EP2448885A1 - Method for producing solid composite aluminized propellants, and solid composite aluminized propellants - Google Patents

Method for producing solid composite aluminized propellants, and solid composite aluminized propellants

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Publication number
EP2448885A1
EP2448885A1 EP10745374A EP10745374A EP2448885A1 EP 2448885 A1 EP2448885 A1 EP 2448885A1 EP 10745374 A EP10745374 A EP 10745374A EP 10745374 A EP10745374 A EP 10745374A EP 2448885 A1 EP2448885 A1 EP 2448885A1
Authority
EP
European Patent Office
Prior art keywords
charge
ammonium perchlorate
weight
value
particle size
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP10745374A
Other languages
German (de)
French (fr)
Other versions
EP2448885B1 (en
Inventor
Hélène BLANCHARD
Marie Gaudre
Jean François GUERY
Guillaume Fouin
Stany Gallier
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ArianeGroup SAS
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SME SA
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Publication of EP2448885A1 publication Critical patent/EP2448885A1/en
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Publication of EP2448885B1 publication Critical patent/EP2448885B1/en
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Classifications

    • 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
    • C06B29/00—Compositions containing an inorganic oxygen-halogen salt, e.g. chlorate, perchlorate
    • C06B29/02—Compositions containing an inorganic oxygen-halogen salt, e.g. chlorate, perchlorate of an alkali metal
    • C06B29/16—Compositions containing an inorganic oxygen-halogen salt, e.g. chlorate, perchlorate of an alkali metal with a nitrated organic compound
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B29/00—Compositions containing an inorganic oxygen-halogen salt, e.g. chlorate, perchlorate
    • C06B29/22—Compositions containing an inorganic oxygen-halogen salt, e.g. chlorate, perchlorate the salt being ammonium perchlorate
    • 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
    • C06B45/02—Compositions or products which are defined by structure or arrangement of component of product comprising particles of diverse size or shape
    • 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

  • the main objects of the present invention are:
  • a process for obtaining a composite solid propellant (with a polyurethane binder loaded with ammonium perchlorate and aluminum), such a solid composite propellant, solid propellant charges and the associated rocket engines.
  • the invention is in the field of solid propellant propulsion and more particularly relates to aluminized composite solid propellants.
  • the object of the invention is to reduce the alumina deposits at the bottom of the engines with integrated nozzle and tend to reduce aerodynamic thrust oscillations while maintaining the ballistic properties, including the combustion rates, the propellants similar to industrial propellants for space application known to date.
  • the solid propellant engines for space launchers are of the type of the Ariane 5 rocket or the American Space Shuttle, large (h ⁇ 20 m, D ⁇ 5 m), with integrated nozzle.
  • the solid propellant loads contained in this type of engine have a mass ranging from a few hundred kilograms to several hundred tons. Their operating time is of the order of a few tens of seconds to a few minutes.
  • the present invention is in this context large solid propellant engines.
  • Solid propellants for these applications are composite propellants with an inert binder of the polyurethane type. They contain a charge of ammonium perchlorate (oxidizing charge) and an aluminum charge (reducing charge).
  • the oxidizing charge of ammonium perchlorate contained in said propellants generally consists of the several charges of perchlorate of ammonium of different monomodal particle size distributions which have been added in the preparation of said propellants. It may be the same for the reducing load of aluminum.
  • This family of propellants is that concerned by the present invention.
  • the mass ratios of these ingredients are generally about 68% for ammonium perchlorate, 20% for aluminum and 12% for binder.
  • the burning rate of the solid propellant depends on the pressure P prevailing in the combustion chamber and conventionally follows a law (called the law of old) expressed in the form:
  • Vc aP n .
  • Said combustion rate Vc and the pressure exponent n of the propellant are fundamental parameters for the ballistic adjustment of a solid propellant engine (combustion time, thrust, combustion stability, etc.),
  • the aluminized composite propellants produce, during their combustion, gases and solid particles consisting mainly of alumina (about 30% of the mass ejected by the propellant).
  • the aluminum introduced into the aluminized composite solid propellants is in the form of grains, more or less spherical, with a median diameter generally between 1 and 50 microns.
  • the combustion of a drop of aluminum, expelled from the burning surface is shown schematically in Figure 1 attached. A flame surrounds the drop of aluminum and a cap of alumina is formed at the bottom of the drop. The combustion generates fumes of alumina (drops of small size, of the order of 1 ⁇ m) and larger drops of alumina from the cap, which explains the bimodal particle size distributions of alumina finally produced by solid propellants.
  • the alumina generated by the combustion of the aluminized propellant represents, as indicated above, approximately 30% of the mass ejected by the propellant.
  • This non-expelled mass penalizes, on the one hand, the performance of the engine and can, on the other hand, generate, after the extinction of the engine and by a vacuum emptying phenomenon, orbital debris of non-dimensional alumina. negligible (ie> to a few millimeters).
  • aluminized solid propellants which, by combustion, produce small diameter alumina (thus promoting the reduction of thrust oscillations in solid propellant propellants and having the combined positive effect of reducing the deposit in the rear bottom of the nozzle) while maintaining ballistic properties, including combustion rates, similar to those of industrial propellants for space application known to date.
  • the results of granulometric measurements of a particle size class are expressed in the form of curves, giving: on the one hand, the histogram of the volume percentages of particles (also called percentages of passing volume) as a function of the diameter (equivalent spherical) of the particles and, on the other hand, the cumulation of the voluminal percentages of particles as a function of the diameter (equivalent spherical) of the particles, cumulated carried out according to the increasing diameters.
  • Dso diameter for which the cumulative volume percentage is equal to 50%
  • a particle size class of a particulate material is defined by its particle size envelope defined by minimum and maximum values of D 10, D 50, D 90 .
  • the present invention relates to solid propellants:
  • the Applicant has been able to select and associate different granulometries (monomodal) of ammonium perchlorate, so that, during the combustion of the propellant, the agglomeration of the aluminum in combustion is limited, in order to reduce, or almost to remove, the production of particles larger than 10 microns diameter, while maintaining the standard values of the ballistic parameters for a propulsive space application.
  • the present invention firstly relates to a process for obtaining a composite solid propellant, said process comprising: - obtaining a paste by mixing, in a mixer, a mixture containing a liquid polyol polymer (generally present in the mixture, at 5 to 15% by weight, more generally at 7 to 14% by weight), an oxidizing charge of ammonium perchlorate (generally present in the mixture at a rate of 40 to 80% by weight).
  • a reducing charge of aluminum generally present in the mixture at a rate of 15 to 20% by weight, more generally at a rate of 16 to 19% in bulk
  • said oxidizing charge of ammonium perchlorate in said paste results from the introduction into said mixer, separately or as a mixture, of at least:
  • class A a first charge whose monomodate granulometric distribution (called class A) has a Dio value between 100 ⁇ m and 10 ⁇ m, a D 5 o value between 170 ⁇ m and 220 ⁇ m and a value of D 9 $ between 315 ⁇ m and 340 ⁇ m, and
  • class B a second charge whose monomodal particle size distribution (called class B) has a Di 0 value between 15 ⁇ m and 20 ⁇ m, a Ds 0 value between 60 ⁇ m and 120 ⁇ m and a D 90 value between 185 ⁇ m and 220 ⁇ m; and eventually,
  • class C a third charge whose monomodal particle size distribution (called class C) has a Dio value of between 1.7 ⁇ m and 3.6 ⁇ m, a D 50 value of between 6 ⁇ m and 12 ⁇ m and a Dgo value of between between 20 ⁇ m and 32 ⁇ m.
  • the method of the invention is a method by analogy which comprises, in a conventional manner, obtaining a paste from the constituent ingredients of the propellant referred to, casting said paste in a mold and its crosslinking by heat treatment (baking ).
  • the ingredients involved are the classic ingredients for this type of propellant. They understand :
  • liquid polyol polymer preferably, said polyol polymer is a hydroxytelechelic polybutadiene;
  • PA ammonium perchlorate
  • said at least one crosslinking agent (generally liquid) of said polyol polymer: said at least one crosslinking agent (at least bifunctional) is generally chosen from polyisocyanates, it preferably consists of an aliphatic polyisocyanate. It advantageously consists of cyclohexylmethylene diisocyanate (MCDI);
  • said at least one plasticizer is preferably chosen from dioctyl azéiate (DOZ), sebacate of isooctyl, isodecyl pelargonate, polyisobutylene, dioctyl phthalate (DOP);
  • DOZ dioctyl azéiate
  • DOP dioctyl phthalate
  • said at least one additive may in particular consist of one or more adhesion agents between the binder and the oxidizing filler, such as, for example, bis (2-methylaziridinyl) -methylaminophosphine oxide (methyl BAPO) or triethylene pentamine acrylonitrile (TEPAN), in one or more antioxidant agents derived from those of the rubber industry, such as, for example, ditertiobutylparacresol (DBC) or 2,2'-methylenebis (4-methyl-6-tertio) ⁇ butylphenol) (MBP5), in one or more crosslinking catalysts, such as iron or copper acetylacetonate, tin dibutyldilaurate (DBTL), in one or more combustion catalysts, such as iron oxide , ...
  • adhesion agents between the binder and the oxidizing filler such as, for example, bis (2-methylaziridinyl) -methylaminophosphine oxide (methyl BAPO) or triethylene pent
  • the charge of ammonium perchlorate is, in the context of the process of the invention, optimized: it is obtained from at least a first and second (or even third) charges having , each, a monomodal particle size distribution as specified above. It results, typically, from the introduction, in the mixer, separately or in mixture, of at least two charges of different monomodal granulometry: the first of class A (see above) and the second of class
  • the charge of ammonium perchlorate of the mixture, in the mixer is at least partly advantageously in its entirety, constituted from a first and second charges (each) of specific monomodal particle size, or even a first, second and third charge (each) of specific monomodafe particle size.
  • the mixture (binary or ternary) of the first and second or first, second and third oxidizing charges of different specific monomodal granulometry can be performed upstream.
  • the oxidizing charge of the propellant is carried out upstream and is then added, pre-constituted, in the mixer.
  • the mixture (binary or ternary) of the first and second or first, second and third oxidizing charges of different specific monomodal granulometry may be carried out only in the mixer within the dough. According to this variant, it is not pre-constituted. The first, second or even third charges can thus be introduced separately. In the context of this variant, when three types of oxidizing charges are introduced, it is however possible to preconstitute a mixture (binary), first and second, first and third, or second and third, oxidizing charges of specific monomodal particle size. Then added to the mixer "said mixture and, respectively, the third, the second, or the first, oxidizing charge (complementary oxidizing charge) so that said first, second and third fillers constitute the oxidizing charge of the propellant.
  • the oxidizing charge of ammonium perchlorate in the dough results only from the introduction into the mixer (separately or in mixture) of the first and the second charge, the monomodal particle size of which has been specified above. (using the value ranges of D I Q, DS ⁇ and D 90 ).
  • oxidizing charge of ammonium perchlorate (100%) in the paste results, generally, from the introduction into the mixer, separately or as a mixture, of:
  • the oxidizing charge of ammonium perchlorate (100%) in the paste results, very generally, from the introduction into the mixer, separately or as a mixture, of;
  • the oxidizing charge of ammonium perchlorate (100%) in the paste results, preferably, from the introduction into the mixer, separately or as a mixture, of:
  • the particle size of the aluminum charge is a second-order parameter, with reference to the technical problems mentioned above.
  • the aluminum particles generally have a median diameter of less than or equal to 40 ⁇ m. The best results, up to the production of alumina of monomodal granulometry centered to 1 to 3 ⁇ m, are obtained with aluminum particles having a median diameter of between 1 and 10 ⁇ m and certain combinations of ammonium perchlorate of class A and B (see examples below) introduced into the mixer to form the ammonium perchlorate charge.
