WO2018106312A2 - Compositions pyrotechniques - Google Patents

Compositions pyrotechniques Download PDF

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Publication number
WO2018106312A2
WO2018106312A2 PCT/US2017/053116 US2017053116W WO2018106312A2 WO 2018106312 A2 WO2018106312 A2 WO 2018106312A2 US 2017053116 W US2017053116 W US 2017053116W WO 2018106312 A2 WO2018106312 A2 WO 2018106312A2
Authority
WO
WIPO (PCT)
Prior art keywords
fuel
metallocene
ferrocene
composition according
oxidizer
Prior art date
Application number
PCT/US2017/053116
Other languages
English (en)
Other versions
WO2018106312A3 (fr
Inventor
Morris C. Buenemann
Toni M. WHALEY
George C. Mei
Original Assignee
Olin Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Olin Corporation filed Critical Olin Corporation
Priority to EP17879169.5A priority Critical patent/EP3523266A4/fr
Publication of WO2018106312A2 publication Critical patent/WO2018106312A2/fr
Publication of WO2018106312A3 publication Critical patent/WO2018106312A3/fr

Links

Classifications

    • 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
    • C06B23/002—Sensitisers or density reducing agents, foam stabilisers, crystal habit modifiers
    • C06B23/004—Chemical sensitisers
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B31/00—Compositions containing an inorganic nitrogen-oxygen salt
    • C06B31/02—Compositions containing an inorganic nitrogen-oxygen salt the salt being an alkali metal or an alkaline earth metal nitrate
    • C06B31/12—Compositions containing an inorganic nitrogen-oxygen salt the salt being an alkali metal or an alkaline earth metal nitrate with a nitrated organic compound
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B31/00—Compositions containing an inorganic nitrogen-oxygen salt
    • C06B31/02—Compositions containing an inorganic nitrogen-oxygen salt the salt being an alkali metal or an alkaline earth metal nitrate
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B39/00—Compositions containing free phosphorus or a binary compound of phosphorus, except with oxygen
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06C—DETONATING OR PRIMING DEVICES; FUSES; CHEMICAL LIGHTERS; PYROPHORIC COMPOSITIONS
    • C06C7/00—Non-electric detonators; Blasting caps; Primers

