JP2007099565A - Solid propellant composition containing nanosize iron oxide - Google Patents
Solid propellant composition containing nanosize iron oxide Download PDFInfo
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- JP2007099565A JP2007099565A JP2005291951A JP2005291951A JP2007099565A JP 2007099565 A JP2007099565 A JP 2007099565A JP 2005291951 A JP2005291951 A JP 2005291951A JP 2005291951 A JP2005291951 A JP 2005291951A JP 2007099565 A JP2007099565 A JP 2007099565A
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 239000004449 solid propellant Substances 0.000 title claims abstract description 46
- 239000000203 mixture Substances 0.000 title claims abstract description 27
- 239000002245 particle Substances 0.000 claims abstract description 34
- 239000011230 binding agent Substances 0.000 claims abstract description 17
- GDDNTTHUKVNJRA-UHFFFAOYSA-N 3-bromo-3,3-difluoroprop-1-ene Chemical compound FC(F)(Br)C=C GDDNTTHUKVNJRA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000007800 oxidant agent Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 238000002485 combustion reaction Methods 0.000 abstract description 25
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 6
- 239000004014 plasticizer Substances 0.000 abstract description 6
- 239000003380 propellant Substances 0.000 description 8
- 238000009826 distribution Methods 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 239000000446 fuel Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000005062 Polybutadiene Substances 0.000 description 4
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 4
- 238000002296 dynamic light scattering Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 229920002857 polybutadiene Polymers 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- QUAMCNNWODGSJA-UHFFFAOYSA-N 1,1-dinitrooxybutyl nitrate Chemical compound CCCC(O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QUAMCNNWODGSJA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- 238000007415 particle size distribution analysis Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- IPPYBNCEPZCLNI-UHFFFAOYSA-N trimethylolethane trinitrate Chemical compound [O-][N+](=O)OCC(C)(CO[N+]([O-])=O)CO[N+]([O-])=O IPPYBNCEPZCLNI-UHFFFAOYSA-N 0.000 description 2
- POCJOGNVFHPZNS-ZJUUUORDSA-N (6S,7R)-2-azaspiro[5.5]undecan-7-ol Chemical group O[C@@H]1CCCC[C@]11CNCCC1 POCJOGNVFHPZNS-ZJUUUORDSA-N 0.000 description 1
- KINVDIZXFAZMTE-UHFFFAOYSA-N 1,1-diphenylpentane-2,4-dione Chemical compound C=1C=CC=CC=1C(C(=O)CC(=O)C)C1=CC=CC=C1 KINVDIZXFAZMTE-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- JSOGDEOQBIUNTR-UHFFFAOYSA-N 2-(azidomethyl)oxirane Chemical compound [N-]=[N+]=NCC1CO1 JSOGDEOQBIUNTR-UHFFFAOYSA-N 0.000 description 1
- GOPVUFFWLXPUBM-UHFFFAOYSA-N 3,3-bis(azidomethyl)oxetane Chemical compound [N-]=[N+]=NCC1(CN=[N+]=[N-])COC1 GOPVUFFWLXPUBM-UHFFFAOYSA-N 0.000 description 1
- VJQHJNIGWOABDZ-UHFFFAOYSA-N 3-methyloxetane Chemical compound CC1COC1 VJQHJNIGWOABDZ-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- NDYLCHGXSQOGMS-UHFFFAOYSA-N CL-20 Chemical compound [O-][N+](=O)N1C2N([N+]([O-])=O)C3N([N+](=O)[O-])C2N([N+]([O-])=O)C2N([N+]([O-])=O)C3N([N+]([O-])=O)C21 NDYLCHGXSQOGMS-UHFFFAOYSA-N 0.000 description 1