  • Said aluminum filler therefore generally has a median diameter (D 50 ) less than or equal to 40 ⁇ m, advantageously between 1 and 10 ⁇ m.
  • D 50 median diameter
  • D 10 and D 90 of said aluminum charge advantageously correspond, respectively, to at least 1/4 and at most 4 times said median diameter
  • the present invention relates to aluminized solid propellants obtainable by the above process, which process involves oxidizing ammonium perchlorate charges of different specific monomodal particle sizes.
  • the solid propellants of the invention generally have combustion rates of between 6 and 12 mm / s and pressure exponents of between 0.15 and 0.4, advantageously between 0.2 and 0.4, over a range of operating pressure of 3 to 10 MPa, which corresponds to the standard values of the ballistic parameters.
  • the great advantage of the method of the invention is thus to allow the production of solid propellants which have such ballistic properties and whose combustion generates particles of alumina of small grain size,
  • the granulometry of the alumina produced by the combustion of the propellants of the invention was determined by means of measuring equipment, recognized by the international community, as "rotary trap or" Quench Party of Combustion Bomb ". by Norton Thiokol (see PC BRAITHWAITE, WN CHRISTENSEN, V. DAUGHERTY (Morton Thiokol), Quench bomb investigation of aluminum oxide formation from solid rocket propellants (part I): experimental metbodology, 25th JANNAF combustion meeting, CPIA Publication 498, vol.l, p. 175, October 1988).
  • the principle is to burn a small sample of propellant at the end of a fixed rod in a chamber at room temperature pressurized, in general, with nitrogen.
  • a bowl containing alcohol rotates around the sample. The distance between the sample and the alcohol film formed in the wall of the bowl is adjustable. Most drops ejected from the burning surface impart the rotating liquid. After the test, the liquid is recovered and the particles analyzed.
  • the particle size distribution, by volume, of the recovered particles is then measured by means of a photon correlation optical particle size analyzer (PCS-DLS, Photons Correlation Spectroscopy-Diffusion Light Scattering).
  • PCS-DLS Photons Correlation Spectroscopy-Diffusion Light Scattering
  • the solid propellants of the invention produce, during their combustion, particles of smaller dimensions than those produced by the propellant combustion of the same type of the prior art.
  • the percentage of the total volume (passing) corresponding to particles of diameter (spherical equivalent) greater than 10 ⁇ m is thus less than 15%, generally between 2% and 10%, for the propellants of the invention, much lower than that reference propellants of the prior art ( ⁇ 30%).
  • the grain size curves of the particles produced by the combustion of the propellants of the invention always show, like those of the propellants of the prior art, a particle size peak centered on approximately 0.1 to 3 ⁇ m.
  • a second particle size peak corresponding to particles of diameter greater than 10 microns. This second peak is centered at 10 to 50 ⁇ m for the propellants of the invention, values lower than those (60 to 100 ⁇ m) observed for propellants of the prior art.
  • the preferred propellants of the invention do not exhibit said second particle size peak and therefore only produce a residual percentage of particles with a diameter greater than 10 ⁇ m.
  • the invention relates to a solid propellant charge containing a solid propellant of the invention. According to yet another of its objects, the invention relates to a rocket engine comprising at least one load containing a propellant of the invention.
  • the invention finally relates to an oxidizing charge of ammonium perchlorate, in particular useful for the implementation of the method for obtaining a composite solid propellant of the invention as described above, in particular useful for obtaining a composite solid propellant of the invention as described above, said charge is obtainable by mixing at least two charges selected from the first, second and third charges as defined above ( binary or ternary mixtures), advantageously obtainable by mixing at least a first charge and at least a second charge (binary mixtures) and optionally at least a third charge (ternary mixtures) as defined herein. above, very advantageously capable of being obtained by mixing at least a first charge and at least a second charge (binary mixtures) as defined above. It advantageously contains said feeds in the weight proportions specified above.
  • Figure 1 shows a diagram of the combustion of a drop of aluminum.
  • FIG. 2 illustrates the phenomena producing the different alumina granulometries generated during the combustion of a solid propellant.
  • FIG. 3 shows the volume particle size curves, measured by means of a photon correlation optical particle size analyzer (PCS-DLS: Photons Correlation Spectroscopy-Diffusion Light Scattering), particles produced by the preferred propellant according to the invention (see FIG. Example 9 below) in comparison with those produced with a reference propellant of prior art (see below).
  • PCS-DLS Photons Correlation Spectroscopy-Diffusion Light Scattering
  • Table 1 below gives the mass percentages of the constituents (PA, AI) of solid propellants according to the invention, the ballistic properties of said propellants as well as the particle sizes of the alumina produced during the combustion of said propellants. These same data are given for three reference propellants.
  • the solid propellants of Table 1 are solid polyurethane-bonded composite propellants and contain an oxidizing charge of ammonium perchlorate and an aluminum charge.
  • Reference propellants 1 and 2 have a conventional composition. They are of the type used for space applications.
  • the reference propellant 3 shows the influence of the strong presence (42%) of small particles of ammonium perchlorate on the rate of combustion (logically small alumina particles are then obtained).
  • the solid propellants of the invention according to Examples 1 to 12 have combustion rates and pressure exponents measured at 5 MPa in the expected speed and exponent ranges for the targeted range of application, close to those of the reference propellots. 1 and 2.
  • the last line of Table 1 relates to the propellant M 12 of Table 3 of Massa et al. (Journal of Propulsion and Power, Vol 24, No. 2,
  • the alumina particles produced by the solid propellants of the Table 1 was recovered using a pressurized chamber equipped with a trapping means (test means "rotary trap described above) .
  • the procedure for capturing the particles is as follows;
  • the alcohol contained in the rotary trap is plated, in the form of a film (about 2 mm thick), on the side walls of the bowl, by rotating of the last ;
  • the pressure inside the chamber is set to 5 MPa relative. Pressurization is carried out by nitrogen and the distance between the propellant sample and the alcohol film is 20 mm from the combustion. The emitted particles are taken horizontally;
  • the free face of the propellant cube facing the alcohol film is lit (the very short duration of the combustion makes it possible to maintain an almost constant combustion surface).
  • the principle of recovery consists in recovering in the alcohol the condensed phase particles emitted in the combustion gases of the propellant sample.
  • PCS-DLS Photons Correlation Spectroscopy-Diffusion Light Scattering
  • the particle size distribution or distribution of the particles collected in ethanol during the combustion of the propellant is expressed in the form of two curves; on the one hand, the histogram giving the volume fraction of the particles as a function of the class of equivalent spherical diameter of the particles analyzed, and, on the other hand, the curve giving the cumulated volume fraction as a function of the class of equivalent spherical diameter particles analyzed.
  • FIG. 3 shows the curves obtained for the reference propellant i and that of example 9 according to the invention.
  • Table 1 shows the characteristic values recorded on the particle size curves of the recovered particles produced by the combustion of the reference solid propellants and examples according to the invention (see the last three columns of Table 1).
  • compositions of the solid propellants of Table 1 are given by the mass percentage of the ammonium perchlorate charge and the constitution of this charge (class A / B / C), the mass percentage of aluminum and its particle size class (specified in Table 2), the complement to 100% of the mass consisting of the polymer polyol polybutadiene hydroxytelechelic PBHT R45HTLO sold by the company Sartomer, the crosslinking agent MDCI, the plasticizer DOZ and additives.
  • the particle size histograms always have at least one granulometric peak for diameters of less than 10 ⁇ m.
  • the values given in the column "Dpkx10 ⁇ m" in Table 1 correspond to the value or the range of values (when there are several peaks, or when a dispersion of the values is measured over several tests) of the maximum said at least one granulometric peak for diameters less than 10 ⁇ m measured.
  • the granulometric curve furthermore has a particle size peak for particles with a diameter of greater than 10 ⁇ m, the value or the range of values recorded (for example taken from several tests) of the diameter of the maximum of said particle size peak for particles with a diameter larger than 10 ⁇ m. 10 ⁇ m is indicated in the column "DpiolO ⁇ m" of Table 1.
  • the solid propellants of the invention produce a reduced amount of alumina particles larger than 10 ⁇ m in diameter, relative to the reference propellants 1 and 2. This is expressed in Table 1 by the value of the volume percentage (volume passing up on the curve giving the cumulative volume fraction as a function of the equivalent spherical diameter class of the particles analyzed) corresponding to the classes of particles with a diameter greater than 10 ⁇ m. All the propellants of the invention lead to a passing volume percentage corresponding to particles of diameter greater than 10 microns much lower than that of the reference propellant.
  • Said propellant M12 has a combustion rate of 14 mm / s at 4 MPa ( Figure 12c). As the burning speed of the solid propellants increases with the pressure, the burning rate of the M12 propellant at a pressure of 5 MPa (reference pressure for the examples of the invention) can only be greater than this value of 14 mm / s. It is therefore much higher than those of the reference propellants 1 and 2.

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Abstract

The present invention mainly relates to a method for producing a solid composite propellant (with a polyurethane binder filled with ammonium perchlorate and aluminum). Typically, the ammonium perchlorate charge of the propellant is obtained from at least two charges each having a specific single mode particle size distribution. It is thus possible to reduce the thrust oscillations and the alumina deposits at the rear bottom of the engine. The invention also relates to a solid composite propellant, to solid propellant charges, and to related rocket engines.

Description

Procédé d'obtention de propergols solides composites aluminisés ; propergols solides composites aluminisés,  Process for obtaining aluminized composite solid propellants aluminized composite solid propellants,
La présente invention a pour principaux objets : The main objects of the present invention are:
- un procédé d'obtention d'un propergol solide composite (à liant polyuréthanne chargé en perchlorate d'ammonium et en aluminium), - un tel propergol solide composite, les chargements de propergol solide et les moteurs de fusée associés.  a process for obtaining a composite solid propellant (with a polyurethane binder loaded with ammonium perchlorate and aluminum), such a solid composite propellant, solid propellant charges and the associated rocket engines.
L'invention se situe dans le domaine de Ia propulsion à propergoi solide et concerne, plus particulièrement, des propergols solides composites aluminisés.  The invention is in the field of solid propellant propulsion and more particularly relates to aluminized composite solid propellants.
Les applications envisagées concernent essentiellement les moteurs à propergol solide pour lanceurs spatiaux (accélérateurs ou étages de lanceurs).  The applications envisaged mainly concern solid propellant engines for space launchers (accelerators or launchers stages).
Le but de l'invention est de réduire les dépôts d'alumine en fond arrière des moteurs avec tuyère intégrée et de tendre à la réduction des oscillations de poussée d'origine aérodynamique tout en conservant les propriétés balistiques, notamment les vitesses de combustion, du propergol proches de celtes des propergols industriels pour application spatiale connus à ce jour.  The object of the invention is to reduce the alumina deposits at the bottom of the engines with integrated nozzle and tend to reduce aerodynamic thrust oscillations while maintaining the ballistic properties, including the combustion rates, the propellants similar to industrial propellants for space application known to date.
Les moteurs à propergol solide pour lanceurs spatiaux sont du type de ceux de la fusée Ariane 5 ou de la navette spatiale américaine, de grandes dimensions (h ~ 20 m, D ~ 5 m), à tuyère intégrée. Les chargements de propergol solide contenus dans ce type de moteurs ont une masse allant de quelques centaines de kilogrammes à plusieurs centaines de tonnes. Leur durée de fonctionnement est de l'ordre de quelques dizaines de secondes à quelques minutes. La présente invention se situe dans ce contexte des moteurs à propergol solide de grandes dimensions. The solid propellant engines for space launchers are of the type of the Ariane 5 rocket or the American Space Shuttle, large (h ~ 20 m, D ~ 5 m), with integrated nozzle. The solid propellant loads contained in this type of engine have a mass ranging from a few hundred kilograms to several hundred tons. Their operating time is of the order of a few tens of seconds to a few minutes. The present invention is in this context large solid propellant engines.
