EP3956277A1 - Composite propellant manufacturing process based on deposition and light-activated polymerization for solid rocket motors - Google Patents
Composite propellant manufacturing process based on deposition and light-activated polymerization for solid rocket motorsInfo
- Publication number
- EP3956277A1 EP3956277A1 EP20720126.0A EP20720126A EP3956277A1 EP 3956277 A1 EP3956277 A1 EP 3956277A1 EP 20720126 A EP20720126 A EP 20720126A EP 3956277 A1 EP3956277 A1 EP 3956277A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- manufacturing process
- composite solid
- solid propellant
- ranging
- process according
- 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.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 81
- 239000002131 composite material Substances 0.000 title claims abstract description 51
- 239000007787 solid Substances 0.000 title claims abstract description 23
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 10
- 230000008021 deposition Effects 0.000 title claims description 23
- 239000003380 propellant Substances 0.000 title description 15
- 239000004449 solid propellant Substances 0.000 claims abstract description 52
- 239000000126 substance Substances 0.000 claims abstract description 44
- 239000003999 initiator Substances 0.000 claims abstract description 27
- 238000004132 cross linking Methods 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims description 39
- 238000000151 deposition Methods 0.000 claims description 24
- 239000000654 additive Substances 0.000 claims description 23
- 229910052751 metal Inorganic materials 0.000 claims description 23
- 239000002184 metal Substances 0.000 claims description 23
- 239000000843 powder Substances 0.000 claims description 23
- 230000000996 additive effect Effects 0.000 claims description 19
- 238000004040 coloring Methods 0.000 claims description 16
- 230000005855 radiation Effects 0.000 claims description 14
- 229920000642 polymer Polymers 0.000 claims description 13
- GDDNTTHUKVNJRA-UHFFFAOYSA-N 3-bromo-3,3-difluoroprop-1-ene Chemical compound FC(F)(Br)C=C GDDNTTHUKVNJRA-UHFFFAOYSA-N 0.000 claims description 12
- 239000005062 Polybutadiene Substances 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- 229920002857 polybutadiene Polymers 0.000 claims description 12
- 239000000446 fuel Substances 0.000 claims description 11
- 239000007800 oxidant agent Substances 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 10
- 238000003860 storage Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 8
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 8
- 230000003213 activating effect Effects 0.000 claims description 8
- 239000004411 aluminium Substances 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 229910052749 magnesium Inorganic materials 0.000 claims description 8
- 239000011777 magnesium Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052726 zirconium Inorganic materials 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 229910052796 boron Inorganic materials 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 5
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 4
- JSOGDEOQBIUNTR-UHFFFAOYSA-N 2-(azidomethyl)oxirane Chemical compound [N-]=[N+]=NCC1CO1 JSOGDEOQBIUNTR-UHFFFAOYSA-N 0.000 claims description 4
- XCYQVKRPRUBCEH-UHFFFAOYSA-N 2-nitroguanidine;perchloric acid Chemical compound OCl(=O)(=O)=O.NC(N)=N[N+]([O-])=O XCYQVKRPRUBCEH-UHFFFAOYSA-N 0.000 claims description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
- NDYLCHGXSQOGMS-UHFFFAOYSA-N CL-20 Chemical compound [O-][N+](=O)N1C2N([N+]([O-])=O)C3N([N+](=O)[O-])C2N([N+]([O-])=O)C2N([N+]([O-])=O)C3N([N+]([O-])=O)C21 NDYLCHGXSQOGMS-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- SQSPRWMERUQXNE-UHFFFAOYSA-N Guanylurea Chemical compound NC(=N)NC(N)=O SQSPRWMERUQXNE-UHFFFAOYSA-N 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 238000010545 Norrish reaction Methods 0.000 claims description 4
- 229920003006 Polybutadiene acrylonitrile Polymers 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 claims description 4
- BRUFJXUJQKYQHA-UHFFFAOYSA-O ammonium dinitramide Chemical compound [NH4+].[O-][N+](=O)[N-][N+]([O-])=O BRUFJXUJQKYQHA-UHFFFAOYSA-O 0.000 claims description 4
- 229910052790 beryllium Inorganic materials 0.000 claims description 4
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 125000004386 diacrylate group Chemical group 0.000 claims description 4
