WO2023197546A1 - Thermoplastic composite solid propellant and preparation method therefor - Google Patents
Thermoplastic composite solid propellant and preparation method therefor Download PDFInfo
- Publication number
- WO2023197546A1 WO2023197546A1 PCT/CN2022/125619 CN2022125619W WO2023197546A1 WO 2023197546 A1 WO2023197546 A1 WO 2023197546A1 CN 2022125619 W CN2022125619 W CN 2022125619W WO 2023197546 A1 WO2023197546 A1 WO 2023197546A1
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- WO
- WIPO (PCT)
- Prior art keywords
- composite solid
- solid propellant
- thermoplastic composite
- thermoplastic
- propellant
- Prior art date
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- 239000004449 solid propellant Substances 0.000 title claims abstract description 71
- 239000002131 composite material Substances 0.000 title claims abstract description 70
- 229920001169 thermoplastic Polymers 0.000 title claims abstract description 68
- 239000004416 thermosoftening plastic Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229920002725 thermoplastic elastomer Polymers 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000007800 oxidant agent Substances 0.000 claims abstract description 18
- 239000004014 plasticizer Substances 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 125000000524 functional group Chemical group 0.000 claims abstract description 11
- 239000000446 fuel Substances 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 17
- 239000013538 functional additive Substances 0.000 claims description 15
- 230000001590 oxidative effect Effects 0.000 claims description 11
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims description 8
- 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 7
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-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
- 239000003381 stabilizer Substances 0.000 claims description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 5
- 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
- GDDNTTHUKVNJRA-UHFFFAOYSA-N 3-bromo-3,3-difluoroprop-1-ene Chemical compound FC(F)(Br)C=C GDDNTTHUKVNJRA-UHFFFAOYSA-N 0.000 claims description 4
- 239000000028 HMX Substances 0.000 claims description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 4
- MIMDHDXOBDPUQW-UHFFFAOYSA-N dioctyl decanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC MIMDHDXOBDPUQW-UHFFFAOYSA-N 0.000 claims description 4
- 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 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
- 238000001816 cooling Methods 0.000 claims description 3
- JGDFBJMWFLXCLJ-UHFFFAOYSA-N copper chromite Chemical compound [Cu]=O.[Cu]=O.O=[Cr]O[Cr]=O JGDFBJMWFLXCLJ-UHFFFAOYSA-N 0.000 claims description 3
- 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 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
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 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
- 150000003839 salts Chemical class 0.000 claims description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-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 1
- 150000002148 esters Chemical class 0.000 claims 1
- 239000000853 adhesive Substances 0.000 abstract description 12
- 230000001070 adhesive effect Effects 0.000 abstract description 12
- 239000007787 solid Substances 0.000 abstract description 11
- 239000000945 filler Substances 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 7
- 239000011159 matrix material Substances 0.000 abstract description 7
- 230000003993 interaction Effects 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract 1
- 238000007791 dehumidification Methods 0.000 abstract 1
- 239000003380 propellant Substances 0.000 description 21
- 239000000463 material Substances 0.000 description 20
- 239000003795 chemical substances by application Substances 0.000 description 12
- 238000012546 transfer Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000004945 emulsification Methods 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 229920001187 thermosetting polymer Polymers 0.000 description 4
- 239000007767 bonding agent Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 239000000126 substance Substances 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
- 238000005516 engineering process Methods 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
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920005596 polymer binder Polymers 0.000 description 2
- 239000002491 polymer binding agent Substances 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 238000012360 testing method 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
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-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
- 239000003963 antioxidant agent Substances 0.000 description 1
- -1 azide compounds 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
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000006352 cycloaddition reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000010438 heat treatment Methods 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
- 150000004702 methyl esters Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 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 invention relates to the technical field of composite solid propellants, and in particular to a thermoplastic composite solid propellant and a preparation method thereof.
- Composite solid propellant is composed of solid fillers such as oxidizer, metal fuel, small component functional additives and polymer binder; by uniformly mixing the solid filler and polymer binder, the binder can combine the solid fillers of the composite solid propellant And other components such as burning rate catalysts, bonding agents, antioxidants and other functional additives bond with each other, while giving the propellant the ideal configuration and structural integrity.
- solid fillers such as oxidizer, metal fuel, small component functional additives and polymer binder
- thermosetting composite solid propellant is generally formed through a chemical cross-linking reaction between a polymer prepolymer and a curing agent, such as the condensation of hydroxyl-terminated polybutadiene and bifunctional isocyanate to form urethane.
- a curing agent such as the condensation of hydroxyl-terminated polybutadiene and bifunctional isocyanate to form urethane.
- the cycloaddition of monosubstituted alkynes and organic azide compounds yields 1,2,3-triazole; the chemical cross-linked network formed through covalent bonds has many advantages, such as regular structure, fewer dangling chains, and flexible curing parameters.
- thermosetting propellant slurry due to the limitation of the "potency period" of the thermosetting propellant slurry, the slurry after mixing or adding the curing agent needs to be poured into the engine combustion chamber as soon as possible; the completion of the curing cross-linking reaction requires a long period of time with temperature, The humidity must be strictly controlled, and the requirements for related facilities in the curing site are stringent; the chemical cross-linked network composed of 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 will be discarded. It can only be burned and destroyed, causing waste of resources and environmental pollution.
- thermoplastic elastomer (TPE) material that does not contain curing agents, avoids the "pot life" limitation of propellant slurries, and is reusable is used in composite solid propellant adhesives;
- thermoplastic Composite solid propellant has plastic-like repetitive processing and molding characteristics and environmental stability. It can be prepared by small-scale continuous mixing. It does not require large-scale and centralized propellant production and is relatively dependent on production conditions and environment such as mixing equipment and sites. It is weak and can achieve solvent-free continuous processing, so it has been widely valued and studied as a green propellant variety.
- Thermoplastic composite solid propellants usually use thermoplastic elastomers as binders.
- Thermoplastic elastomers are generally linear block polymers, which are composed of linear soft segments and linear hard segments copolymerized. Among them, reversible physical hydrogen bonds between hard segments form The crystalline network realizes the solid-liquid conversion of the propellant; however, since no reactive curing agent and bonding agent are used, the bulk structural characteristics of the elastomer microphase separation determine the mechanical properties of the thermoplastic composite solid propellant, that is, the thermoplastic adhesive matrix and the solid
- the interface effect between fillers is weak, and the propellant is prone to "dewetting" during the tensile failure process; therefore, there is an urgent need to develop a thermoplastic composite solid propellant with enhanced interface effect, and at the same time, a safer and more efficient Preparation of thermoplastic composite solid propellant by slurry-free mixing method.
- the 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 bonded functional groups is used as an adhesive.
- the adhesive matrix and the solid propellant are Fillers have strong interaction, which can enhance the interface effect and slow down the occurrence of "dewetting" phenomenon during tensile failure.
- the second object of the present invention is to provide the above-mentioned preparation method of thermoplastic composite solid propellant. This method overcomes the shortcomings of the existing technology and uses acoustic resonance mixing to safely and efficiently prepare thermoplastic composite solid propellant to meet the needs of solid engines. Rapid charging requirements.
- thermoplastic composite solid propellant which includes the following components in mass percentage:
- Thermoplastic elastomer with bonding function 5% ⁇ 16%
- Plasticizer 5% ⁇ 25%
- Metal fuel 5% ⁇ 18%
- Oxidizing agent 50% ⁇ 70%
- the bonding functional groups or blocks in the thermoplastic elastomer with bonding function include maleic anhydride, styrene, glycidyl methacrylate, butyl acrylate, hydroxyethyl acrylate, acrylic acid and methacrylic acid.