- OYBMVMAXKOGYDC-UHFFFAOYSA-N CTPB Chemical compound CCCCCCCCCCCCCCCC1=CC=CC(OCC)=C1C(=O)NC1=CC=C(Cl)C(C(F)(F)F)=C1 OYBMVMAXKOGYDC-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- QORUGOXNWQUALA-UHFFFAOYSA-N N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 Chemical compound N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 QORUGOXNWQUALA-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- SNIOPGDIGTZGOP-UHFFFAOYSA-N Nitroglycerin Chemical compound [O-][N+](=O)OCC(O[N+]([O-])=O)CO[N+]([O-])=O SNIOPGDIGTZGOP-UHFFFAOYSA-N 0.000 description 1
- 239000000006 Nitroglycerin Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 229910026551 ZrC Inorganic materials 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- OTCHGXYCWNXDOA-UHFFFAOYSA-N [C].[Zr] Chemical compound [C].[Zr] OTCHGXYCWNXDOA-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- IVRMZWNICZWHMI-UHFFFAOYSA-N azide group Chemical group [N-]=[N+]=[N-] IVRMZWNICZWHMI-UHFFFAOYSA-N 0.000 description 1
- 150000001540 azides Chemical group 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 1
- YMLFYGFCXGNERH-UHFFFAOYSA-K butyltin trichloride Chemical compound CCCC[Sn](Cl)(Cl)Cl YMLFYGFCXGNERH-UHFFFAOYSA-K 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 229940105990 diglycerin Drugs 0.000 description 1
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229960003711 glyceryl trinitrate Drugs 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- TZMQHOJDDMFGQX-UHFFFAOYSA-N hexane-1,1,1-triol Chemical compound CCCCCC(O)(O)O TZMQHOJDDMFGQX-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- -1 isocyanate compound Chemical class 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 229910001120 nichrome Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- ZHXAZZQXWJJBHA-UHFFFAOYSA-N triphenylbismuthane Chemical compound C1=CC=CC=C1[Bi](C=1C=CC=CC=1)C1=CC=CC=C1 ZHXAZZQXWJJBHA-UHFFFAOYSA-N 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
本発明は、ロケット用の推進剤として利用される固体推進薬組成物に関する。 The present invention relates to a solid propellant composition used as a propellant for a rocket.
ロケットモータに用いられる固体推進薬は、酸化剤と燃料兼結合剤からなるコンポジット推進薬と、ニトログリセリンとニトロセルロースを主成分とするダブルベース推進薬とに大別される。現在、これらの固体推進薬の中で過塩素酸アンモニウムを酸化剤とし、アルミニウム粉を金属燃料とし、ポリブタジエンを主成分とする燃料兼結合剤からなるコンポジット推進薬が、その優れた燃焼特性と機械的特性により広く使用されている。 Solid propellants used in rocket motors are roughly classified into composite propellants composed of an oxidizer and a fuel / binder, and double base propellants composed mainly of nitroglycerin and nitrocellulose. Currently, among these solid propellants, composite propellants consisting of a fuel and binder mainly composed of ammonium perchlorate as an oxidizer, aluminum powder as a metal fuel, and polybutadiene as a main component have excellent combustion characteristics and machinery. Widely used due to its mechanical properties.
近年、ロケットモータの設計範囲の拡大と高性能化を目的として、固体推進薬に対して幅広い燃焼速度の調整が求められるようになっている。固体推進薬の燃焼速度を調整する方法の一つとして燃焼触媒を用いる方法がある。酸化鉄は過塩素酸アンモニウムを含む固体推進薬の燃焼速度を高め短時間に大きな推力を得ることができる正燃焼触媒として知られている（例えば特許文献１参照）
一方、固体推進薬の燃焼速度を低下させ長時間の使用を可能とする負燃焼触媒としてはフッ化リチウムのようなリチウム化合物が知られている。（例えば非特許文献１参照）
In recent years, a wide range of combustion speed adjustments have been required for solid propellants for the purpose of expanding the design range and improving the performance of rocket motors. One method for adjusting the combustion rate of the solid propellant is to use a combustion catalyst. Iron oxide is known as a positive combustion catalyst capable of increasing the combustion rate of a solid propellant containing ammonium perchlorate and obtaining a large thrust in a short time (see, for example, Patent Document 1).