- AXZAYXJCENRGIM-UHFFFAOYSA-J dipotassium;tetrabromoplatinum(2-) Chemical compound [K+].[K+].[Br-].[Br-].[Br-].[Br-].[Pt+2] AXZAYXJCENRGIM-UHFFFAOYSA-J 0.000 claims description 4
- 150000002222 fluorine compounds Chemical class 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 150000002576 ketones Chemical class 0.000 claims description 4
- 238000003475 lamination Methods 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 239000000320 mechanical mixture Substances 0.000 claims description 4
- 229910001092 metal group alloy Inorganic materials 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- 229920000233 poly(alkylene oxides) Polymers 0.000 claims description 4
- 229920001610 polycaprolactone Polymers 0.000 claims description 4
- 239000004632 polycaprolactone Substances 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 229920000151 polyglycol Polymers 0.000 claims description 4
- 239000010695 polyglycol Substances 0.000 claims description 4
- 229920001451 polypropylene glycol Polymers 0.000 claims description 4
- 235000010333 potassium nitrate Nutrition 0.000 claims description 4
- 239000004323 potassium nitrate Substances 0.000 claims description 4
- 229910001487 potassium perchlorate Inorganic materials 0.000 claims description 4
- 238000010526 radical polymerization reaction Methods 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- MJVUDZGNBKFOBF-UHFFFAOYSA-N n-nitronitramide Chemical compound [O-][N+](=O)N[N+]([O-])=O MJVUDZGNBKFOBF-UHFFFAOYSA-N 0.000 claims description 3
- FIDRAVVQGKNYQK-UHFFFAOYSA-N 1,2,3,4-tetrahydrotriazine Chemical compound C1NNNC=C1 FIDRAVVQGKNYQK-UHFFFAOYSA-N 0.000 claims description 2
- XTFIVUDBNACUBN-UHFFFAOYSA-N 1,3,5-trinitro-1,3,5-triazinane Chemical compound [O-][N+](=O)N1CN([N+]([O-])=O)CN([N+]([O-])=O)C1 XTFIVUDBNACUBN-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 238000007906 compression Methods 0.000 claims description 2
- 230000006835 compression Effects 0.000 claims description 2
- 238000011109 contamination Methods 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 230000000007 visual effect Effects 0.000 claims description 2
- 239000002360 explosive Substances 0.000 abstract description 2
- 230000002940 repellent Effects 0.000 abstract 1
- 239000005871 repellent Substances 0.000 abstract 1
- 230000001988 toxicity Effects 0.000 abstract 1
- 231100000419 toxicity Toxicity 0.000 abstract 1
- 239000000306 component Substances 0.000 description 18
- 238000000034 method Methods 0.000 description 13
- 239000012948 isocyanate Substances 0.000 description 11
- 150000002513 isocyanates Chemical class 0.000 description 11
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 description 7
- 239000003431 cross linking reagent Substances 0.000 description 7
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 230000008030 elimination Effects 0.000 description 4
- 238000003379 elimination reaction Methods 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000001419 dependent effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- JOBBTVPTPXRUBP-UHFFFAOYSA-N [3-(3-sulfanylpropanoyloxy)-2,2-bis(3-sulfanylpropanoyloxymethyl)propyl] 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(COC(=O)CCS)(COC(=O)CCS)COC(=O)CCS JOBBTVPTPXRUBP-UHFFFAOYSA-N 0.000 description 2
- 230000000711 cancerogenic effect Effects 0.000 description 2
- 231100000357 carcinogen Toxicity 0.000 description 2
- 239000003183 carcinogenic agent Substances 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- RIWRBSMFKVOJMN-UHFFFAOYSA-N 2-methyl-1-phenylpropan-2-ol Chemical compound CC(C)(O)CC1=CC=CC=C1 RIWRBSMFKVOJMN-UHFFFAOYSA-N 0.000 description 1
- 238000010146 3D printing Methods 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- RGXCTRIQQODGIZ-UHFFFAOYSA-O isodesmosine Chemical compound OC(=O)C(N)CCCC[N+]1=CC(CCC(N)C(O)=O)=CC(CCC(N)C(O)=O)=C1CCCC(N)C(O)=O RGXCTRIQQODGIZ-UHFFFAOYSA-O 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001141 propulsive effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B21/00—Apparatus or methods for working-up explosives, e.g. forming, cutting, drying
- C06B21/0008—Compounding the ingredient
- C06B21/0025—Compounding the ingredient the ingredient being a polymer bonded explosive or thermic component
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- 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 present invention relates to heterogeneous energy materials and, in particular, to composite solid propellants for chemical rocket motors.