- the bonding functional groups or blocks in the thermoplastic elastomer with bonding function include maleic anhydride, styrene, glycidyl methacrylate, butyl acrylate, hydroxyethyl acrylate, acrylic acid and methacrylic acid.
- One or more of the methyl esters include maleic anhydride, styrene, glycidyl methacrylate, butyl acrylate, hydroxyethyl acrylate, acrylic acid and methacrylic acid.
- One or more of the methyl esters include maleic anhydride, styrene, glycidyl methacrylate, butyl acrylate, hydroxyethy
- the mass percentage of bonded functional groups or blocks in the thermoplastic elastomer with bonding function is 0.1 wt% to 5 wt%.
- the plasticizer includes one or more of naphthenic oil, dioctyl sebacate, liquid paraffin and dioctyl phthalate.
- the oxidizing agent includes ammonium perchlorate, ammonium nitrate, phase-stable ammonium nitrate, rhodamine, octogen and 5,5'-bistetrazole-1,1'-dioxodihydroxylammonium salt one or more of them.
- the functional auxiliary agent includes a stabilizer and a burning rate catalyst, wherein the stabilizer includes one or more of N,N-dimethylaniline, N-methylaniline and diphenylamine;
- the burning rate catalyst includes one or more of n-octylferrocene, ferric oxide and copper chromite.
- thermoplastic composite solid propellant including the following steps:
- the preparation method of the thermoplastic composite solid propellant further includes: pouring the prepared thermoplastic composite solid propellant into a mold, and allowing natural cooling and solidification to form.
- the melting temperature in step S1 is 85°C to 95°C.
- the mixing temperature in step S2 is 85°C to 95°C
- the acoustic resonance intensity is 30g to 70g
- the resonance time is 5min to 10min.
- thermoplastic composite solid propellant There is currently no effective bonding agent for thermoplastic composite solid propellants. Therefore, the interface effect between the adhesive matrix and the solid filler is weak, and the "dewetting" phenomenon is prone to occur during the tensile failure process; based on neutral macromolecular bonds
- NPBA neutral macromolecular bonds
- a thermoplastic composite solid propellant disclosed by the present invention uses a thermoplastic elastomer grafted or copolymerized with bonded functional groups as an adhesive.
- the adhesive matrix has strong interaction with the solid filler, and can Enhance the interface effect, slow down the occurrence of "dewetting" phenomenon, and improve the mechanical properties of propellant.
- thermoplastic composite solid propellant uses an acoustic resonance mixer to prepare a thermoplastic composite solid propellant. It is a brand-new slurry-free mixing technology that uses the principle of mechanical resonance to break the mixing of materials with minimal energy. Boundary conditions stimulate materials to undergo self-vibration and rapid mixing, which not only improves process safety but also greatly improves preparation efficiency.
- thermosetting composite solid propellant forms a chemical cross-linked network through the irreversible reaction between the polymer prepolymer and the curing agent.
- the completion of the curing cross-linking reaction requires strict control of temperature and humidity, and strict requirements for the relevant facilities of the curing site.
- the thermoplastic composite solid propellant prepared by the present invention uses a reversible physical crystallization network composed of hydrogen bonds between elastomer hard segments to achieve solid-liquid conversion, and has repeatable processing and molding characteristics; the remaining materials generated during the processing can be recycled and reused, and expired Or the scrapped drug columns can also be reused after post-processing through green processes, which is in line with the concept of green environmental protection.
- thermoplastic composite solid propellant In the preparation method of a thermoplastic composite solid propellant disclosed in the present invention, the softening point temperature of the thermoplastic adhesive and the propellant is 85°C to 95°C, and has repeatable processability.
- thermoplastic composite solid propellant in the preparation method of a thermoplastic composite solid propellant disclosed in the present invention, an acoustic resonance mixer is used to prepare the thermoplastic propellant. Slurry-free mixing greatly improves the mixing and preparation efficiency while improving the safety of the process; and the thermoplastic propellant agent The slurry is not limited by the "potency period" and the mixing and pouring processes are completely independent. The propellant has good application prospects in the fields of rapid charging of solid engines and controllable energy release.
- Figure 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 includes the following components in mass percentage: thermoplastic elastomer with bonding function 5% to 16%; plasticizer: 5% to 25%; metal fuel: 5% to 25%. 18%; oxidizer: 50% to 70%; functional additives: 0.4% to 5%; the sum of the mass percentages of the raw materials of the thermoplastic composite solid propellant is 100%.
- the thermoplastic elastomer with bonding function (Bonding functional TPE) of the present invention is obtained by grafting or copolymerizing the bonding functional group or block onto the thermoplastic elastomer.
- the bonding functional group or block includes maleic anhydride (MAH). , one of styrene (St), glycidyl methacrylate (GMA), butyl acrylate (BA), hydroxyethyl acrylate (HEA), acrylic acid (AA) and methyl methacrylate (MMA) or
- St styrene
- GMA glycidyl methacrylate
- BA butyl acrylate
- HOA hydroxyethyl acrylate
- acrylic acid AA
- MMA methyl methacrylate
- the mass percentage of bonded functional groups or blocks in thermoplastic elastomers with bonding function is 0.1wt% to 5wt%.
- thermoplastic elastomer with bonding function is, for example, maleic anhydride grafted ethylene-vinyl acetate copolymer; the relative molecular mass of the thermoplastic elastomer with bonding function is 21,000 to 40,000, and its softening point temperature as an adhesive is 85 ⁇ 95°C, the maximum tensile strength at 20°C is 0.7MPa ⁇ 4.9MPa, and the maximum elongation at break is 485% ⁇ 1330%.
- the plasticizer includes one or more of naphthenic oil (KN), dioctyl sebacate (DOS), liquid paraffin and dioctyl phthalate; the plasticizer and thermoplastic elasticity with bonding function
- KN naphthenic oil
- DOS dioctyl sebacate
- the mass ratio of the body is (0.6 ⁇ 1.55):1.
- Metallic fuels include, but are not limited to, aluminum powder (Al).
- Oxidizing agents include ammonium perchlorate (AP), ammonium nitrate (AN), phase-stable ammonium nitrate (PSAN), redoxin (RDX), octogen (HMX), and 5,5'-bistetrazolium-1 , one or more of 1'-dioxodihydroxylammonium salts (TKX-50).
- AP ammonium perchlorate
- AN ammonium nitrate
- PSAN phase-stable ammonium nitrate
- RDX redoxin
- HMX octogen
- TKX-50 1,5'-bistetrazolium-1
- Functional auxiliaries include but are not limited to stabilizers and burning rate catalysts, wherein the stabilizers include one of N,N-dimethylaniline (NN), N-methylaniline (NMA) and diphenylamine (NPA) or A variety of; burning rate catalysts include one or more of n-octylferrocene, ferric oxide, copper chromite, etc.
- the stabilizers include one of N,N-dimethylaniline (NN), N-methylaniline (NMA) and diphenylamine (NPA) or A variety of
- burning rate catalysts include one or more of n-octylferrocene, ferric oxide, copper chromite, etc.
- thermoplastic composite solid propellant is prepared through the following steps:
- thermoplastic elastomer with bonding function and plasticizer to 85°C ⁇ 95°C to melt in a high-shear dispersing emulsifier (but not limited to this), add functional additives and mix evenly;
- the method further includes pouring the thermoplastic composite solid propellant into the mold, and storing it after natural cooling and solidification.