On the other hand, lithium compounds such as lithium fluoride are known as negative combustion catalysts that reduce the burning rate of solid propellants and enable long-term use. (For example, see Non-Patent Document 1)
前記特許文献１で燃焼触媒として開示されている酸化鉄は固体推進薬の燃焼速度を増大させるものの、添加量に対する燃焼速度の変化量はそれ程大きくないため、目的とする効果を確保するためには添加量が必然的に多くなるが、その一方で、酸化鉄の添加量が増すと推進薬の比推力が低下する。このため、少量の添加で要求される燃焼速度が得られる触媒効果の高い燃焼触媒の開発が要望されていた。
本発明は、ロケットモータの設計範囲の拡大と高性能化を行うための、幅広い燃焼速度の調整が可能な固体推進薬組成物、および固体推進薬組成物の燃焼速度を調整する方法の提供を目的としている。
Although iron oxide disclosed as a combustion catalyst in Patent Document 1 increases the combustion rate of the solid propellant, the amount of change in the combustion rate relative to the addition amount is not so large, so in order to ensure the intended effect The amount added is inevitably increased, but on the other hand, the specific thrust of the propellant decreases as the amount of iron oxide added increases. For this reason, there has been a demand for the development of a combustion catalyst having a high catalytic effect that can achieve the required combustion rate with a small amount of addition.
The present invention provides a solid propellant composition capable of adjusting a wide range of burning rates and a method for adjusting the burning rate of a solid propellant composition in order to expand the design range and performance of a rocket motor. It is aimed.
本発明者らは、前記の問題点を考慮し鋭意研究した結果、特定の酸化鉄を用いることによって、これらの問題点が解決できることの知見を得て本発明を完成するに至った。即ち本発明は、以下の通りである。
（１）過塩素酸アンモニウムを主成分とする酸化剤及びバインダを含む固体推進薬組成物に平均粒径１〜５０ｎｍの酸化鉄を配合してなることを特徴とする固体推進薬組成物。
（２）過塩素酸アンモニウムを主成分とする酸化剤及びバインダを含む固体推進薬組成物に平均粒径１〜５０ｎｍの酸化鉄を配合することを特徴とする固体推進薬組成物の燃焼速度を調整する方法。
As a result of intensive studies in view of the above problems, the present inventors have obtained the knowledge that these problems can be solved by using specific iron oxide, and have completed the present invention. That is, the present invention is as follows.
(1) A solid propellant composition comprising iron oxide having an average particle size of 1 to 50 nm blended with a solid propellant composition containing an oxidant mainly composed of ammonium perchlorate and a binder.
(2) Combustion rate of a solid propellant composition characterized in that iron oxide having an average particle size of 1 to 50 nm is blended with a solid propellant composition containing an oxidizer mainly composed of ammonium perchlorate and a binder. How to adjust.
本発明の固体推進薬組成物は、幅広い燃焼速度の調整が可能であるため、ロケットモータの設計範囲の拡大と高性能化を達成することができる。 Since the solid propellant composition of the present invention can be adjusted over a wide range of combustion speeds, it is possible to expand the design range of the rocket motor and achieve high performance.
本発明について、以下具体的に説明する。
本発明の固体推進薬組成物は、過塩素酸アンモニウムを主成分とする酸化剤とバインダ（燃料兼結合剤）及び平均粒径が１〜５０ｎｍの範囲にあるナノサイズの酸化鉄を含有することを特徴としている。
本発明において使用される過塩素酸アンモニウムの平均粒径は、特に限定されないが、１〜５００μｍの範囲にあるものが好ましい。平均粒径が１μｍ未満の場合は推進薬の製造性が悪くなり、５００μｍを超えた場合は推進薬の燃焼速度が低下する。
The present invention will be specifically described below.
The solid propellant composition of the present invention contains an oxidizing agent mainly composed of ammonium perchlorate, a binder (fuel and binder), and nano-sized iron oxide having an average particle size in the range of 1 to 50 nm. It is characterized by.
The average particle diameter of ammonium perchlorate used in the present invention is not particularly limited, but is preferably in the range of 1 to 500 μm. When the average particle size is less than 1 μm, the productivity of the propellant is deteriorated, and when it exceeds 500 μm, the combustion rate of the propellant is decreased.