- the present invention relates to a manufacturing process, and to the relevant manufacturing plant, of composite solid propellants for chemical rocket motors.
- the present invention finds advantageous applications in the fields of civil and military aerospace propulsion (missiles, space launchers, naval guns), security (airbag) and emergency power generation systems (gas-generators, swelling systems, portable chemical extinguishing systems, warning signs) as well as in the civil and military explosive field.
- a polymer (step 100) is added with a photosensitive polymer (step 101), into which powdered oxidising elements (step 102), suitable crosslinking agents of the family of isocyanates (step 103) and a photo-initiator (step 104) are incorporated.
- the desired shape is imposed to the propellant thanks to a partial polymeric crosslinking borne by the photosensitive fraction (step 107), in order to obtain a structure capable of self-sustaining white maintaining the shape.
- step 108 provides the real and actual solidification ("curing") (step 108), which is carried out in a conventional way, by means of thermal cycles in appropriate ovens; this step is necessary for the definitive curing process by means of isocyanates, allowing the crosslinking of the remaining polymeric component.
- the process according to the aforesaid document does not make it possible to produce grains characterized by desired chemical non-uniformities, in order to better control the final performances of the grains themselves; in fact, it is not possible to vary the composition of the mixture and to obtain local modifications of the chemical composition used.
- a manufacturing process, and the relevant manufacturing plant, of composite solid propellants for chemical rocket motors able to realize geometries of the grain currently precluded with chemical gradients thereinside, would satisfy the needs of several applications such as, for example, the civil and military aerospace propulsion, security and emergency power generation systems.
- the present invention which relates to such a manufacturing process and to the relevant manufacturing plant, aims at responding to the aforesaid needs.
- the present invention aims at solving the technical problem concerning the internal geometries of the grain, necessary for the correct control and sizing of the thrust of the produced gas, currently severely limited by the manufacturing process based on mould casting and shaping with chuck.
- the present invention aims at achieving control of the chemical composition of the grain, allowing variations in the composition to better control the performance profile of the finished product; currently this has been achieved only with two different compositions with simple stratification (first part of grain composition A and second part of grain composition B, as per known technique developed for some military applications), therefore without a targeted local control.
- the present invention aims at decreasing the manufacturing risk associated with the curing step in oven with controlled temperature cycles; the elimination of this step not only aims at reducing costs, but also aims at reducing the risks associated with keeping at controlled temperature the almost shaped propellant grain.
- the present invention aims at reducing the chemical risk associated with the use of normally adopted crosslinking agents (isocyanates), which are known carcinogens; the replacement of these with suitable photo-initiators having characteristics of almost total non-toxicity reduces the risks associated with exposure during manufacturing, as well as the environmental impact during use, as well as the manufacturing cost.
- crosslinking agents isocyanates
- suitable photo-initiators having characteristics of almost total non-toxicity reduces the risks associated with exposure during manufacturing, as well as the environmental impact during use, as well as the manufacturing cost.
