Classifications

• • C—CHEMISTRY; METALLURGY
  • C06—EXPLOSIVES; MATCHES
  • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
  • C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
• • C—CHEMISTRY; METALLURGY
  • C06—EXPLOSIVES; MATCHES
  • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
  • C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
  • C06B23/007—Ballistic modifiers, burning rate catalysts, burning rate depressing agents, e.g. for gas generating
• • C—CHEMISTRY; METALLURGY
  • C06—EXPLOSIVES; MATCHES
  • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
  • C06B33/00—Compositions containing particulate metal, alloy, boron, silicon, selenium or tellurium with at least one oxygen supplying material which is either a metal oxide or a salt, organic or inorganic, capable of yielding a metal oxide
  • C06B33/06—Compositions containing particulate metal, alloy, boron, silicon, selenium or tellurium with at least one oxygen supplying material which is either a metal oxide or a salt, organic or inorganic, capable of yielding a metal oxide the material being an inorganic oxygen-halogen salt
• • 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

Definitions

• Composite solid propellant composition comprising a ferrocene derivative and a submicron aluminum charge, solid propellant and loading
• the present invention relates to composite compositions for solid propellant, propellants (pasty or solid) based on such compositions and loadings comprising such solid propellants.
• the solid propellants considered are propellants with high combustion rate and high specific impulse. They are particularly suitable for rocket and missile propulsion loads.
• the propellant compositions consisting of an oxidizing filler, generally ammonium perchlorate (PA), an aluminum (Al) micrometric filler, generally having a median diameter of between 5 ⁇ m and 30 ⁇ m, and a binder Polyurethane (PU), are widely used for rocket propulsion applications in the military and civilian fields.
• PA ammonium perchlorate
• Al aluminum
• PU binder Polyurethane
• the propellants are in the paste state in the mixing and casting phases for obtaining the charges (the crosslinking agent of the polymer of the polyurethane binder not yet being added to the composition, or the crosslinking agent having added, the crosslinking of the binder polymer is not yet complete), and in the solid state when the binder is crosslinked.
• Conventional composite propellants (of the type used for accelerators of the Ariane rocket) typically have a combustion rate of between 8 and 14 mm / s at a pressure of 7 MPa.
• ferrocene derivatives as a combustion catalyst in this type of composition, to increase the rate of combustion.
• Propellants can thus, following incorporation into their Within a liquid ferrocenic product, present combustion rates up to 50 mm / s at 7 MPa.
• the rate of catalyst introduced into the compositions must remain limited (a few percent by weight), because of the increase in propellant sensitivity which results from the use of said catalyst.
• the combustion speeds accessible thereby remain limited and between 20 and 30 mm / s (at 7 MPa).
• micrometric aluminum particles contained in the propellant burn with the oxidizing charge in the rocket or missile combustion chamber and are in the form of micrometric alumina particles.
• the presence of particles of micrometric dimensions in the combustion chamber is favorable to the reduction of the instabilities of combustion (leading to pressure oscillations).
• the micrometric aluminum particles contained in the propellants concerned may, because of their limited residence time in the combustion chamber of the rocket or the missile, not burn completely before being ejected by the nozzle. This results in a loss of energy performance of the engine.
• the larger particles of alumina may not follow the flow of gases and accumulate in the rear part of the combustion chamber, creating an embedded inert mass increasing as the propellant charge burns.
• micrometric granulometry Dmedian ⁇ 5 to 30 ⁇ m
• submicron aluminum 0.1 ⁇ m ⁇ Dmedian ⁇ 1 ⁇ m
• nanometric 50 nm ⁇ Dmedian ⁇ 100 nm
• compositions for solid propellant propellant leading to a propellant, at high speed of combustion having, especially in paste state, an impact sensitivity and sensitivity at friction, close to those of the reference propellants, at a lower rate of combustion.