本発明において使用される燃料兼結合剤としては、従来公知の全てのバインダが使用可能である。例えば、末端水酸基ポリブタジエン（ＨＴＰＢ）、末端カルボキシル基ポリブタジエン（ＣＴＰＢ）、末端水酸基ポリエーテル（ＨＴＰＥ）、グリシジルアジドポリマー（ＧＡＰ）や、３，３−ビス（アジドメチル）オキセタン（ＢＡＭＯ）と３−ニトラトメチル−３−メチルオキセタン（ＮＭＭＯ）の共重合体のようなアジド基及びニトラト基含有ポリマー等を主剤とするバインダである。 As the fuel and binder used in the present invention, all conventionally known binders can be used. For example, terminal hydroxyl group polybutadiene (HTPB), terminal carboxyl group polybutadiene (CTPB), terminal hydroxyl group polyether (HTPE), glycidyl azide polymer (GAP), 3,3-bis (azidomethyl) oxetane (BAMO) and 3-nitratomethyl- It is a binder mainly composed of an azide group- and nitrato group-containing polymer such as a copolymer of 3-methyloxetane (NMMO).
前記バインダには、硬化剤としてイソシアネート化合物、例えばイソホロンジイソシアネート、トリレジンイソシアネート、ヘキサメチレンジイソシアネート、ジフェニルメソシアネート、トリフェニルメタントリイソシアネート等が加えられる。また、架橋剤として多官能の水酸基をもつ化合物、例えばトリトリメチロールエタン、トリメチロールプロパン、グリセリン、ヘキサントリオール、ジグリセリン等や、多官能のイソシアネートをもつ化合物等を用いることができる。 An isocyanate compound such as isophorone diisocyanate, triresin isocyanate, hexamethylene diisocyanate, diphenyl mesocyanate, triphenylmethane triisocyanate or the like is added to the binder as a curing agent. In addition, a compound having a polyfunctional hydroxyl group such as tritrimethylolethane, trimethylolpropane, glycerin, hexanetriol, diglycerin, or the like, or a compound having polyfunctional isocyanate can be used as a crosslinking agent.
更に、硬化触媒として、ブチルチントリクロライド、ジブチルチンジアセテート、ジブチルチンジラウレート等の有機錫化合物や、フェリックアセチルアセトン、フェリックジフェニルアセチルアセトン等の有機鉄化合物、トリスパラ−エトキシフェニルビスマス、トリフェニルビスマス、無水マレイン酸等の触媒が使用できる。 Further, as a curing catalyst, organic tin compounds such as butyltin trichloride, dibutyltin diacetate, dibutyltin dilaurate, organic iron compounds such as ferric acetylacetone and ferric diphenylacetylacetone, trispara-ethoxyphenylbismuth, triphenylbismuth, maleic anhydride Etc. can be used.
また、必要に応じてジオクチルアジペート（ＤＯＡ）、ジブチルジグリコールアジペート（ＢＸＡ）、ジブチルフタレート（ＤＢＰ）等の不活性可塑剤や、トリメチロールエタントリナイトレート（ＴＭＥＴＮ）、ブタントリオールトリナイトレート（ＢＴＴＮ）、ブチルニトラトメチルニトラミン（ＢｕＮＥＮＡ）等のようなニトラト基、ニトラミン基を持った化合物や、ＧＡＰ可塑剤のようなアジド基を持った化合物をエネルギー可塑剤として添加することができる。 If necessary, inert plasticizers such as dioctyl adipate (DOA), dibutyl diglycol adipate (BXA), dibutyl phthalate (DBP), trimethylol ethane trinitrate (TMETN), butane triol trinitrate (BTTN) ), A compound having a nitrato group or a nitramine group such as butylnitratomethylnitramine (BuNENA), or a compound having an azide group such as a GAP plasticizer can be added as an energy plasticizer.
本発明において使用される酸化鉄としては、例えば、ＦｅＯ、Ｆｅ２Ｏ３、Ｆｅ３Ｏ４を挙げることができ、その１種類または２種類以上を使用することができる。酸化鉄の粒子形状については特に限定されないが、配合する酸化鉄粒子の平均粒径は１〜５０ｎｍであることが必要である。また、配合後に固体推進薬組成物中に分散して存在する酸化鉄粒子もこの平均粒径を維持することが好ましい。
配合する酸化鉄粒子の平均粒径が１ｎｍ未満の場合は固体推進薬の製造性が悪くなり、５０ｎｍを超えた場合は固体推進薬の燃焼速度増大率が低下する傾向がある。また、このナノサイズの酸化鉄は、バインダもしくは可塑剤と予め混合したものを用いる方が好ましい。これにより、酸化鉄の粒子が凝集することによって起こる固体推進薬の燃焼速度増大率の低下を防止することができる。ナノサイズの酸化鉄の透過型電子顕微鏡写真を図１に示す。
Examples of the iron oxide used in the present invention include FeO, Fe 2 O 3 , and Fe 3 O 4, and one or more of them can be used. Although it does not specifically limit about the particle shape of an iron oxide, The average particle diameter of the iron oxide particle to mix | blend needs to be 1-50 nm. Moreover, it is preferable that the iron oxide particles dispersed and present in the solid propellant composition after blending also maintain this average particle size.