Definitions

  • the present disclosure relates to pyrotechnic compositions, such as priming mix compositions and propellant compositions, and in particular to low and no lead pyrotechnic compositions.
  • Pyrotechnic compositions such as priming mixes, detonating mixtures, propellants, initiators, and similar compositions usually include substances to increase their performances such as sensitivity, propagation, and smoothness of burning (for propellant compositions, meaning without self- extinguishing or transition into detonation).
  • substances to increase their performances such as sensitivity, propagation, and smoothness of burning (for propellant compositions, meaning without self- extinguishing or transition into detonation).
  • sensitivity, propagation, and smoothness of burning for propellant compositions, meaning without self- extinguishing or transition into detonation.
  • lead styphnate C 6 HN 3 O 8 Pb also known as lead 2,4,6-trinitroresorcinate. While lead styphnate is highly effective in these pyrotechnic compositions there are environmental and health and safety concerns over the presences of lead. Efforts have been made to reduce or eliminate lead styphnate without detracting from the performance of the pyrotechnic compositions in which it is used.
  • pyrotechnic compositions with satisfactory sensitivity and propagation with low levels or no levels (other than as inherent impurities) of lead, through the inclusion of a metallocene, and in particular ferrocene.
  • the pyrotechnic compositions according to the various embodiments of this invention generally include a fuel, an oxidizer, and metallocene, a burn modifier, in an amount effective to provide the desired sensitivity and propagation.
  • the metallocene is ferrocene, or a mixture of metallocenes including ferrocene.
  • pyrotechnic compositions designed to produce an effect by heat, light, sound, gas/smoke or a combination of these, from non-detonative self-sustaining exothermic chemical reaction, generally without reliance on oxygen from external sources to sustain the reaction.
  • These compositions comprise flash powders, gunpowders, propellants, pyrotechnic initiators, gas generators, ejection charges, burst charges, smoke compositions, delay compositions; pyrotechnic heat sources, and flares.
  • pyrotechnic compositions according to the principles of this invention include at least a fuel, an oxidizer, and an amount of at least one metallocene effective to improve sensitivity of the composition. This metallocene preferably is or includes ferrocene.
  • a first embodiment pyrotechnic composition in accordance with the principles of this invention is a priming mix for example for a primer for a centerfire cartridge, and comprises a primary explosive, a propagation aid, an oxidizer, and a fuel.
  • the primary explosive can comprise between about 30% and about 60%, and more preferably between about 35% and about 50%, of at least one of KDNBF, dinol, and Tetrazene.
  • the propagation aid can comprise between about 10% and about 35%, and more preferably between about 10% and about 30%, of a metallocene.
  • metallocene is preferably Ferrocene.
  • the oxidizer can comprise between about 5% and about 40%, and more preferably of at least one nitrate, peroxide, or oxide.
  • the oxidizer is preferably at least one of Ba(N0 3 ) 2 , Sr(N0 3 ) 2 , KN0 3 .
  • the fuel can comprise between about 5% and about 25% of at least one of nitrocellulose or PETN as a reactive fuel, and at least one other fuel.
  • This fuel is preferably at least one of boron, aluminum, carbon, metal shavings, or metal sulfides.
  • a second preferred embodiment of the pyrotechnic mix according to the principles of this invention also is a priming mix for example for a primer for a centerfire cartridge, similar to the priming mix of the first preferred embodiment.
  • the primary explosive comprises between about 30% and about 50%, and more preferably between about 35% and about 45%, KDNBF as a primary explosive;
  • the sensitizer comprises between about 2% and about 8% of
  • Tetrazene as a sensitizer; between about 10% and about 30% of a metallocene, such as ferrocene, as a propagation aid; between about 5% and about 40% of an oxidizer, such as at least one of Sr(N0 3 ) 2 and KN0 3 ; and between about 5% and about 20% of a reactive fuel such as powder fines, such as SMP1 1 1 , and/or PETN; and at least one other fuel, such as boron, aluminum, carbon, metal shavings, or metal sulfides.
  • a metallocene such as ferrocene
  • an oxidizer such as at least one of Sr(N0 3 ) 2 and KN0 3
  • a reactive fuel such as powder fines, such as SMP1 1 1 , and/or PETN
  • at least one other fuel such as boron, aluminum, carbon, metal shavings, or metal sulfides.
  • a third preferred embodiment of the pyrotechnic mix of this invention is also a priming mix for example for a primer for a centerfire cartridge similar to the first and second embodiments, in which the primary explosive can comprise between about 35% and about 45% KDNBF; the sensitizer can comprise between about 3% and about 7% of Tetrazene; the propagation aid can comprise between about 12% and about 18% of Ferrocene; the oxidizer can comprise between about 25% and about 35% of Sr(N0 3 ) 2 as an oxidizer; the fuel can include between about 8% and about 12% of PETN, and preferably at least one of boron, aluminum, carbon, metal shavings, or metal sulfides.
  • KDNBF is preferred over dinol, which has a DSC peak decomposition temperature of around 160°C.
  • KDNBF's decomposition temperature is much higher, around 210°C - in the similar range for nitrocellulose or PETN, used in leaded priming mixes.
  • the KDNBF/ferrocene based lead free primers of the preferred embodiments performed as good as or better than prior leaded priming mixes, while dinol-based priming mixes became non-functional.
  • KDNBF may not be as sensitive as lead styphnate.
