EP3770136A1 - Festes verbund-treibmittel - Google Patents
Festes verbund-treibmittel Download PDFInfo
- Publication number
- EP3770136A1 EP3770136A1 EP20187229.8A EP20187229A EP3770136A1 EP 3770136 A1 EP3770136 A1 EP 3770136A1 EP 20187229 A EP20187229 A EP 20187229A EP 3770136 A1 EP3770136 A1 EP 3770136A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- particles
- propellant
- cuo
- composite solid
- solid propellant
- 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
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Classifications
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- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06D—MEANS FOR GENERATING SMOKE OR MIST; GAS-ATTACK COMPOSITIONS; GENERATION OF GAS FOR BLASTING OR PROPULSION (CHEMICAL PART)
- C06D5/00—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets
- C06D5/06—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets by reaction of two or more solids
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
- C06B23/007—Ballistic modifiers, burning rate catalysts, burning rate depressing agents, e.g. for gas generating
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B29/00—Compositions containing an inorganic oxygen-halogen salt, e.g. chlorate, 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
Definitions
- a composite propellant having a combustion rate exhibiting reduced sensitivity to pressure changes.
- the invention also relates to the application of this composite propellant as a propellant change of a rocket engine.
- Composite propellants are known for rocket propulsion and generally use a binder in which energetic charges are dispersed.
- a ballistic catalyst can be added to these compositions in order to increase the combustion rate and the thrust produced.
- iron oxide Fe 2 O 3 as a ballistic catalyst is known.
- size D50 is understood to mean the dimension given by the statistical particle size distribution to half of the population.
- the incorporation of a CuO copper oxide ballistic catalyst within the composite solid propellant formulation described above jointly achieves a high burn rate associated with a significant reduction in the pressure exponent, and this over a wide pressure range.
- the reduction of the pressure exponent n makes it possible to reduce the dependence of the combustion speed on the pressure and thus makes it possible to envisage being able to access a significant reduction in the operating dispersion of a solid propellant engine.
- the reduction of the pressure exponent makes it possible to reduce the operating fluctuations linked to the pressure fluctuations during the operation of the engine, thus leading to obtaining a more stable operating point of the engine.
- the reduction in operating dispersions contributes in particular to reducing the mechanical stresses to which the engine structure could be subjected in the event of maximum internal pressurization.
- the beneficial effect of the copper oxide CuO ballistic catalyst is obtained for a composite solid propellant exhibiting the bimodal size distribution described above for the oxidizing charge.
- Such a propellant is suitable for integration as a propellant charge for a space vehicle.
- the effect of lowering the pressure exponent following the incorporation of copper oxide CuO is not obtained in a notable manner if the particle size of the oxidizing charge differs from that described above.
- the copper oxide particles CuO have a BET specific surface area greater than or equal to 10 m 2 / g.
- Such a specific surface area advantageously makes it possible to further increase the combustion rate of the propellant.
- the mass content of copper oxide particles CuO is between 0.01% and 1%.
- the invention also relates to a propellant comprising a propellant body defining a combustion chamber in which a charge of the composite propellant as described above is present.
- the invention also relates to a space vehicle comprising a thruster as described above.
- the space vehicle can be a rocket launcher.
- the propellant comprises a binder comprising a crosslinked polymer polyol.
- the crosslinked polyol polymer is, for example, a crosslinked hydroxytelechelic polybutadiene (PBHT).
- the polymer polyol is crosslinked by a crosslinking agent.
- the crosslinking agent can be a diisocyanate. In this case, a polyurethane is obtained by crosslinking the polyol with the diisocyanate crosslinking agent.
- the binder may comprise a polymer polyol chain extender in a manner known per se.
- the oxidizing and reducing charges can be dispersed in the binder.
- the binder can constitute a polymer matrix coating the oxidizing and reducing charges.
- the oxidizing charge comprises particles of inorganic perchlorate.
- the inorganic perchlorate can be ammonium perchlorate (NH 4 ClO 4 ).