When the average particle diameter of the iron oxide particles to be blended is less than 1 nm, the productivity of the solid propellant is deteriorated, and when it exceeds 50 nm, the burning rate increase rate of the solid propellant tends to decrease. Further, it is preferable to use the nano-sized iron oxide previously mixed with a binder or a plasticizer. Thereby, the fall of the burning rate increase rate of a solid propellant which arises when the particle | grains of an iron oxide aggregate can be prevented. A transmission electron micrograph of nanosized iron oxide is shown in FIG.
本発明の固体推進薬組成物には用途に応じて、過塩素酸アンモニウム以外の酸化剤、助燃剤としての金属粉末及びその他の添加剤を加えることができる。
過塩素酸アンモニウム以外の酸化剤とは、例えば、硝酸アンモニウム、硝酸カリウム等の硝酸塩や、シクロテトラメチレンテトラニトラミン（ＨＭＸ）、シクロトリメチレントリニトラミン（ＲＤＸ）、ヘキサニトロヘキサアザイソウルチタン（ＨＮＩＷ）等のニトラミン化合物や、三酸化モリブデン、三酸化ビスマス等の金属酸化物があげられる。これらの酸化剤は、固体推進薬の安全性向上や環境に対する影響の低減及び高エネルギー化を達成するための手段として過塩素酸アンモニウムと併用される。
The solid propellant composition of the present invention may contain an oxidizing agent other than ammonium perchlorate, a metal powder as a combustion aid, and other additives depending on the application.
Examples of the oxidizing agent other than ammonium perchlorate include nitrates such as ammonium nitrate and potassium nitrate, cyclotetramethylenetetranitramine (HMX), cyclotrimethylenetrinitramine (RDX), and hexanitrohexazayl soul titanium (HNIW). ) And other metal oxides such as molybdenum trioxide and bismuth trioxide. These oxidizing agents are used in combination with ammonium perchlorate as a means for improving the safety of the solid propellant, reducing the influence on the environment, and achieving high energy.
助燃剤としての金属粉末としては、例えば、アルミニウム粉末、マグネシウム粉末等である。金属粉末の平均粒径は通常１００μｍ以下であり、好ましくは０．１〜５０μｍである。平均粒径が１００μｍを超える場合は、金属粉末が完全燃焼しにくくなるため、固体推進薬の燃焼効率が低下する傾向にある。 Examples of the metal powder as the auxiliary combustion agent include aluminum powder and magnesium powder. The average particle diameter of the metal powder is usually 100 μm or less, preferably 0.1 to 50 μm. When the average particle size exceeds 100 μm, the metal powder is hardly combusted, and the combustion efficiency of the solid propellant tends to be reduced.
その他の添加剤としては、アルミナのような金属酸化物や炭化ジルコニウムのような金属炭化物を挙げることができる。これらは固体推進薬の振動燃焼抑制剤として使用することができる。 Examples of other additives include metal oxides such as alumina and metal carbides such as zirconium carbide. These can be used as vibration combustion inhibitors for solid propellants.
前記各成分の固体推進薬組成物中の配合量は、通常、酸化剤が５０〜９０重量％、燃料兼結合剤が１０〜３０重量％、ナノサイズの酸化鉄が０．１〜５重量％、助燃剤が０〜３０重量％、その他の添加剤が０〜５重量％である。 The blending amount of each component in the solid propellant composition is usually 50 to 90% by weight for the oxidizing agent, 10 to 30% by weight for the fuel and binder, and 0.1 to 5% by weight for the nano-sized iron oxide. The auxiliary combustor is 0 to 30% by weight, and other additives are 0 to 5% by weight.
