CN107056565A - A kind of Pressure Exponent conditioning agent of solid propellant - Google Patents

A kind of Pressure Exponent conditioning agent of solid propellant Download PDF

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Publication number
CN107056565A
CN107056565A CN201611127275.7A CN201611127275A CN107056565A CN 107056565 A CN107056565 A CN 107056565A CN 201611127275 A CN201611127275 A CN 201611127275A CN 107056565 A CN107056565 A CN 107056565A
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China
Prior art keywords
pressure exponent
conditioning agent
solid propellant
propellant
nitramine
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CN201611127275.7A
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CN107056565B (en
Inventor
宋会彬
庞爱民
汪越
潘新洲
尹欣梅
唐根
张�林
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Hubei Institute of Aerospace Chemical Technology
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Hubei Institute of Aerospace Chemical Technology
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    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06D—MEANS FOR GENERATING SMOKE OR MIST; GAS-ATTACK COMPOSITIONS; GENERATION OF GAS FOR BLASTING OR PROPULSION (CHEMICAL PART)
    • C06D5/00—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets
    • C06D5/06—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets by reaction of two or more solids
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B25/00—Compositions containing a nitrated organic compound
    • C06B25/34—Compositions containing a nitrated organic compound the compound being a nitrated acyclic, alicyclic or heterocyclic amine

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Fire-Extinguishing Compositions (AREA)
  • Medicinal Preparation (AREA)

Abstract

The present invention relates to a kind of Pressure Exponent conditioning agent of solid propellant.Not enough in order to solve the too high prior art of PEG/ nitrates/nitramine system solid propellant combustion rate Pressure Exponent, the present invention provides a kind of Pressure Exponent conditioning agent of solid propellant, and it is by Co3O4With CuO in mass ratio 1:1 compounding is formed.For PEG/ nitrates/nitramine system solid propellant, adding the compound Pressure Exponent conditioning agent of 1.0% content metal oxide can make propellant Pressure Exponent highest be reduced to 0.53 by 0.71, and burn rate is held essentially constant.Popularization of the conditioning agent in PEG/ nitrates/nitramine system propellant, has promoted application of the propellant formulation in tactical missile engine, with highly important military significance.