- the billet the solidified thermoplastic composite solid propellant
- the heating temperature during charging is 95°C to 100°C.
- Density refer to QJ 917A-97 to detect the density under the test conditions of 20°C, g/ cm3 ;
- thermoplastic elastomer with bonding function (Bonding functional TPE) and plasticizer into the high-shear emulsification dispersing machine, heat it to 90°C to melt it, and then add functional additives. agent and mix evenly; transfer the above materials to an acoustic resonance mixer, raise the temperature to 90°C, add Al and premix, use acoustic resonance to mix the Al evenly, the resonance intensity is 50g, the resonance time is 5min, and then add a certain amount of Al in batches
- the oxidant is mixed evenly using acoustic resonance to obtain a thermoplastic composite solid propellant; it is poured into a mold and allowed to cool and solidify naturally to obtain a propellant sample.
- thermoplastic elastomer with bonding function (Bonding functional TPE) and plasticizer into the high-shear emulsification dispersing machine, heat it to 85°C to melt it, and then add functional additives. agent and mix evenly; transfer the above materials to the acoustic resonance mixer, raise the temperature to 85°C, add Al and premix, use acoustic resonance to mix the Al evenly, the resonance intensity is 30g, the resonance time is 10min, and then add a certain amount of Al in batches
- the oxidant is mixed evenly using acoustic resonance to obtain a thermoplastic composite solid propellant; it is poured into a mold and allowed to cool and solidify naturally to obtain a propellant sample.
- thermoplastic elastomer (Bonding functional TPE) and plasticizer into the high-shear emulsification dispersing machine, heat it to 85°C to melt it, and then add functional additives. agent and mix evenly; transfer the above materials to the acoustic resonance mixer, raise the temperature to 90°C, add Al and premix, use acoustic resonance to mix the Al evenly, the resonance intensity is 70g, the resonance time is 5 minutes, and then add a certain amount of Al in batches
- the oxidant is mixed evenly using acoustic resonance to obtain a thermoplastic composite solid propellant; it is poured into a mold and allowed to cool and solidify naturally to obtain a propellant sample.
- thermoplastic elastomer with bonding function (Bonding functional TPE) and plasticizer into the high-shear emulsification dispersing machine, heat it to 95°C to melt it, and then add functional additives. agent and mix evenly; transfer the above materials to an acoustic resonance mixer, raise the temperature to 95°C, add Al and premix, use acoustic resonance to mix the Al evenly, the resonance intensity is 50g, the resonance time is 8 minutes, and then add a certain amount of The oxidant is mixed evenly using acoustic resonance to obtain a thermoplastic composite solid propellant; it is poured into a mold and allowed to cool and solidify naturally to obtain a propellant sample.
- Bonding functional TPE Bonding functional TPE
- plasticizer plasticizer into the high-shear emulsification dispersing machine, heat it to 95°C to melt it, and then add functional additives. agent and mix evenly; transfer the above materials to an acoustic resonance mixer, raise the temperature to 95°C, add
- thermoplastic elastomer (Bonding functional TPE) and plasticizer into the high-shear emulsification dispersing machine, heat it to 95°C to melt it, and then add functional additives. agent and mix evenly; transfer the above materials to the acoustic resonance mixer, raise the temperature to 95°C, add Al and premix, use acoustic resonance to mix the Al evenly, the resonance intensity is 50g, the resonance time is 5min, and then add a certain amount of Al in batches
- the oxidant is mixed evenly using acoustic resonance to obtain a thermoplastic composite solid propellant; it is poured into a mold and allowed to cool and solidify naturally to obtain a propellant sample.
- thermoplastic elastomer with bonding function (Bonding functional TPE) and plasticizer into the high-shear emulsification dispersing machine, heat it to 95°C to melt it, and then add functional additives. agent and mix evenly; transfer the above materials to the acoustic resonance mixer, raise the temperature to 95°C, add Al and premix, use acoustic resonance to mix the Al evenly, the resonance intensity is 50g, the resonance time is 5min, and then add a certain amount of Al in batches
- the oxidant is mixed evenly using acoustic resonance to obtain a thermoplastic composite solid propellant; it is poured into a mold and allowed to cool and solidify naturally to obtain a propellant sample.
- thermoplastic elastomer that is, a thermoplastic elastomer without bonding function
- plasticizer into a high-shear emulsifying disperser, heat it to 90°C to melt it, and then add Functional additives and mix evenly; transfer the above materials to the acoustic resonance mixer, raise the temperature to 90°C, add Al and premix, use acoustic resonance to mix the Al evenly, the resonance intensity is 50g, the resonance time is 5min, and then add in batches
- a certain amount of oxidant is mixed uniformly using acoustic resonance to obtain a thermoplastic composite solid propellant; it is poured into a mold and allowed to cool and solidify naturally to obtain a propellant sample.
- thermoplastic composite solid propellant prepared by using a thermoplastic elastomer without bonding function maximum tensile strength ⁇ b is 0.43MPa, elongation at break ⁇ m is 12%) is significantly lower than the mechanical properties of the thermoplastic composite solid propellant made by using thermoplastic elastomers with bonding functions ( ⁇ b is 1.62MPa, ⁇ m is 25.5%), that is, the present invention uses bonded functional groups to graft or
- the copolymerized thermoplastic elastomer serves as a binder, which enables a strong interaction between the binder matrix and the solid filler, which can enhance the interface effect and improve the mechanical properties of the propellant, thereby slowing down the occurrence of "dewetting".
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Abstract
Disclosed in the present invention is a thermoplastic composite solid propellant, which comprises, in percentages 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 can be enhanced, and the phenomenon of "dehumidification" in the tensile failure process can be slowed down. Further disclosed in the present invention is a preparation method for 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
本发明涉及复合固体推进剂技术领域,具体涉及一种热塑性复合固体推进剂及其制备方法。The invention relates to the technical field of composite solid propellants, and in particular to a thermoplastic composite solid propellant and a preparation method thereof.
复合固体推进剂由固体填料如氧化剂、金属燃料、小组分功能助剂与高分子粘合剂构成;通过固体填料与高分子粘合剂均匀混合,粘合剂能够将复合固体推进剂的固体填料及其他组分如燃速催化剂、键合剂、防老剂等功能添加剂彼此粘结,同时赋予推进剂理想构型与结构完整性。Composite solid propellant is composed of solid fillers such as oxidizer, metal fuel, small component functional additives and polymer binder; by uniformly mixing the solid filler and polymer binder, the binder can combine the solid fillers of the composite solid propellant And other components such as burning rate catalysts, bonding agents, antioxidants and other functional additives bond with each other, while giving the propellant the ideal configuration and structural integrity.