本発明の固体推進薬組成物の製造方法は、ナノサイズの酸化鉄を用いること以外は、通常の固体推進薬の製造方法がそのまま適用できる。例えば、全ての原材料を所定の温度で混和・脱泡し、その後、このスラリー薬を所定の型に減圧注型して、所定の温度と時間をかけて硬化させる方法である。尚、ナノサイズの酸化鉄については、バインダもしくは可塑剤に予め添加してペースト状にしたものを用いてもよい。 As a method for producing the solid propellant composition of the present invention, a normal method for producing a solid propellant can be applied as it is, except that nano-sized iron oxide is used. For example, all the raw materials are mixed and degassed at a predetermined temperature, and then the slurry is poured into a predetermined mold under reduced pressure and cured over a predetermined temperature and time. In addition, about nanosized iron oxide, you may use what was previously added to the binder or the plasticizer, and was made into the paste form.
本発明を実施例に基づいて説明する。
〔実施例１〕
末端水酸基ポリブタジエン（ＨＴＰＢ）１２．５重量部にジオクチルアジペート（ＤＯＡ）２．５重量部を加え混合した。この中に、平均粒径５ｎｍの酸化鉄（Ｆｅ２Ｏ３）０．５重量部を仕込み３０分間混合した。次に、この混合物にイソホロンジイソシアネート（ＩＰＤＩ）１．０重量部と過塩素酸アンモニウム（ＡＰ）８４．０重量部を加えて５０℃で３０分間混和・脱泡を行った。その後、このスラリー薬を所定の型に減圧注型して、６０℃の条件下で１０日間反応させることにより固体推進薬を得た。尚、ここで使用した平均粒径５ｎｍの酸化鉄は、X線小角散乱装置により平均粒径の測定を行った。また、今回、平均粒径は最大分布径として求めた。まず、前処理として酸化鉄をエタノール中で超音波分散処理後に内径０．７ｍｍの石英キャピラリーに封入した。測定されたデータは変換ソフトを使って通常の２θ−I（１次元散乱パターン）表示に変換した。解析は、粒子を球形と仮定し、また分布がΓ分布に従うとして、実験データとのフィッティングを行った。測定結果を図１に、解析結果を図２、３に示す。Ｘ線小角散乱による最大分布径は５．４ｎｍであった。
The present invention will be described based on examples.
[Example 1]
2.5 parts by weight of dioctyl adipate (DOA) was added to 12.5 parts by weight of terminal hydroxyl group polybutadiene (HTPB) and mixed. In this, 0.5 weight part of iron oxide (Fe 2 O 3 ) having an average particle diameter of 5 nm was charged and mixed for 30 minutes. Next, 1.0 part by weight of isophorone diisocyanate (IPDI) and 84.0 parts by weight of ammonium perchlorate (AP) were added to this mixture and mixed and degassed at 50 ° C. for 30 minutes. Thereafter, the slurry was poured into a predetermined mold under reduced pressure and reacted at 60 ° C. for 10 days to obtain a solid propellant. In addition, the average particle diameter of the iron oxide having an average particle diameter of 5 nm used here was measured by an X-ray small angle scattering apparatus. In addition, this time, the average particle diameter was determined as the maximum distribution diameter. First, as a pretreatment, iron oxide was encapsulated in a quartz capillary having an inner diameter of 0.7 mm after ultrasonic dispersion treatment in ethanol. The measured data was converted into a normal 2θ-I (one-dimensional scattering pattern) display using conversion software. In the analysis, it was assumed that the particles were spherical, and fitting with experimental data was performed assuming that the distribution follows the Γ distribution. The measurement results are shown in FIG. 1, and the analysis results are shown in FIGS. The maximum distribution diameter by X-ray small angle scattering was 5.4 nm.
硬化した固体推進薬の燃焼速度は以下の方法により測定を行った。
固体推進薬から外径７ｍｍ、長さ７０ｍｍの円柱状の試料を切り出し、円柱の側面を１ｍｍ厚の樹脂層で被覆した。この試料の上部から約１０ｍｍのところに点火用のニクロム線を通し、２０ｍｍと６０ｍｍの箇所に燃焼速度測定用のヒューズ線を通した。このような試料はストランド試料と呼ばれる。ストランド試料を２０℃に調温された圧力容器内に挿入し、窒素ガスで加圧した後に着火燃焼させて、２本のヒューズ線が切断した時間差とヒューズ線間の距離から固体推進薬の燃焼速度を求めた。測定結果を表２に示す。
また、本組成の固体推進薬の比推力は通常の理論性能計算により求めた。計算結果を表２に示す。
The burning rate of the cured solid propellant was measured by the following method.
