WO2016079453A1 - Produits explosifs composites de faible epaisseur et leur preparation - Google Patents
Produits explosifs composites de faible epaisseur et leur preparation Download PDFInfo
- Publication number
- WO2016079453A1 WO2016079453A1 PCT/FR2015/053158 FR2015053158W WO2016079453A1 WO 2016079453 A1 WO2016079453 A1 WO 2016079453A1 FR 2015053158 W FR2015053158 W FR 2015053158W WO 2016079453 A1 WO2016079453 A1 WO 2016079453A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- charges
- advantageously
- sheet
- polyurethane
- product according
- Prior art date
Links
Classifications
-
- 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
- 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
- C06B45/12—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.
- explosives with a critical dimension of detonation are also sought. as small as possible to constitute the channels of said networks (having a section as small as possible but capable of ensuring the propagation of the detonation, including in the angles).
- US Pat. No. 3,354,010 discloses explosive products, in the form of flexible sheets (typically of a thickness of 6.3 mm), the composition of which contains organic energy charges of hexogen (HMX) and / or octogenous (RDX) type. ), in a binder (nitrocellulose) plasticized (tributyl acetyl citrate).
- HMX hexogen
- RDX octogenous
- Elastomers (gums, "raw” (non-crosslinked) rubbers) of the polyurethane-polyester type (ie of polyurethane type with flexible segments of polyester type) and / or polyurethane-polyether (ie of polyurethane type with flexible segments of polyether type), are by elsewhere marketed, in recent years, particularly under the trademark UREPAN ® by RheinChemie and under the Millathane ® brand by TSE Industries.
- the present invention provides an original outlet for this type of elastomer.
- composition expressed in percentages by weight, which contains:
- organic energy charges being selected from octogen (HMX), hexogen (RDX), hexanitrohexaazaisowurtzitane (CL20), pentrite (PETN) and mixtures thereof and b) having a particle size distribution with a value of of D 90 less than 15 ⁇ m and a value of D 50 less than or equal to 5 ⁇ m; and
- a polymeric gum chosen from polyurethane-polyester gums, polyurethane-polyether gums and mixtures thereof, the number-average molecular mass of which is greater than 20,000 g / mol and whose Mooney viscosity is between 20 and 70 ML (5 + 4) at 100 ° C; and
- the composite explosive products of the invention thus contain a high level of "Strongly" energetic ("sensitive”) organic and fine granulometry in a binder of a new type.
- the composite explosive products of the invention contain from 85 to 92%, advantageously from 88 to 90% (% by weight), of specific organic energy charges.
- the charges in question are "highly" energetic ("sensitive") charges. These are octogen (H MX) charges, hexogen (RDX) charges, hexaazaisowurtzitane (CL20) charges, pentrite charges ( ⁇ ) or a mixture of such charges.
- H MX octogen
- RDX hexogen
- CL20 hexaazaisowurtzitane
- pentrite charges ⁇
- these are charges of hexogen (RDX), charges of hexanitrohexaazaisowurtzitane (CL20) or a mixture of these two types of charges (the most energetic).
- the charges in question are not present in the form of large and small crystals, they are present only in the form of small crystals.
- the value of D 10 is not specified as it is in no way critical. It was understood that the more the charges are fine (ie the lower the value of the D i0 (for example a value of 100 nm or less)), the more interesting the products in question are.
- Such fine fillers are generally obtained by grinding "large" crystals.
- the skilled person knows many grinding processes, adapted to the sensitivity of the loads in question. We can in no way limit mention the possible use of SWECO ® crushers.
- the Applicant has moreover described in the patent application FR 14 00669, published under No. 3,018,807 (September 25, 2015), an original grinding process for obtaining charges of CL20 submicron monomodal particle size.
- Said method comprises the continuous grinding of a charge of CL20 crystals, with a granulometry beyond the micron (D 50 > 1 ⁇ ), in suspension in a liquid; said grinding being carried out, with cooling, by multi-pass the suspension in a circulation mill, horizontal axis, attrition with agitated grinding media.
- Said binder is a polymeric gum:
- the binder of the products of the invention generally consists of a polyurethane-polyester gum or a polyurethane-polyether gum, but mixtures of at least two gums (at least two polyurethane-polyester gums, at least two polyurethane-polyether gums or at least two gums). less a polyurethane-polyester gum and at least a polyurethane-polyether gum; such mixtures of gums (gums within the meaning of the invention) constituting a gum within the meaning of the invention) having the required properties (referred to above) may be used.