Les propergols solides, pour ces applications, sont des propergols composites à liant inerte du type polyuréthanne. Ils contiennent une charge de perchlorate d'ammonium (charge oxydante) et une charge d'aluminium (charge réductrice). La charge oxydante de perchlorate d'ammonium contenue dans lesdits propergols est généralement constituée des plusieurs charges de perchlorate d'ammonium de distributions granulométriques monomodales différentes qui ont été ajoutées lors de Ia préparation desdits propergols. Il peut en être de même pour la charge réductrice d'aluminium» Cette famille de propergols est celle concernée par Ia présente invention. Les ratios en masse de ces ingrédients sont généralement d'environ 68 % pour Ie perchlorate d'ammonium, 20% pour l'aluminium et 12 % pour Ie liant. Solid propellants for these applications are composite propellants with an inert binder of the polyurethane type. They contain a charge of ammonium perchlorate (oxidizing charge) and an aluminum charge (reducing charge). The oxidizing charge of ammonium perchlorate contained in said propellants generally consists of the several charges of perchlorate of ammonium of different monomodal particle size distributions which have been added in the preparation of said propellants. It may be the same for the reducing load of aluminum. This family of propellants is that concerned by the present invention. The mass ratios of these ingredients are generally about 68% for ammonium perchlorate, 20% for aluminum and 12% for binder.
La vitesse de combustion du propergol solide dépend de la pression P régnant dans la chambre de combustion et suit classiquement une loi (dite loi de Vieille) exprimée sous la forme :  The burning rate of the solid propellant depends on the pressure P prevailing in the combustion chamber and conventionally follows a law (called the law of old) expressed in the form:
Vc= aPn. Vc = aP n .
Ladite vitesse de combustion Vc et l'exposant de pression n du propergol sont des paramètres fondamentaux pour le réglage balistique d'un moteur à propergol solide (durée de combustion, poussée, stabilité de combustion..,),  Said combustion rate Vc and the pressure exponent n of the propellant are fundamental parameters for the ballistic adjustment of a solid propellant engine (combustion time, thrust, combustion stability, etc.),
Les valeurs standard des paramètres balistiques pour les applications propulsives concernées par la présente invention, utilisant des propergols composites aluminisés à liant polyuréthanne, sont une vitesse de combustion Vc de quelques mm/s à 10 mm/s et un exposant de pression n = 0,2 à 0,4, dans une plage de pression de fonctionnement de 3 à 10 MPa.  The standard values of the ballistic parameters for the propulsion applications concerned by the present invention, using polyurethane-bonded aluminized composite propellants, are a combustion rate Vc of a few mm / s to 10 mm / s and a pressure exponent n = 0, 2 to 0.4, in an operating pressure range of 3 to 10 MPa.
L'homme du métier sait choisir les granulométries des matières premières constitutives du propergol solide pour contrôler les niveaux de vitesse de combustion dudit propergol solide.  The person skilled in the art knows how to choose the particle sizes of the constituent raw materials of the solid propellant for controlling the combustion speed levels of said solid propellant.
M. M. Iqbal et W. Liang se sont intéressés, dans le Journal of Propulsion and Power, vol. 23, N°5, September 2007, à l'effet de la granulométrie du perchlorate d'ammonium sur la vitesse de combustion de propergols solides. Leur objectif a été de valider un modèle mathématique de combustion en surface, permettant de prédire les vitesses de combustion de ce type de propergol,  M. Iqbal and W. Liang were interested in the Journal of Propulsion and Power, vol. 23, No. 5, September 2007, the effect of the particle size of ammonium perchlorate on the burning rate of solid propellants. Their objective was to validate a mathematical model of surface combustion, making it possible to predict the combustion rates of this type of propellant,
L. Massa et T, L, Jackson se sont intéressés, dans le Journal of L. Massa and T, L, Jackson were interested, in the Journal of
Propulsion and Power, vol. 24, N°2, March-Λprif 2008, à l'effet de la granulométrie de l'aluminium sur la vitesse de combustion de propergols solides. Leur objectif a aussi été de valider un modèle mathématique de combustion en surface permettant de prédire les vitesses de combustion de ce type de propergol. Ces deux publications ne donnent aucune information sur la granulométrîe de l'alumine générée suite à la combustion des propergols et sur les problèmes techniques associés à cette granulométrie (voir plus loin). Par ailleurs, tes différentes charges de perchlorate d'ammonium, dont il est question dans lesdïtes publications, ne sont caractérisées que par un paramètre, à savoir Ie diamètre des particules au maximum du pic de leur distribution granulométrique. Propulsion and Power, vol. 24, No. 2, March-Λprif 2008, to the effect of the particle size of aluminum on the burning rate of solid propellants. Their objective was also to validate a mathematical model of surface combustion allowing to predict the combustion rates of this type of propellant. These two publications give no information on the particle size of the alumina generated following the combustion of the propellants and on the technical problems associated with this particle size distribution (see below). Moreover, the various charges of ammonium perchlorate, referred to in the said publications, are characterized only by one parameter, namely the particle diameter at the maximum of the peak of their particle size distribution.
Les propergols composites aluminîsés produisent, lors de leur combustion, des gaz et des particules solides constituées très majoritairement d'alumine (environ 30% de la masse éjectée par le propulseur).  The aluminized composite propellants produce, during their combustion, gases and solid particles consisting mainly of alumina (about 30% of the mass ejected by the propellant).
La combustion de l'aluminium en alumine dans les propergols composites a été largement étudiée. Pour autant, l'homme du métier ne sait pas maîtriser la granulométrie de l'alumine produite par ladite combustion du propergol.  The combustion of alumina aluminum in composite propellants has been extensively studied. However, those skilled in the art do not know how to control the particle size of the alumina produced by said propellant combustion.
L'aluminium introduit dans les propergols solides composites aluminisés se présente sous la forme de grains, plus ou moins sphériques, de diamètre médian généralement compris entre 1 et 50 μm. La combustion d'une goutte d'aluminium, expulsée de la surface en combustion, est schématisée sur la figure 1 annexée. Une flamme entoure la goutte d'aluminium et une calotte d'alumine est formée au bas de la goutte. La combustion génère des fumées d'alumine (gouttes de faible taille, de l'ordre de 1 μm) et des gouttes d'alumine de plus grande taille provenant de la calotte, ce qui explique les distributions granulométrîques bimodales d'alumine finalement produites par les propergols solides. Les études menées sur la combustion de ces propergols aluminîsés (la figure 2 explicite, sous forme graphique, les phénomènes mis en jeu) montrent que tes particules d'aluminium qui s'échappent de la surface du propergol sont susceptibles de s'agglomérer pour former des gouttes d'une tailfe bien supérieure à celle de l'aluminium introduit. Le reste quitte la surface sans s'agglomérer. Des observations de laboratoire montrent que la répartition granulométrique des résidus de combustion générés par un propergol composite aluminisé présente généralement deux pics, un principal centré autour d'un diamètre de 60 μm et un second centré autour de 0,5 μm à 3 μm» indépendamment de la granulométrie de l'aluminium introduit. Le pourcentage du volume total représenté par des particules de diamètres supérieurs à 10 μm est typiquement d'environ 30%. The aluminum introduced into the aluminized composite solid propellants is in the form of grains, more or less spherical, with a median diameter generally between 1 and 50 microns. The combustion of a drop of aluminum, expelled from the burning surface, is shown schematically in Figure 1 attached. A flame surrounds the drop of aluminum and a cap of alumina is formed at the bottom of the drop. The combustion generates fumes of alumina (drops of small size, of the order of 1 μm) and larger drops of alumina from the cap, which explains the bimodal particle size distributions of alumina finally produced by solid propellants. The studies carried out on the combustion of these aluminized propellants (Figure 2 explicit, graphically, the phenomena involved) show that the aluminum particles that escape from the surface of the propellant are likely to agglomerate to form drops of a much greater size than that of the introduced aluminum. The rest leaves the surface without agglomerating. Laboratory observations show that the particle size distribution of the combustion residues generated by an aluminized composite propellant generally has two peaks, one main centered around a diameter of 60 μm and a second centered around 0.5 μm to 3 μm " independently. the particle size of the aluminum introduced. The percentage of the total volume represented by particles with diameters greater than 10 μm is typically about 30%.
L'alumine générée par la combustion du propergol aluminisé représente, comme indiqué ci-dessus, environ 30 % de la masse éjectée par le propulseur.  The alumina generated by the combustion of the aluminized propellant represents, as indicated above, approximately 30% of the mass ejected by the propellant.
Sur un premier plan, la production de particules d'alumine de gros diamètre (> 10 μm) conduit, dans les propulseurs spatiaux équipés d'une tuyère intégrée, à une accumulation dans le fond arrière entraînant une réduction de l'impulsion. On estime que plus de 0,5% de la masse du propergol se retrouve ainsi sous la forme d'alumine piégée dans le fond arrière, et donc non éjectée du moteur. En effet, les plus grosses particules ont une traînée aérodynamique élevée, ne suivent pas tes lignes d'écoulement et sont piégées dans le fond arrière du moteur (en forme de bol formé par la structure intégrée de la tuyère). Cette masse non expulsée pénalise, d'une part, les performances du moteur et peut, d'autre part, générer, après l'extinction du moteur et par un phénomène de vidange dans le vide, des débris orbitaux d'alumine de dimensions non négligeables (i.e. > à quelques millimètres).  In the foreground, the production of large-diameter (> 10 μm) alumina particles leads to an accumulation in the backplane in space thrusters equipped with an integrated nozzle, resulting in a reduction of the impulse. It is estimated that more than 0.5% of the mass of the propellant is thus in the form of alumina trapped in the rear bottom, and therefore not ejected from the engine. Indeed, the larger particles have a high aerodynamic drag, do not follow your flow lines and are trapped in the back of the engine (bowl shaped formed by the integrated structure of the nozzle). This non-expelled mass penalizes, on the one hand, the performance of the engine and can, on the other hand, generate, after the extinction of the engine and by a vacuum emptying phenomenon, orbital debris of non-dimensional alumina. negligible (ie> to a few millimeters).
L'homme du métier souhaite donc disposer d'un propergol solide générant de l'alumine de fines granulométries, puisque de plus petites particules vont mieux suivre les lignes de courant pour être éjectées par la tuyère, évitant ainsi leur accumulation dans le fond arrière du moteur.  The person skilled in the art therefore wishes to have a solid propellant generating alumina of fine particle size, since smaller particles will better follow the current lines to be ejected by the nozzle, thus avoiding their accumulation in the back of the container. engine.
Sur un deuxième plan, des problèmes d'instabilité aérodynamique inhérents à la géométrie interne des moteurs à propergof solide de grandes dimensions peuvent apparaître (injection latérale des produits de combustion, confluence de jets, accidents géométriques ou battements d'éléments dépassant...). Ces instabilités aérodynamiques peuvent interagir avec la combustion du propergol et/ou l'acoustique de la chambre de combustion et induire des phénomènes de résonance. De tels phénomènes entraînent des vibrations mécaniques sur la charge utile du lanceur. On cherche donc toujours à réduire ces phénomènes afin de préserver la charge utile.  On a second level, problems of aerodynamic instability inherent to the internal geometry of large solid propellant engines may appear (lateral injection of combustion products, jets confluence, geometric accidents or beats of elements exceeding ...) . These aerodynamic instabilities can interact with propellant combustion and / or combustion chamber acoustics and induce resonance phenomena. Such phenomena cause mechanical vibrations on the launcher payload. So we always try to reduce these phenomena to preserve the payload.