热固性复合固体推进剂的粘合剂基体网络结构一般通过高分子预聚物与固化剂之间的化学交联反应形成,如端羟基聚丁二烯与双官能度异氰酸酯缩合生成氨基甲酸酯,单取代的炔与有机叠氮化合物环加成得到1,2,3-三氮唑;通过共价键形成的化学交联网络具有诸多优点,如结构规整、悬吊链较少、固化参数可控;然而,受到热固性推进剂药浆“适用期”的限制,混合结束或加入固化剂的药浆需尽快浇注进入发动机燃烧室;固化交联反应的完成需在较长一段时间内对温度、湿度进行严格控制,对固化场所的相关设施要求严苛;由非可逆共价键构成的化学交联网络使热固性复合固体推进剂不能够二次加工成型,推进剂一旦出现质量问题或过期报废,只能作燃烧销毁处理,造成资源浪费与环境污染。The adhesive matrix network structure of thermosetting composite solid propellant is generally formed through a chemical cross-linking reaction between a polymer prepolymer and a curing agent, such as the condensation of hydroxyl-terminated polybutadiene and bifunctional isocyanate to form urethane. The cycloaddition of monosubstituted alkynes and organic azide compounds yields 1,2,3-triazole; the chemical cross-linked network formed through covalent bonds has many advantages, such as regular structure, fewer dangling chains, and flexible curing parameters. However, due to the limitation of the "potency period" of the thermosetting propellant slurry, the slurry after mixing or adding the curing agent needs to be poured into the engine combustion chamber as soon as possible; the completion of the curing cross-linking reaction requires a long period of time with temperature, The humidity must be strictly controlled, and the requirements for related facilities in the curing site are stringent; the chemical cross-linked network composed of 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 will be discarded. It can only be burned and destroyed, causing waste of resources and environmental pollution.
为克服以上不足,一类不含固化剂,避免推进剂药浆“适用期”限制,并且可重复利用的热塑性弹性体(Thermoplastic Elastomer,TPE)材料被应用于复合固体推进剂粘合剂;热塑性复合固体推进剂具有塑料般的重复加工成型特性以及环境稳定性,可以进行小规模的连续混合制备,不需要大量、集中地进行推进剂生产,对混合设备、场地等生产条件与环境依赖性较弱,并且能够实现无溶剂连续加工,因而作为绿色推进剂品种被广泛重视及研究。In order to overcome the above shortcomings, a type of thermoplastic elastomer (TPE) material that does not contain curing agents, avoids the "pot life" limitation of propellant slurries, and is reusable is used in composite solid propellant adhesives; thermoplastic Composite solid propellant has plastic-like repetitive processing and molding characteristics and environmental stability. It can be prepared by small-scale continuous mixing. It does not require large-scale and centralized propellant production and is relatively dependent on production conditions and environment such as mixing equipment and sites. It is weak and can achieve solvent-free continuous processing, so it has been widely valued and studied as a green propellant variety.
热塑性复合固体推进剂通常以热塑性弹性体作为粘合剂,热塑性弹性体一般为线性嵌段聚合物,由线性软链段与线性硬链段共聚组成,其中,硬段间氢键构成的可逆物理结晶网络实现推进剂的固液转换;但是由于不使用反应型固化剂与键合剂,弹性体微相分离的本体结构特征决定了热塑性复合固体推进剂的力学性能,即热塑性粘合剂基体与固体填料间界面效应较弱,在拉伸破坏过程中推进剂极易发生“脱湿”现象;因此,亟需研发一种界面效应增强的热塑性复合固体推进剂,同时,寻求一种更加安全、高效的无浆混合方式 制备热塑性复合固体推进剂。Thermoplastic composite solid propellants usually use thermoplastic elastomers as binders. Thermoplastic elastomers are generally linear block polymers, which are composed of linear soft segments and linear hard segments copolymerized. Among them, reversible physical hydrogen bonds between hard segments form The crystalline network realizes the solid-liquid conversion of the propellant; however, since no reactive curing agent and bonding agent are used, the bulk structural characteristics of the elastomer microphase separation determine the mechanical properties of the thermoplastic composite solid propellant, that is, the thermoplastic adhesive matrix and the solid The interface effect between fillers is weak, and the propellant is prone to "dewetting" during the tensile failure process; therefore, there is an urgent need to develop a thermoplastic composite solid propellant with enhanced interface effect, and at the same time, a safer and more efficient Preparation of thermoplastic composite solid propellant by slurry-free mixing method.
发明内容Contents of the invention
针对上述问题,本发明的第一个目的是提供一种热塑性复合固体推进剂,热塑性复合固体推进剂中采用键合官能团接枝或共聚的热塑性弹性体作为粘合剂,粘合剂基体与固体填料具有较强的相互作用,可增强界面效应,能减缓拉伸破坏过程中“脱湿”现象的发生。In response to the above problems, the 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 bonded functional groups is used as an adhesive. The adhesive matrix and the solid propellant are Fillers have strong interaction, which can enhance the interface effect and slow down the occurrence of "dewetting" phenomenon during tensile failure.
本发明的第二个目的是提供上述一种热塑性复合固体推进剂的制备方法,该方法克服现有技术的不足,采用声共振混合方式来安全、高效地制备热塑性复合固体推进剂,满足固体发动机快速装药需求。The second object of the present invention is to provide the above-mentioned preparation method of thermoplastic composite solid propellant. This method overcomes the shortcomings of the existing technology and uses acoustic resonance mixing to safely and efficiently prepare thermoplastic composite solid propellant to meet the needs of solid engines. Rapid charging requirements.
本发明所采用的第一个技术方案是:一种热塑性复合固体推进剂,按质量百分比包括以下组分:The first technical solution adopted by the present invention is: a thermoplastic composite solid propellant, which includes the following components in mass percentage:
具有键合功能的热塑性弹性体:5%~16%;Thermoplastic elastomer with bonding function: 5% ~ 16%;
增塑剂:5%~25%;Plasticizer: 5% ~ 25%;
金属燃料:5%~18%;Metal fuel: 5% ~ 18%;
氧化剂:50%~70%;Oxidizing agent: 50% ~ 70%;
功能助剂:0.4%~5%。Functional additives: 0.4% ~ 5%.
优选地,所述具有键合功能的热塑性弹性体中的键合官能团或嵌段包括马来酸酐、苯乙烯、甲基丙烯酸缩水甘油酯、丙烯酸丁酯、丙烯酸羟乙酯、丙烯酸和甲基丙烯酸甲酯中的一种或多种。Preferably, the bonding functional groups or blocks in the thermoplastic elastomer with bonding function include maleic anhydride, styrene, glycidyl methacrylate, butyl acrylate, hydroxyethyl acrylate, acrylic acid and methacrylic acid. One or more of the methyl esters.
优选地,所述具有键合功能的热塑性弹性体中键合官能团或嵌段的质量百分比为0.1wt%~5wt%。Preferably, the mass percentage of bonded functional groups or blocks in the thermoplastic elastomer with bonding function is 0.1 wt% to 5 wt%.
优选地,所述增塑剂包括环烷油、癸二酸二辛酯、液体石蜡和邻苯二甲酸二辛酯中的一种或多种。Preferably, the plasticizer includes one or more of naphthenic oil, dioctyl sebacate, liquid paraffin and dioctyl phthalate.
优选地,所述氧化剂包括高氯酸铵、硝酸铵、相稳定型硝酸铵、黑索今、奥克托金和5,5’-双四唑-1,1’-二氧二羟铵盐中的一种或多种。Preferably, the oxidizing agent includes ammonium perchlorate, ammonium nitrate, phase-stable ammonium nitrate, rhodamine, octogen and 5,5'-bistetrazole-1,1'-dioxodihydroxylammonium salt one or more of them.
优选地,所述功能助剂包括安定剂和燃速催化剂,其中,所述安定剂包括N,N-二甲基苯胺、N-甲基苯胺和二苯胺中的一种或多种;所述燃速催化剂包括正辛基二茂铁、三氧化二铁和亚铬酸铜中的一种或多种。Preferably, the functional auxiliary agent includes a stabilizer and a burning rate catalyst, wherein the stabilizer includes one or more of N,N-dimethylaniline, N-methylaniline and diphenylamine; The burning rate catalyst includes one or more of n-octylferrocene, ferric oxide and copper chromite.