- Said binder advantageously consists of a polyurethane-polyester gum.
- composition of the composite pyrotechnic products of the invention is capable of containing at least one plasticizer chosen from energetic plasticizers, non-energetic plasticizers and mixtures thereof; it may also contain in general up to 4% by weight of at least one such plasticizer.
- Said at least one plasticizer is therefore chosen from non-energetic plasticizers (for example, di-octyl azelate (DOZ), di-2-ethylhexyl sebacate (DOS), di-n-octyl phthalate (DOP), triacetin and mixtures thereof), energetic plasticizers (advantageously nitrate or nitramine type, for example, diethylene glycol dinitrate (DEGDN), triethylene glycol dinitrate (TEGDN), butanetriol trinitrate (BTTN), trimethylolethane trinitrate ( TMETN), a mixture of 2,4-dinitro-2,4-diaza-pentane, 2,4-dinitro-2,4-diaza-hexane and 3,5-dinitro-3,5-diaza-heptane ( and most particularly DNDA 5,7), nitrato ethyl nitramines (and especially methyl-2-nitratomethyl n
- the composition of the composite pyrotechnic products of the invention contains, according to a preferred variant, as a plasticizer, triethylene glycol dinitrate (TEGDN).
- TAGDN triethylene glycol dinitrate
- composition of the composite explosive products of the invention thus comprises:
- organic energy charges a) being selected from octogen (HMX), hexogen (RDX), hexanitrohexaazaisowurtzitane (CL20), pentrite (PETN) and mixtures thereof and b) having a particle size distribution with a value of of D 90 less than 15 ⁇ and a value of D 5 o less than or equal to 5 ⁇ m;
- composition generally consists of what is specified.
- a product of the invention has a thickness (e), a thickness (e) uniform, constant (controlled): 0.4 mm ⁇ e ⁇ 5 mm, preferably 1 mm ⁇ e ⁇ 2 mm. Very advantageously, e ⁇ 1.5 mm.
- the person skilled in the art understands all the It is up to the inventors to propose such high performance composite explosive products (the explosive in question must therefore necessarily have a critical dimension of detonation below these low values) and the appropriate mechanical properties (mechanical strength, cohesion, conformability).
- the good results obtained are essentially based on the binder (the nature of the binder) which, combined with a adequate process (see below), authorizes the incorporation within it of a high rate of charges ("sensitive”) of fine particle size.
- the composite pyrotechnic products of the invention may have any type of shape and may be in particular:
- said elements consist of pieces of sheets, such as (strips, bars, for example) or possibly worked on a part (only part) of their thickness), or
- the cuttings in question are conventional cuttings, implemented with conventional mechanical means (advantageously cutting by jet (s) of water, with two parallel blades or die cutter).
- the composite pyrotechnic products of the invention can thus notably consist of:
- V-groove usable as part of a detonating cutting line, said V-groove being intended to be covered with a metallic coating or a coating loaded with metallic particles
- a miniaturized multi-point explosive charge initiation network see (c) above.
- the channels of the miniaturized network obviously have a minimum section equal to the critical dimension of detonation of the composition in question. They may exhibit directional changes with high angles up to 90 ° (in view of the low values of said critical dimensions). They generally have a square or rectangular section.
- Such networks according to the invention are particularly interesting. Their conformability (inherent to the nature of the binder present in their composition and their small thickness) allows their use both on flat surfaces (one can conventionally initiate a cylindrical shaped load with such a network positioned on one of the bases of the load) only on curved surfaces (such unconventional positioning may be particularly interesting for increasing the speed of flashes in one direction).
- the invention relates to a method for preparing (obtaining) composite pyrotechnic products of the invention, as described above.
- Said method is based, typically, on the use of at least one roll mill. It typically comprises incorporating the charges into the binder in a roll mill. It includes, more precisely:
- the incorporation of the fillers into the eraser raised to a temperature of at least 50 ° C., generally at a temperature between 60 and 80 ° C .; said incorporation being carried out in a roll mill, and
- the roller mixer is a known Persian device. Its use has made it possible to obtain the products of the invention (it has made it possible to incorporate the high level of small charges into the gum), it has made it possible to obtain the said advantageously (without using a solvent (this is very advantageous compared to certain processes of the prior art) at temperatures compatible with the sensitivity of the charges, mixing and rolling being provided in a single step, at the same station (this is very advantageous compared to some processes of the prior art)).