  • the inventors have found that the sensitivity of a KDNBF mixture can be adjusted by including either a stronger reducing agent (fuel), or a stronger oxidizer, or both.
  • a strong reducing agent such as a metallocene like ferrocene
  • Ferrocene readily loses electrons, which are available to other oxidizers such as KDNBF, reducing the activation energy for the explosive reaction and thus increasing the mixture's sensitivity.
  • a fourth embodiment of the pyrotechnic composition according to the principles of this invention is a priming mix for a rim fire cartridge.
  • the rim fire priming mix comprises a primary explosive, a propagation aid, an oxidizer, a fuel, and a frictionator.
  • the primary explosive can comprise between 25-35% of KDNBF; an optional sensitizer can comprise between 3-7% Tetrazene; the propagation aid can comprise between 10-20% of Ferrocene; the oxidizer can include up to 30% of Sr(N0 3 ) 2 ; up to 25% reactive fuel such as propellant powder fines, and the frictionator can comprise of 30-45% glass shards or beads.
  • Examples of priming mixes according to the compositions in the Table were prepared by pre-weighing all of the ingredients and adding them in layers to a mixing bowl. A proper level of moisture was maintained to ensure safe handling of the mix. The layering separates oxidizers from fuels and the reactive components from the sensitizers. Additional moisture was added as necessary to maintain the final moisture content of the mixture at around 25%. The mixing was carried out remotely and closely monitored. After mixing, the thoroughly mixed and uniformed wet priming mix was removed from the mixing bowl, and pellets of a predetermined volume of the wet mix are made and charged into primer cups, followed by the installation of the anvils. Finally, the assembled primers are dried in an oven before tests. KDNBF KDNBF KDNBF KDNBF KDNBF KDNBF KDNBF KDNBF KDNBF KDNBF KDNBF KDNBF KDNBF KDNBF KDNBF KDNBF KDNBF KDNBF
  • primers from each example were dried, they were subject to sensitivity test, a standard test which has been employed by the ammunition industry.
  • a primer or a primed shell case is installed into a steel die fitted with a firing pin.
  • a steel ball of fixed weight typically 1 .92 oz. for center fire primers
  • the energy of firing pin is controlled.
  • a series of drop tests is performed.
  • a primer either fires or not.
  • the sensitivity of the primer is then quantified statistically by H bar where 50% of the primers will fire, and S, the standard deviation.
  • a sensitivity specification of a primer is based on the H and S system.
  • H+4S and H-2S must fit.
  • a typical sensitivity (H+4S; H-2S) bracket for pistol primer is (9.2"; 2").
  • the KDNBF/ferrocene LF502 primer from Example 1 has (7.63; 4.8), Example 3 (9.0; 4.35); Example 4 (9.7; 3.82), Example 5A has (10.87; 3.65), Example 5B has (10.05; 4.75); Example 6 has (13.3; 3.70); and Example 7 has (14.88, 3.75).
  • the primers were also subjected to full ballistic tests. Results of such tests showed a total transparency by swapping the control ("leaded") primer with the Exhibit 1 (LF502) primer.
  • LF502 Exhibit 1
  • ferrocene will work with any types of explosives containing a nitro, nitrate ester or nitroso group will work with ferrocene.
  • nitro, nitrate ester or nitroso group tends to grab electrons, beginning with the easiest source, in our case, ferrocene.
  • Such explosive could be dinol, or PETN, TNT, RDX, HMX, or any other suitable explosive.
  • Ferrocene could also work with other oxidizers in addition to strontium nitrate, such as nitrates, oxides, dioxides, and/or peroxides.
  • Example 4 (LF495) uses barium nitrate instead of strontium nitrate (9.64; 5.64). Barium is not as toxic as lead, and there is lead free ammunition which still contains barium, but still it is considered as heavy metal.
  • a composition of a priming mix is based upon practicality and governed by sensitivity of the mix, and by the ignition requirements.
  • the initiating explosive (dinol, lead styphnate, KDNBF, etc.) content usually has to be above some threshold to maintain adequate mix sensitivity. This percentage varies depending on the type of initiating explosive and the other ingredients.
  • Tetrazene is a sensitizer and only to be needed at a low level, typically 2-6%. Since tetrazene is a poor energy generator, too much of it reduces the mix performance.
  • PETN or nitrocellulose/nitroglycerin ensures the burn transition from initiating explosive to fuel/oxidizer mixture.
  • the explosive usually burns too fast to allow fuel/oxidizer mixture to catch on.
  • PETN or nitrocellulose/nitroglycerin is like kindling, they are easily ignited but burn slower. Typically, they are in the range from about 5% to about 10%, but can be higher.
  • the ingredients described above are fuel rich, meaning they have insufficient oxygen to burn all carbon to carbon dioxides. Furthermore, their combustion products are mostly gasses, which are not the most efficient form to transfer energy to a propellant bed. Adding fuel and oxidizer generates hot particles which physically touch propellant grains and causing them to ignite much more quickly. Also, they can affect the sensitivity of a mix to a large extent by being a strong fuel or a strong oxidizer.
  • the percentage of fuel and oxidizer varies greatly depending on their chemical composition and a mix's application. Fuel typically is presented at a smaller percentage as the energetics (explosives, PETN, nitrocellulose/nitroglycerin, etc.) in a mix are already fuel rich. As a result, fuel typically runs between 5 to 20%. Oxidizer will then take up the rest of the percentages and are usually at higher percentage, from 25 to 45%.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Air Bags (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)