本发明所采用的第二个技术方案是:一种热塑性复合固体推进剂的制备方法,包括以 下步骤:The second technical solution adopted by the present invention is: a preparation method of thermoplastic composite solid propellant, including the following steps:
S1:将具有键合功能的热塑性弹性体与增塑剂加热熔融,加入功能助剂后混合均匀;S1: Heat and melt the thermoplastic elastomer with bonding function and plasticizer, add functional additives and mix evenly;
S2:添加金属燃料,通过声共振混合均匀;S2: Add metal fuel and mix it evenly through acoustic resonance;
S3:分批加入氧化剂,通过声共振混合均匀,制得热塑性复合固体推进剂。S3: Add the oxidant in batches and mix evenly through acoustic resonance to prepare a thermoplastic composite solid propellant.
优选地,热塑性复合固体推进剂的制备方法中还包括:将制得的热塑性复合固体推进剂浇注至模具中,自然冷却固化成型。Preferably, the preparation method of the thermoplastic composite solid propellant further includes: pouring the prepared thermoplastic composite solid propellant into a mold, and allowing natural cooling and solidification to form.
优选地,所述步骤S1中的熔融温度为85℃~95℃。Preferably, the melting temperature in step S1 is 85°C to 95°C.
优选地,所述步骤S2中的混合温度为85℃~95℃,声共振强度为30g~70g,共振时间为5min~10min。Preferably, the mixing temperature in step S2 is 85°C to 95°C, the acoustic resonance intensity is 30g to 70g, and the resonance time is 5min to 10min.
上述技术方案的有益效果:Beneficial effects of the above technical solution:
(1)目前没有针对热塑性复合固体推进剂的有效键合剂,因此粘合剂基体与固体填料的界面效应较弱,在拉伸破坏过程中容易发生“脱湿”现象;基于中性大分子键合剂(NPBA)的理论,本发明公开的一种热塑性复合固体推进剂采用键合官能团接枝或共聚的热塑性弹性体作为粘合剂,粘合剂基体与固体填料具有较强的相互作用,可增强界面效应,减缓“脱湿”现象的发生,提升推进剂的力学性能。(1) There is currently no effective bonding agent for thermoplastic composite solid propellants. Therefore, the interface effect between the adhesive matrix and the solid filler is weak, and the "dewetting" phenomenon is prone to occur during the tensile failure process; based on neutral macromolecular bonds The theory of mixture (NPBA), a thermoplastic composite solid propellant disclosed by the present invention uses a thermoplastic elastomer grafted or copolymerized with bonded functional groups as an adhesive. The adhesive matrix has strong interaction with the solid filler, and can Enhance the interface effect, slow down the occurrence of "dewetting" phenomenon, and improve the mechanical properties of propellant.
(2)本发明公开的一种热塑性复合固体推进剂的制备方法采用声共振混合机制备热塑性复合固体推进剂,是一种全新的无浆混合技术,通过机械共振原理以最小的能量打破物料混合边界条件,激发物料进行自振动快速混合,在提升工艺安全性的同时大幅提高制备效率。(2) The method for preparing a thermoplastic composite solid propellant disclosed in the present invention uses an acoustic resonance mixer to prepare a thermoplastic composite solid propellant. It is a brand-new slurry-free mixing technology that uses the principle of mechanical resonance to break the mixing of materials with minimal energy. Boundary conditions stimulate materials to undergo self-vibration and rapid mixing, which not only improves process safety but also greatly improves preparation efficiency.
(3)热固性复合固体推进剂通过高分子预聚物与固化剂之间的不可逆反应形成化学交联网络,完成固化交联反应需对温度、湿度进行严格控制,对固化场所相关设施要求严苛;而本发明制备的热塑性复合固体推进剂以弹性体硬段间氢键构成的可逆物理结晶网络实现固液转换,具有可重复加工成型特性;加工过程中产生的余料可回收再利用,过期或报废药柱也可通过绿色工艺对其进行后处理后再利用,符合绿色环保理念。(3) The thermosetting composite solid propellant forms a chemical cross-linked network through the irreversible reaction between the polymer prepolymer and the curing agent. The completion of the curing cross-linking reaction requires strict control of temperature and humidity, and strict requirements for the relevant facilities of the curing site. ; The thermoplastic composite solid propellant prepared by the present invention uses a reversible physical crystallization network composed of hydrogen bonds between elastomer hard segments to achieve solid-liquid conversion, and has repeatable processing and molding characteristics; the remaining materials generated during the processing can be recycled and reused, and expired Or the scrapped drug columns can also be reused after post-processing through green processes, which is in line with the concept of green environmental protection.
(4)本发明公开的一种热塑性复合固体推进剂的制备方法中热塑性粘合剂与推进剂的软化点温度为85℃~95℃,具有可重复加工性。(4) In the preparation method of a thermoplastic composite solid propellant disclosed in the present invention, the softening point temperature of the thermoplastic adhesive and the propellant is 85°C to 95°C, and has repeatable processability.
(5)本发明公开的一种热塑性复合固体推进剂的制备方法中采用声共振混合机制备热塑性推进剂,无浆混合在提高工艺安全性的同时大幅提升了混合制备效率;且热塑性推进剂药浆不受“适用期”限制,混合与浇注工序完全独立,该推进剂在固体发动机快速装 药、能量可控释放等领域应用前景良好。(5) In the preparation method of a thermoplastic composite solid propellant disclosed in the present invention, an acoustic resonance mixer is used to prepare the thermoplastic propellant. Slurry-free mixing greatly improves the mixing and preparation efficiency while improving the safety of the process; and the thermoplastic propellant agent The slurry is not limited by the "potency period" and the mixing and pouring processes are completely independent. The propellant has good application prospects in the fields of rapid charging of solid engines and controllable energy release.
图1为本发明一种热塑性复合固体推进剂的制备方法的工艺流程图。Figure 1 is a process flow chart of a method for preparing a thermoplastic composite solid propellant of the present invention.
下面通过具体的实施例对本发明进一步说明,应当指出,对于本领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干变型和改进,这些也应视为属于本发明的保护范围。The present invention will be further described below through specific embodiments. It should be pointed out that for those of ordinary skill in the art, several modifications and improvements can be made without departing from the principles of the present invention, and these should also be regarded as belonging to this invention. protection scope of the invention.
本发明说明书中未作详细描述的内容属于本领域专业技术人员的公知技术。Contents not described in detail in the specification of the present invention belong to the well-known techniques of those skilled in the art.
本发明公开了一种热塑性复合固体推进剂,按质量百分比包括以下组分:具有键合功能的热塑性弹性体5%~16%;增塑剂:5%~25%;金属燃料:5%~18%;氧化剂:50%~70%;功能助剂:0.4%~5%;热塑性复合固体推进剂各原料的质量百分比之和为100%。The invention discloses a thermoplastic composite solid propellant, which includes the following components in mass percentage: thermoplastic elastomer with bonding function 5% to 16%; plasticizer: 5% to 25%; metal fuel: 5% to 25%. 18%; oxidizer: 50% to 70%; functional additives: 0.4% to 5%; the sum of the mass percentages of the raw materials of the thermoplastic composite solid propellant is 100%.
