechnic products of the invention were prepared and tested as follows.
Leur composition massique et leur diamètre critique de détonation (mesuré) sont respectivement donnés dans le tableau ci-après.Their mass composition and their critical diameter of detonation (measured) are respectively given in the table below.
Ces produits pyrotechniques composites de l'invention ont été obtenus à partir des matières premières identifiées ci-dessus.These composite pyrotechnic products of the invention were obtained from the raw materials identified above.
Etape a du procédé : des mélanges pâteux ont été obtenus au mélangeur à cylindres, de façon connue per se. Pour l'obtention de chacun desdits mélanges, la gomme concernée a tout d'abord été introduite entre les rouleaux, portés à une température de 70°C. Elle a ainsi été ramollie. Ensuite, un mélange charges + plastifiant, préalablement réalisé dans un récipient, a été ajouté. Selon l'exemple 8, seules les charges ont été ajoutées. Lorsque toutes les charges ont été incorporées dans la gomme, le mélange a été poursuivi pendant environ 15 minutes. A ce stade (voir l'exemple 1), on a pu incorporer de façon très progressive de la cire de candellila en petite quantité (0,3 % selon ledit exemple 1) afin de lubrifier la gomme chargée et les cylindres. Après incorporation de la cire, on a poursuivi le mélangeage pendant cinq minutes. Un enrobage d'un des cylindres a alors été obtenu. Enfin, on a stoppé la rotation des cylindres et coupé l'enrobage dans sa largeur pour le récupérer sous la forme d'une feuille (dimensions : 250 mm x 150 mm). Les feuilles obtenues présentaient, selon l'écartement des cylindres, « une » épaisseur d'environ 2 mm, 1,5 mm ou 1 mm. Step a of the process : pasty mixtures were obtained with the roll mill, in a known manner per se. To obtain each of said mixtures, the gum concerned was first introduced between the rolls, brought to a temperature of 70 ° C. It has been softened. Then, 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. At this stage (see Example 1), it has been possible to incorporate candelilla wax in a very gradual manner in a small amount (0.3% according to example 1) in order to lubricate the loaded gum and the rolls. After incorporation of the wax, mixing was continued for five minutes. A coating of one of the cylinders was then obtained. Finally, the rotation of the cylinders was stopped and the coating was cut in its width 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, "a" thickness of about 2 mm, 1.5 mm or 1 mm.
Etape b du procédé : un calandrage a été mis en oeuvre pour un ajustement et/ou une uniformisation de l'épaisseur des feuilles obtenues. Lesdites feuilles ont été passées entre les deux cylindres du même mélangeur à cylindres, réglés à l'écartement voulu, tournant dans le même sens à la même vitesse. Cette fois-ci, il n'y a pas eu enroulement des feuilles autour d'un cylindre. Il y a eu mis en oeuvre d'un calandrage. Une fois la phase de calandrage terminée, le produit obtenu sous forme de feuille était homogène et possédait une épaisseur constante (de 2 mm, 1,5 mm ou 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).
Etape c du procédé : le découpage en canaux de sections différentes a été réalisé grâce à un outillage spécifique, composé essentiellement de deux lames parallèles dont l'écartement est garanti par des rondelles d'épaisseurs calibrées. Les feuilles ont été découpées, après avoir été portées à une température de 45°C. 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.
Les compositions des exemples 1, 2, et 3, renfermant des charges de RDX, sont particulièrement intéressantes en ce qu'elles présentent une section critique de détonation inférieure ou égale à 1 mm2.The 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 .
Les compositions des exemples 6 et 7, renfermant des charges de CL20, présentent des sections critiques de détonation plus élevées (la section critique de détonation de la composition de l'exemple 6 est supérieure à 1,5 mm2 et la section critique de détonation de la composition de l'exemple 7 se situe entre 1 et 1,5 mm2) que celles desdits exemples 1, 2 et 3, renfermant des charges de RDX. L'augmentation du taux de charge entraine logiquement la diminution de la section critique de détonation (le taux de charges de la composition de l'exemple 6 est de 86 % alors que le taux de charges de la composition de l'exemple 7 est de 87 %).The 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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a) Liant = PBHT (commercialisé par la société CRAY VALLEY sous la dénomination : R45HT) de masse moléculaire en nombre de 2800 g/mol (liant conventionnellement utilisé dans le contexte des produits énergétiques composites).