Abstract

Cette invention concerne une composition de type mélange d'amorçage comprenant entre environ 30 et environ 60 % d'au moins un composé parmi le KDNBF et/ou dinol et/ou tétrazène à titre d'explosif primaire ; entre environ 10 et environ 35 % d'un métallocène à titre d'aide à la propagation ; entre environ 5 et environ 40 % d'au moins un nitrate et/ou peroxyde ou oxyde, à titre d'oxydant ; entre environ 5 et environ 25 % d'au moins une nitrocellulose et/ou un PETN à titre de combustible réactif ; et un combustible. Le métallocène est de préférence le ferrocène.
PCT/US2017/053116 2016-10-05 2017-09-22 Compositions pyrotechniques WO2018106312A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP17879169.5A EP3523266A4 (fr) 2016-10-05 2017-09-22 Compositions pyrotechniques

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201662404624P 2016-10-05 2016-10-05
US62/404,624 2016-10-05

Publications (2)

Publication Number Publication Date
WO2018106312A2 true WO2018106312A2 (fr) 2018-06-14
WO2018106312A3 WO2018106312A3 (fr) 2018-07-12

Family

ID=62492198

Family Applications (1)

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PCT/US2017/053116 WO2018106312A2 (fr) 2016-10-05 2017-09-22 Compositions pyrotechniques

Country Status (3)

Country Link
US (1) US20190023629A1 (fr)
EP (1) EP3523266A4 (fr)
WO (1) WO2018106312A2 (fr)

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3689331A (en) * 1964-02-28 1972-09-05 Us Army Nitrocellulose base compositions and method for making same
US3673015A (en) * 1969-05-23 1972-06-27 Us Army Explosive pyrotechnic complexes of ferrocene and inorganic nitrates
CH676389A5 (fr) * 1987-07-29 1991-01-15 Eidgenoess Munitionsfab Thun
US4963201A (en) * 1990-01-10 1990-10-16 Blount, Inc. Primer composition
DE19616627A1 (de) * 1996-04-26 1997-11-06 Dynamit Nobel Ag Anzündmischungen
GB2329380B (en) * 1997-09-13 1999-08-18 Royal Ordnance Plc Priming composition
US6478903B1 (en) * 2000-10-06 2002-11-12 Ra Brands, Llc Non-toxic primer mix
US6878221B1 (en) * 2003-01-30 2005-04-12 Olin Corporation Lead-free nontoxic explosive mix
US8784583B2 (en) * 2004-01-23 2014-07-22 Ra Brands, L.L.C. Priming mixtures for small arms
WO2012011897A1 (fr) * 2010-07-20 2012-01-26 Olin Corporation Mélange d'amorçage
WO2016075159A1 (fr) * 2014-11-10 2016-05-19 Ruag Ammotec Gmbh Produit de mise à feu à basse température de mise à feu
KR20170134319A (ko) * 2014-12-23 2017-12-06 제너럴 다이나믹스 오드넌스 앤드 택티컬 시스템즈 - 캐나다 인코포레이션 텅스텐 산화물 및 금속 텅스테이트 프라이머 조성물
US9409830B1 (en) * 2015-03-30 2016-08-09 The United States Of America As Represented By The Secretary Of The Army Non-toxic primer mix

Also Published As

Publication number Publication date
EP3523266A2 (fr) 2019-08-14
WO2018106312A3 (fr) 2018-07-12
EP3523266A4 (fr) 2020-06-10
US20190023629A1 (en) 2019-01-24

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