本发明的具有键合功能的热塑性弹性体(Bonding functional TPE)是通过将键合官能团或嵌段接枝或共聚到热塑性弹性体上获得的,键合官能团或嵌段包括马来酸酐(MAH)、苯乙烯(St)、甲基丙烯酸缩水甘油酯(GMA)、丙烯酸丁酯(BA)、丙烯酸羟乙酯(HEA)、丙烯酸(AA)和甲基丙烯酸甲酯(MMA)中的一种或多种,具有键合功能的热塑性弹性体中键合官能团或嵌段的质量百分比为0.1wt%~5wt%。The thermoplastic elastomer with bonding function (Bonding functional TPE) of the present invention is obtained by grafting or copolymerizing the bonding functional group or block onto the thermoplastic elastomer. The bonding functional group or block includes maleic anhydride (MAH). , one of styrene (St), glycidyl methacrylate (GMA), butyl acrylate (BA), hydroxyethyl acrylate (HEA), acrylic acid (AA) and methyl methacrylate (MMA) or Various, the mass percentage of bonded functional groups or blocks in thermoplastic elastomers with bonding function is 0.1wt% to 5wt%.
具有键合功能的热塑性弹性体例如为马来酸酐接枝乙烯-醋酸乙烯共聚物;具有键合功能的热塑性弹性体的相对分子质量为21000~40000,其作为粘合剂的软化点温度为85~95℃,20℃时的最大抗拉强度为0.7MPa~4.9MPa,最大断裂伸长率为485%~1330%。The thermoplastic elastomer with bonding function is, for example, maleic anhydride grafted ethylene-vinyl acetate copolymer; the relative molecular mass of the thermoplastic elastomer with bonding function is 21,000 to 40,000, and its softening point temperature as an adhesive is 85 ~95℃, the maximum tensile strength at 20℃ is 0.7MPa~4.9MPa, and the maximum elongation at break is 485%~1330%.
增塑剂包括环烷油(KN)、癸二酸二辛酯(DOS)、液体石蜡和邻苯二甲酸二辛酯中的一种或多种;增塑剂与具有键合功能的热塑性弹性体的质量比为(0.6~1.55):1。The plasticizer includes one or more of naphthenic oil (KN), dioctyl sebacate (DOS), liquid paraffin and dioctyl phthalate; the plasticizer and thermoplastic elasticity with bonding function The mass ratio of the body is (0.6~1.55):1.
金属燃料包括但不限于铝粉(Al)。Metallic fuels include, but are not limited to, aluminum powder (Al).
氧化剂包括高氯酸铵(AP)、硝酸铵(AN)、相稳定型硝酸铵(PSAN)、黑索今(RDX)、奥克托金(HMX)和5,5’-双四唑-1,1’-二氧二羟铵盐(TKX-50)中的一种或多种。Oxidizing agents include ammonium perchlorate (AP), ammonium nitrate (AN), phase-stable ammonium nitrate (PSAN), redoxin (RDX), octogen (HMX), and 5,5'-bistetrazolium-1 , one or more of 1'-dioxodihydroxylammonium salts (TKX-50).
功能助剂包括但不限于安定剂和燃速催化剂,其中,安定剂包括N,N-二甲基苯胺(NN)、N-甲基苯胺(NMA)和二苯胺(NPA)中的一种或多种;燃速催化剂包括正辛基二茂铁、三氧化二铁、亚铬酸铜等中的一种或多种。Functional auxiliaries include but are not limited to stabilizers and burning rate catalysts, wherein the stabilizers include one of N,N-dimethylaniline (NN), N-methylaniline (NMA) and diphenylamine (NPA) or A variety of; burning rate catalysts include one or more of n-octylferrocene, ferric oxide, copper chromite, etc.
如图1所示,通过以下步骤制备热塑性复合固体推进剂:As shown in Figure 1, the thermoplastic composite solid propellant is prepared through the following steps:
S1:在高剪切分散乳化机(但并不限于此)内将具有键合功能的热塑性弹性体与增 塑剂加热至85℃~95℃熔融,添加功能助剂后混合均匀;S1: Heat the thermoplastic elastomer with bonding function and plasticizer to 85℃~95℃ to melt in a high-shear dispersing emulsifier (but not limited to this), add functional additives and mix evenly;
S2:将混合均匀的物料转移至声共振混合机内,添加金属燃料,在混合温度为85℃~95℃,共振强度为30g~70g下,通过声共振共振5min~10min混合均匀;S2: Transfer the uniformly mixed materials to the acoustic resonance mixer, add metal fuel, and mix evenly through acoustic resonance for 5 to 10 minutes at a mixing temperature of 85°C to 95°C and a resonance intensity of 30g to 70g;
S3:向上述物料中分批加入定量的氧化剂,通过声共振混合均匀得到热塑性复合固体推进剂;S3: Add a certain amount of oxidant to the above materials in batches, and mix them uniformly through acoustic resonance to obtain a thermoplastic composite solid propellant;
进一步的,在一个实施例中,还包括将热塑性复合固体推进剂浇注至模具中,自然冷却固化成型后储存,装药时将方坯(固化成型后的热塑性复合固体推进剂)熔融浇注到发动机壳体中成型,或将方坯装填至发动机壳体中再熔融成型;其中,装药时的加热温度为95℃~100℃。Further, in one embodiment, the method further includes pouring the thermoplastic composite solid propellant into the mold, and storing it after natural cooling and solidification. During charging, the billet (the solidified thermoplastic composite solid propellant) is melted and poured into the engine. Molding in the casing, or filling the billet into the engine casing and then melting and molding; the heating temperature during charging is 95°C to 100°C.
将制得的热塑性复合固体推进剂进行以下表征:The prepared thermoplastic composite solid propellant was characterized as follows:
1)力学性能,参照GJB 770B-2005在20℃,100mm/min的测试条件下检测力学性能中的最大抗拉强度σ
b和断裂伸长率ε
m;
1) Mechanical properties, refer to GJB 770B-2005 and detect the maximum tensile strength σ b and elongation at break ε m in the mechanical properties under the test conditions of 20°C and 100mm/min;
2)密度,参照QJ 917A-97在20℃,g/cm
3的测试条件下检测密度;
2) Density, refer to QJ 917A-97 to detect the density under the test conditions of 20℃, g/ cm3 ;
3)理论比冲。3) Theoretical specific impulse.
实施例1Example 1
按表1中的配方分别称取各物料,将具有键合功能的热塑性弹性体(Bonding functional TPE)与增塑剂投入高剪切乳化分散机,升温至90℃使其熔融,再添加功能助剂并混合均匀;将上述物料转移至声共振混合机中,升温至90℃,添加Al并预混,采用声共振方式将Al混合均匀,共振强度50g,共振时间5min,再分批加入定量的氧化剂,采用声共振方式混合均匀得到热塑性复合固体推进剂;浇注至模具内使其自然冷却固化后得到推进剂样品。Weigh each material according to the formula in Table 1, put the thermoplastic elastomer with bonding function (Bonding functional TPE) and plasticizer into the high-shear emulsification dispersing machine, heat it to 90°C to melt it, and then add functional additives. agent and mix evenly; transfer the above materials to an acoustic resonance mixer, raise the temperature to 90°C, add Al and premix, use acoustic resonance to mix the Al evenly, the resonance intensity is 50g, the resonance time is 5min, and then add a certain amount of Al in batches The oxidant is mixed evenly using acoustic resonance to obtain a thermoplastic composite solid propellant; it is poured into a mold and allowed to cool and solidify naturally to obtain a propellant sample.
