US20240286972A1 - Thermoplastic composite solid propellant and preparation method therefor - Google Patents
Thermoplastic composite solid propellant and preparation method therefor Download PDFInfo
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- US20240286972A1 US20240286972A1 US18/636,257 US202418636257A US2024286972A1 US 20240286972 A1 US20240286972 A1 US 20240286972A1 US 202418636257 A US202418636257 A US 202418636257A US 2024286972 A1 US2024286972 A1 US 2024286972A1
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- composite solid
- solid propellant
- thermoplastic composite
- thermoplastic
- bonding functional
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- 239000002131 composite material Substances 0.000 title claims abstract description 70
- 239000004449 solid propellant Substances 0.000 title claims abstract description 70
- 229920001169 thermoplastic Polymers 0.000 title claims abstract description 67
- 239000004416 thermosoftening plastic Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title description 4
- 229920002725 thermoplastic elastomer Polymers 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 26
- 238000002156 mixing Methods 0.000 claims abstract description 23
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 18
- 239000007800 oxidant agent Substances 0.000 claims abstract description 18
- 239000004014 plasticizer Substances 0.000 claims abstract description 18
- 125000000524 functional group Chemical group 0.000 claims abstract description 10
- 239000000446 fuel Substances 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 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 14
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims description 12
- 238000002844 melting Methods 0.000 claims description 12
- 230000008018 melting Effects 0.000 claims description 12
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 claims description 10
- MIMDHDXOBDPUQW-UHFFFAOYSA-N dioctyl decanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC MIMDHDXOBDPUQW-UHFFFAOYSA-N 0.000 claims description 10
- 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 8
- 238000002485 combustion reaction Methods 0.000 claims description 8
- GDDNTTHUKVNJRA-UHFFFAOYSA-N 3-bromo-3,3-difluoroprop-1-ene Chemical compound FC(F)(Br)C=C GDDNTTHUKVNJRA-UHFFFAOYSA-N 0.000 claims description 7
- 239000000028 HMX Substances 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 7
- UZGLIIJVICEWHF-UHFFFAOYSA-N octogen Chemical compound [O-][N+](=O)N1CN([N+]([O-])=O)CN([N+]([O-])=O)CN([N+]([O-])=O)C1 UZGLIIJVICEWHF-UHFFFAOYSA-N 0.000 claims description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- XYVVCFFJQVMSNN-UHFFFAOYSA-N cyclopenta-1,3-diene iron(2+) 5-octylcyclopenta-1,3-diene Chemical compound [Fe++].c1cc[cH-]c1.CCCCCCCC[c-]1cccc1 XYVVCFFJQVMSNN-UHFFFAOYSA-N 0.000 claims description 6
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 239000003381 stabilizer Substances 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 4
- JGDFBJMWFLXCLJ-UHFFFAOYSA-N copper chromite Chemical compound [Cu]=O.[Cu]=O.O=[Cr]O[Cr]=O JGDFBJMWFLXCLJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 4
- 238000007493 shaping process Methods 0.000 claims description 4
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 3
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 3
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 3
- 229940057995 liquid paraffin Drugs 0.000 claims description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 abstract description 18
- 230000001070 adhesive effect Effects 0.000 abstract description 18
- 239000007787 solid Substances 0.000 abstract description 12
- 239000000945 filler Substances 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 7
- 239000011159 matrix material Substances 0.000 abstract description 7
- 238000007791 dehumidification Methods 0.000 abstract description 6
- 230000003993 interaction Effects 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract 1
- 239000000463 material Substances 0.000 description 21
- 239000003380 propellant Substances 0.000 description 21
- 238000012360 testing method Methods 0.000 description 16
- 239000003995 emulsifying agent Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000007767 bonding agent Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 229920001187 thermosetting polymer Polymers 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- QWENRTYMTSOGBR-UHFFFAOYSA-N 1H-1,2,3-Triazole Chemical compound C=1C=NNN=1 QWENRTYMTSOGBR-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- -1 azide compound Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000006352 cycloaddition reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 239000013538 functional additive Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
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- 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
- C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
- C06B23/001—Fillers, gelling and thickening agents (e.g. fibres), absorbents for nitroglycerine
-
- 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
- C06B33/12—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 two or more oxygen-yielding compounds
- C06B33/14—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 two or more oxygen-yielding compounds at least one being an inorganic nitrogen-oxygen salt
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B45/00—Compositions or products which are defined by structure or arrangement of component of product
- C06B45/04—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive
- C06B45/06—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component
- C06B45/10—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component the organic component containing a resin
-
- 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
Definitions
- the present invention relates to the field of composite solid propellant technology, and in particular to a thermoplastic composite solid propellant and a preparation method thereof.
- Composite solid propellant is composed of a solid filler such as an oxidizing agent, a metal fuel, a small component functional auxiliary agent, and a polymeric adhesive.
- a solid filler such as an oxidizing agent, a metal fuel, a small component functional auxiliary agent, and a polymeric adhesive.
- the adhesive can bind the solid filler of the composite solid propellant and other components such as combustion catalyst, bonding agent, anti-aging agent and other functional additives to each other, while imparting an ideal configuration and structural integrity to the propellant.
- the adhesive matrix network structure of a thermosetting composite solid propellant is typically formed by chemical crosslinking reaction between a macromolecular prepolymer and a curing agent, such as, the condensation of hydroxyl-terminated polybutadiene and bifunctional isocyanate to generate an urethane, and the cycloaddition of a monosubstituted alkyne and an organic azide compound to yield a 1,2,3-triazole.