- the inorganic perchlorate particles exhibit a bimodal size distribution with (i) a first set of inorganic perchlorate particles having a first size D50 of between 150 ⁇ m and 250 ⁇ m and present in an amount of 50% to 60% by mass in the composite solid propellant, and (ii) a second set of inorganic perchlorate particles having a second size D50 of between 5 ⁇ m and 20 ⁇ m and present in an amount of 7% to 17% by mass in the composite solid propellant.
- the inorganic perchlorate particles can be present in the composite solid propellant in an overall mass content of between 64% and 70% (corresponding to the sum of the contents of the particles of the first and second sets).
- the size distribution of the inorganic perchlorate particles can be determined by laser diffraction technique, in a manner known per se.
- the figure 1 illustrates the bimodal size distribution of the inorganic perchlorate particles which can be used within the scope of the invention.
- the ordinate indicates the mass content in the propellant of the particles having this size x.
- the inorganic perchlorate particles define a first set E1 of perchlorate particles inorganic and a second set E2 of inorganic perchlorate particles.
- the bimodal distribution is asymmetric.
- the bimodal distribution presents two distinct peaks (maxima) P1 and P2.
- the height of the peak P1 of the distribution of the first set E1 may be different, for example greater than the height of the peak P2 of the distribution of the second set E2.
- the distribution of each of the first and second sets E1 and E2 can correspond to a normal distribution.
- the particles of the first set E1 have a first size D50 TM1 and the particles of the second set E2 have a second size D50 TM2.
- the first size D50 TM1 is larger than the second size D50 TM2.
- the second size D50 TM2 can be spaced from the first size D50 TM1 by at least two, or even at least three, standard deviations of the distribution of the first set E1.
- the reducing filler comprises particles of aluminum and / or an aluminum compound.
- the aluminum compound can be at least one of an aluminum alloy or alumina (Al 2 O 3 ).
- the particles of aluminum and / or of the aluminum compound can be present in the composite solid propellant in a mass content of between 17% and 23%.
- the propellant further comprises a ballistic catalyst comprising particles of copper oxide CuO.
- a ballistic catalyst comprising particles of copper oxide CuO.
- the mass content of copper oxide particles CuO in the propellant can be between 0.01% and 1%, for example between 0.1% and 1%, for example between 0.1% and 0.3% or between 0.3% and 1%.
- the particles of copper oxide CuO may have a BET specific surface area greater than or equal to 10 m 2 / g.
- Copper oxide CuO may be the sole ballistic catalyst present in the composite solid propellant.
- the composite propellant can be devoid of at least one of the following ballistic catalysts: a copper salt, an iron oxide, catalysts based on ferrocene, a chromium oxide, a nickel oxide, a cobalt oxide, a salt metallic lead, a salt of bismuth.
- the composite propellant may be devoid of at least one of the following compounds: nitrocellulose or nitroglycerin.
- the propellant can be made from the constituents mentioned above by using mixing and crosslinking techniques known to those skilled in the art which are not repeated here for the sake of brevity.
- the figure 2 shows a thruster body 1 comprising a structural envelope 11 defining a combustion chamber in which is present the charge of composite propellant 10.
- the thruster body comprises an igniter (not shown) intended to initiate the charging of propellant 10.
- the body of thruster can be part of a rocket engine and be a rocket launcher thruster body.
- the composite solid propellant may have a pressure exponent n in Vieille's law less than or equal to 0.2, preferably less than or equal to 0.1, over all or part of the pressure range 8-15 MPa in the combustion chamber.
- Example 1 comparison between the use of copper oxide CuO and iron oxide Fe 2 O 3 as a ballistic catalyst in a propellant formulation incorporating a bimodal distribution of oxidizing charge
- the aluminum powder used was a variety characterized by a regular grain morphology, obtained by atomization under an inert atmosphere (nitrogen) and of size D50 of about 30 ⁇ m.
- the figures 3 and 4 provide the results of the comparison of the ballistic characteristics obtained with this formulation depending on whether copper oxide CuO or iron Fe 2 O 3 is used as a ballistic catalyst.