- the aforesaid publication reports how it is possible to print small specimens by exploiting the characteristic of high viscosity of the propellant using HTPB as a binder and then curing in oven, and how it is possible to obtain crosslinking with ultraviolet radiation for 30 minutes through the use of Illumabond 60-7105.
- the manufacturing process, and the relevant manufacturing plant, of composite solid propellant for chemical rocket motors according to the present invention for the first time, as far as the Inventors know, allows geometries nor realizable so far and local control of the chemical composition, substantially simplifying the associated manufacturing method, as well as reducing the risks related thereto (both in terms of safety, as well as from the point of view of chemical exposure to reagents).
- the present invention has, as advantages, the simplification of the process capable of reducing manufacturing and chemical exposure risks, as well as the total replacement of the curing step with temperature cycles, by means of ultraviolet radiation sufficient to obtain the finished product with exposure of only few seconds; the use of non-highly functionalized polymers also involves, together with the elimination of the isocyanates and the curing step under temperature control, the lowering of the manufacturing costs.
- Another independent aspect of the present invention relates to a manufacturing plant and forms the subject matter of claim 14.
- Another independent aspect of the present invention relates to a composite solid propellant for a chemical rocket motor and forms the subject matter of claim 20.
- FIG. 1 is a flowchart of a manufacturing process according to the prior art
- FIG. 2 is a flowchart of the manufacturing process according to the present invention
- FIG. 3 is a cut-away perspective view of a solid propellant rocket motor with the main components highlighted;
- FIG. 4 is a schematic representation of the manufacturing plant according to the present invention.
- the present invention is based on the innovative concept of using the photo crosslinking of a photosensitive polymer or of a resin made photosensitive by the addition of a suitable additive.
- HTPB hydroxyl terminated polybutadiene
- a normal polyaddition crosslinking requires the addition of isocyanates (NCO functional group) in order to connect the molecules to each other by the action between the NCO functional groups and the hydroxyl terminations.
- NCO functional group isocyanates
- photo-initiator means Darocur 1173 or similar for function and ability to actively interact with the selected polymeric components.
- crosslinking agent / curing agent means a compound belonging to the family of isocyanates.
- additive means all those components, solid or liquid, added to the mixture with the intention of modifying its rheological characteristics during processing, as well as the mechanical and/or ballistic performances of the finished product and/or of stability and/or of aging; in order to consider the compound as an additive and not as a main reagent, the concentration preferably stands at maximum values of 5% by weight and certainly not higher than 10% by weight.
- a manufacturing process according to the prior art comprises the following steps:
- step 106 continuously depositing the material
- step 108 curing the finished product with controlled temperature cycles
- a manufacturing process of a composite solid propellant 1 for a chemical rocket motor 50 forms an aspect independent and usable autonomously with respect to the other aspects of the invention, which process comprises the following steps:
- step 200 preparing at least one oxidising solid component 2 (step 200);
- step 201 - preparing at least one polymeric liquid component 3 (step 201);
- step 204 letting the mixture 5 to deposit through a deposition device 17 on a substrate or directly in the chemical rocket motor 50
- step 205 letting the mixture 5 to cure by light-activated polymerization through a lighting system 18, thus obtaining, by immediate crosslinking, the composite solid propellant 1 (step 205).
- the manufacturing process of a composite solid propellant 1 for a chemical rocket motor 50 further comprises, between steps 202 and 203, the following steps:
- the composite solid propellant 1 according to the present invention is a grain that, preferably, has a diameter ranging between 1 cm and 500 cm, preferably between 10 cm and 350 cm, with a length/ diameter ratio ranging between 0.1 and 50, preferably between 1 and 15.
- the oxidising solid component 2 is chosen from ammonium perchlorate, ammonium nitrate, ammonium dinitramide, l,3,5-Trinitroperhydro-l,3,5-triazine, l,3,5,7-Tetranitro-l,3,5,7-tetrazocane, 2,2-Dinitroethene-l,l-diammine, guanylurea dinitramide, Hexanitrohexaazaisowurtzitane, potassium nitrate, potassium perchlorate, sodium and nitro guanidine perchlorate, more preferably it is a crystalline oxidiser.