- a macromolecular prepolymer such as, the condensation of hydroxyl-terminated polybutadiene and bifunctional isocyanate to generate an urethane, and the cycloaddition of a monosubstituted alkyne and an organic azide compound to yield a 1,2,3-triazole.
- the chemically crosslinked network formed by covalent bond has many advantages, such as structural regularity, fewer dangling chains, and controllable curing parameters.
- thermosetting propellant slurry due to the limitation of “pot life” of the thermosetting propellant slurry, the slurry in which the mixing has been done or the curing agent has been added has to be poured into the engine combustion chamber as soon as possible.
- the temperature and humidity need to be strictly controlled for a long period of time to complete the curing crosslinking reaction, and the requirements for the related facilities in the curing site are harsh.
- the chemically crosslinked network formed by non-reversible covalent bonds makes the thermosetting composite solid propellant unable to be re-processed and formed. Once the propellant has quality problems or expires, it can only be destroyed by burning, causing waste of resources and environmental pollution.
- thermoplastic composite solid propellant has plastic-like repeatable molding characteristic and environmental stability, which can be prepared by small-scale continuous mixing, and does not require to produce the propellant massively and intensively. It is less dependent on the production conditions and environment such as mixing equipment and site, and can achieve a solvent-free, continuous processing. Thus, it is widely valued and studied as a green propellant variety.
- thermoplastic elastomer In the thermoplastic composite solid propellants, a thermoplastic elastomer is typically used as adhesive.
- the thermoplastic elastomer is generally a linear block polymer formed by copolymerization of linear soft segments and linear hard segments. Among them, a reversible physical crystalline network formed by hydrogen bonds between the hard segments achieves the solid-liquid conversion of the propellant.
- thermoplastic composite solid propellant determines the mechanical property of the thermoplastic composite solid propellant, that is, a weak interfacial effect between the thermoplastic adhesive matrix and the solid filler, so that a “dehumidification” phenomenon is very prone to occur in the propellant during the tensile failure process. Therefore, there is an urgent need to develop a thermoplastic composite solid propellant with enhanced interfacial effect, while seeking a safer and more efficient method for preparing a thermoplastic composite solid propellant in a slurry-free mixing manner.
- a first object of the present invention is to provide a thermoplastic composite solid propellant.
- a thermoplastic composite solid propellant a thermoplastic elastomer grafted or copolymerized with a bonding functional group is used as adhesive so that the adhesive matrix has a strong interaction with the solid filler, which can enhance the interfacial effect, and slow down the occurrence of “dehumidification” phenomenon in the tensile failure process.
- a second object of the present invention is to provide a method for preparing the above-described thermoplastic composite solid propellant. This method overcomes the shortcomings of the existing technology, and safely and efficiently prepares the thermoplastic composite solid propellant by means of acoustic resonance mixing, meeting the requirement for rapid charging of solid engines.
- thermoplastic composite solid propellant which comprises, in percentages by mass:
- the bonding functional group or block in the bonding functional thermoplastic elastomer comprises one or more of maleic anhydride, styrene, glycidyl methacrylate, butyl acrylate, hydroxyethyl acrylate, acrylic acid and methacrylic acid.
- the bonding functional group or block in the bonding functional thermoplastic elastomer has a mass percentage of 0.1 wt % to 5 wt %.
- the plasticizer comprises one or more of naphthenic oil, dioctyl sebacate, liquid paraffin and dioctyl phthalate.
- the oxidizing agent comprises one or more of ammonium perchlorate, ammonium nitrate, phase-stable ammonium nitrate, hexogen, octogen and 5,5′-bistetrazole-1,1′-dioxodihydroxylammonium salt.
- the functional auxiliary agent comprises a stabilizing agent and a combustion catalyst, wherein the stabilizing agent comprises one or more of N,N-dimethylaniline, N-methylaniline and diphenylamine; and the combustion catalyst comprises one or more of n-octylferrocene, ferric oxide and copper chromite.
- the stabilizing agent comprises one or more of N,N-dimethylaniline, N-methylaniline and diphenylamine
- the combustion catalyst comprises one or more of n-octylferrocene, ferric oxide and copper chromite.
- thermoplastic composite solid propellant comprising the steps of:
- the method for preparing the thermoplastic composite solid propellant further comprises: pouring the prepared thermoplastic composite solid propellant into a mold, which is naturally cooled and cured for shaping.
- the step S1 has a melting temperature of 85° C. to 95° C.
- the step S2 has a mixing temperature of 85° C. to 95° C., an acoustic resonance strength of 30 g to 70 g, and a resonance time of 5 min to 10 min.
- FIG. 1 is a process flow chart of a method for preparing a thermoplastic composite solid propellant of the present invention.
- thermoplastic composite solid propellant which comprises in percentages by mass: 5% to 16% of a bonding functional thermoplastic elastomer; 5% to 25% of a plasticizer; 5% to 18% of a metal fuel; 50% to 70% of an oxidizing agent; and 0.4% to 5% of a functional auxiliary agent; wherein a sum of the mass percentages of various materials in the thermoplastic composite solid propellant is 100%.
- the bonding functional thermoplastic elastomer (Bonding Functional TPE) of the present invention is obtained by grafting or copolymerizing a bonding functional group or block onto a thermoplastic elastomer, wherein the bonding functional group or block comprises one or more of maleic anhydride (MAH), styrene (St), glycidyl methacrylate (GMA), butyl acrylate (BA), hydroxyethyl acrylate (HEA), acrylic acid (AA) and methyl methacrylate (MMA), and the bonding functional group or block in the bonding functional thermoplastic elastomer has a mass percentage of 0.1 wt % to 5 wt %.