- the present invention is based on the selection of the binder associated with the selection of the process, this dual selection making it not only possible to obtain the products of the invention (products heavily loaded with fine sensitive fillers) possible (the feasibility of said process was not acquired in advance) but possible under simple implementation conditions.
- the formation of the mixture in the roll mixer is conventionally carried out with the rolls rotated in opposite directions at different speeds.
- the gum when it is in the form of granules, is first of all roughly shaped to the mill to obtain a thin strip (1 mm to a few mm).
- Said gum is generally first introduced into the roll mixer, the rolls of which are brought to a temperature (T) of at least 50 ° C. (below 120 ° C., generally below 100 ° C.), advantageously between 60 and 80 ° C (60 ° C ⁇ T ⁇ 80 ° C), for example 70 ° C.
- T temperature
- the fillers and any other ingredient (s) are then introduced separately or as a mixture. It is generally carried out beforehand a mixture fillers + ingredient (s), when at least one such ingredient is involved, and then introducing said mixture.
- the introduction of the charges can conveniently be carried out in several sequences after a setting of the spacing of the rolls.
- the coating formed around the fastest rotating cylinder can be recovered (cut with a cutter), folded and reintroduced between the cylinders (in order to homogenize the distribution of charges), according to the usual methods applied to this process.
- a sheet (a film) of small thickness (corresponding to the spacing between the rolls) is thus obtained.
- said sheet is calendered in a roll mill (the rolls of said roll mixer then rotating in the same direction, at the same speed, and their spacing being set to the value of desired thickness, or to a lower value because two phenomena are likely to occur: the material may force the spacing of the rolls and there may be a relaxation of the product after rolling).
- the method of the invention may therefore comprise, in addition, the cutting, advantageously by jet (s) of water, with two parallel blades or punch, the calendered filled sheet.
- the cutting advantageously by jet (s) of water, with two parallel blades or punch, the calendered filled sheet.
- This produces cut elements as specified above. We have seen that said cut elements can further be worked.
- the cutting of the leaves, more particularly with blades, can be facilitated by previously heating said sheets between 40 and 50 ° C.
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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)
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP15804911.4A EP3221283B1 (de) | 2014-11-21 | 2015-11-20 | Dünne zusammengesetzte explosive produkte und herstellung davon |
CA2968255A CA2968255A1 (fr) | 2014-11-21 | 2015-11-20 | Produits explosifs composites de faible epaisseur et leur preparation |
US15/527,932 US20180346393A1 (en) | 2014-11-21 | 2015-11-20 | Thin composite explosive products and preparation thereof |
IL252369A IL252369B (en) | 2014-11-21 | 2017-05-18 | Fine composition explosive products and their preparation |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR1402626 | 2014-11-21 | ||
FR1402626A FR3028852B1 (fr) | 2014-11-21 | 2014-11-21 | Produits explosifs composites de faible epaisseur et leur preparation |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2016079453A1 true WO2016079453A1 (fr) | 2016-05-26 |
Family
ID=53008554
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/FR2015/053158 WO2016079453A1 (fr) | 2014-11-21 | 2015-11-20 | Produits explosifs composites de faible epaisseur et leur preparation |
Country Status (6)
Country | Link |
---|---|
US (1) | US20180346393A1 (de) |
EP (1) | EP3221283B1 (de) |
CA (1) | CA2968255A1 (de) |
FR (1) | FR3028852B1 (de) |
IL (1) | IL252369B (de) |
WO (1) | WO2016079453A1 (de) |
Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1400669A (fr) | 1963-05-27 | 1965-05-28 | Correcta Werke Gmbh | Dispositif pour l'obtention d'un corps en forme non plan |
US3227588A (en) * | 1963-03-14 | 1966-01-04 | Jones Walter Thomas | Crystalline explosives in a viscoelastic binder of sheet form |
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 |