Description

A kind of Pressure Exponent conditioning agent of solid propellant
Technical field
The present invention relates to a kind of Pressure Exponent conditioning agent of solid propellant, and in particular to one kind is applied to solid propellant Metal oxide be combined Pressure Exponent conditioning agent.
Background technology
Nitrate is plasticized (NEPE) Polyether propellants, is the representative of contemporary high-energy solid propellant, both possesses modified double base The high advantage of propellant energy obtains good mechanical property for adhesive due to introducing macromolecule prepolymer again.PEG/ nitric acid Ester/nitramine system high-energy solid propellant is then the solid propellant of current practical highest level in NEPE propellants, the U.S. The Multiple Type guided missiles such as " trident " II, " dwarf " are had been used for, China is also had been used in a variety of strategic missile weapons of new generation, greatly Amplitude improves the performance level of strategic arms.And as current high-energy solid propellant application is progressively opened up by strategic arms Open up and lay equal stress on to strategy and tactics, its due to the introducing of a large amount of HMX and nitrate make the burning rate pressure exponent of propellant significantly improve with The contradiction of the relatively low Pressure Exponent requirement of tactics engine, and due in PEG/ nitrates/nitramine system propellant Nitric acid ester content is higher so that the original obvious ferrocene class of effect, ammonium salt, lead bronze salt also effect in fourth hydroxyl and double base propellant Also not substantially, it significantly limit application of the high-energy solid propellant in tactical weapon.
Due to the demand of high-energy in PEG/ nitrates/nitramine system propellant, more than 40.0% has been used in system HMX (or RDX) and more than 8.0% nitrate, therefore its combustibility depends primarily on the thermal decomposition of HMX and nitrate Journey.It is N that nitramine and nitrate, which thermally decompose condensed phase and its primary product on surface,2O, NO, HCN and CO2Deng, they combustion face it is attached Proximal response activity is not high, thus can not feed back the enough heats in combustion face, there is thicker dark space in flame structure, thus Relatively low burn rate is shown during low pressure, but with the rising of pressure, dark space starts thinning, and burn rate is sharply increased, and causes propellant Show as higher Pressure Exponent.
Mainly use regulation oxidation for the technological approaches of the Pressure Exponent of reduction high-energy propellant both at home and abroad at present Agent AP grain size distribution and the species for changing plasticizer.The AP of regulation oxidant granularity can be reduced to a certain extent to be pushed away Enter the Pressure Exponent of agent, but propellant burning rate can be increased substantially simultaneously；And the species for changing plasticizer refers in reduction pressure It can then cause being greatly lowered for Propellant warp while number.
The content of the invention
The technical problems to be solved by the invention are：For PEG/ nitrates/nitramine system high-energy propellant Pressure Exponent Higher the problem of, using cobaltosic oxide (Co3O4) and cupric oxide (CuO) metal composite oxide, propellant burning rate can kept In the case of without significant change, propellant Pressure Exponent is effectively reduced.
It has been found that Co type oxides and Cu type oxides, are compounded by certain proportion, its herbicide interactions can promoted Play a part of catalytic reaction during agent nitramine and nitrate decomposition of components, promote OH, H in product2The high activities such as O, CO are produced The content of thing is increased considerably, so that combustion flame dark space thickness reduces and feeds back enough heat to combustion face, promote nitramine and The low pressure decomposition of nitrate, so as to reach the purpose of reduction Pressure Exponent.The compounding use of Co type oxides and Cu type oxides, Add 1% content, can in PEG/ nitrates/nitramine system in propellant burning rate without significant change in the case of, make propellant 3~12MPa under Pressure Exponent highest be reduced to 0.53 from 0.71, effectively advance PEG/ nitrates/nitramine system high Application of the energy propellant in tactical missile weapon, and Co is had no both at home and abroad at present3O4It is solid for high energy with CuO composite oxides The relevant report of body propellant Pressure Exponent regulation.
The present invention technical solution be：
A kind of Pressure Exponent conditioning agent of solid propellant, it is formed by cobaltosic oxide and cupric oxide compounding.
Preferably, the mass ratio of cobaltosic oxide and cupric oxide is 1 in the Pressure Exponent conditioning agent:1.
Preferably, content of the Pressure Exponent conditioning agent in solid propellant is 0.5%~1.0%.
Preferably, the formula system of the solid propellant is PEG/ nitrates/nitramine system.
Preferably, adhesive composition is polyethylene glycol (PEG) in described PEG/ nitrates/nitramine system.