- the bonding functional group or block comprises one or more of maleic anhydride (MAH), styrene (St), glycidyl methacrylate (GMA), butyl acrylate (BA), hydroxyethyl acrylate (HEA), acrylic acid (AA)
- the bonding functional thermoplastic elastomer is, e.g., a maleic anhydride-grafted ethylene-vinyl acetate copolymer; and the bonding functional thermoplastic elastomer has a relative molecular mass of 21,000 to 40,000, a softening point temperature as adhesive of 85° C. to 95° C., a maximum tensile strength at 20° C. of 0.7 MPa to 4.9 MPa, and a maximum elongation at break of 485% to 1330%.
- the plasticizer comprises one or more of naphthenic oil (KN), dioctyl sebacate (DOS), liquid paraffin and dioctyl phthalate; and a mass ratio of the plasticizer to the bonding functional thermoplastic elastomer is (0.6-1.55):1.
- the metal fuel comprises, but is not limited to, aluminum powder (Al).
- the oxidizing agent comprises one or more of ammonium perchlorate (AP), ammonium nitrate (AN), phase-stable ammonium nitrate (PSAN), hexogen (RDX), octogen (HMX) and 5,5′-bistetrazole-1,1′-dioxodihydroxylammonium salt (TKX-50).
- AP ammonium perchlorate
- AN ammonium nitrate
- PSAN phase-stable ammonium nitrate
- RDX hexogen
- HMX octogen
- TKX-50 5,5′-bistetrazole-1,1′-dioxodihydroxylammonium salt
- the functional auxiliary agent comprises, but is not limited to, a stabilizing agent and a combustion catalyst, wherein the stabilizing agent comprises one or more of N,N-dimethylaniline (NN), N-methylaniline (NMA) and diphenylamine (NPA); and the combustion catalyst comprises one or more of n-octylferrocene, ferric oxide and copper chromite.
- the stabilizing agent comprises one or more of N,N-dimethylaniline (NN), N-methylaniline (NMA) and diphenylamine (NPA)
- the combustion catalyst comprises one or more of n-octylferrocene, ferric oxide and copper chromite.
- thermoplastic composite solid propellant is prepared by the steps of:
- the method further comprises pouring the thermoplastic composite solid propellant into a mold, which is naturally cooled, cured for shaping, and then stored.
- a square billet (shaped by curing of the thermoplastic composite solid propellant) is melted and poured into an engine shell for shaping, or loading the square billet into the engine shell and then melt and shaped, wherein a heating temperature during charging is 95° C. to 100° C.
- thermoplastic composite solid propellant which was poured into a mold, naturally cooled, and cured to give a propellant sample.
- thermoplastic composite solid propellant which was poured into a mold, naturally cooled, and cured to give a propellant sample.
- thermoplastic composite solid propellant which was poured into a mold, naturally cooled, and cured to give a propellant sample.
- thermoplastic composite solid propellant which was poured into a mold, naturally cooled, and cured to give a propellant sample.
- thermoplastic composite solid propellant which was poured into a mold, naturally cooled, and cured to give a propellant sample.
- thermoplastic composite solid propellant which was poured into a mold, naturally cooled, and cured to give a propellant sample.
- thermoplastic elastomer i.e., a non-Bonding Functional TPE
- plasticizer i.e., a high-shear dispersing emulsifier
- a functional auxiliary agent was added and mixed uniformly.
- the materials were transferred to an acoustic resonance mixer, heated to 90° C., and Al was added and pre-mixed.
- the Al was mixed uniformly by means of acoustic resonance with a resonance strength of 50 g for a resonance time of 5 min.
- thermoplastic composite solid propellant which was poured into a mold, naturally cooled, and cured to give a propellant sample.
- thermoplastic composite solid propellant prepared from the non-bonding functional thermoplastic elastomer the mechanical properties of the thermoplastic composite solid propellant prepared from the non-bonding functional thermoplastic elastomer (the maximum tensile strength ⁇ b is 0.43 MPa, and the elongation at break ⁇ m is 12%) are significantly lower than the mechanical properties of the thermoplastic composite solid propellant prepared from the bonding functional thermoplastic elastomer ( ⁇ b is 1.62 MPa, and ⁇ m is 25.5%).
- the present invention utilizes the bonding functional group-grafted or copolymerized thermoplastic elastomer as adhesive, so that the adhesive matrix has a strong interaction with the solid filler, which can enhance the interfacial effect and improve the mechanical properties of the propellant, thereby slowing down the occurrence of “dehumidification” phenomenon.
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- Crystallography & Structural Chemistry (AREA)
- Molecular Biology (AREA)
- Dispersion Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
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Abstract
Disclosed in the present invention is a thermoplastic composite solid propellant, which comprises, by mass: 5-16% of a thermoplastic elastomer having a bonding function; 5-25% of a plasticizer; 5-18% of a metal fuel; 50-70% of an oxidizing agent; and 0.4-5% of a functional auxiliary agent. In the thermoplastic composite solid propellant, a thermoplastic elastomer grafted or copolymerized with a bonding functional group is used as an adhesive, and an adhesive matrix and a solid filler have relatively strong interaction, such that an interfacial effect is enhanced, and the phenomenon of “dehumidification” in the tensile failure process can be slowed down. Further disclosed is a method for preparing the thermoplastic composite solid propellant. The method overcomes defects in the prior art, safely and efficiently prepares the thermoplastic composite solid propellant in an acoustic resonance mixing manner, and meets the requirements of a solid engine for rapid charging.