- a1) Des pâtes (très visqueuses) ont été obtenues, par malaxage, à partir dudit liant (20 % en masse) et de charges de RDX (80 % en masse), référence M3c d'EURENCO, dont la distribution granulométrique présentait une valeur de D10 de 1 µm, une valeur de D50 de 4 µm et une valeur de D90 de 9 µm (voir ci-dessus). Elles ont été coulées, avec difficulté, (sous de faibles épaisseurs) dans des moules en PMMA (éprouvettes à gradins) et testées au sein desdits moules (tout démoulage impliquant des altérations) pour évaluation de leur section critique. Ladite section critique était de l'ordre de 3 mm2.
- a2) Des pâtes du même type (très visqueuses), renfermant, en sus du PBHT et des charges, une quantité efficace d'un agent de réticulation (diisocyanate), ont été préparées par malaxage. Elles ont été coulées dans des moules pour se présenter sous la forme de feuilles de faibles épaisseurs. Lesdites feuilles ont été traitées thermiquement pour la réticulation du PBHT (via ses fonctions hydroxy téléchéliques). Le rétreint qui s'est produit lors de la réticulation n'a pas permis de maîtriser l'épaisseur des feuilles réticulées. En fait, pour obtenir des feuilles de faible épaisseur maîtrisée (2 mm, par exemple), il a été nécessaire de procéder comme suit : obtenir, par moulage, des feuilles d'épaisseur substantielle (par exemple de 10 mm d'épaisseur), les traiter thermiquement puis les usiner à ladite faible épaisseur maîtrisée.
- a3) Il n'a pas été possible d'obtenir par malaxage des pâtes renfermant dans ledit liant plus de 80 % en masse de petites charges de RDX (D10 = 1 µm, D50 = 4 µm et D90 = 9 µm ; référence M3c d'EURENCO (voir ci-dessus)).
- a4) Un taux de charges de RDX de 85 % en masse, dans ledit liant (15 % en masse), n'a pu être obtenu qu'en employant plusieurs granulométries de charges de RDX : 65 % en masse de RDX, référence M3c d'EURENCO (voir ci-dessus) et 20 % en masse de RDX de plus grosse granulométrie (D50 = 35 µm). Les pâtes obtenues n'ont toutefois pas pu être laminées entre des rouleaux, au vu de leur caractère collant. Elles ont été coulées (sous de faibles épaisseurs) dans des moules en PMMA (éprouvettes à gradins) et testées au sein desdits moules (tout démoulage impliquant des altérations) pour évaluation de leur section critique. Leur section critique, compte tenu de la présence de grosses charges de RDX, était supérieure à 5 mm2.
- a1) Pastes (very viscous) were obtained, by mixing, from said binder (20% by weight) and RDX fillers (80% by weight), reference M3c of EURENCO, whose particle size distribution had a value of D 10 of 1 μm, a D 50 value of 4 μm and a D 90 value of 9 μm (see above). They were cast, with difficulty, (in small thicknesses) in PMMA molds (stepped specimens) and tested in said molds (any moldings involving alterations) for evaluation of their critical section. Said critical section was of the order of 3 mm 2 .
- a2) Pastes of the same type (highly viscous), containing, in addition to the PBHT and fillers, an effective amount of a crosslinking agent (diisocyanate), were prepared by kneading. They were cast in molds to be in the form of sheets of low thickness. Said sheets have been heat treated for the crosslinking of PBHT ( via its telechelic hydroxy functions). The shrinkage that occurred during the crosslinking failed to control the thickness of the crosslinked sheets. In fact, in order to obtain controlled thin sheets (2 mm, for example), it was necessary to proceed as follows: to obtain, by molding, sheets of substantial thickness (for example 10 mm thick), treat them thermally then machine them to said small controlled thickness.
- a3) It was not possible to obtain, by kneading, pasta containing in said binder more than 80% by mass of small RDX fillers (D 10 = 1 μm, D 50 = 4 μm and D 90 = 9 μm; EURENCO reference M3c (see above)).
- a4) An RDX loading rate of 85% by mass, in said binder (15% by mass), could only be obtained by using several particle sizes of RDX charges: 65% by mass of RDX, reference M3c EURENCO (see above) and 20% by mass of RDX of larger particle size (D 50 = 35 μm). Pasta obtained however could not be rolled between rolls, given their stickiness. They were cast (in small thicknesses) in PMMA molds (stepped test pieces) and tested in said molds (any moldings involving alterations) to evaluate their critical section. Their critical section, given the presence of large RDX charges, was greater than 5 mm 2 .