Preferably, plasticizer is nitroglycerine (NG), BTTN in described PEG/ nitrates/nitramine system (BTTN), one or both of triethylene glycol dinitrate (TEGDN) combination of the above.
Preferably, oxidant includes ammonium perchlorate and energetic oxidizer in described PEG/ nitrates/nitramine system, described Oxidant account for the 55%~65% of system quality, wherein described energetic oxidizer be hexogen and HMX one kind or Two kinds.Preferably, fuel is aluminium powder in described PEG/ nitrates/nitramine system, and content accounts for the 15%~20% of system quality.
Preferably, curing agent is toluene di-isocyanate(TDI) ester (TDI), many officials in described PEG/ nitrates/nitramine system One or both of energy degree isocyanates (N-100) combination of the above.
It is an advantage of the invention that：Consumption is few, and effect substantially, and does not make significant difference to propellant burning rate.Using Co3O4·CuO Pressure under metal composite oxide Pressure Exponent conditioning agent, addition (accounting for propellant gross mass) 0.5%, 3~12MPa of propellant Index highest is reduced to 0.64 from 0.71；Pressure Exponent under addition (accounting for propellant gross mass) 1.0%, 3~12MPa of propellant 0.53 is reduced to from 0.71；And while propellant Pressure Exponent is reduced, propellant burning rate is not made significant difference, and it is existing Propellant Pressure Exponent technology is reduced, while propellant Pressure Exponent is reduced, propellant burning rate is generally resulted in significantly Degree lifting.
Embodiment
With reference to embodiment, the present invention will be described, but is in no way limited to this.Those skilled in the art exist Made modification or replacement should be included within the scope of patent protection of the present invention on the basis of technical solution of the present invention.
Embodiment 1
PEG/NG/BTTN/HMX propellant blank formulas, no Co3O4CuO metal composite oxides Pressure Exponent is adjusted Agent, propellant composition is shown in Table 1.
The PEG/NG/BTTN/HMX propellants blank formula of table 1 is constituted
Without Co3O4CuO metal composite oxide Pressure Exponent conditioning agent blank propellant formulation combustibilities are as follows：
1) propellant burning rate under 6.86MPa normal pressures：r6.86MPa=12.82mm/s
2) propellant burning rate Pressure Exponent meets r=3.2666p under 3~12MPa pressure0.71, n=0.71
Embodiment 2
In PEG/NG/BTTN/HMX propellant blank formulas, 0.5% Co is added3O4CuO metal composite oxide pressures Strong index conditioning agent, propellant composition is shown in Table 2.
The PEG/NG/BTTN/HMX propellant formulations of table 2 are constituted
Containing 0.5%Co3O4The propellant formulation combustibility of CuO metal composite oxide Pressure Exponent conditioning agents is as follows：
1) propellant burning rate under 6.86MPa normal pressures：r6.86MPa=12.80mm/s
2) propellant burning rate Pressure Exponent meets r=3.7322p under 3~12MPa pressure0.64, n=0.64
Embodiment 3
In PEG/NG/BTTN/HMX propellant blank formulas, 1.0% Co is added3O4CuO metal composite oxide pressures Strong index conditioning agent, propellant composition is shown in Table 3.
The PEG/NG/BTTN/HMX propellant formulations of table 3 are constituted
Containing 0.5%Co3O4The propellant formulation combustibility of CuO metal composite oxide Pressure Exponent conditioning agents is as follows：
1) propellant burning rate under 6.86MPa normal pressures：r6.86MPa=12.81mm/s
2) propellant burning rate Pressure Exponent meets r=4.6163p under 3~12MPa pressure0.53, n=0.53
Embodiment 4
PEG/NG/TEGDN/HMX propellant blank formulas, no Co3O4CuO metal composite oxides Pressure Exponent is adjusted Agent, propellant composition is shown in Table 4.
The PEG/NG/TEGDN/HMX propellants blank formula of table 4 is constituted
Without Co3O4CuO metal composite oxide Pressure Exponent conditioning agent blank propellant formulation combustibilities are as follows：
1) propellant burning rate under 6.86MPa normal pressures：r6.86MPa=10.86mm/s
2) propellant burning rate Pressure Exponent meets r=2.9318p under 3~12MPa pressure0.68, n=0.68
Embodiment 5
PEG/NG/TEGDN/HMX propellant blank formulas, the Co of addition 0.5%3O4CuO metal composite oxide pressure Index conditioning agent, propellant composition is shown in Table 5.
The PEG/NG/TEGDN/HMX propellant formulations of table 5 are constituted
The Co of addition 0.5%3O4CuO metal composite oxide Pressure Exponent conditioning agent blank propellant formulation flammabilities Can be as follows：
1) propellant burning rate under 6.86MPa normal pressures：r6.86MPa=10.88mm/s
2) propellant burning rate Pressure Exponent meets r=3.3610p under 3~12MPa pressure0.61, n=0.61
Embodiment 6
PEG/NG/TEGDN/HMX propellant blank formulas, the Co of addition 1.0%3O4CuO metal composite oxide pressure Index conditioning agent, propellant composition is shown in Table 6.
The PEG/NG/TEGDN/HMX propellants blank formula of table 6 is constituted
The Co of addition 1.0%3O4CuO metal composite oxide Pressure Exponent conditioning agent blank propellant formulation flammabilities Can be as follows：
1) propellant burning rate under 6.86MPa normal pressures：r6.86MPa=10.90mm/s
2) propellant burning rate Pressure Exponent meets r=3.7075p under 3~12MPa pressure0.56, n=0.56.