• the inventors have, however, jointly introduced said ferrocene and submicron aluminum catalyst into the composition of a composite solid propellant and have obtained surprising results (see in particular those given in Table 2 below: increase in the rate of combustion without increasing the sensitivity), which invalidate the prejudice.
• the first subject of the invention concerns composite compositions for solid composite propellants making it possible to achieve the desired properties for said propellants, by combining, in a solid propellant composition, a ferrocene catalyst and a particle size aluminum filler. submicron or even nanometric.
• compositions of the invention thus comprise an oxidizing filler, a liquid polyol polymer (precursor of the binder), a combustion catalyst consisting of a ferrocene derivative, and an aluminum filler.
• said aluminum filler has a median diameter of less than 1 ⁇ m.
• said aluminum filler has a median diameter of between 800 nm and 50 nm, very advantageously between 400 nm and 80 nm.
• compositions of the invention generally contain:
• the ferrocene derivative is chosen from ferrocene, n-butylferrocene, di-n-butylferrocene, 2,2-bis-butylferrocenylpropane (catocene); b) the ferrocene derivative is grafted onto a fraction of said liquid polyol polymer (precursor of the binder).
• the graft polymer is generally a polymer with ethylenic unsaturations comprising, on at least some of said unsaturations, silylmetallocene groups. It can in particular be a polymer, as described in patent application FR 2 567 895, the silylmetallocene groups of which have the following formula: R 3
• R 1 represents a substituted or unsubstituted aliphatic radical, a substituted or unsubstituted aromatic radical
• R 2, R 3 which may be identical or different, represent a substituted or unsubstituted aliphatic radical, a substituted or unsubstituted aromatic radical, a - C 5 H 4 ) Fe (C 5 H 5 )].
• Butacene® the intervention of the product known as Butacene® is particularly recommended.
• the product is a low molecular weight hydroxytelechelic polybutadiene (molecular weight less than 4000 g / mol) to which a ferrocene silane has been grafted. Its chemical formula is shown in Figure 2 attached.
• Butacène® is produced and marketed by SNPE Matériaux Energétiques. Its added iron content is 8%, its mass percentage of ferrocene is 26.57%.
• the characteristics of Butacene® are given in Table 1 below.
• said oxidizing charge comprises or even consists of ammonium perchlorate (PA) (it advantageously consists of PA); d) said liquid polyol polymer is a hydroxytelechelic polybutadiene.
• PA ammonium perchlorate
• the crosslinking agent (at least bifunctional) is generally a polyisocyanate, preferably an alicyclic polyisocyanate. It advantageously consists of diisocyanate isophorone (IPDI).
• IPDI diisocyanate isophorone
• Said at least one plasticizer is preferably selected from dioctyl azelate (DOZ), diisooctyl sebacate, isodecyl pelargonate, polyisobutylene, dioctyl phthalate (DOP).
• DOZ dioctyl azelate
• DOP dioctyl phthalate
• Said at least one additive may especially consist of one or more adhesion agents between the binder and the oxidizing charge, such as, for example, bis (2-methylaziridinyl) methylaminophosphine oxide (methyl BAPO) or triethylene pentamine acrylonitrile (TEPAN) one or more antioxidants derived from those of the rubber industry, such as, for example, ditertiobutylparacresol (DBC) or 2,2'-methylenebis (4-methyl-6-tert-butylphenol) (MBP5), in one or more crosslinking catalysts, such as, for example, iron or copper acetylacetonate, tin dibutyldilaurate (DBTL).
• adhesion agents between the binder and the oxidizing charge such as, for example, bis (2-methylaziridinyl) methylaminophosphine oxide (methyl BAPO) or triethylene pentamine acrylonitrile (TEPAN) one or more antioxidants derived from those of
• the invention relates to propellants based on said composite compositions (at least partly constituted by such compositions), propellants which are present in the pasty state (the crosslinking agent of the polymer of the polyurethane binder being not yet added to the composition, or the crosslinking agent has been added, the crosslinking of the binder is not yet complete) or in the solid state.