- the formulation using copper oxide CuO incorporated at a rate of 0.25% by weight corresponds to curve “A” in these figures.
- Different grades of iron oxide Fe 2 O 3 were evaluated, corresponding to products of different particle size and / or specific surface area and / or purity and / or obtained by different manufacturing processes in order to demonstrate in each case l 'advantageous effect produced by the use of copper oxide CuO.
- These Fe 2 O 3 grades have been supplied from various producers / suppliers in the field and are representative of Fe 2 O 3 grades which can be used as a ballistic catalyst in space vehicle propellants.
- the propellant samples were produced on the same manufacturing means, namely a horizontal type mixer with a capacity of 5 liters.
- the formulations were identical except in terms of the nature of the ballistic catalyst (CuO or Fe 2 O 3 ).
- the propellant firing time was identical in each of the tests carried out.
- the test method and parameters were identical for the characterization ballistic.
- the combustion rate was measured by ultrasonic echo analysis, the samples having been preconditioned at + 20 ° C. before testing.
- the results obtained are provided to the figure 3 which shows the curves of combustion rate (Vc in mm / s) as a function of pressure (in MPa) for formulations catalyzed with CuO in comparison with those catalyzed by Fe 2 O 3 .
- the figure 4 shows the variation of the pressure exponent (n) as a function of the pressure (in MPa) for formulations catalyzed with CuO in comparison with those catalyzed by Fe 2 O 3 .
- the figures 3 and 4 illustrate the favorable impact generated by the use of copper oxide CuO on the ballistic characteristics of the propellant.
- This result should be compared with those obtained when Fe 2 O 3 is used for which the pressure exponent n is greater than or equal to 0.3 over the range 7-15 MPa.
- the nominal operating pressure range of the engine is between 4 MPa and 9.5 MPa.
- the maximum pressure, taking into account possible operating fluctuations during the combustion of the propellant charge, is around 10 MPa.
- the figure 3 shows that the use of CuO makes it possible to achieve combustion speed levels quite comparable to those obtained with Fe 2 O 3 over the operational operating range of the engine.
- the pressure exponent value decreases very strongly as it approaches 10 MPa, which corresponds to the upper limit of the operating range.
- the risk of pressure fluctuation which can generate a fluctuation of the operating point, and possibly a mechanical overpressure of the engine structure which can adversely affect its integrity is significantly reduced.
- the ballistic characteristics induced by the use of CuO thus make it possible to consider accessing more stable engine operations in this pressure range (when approaching the upper limit of 10 MPa), or even to consider being able to access optimized engine architectures as indicated previously. .
- the figure 5 makes it possible to indirectly confirm the advantageous impact induced by the use of CuO.
- the evolution of the combustion speed as a function of the pressure was determined for two formulations of propellant for space launchers:
- the first formulation evaluated was identical to that described above but catalyzed with 0.20% by mass of Fe 2 O 3 and implementation on a mixer of different technology (mixer with vertical blades of 1 gallon capacity).
- the curve marked "F” at figure 5 corresponds to the results obtained for this first formulation.
- the mass content of AP of average dimension centered on 200 ⁇ m was 54.8% by mass.
- the second formulation evaluated was identical to the first formulation but without Fe 2 O 3 ballistic catalyst. In this second formulation, the Fe 2 O 3 content was transferred to the AP content of average dimension centered on 200 ⁇ m which then represented 55% by mass.
- the curve marked "G” at figure 5 corresponds to the results obtained for this second formulation.
- the figure 5 illustrates the fact that the incorporation of Fe 2 O 3 within a composite propellant formulation leads, compared to an uncatalyzed base, to a notable increase in the value of the combustion speed over the operational operating range of the engine for space launcher. However, there is no appreciable improvement in the value of the pressure exponent over this same functional range compared to an uncatalyzed formulation (ie free of Fe 2 O 3 ).