Description
- The present invention relates to the field of composite solid propellant technology, and in particular to a thermoplastic composite solid propellant and a preparation method thereof.
- Composite solid propellant is composed of a solid filler such as an oxidizing agent, a metal fuel, a small component functional auxiliary agent, and a polymeric adhesive. By mixing the solid filler with the polymeric adhesive uniformly, the adhesive can bind the solid filler of the composite solid propellant and other components such as combustion catalyst, bonding agent, anti-aging agent and other functional additives to each other, while imparting an ideal configuration and structural integrity to the propellant.
- The adhesive matrix network structure of a thermosetting composite solid propellant is typically formed by chemical crosslinking reaction between a macromolecular prepolymer and a curing agent, such as, the condensation of hydroxyl-terminated polybutadiene and bifunctional isocyanate to generate an urethane, and the cycloaddition of a monosubstituted alkyne and an organic azide compound to yield a 1,2,3-triazole. The chemically crosslinked network formed by covalent bond has many advantages, such as structural regularity, fewer dangling chains, and controllable curing parameters. However, due to the limitation of “pot life” of the thermosetting propellant slurry, the slurry in which the mixing has been done or the curing agent has been added has to be poured into the engine combustion chamber as soon as possible. The temperature and humidity need to be strictly controlled for a long period of time to complete the curing crosslinking reaction, and the requirements for the related facilities in the curing site are harsh. Also, the chemically crosslinked network formed by non-reversible covalent bonds makes the thermosetting composite solid propellant unable to be re-processed and formed. Once the propellant has quality problems or expires, it can only be destroyed by burning, causing waste of resources and environmental pollution.
- In order to overcome the above shortcomings, a class of curing agent-free, reusable thermoplastic elastomer (TPE) materials that avoid the limitation for the “pot life” of propellant slurry are used as the adhesive in the composite solid propellants. The thermoplastic composite solid propellant has plastic-like repeatable molding characteristic and environmental stability, which can be prepared by small-scale continuous mixing, and does not require to produce the propellant massively and intensively. It is less dependent on the production conditions and environment such as mixing equipment and site, and can achieve a solvent-free, continuous processing. Thus, it is widely valued and studied as a green propellant variety.
- In the thermoplastic composite solid propellants, a thermoplastic elastomer is typically used as adhesive. The thermoplastic elastomer is generally a linear block polymer formed by copolymerization of linear soft segments and linear hard segments. Among them, a reversible physical crystalline network formed by hydrogen bonds between the hard segments achieves the solid-liquid conversion of the propellant. However, because neither a reactive curing agent nor a bonding agent is used, the bulk structural characteristic of microphase separation in the elastomer determines the mechanical property of the thermoplastic composite solid propellant, that is, a weak interfacial effect between the thermoplastic adhesive matrix and the solid filler, so that a “dehumidification” phenomenon is very prone to occur in the propellant during the tensile failure process. Therefore, there is an urgent need to develop a thermoplastic composite solid propellant with enhanced interfacial effect, while seeking a safer and more efficient method for preparing a thermoplastic composite solid propellant in a slurry-free mixing manner.
- In response to the above problems, a first object of the present invention is to provide a thermoplastic composite solid propellant. In the thermoplastic composite solid propellant, a thermoplastic elastomer grafted or copolymerized with a bonding functional group is used as adhesive so that the adhesive matrix has a strong interaction with the solid filler, which can enhance the interfacial effect, and slow down the occurrence of “dehumidification” phenomenon in the tensile failure process.
- A second object of the present invention is to provide a method for preparing the above-described thermoplastic composite solid propellant. This method overcomes the shortcomings of the existing technology, and safely and efficiently prepares the thermoplastic composite solid propellant by means of acoustic resonance mixing, meeting the requirement for rapid charging of solid engines.
- A first technical solution adopted by the present invention is: a thermoplastic composite solid propellant, which comprises, in percentages by mass:
-
- 5% to 16% of a bonding functional thermoplastic elastomer;
- 5% to 25% of a plasticizer;
- 5% to 18% of a metal fuel;
- 50% to 70% of an oxidizing agent; and
- 0.4% to 5% of a functional auxiliary agent.
- Preferably, the bonding functional group or block in the bonding functional thermoplastic elastomer comprises one or more of maleic anhydride, styrene, glycidyl methacrylate, butyl acrylate, hydroxyethyl acrylate, acrylic acid and methacrylic acid.
- Preferably, the bonding functional group or block in the bonding functional thermoplastic elastomer has a mass percentage of 0.1 wt % to 5 wt %.
- Preferably, the plasticizer comprises one or more of naphthenic oil, dioctyl sebacate, liquid paraffin and dioctyl phthalate.
- Preferably, the oxidizing agent comprises one or more of ammonium perchlorate, ammonium nitrate, phase-stable ammonium nitrate, hexogen, octogen and 5,5′-bistetrazole-1,1′-dioxodihydroxylammonium salt.
- Preferably, the functional auxiliary agent comprises a stabilizing agent and a combustion catalyst, wherein the stabilizing agent comprises one or more of N,N-dimethylaniline, N-methylaniline and diphenylamine; and the combustion catalyst comprises one or more of n-octylferrocene, ferric oxide and copper chromite.
- A second technical solution adopted by the present invention is: a method for preparing a thermoplastic composite solid propellant comprising the steps of:
-
- S1: heating and melting a bonding functional thermoplastic elastomer and a plasticizer, adding a functional auxiliary agent, and mixing them uniformly;
- S2: adding a metal fuel and mix them uniformly by means of acoustic resonance;
- S3: adding an oxidizing agent in batches and mixing them uniformly by means of acoustic resonance to prepare the thermoplastic composite solid propellant.