L'homme de l'art a cherché par divers moyens, tous pénalisants, à réduire ces instabilités aérodynamiques. Une méthode consiste à introduire dans l'écoulement des obstacles tels que des chicanes, inserts ou des tiges de résonances, des cavités (on peut voir à ce propos les enseignements des documents FR 2,844,557, US 3,795,106 et FR 2,764,645). La mise en œuvre de ces méthodes nécessite des essais de mise au point et se fait toujours au détriment des performances du moteur, en raison d'une augmentation de la masse inerte embarquée. Those skilled in the art have sought by various means, all penalizing, to reduce these aerodynamic instabilities. One method is to introduce into the flow obstacles such as baffles, inserts or rods of resonances, cavities (we can see in this regard the teachings of FR 2,844,557, US 3,795,106 and FR 2,764,645). The implementation of these methods requires development tests and is always detrimental to the performance of the engine, due to an increase in the embedded inert mass.
Plus récemment, selon des considérations théoriques complexes, il a été démontré que, dans Ie cas des moteurs de grandes dimensions, il faut privilégier la production d'alumine de faible granulométrie (diamètre ~ 1 μm), pour réduire ces instabilités aérodynamiques.  More recently, according to complex theoretical considerations, it has been demonstrated that in the case of large engines, it is necessary to favor the production of alumina small particle size (diameter ~ 1 micron), to reduce these aerodynamic instabilities.
L'homme du métier souhaite donc disposer de propergols solides aluminîsés qui produisent, par combustion, de l'alumine de faible diamètre (favorisant ainsi la réduction des oscillations de poussée dans les propulseurs à propergol solide et ayant l'effet positif combiné de réduire le dépôt dans le fond arrière de la tuyère) tout en conservant des propriétés balistiques, notamment des vitesses de combustion, proches de celles des propergols industriels pour application spatiale connus à ce jour.  Those skilled in the art therefore wish to have aluminized solid propellants which, by combustion, produce small diameter alumina (thus promoting the reduction of thrust oscillations in solid propellant propellants and having the combined positive effect of reducing the deposit in the rear bottom of the nozzle) while maintaining ballistic properties, including combustion rates, similar to those of industrial propellants for space application known to date.
Dans la suite du document, l'ensemble des données granulométriques est issu de mesures réalisées au moyen d'un granulomètre optique à corrélation de photons (PCS-DLS : Photons Corrélation Spectroscopy-Diffusion Lïght Scattering), selon un mode opératoire défini par la norme NF 11-666.  In the remainder of the document, all the particle size data are obtained from measurements carried out using 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.
Les résultats des mesures granulométriques d'une classe granulométrique sont exprimés sous la forme de courbes, donnant : d'une part, l'histogramme des pourcentages volumiques de particules (appelé aussi pourcentages de volume passant) en fonction du diamètre (sphérîque équivalent) des particules et, d'autre part, le cumul des pourcentages volumîques de particules en fonction du diamètre (sphérique équivalent) des particules, cumul effectué selon les diamètres croissants.  The results of granulometric measurements of a particle size class are expressed in the form of curves, giving: on the one hand, the histogram of the volume percentages of particles (also called percentages of passing volume) as a function of the diameter (equivalent spherical) of the particles and, on the other hand, the cumulation of the voluminal percentages of particles as a function of the diameter (equivalent spherical) of the particles, cumulated carried out according to the increasing diameters.
Trois valeurs caractéristiques de l'échantillon analysé sont relevées sur Ia courbe cumulée des pourcentages volumiques :  Three characteristic values of the analyzed sample are recorded on the cumulative curve of volume percentages:
D1O : diamètre pour lequel le pourcentage volumique cumulé est égal à 10 % ; D 1 O: diameter for which the cumulative volume percentage is equal to 10%;
Dso : diamètre pour lequel Ie pourcentage volumique cumulé est égal à 50 % ;  Dso: diameter for which the cumulative volume percentage is equal to 50%;
D§o : diamètre pour lequel Ie pourcentage vofumique cumulé est égal à 90 %. On définit ainsi une classe granulométrique d'une matière particulaire par son enveloppe granulométrique définie par des valeurs minimum et maximum de Dio, D50, D90. La présente invention concerne des propergols solides :D: diameter for which the cumulated volume percentage is equal to 90%. A particle size class of a particulate material is defined by its particle size envelope defined by minimum and maximum values of D 10, D 50, D 90 . The present invention relates to solid propellants:
- à liant polyuréthanne renfermant une charge de perchlorate d'ammonium et une charge d'aluminium, with a polyurethane binder containing a charge of ammonium perchlorate and an aluminum charge,
- présentant des propriétés balistiques (Vc, n) adéquates pour des applications de propulsion, et  - having adequate ballistic properties (Vc, n) for propulsion applications, and
- générant, lors de leur combustion, des particules d'alumine de faible granulométrie. generating, during their combustion, particles of alumina of small particle size.
La demanderesse a su sélectionner et associer différentes granulométries (monomodales) de perchlorate d'ammonium, de sorte que, lors de la combustion du propergol, l'agglomération de l'aluminium en combustion soit limitée, ce, en vue de réduire, voire quasi supprimer, la production de particules de diamètre supérieur à 10 μm, tout en conservant les valeurs standards des paramètres balistiques pour une application propulsive spatiale.  The Applicant has been able to select and associate different granulometries (monomodal) of ammonium perchlorate, so that, during the combustion of the propellant, the agglomeration of the aluminum in combustion is limited, in order to reduce, or almost to remove, the production of particles larger than 10 microns diameter, while maintaining the standard values of the ballistic parameters for a propulsive space application.
Grâce à la fine granulométrie d'alumine produite par les propergols solides (en combustion) de la présente invention, les dépôts dans les fonds arrière de moteurs sont réduits et les oscillations de pression sont atténuées.  Thanks to the fine particle size of alumina produced by the solid propellants (in combustion) of the present invention, deposits in the rear engine bottoms are reduced and the pressure oscillations are attenuated.
La présente invention a pour premier objet un procédé d'obtention d'un propergol solide composite, ledit procédé comprenant : - l'obtention d'une pâte par malaxage, dans un mélangeur, d'un mélange renfermant un polymère polyol liquide (généralement présent, dans le mélange, à raison de 5 à 15 % en masse, plus généralement à raison de 7 à 14 % en masse), une charge oxydante de perchlorate d'ammonium (généralement présente, dans le mélange, à raison de 40 à 80 % en masse, plus généralement à raison de 60 à 75 % en masse), une charge réductrice d'aluminium (généralement présente, dans le mélange, à raison de 15 à 20 % en masse, plus généralement à raison de 16 à 19 % en masse), au moins un agent de rétîculatîon dudit polymère polyol liquide en une quantité telle que le rapport de pontage NCO/OH soit compris entre 0,8 et 1,1, soit avantageusement de 1, au moins un plastifiant et au moins un additif (lesdits agent(s) de réticulation, plastifiants) et additif(s) étant généralement présents, dans Ie mélange, à raison de moins de 5 % en masse, plus généralement à raison de 1 à 3 % en masse) ; The present invention firstly relates to a process for obtaining a composite solid propellant, said process comprising: - obtaining a paste by mixing, in a mixer, a mixture containing a liquid polyol polymer (generally present in the mixture, at 5 to 15% by weight, more generally at 7 to 14% by weight), an oxidizing charge of ammonium perchlorate (generally present in the mixture at a rate of 40 to 80% by weight). % by weight, more generally at 60 to 75% by weight), a reducing charge of aluminum (generally present in the mixture at a rate of 15 to 20% by weight, more generally at a rate of 16 to 19% in bulk), at least one agent for reticulating said liquid polyol polymer in an amount such that the NCO / OH bridging ratio is between 0.8 and 1.1, advantageously at least 1, at least one plasticizer and at least one additive (said crosslinking agent (s), plasticizer s) and additive (s) being generally present in the mixture at less than 5% by weight, more generally at 1 to 3% by weight);
- la coulée de la pâte obtenue dans un moule ;  - The casting of the paste obtained in a mold;
- la réticulation thermique de ladite pâte dans ledit moule,  the thermal crosslinking of said paste in said mold,
De façon caractéristique, ladite charge oxydante de perchlorate d'ammonium dans ladite pâte résulte de l'introduction, dans ledit mélangeur, séparément ou en mélange, d'au moins :  Typically, said oxidizing charge of ammonium perchlorate in said paste results from the introduction into said mixer, separately or as a mixture, of at least:
+ une première charge dont la distribution granutométrique monomodate (dite de classe A) présente une valeur de Dio comprise entre 100 μm et IiO μm, une valeur de D5o comprise entre 170 μm et 220 μm et une valeur de D9$ comprise entre 315 μm et 340 μm, et + a first charge whose monomodate granulometric distribution (called class A) has a Dio value between 100 μm and 10 μm, a D 5 o value between 170 μm and 220 μm and a value of D 9 $ between 315 μm and 340 μm, and
+ une seconde charge dont la distribution granulométrique monomodale (dite de classe B) présente une valeur de Di0 comprise entre 15 μm et 20 μm, une valeur de Ds0 comprise entre 60 μm et 120 μm et une valeur de D90 comprise entre 185 μm et 220 μm ; et, éventuellement, + a second charge whose monomodal particle size distribution (called class B) has a Di 0 value between 15 μm and 20 μm, a Ds 0 value between 60 μm and 120 μm and a D 90 value between 185 μm and 220 μm; and eventually,
+ une troisième charge dont la distribution granulométrique monomodale (dite de classe C) présente une valeur de Dio comprise entre 1,7 μm et 3,6 μm, une valeur de D50 comprise entre 6 μm et 12 μm et une valeur de Dgo comprise entre 20 μm et 32 μm. + a third charge whose monomodal particle size distribution (called class C) has a Dio value of between 1.7 μm and 3.6 μm, a D 50 value of between 6 μm and 12 μm and a Dgo value of between between 20 μm and 32 μm.
Le procédé de l'invention est un procédé par analogie qui comprend, de façon classique, l'obtention d'une pâte à partir des ingrédients constitutifs du propergol visé, la coulée de ladite pâte dans un moule et sa réticulation par traitement thermique (cuisson). Les ingrédients en cause sont les ingrédients classiques pour ce type de propergol. Ils comprennent :  The method of the invention is a method by analogy which comprises, in a conventional manner, obtaining a paste from the constituent ingredients of the propellant referred to, casting said paste in a mold and its crosslinking by heat treatment (baking ). The ingredients involved are the classic ingredients for this type of propellant. They understand :
- un polymère polyol liquide ; de façon préférée, ledit polymère polyol est un polybutadiène hydroxytéléchéltque ;  a liquid polyol polymer; preferably, said polyol polymer is a hydroxytelechelic polybutadiene;
- une charge oxydante de perchlorate d'ammonium (PA) ;  an oxidizing charge of ammonium perchlorate (PA);
- une charge réductrice d'aluminium (Al) ;  a reducing charge of aluminum (Al);
- au moins un agent de réticulation (généralement liquide) dudit polymère polyol : ledit au moins un agent de réticulation (au moins bifonctîonnel) est généralement choisi parmi tes polyisocyanates, il consiste de préférence en un polyisocyanate alîcycltque. Il consiste avantageusement en le dïcyclonexylméthylène diîsocyanate (MCDI) ;  at least one crosslinking agent (generally liquid) of said polyol polymer: said at least one crosslinking agent (at least bifunctional) is generally chosen from polyisocyanates, it preferably consists of an aliphatic polyisocyanate. It advantageously consists of cyclohexylmethylene diisocyanate (MCDI);
- au moins un plastifiant : ledit au moins un plastifiant est choisi préférentiellement parmi l'azéiate de dioctyle (DOZ), Ie sébaçate de dîisooctyle, le pélargonate d'isodécyle, Ie polyisobutylène, Ie phtalate de dîoctyle (DOP) ; at least one plasticizer: said at least one plasticizer is preferably chosen from dioctyl azéiate (DOZ), sebacate of isooctyl, isodecyl pelargonate, polyisobutylene, dioctyl phthalate (DOP);
- au moins un additif : ledit au moins un additif peut notamment consister en un ou plusieurs agents d'adhésion entre Ie liant et la charge oxydante, comme par exemple l'oxyde de bîs(2-méthylazîridinyl)- méthylaminophosphine (méthyl BAPO) ou le triéthylène pentamine acrylonitrile (TEPAN), en un ou plusieurs agents antioxydants issus de ceux de l'industrie du caoutchouc, comme par exemple le ditertiobutylparacrésol (DBC) ou Ie 2,2'-méthylène~bis(4-méthyl~6-tertio~ butylphénol) (MBP5), en un ou plusieurs catalyseurs de réticulatîon, comme par exemple l'acétylacétonate de fer ou de cuivre, le dibutyldilaurate d'étain (DBTL), en un ou plusieurs catalyseurs de combustion, comme l'oxyde de fer, ...  at least one additive: said at least one additive may in particular consist of one or more adhesion agents between the binder and the oxidizing filler, such as, for example, bis (2-methylaziridinyl) -methylaminophosphine oxide (methyl BAPO) or triethylene pentamine acrylonitrile (TEPAN), in one or more antioxidant agents derived from those of the rubber industry, such as, for example, ditertiobutylparacresol (DBC) or 2,2'-methylenebis (4-methyl-6-tertio) ~ butylphenol) (MBP5), in one or more crosslinking catalysts, such as iron or copper acetylacetonate, tin dibutyldilaurate (DBTL), in one or more combustion catalysts, such as iron oxide , ...