- Example 1 demonstrated the advantage linked to the incorporation of copper oxide CuO as a ballistic catalyst.
- the tests in Example 1 were conducted on a propellant basis having a particular bimodal oxidative charge distribution which is suitable for use in a space vehicle.
- Example 2 to follow will now focus on evaluating the influence of the particle size of the oxidizing charge on the ballistic characteristics obtained for the propellant.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Adhesives Or Adhesive Processes (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR1908448A FR3099155B1 (fr) | 2019-07-25 | 2019-07-25 | Propergol solide composite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP3770136A1 true EP3770136A1 (de) | 2021-01-27 |
| EP3770136B1 EP3770136B1 (de) | 2021-10-20 |
Family
ID=69172859
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP20187229.8A Active EP3770136B1 (de) | 2019-07-25 | 2020-07-22 | Festes verbund-treibmittel |
Country Status (2)
| Country | Link |
|---|---|
| EP (1) | EP3770136B1 (de) |
| FR (1) | FR3099155B1 (de) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3255059A (en) * | 1962-07-09 | 1966-06-07 | North American Aviation Inc | Fluoroalkyl acrylate polymeric propellant compositions |
| EP0685368A1 (de) * | 1994-05-31 | 1995-12-06 | Morton International, Inc. | Extrudierbarer Gaserzeuger für hybride Airbagaufblasvorrichtung |
| US6217682B1 (en) * | 1997-10-27 | 2001-04-17 | Cordant Technologies Inc. | Energetic oxetane propellants |
| EP1216977A2 (de) * | 2000-12-22 | 2002-06-26 | Snpe | Kohlenwasserstoffbindemittel enthaltende pyrotechnische gaserzeugende Zusammensetzungen und Verfahren zur kontinuierlichen Herstellung |
| US20090260730A1 (en) * | 2006-05-02 | 2009-10-22 | Nippon Kayaku Kabushiki Kaisha | Gas generant composition for gas actuator for activating safety device and gas generator for gas actuator using the same |
| EP2551253A2 (de) * | 2011-07-27 | 2013-01-30 | Autoliv ASP, Inc. | Gaserzeugung über elementare carbonbasierte Zusammensetzungen |
| US20180170821A1 (en) * | 2016-12-15 | 2018-06-21 | Goodrich Corporation | Propellant |
-
2019
- 2019-07-25 FR FR1908448A patent/FR3099155B1/fr active Active
-
2020
- 2020-07-22 EP EP20187229.8A patent/EP3770136B1/de active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3255059A (en) * | 1962-07-09 | 1966-06-07 | North American Aviation Inc | Fluoroalkyl acrylate polymeric propellant compositions |
| EP0685368A1 (de) * | 1994-05-31 | 1995-12-06 | Morton International, Inc. | Extrudierbarer Gaserzeuger für hybride Airbagaufblasvorrichtung |
| US6217682B1 (en) * | 1997-10-27 | 2001-04-17 | Cordant Technologies Inc. | Energetic oxetane propellants |
| EP1216977A2 (de) * | 2000-12-22 | 2002-06-26 | Snpe | Kohlenwasserstoffbindemittel enthaltende pyrotechnische gaserzeugende Zusammensetzungen und Verfahren zur kontinuierlichen Herstellung |
| US20090260730A1 (en) * | 2006-05-02 | 2009-10-22 | Nippon Kayaku Kabushiki Kaisha | Gas generant composition for gas actuator for activating safety device and gas generator for gas actuator using the same |
| EP2551253A2 (de) * | 2011-07-27 | 2013-01-30 | Autoliv ASP, Inc. | Gaserzeugung über elementare carbonbasierte Zusammensetzungen |
| US20180170821A1 (en) * | 2016-12-15 | 2018-06-21 | Goodrich Corporation | Propellant |
Also Published As
| Publication number | Publication date |
|---|---|
| EP3770136B1 (de) | 2021-10-20 |
| FR3099155B1 (fr) | 2021-07-30 |
| FR3099155A1 (fr) | 2021-01-29 |
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