表1热塑性复合固体推进剂的配方及性能Table 1 Formula and properties of thermoplastic composite solid propellant
实施例2Example 2
按表2中的配方分别称取各物料,将具有键合功能的热塑性弹性体(Bonding functional TPE)与增塑剂投入高剪切乳化分散机,升温至85℃使其熔融,再添加功能助剂并混合均匀;将上述物料转移至声共振混合机中,升温至85℃,添加Al并预混,采用声共振方式将Al混合均匀,共振强度30g,共振时间10min,再分批加入定量的氧化剂,采用声共振方式混合均匀得到热塑性复合固体推进剂;浇注至模具内使其自然冷却固化后得到推进剂样品。Weigh each material according to the formula in Table 2, put the thermoplastic elastomer with bonding function (Bonding functional TPE) and plasticizer into the high-shear emulsification dispersing machine, heat it to 85°C to melt it, and then add functional additives. agent and mix evenly; transfer the above materials to the acoustic resonance mixer, raise the temperature to 85°C, add Al and premix, use acoustic resonance to mix the Al evenly, the resonance intensity is 30g, the resonance time is 10min, and then add a certain amount of Al in batches The oxidant is mixed evenly using acoustic resonance to obtain a thermoplastic composite solid propellant; it is poured into a mold and allowed to cool and solidify naturally to obtain a propellant sample.
表2热塑性复合固体推进剂的配方及性能Table 2 Formula and properties of thermoplastic composite solid propellant
实施例3Example 3
按表3中的配方分别称取各物料,将具有键合功能的热塑性弹性体(Bonding functional TPE)与增塑剂投入高剪切乳化分散机,升温至85℃使其熔融,再添加功能助剂并混合均匀;将上述物料转移至声共振混合机中,升温至90℃,添加Al并预混,采用声共振方式将Al混合均匀,共振强度70g,共振时间5min,再分批加入定量的氧化剂,采用声共振方 式混合均匀得到热塑性复合固体推进剂;浇注至模具内使其自然冷却固化后得到推进剂样品。Weigh each material according to the formula in Table 3, put the thermoplastic elastomer (Bonding functional TPE) and plasticizer into the high-shear emulsification dispersing machine, heat it to 85°C to melt it, and then add functional additives. agent and mix evenly; transfer the above materials to the acoustic resonance mixer, raise the temperature to 90°C, add Al and premix, use acoustic resonance to mix the Al evenly, the resonance intensity is 70g, the resonance time is 5 minutes, and then add a certain amount of Al in batches The oxidant is mixed evenly using acoustic resonance to obtain a thermoplastic composite solid propellant; it is poured into a mold and allowed to cool and solidify naturally to obtain a propellant sample.
表3热塑性复合固体推进剂的配方及性能Table 3 Formula and properties of thermoplastic composite solid propellant
实施例4Example 4
按表4中的配方分别称取各物料,将具有键合功能的热塑性弹性体(Bonding functional TPE)与增塑剂投入高剪切乳化分散机,升温至95℃使其熔融,再添加功能助剂并混合均匀;将上述物料转移至声共振混合机中,升温至95℃,添加Al并预混,采用声共振方式将Al混合均匀,共振强度50g,共振时间8min,再分批加入定量的氧化剂,采用声共振方式混合均匀得到热塑性复合固体推进剂;浇注至模具内使其自然冷却固化后得到推进剂样品。Weigh each material according to the formula in Table 4, put the thermoplastic elastomer with bonding function (Bonding functional TPE) and plasticizer into the high-shear emulsification dispersing machine, heat it to 95°C to melt it, and then add functional additives. agent and mix evenly; transfer the above materials to an acoustic resonance mixer, raise the temperature to 95°C, add Al and premix, use acoustic resonance to mix the Al evenly, the resonance intensity is 50g, the resonance time is 8 minutes, and then add a certain amount of The oxidant is mixed evenly using acoustic resonance to obtain a thermoplastic composite solid propellant; it is poured into a mold and allowed to cool and solidify naturally to obtain a propellant sample.
表4热塑性复合固体推进剂的配方及性能Table 4 Formula and properties of thermoplastic composite solid propellant
实施例5Example 5
按表5中的配方分别称取各物料,将具有键合功能的热塑性弹性体(Bonding functional TPE)与增塑剂投入高剪切乳化分散机,升温至95℃使其熔融,再添加功能助剂并混合均匀;将上述物料转移至声共振混合机中,升温至95℃,添加Al并预混,采用声共振方式将Al混合均匀,共振强度50g,共振时间5min,再分批加入定量的氧化剂,采用声共振方式混合均匀得到热塑性复合固体推进剂;浇注至模具内使其自然冷却固化后得到推进剂样品。Weigh each material according to the formula in Table 5, put the thermoplastic elastomer (Bonding functional TPE) and plasticizer into the high-shear emulsification dispersing machine, heat it to 95°C to melt it, and then add functional additives. agent and mix evenly; transfer the above materials to the acoustic resonance mixer, raise the temperature to 95°C, add Al and premix, use acoustic resonance to mix the Al evenly, the resonance intensity is 50g, the resonance time is 5min, and then add a certain amount of Al in batches The oxidant is mixed evenly using acoustic resonance to obtain a thermoplastic composite solid propellant; it is poured into a mold and allowed to cool and solidify naturally to obtain a propellant sample.
表5热塑性复合固体推进剂的配方及性能Table 5 Formula and properties of thermoplastic composite solid propellant
实施例6Example 6
按表6中的配方分别称取各物料,将具有键合功能的热塑性弹性体(Bonding functional TPE)与增塑剂投入高剪切乳化分散机,升温至95℃使其熔融,再添加功能助剂并混合均匀;将上述物料转移至声共振混合机中,升温至95℃,添加Al并预混,采用声共振方式将Al混合均匀,共振强度50g,共振时间5min,再分批加入定量的氧化剂,采用声共振方式混合均匀得到热塑性复合固体推进剂;浇注至模具内使其自然冷却固化后得到推进剂样 品。Weigh each material according to the formula in Table 6, put the thermoplastic elastomer with bonding function (Bonding functional TPE) and plasticizer into the high-shear emulsification dispersing machine, heat it to 95°C to melt it, and then add functional additives. agent and mix evenly; transfer the above materials to the acoustic resonance mixer, raise the temperature to 95°C, add Al and premix, use acoustic resonance to mix the Al evenly, the resonance intensity is 50g, the resonance time is 5min, and then add a certain amount of Al in batches The oxidant is mixed evenly using acoustic resonance to obtain a thermoplastic composite solid propellant; it is poured into a mold and allowed to cool and solidify naturally to obtain a propellant sample.
表6热塑性复合固体推进剂的配方及性能Table 6 Formula and properties of thermoplastic composite solid propellant
对比例1Comparative example 1
按表7中的配方分别称取各物料,将热塑性弹性体(即不具有键合功能的热塑性弹性体)与增塑剂投入高剪切乳化分散机,升温至90℃使其熔融,再添加功能助剂并混合均匀;将上述物料转移至声共振混合机中,升温至90℃,添加Al并预混,采用声共振方式将Al混合均匀,共振强度50g,共振时间5min,再分批加入定量的氧化剂,采用声共振方式混合均匀得到热塑性复合固体推进剂;浇注至模具内使其自然冷却固化后得到推进剂样品。Weigh each material according to the formula in Table 7, put the thermoplastic elastomer (that is, a thermoplastic elastomer without bonding function) and plasticizer into a high-shear emulsifying disperser, heat it to 90°C to melt it, and then add Functional additives and mix evenly; transfer the above materials to the acoustic resonance mixer, raise the temperature to 90°C, add Al and premix, use acoustic resonance to mix the Al evenly, the resonance intensity is 50g, the resonance time is 5min, and then add in batches A certain amount of oxidant is mixed uniformly using acoustic resonance to obtain a thermoplastic composite solid propellant; it is poured into a mold and allowed to cool and solidify naturally to obtain a propellant sample.