Lesdits ingrédients interviennent en les quantités (pourcentages massiques) classiques indiquées ci-dessus.  Said ingredients are involved in the amounts (percentages by mass) conventional indicated above.
On note incidemment ici que la liste des ingrédients donnée ci- dessus n'est pas exhaustive. Ainsi, il n'est pas exclu qu'une autre charge énergétique soit introduite dans le mélangeur.  Incidentally, the list of ingredients given above is not exhaustive. Thus, it is not excluded that another energy charge is introduced into the mixer.
En référence aux problèmes techniques invoqués ci-dessus, la charge de perchlorate d'ammonium est, dans le cadre du procédé de l'invention, optimisée : elle est obtenue à partir d'au moins une première et seconde (voire troisième) charges présentant, chacune, une distribution granulométrie monomodale telle que précisée ci-dessus. Elle résulte, de façon caractéristique, de l'introduction, dans le mélangeur, séparément ou en mélange, d'au moins deux charges de granulométrie monomodale différente : la première de classe A (voir ci-dessus) et la seconde de classe With reference to the technical problems mentioned above, the charge of ammonium perchlorate is, in the context of the process of the invention, optimized: it is obtained from at least a first and second (or even third) charges having , each, a monomodal particle size distribution as specified above. It results, typically, from the introduction, in the mixer, separately or in mixture, of at least two charges of different monomodal granulometry: the first of class A (see above) and the second of class
B (voir ci-dessus). L'introduction d'une troisième charge de classe C (voir ci-dessus) est expressément prévue. L'introduction d'au moins une autre charge (en sus de celles de classe A, B et C) n'est pas exclue du cadre de l'invention. Elle n'est a priori guère opportune. B (see above). The introduction of a third class C load (see above) is expressly provided for. The introduction of at least one other load (in addition to those of class A, B and C) is not excluded from the scope of the invention. It is a priori hardly advisable.
De façon caractéristique, la charge de perchlorate d'ammonium du mélange, dans le mélangeur, est, au moins en partie, avantageusement en totalité, constituée à partir d'une première et seconde charges (chacune) de granulométrie monomodale spécifique, voire d'une première, seconde et troisième charges (chacune) de granulométrie monomodafe spécifique. Le mélange (binaire ou ternaire) des première et seconde ou première, seconde et troisième charges oxydantes de granulométrie monomodale spécifique différente peut être réalisé en amont. Selon cette variante, la charge oxydante du propergol est réalisée en amont et est ensuite ajoutée, pré-constituée, dans le mélangeur. Typically, the charge of ammonium perchlorate of the mixture, in the mixer, is at least partly advantageously in its entirety, constituted from a first and second charges (each) of specific monomodal particle size, or even a first, second and third charge (each) of specific monomodafe particle size. The mixture (binary or ternary) of the first and second or first, second and third oxidizing charges of different specific monomodal granulometry can be performed upstream. According to this variant, the oxidizing charge of the propellant is carried out upstream and is then added, pre-constituted, in the mixer.
Le mélange (binaire ou ternaire) des première et seconde ou première, seconde et troisième charges oxydantes de granulométrie monomodale spécifique différente peut n'être réalisé que dans le mélangeur au sein de la pâte. Il n'est, selon cette variante, pas pré- constitué. Les première, seconde, voire troisième charges peuvent ainsi être introduites séparément. Dans le cadre de cette variante, lorsque trois types de charges oxydantes sont introduits, on peut toutefois préconstituer un mélange (binaire), première et seconde, première et troisième, ou seconde et troisième, charges oxydantes de granulométrie monomodale spécifique. On ajoute ensuite, dans le mélangeur» ledit mélange puis, respectivement, la troisième, la seconde, ou la première, charge oxydante (la charge oxydante complémentaire) de sorte que lesdites première, seconde et troisième charges constituent la charge oxydante du propergol. The mixture (binary or ternary) of the first and second or first, second and third oxidizing charges of different specific monomodal granulometry may be carried out only in the mixer within the dough. According to this variant, it is not pre-constituted. The first, second or even third charges can thus be introduced separately. In the context of this variant, when three types of oxidizing charges are introduced, it is however possible to preconstitute a mixture (binary), first and second, first and third, or second and third, oxidizing charges of specific monomodal particle size. Then added to the mixer "said mixture and, respectively, the third, the second, or the first, oxidizing charge (complementary oxidizing charge) so that said first, second and third fillers constitute the oxidizing charge of the propellant.
On comprend que les notions ci-dessus d'introduction séparée ou d'introduction en mélange (mélanges binaires ou ternaires) couvrent toutes ces variantes.  It will be understood that the above notions of separate introduction or introduction in a mixture (binary or ternary mixtures) cover all these variants.
Il est du mérite des inventeurs d'avoir identifié les classes granulométrîques monomodales A, B et C de perchlorate d'ammonium et démontré leur intérêt dans la constitution de la charge oxydante d'un propergol solide composite aluminisé.  It is the merit of the inventors to have identified monomodal granulometric classes A, B and C of ammonium perchlorate and demonstrated their interest in the constitution of the oxidizing charge of an aluminized composite solid propellant.
Selon une variante avantageuse, la charge oxydante de perchlorate d'ammonium dans la pâte ne résulte que de l'introduction dans le mélangeur (séparément ou en mélange) de la première et de la seconde charge dont la granulométrie monomodale a été ci-dessus précisée (au moyen des plages de valeurs de DIQ, DS§ et D90). According to an advantageous variant, the oxidizing charge of ammonium perchlorate in the dough results only from the introduction into the mixer (separately or in mixture) of the first and the second charge, the monomodal particle size of which has been specified above. (using the value ranges of D I Q, DS§ and D 90 ).
Pour ce qui concerne les quantités d'intervention respectives desdites première, seconde, voire troisième, charges oxydantes, on peut, de façon nullement limitative, préciser ce qui suit. La charge oxydante de perchlorate d'ammonium (100 %) dans la pâte résulte, généralement, de l'introduction dans le mélangeur, séparément ou en mélange, de : With regard to the respective amounts of intervention of said first, second or even third, oxidizing charges, it is possible, in no way limiting, to specify the following. The oxidizing charge of ammonium perchlorate (100%) in the paste results, generally, from the introduction into the mixer, separately or as a mixture, of:
- 12 à 70 % en masse de ladite première charge (classe A), - 10 à 81 % en masse de ladite seconde charge (classe B), - 12 to 70% by weight of said first charge (class A), - 10 to 81% by weight of said second charge (class B),
- 0 à 23 % en masse de ladite troisième charge (classe C).0 to 23% by weight of said third charge (class C).
Elle peut notamment résulter de l'introduction dans Ie mélangeur, séparément ou en mélange, de : It may in particular result from the introduction into the mixer, separately or as a mixture, of:
- 20 à 65 % (voire 20 à 60 %) en masse de ladite première charge (classe A),  20 to 65% (or even 20 to 60%) by mass of said first charge (class A),
- 35 à 80 % (voire, respectivement, 40 à 80 %) en masse de ladite seconde charge (classe B),  - 35 to 80% (or, respectively, 40 to 80%) by mass of said second load (class B),
- 0 à 22 % en masse de ladite troisième charge (classe C).  0 to 22% by weight of said third charge (class C).
La charge oxydante de perchlorate d'ammonium (100%) dans la pâte résulte, très généralement, de l'introduction dans le mélangeur, séparément ou en mélange, de ;  The oxidizing charge of ammonium perchlorate (100%) in the paste results, very generally, from the introduction into the mixer, separately or as a mixture, of;
- 12 à 61% en masse de ladite première charge (classe A), 12 to 61% by weight of said first charge (class A),
- 36 à 81 % en masse de ladite seconde charge (classe B),36 to 81% by weight of said second charge (class B),
- 0 à 23 % en masse de ladite troisième charge (classe C). 0 to 23% by weight of said third charge (class C).
Dans le cadre de la variante avantageuse précisée ci-dessus In the context of the advantageous variant specified above
(intervention des première et seconde charges oxydantes uniquement), la charge oxydante de perchlorate d'ammonium (100%) dans la pâte résulte, de façon préférée, de l'introduction dans le mélangeur, séparément ou en mélange, de : (Intervention of the first and second oxidizing charges only), the oxidizing charge of ammonium perchlorate (100%) in the paste results, preferably, from the introduction into the mixer, separately or as a mixture, of:
- 20 à 65% en masse de ladite première charge (classe A), 20 to 65% by weight of said first charge (class A),
- 35 à 80 % en masse de ladite seconde charge (classe B) ; 35 to 80% by weight of said second charge (class B);
de façon encore plus préférée, de :  even more preferably, of:
- 42 à 61 % en masse de ladite première charge (classe A), 42 to 61% by weight of said first charge (class A),
- 39 à 58 % en masse de ladite seconde charge (classe B). - 39 to 58% by weight of said second load (class B).
La granulométrie de la charge d'aluminium (rappelons ici que çfes charges d'aluminium de distribution granulométrique monomodale différentes peuvent aussi intervenir (voir les exemptes ci-après)) est un paramètre de second ordre, en référence aux problèmes techniques invoqués ci-dessus. Les particules d'aluminium ont généralement un diamètre médian inférieur ou égal à 40 μm. Les meilleurs résultats, allant jusqu'à la production d'alumine de granulométrie monomodale centrée vers 1 à 3 μm, sont obtenus avec des particules d'aluminium de diamètre médian compris entre 1 et 10 μm et certaines associations de perchlorate d'ammonium de classe A et B (voir les exemples ci-après) introduites dans Ie mélangeur pour former la charge de perchlorate d'ammonium. The particle size of the aluminum charge (let us recall here that the aluminum charges of different monomodal particle size distribution can also be used (see the examples below)) is a second-order parameter, with reference to the technical problems mentioned above. . The aluminum particles generally have a median diameter of less than or equal to 40 μm. The best results, up to the production of alumina of monomodal granulometry centered to 1 to 3 μm, are obtained with aluminum particles having a median diameter of between 1 and 10 μm and certain combinations of ammonium perchlorate of class A and B (see examples below) introduced into the mixer to form the ammonium perchlorate charge.