- the polymeric liquid component 3 is chosen from diacrylate polybutadiene, hydroxyl polybutadiene, carboxylic polybutadiene, polypropylene glycol, polyethylene glycol, polybutadiene acrylonitrile and similar acrylates, polyalkylene oxide, polycaprolactone, adipate polyglycol, glycidyl azide polymer, polyglycidyl nitrate, biazidomethyloxethane in copolymer with other polymeric or monomeric substances or with catalysts, more preferably it is a monomer or a prepolymer.
- the photo-initiator 4 is chosen from the compounds of the ketone family capable of activating radical polymerization reactions and, more preferably, from the compounds capable of activating the Norrish reactions; even more preferably the photo-initiator 4 is Darocure 1173.
- the powdered fuel 6, having micrometric or nanometric size is chosen from metal or metal alloys powders of beryllium, aluminium, boron, zirconium or magnesium, even mixed together; more preferably it is an aluminium metal powder; it is also possible the inclusion of nano-materials in the mixture with percentages higher than 5% .
- the specific advantage given by the addition of the powdered fuel 6 resides in the ballistic characteristics of the propellant, given the density increase of the propellant and the combustion temperature increase.
- the additive 7 is chosen from metal oxides (preferably of iron, lead, zirconium, copper, silicon or magnesium), their combinations at a level both atomic and in mechanical mixture, and fluorides (preferably of lithium).
- metal oxides preferably of iron, lead, zirconium, copper, silicon or magnesium
- fluorides preferably of lithium
- step 203 takes place under conditions below the ambient pressure, preferably between 300 mbar and 1 bar, for a mixing time ranging between half an hour and one day depending on the materials used and of the quantities employed, and at a temperature ranging between 35 °C and 100 °C, preferably ranging between 50 °C and 70 °C.
- the mixture 5 has viscosity property ranging between 400 Pa.s and 10,000 Pa.s.
- the deposition of step 204 takes place under conditions of ambient pressure and temperature, in a controlled composition atmosphere or standard air, with a speed ranging between 10 and 500 mm/s depending on the adopted deposition device 17, for a time ranging between 1 hour and 5 days, in relation to the size of the extruder nozzle (ranging from 0.5 mm to 5 cm in diameter), to the deposition thickness as well as to the volume to be extruded in order to realise the composite solid propellant 1.
- a cylindrical grain is considered characterized by a diameter of 50 cm and a height of 1.5 m with a central hole of 10 cm in diameter; this will be characterized by a volume of about 28.2743 cm 3 .
- step 205 takes place simultaneously with the deposition step 204, by means of an ultraviolet radiation system suitable for obtaining the composite solid propellant 1 and by radiating with the equivalent (in terms of exposure/ power ratio) of 100 mW / cm 2 for 30-60 seconds.
- the light-activated polymerization of step 205 takes place under conditions of ambient pressure and temperature, in a controlled composition atmosphere or standard air, by means of light-activated polymerization/ curing reaction of radical type, following radiation with an ultraviolet system suitable for obtaining the composite solid propellant 1.
- a chemical rocket motor 50 comprises a casing 55, often internally lined with an insulating layer 54, that insulates the casing 55 from the real and actual grain 1 and from the high temperatures during operation.
- a manufacturing plant 10 of a composite solid propellant 1 for a chemical rocket motor 50 also forms an aspect independent and usable autonomously with respect to the other aspects of the invention, which plant comprises:
- the manufacturing plant 10 further comprises:
- the manufacturing plant 10 further comprises:
- the mixer 16 is a device equipped with mechanical agitators capable of making the product homogeneous and with sealing systems to prevent contamination of the mixture 5 mixture, and it is made available to the deposition and/ or extrusion system.
- the deposition device 17 is a system equipped with a dispenser having known shape and dimensions with suitable apparatus for continuous supply of mixed product, which supply may occur by piston system, by worm screw or by other similar system; more preferably it is an extruder or a lamination system.