- Preferably, the method for preparing the thermoplastic composite solid propellant further comprises: pouring the prepared thermoplastic composite solid propellant into a mold, which is naturally cooled and cured for shaping.
- Preferably, the step S1 has a melting temperature of 85° C. to 95° C.
- Preferably, the step S2 has a mixing temperature of 85° C. to 95° C., an acoustic resonance strength of 30 g to 70 g, and a resonance time of 5 min to 10 min.
- The above technical solutions have the following beneficial effects:
-
- (1) Currently, there is no effective bonding agent for the thermoplastic composite solid propellants. Therefore, there is a weak interfacial effect between the adhesive matrix and the solid filler, and a “dehumidification” phenomenon is prone to occur during the tensile failure process. Based on the theory of Neutral Polymeric Bonding Agent (NPBA), the thermoplastic composite solid propellant disclosed in the present invention utilizes a thermoplastic elastomer grafted or copolymerized with a bonding functional group as adhesive, so that the adhesive matrix has a strong interaction with the solid filler, which can enhance the interfacial effect, and slow down the occurrence of “dehumidification” phenomenon, improving the mechanical properties of the propellant.
- (2) The method for preparing the thermoplastic composite solid propellant disclosed in the present invention utilizes an acoustic resonance mixer to prepare the thermoplastic composite solid propellant. It is a brand-new slurry-free mixing technology, which breaks the material mixing boundary conditions with minimum energy by the principle of mechanical resonance and stimulates the materials to mix rapidly by self-vibration, greatly improving the preparation efficiency while increasing the process safety.
- (3) The thermosetting composite solid propellant forms a chemically crosslinked network by a irreversible reaction between a macromolecular prepolymer and a curing agent, in which the temperature and humidity need to be strictly controlled to complete the curing crosslinking reaction, and the requirements for the related facilities in the curing site are harsh. However, the thermoplastic composite solid propellant prepared in the present invention achieves the solid-liquid conversion by a reversible physical crystalline network formed by hydrogen bonds between the elastomer hard segments, which has repeatable molding characteristic. The residual materials generated during the processing can be recycled for reuse, and the expired or scrapped grain can also be post-processed via green process for reuse, meeting the green and environmental friendly concept.
- (4) In the method for preparing the thermoplastic composite solid propellant disclosed in the present invention, the thermoplastic adhesive and the propellant have a softening point temperature of 85° C. to 95° C., and has a repeatable processability.
- (5) In the method for preparing the thermoplastic composite solid propellant disclosed in the present invention, the acoustic resonance mixer is used to prepare the thermoplastic propellant; the slurry-free mixing greatly improves the mixing and preparation efficiency while improving the process safety; and the thermoplastic propellant slurry is not limited by the “pot life”, and the mixing and pouring processes are completely independent. The propellant has good application prospects in the fields such as rapid charging of solid engines and controllable energy release.
-
FIG. 1 is a process flow chart of a method for preparing a thermoplastic composite solid propellant of the present invention. - Hereinafter the present invention is further described by specific embodiments. It should be noted that several variations and improvements can be made by persons of ordinary skills in the art without departing from the principles of the present invention, which should be considered to fall within the protection scope of the present invention.
- The contents which are not described in detail in the specification of the present invention belong to well-known techniques of those skilled in the art.
- The present invention discloses a thermoplastic composite solid propellant, which comprises in percentages by mass: 5% to 16% of a bonding functional thermoplastic elastomer; 5% to 25% of a plasticizer; 5% to 18% of a metal fuel; 50% to 70% of an oxidizing agent; and 0.4% to 5% of a functional auxiliary agent; wherein a sum of the mass percentages of various materials in the thermoplastic composite solid propellant is 100%.
- The bonding functional thermoplastic elastomer (Bonding Functional TPE) of the present invention is obtained by grafting or copolymerizing a bonding functional group or block onto a thermoplastic elastomer, wherein the bonding functional group or block comprises one or more of maleic anhydride (MAH), styrene (St), glycidyl methacrylate (GMA), butyl acrylate (BA), hydroxyethyl acrylate (HEA), acrylic acid (AA) and methyl methacrylate (MMA), and the bonding functional group or block in the bonding functional thermoplastic elastomer has a mass percentage of 0.1 wt % to 5 wt %.
- The bonding functional thermoplastic elastomer is, e.g., a maleic anhydride-grafted ethylene-vinyl acetate copolymer; and the bonding functional thermoplastic elastomer has a relative molecular mass of 21,000 to 40,000, a softening point temperature as adhesive of 85° C. to 95° C., a maximum tensile strength at 20° C. of 0.7 MPa to 4.9 MPa, and a maximum elongation at break of 485% to 1330%.
- The plasticizer comprises one or more of naphthenic oil (KN), dioctyl sebacate (DOS), liquid paraffin and dioctyl phthalate; and a mass ratio of the plasticizer to the bonding functional thermoplastic elastomer is (0.6-1.55):1.
- The metal fuel comprises, but is not limited to, aluminum powder (Al).
- The oxidizing agent comprises one or more of ammonium perchlorate (AP), ammonium nitrate (AN), phase-stable ammonium nitrate (PSAN), hexogen (RDX), octogen (HMX) and 5,5′-bistetrazole-1,1′-dioxodihydroxylammonium salt (TKX-50).