Ladite charge d'aluminium a donc généralement un diamètre médian (D50) inférieur ou égal à 40 μm, avantageusement compris entre 1 et 10 μm. Les valeurs de D1O et D90 de ladite charge d'aluminium correspondent avantageusement, respectivement, à au moins 1/4 et au plus 4 fois ledit diamètre médian, Said aluminum filler therefore generally has a median diameter (D 50 ) less than or equal to 40 μm, advantageously between 1 and 10 μm. The values of D 10 and D 90 of said aluminum charge advantageously correspond, respectively, to at least 1/4 and at most 4 times said median diameter,
Selon son second objet, Ia présente invention concerne les propergols solides aluminisés susceptibles d'être obtenus par Ie procédé ci-dessus, procédé qui fait intervenir des charges oxydantes de perchlorate d'ammonium de granulométries monomodales différentes spécifiques.  According to its second object, the present invention relates to aluminized solid propellants obtainable by the above process, which process involves oxidizing ammonium perchlorate charges of different specific monomodal particle sizes.
Le procédé de l'invention, tel que décrit ci-dessus, conduit en effet à des propergols solides composites nouveaux. De tels propergols solides composites - à liant polyuréthanne chargé en perchlorate d'ammonium et en aluminium - dont la combustion génère moins de 15 %, généralement entre 2 et 10 %, en volume de particules d'alumine dont le diamètre est supérieur à 10 μm, sont revendiqués per se. Leur diamètre (équivalent sphérique) est mesuré au moyen d'un granulomètre optique à corrélation de photons (voir ci-dessus et ci-après).  The process of the invention, as described above, leads indeed to new composite solid propellants. Such composite solid propellants - with polyurethane binder loaded with ammonium perchlorate and aluminum - whose combustion generates less than 15%, generally between 2 and 10% by volume of alumina particles whose diameter is greater than 10 μm , are claimed per se. Their diameter (spherical equivalent) is measured by means of an optical photon correlation particle size analyzer (see above and below).
Les propergols solides de l'invention ont généralement des vitesses de combustion comprises entre 6 et 12 mm/s et des exposants de pression compris entre 0,15 et 0,4, avantageusement entre 0,2 et 0,4, sur une plage de pression de fonctionnement de 3 à 10 MPa, ce qui correspond aux valeurs standard des paramètres balistiques. Le grand intérêt du procédé de l'invention est ainsi de permettre l'obtention de propergols solides qui présentent de telles propriétés balistiques et dont la combustion génère des particules d'alumine de faible granufométrîe,  The solid propellants of the invention generally have combustion rates of between 6 and 12 mm / s and pressure exponents of between 0.15 and 0.4, advantageously between 0.2 and 0.4, over a range of operating pressure of 3 to 10 MPa, which corresponds to the standard values of the ballistic parameters. The great advantage of the method of the invention is thus to allow the production of solid propellants which have such ballistic properties and whose combustion generates particles of alumina of small grain size,
La granutométrîe de l'alumine produite par la combustion des propergols de l'invention a été déterminée au moyen d'un équipement de mesure, reconnu par la communauté internationale, nommé "piège rotatif ou "Quench Partide Combustion Bomb". Il a été développé par la société Norton Thiokol (voir P.C. BRAITHWAITE, W.N. CHRISTENSEN. V. DAUGHERTY (Morton Thiokol), Quench bomb investigation of aluminium oxide formation from solid rocket propellants (part I) : expérimental metbodology, 25th JANNAF combustion meeting, CPIA Publication 498, vol.l, p. 175, octobre 1988). Le principe consiste à faire brûler un petit échantillon de propergol au bout d'une tige fixe dans une enceinte à température ambiante pressurisée, en général, à l'azote. Un bol contenant de l'alcool tourne autour de l'échantillon. La distance entre l'échantillon et Ie film d'alcool formé en paroi du bol est réglable. La plupart des gouttes éjectées de la surface en combustion impartent le liquide tournant. Après l'essai, le liquide est récupéré et les particules analysées. The granulometry of the alumina produced by the combustion of the propellants of the invention was determined by means of measuring equipment, recognized by the international community, as "rotary trap or" Quench Party of Combustion Bomb ". by Norton Thiokol (see PC BRAITHWAITE, WN CHRISTENSEN, V. DAUGHERTY (Morton Thiokol), Quench bomb investigation of aluminum oxide formation from solid rocket propellants (part I): experimental metbodology, 25th JANNAF combustion meeting, CPIA Publication 498, vol.l, p. 175, October 1988). The principle is to burn a small sample of propellant at the end of a fixed rod in a chamber at room temperature pressurized, in general, with nitrogen. A bowl containing alcohol rotates around the sample. The distance between the sample and the alcohol film formed in the wall of the bowl is adjustable. Most drops ejected from the burning surface impart the rotating liquid. After the test, the liquid is recovered and the particles analyzed.
La distribution granulométrique, en volume, des particules récupérées est ensuite mesurée au moyen d'un granulomètre optique à corrélation de photons (PCS-DLS ; Photons Corrélation Spectroscopy- Diffusion Light Scattering).  The particle size distribution, by volume, of the recovered particles is then measured by means of a photon correlation optical particle size analyzer (PCS-DLS, Photons Correlation Spectroscopy-Diffusion Light Scattering).
Les propergols solides de l'invention produisent, lors de leur combustion, des particules de plus petites dimensions que celles produites par la combustion de propergol de même type de l'art antérieur. Le pourcentage du volume total (passant) correspondant à des particules de diamètre (équivalent sphérique) supérieur à 10 μm est ainsi inférieur à 15 %, généralement compris entre 2% et 10 %, pour les propergols de l'invention, bien inférieur à celui des propergols de référence de l'art antérieur (~ 30 %).  The solid propellants of the invention produce, during their combustion, particles of smaller dimensions than those produced by the propellant combustion of the same type of the prior art. The percentage of the total volume (passing) corresponding to particles of diameter (spherical equivalent) greater than 10 μm is thus less than 15%, generally between 2% and 10%, for the propellants of the invention, much lower than that reference propellants of the prior art (~ 30%).
Les courbes granulométriques des particules produites par la combustion des propergols de l'invention montrent toujours, comme celtes des propergols de l'art antérieur, un pic granulométrique centré sur environ 0,1 à 3 μm. Pour certains propergols de l'invention, on observe aussi, comme pour les propergols de l'art antérieur, un deuxième pic granulométrique correspondant à des particules de diamètre supérieur à 10 μm. Ce deuxième pic est centré vers 10 à 50 μm pour tes propergols de l'invention, valeurs inférieures à celles (60 à 100 μm) observées pour les propergols de l'art antérieur. Les propergols préférés de l'invention ne présentent pas ledit deuxième pic granulométrique et ne produisent donc qu'un pourcentage résiduel de particules de diamètre supérieur à 10 μm.  The grain size curves of the particles produced by the combustion of the propellants of the invention always show, like those of the propellants of the prior art, a particle size peak centered on approximately 0.1 to 3 μm. For some propellants of the invention, there is also observed, as for the propellants of the prior art, a second particle size peak corresponding to particles of diameter greater than 10 microns. This second peak is centered at 10 to 50 μm for the propellants of the invention, values lower than those (60 to 100 μm) observed for propellants of the prior art. The preferred propellants of the invention do not exhibit said second particle size peak and therefore only produce a residual percentage of particles with a diameter greater than 10 μm.
Selon un autre de ses objets, l'invention concerne un chargement de propergol solide contenant un propergol solide de l'invention. Selon encore un autre de ses objets, l'invention concerne un moteur de fusée comprenant au moins un chargement contenant un propergol de l'invention. According to another of its objects, the invention relates to a solid propellant charge containing a solid propellant of the invention. According to yet another of its objects, the invention relates to a rocket engine comprising at least one load containing a propellant of the invention.
L'invention a enfin pour objet une charge oxydante de perchlorate d'ammonium, notamment utile à la mise en œuvre du procédé d'obtention d'un propergol solide composite de l'invention tel que décrit ci- dessus, notamment utile à l'obtention d'un propergol solide composite de l'invention tel que décrit ci-dessus, Ladite charge est susceptible d'être obtenue par mélange d'au moins deux charges choisies parmi les première, seconde et troisième charges telles que définies ci-dessus (mélanges binaires ou ternaires), avantageusement susceptible d'être obtenue par mélange d'au moins une première charge et d'au moins une seconde charge (mélanges binaires) et éventuellement d'au moins une troisième charge (mélanges ternaires) telles que définies ci-dessus, très avantageusement susceptible d'être obtenue par mélange d'au moins une première charge et d'au moins une seconde charge (mélanges binaires) telles que définies ci-dessus. Elle contient avantageusement lesdites charges en les proportions pondérales précisées ci-dessus. L'invention est maintenant décrite, de façon nullement limitative, en référence aux figures annexées et aux exemples ci-après.  The invention finally relates to an oxidizing charge of ammonium perchlorate, in particular useful for the implementation of the method for obtaining a composite solid propellant of the invention as described above, in particular useful for obtaining a composite solid propellant of the invention as described above, said charge is obtainable by mixing at least two charges selected from the first, second and third charges as defined above ( binary or ternary mixtures), advantageously obtainable by mixing at least a first charge and at least a second charge (binary mixtures) and optionally at least a third charge (ternary mixtures) as defined herein. above, very advantageously capable of being obtained by mixing at least a first charge and at least a second charge (binary mixtures) as defined above. It advantageously contains said feeds in the weight proportions specified above. The invention is now described, in no way limiting, with reference to the accompanying figures and examples below.
La figure 1 montre un schéma de la combustion d'une goutte d'aluminium.  Figure 1 shows a diagram of the combustion of a drop of aluminum.
La figure 2 illustre les phénomènes produisant tes différentes granulométries d'alumine générées lors de la combustion d'un propergol solide.  FIG. 2 illustrates the phenomena producing the different alumina granulometries generated during the combustion of a solid propellant.
La figure 3 présente tes courbes granulométriques en volume, mesurées au moyen d'un granulomètre optique à corrélation de photons (PCS-DLS : Photons Corrélation Spectroscopy-Diffusion Light Scattering), des particules produites par le propergol préféré selon l'invention (voir l'exemple 9 ci-après) en comparaison à celles produites avec un propergol de référence de fart antérieur (voir ci-après).  FIG. 3 shows the volume particle size curves, measured by means of a photon correlation optical particle size analyzer (PCS-DLS: Photons Correlation Spectroscopy-Diffusion Light Scattering), particles produced by the preferred propellant according to the invention (see FIG. Example 9 below) in comparison with those produced with a reference propellant of prior art (see below).
Sur la figure 1, on a référencé ; en 1, le propergol solide, en 2, la surface de combustion dudît propergol solide, en 3, une goutte d'aluminium en combustion, en 4, la calotte d'alumine au bas de ladite goutte 3, en 5, la flamme et en 6, le panache de fumées. Sur la figure 2, on retrouve en 1 le propergol solide, en 2 sa surface de combustion, en 3 des gouttes d'aluminium, en 4 la calotte d'alumine au bas de gouttes 3 en combustion. Sur ladite figure 2, on a montré en 3' une goutte d'aluminium aggloméré, en 7 des fumées chargées en petites particules (diamètre d'environ 1 μm) et en 8 et 81 des particules d'oxydes résiduels (diamètre d'environ 0,5 - 4 μm et 40 - 100 μm, respectivement). In Figure 1, reference is made; in 1, the solid propellant, at 2, the combustion surface of said solid propellant, at 3, a drop of aluminum in combustion, at 4, the alumina cap at the bottom of said drop 3, at 5, the flame and in 6, the plume of smoke. In Figure 2, there is 1 solid propellant, 2 combustion surface, 3 drops of aluminum, 4 the alumina cap at the bottom of the drops 3 in combustion. In FIG. 2, a droplet of agglomerated aluminum is shown at 3 ', fumes loaded into small particles (diameter of about 1 μm) in 7, and residual oxide particles (diameter of 8 and 8) in 8 and 8 1 . about 0.5 - 4 μm and 40 - 100 μm, respectively).
On se propose maintenant d'illustrer l'invention par les exemples It is now proposed to illustrate the invention by the examples
(exemples de formulation de propergots de l'invention) ci-après. (Examples of propellant formulation of the invention) hereinafter.