- the deposition device 17 is, in general, a supply system of the mixture then capable of extruding it through an opening or a nozzle of known dimensions, or by lamination of successive states with controlled thickness.
- the lighting system 18 is an ultraviolet or visible radiation lighting system and it is positioned together with the deposition device 17 for obtaining the immediate crosslinking of the mixture 5 and, consequently, the composite solid propellant 1.
- a composite solid propellant 1 for a chemical rocket motor 50 forms an aspect independent and usable autonomously with respect to the other aspects of the invention, which composite solid propellant 1 comprises:
- the composite solid propellant 1 is obtained by the manufacturing process or is produced in the manufacturing plant as previously described.
- the composite solid propellant 1 is a grain having a diameter ranging between 1 cm and 500 cm, preferably between 10 cm and 350 cm, with a length/ diameter ratio ranging between 0.1 and 50, preferably between 1 and 15.
- the composite solid propellant 1 of the invention contains oxidiser between 40 and 95% by weight, preferably between 60 and 90% by weight, metal powders between 0 and 30% by weight, preferably between 0 and 22% by weight, polymer or prepolymer between 5% and 40% by weight, preferably between 10 and 20% by weight, and has visual properties of an opaque solid, having a white colouring if formed without the use of metal powders and additives, or a light grey colouring if enriched with metal powders, or a different colouring depending on the possible additive used and on its natural colouring; to the touch it is a compact and homogeneous solid with a gummy-tending consistency; the desired mechanical characteristics requires a tensile failure strength ranging between 0.3 and 0.9 MPa and a compression failure strength ranging between 7 and 17 MPa.
- the at least one oxidising solid component 2 is chosen from ammonium perchlorate, ammonium nitrate, ammonium dinitramide, 1,3,5-Trinitroperhydro- 1,3,5-triazine, l,3,5,7-Tetranitro-l,3,5,7-tetrazocane, 2 2-Dinitroethene-l l-diammine guanylurea d ini tram ide, Hexanitrohexaazaisowurtzitane, potassium nitrate, potassium perchlorate, sodium and nitroguanidine perchlorate, more preferably it is a crystalline oxidiser.
- the at least one polymeric liquid component 3 is chosen from diacrylate polybutadiene, hydroxyl polybutadiene, carboxylic polybutadiene, polypropylene glycol, polyethylene glycol, polybutadiene acrylonitrile and similar acrylates, polyalkylene oxide, polycaprolactone, adipate polyglycol, glycidyl azide polymer, polyglycidyl nitrate, biazidomethyloxethane in copolymer with other polymeric or monomeric substances or with catalysts, more preferably it is a monomer or a prepolymer.
- the at least one photo-initiator 4 is chosen from the compounds of the ketone family capable of activating radical polymerization reactions and, more preferably, from the compounds capable of activating the Norrish reactions; even more preferably, the at least one photo initiator 4 is Darocure 1173.
- the composite solid propellant 1 further comprises:
- the at least one powdered fuel 6, having micrometric or nanometric size is chosen from metal or metal alloys powders of beryllium, aluminium, boron, zirconium or magnesium, even mixed together; more preferably it is an aluminium metal powder; it is also possible the inclusion of nano-materials in the mixture with percentages higher than 5% .
- the additive 7 is chosen from metal oxides (preferably of iron, lead, zirconium, copper, silicon or magnesium), their combinations at a level both atomic and in mechanical mixture, and fluorides (preferably of lithium).
- metal oxides preferably of iron, lead, zirconium, copper, silicon or magnesium
- fluorides preferably of lithium
- Example 1 The manufacturing process, the manufacturing plant and the composite solid propellant for chemical rocket motors according to the present invention are described in greater detail hereinbelow with reference to the following Examples, which have been developed on the basis of experimental data and which must be intended as illustrative but not limitative of the present invention.