• the manufacturing processes used to obtain said propellants are known to those skilled in the art and are advantageously optimized according to the exact composition of said propellants. It is possible in particular to proceed by kneading the composition in the pasty state, pouring the dough into a mold in the form of the desired loading and baking said dough, for its crosslinking, in said mold.
• the invention relates to a solid propellant charge (propellant charge) at least partially (partially or totally) consisting of at least one solid propellant of the invention, as described above.
• composition formulation examples of composition formulation
• FIG. 1 shows the combustion rates as a function of pressure for reference propellants (A, B, C of the prior art) and a propellant of the invention (D) containing a ferrocenic combustion catalyst and the micron or submicron aluminum.
• Figure 2 shows the developed chemical formula of Butacene®.
• Table 2 below gives the characteristics and properties of compositions and propellants k, B, C, D. These four compositions contain an oxidizing charge of ammonium perchlorate, an aluminum filler, a polymer liquid polyol, a plasticizer (azelate dioctyl), a crosslinking agent and known additives, and for compositions C and D, in addition a ferrocene combustion catalyst; Butacene®.
• compositions A and B are not strictly comparable to compositions C and D for their common parts, the orders of magnitude given are significant of the interest of the invention.
• Composition A is a conventional composition of the prior art of the type used for space applications. It does not contain a ferrocene derivative and comprises micrometric aluminum with a Dmedian of 30 ⁇ m.
• Composition B is of the same type as composition A. It differs mainly from this with respect to the particle size of aluminum, which is submicron.
• Composition C contains a ferrocene derivative grafted on a fraction of the liquid polyol polymer (product referenced Butacene ® ) and micron aluminum with a Dmedian of 30 microns.
• Composition D is a composition of the invention comprising both a ferrocene derivative (Butacene®) and submicron aluminum.
• Butacene® is a low molecular weight hydroxytelechelic polybutadiene (molecular weight less than 4000 g / mol) to which a ferrocenic silane has been grafted.
• Butacène® is produced and marketed by SNPE energetic materials. Its added iron content is 8%, its mass percentage of ferrocene is 26.57% (see Table 1 above).
• the burning rate measured on the solid propellant of each composition A, B, C and D is therefore shown in FIG. 1 as a function of the pressure and indicated in Table 2 at a pressure of 7 MPa.
• the propellant D of the invention has a combustion rate much higher than those of the three propellants A, B, C of the prior art.
• the propellant D according to the invention thus has a combustion rate much higher than that of propellant A of (reference of) the prior art with a sensitivity (impact (ISI *) and friction (ISF **) ) of the same order of magnitude as that of said propellant A of the prior art.
• sensitivity to impact (ISI) The test carried out corresponds to that described in standard NF T 70-500, itself similar to UN test 3a) ii) derived from the "Recommendations on the Transport of Dangerous Goods - Manual of Tests and Criteria, Fourth Edition. revised edition, ST / SG / AC.10 / 11 / Rev.4, ISBN 92-1 -239083-8ISSN 1014-7179 ".
• the energy resulting in 50% (method of treatment of Bruceton results) of positive results of an explosive substance subjected to shocks of a sheep is determined.
• the material to be tested is confined in a steel device consisting of two rollers and a guide ring.
• the energy can be varied from 1 to 50 J. Given the small amount of material available for some of the products tested, it was not realized for these products. , that a reduced number of reproducibility tests, compared to the recommendations of standard NF T 70-500.

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• 2008
  • 2008-11-25 FR FR0858001A patent/FR2938837B1/fr active Active
• 2009
  • 2009-11-24 EP EP09797078A patent/EP2349953A2/de not_active Withdrawn
  • 2009-11-24 WO PCT/FR2009/052285 patent/WO2010061127A2/fr not_active Ceased
  • 2009-11-24 CN CN2009801464763A patent/CN102256915A/zh active Pending
  • 2009-11-24 KR KR1020117014683A patent/KR20110110131A/ko not_active Ceased
• 2011
  • 2011-05-09 IL IL212794A patent/IL212794A0/en unknown

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