- The functional auxiliary agent comprises, but is not limited to, a stabilizing agent and a combustion catalyst, wherein the stabilizing agent comprises one or more of N,N-dimethylaniline (NN), N-methylaniline (NMA) and diphenylamine (NPA); and the combustion catalyst comprises one or more of n-octylferrocene, ferric oxide and copper chromite.
- As shown in
FIG. 1 , the thermoplastic composite solid propellant is prepared by the steps of: -
- S1: heating the bonding functional thermoplastic elastomer and the plasticizer in a high-shear dispersing emulsifier (but not limited hereto) to 85° C. to 95° C. for melting, adding a functional auxiliary agent, and then mixing them uniformly;
- S2: transferring the uniformly mixed materials to an acoustic resonance mixer, adding a metal fuel, and mixing them uniformly by means of acoustic resonance for 5 min to 10 min at a mixing temperature of 85° C. to 95° C. and a resonance strength of 30 g to 70 g; and
- S3: adding a certain amount oxidizing agent in batches to the above materials, and mixing them uniformly by means of acoustic resonance to give the thermoplastic composite solid propellant.
- Further, in an embodiment, the method further comprises pouring the thermoplastic composite solid propellant into a mold, which is naturally cooled, cured for shaping, and then stored. During charging, a square billet (shaped by curing of the thermoplastic composite solid propellant) is melted and poured into an engine shell for shaping, or loading the square billet into the engine shell and then melt and shaped, wherein a heating temperature during charging is 95° C. to 100° C.
- The prepared thermoplastic composite solid propellant is characterized as follows:
-
- 1) Mechanical properties: the maximum tensile strength, σb, and the elongation at break, εm, of the mechanical properties are measured under the testing conditions of 20° C. and 100 mm/min with reference to GJB 770B-2005;
- 2) Density: the density is measured under the test conditions of 20° C., g/cm3 with reference to QJ 917A-97; and
- 3) Theoretical specific impulse.
- Materials were weighed according to the formula in Table 1. The bonding functional thermoplastic elastomer (Bonding Functional TPE) and the plasticizer were put into a high-shear dispersing emulsifier and heated to 90° C. for melting. Then, a functional auxiliary agent was added and mixed uniformly. The materials were transferred to an acoustic resonance mixer, heated to 90° C., and Al was added and pre-mixed. The Al was mixed uniformly by means of acoustic resonance with a resonance strength of 50 g for a resonance time of 5 min. Then, a certain amount of oxidizing agent was added in batches, and mixed uniformly by means of acoustic resonance to give the thermoplastic composite solid propellant, which was poured into a mold, naturally cooled, and cured to give a propellant sample.
-
TABLE 1 Formula and Properties of The Thermoplastic Composite Solid Propellant Composition of Formula Mass Percent/% wt Bonding Functional TPE 8.55 KN 6 DOS 2 Al 18 AP 59 AN / PSAN / RDX 6 NPA 0.1 n-octylferrocene 0.35 Maximum Tensile Elongation Sample Test Test Strength at Break Properties Standards Conditions σb/MPA εm/% Mechanical GJB 770B- 20° C., 1.62 25.5 Properties 2005 100 mm/min Density QJ 917A-97 20° C., g/cm3 1.71 Theoretical 20° C., 6.86 MPa, s 261.977 Specific Impulse - Various materials were weighed according to the formula in Table 2. The bonding functional thermoplastic elastomer (Bonding Functional TPE) and the plasticizer were put into a high-shear dispersing emulsifier and heated to 85° C. for melting. Then, a functional auxiliary agent was added and mixed uniformly. The materials were transferred to an acoustic resonance mixer, heated to 85° C., and Al was added and pre-mixed. The Al was mixed uniformly by means of acoustic resonance with a resonance strength of 30 g for a resonance time of 10 min. Then, a certain amount of oxidizing agent was added in batches, and mixed uniformly by means of acoustic resonance to give the thermoplastic composite solid propellant, which was poured into a mold, naturally cooled, and cured to give a propellant sample.
-
TABLE 2 Formula and Properties of The Thermoplastic Composite Solid Propellant Composition of Formula Mass Percent/% wt Bonding Functional TPE 7.6 KN 7.2 DOS 1.7 Al 17 AP 59 AN 7 PSAN / 5,5′-bistetrazole-1,1′- / dioxodihydroxylammonium salt RDX / NN 0.1 n-octylferrocene 0.4 Sample Test Test Properties Standards Conditions σb/MPA εm/% Mechanical GJB 770B- 20° C., 1.57 23.8 Properties 2005 100 mm/min Density QJ 917A-97 20° C., g/cm3 1.696 Theoretical 20° C., 6.86 MPa, s 259.975 Specific Impulse - Materials were weighed according to the formula in Table 3. The bonding functional thermoplastic elastomer (Bonding Functional TPE) and the plasticizer were put into a high-shear dispersing emulsifier and heated to 85° C. for melting. Then, a functional auxiliary agent was added and mixed uniformly. The materials were transferred to an acoustic resonance mixer, heated to 90° C., and Al was added and pre-mixed. The Al was mixed uniformly by means of acoustic resonance with a resonance strength of 70 g for a resonance time of 5 min. Then, a certain amount of oxidizing agent was added in batches, and mixed uniformly by means of acoustic resonance to give the thermoplastic composite solid propellant, which was poured into a mold, naturally cooled, and cured to give a propellant sample.