Claims (9)

1. a kind of Pressure Exponent conditioning agent of solid propellant, it is characterised in that：The Pressure Exponent conditioning agent is by four oxidations three Cobalt and cupric oxide compounding are formed.
2. the Pressure Exponent conditioning agent of solid propellant according to claim 1, it is characterised in that：The Pressure Exponent is adjusted The mass ratio for saving cobaltosic oxide and cupric oxide in agent is 1:1.
3. solid propellant Pressure Exponent conditioning agent according to claim 1, it is characterised in that：The Pressure Exponent regulation Content of the agent in solid propellant is 0.5%~1.0%.
4. the Pressure Exponent conditioning agent of solid propellant according to claim 1, it is characterised in that：The solid propellant Formula system be PEG/ nitrates/nitramine system.
5. the Pressure Exponent conditioning agent of solid propellant according to claim 4, it is characterised in that：Described PEG/ nitric acid Adhesive composition is polyethylene glycol in ester/nitramine system.
6. the Pressure Exponent conditioning agent of solid propellant according to claim 4, it is characterised in that：Described PEG/ nitric acid Plasticizer is one kind or two in nitroglycerine, BTTN, triethylene glycol dinitrate in ester/nitramine system Plant combination of the above.
7. the Pressure Exponent conditioning agent of solid propellant according to claim 4, it is characterised in that：Described PEG/ nitric acid In ester/nitramine system oxidant include ammonium perchlorate and energetic oxidizer, described oxidant account for system quality 55%~ 65%, wherein described energetic oxidizer is the one or two of hexogen and HMX.
8. the Pressure Exponent conditioning agent of solid propellant according to claim 4, it is characterised in that：Described PEG/ nitric acid Fuel is aluminium powder in ester/nitramine system, and content accounts for the 15%~20% of system quality.
9. the Pressure Exponent conditioning agent of solid propellant according to claim 4, it is characterised in that：Described PEG/ nitric acid Curing agent is one or both of toluene di-isocyanate(TDI) ester, polyfunctionality isocyanates combination of the above in ester/nitramine system.
CN201611127275.7A 2016-12-09 2016-12-09 Pressure index regulator of solid propellant Active CN107056565B (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1935662A (en) * 2006-10-19 2007-03-28 浙江大学 Nano crystal constructed porous copper oxide aggregate and its preparing method
CN101402464A (en) * 2008-10-15 2009-04-08 江南大学 Method for producing nano-cupric oxide with film method
CN103212429A (en) * 2012-01-20 2013-07-24 中北大学 Catalyst for accelerating burning rate used for reducing pressure exponent of nitramine propellant
CN103711609A (en) * 2013-12-11 2014-04-09 湖北航天化学技术研究所 Method for improving interface bonding performance of EPDM (ethylene prophlenediene monomer) heat insulating layer, HTPB (hydroxyl-terminated polybutadiene) lining and NEPE (nitrate ester plasticized polyether propellant)
CN105198681A (en) * 2014-06-10 2015-12-30 湖北航天化学技术研究所 Room-temperature-cured-type clean solid propellant
US20160054109A1 (en) * 2014-01-21 2016-02-25 Jonathan Mohler Self-Propelled Projectile Having a Fuel-Rich Propellant that Reacts with Water

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1935662A (en) * 2006-10-19 2007-03-28 浙江大学 Nano crystal constructed porous copper oxide aggregate and its preparing method
CN101402464A (en) * 2008-10-15 2009-04-08 江南大学 Method for producing nano-cupric oxide with film method
CN103212429A (en) * 2012-01-20 2013-07-24 中北大学 Catalyst for accelerating burning rate used for reducing pressure exponent of nitramine propellant
CN103711609A (en) * 2013-12-11 2014-04-09 湖北航天化学技术研究所 Method for improving interface bonding performance of EPDM (ethylene prophlenediene monomer) heat insulating layer, HTPB (hydroxyl-terminated polybutadiene) lining and NEPE (nitrate ester plasticized polyether propellant)
US20160054109A1 (en) * 2014-01-21 2016-02-25 Jonathan Mohler Self-Propelled Projectile Having a Fuel-Rich Propellant that Reacts with Water
CN105198681A (en) * 2014-06-10 2015-12-30 湖北航天化学技术研究所 Room-temperature-cured-type clean solid propellant

Non-Patent Citations (1)

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Title
刘建勋: "新型碳纳米管基复合燃烧催化剂的制备及其在固体推进剂中的应用", 《中国博士学位论文全文数据库工程科技I辑》 *

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