A cylindrical sample having an outer diameter of 7 mm and a length of 70 mm was cut out from the solid propellant, and the side surface of the cylinder was covered with a 1 mm thick resin layer. A nichrome wire for ignition was passed through about 10 mm from the top of the sample, and a fuse wire for burning speed measurement was passed through the 20 mm and 60 mm locations. Such a sample is called a strand sample. Insert the strand sample into a pressure vessel adjusted to 20 ° C, pressurize it with nitrogen gas, ignite and burn it, and burn the solid propellant from the time difference between the two fuse wires and the distance between the fuse wires The speed was determined. The measurement results are shown in Table 2.
Further, the specific thrust of the solid propellant having this composition was obtained by ordinary theoretical performance calculation. The calculation results are shown in Table 2.
〔実施例２〜４〕
平均粒径５ｎｍの酸化鉄の配合量を表１のように変えた以外は、実施例１と同様の操作を行って固体推進薬の製造を行い、その燃焼速度と比推力を求めた。結果を表２に示す。
[Examples 2 to 4]
Except that the blending amount of iron oxide having an average particle size of 5 nm was changed as shown in Table 1, the same procedure as in Example 1 was performed to produce a solid propellant, and the combustion rate and specific thrust were obtained. The results are shown in Table 2.
〔比較例１〕
平均粒径５ｎｍの酸化鉄を配合しないこと以外は、実施例１と同様の操作を行って固体推進薬の製造を行い、その燃焼速度と比推力を求めた。結果を表２に示す。
[Comparative Example 1]
A solid propellant was produced in the same manner as in Example 1 except that iron oxide having an average particle size of 5 nm was not blended, and the combustion rate and specific thrust were obtained. The results are shown in Table 2.
〔比較例２〜５〕
平均粒径５ｎｍの酸化鉄の代わりに平均粒径０．４μｍの酸化鉄（Ｆｅ２Ｏ３）を用いること以外は、表１の配合組成で実施例１と同様の操作を行って固体推進薬の製造を行い、その燃焼速度と比推力を求めた。結果を表２に示す。尚、ここで使用した平均粒径０．４μｍの酸化鉄は、動的光散乱装置により平均粒径の測定を行った。また、今回、平均粒径は最大分布径として求めた。まず、前処理として酸化鉄を純水中で超音波分散処理した。動的光散乱測定結果を図４に示す。動的光散乱による最大分布径は０．３６μｍ、メディアン径は０．４３μｍであった。
[Comparative Examples 2 to 5]
A solid propellant was obtained by performing the same operation as in Example 1 with the composition shown in Table 1, except that iron oxide (Fe 2 O 3 ) having an average particle diameter of 0.4 μm was used instead of iron oxide having an average particle diameter of 5 nm. The combustion rate and specific thrust were obtained. The results are shown in Table 2. In addition, the average particle diameter of the iron oxide having an average particle diameter of 0.4 μm used here was measured by a dynamic light scattering apparatus. In addition, this time, the average particle diameter was determined as the maximum distribution diameter. First, as a pretreatment, iron oxide was ultrasonically dispersed in pure water. The dynamic light scattering measurement results are shown in FIG. The maximum distribution diameter by dynamic light scattering was 0.36 μm, and the median diameter was 0.43 μm.
表２に示されている実施例1〜４と比較例１〜５を比較すると、本発明の固体推進薬が高い燃焼速度を有しており、幅広い燃焼速度の調整が可能であることが良く分かる。 Comparing Examples 1 to 4 and Comparative Examples 1 to 5 shown in Table 2, the solid propellant of the present invention has a high burning rate, and it is preferable that a wide range of burning rates can be adjusted. I understand.
本発明の固体推進薬組成物は、ロケットモータの分野で幅広い燃焼速度の調整が可能な推進剤として好適に用いられる。 The solid propellant composition of the present invention is suitably used as a propellant capable of adjusting a wide range of combustion rates in the field of rocket motors.
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