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b) Liant = méthacrylate de lauryle
Ce liant, très liquide, a permis l'incorporation d'un fort taux de petites charges en son sein. Il doit toutefois être obligatoirement réticulé. Des pâtes renfermant 14 % en masse de méthacrylate de lauryle (+ agent de réticulation : diisocyanate) et 86 % en masse de CL20 (dont la distribution granulométrique présentait une valeur de D10 = 0,5 µm, une valeur de D50 = 4,7 µm et une valeur de D90 = 12,2 µm (voir ci-dessus)) ont été préparées. Elles ont été coulées dans des moules pour se présenter sous la forme de feuilles de faibles épaisseurs. Lesdites feuilles ont été traitées thermiquement pour la réticulation du méthacrylate de lauryle. Le rétreint qui s'est produit lors de la réticulation n'a pas permis de maîtriser l'épaisseur des feuilles réticulées. En fait, pour obtenir des feuilles de faible épaisseur maitrisée (2 mm, par exemple), il a été nécessaire de procéder comme suit : obtenir, par moulage, des feuilles d'épaisseur substantielle (par exemple de 10 mm d'épaisseur), les traiter thermiquement puis les usiner à ladite faible épaisseur maîtrisée. b) Binder = lauryl methacrylate
This binder, very liquid, allowed the incorporation of a high rate of small charges within it. However, it must be cross-linked. Pasta containing 14% by mass of lauryl methacrylate (+ crosslinking agent: diisocyanate) and 86% by weight of CL20 (whose particle size distribution had a value of D 10 = 0.5 μm, a value of D 50 = 4 , 7 μm and a value of D 90 = 12.2 μm (see above)) were prepared. They were cast in molds to be in the form of sheets of low thickness. Said sheets have been heat-treated for the crosslinking of lauryl methacrylate. The shrinkage that occurred during crosslinking did not allow to control the thickness of the crosslinked sheets. In fact, to obtain sheets of controlled thickness (2 mm, for example), it was necessary to proceed as follows: to obtain, by molding, sheets of substantial thickness (for example 10 mm thick), treat them thermally then machine them to said small controlled thickness.
Claims (11)
- A composite explosive product characterized in that:- its composition expressed as percentages by weight comprises:85% to 92%, advantageously 88% to 90% of organic energetic charges; said organic energetic charges a) being selected from charges of octogen (HMX), hexogen (RDX), hexanitrohexaazaisowurtzitane (CL20), penthrite (PETN), and mixtures thereof, and b) presenting a grain size distribution with a value for D90 less than 15 µm and a value for D50 less than or equal to 5 µm; and7% to 12%, advantageously 8% to 10% of a polymer gum selected from polyurethane-polyester gums, polyurethane-polyether gums, and mixtures thereof, of number average molecular weight greater than 20,000 g/mol and of Mooney viscosity lying in the range 20 to 70 ML (5+4) at 100°C; and- it presents a thickness lying in the range 0.4 mm to 5 mm, advantageously in the range 1 mm to 2 mm.
- The composite explosive product according to claim 1, characterized in that said energetic charges are selected from charges of hexogen (RDX), of hexanitrohexaazaisowurtzitane (CL20), and mixtures thereof.
- The composite explosive product according to claim 1 or claim 2, characterized in that said polymer gum is a polyurethane-polyester gum or a polyurethane-polyether gum, advantageously a polyurethane-polyester gum.
- The composite explosive product according to any one of claims 1 to 3, characterized in that said polymer gum has a number average molecular weight greater than 35,000 g/mol, very advantageously greater than 75,000 g/mol.
- The composite explosive product according to any one of claims 1 to 4, characterized in that its composition further includes at least one plasticizer, selected from energetic plasticizers, non-energetic plasticizers, and mixtures thereof; said at least one plasticizer generally being present at a content of 1% to 4% by weight, advantageously at a content of 2% by 3% by weight.
- The composite explosive product according to any one of claims 1 to 5, characterized in that its composition further includes at least one additive; said at least one additive generally being present at a content of 0.1% to 1% by weight.
- The composite explosive product according to any one of claims 1 to 6, characterized in that it is in the form of a sheet or of an element cut out from a sheet without cutting out holes passing through the thickness of said sheet, or in the form of an element cut out from a sheet with through hole(s) being cut out in the thickness of said sheet.
- The composite explosive product according to claim 7, characterized in that it consists in an explosive sheet, an explosive bar with a V-groove, or in a miniaturized array for multipoint initiation of explosive charges.