-
TABLE 3 Formula and Properties of The Thermoplastic Composite Solid Propellant Composition of Formula Mass Percent/% wt Bonding Functional TPE 9.94 KN 9.5 Al 17 AP 51 AN / PSAN 8 5,5′-bistetrazole-1,1′- / dioxodihydroxylammonium salt HMX 4 NMA 0.16 Fe2O3 0.4 Sample Test Test Properties Standards Conditions σb/MPA εm/% Mechanical GJB 770B- 20° C., 1.29 36.6 Properties 2005 100 mm/min Density QJ 917A-97 20° C., g/cm3 1.657 Theoretical 20° C., 6.86 MPa, s 253.397 Specific Impulse - Materials were weighed according to the formula in Table 4. The bonding functional thermoplastic elastomer (Bonding Functional TPE) and the plasticizer were put into a high-shear dispersing emulsifier and heated to 95° C. for melting. Then, a functional auxiliary agent was added and mixed uniformly. The materials were transferred to an acoustic resonance mixer, heated to 95° C., and Al was added and pre-mixed. The Al was mixed uniformly by means of acoustic resonance with a resonance strength of 50 g for a resonance time of 8 min. Then, a certain amount of oxidizing agent was added in batches, and mixed uniformly by means of acoustic resonance to give the thermoplastic composite solid propellant, which was poured into a mold, naturally cooled, and cured to give a propellant sample.
-
TABLE 4 Formula and Properties of The Thermoplastic Composite Solid Propellant Composition of Formula Mass Percent/% wt Bonding Functional TPE 6 DOS 5.5 Al 18 AP 49 AN / PSAN / 5,5′-bistetrazole-1,1′- / dioxodihydroxylammonium salt RDX 21 NN 0.15 Copper Chromite 0.5 Sample Test Test Properties Standards Conditions σb/MPA εm/% Mechanical GJB 770B- 20° C., 1.42 16.8 Properties 2005 100 mm/min Density QJ 917A-97 20° C., g/cm3 1.784 Theoretical 20° C., 6.86 MPa, s 266.391 Specific Impulse - Materials were weighed according to the formula in Table 5. The bonding functional thermoplastic elastomer (Bonding Functional TPE) and the plasticizer were put into a high-shear dispersing emulsifier and heated to 95° C. for melting. Then, a functional auxiliary agent was added and mixed uniformly. The materials were transferred to an acoustic resonance mixer, heated to 95° C., and Al was added and pre-mixed. The Al was mixed uniformly by means of acoustic resonance with a resonance strength of 50 g for a resonance time of 5 min. Then, a certain amount of oxidizing agent was added in batches, and mixed uniformly by means of acoustic resonance to give the thermoplastic composite solid propellant, which was poured into a mold, naturally cooled, and cured to give a propellant sample.
-
TABLE 5 Formula and Properties of Thermoplastic Composite Solid Propellant Composition of Formula Mass Percent/% wt Bonding Functional TPE 15.2 KN 6.2 DOS 3 Al 17 AP 48 AN / PSAN 4 HMX 6 NBA 0.15 Fe2O3 0.45 Sample Test Test Properties Standards Conditions σb/MPA εm/% Mechanical GJB 770B- 20° C., 0.86 48.3 Properties 2005 100 mm/min Density QJ 917A-97 20° C., g/cm3 1.597 Theoretical 20° C., 6.86 MPa, s 246.029 Specific Impulse - Materials were weighed according to the formula in Table 6. The bonding functional thermoplastic elastomer (Bonding Functional TPE) and the plasticizer were put into a high-shear dispersing emulsifier and heated to 95° C. for melting. Then, a functional auxiliary agent was added and mixed uniformly. The materials were transferred to an acoustic resonance mixer, heated to 95° C., and Al was added and pre-mixed. The Al was mixed uniformly by means of acoustic resonance with a resonance strength of 50 g for a resonance time of 5 min. Then, a certain amount of oxidizing agent was added in batches, and mixed uniformly by means of acoustic resonance to give the thermoplastic composite solid propellant, which was poured into a mold, naturally cooled, and cured to give a propellant sample.
-
TABLE 6 Formula and Properties of Thermoplastic Composite Solid Propellant Composition of Formula Mass Percent/% wt Bonding Functional TPE 15 KN 20 DOS 5 Al 5 AP 40 AN / PSAN 4 HMX 6 NBA 1 Fe2O3 4 Sample Test Test Properties Standards Conditions σb/MPA εm/% Mechanical GJB 770B- 20° C., 0.59 57.6% Properties 2005 100 mm/min Density QJ 917A-97 20° C., g/cm3 1.382 Theoretical 20° C., 6.86 MPa, s 194.914 Specific Impulse - Materials were weighed according to the formula in Table 7. The thermoplastic elastomer (i.e., a non-Bonding Functional TPE) and the plasticizer were put into a high-shear dispersing emulsifier and heated to 90° C. for melting. Then, a functional auxiliary agent was added and mixed uniformly. The materials were transferred to an acoustic resonance mixer, heated to 90° C., and Al was added and pre-mixed. The Al was mixed uniformly by means of acoustic resonance with a resonance strength of 50 g for a resonance time of 5 min. Then, a certain amount of oxidizing agent was added in batches, and mixed uniformly by means of acoustic resonance to give the thermoplastic composite solid propellant, which was poured into a mold, naturally cooled, and cured to give a propellant sample.