US4718346A (en) * | 1985-06-20 | 1988-01-12 | Nobel Kemi Ab | Explosive charge for the explosive welding of large diameter pipes, and a method for its manufacture |
EP0406190A2 (de) * | 1989-06-21 | 1991-01-02 | Bofors Explosives AB | Verfahren zur Herstellung von Explosivstoffen |
US5596232A (en) * | 1994-07-29 | 1997-01-21 | Societe Nationale Des Poudres Et Explosifs | Continuous process for the solventless manufacture of composite pyrotechnic products |
US20050267245A1 (en) * | 2003-03-18 | 2005-12-01 | Sandusky Donald A | Alloy blends of polyurethane and rubber |
WO2010011361A1 (en) * | 2008-07-24 | 2010-01-28 | Xiper Innovations, Inc. | Laser engravable flexographic printing articles based on millable polyurethanes, and method |
WO2010066752A1 (fr) | 2008-12-12 | 2010-06-17 | Tda Armements S.A.S | Charge pyrotechnique a faible vulnerabilite |
FR3018807A1 (fr) | 2014-03-20 | 2015-09-25 | Herakles | Procede d'obtention de charges de cristaux d'hexanitrohexaazaisowurtzitane (cl20) de granulometrie monomodale submicronique, lesdites charges et leur utilisation comme charges d'ensemencement |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
WO2010120852A1 (en) * | 2009-04-16 | 2010-10-21 | Aerojet-General Corporation | Cyclic energetic nitramines desensitized with linear nitramines |
US8172965B2 (en) * | 2009-10-14 | 2012-05-08 | Raytheon Company | Explosive compositions and methods for fabricating explosive compositions |
FR2954309B1 (fr) * | 2009-12-21 | 2012-03-23 | Eurenco France | Explosif solide malleable et son obtention |
FR3013705B1 (fr) * | 2013-11-22 | 2016-07-01 | Herakles | Produit pyrotechnique composite a liant non reticule et son procede de preparation |
-
2014
- 2014-11-21 FR FR1402626A patent/FR3028852B1/fr not_active Expired - Fee Related
-
2015
- 2015-11-20 EP EP15804911.4A patent/EP3221283B1/de active Active
- 2015-11-20 CA CA2968255A patent/CA2968255A1/fr not_active Abandoned
- 2015-11-20 WO PCT/FR2015/053158 patent/WO2016079453A1/fr active Application Filing
- 2015-11-20 US US15/527,932 patent/US20180346393A1/en not_active Abandoned
-
2017
- 2017-05-18 IL IL252369A patent/IL252369B/en active IP Right Grant
Patent Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3227588A (en) * | 1963-03-14 | 1966-01-04 | Jones Walter Thomas | Crystalline explosives in a viscoelastic binder of sheet form |
FR1400669A (fr) | 1963-05-27 | 1965-05-28 | Correcta Werke Gmbh | Dispositif pour l'obtention d'un corps en forme non plan |
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 |
US4718346A (en) * | 1985-06-20 | 1988-01-12 | Nobel Kemi Ab | Explosive charge for the explosive welding of large diameter pipes, and a method for its manufacture |
EP0406190A2 (de) * | 1989-06-21 | 1991-01-02 | Bofors Explosives AB | Verfahren zur Herstellung von Explosivstoffen |
US5596232A (en) * | 1994-07-29 | 1997-01-21 | Societe Nationale Des Poudres Et Explosifs | Continuous process for the solventless manufacture of composite pyrotechnic products |
US20050267245A1 (en) * | 2003-03-18 | 2005-12-01 | Sandusky Donald A | Alloy blends of polyurethane and rubber |
WO2010011361A1 (en) * | 2008-07-24 | 2010-01-28 | Xiper Innovations, Inc. | Laser engravable flexographic printing articles based on millable polyurethanes, and method |
WO2010066752A1 (fr) | 2008-12-12 | 2010-06-17 | Tda Armements S.A.S | Charge pyrotechnique a faible vulnerabilite |
FR3018807A1 (fr) | 2014-03-20 | 2015-09-25 | Herakles | Procede d'obtention de charges de cristaux d'hexanitrohexaazaisowurtzitane (cl20) de granulometrie monomodale submicronique, lesdites charges et leur utilisation comme charges d'ensemencement |
Non-Patent Citations (1)
Title |
---|
NATH T ET AL: "STUDIES ON RDX BASED SHEET EXPLOSIVES WITH EVA & ESTANE BINDERS", CHEMICAL ABSTRACTS, CHEMICAL ABSTRACTS SERVICE (C A S), US, vol. 128, no. 12, 23 March 1998 (1998-03-23), pages 757, XP000764234, ISSN: 0009-2258 * |
Also Published As
Publication number | Publication date |
---|---|
FR3028852B1 (fr) | 2017-01-06 |
FR3028852A1 (fr) | 2016-05-27 |
CA2968255A1 (fr) | 2016-05-26 |
IL252369A0 (en) | 2017-07-31 |
EP3221283A1 (de) | 2017-09-27 |
EP3221283B1 (de) | 2019-07-24 |
IL252369B (en) | 2020-07-30 |
US20180346393A1 (en) | 2018-12-06 |
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