- Example 1 The manufacturing process, the manufacturing plant and the composite solid propellant for chemical rocket motors according to the present invention are described in greater detail hereinbelow with reference to the following Examples, which have been developed on the basis of experimental data and which must be intended as illustrative but not limitative of the present invention.
- the samples obtained show integrity and compactness, they are characterized by a white colouring if in the absence of metal powders, a silver colouring in the presence of metal powders; the surface is corrugated and dry to the touch.
- the samples obtained show integrity and compactness, they are characterized by a white colouring if in the absence of metal powders, a light grey colouring in the presence of metal powders; the surface is corrugated and dry to the touch.
- variable thickness tested 0.5 - 0.8 - 1.0 - 1.3 - 1.5 - 1.8 - 2.0 - 2.2 mm
- intensity equal to about 100 mW / cm 2 for 30-60 seconds.
- the samples obtained show integrity and compactness, they are characterized by a slightly amber colouring if in the absence of metal powders, a light grey colouring in the presence of metal powders; the surface is corrugated and dry to the touch.
- variable thickness tested 0.5 - 0.8 - 1.0 - 1.3 - 1.5 - 1.8 - 2.0 - 2.2 mm
- intensity equal to about 100 mW / cm 2 for 30-60 seconds.
- the samples obtained show integrity and compactness, they are characterized by a slightly amber colouring if in the absence of metal powders, light grey colouring in the presence of metal powders; the surface is corrugated and dry to the touch.
- the tested ranges and values for the propellants according to the invention are calculated as the maximum and minimum obtained values from tests performed on the family of specimens made for each composition.
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Abstract
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IT102019000005788A IT201900005788A1 (en) | 2019-04-15 | 2019-04-15 | Composite propellant production process by deposition and photo-activated polymerization for solid propellant rockets |
PCT/IB2020/052947 WO2020212785A1 (en) | 2019-04-15 | 2020-03-27 | Composite propellant manufacturing process based on deposition and light-activated polymerization for solid rocket motors |
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US11879023B2 (en) * | 2020-08-21 | 2024-01-23 | United States Of America As Represented By The Secretary Of The Air Force | Articles comprising crosslinked polymer network comprising thioether crosslinks and process of making and using same |
CN113072415B (en) * | 2021-03-09 | 2022-04-19 | 西安近代化学研究所 | Ammonium dinitramide with moisture absorption preventing coating layer and preparation method thereof |
CN115073245A (en) * | 2021-03-10 | 2022-09-20 | 南京理工大学 | Rapid 3D printing and forming method for photo-thermal composite curing of butylated hydroxytoluene solid propellant |
CN113358429B (en) * | 2021-04-29 | 2022-10-14 | 上海航天化工应用研究所 | Medicine strip sample preparation device for static burning rate test of metal wire embedded propellant |
CN116947579B (en) * | 2023-07-31 | 2024-06-18 | 西安交通大学 | Method for improving curing depth of ultraviolet curing propellant by modifying aluminum powder surface |
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US5377593A (en) * | 1992-02-20 | 1995-01-03 | Thiokol Corporation | Interpenetrating network combination of ultraviolet and thermally cured rocket motor liner composition and method |
FR2983194B1 (en) * | 2011-11-29 | 2014-06-13 | Nexter Munitions | METHOD FOR MANUFACTURING PELLETS OF A COMPRESSABLE EXPLOSIVE COMPOSITION AND EXPLOSIVE MATERIAL OBTAINED WITH SUCH A METHOD |
EP3222408A1 (en) * | 2016-03-22 | 2017-09-27 | Nederlandse Organisatie voor toegepast- natuurwetenschappelijk onderzoek TNO | Energetic materials |
US20180194699A1 (en) * | 2016-12-05 | 2018-07-12 | Capco, Llc | Radiation curable energetic material compositions and methods of use |
CN107283826A (en) | 2017-06-28 | 2017-10-24 | 南京理工大学 | A kind of solid propellant 3D printing forming method solidified based on ultraviolet light |
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