-
TABLE 7 Formula and Properties of Thermoplastic Composite Solid Propellant Composition of Formula Mass Percent/% wt TPE 8.55 KN 6 DOS 2 Al 18 AP 59 AN / PSAN / RDX 6 NPA 0.1 n-octylferrocene 0.35 Sample Test Test Properties Standards Conditions σb/MPA εm/% Mechanical GJB 770B- 20° C., 0.43 12 Properties 2005 100 mm/min Density QJ 917A-97 20° C., g/cm3 1.69 Theoretical 20° C., 6.86 MPa, s 259.312 Specific Impulse - It can be seen from the data in Example 1 and Comparative Example 1, the mechanical properties of the thermoplastic composite solid propellant prepared from the non-bonding functional thermoplastic elastomer (the maximum tensile strength σb is 0.43 MPa, and the elongation at break εm is 12%) are significantly lower than the mechanical properties of the thermoplastic composite solid propellant prepared from the bonding functional thermoplastic elastomer (σb is 1.62 MPa, and εm is 25.5%). That is, the present invention utilizes the bonding functional group-grafted or copolymerized thermoplastic elastomer as adhesive, so that the adhesive matrix has a strong interaction with the solid filler, which can enhance the interfacial effect and improve the mechanical properties of the propellant, thereby slowing down the occurrence of “dehumidification” phenomenon.
- The present invention has been detailedly described as above with reference to the specific embodiments and exemplary examples. However, these descriptions should not be construed to limit the present invention. It is appreciated by those skilled in the art that various equivalent substitutions, modifications or improvements can be made to the technical solutions and embodiments of the invention without departing from the spirit and scope of the invention, all of which all fall within the scope of the invention. The scope of protection of the present invention is defined by the appended claims.
Claims (10)
1. A thermoplastic composite solid propellant, characterized by comprising, in percentages by mass: 5% to 16% of a thermoplastic elastomer with bonding function; 5% to 25% of a plasticizer; 5% to 18% of a metal fuel; 50% to 70% of an oxidizing agent; and 0.4% to 5% of a functional auxiliary agent.
2. The thermoplastic composite solid propellant according to claim 1 , characterized by that a bonding functional group or block in the bonding functional thermoplastic elastomer comprises one or more of maleic anhydride, styrene, glycidyl methacrylate, butyl acrylate, hydroxyethyl acrylate, acrylic acid and methacrylic acid.
3. The thermoplastic composite solid propellant according to claim 2 , characterized by that the bonding functional group or block in the bonding functional thermoplastic elastomer has a mass percentage of 0.1 wt % to 5 wt %.
4. The thermoplastic composite solid propellant according to claim 1 , characterized by that the plasticizer comprises one or more of naphthenic oil, dioctyl sebacate, liquid paraffin and dioctyl phthalate.
5. The thermoplastic composite solid propellant according to claim 1 , characterized by that the oxidizing agent comprises one or more of ammonium perchlorate, ammonium nitrate, phase-stable ammonium nitrate, hexogen, octogen and 5,5′-bistetrazole-1,1′-dioxodihydroxylammonium salt.
6. The thermoplastic composite solid propellant according to claim 1 , characterized by that the functional auxiliary agent comprises a stabilizing agent and a combustion catalyst, wherein the stabilizing agent comprises one or more of N,N-dimethylaniline, N-methylaniline and diphenylamine; and the combustion catalyst comprises one or more of n-octylferrocene, ferric oxide and copper chromite.
7. A method for preparing a thermoplastic composite solid propellant, characterized by comprising the steps of: S1: heating and melting a bonding functional thermoplastic elastomer and a plasticizer, adding a functional auxiliary agent, and mixing them uniformly; S2: adding a metal fuel and mixing them uniformly by means of acoustic resonance; and S3: add an oxidizing agent in batches and mixing them uniformly by means of acoustic resonance, to give the thermoplastic composite solid propellant.
8. The method for preparing the thermoplastic composite solid propellant according to claim 7 , characterized by further comprising: pouring the prepared thermoplastic composite solid propellant into a mold, which is naturally cooled and cured for shaping.
9. The method for preparing the thermoplastic composite solid propellant according to claim 7 , characterized by that the step S1 has a melting temperature of 85° C. to 95° C.
10. The method for preparing the thermoplastic composite solid propellant according to claim 7 , characterized by that the step S2 has a mixing temperature of 85° C. to 95° C., an acoustic resonance strength of 30 g to 70 g, and a resonance time of 5 min to 10 min.
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CN115322064A (en) * | 2022-07-28 | 2022-11-11 | 上海航天化工应用研究所 | Process method for rapidly mixing solid propellant through acoustic resonance and propellant |
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US3501357A (en) * | 1967-04-12 | 1970-03-17 | Asahi Chemical Ind | Composite propellants containing block copolymers |
US4361526A (en) * | 1981-06-12 | 1982-11-30 | The United States Of America As Represented By The Secretary Of The Army | Thermoplastic composite rocket propellant |
US4997498A (en) * | 1989-01-17 | 1991-03-05 | Sartomer Company, Inc. | Propellant with thermoplastic elastomer binder composed of macromolecular block with alkoxyalkyl acrylate termination |
US4986940A (en) * | 1989-11-06 | 1991-01-22 | Sartomer Company, Inc. | Curing process for the manufacture of thermoplastic elastomer binders |
US5009728A (en) * | 1990-01-12 | 1991-04-23 | The United States Of America As Represented By The Secretary Of The Navy | Castable, insensitive energetic compositions |
US4985094A (en) * | 1990-03-07 | 1991-01-15 | The United States Of America As Represented By The Secretary Of The Air Force | Thermoplastic castable composite rocket propellant |
US5368662A (en) * | 1992-09-29 | 1994-11-29 | Thiokol Corporation | TPE binder containing crystalline modifiers and solid propellants based thereon |
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