表7热塑性复合固体推进剂的配方及性能Table 7 Formula and properties of thermoplastic composite solid propellant
由实施例1和对比例1中的数据可知,采用不具有键合功能的热塑性弹性体制得的热塑性复合固体推进剂的力学性能(最大抗拉强度σ
b为0.43MPa,断裂伸长率ε
m为12%)明显低于采用具有键合功能的热塑性弹性体制得的热塑性复合固体推进剂的力学性能(σ
b为1.62MPa,ε
m为25.5%),即本发明采用键合官能团接枝或共聚的热塑性弹性体作为粘合剂,使粘合剂基体与固体填料具有较强的相互作用,可增强界面效应,提升推进剂的力学性能,从而减缓“脱湿”现象的发生。
From the data in Example 1 and Comparative Example 1, it can be seen that the mechanical properties of the thermoplastic composite solid propellant prepared by using a thermoplastic elastomer without bonding function (maximum tensile strength σ b is 0.43MPa, elongation at break ε m is 12%) is significantly lower than the mechanical properties of the thermoplastic composite solid propellant made by using thermoplastic elastomers with bonding functions (σ b is 1.62MPa, ε m is 25.5%), that is, the present invention uses bonded functional groups to graft or The copolymerized thermoplastic elastomer serves as a binder, which enables a strong interaction between the binder matrix and the solid filler, which can enhance the interface effect and improve the mechanical properties of the propellant, thereby slowing down the occurrence of "dewetting".
以上结合具体实施方式和范例性实例对本发明进行了详细说明,不过这些说明并不能理解为对本发明的限制。本领域技术人员理解,在不偏离本发明精神和范围的情况下,可以对本发明技术方案及其实施方式进行多种等价替换、修饰或改进,这些均落入本发明的范围内。本发明的保护范围以所附权利要求为准。The present invention has been described in detail above with reference to specific embodiments and exemplary examples. However, these descriptions should not be construed as limitations of the present invention. Those skilled in the art understand that without departing from the spirit and scope of the invention, various equivalent substitutions, modifications or improvements can be made to the technical solution and its implementation of the invention, and these all fall within the scope of the invention. The scope of protection of the present invention is determined by the appended claims.
Claims (10)
- 一种热塑性复合固体推进剂,其特征在于,按质量百分比包括以下组分:A thermoplastic composite solid propellant, characterized in that it includes the following components in mass percentage:具有键合功能的热塑性弹性体:5%~16%;Thermoplastic elastomer with bonding function: 5% ~ 16%;增塑剂:5%~25%;Plasticizer: 5% ~ 25%;金属燃料:5%~18%;Metal fuel: 5% ~ 18%;氧化剂:50%~70%;Oxidizing agent: 50% ~ 70%;功能助剂:0.4%~5%。Functional additives: 0.4% ~ 5%.
- 根据权利要求1所述的一种热塑性复合固体推进剂,其特征在于,所述具有键合功能的热塑性弹性体中的键合官能团或嵌段包括马来酸酐、苯乙烯、甲基丙烯酸缩水甘油酯、丙烯酸丁酯、丙烯酸羟乙酯、丙烯酸和甲基丙烯酸甲酯中的一种或多种。A thermoplastic composite solid propellant according to claim 1, characterized in that the bonding functional groups or blocks in the thermoplastic elastomer with bonding function include maleic anhydride, styrene, glycidyl methacrylate One or more of ester, butyl acrylate, hydroxyethyl acrylate, acrylic acid and methyl methacrylate.
- 根据权利要求2所述的一种热塑性复合固体推进剂,其特征在于,所述具有键合功能的热塑性弹性体中键合官能团或嵌段的质量百分比为0.1wt%~5wt%。A thermoplastic composite solid propellant according to claim 2, characterized in that the mass percentage of bonded functional groups or blocks in the thermoplastic elastomer with bonding function is 0.1wt% to 5wt%.
- 根据权利要求1所述的一种热塑性复合固体推进剂,其特征在于,所述增塑剂包括环烷油、癸二酸二辛酯、液体石蜡和邻苯二甲酸二辛酯中的一种或多种。A thermoplastic composite solid propellant according to claim 1, characterized in that the plasticizer includes one of naphthenic oil, dioctyl sebacate, liquid paraffin and dioctyl phthalate. or more.
- 根据权利要求1所述的一种热塑性复合固体推进剂,其特征在于,所述氧化剂包括高氯酸铵、硝酸铵、相稳定型硝酸铵、黑索今、奥克托金和5,5’-双四唑-1,1’-二氧二羟铵盐中的一种或多种。A thermoplastic composite solid propellant according to claim 1, characterized in that the oxidant includes ammonium perchlorate, ammonium nitrate, phase-stable ammonium nitrate, RDX, Octogen and 5,5' - One or more bistetrazole-1,1'-dioxodihydroxylammonium salts.
- 根据权利要求1所述的一种热塑性复合固体推进剂,其特征在于,所述功能助剂包括安定剂和燃速催化剂,其中,所述安定剂包括N,N-二甲基苯胺、N-甲基苯胺和二苯胺中的一种或多种;所述燃速催化剂包括正辛基二茂铁、三氧化二铁和亚铬酸铜中的一种或多种。A thermoplastic composite solid propellant according to claim 1, characterized in that the functional auxiliary agent includes a stabilizer and a burning rate catalyst, wherein the stabilizer includes N, N-dimethylaniline, N- One or more of methylaniline and diphenylamine; the burning rate catalyst includes one or more of n-octylferrocene, ferric oxide and copper chromite.
- 一种热塑性复合固体推进剂的制备方法,其特征在于,包括以下步骤:A method for preparing thermoplastic composite solid propellant, which is characterized by including the following steps:S1:将具有键合功能的热塑性弹性体与增塑剂加热熔融,加入功能助剂后混合均匀;S1: Heat and melt the thermoplastic elastomer with bonding function and plasticizer, add functional additives and mix evenly;S2:添加金属燃料,通过声共振混合均匀;S2: Add metal fuel and mix it evenly through acoustic resonance;S3:分批加入氧化剂,通过声共振混合均匀,制得热塑性复合固体推进剂。S3: Add the oxidant in batches and mix evenly through acoustic resonance to prepare a thermoplastic composite solid propellant.
- 根据权利要求7所述的一种热塑性复合固体推进剂的制备方法,其特征在于,还包括:将制得的热塑性复合固体推进剂浇注至模具中,自然冷却固化成型。The method for preparing a thermoplastic composite solid propellant according to claim 7, further comprising: pouring the prepared thermoplastic composite solid propellant into a mold, and cooling and solidifying it naturally.
- 根据权利要求7所述的一种热塑性复合固体推进剂的制备方法,其特征在于,所述步骤S1中的熔融温度为85℃~95℃。The method for preparing a thermoplastic composite solid propellant according to claim 7, wherein the melting temperature in step S1 is 85°C to 95°C.
- 根据权利要求7所述的一种热塑性复合固体推进剂的制备方法,其特征在于,所述步骤S2中的混合温度为85℃~95℃,声共振强度为30g~70g,共振时间为5min~10min。The preparation method of a thermoplastic composite solid propellant according to claim 7, characterized in that the mixing temperature in step S2 is 85°C~95°C, the acoustic resonance intensity is 30g~70g, and the resonance time is 5min~ 10 minutes.
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