Le tableau 1 ci-après donne les pourcentages massiques des constituants (PA, AI) de propergols solides selon l'invention, les propriétés balistiques desdits propergols ainsi que les granulométries de l'alumine produite lors de la combustion desdits propergols. Ces mêmes données sont indiquées pour trois propergols de référence. Les propergols solides du tableau 1 sont des propergols solides composites à liant polyuréthanne et contiennent une charge oxydante de perchlorate d'ammonium et une charge d'aluminium.  Table 1 below gives the mass percentages of the constituents (PA, AI) of solid propellants according to the invention, the ballistic properties of said propellants as well as the particle sizes of the alumina produced during the combustion of said propellants. These same data are given for three reference propellants. The solid propellants of Table 1 are solid polyurethane-bonded composite propellants and contain an oxidizing charge of ammonium perchlorate and an aluminum charge.
Les propergols de référence 1 et 2 ont une composition classique. Ils sont du type de ceux utilisés pour les applications spatiales. Le propergol de référence 3 montre l'influence de la forte présence (42 %) de petites particules de perchlorate d'ammonium sur la vitesse de combustion (logiquement on obtient alors de petites particules d'alumine).  Reference propellants 1 and 2 have a conventional composition. They are of the type used for space applications. The reference propellant 3 shows the influence of the strong presence (42%) of small particles of ammonium perchlorate on the rate of combustion (logically small alumina particles are then obtained).
Les propergols solides de l'invention selon tes exemples 1 à 12 présentent des vitesses de combustion et des exposants de pression mesurés à 5 MPa dans les gammes de vitesse et exposant attendues pour le domaine d'application ciblée, proches de ceux des propergots de référence 1 et 2.  The solid propellants of the invention according to Examples 1 to 12 have combustion rates and pressure exponents measured at 5 MPa in the expected speed and exponent ranges for the targeted range of application, close to those of the reference propellots. 1 and 2.
La dernière ligne du tableau 1 est relative au propergol M 12 du tableau 3 de Massa et al. (Journal of Propulsion and Power, vol. 24, N°2, The last line of Table 1 relates to the propellant M 12 of Table 3 of Massa et al. (Journal of Propulsion and Power, Vol 24, No. 2,
March-April 2008). Il renferme des particules de perchlorate d'ammonium de 200 μm (26,92 % = 27 %) et de 82,5 μm (40,38 % = 40 %) ainsi que des particules d'aluminium de 3 μm (20 %). March-April 2008). It contains ammonium perchlorate particles of 200 μm (26.92% = 27%) and 82.5 μm (40.38% = 40%) as well as aluminum particles of 3 μm (20%) .
Les enveloppes granulométriques des charges d'aluminium référencés dans Ie tableau 1 sont indiquées dans Ie tableau 2.  The size envelopes of the aluminum charges referenced in Table 1 are shown in Table 2.
Les particules d'alumine produites par les propergols solides du tableau 1 ont été récupérées en utilisant une enceinte pressurisée équipée d'un moyen de piégeage (moyen d'essai "piège rotatif précédemment décrit). Le mode opératoire de captation des particules est le suivant; The alumina particles produced by the solid propellants of the Table 1 was recovered using a pressurized chamber equipped with a trapping means (test means "rotary trap described above) .The procedure for capturing the particles is as follows;
- l'échantillon de propergol testé a Ia forme d'un cube (d'un centimètre d'arête) sans face inhibée ;  the propellant sample tested in the form of a cube (one centimeter of edge) without an inhibited face;
- le porte échantillon sur lequel est collé l'échantillon à tester est placé à l'intérieur du piège rotatif ;  the sample holder on which the sample to be tested is glued is placed inside the rotary trap;
- pendant l'essai, l'alcool contenu dans le piège rotatif se retrouve plaqué, sous la forme d'un film (d'une épaisseur d'environ 2 mm), sur les parois latérales du bol, grâce à la mise en rotation de ce dernier ;  during the test, the alcohol contained in the rotary trap is plated, in the form of a film (about 2 mm thick), on the side walls of the bowl, by rotating of the last ;
- la pression à l'intérieur de l'enceinte est réglée à 5 MPa relatifs. La pressurisation est effectuée par de l'azote et la distance entre l'échantillon de propergol et Ie film d'alcool est de 20 mm au départ de la combustion. Les particules émises sont prélevées horizontalement ;  - the pressure inside the chamber is set to 5 MPa relative. Pressurization is carried out by nitrogen and the distance between the propellant sample and the alcohol film is 20 mm from the combustion. The emitted particles are taken horizontally;
- la face libre du cube de propergol faisant face au film d'alcool est allumée (la durée très brève de la combustion permet de maintenir une surface de combustion quasi-constante).  the free face of the propellant cube facing the alcohol film is lit (the very short duration of the combustion makes it possible to maintain an almost constant combustion surface).
Le principe de récupération consiste à récupérer dans l'alcool les particules de la phase condensée émises dans les gaz de combustion de l'échantillon de propergol.  The principle of recovery consists in recovering in the alcohol the condensed phase particles emitted in the combustion gases of the propellant sample.
La distribution granulométrique, en volume, des particules récupérées est ensuite mesurée au moyen d'un granulomètre optique à corrélation de photons (PCS-DLS : Photons Corrélation Spectroscopy- Diffusion Light Scattering),  The particle size distribution, by volume, of the recovered particles is then measured by means of a photon correlation optical particle size analyzer (PCS-DLS: Photons Correlation Spectroscopy-Diffusion Light Scattering),
Avant d'être introduits dans le granulomètre, les résidus récupérés en suspension dans l'éthanol sont soumis à des ultrasons.  Before being introduced into the granulometer, the residues recovered in suspension in ethanol are subjected to ultrasound.
En référence à la figure 3, la distribution ou répartition granulométrique des particules recueillies dans l'éthanol pendant la combustion du propergol est exprimée sous la forme de deux courbes ; d'une part, l'histogramme donnant la fraction volumique des particules en fonction de la classe de diamètre sphérique équivalent des particules analysées, et, d'autre part, la courbe donnant la fraction volumique cumulée en fonction de la classe de diamètre sphérique équivalent des particules analysées. La figure 3 montre les courbes obtenues pour Ie propergol de référence i et celui de l'exemple 9 selon l'invention. With reference to FIG. 3, the particle size distribution or distribution of the particles collected in ethanol during the combustion of the propellant is expressed in the form of two curves; on the one hand, the histogram giving the volume fraction of the particles as a function of the class of equivalent spherical diameter of the particles analyzed, and, on the other hand, the curve giving the cumulated volume fraction as a function of the class of equivalent spherical diameter particles analyzed. FIG. 3 shows the curves obtained for the reference propellant i and that of example 9 according to the invention.
Le tableau 1 présente tes valeurs caractéristiques relevées sur les courbes granulométriques des particules récupérées produites par la combustion des propergols solides de référence et des exemples selon l'invention (voir les trois dernières colonnes dudit tableau 1).  Table 1 shows the characteristic values recorded on the particle size curves of the recovered particles produced by the combustion of the reference solid propellants and examples according to the invention (see the last three columns of Table 1).
Les compositions des propergols solides du tableau 1 sont données par Ie pourcentage massique de la charge de perchlorate d'ammonium et la constitution de cette charge (classe A/B/C), Ie pourcentage massique d'aluminium et sa classe granulométrique (précisée dans le tableau 2), le complément à 100% de la masse étant constitué du polymère polyol polybutadiène hydroxytéléchélique PBHT R45HTLO commercialisé par la société Sartomer, du réticulant MDCI, du plastifiant DOZ et d'additifs.  The compositions of the solid propellants of Table 1 are given by the mass percentage of the ammonium perchlorate charge and the constitution of this charge (class A / B / C), the mass percentage of aluminum and its particle size class (specified in Table 2), the complement to 100% of the mass consisting of the polymer polyol polybutadiene hydroxytelechelic PBHT R45HTLO sold by the company Sartomer, the crosslinking agent MDCI, the plasticizer DOZ and additives.
Les histogrammes granulométriques présentent toujours au moins un pic granulométrique pour des diamètres inférieurs à 10 μm. Les valeurs indiquées dans la colonne "DpkxlO μm" du tableau 1 correspondent à la valeur ou à la plage de valeurs (lorsqu'il y a plusieurs pics, où lorsque qu'une dispersion des valeurs est mesurée sur plusieurs essais) du ou des maximum desdits au moins un pic granulométrique pour des diamètres inférieurs à 10 μm mesurés. Lorsque la courbe granulométrique présente de plus un pic granulométrique pour des particules de diamètre supérieur à 10 μm, la valeur ou la plage de valeurs relevées (par exemple relevés sur plusieurs essais) du diamètre du maximum dudit pic granulométrique pour des particules de diamètre supérieur à 10 μm est indiquée dans la colonne "DpiolO μm" du tableau 1.  The particle size histograms always have at least one granulometric peak for diameters of less than 10 μm. The values given in the column "Dpkx10 μm" in Table 1 correspond to the value or the range of values (when there are several peaks, or when a dispersion of the values is measured over several tests) of the maximum said at least one granulometric peak for diameters less than 10 μm measured. When the granulometric curve furthermore has a particle size peak for particles with a diameter of greater than 10 μm, the value or the range of values recorded (for example taken from several tests) of the diameter of the maximum of said particle size peak for particles with a diameter larger than 10 μm. 10 μm is indicated in the column "DpiolO μm" of Table 1.
Les valeurs relevées pour "Dpic <10 μm" pour les propergols de l'invention sont proches de celles des références. Par contre, les valeurs de "DpiolO μm" pour les propergols de l'invention sont toutes inférieures à celtes des références 1 et 2. Pour les exemples 7, 8, 9, 11 et 12 selon l'invention, aucun pic de granuiométrie supérieure à 10 μm n'est observé.  The values recorded for "Dpic <10 μm" for the propellants of the invention are close to those of the references. On the other hand, the values of "DpiolO μm" for the propellants of the invention are all less than those of references 1 and 2. For Examples 7, 8, 9, 11 and 12 according to the invention, no peak of greater granulometry at 10 μm is observed.
Les propergols solides de l'invention produisent une quantité réduite de particules d'alumine de diamètre supérieur à 10 μm, par rapport aux propergols de référence 1 et 2. Ceci est exprimé, dans te tableau 1, par la valeur du pourcentage de volume (volume passant relevé sur la courbe donnant la fraction volumique cumulée en fonction de la classe de diamètre spbérique équivalent des particules analysées) correspondant aux classes de particules de diamètre supérieur à 10 μm. Tous les propergols de l'invention conduisent à un pourcentage de volume passant correspondant à des particules de diamètre supérieur à 10 μm très inférieur à celui du propergol de référence. The solid propellants of the invention produce a reduced amount of alumina particles larger than 10 μm in diameter, relative to the reference propellants 1 and 2. This is expressed in Table 1 by the value of the volume percentage ( volume passing up on the curve giving the cumulative volume fraction as a function of the equivalent spherical diameter class of the particles analyzed) corresponding to the classes of particles with a diameter greater than 10 μm. All the propellants of the invention lead to a passing volume percentage corresponding to particles of diameter greater than 10 microns much lower than that of the reference propellant.
Parmi les propergols solides listés dans le tableau 1 , on peut noter l'intérêt de ceux des exemples 8 et 9, qui présentent une vitesse de combustion proche de celle des propergols de référence (1 et 2) et produisent un très faible pourcentage de particules de diamètre supérieur à 10 μm.  Among the solid propellants listed in Table 1, we can note the interest of those of Examples 8 and 9, which have a combustion rate close to that of the reference propellants (1 and 2) and produce a very low percentage of particles. of diameter greater than 10 μm.