- The composite explosive product according to any one of claims 1 to 8, characterized in that it consists in a miniaturized array for multipoint initiation of explosive charges suitable for use on a plane surface or on a curved surface of said explosive charges.
- A method for obtaining a composite explosive product according to any one of claims 1 to 9, characterized in that it comprises:- incorporating said charges in said gum raised to a temperature of at least 50°C, advantageously to a temperature in the range between 60°C and 80°C; said incorporating being performed in a cylinder mill; and- calendaring the resulting loaded sheet in a cylinder mill.
- The method according to claim 10, characterized in that it further comprises:- cutting up the calendared loaded sheet, advantageously with waterjet(s), with two parallel blades, or with a cutter die.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR1402626A FR3028852B1 (en) | 2014-11-21 | 2014-11-21 | LOW THICK COMPOSITE EXPLOSIVE PRODUCTS AND THEIR PREPARATION |
| PCT/FR2015/053158 WO2016079453A1 (en) | 2014-11-21 | 2015-11-20 | Thin composite explosive products and preparation thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP3221283A1 EP3221283A1 (en) | 2017-09-27 |
| EP3221283B1 true EP3221283B1 (en) | 2019-07-24 |
Family
ID=53008554
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP15804911.4A Active EP3221283B1 (en) | 2014-11-21 | 2015-11-20 | Thin composite explosive products and preparation thereof |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US20180346393A1 (en) |
| EP (1) | EP3221283B1 (en) |
| CA (1) | CA2968255A1 (en) |
| FR (1) | FR3028852B1 (en) |
| IL (1) | IL252369B (en) |
| WO (1) | WO2016079453A1 (en) |
Family Cites Families (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1082641A (en) * | 1963-03-14 | 1967-09-06 | Secr Defence | Explosive compositions |
| CH412301A (en) | 1963-05-27 | 1966-04-30 | Correcta Werke Gmbh | Device for producing a non-planar shaped body |
| 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 (en) * | 1985-06-20 | 1988-12-19 | Nobel Kemi Ab | EXPLOSIVE CHARGING FOR EXPLOSION OF ROUGH PIPES, AND WAY TO MANUFACTURE THEM |
| 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 (en) * | 1989-06-21 | 1991-09-30 | Nobel Kemi Ab | SET AND DEVICE FOR PREPARING EXPLOSIVE SUBSTANCES |
| FR2723086B1 (en) * | 1994-07-29 | 1996-09-13 | Poudres & Explosifs Ste Nale | CONTINUOUS PROCESS FOR THE SOLVENT-FREE MANUFACTURE OF COMPOSITE PYROTECHNIC PRODUCTS |
| 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 (en) | 2008-12-12 | 2011-02-11 | Tda Armements Sas | PYROTECHNIC LOAD WITH LOW VULNERABILITY |
| 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 (en) * | 2009-12-21 | 2012-03-23 | Eurenco France | MALLEABLE SOLID EXPLOSIVE AND ITS OBTAINING |
| FR3013705B1 (en) * | 2013-11-22 | 2016-07-01 | Herakles | NON-RETICULATED BINDER COMPOSITE PYROTECHNIC PRODUCT AND PROCESS FOR PREPARING THE SAME |
| FR3018807B1 (en) | 2014-03-20 | 2016-04-15 | Herakles | PROCESS FOR OBTAINING SUBMICRON MONOMODAL GRANULOMETRY HEXANITROHEXAAZAISOWURTZITANE CRYSTAL (CL20) CHARGES, THE SAME CHARGES AND THEIR USE AS SEWING LOADS |
-
2014
- 2014-11-21 FR FR1402626A patent/FR3028852B1/en 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/en not_active Abandoned
- 2015-11-20 WO PCT/FR2015/053158 patent/WO2016079453A1/en active Application Filing
- 2015-11-20 EP EP15804911.4A patent/EP3221283B1/en active Active
-
2017
- 2017-05-18 IL IL252369A patent/IL252369B/en active IP Right Grant
Non-Patent Citations (1)
| Title |
|---|
| None * |
Also Published As
| Publication number | Publication date |
|---|---|
| US20180346393A1 (en) | 2018-12-06 |
| FR3028852B1 (en) | 2017-01-06 |
| EP3221283A1 (en) | 2017-09-27 |
| WO2016079453A1 (en) | 2016-05-26 |
| IL252369B (en) | 2020-07-30 |
| FR3028852A1 (en) | 2016-05-27 |
| IL252369A0 (en) | 2017-07-31 |
| CA2968255A1 (en) | 2016-05-26 |
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