Le propergoi M12 du tableau 3 de Massa et al. (Journal of Propulsion and Power, vol. 24, N°2, March-April 2008) contient deux charges de perchlorate d'ammonium constituées de perchlorate d'ammonium de distribution granulométriques centrées, respectivement, sur 200 μm et 82,5 μm (donc centrées dans la plage des D50 des charges de classe A et B selon l'invention). The M12 propergoi of Table 3 of Massa et al. (Journal of Propulsion and Power, Volume 24, No. 2, March-April 2008) contains two ammonium perchlorate ammonium perchlorate feeds of particle size distribution centered on 200 μm and 82.5 μm, respectively ( therefore centered in the range of D 50 class A and B loads according to the invention).
Ledit propergol M12 présente une vitesse de combustion de 14 mm/s à 4 MPa (figure 12c). La vitesse de combustion des propergols solides augmentant avec la pression, la vitesse de combustion du propergol M12 à une pression de 5MPa (pression de référence pour, les- exemples de l'invention) ne peut être que supérieure à cette valeur de 14 mm/s. Elle est donc très supérieure à celles des propergols de référence 1 et 2.  Said propellant M12 has a combustion rate of 14 mm / s at 4 MPa (Figure 12c). As the burning speed of the solid propellants increases with the pressure, the burning rate of the M12 propellant at a pressure of 5 MPa (reference pressure for the examples of the invention) can only be greater than this value of 14 mm / s. It is therefore much higher than those of the reference propellants 1 and 2.
Ceci montre que la sélection de charges de perchlorate d'ammonium sur le seul critère de leur diamètre médian (D50) est insuffisante pour assurer à la fois une vitesse de combustion très proche de celtes des propergols de référence 1 et 2 et; un très faible pourcentage de particules d'alumine produite de diamètre supérieur à 10 μm (on rappelle incidemment ici que Massa et al. ne donne aucune information sur la granulométrie de i'aiumine produite). C'est donc en sélectionnant des charges de perchlorate de d'ammonium à spectres D10, D50 et D90 adaptés que la demanderesse a atteint l'objectif recherché. This shows that the selection of ammonium perchlorate feeds solely on the basis of their median diameter (D 50 ) is insufficient to ensure both a rate of combustion very close to that of the reference propellants 1 and 2 and; a very small percentage of alumina particles produced with a diameter of greater than 10 μm (it is recalled here incidentally that Massa et al does not give any information on the particle size of the product albumin). It is therefore by selecting charges of ammonium perchlorate with D 10 , D 50 and D 90 spectra adapted that the applicant has achieved the desired objective.

Claims

REVENDICATIONS
1. Procédé d'obtention d'un propergol solide composite, comprenant ;A process for obtaining a composite solid propellant, comprising;
- l'obtention d'une pâte par malaxage, dans un mélangeur, d'un mélange renfermant un polymère polyol liquide, une charge oxydante de perchlorate d'ammonium, une charge réductrice d'aluminium, au moins un agent de réticulation dudit polymère polyol liquide en une quantité telle que le rapport de pontage NCO/OH soit compris entre 0,8 et 1,1, soit avantageusement de 1, au moins un plastifiant, et au moins un additif ; - Obtaining a paste by mixing, in a mixer, a mixture containing a liquid polyol polymer, an oxidizing charge of ammonium perchlorate, a reducing charge of aluminum, at least one crosslinking agent of said polymer polyol liquid in an amount such that the NCO / OH bridging ratio is between 0.8 and 1.1, or preferably 1, at least one plasticizer, and at least one additive;
- la coulée de la pâte obtenue dans un moule ; - The casting of the paste obtained in a mold;
- la réticulation thermique de ladite pâte dans ledit moule ;  the thermal crosslinking of said paste in said mold;
caractérisé en ce que ladite charge oxydante de perchlorate d'ammonium dans ladite pâte résulte de l'introduction, dans ledit mélangeur, séparément ou en mélange, d'au moins : characterized in that said oxidative charge of ammonium perchlorate in said paste results from the introduction into said mixer, separately or in mixture, of at least:
+ une première charge dont la distribution granulométrique monomodale présente une valeur de Dio comprise entre 100 μm et 110 μm, une valeur de D50 comprise entre 170 μm et 220 μm et une valeur de D90 comprise entre 315 μm et 340 μm, et + a first charge whose monomodal particle size distribution has a Dio value between 100 μm and 110 μm, a D 50 value between 170 μm and 220 μm and a D 90 value between 315 μm and 340 μm, and
+ une seconde charge dont la distribution granulométrique monomodale présente une valeur de Dio comprise entre 15 μm et 20 μm, une valeur de D50 comprise entre 60 μm et 120 μm et une valeur de D90 comprise entre 185 μm et 220 μm ; et, éventuellement, + a second charge whose monomodal particle size distribution has a Dio value of between 15 μm and 20 μm, a value of D 50 of between 60 μm and 120 μm and a value of D 90 of between 185 μm and 220 μm; and eventually,
+ une troisième charge dont la distribution granulométrique monomodale présente une valeur de Dio comprise entre 1,7 μm et 3,6 μm, une valeur de D50 comprise entre 6 μm et 12 μm et une valeur de D90 comprise entre 20 μm et 32 μm. + a third charge whose monomodal particle size distribution has a Dio value between 1.7 μm and 3.6 μm, a D 50 value between 6 μm and 12 μm and a D 90 value between 20 μm and 32 μm. .mu.m.
2. Procédé selon la revendication 1, caractérisé en ce que ladite charge oxydante de perchlorate d'ammonium dans ladite pâte résulte de l'introduction, dans ledit mélangeur, séparément ou en mélange, de ladite première charge et de ladite seconde charge.  2. Method according to claim 1, characterized in that said oxidizing charge of ammonium perchlorate in said paste results from the introduction into said mixer, separately or in mixture, said first charge and said second charge.
3, Procédé selon la revendication 1 ou 2, caractérisé en ce que ladite charge oxydante de perchlorate d'ammonium dans ladite pâte résulte de l'introduction, dans ledit mélangeur, séparément ou en mélange, de ;  3, The method of claim 1 or 2, characterized in that said oxidizing charge of ammonium perchlorate in said dough results from the introduction into said mixer, separately or in mixture, of;
+ 12 à 70 % en masse de ladite première charge,  + 12 to 70% by weight of said first charge,
+ 10 à 81 % en masse de ladite seconde charge, + 0 à 23 % en masse de ladite troisième charge. + 10 to 81% by weight of said second charge, + 0 to 23% by weight of said third charge.
4. Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce que ladite charge oxydante de perchlorate d'ammonium dans ladite pâte résulte de l'introduction, dans ledit mélangeur, séparément ou en mélange, de :  4. Method according to any one of claims 1 to 3, characterized in that said oxidizing charge of ammonium perchlorate in said paste results from the introduction into said mixer, separately or in a mixture, of:
+ 12 à 61 % en masse de ladite première charge,  + 12 to 61% by weight of said first charge,
+ 36 à 81 % en masse de ladite seconde charge,  + 36 to 81% by weight of said second charge,
+ 0 à 23 % en masse de ladite troisième charge.  + 0 to 23% by weight of said third charge.
5. Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce que ladite charge oxydante de perchlorate d'ammonium dans ladite pâte résulte de l'introduction, dans ledit mélangeur, séparément ou en mélange, de :  5. Method according to any one of claims 1 to 3, characterized in that said oxidizing charge of ammonium perchlorate in said paste results from the introduction into said mixer, separately or in mixture, of:
+ 20 à 65 % en masse de ladite première charge, et  + 20 to 65% by weight of said first charge, and
+ 35 à 80 % en masse de ladite seconde charge,  + 35 to 80% by weight of said second charge,
6, Procédé selon la revendication 5, caractérisé en ce que ladite charge oxydante de perchlorate d'ammonium dans ladite pâte résulte de l'introduction, dans ledit mélangeur, séparément ou en mélange, de :  6, Process according to claim 5, characterized in that said oxidizing charge of ammonium perchlorate in said paste results from the introduction into said mixer, separately or as a mixture, of:
+ 42 à 61 % en masse de ladite première charge,  + 42 to 61% by weight of said first charge,
+ 39 à 58 % en masse de ladite seconde charge.  + 39 to 58% by weight of said second charge.
7. Procédé selon l'une quelconque des revendications 1 à 6, caractérisé en ce que ladite charge d'aluminium réductrice présente un diamètre médian inférieur ou égal à 40 μm, avantageusement compris entre 1 et 10 μm, avantageusement avec des valeurs de Dio et Dg0 de sa distribution granulométrique correspondant, respectivement, à au moins un quart de la valeur dudit diamètre médian et au plus à 4 fois la valeur dudit diamètre médian. 7. Method according to any one of claims 1 to 6, characterized in that said reducing aluminum charge has a median diameter less than or equal to 40 microns, advantageously between 1 and 10 microns, preferably with values of Dio and Dg 0 of its particle size distribution corresponding, respectively, to at least a quarter of the value of said median diameter and at most to 4 times the value of said median diameter.
8. Propergol solide composite à liant polyuréthanne chargé en perchlorate d'ammonium et en aluminium susceptible d'être obtenu par le procédé selon l'une quelconque des revendications 1 à 7.  8. Composite solid propellant with polyurethane binder loaded with ammonium perchlorate and aluminum obtainable by the method according to any one of claims 1 to 7.
9. Propergol solide selon la revendication 8, dont Ia combustion génère moins de 15 %, généralement entre 2 et 10 %, en volume de particules d'alumine dont le diamètre est supérieur à 10 μm.  9. Solid propellant according to claim 8, whose combustion generates less than 15%, generally between 2 and 10% by volume of alumina particles whose diameter is greater than 10 microns.
10. Propergol solide selon la revendication 8 ou 9, caractérisé en ce que, sur une plage de pression de fonctionnement de 3 à 10 MPa, sa vitesse de combustion est comprise entre 6 et 12 mm/s et son exposant de pression est compris entre 0,15 et 0,4; avantageusement entre 0,2 et 0,4. Solid propellant according to claim 8 or 9, characterized in that, over an operating pressure range of 3 to 10 MPa, its combustion is between 6 and 12 mm / s and its pressure exponent is between 0.15 and 0.4; advantageously between 0.2 and 0.4.
11. Chargement de propergol solide, caractérisé en ce qu'il contient un propergol solide selon l'une quelconque des revendications 8 à 10.  11. Loading solid propellant, characterized in that it contains a solid propellant according to any one of claims 8 to 10.
12. Moteur de fusée, caractérisé en ce qu'il comprend au moins un chargement selon la revendication 11.  Rocket engine, characterized in that it comprises at least one load according to claim 11.
13. Charge oxydante de perchlorate d'ammonium, notamment utile à la mise en œuvre du procédé d'obtention d'un propergol solide composite selon l'une quelconque des revendications 1 à 7, susceptible d'être obtenue par mélange d'au moins deux charges choisies parmi les première, seconde et troisième charges telles que définies à la revendication 1, avantageusement susceptible d'être obtenue par mélange d'au moins une première charge et d'au moins une seconde charge et éventuellement d'au moins une troisième charge telles que définies à la revendication 1, très avantageusement susceptible d'être obtenue par mélange d'au moins une première charge et d'au moins une seconde charge telles que définies à la revendication 1.  13. An oxidizing charge of ammonium perchlorate, in particular useful for carrying out the process for obtaining a composite solid propellant according to any one of claims 1 to 7, obtainable by mixing at least two charges selected from the first, second and third charges as defined in claim 1, advantageously obtainable by mixing at least a first charge and at least a second charge and possibly at least a third charge; charge as defined in claim 1, very advantageously obtainable by mixing at least a first charge and at least a second charge as defined in claim 1.
14. Charge oxydante selon la revendication 13, renfermant lesdites première, seconde et éventuellement troisième charges en les pourcentages massiques indiqués à l'une quelconque des revendications 3 à 6.  14. Oxidizing charge according to claim 13, containing said first, second and optionally third charges in the mass percentages indicated in any one of claims 3 to 6.
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