ENERGETIC MATERIALS CO. 1/24 INVESTIGATING ALTERNATIVE ‘GREEN’ PRIMARY EXPLOSIVES John Hirlinger US Army ARDEC Mounted & Dismounted Infantry Munitions

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ENERGETIC MATERIALS CO.

INVESTIGATING ALTERNATIVE ‘GREEN’ PRIMARY EXPLOSIVES

John Hirlinger US Army ARDEC

Mounted & Dismounted Infantry Munitions GroupArmament Engineering & Technology Center

973-724-6498 [email protected]

39th Annual Guns & Ammunition Conference

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• Develop environmentally friendly alternatives to replace Lead and other Heavy Metals, Volatile Organic Compounds (VOCs), & Carcinogens while maintaining ammunition safety and performance requirements

Program Goal

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ENVIRONMENTALLY UNFRIENDLY COMPOUNDS USED IN MEDIUM CALIBER MUNITIONS

HEAVY METALS VOCs SUSPECTEDCARCINOGENS

Antimony Sulfide 2- Butoxyethanol Methylene ChlorideBarium Nitrate N-methyl 2-Pyrrolidone DiphenylamineDepleted Uranium Ethyl Alcohol DibutylphthalateLead Azide Ethyl Benzene NitroglycerineLead Styphnate Methyl Isobutyl KetoneCadmium XyleneNickel Acetate TolueneChromium VII LoctiteLead Formaldehyde

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Sponsor/Customer• Strategic Environmental Research &

Development Program (SERDP) – Dept of Defense’s (DoD) corporate environmental

R&D activityPartnered with Dept of Energy (DoE) + Environmental

Protection Agency (EPA)

– Identifies & develops environmental technologies directly related to defense mission accomplishment

– Providing funding

• SERDP Web Site – www.serdp.org

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Multi-Year Priority Sequencing of Green Activities & Program Funding

FY02 StartFY03 Start

Planned

Task NameIgnition Systems

Percussion

Electric

Miniature Detonators

Miniature Fuze Electronics

Detonators & Explosive Boosters

Propellants

Tracers/Incendiaries

Sealants/Adhesives

Paints

Metal Parts

'00 '01 '02 '03 '04 '05 '06 '07 '08

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M r. M ike E llisP P -1 3 08

U S A rm y T A C O M -A R D E CL e a d F re e P e rc P rim er

M r. R o n Jo n esP P -1 3 31

U S N a vy N A V A IRL e a d Fre e E le c tric P rim er

M r. Jo h n H irlin g erP P -1 3 07

U S A rm y T A C O M -A R D E CA lt C o m p fo r E lec tric D e ts

D r. R o ss M illa rP P - 13 06

Q in e tiQ , Inc . UKL e a d F re e M tls fo r E lec D e ts

D r. A le xa nd e r G a shP P -1 3 62

L a w ren ce L ive rm o re NLB e n ig n Im p a ct D ev ices

D r. Je ff A ke s terP P -1 3 63

A T K T h io ko l P ro p u ls ionE n v Frie nd ly G u n P ro p e lla n t

M r. Jo h n H irlin g erP P -1 3 64

U S A rm y T A C O M -A R D E CN e w P rim a ry De to n a to r E xp ls

D r. N icho la s P ro ko p ukP P -1 3 59

U s N a vy N A V A IRA ll o rg a n ic su p erca pa c ito r

D r. D a vid C h uaP P -1 3 60

M a xpo w e r, In c.M n 02 Ca th od e fo r B a tte ries

R o m a n F ed ynaP rin cip a l Inve s tig a to r

U S A rm y T A C O M -A R D E CP ica tinn y A rsen a l, NJ

D r. R o b in N issanT A C C h a ir

U S N a vy, N A V A IRC h in a L a ke , CA

Green Medium Caliber MunitionsProgram Organization

= FY02 = FY03

*

*

*

*

** Denotes SEED Program

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Environmental Focus

Heavy Metal Free Primers (Percussion/Electric)Lead Free Detonators/Initiators• Thermo-Plastic Elastomer (TPE) Propellants• Organic Super capacitors

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PRIMERS

MIC + ADDITIVESAluminumMolybdenum TrioxideEthyl CelluloseCalcium ResinatePETNBTATZ

HydrogenCarbon Monoxide

CarbonAluminum

AluminaMolybdenum

Aluminum OxideAluminum Nitride...and other traces

Green Primer Composition

YIELDS

Lead StyphnateBarium NitrateAntimony SulfideAluminumPETNTetracene

Carbon MonoxideNitrogen

Carbon DioxideWater

AluminaAntimony Sulfide

Barium OxideSulfur Dioxide

HydrogenLead

Barium HydroxideSulfer Monoxide

Lead Sulfide...and other traces

Conventional Primer Composition

YIELDS

Environmentally acceptable medium caliber percussion primer yields no toxic by-products in comparison to conventional primer compositions

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+ ++

WHAT’S MIC ?

METASTABLE INTERMOLECULAR COMPOSITES

Super-thermite mixture of Aluminum + OxidizerApplying Nano-Technology (nanometer sized particles)Reactant clusters in atomic-scale proximityTailored EnergeticTunable IgnitionReduced Toxicity / No Heavy MetalsNano Aluminum behaves different than micron size

2Al MoO3 Al2O3 Mo Heat

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MICs RELEASE MORE ENERGY THAN HIGH EXPLOSIVES

10 2 3 4 5 6 7

H mass (kcal/g)

volume

EXPLOSIVES

MICs

H (kcal/cc)

Al/CuO

Al/MoO3

Al/Teflon

Al/KClO4

PBX 9502

TNT

OCTOL

HMX

H volume

H mass

10 2 3

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Primer Output Flame Test Comparisons For Primers

Al/MoO3-based MIC Primer Standard PVU-1A Primer (Lead Styphnate)

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Transmission Electron Microscopy (TEM) of MIC East Nano Aluminum Powder

2.5 nm thick Al2O3

passivation layer

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Percussion Primer Formulations Tested• M793 TP-T Ballistic Test Series (Mar 04)

• M115 w/o booster • MIC +10 w/o booster• MIC +10 w/ booster pellet (BKNO3)• MIC w/ booster (BKNO3)

Primer Mid Case Chamber Press (psi)

Req’t < 72,000 psi

Muzzle Velocity (m/s)

Req’t = 1,100 m/s

Action Time (msec)

Req’t < 6.0 msec

Standard M115

(7 rounds)64,443 1,100 4.225

MIC + 10 w/o booster (5 rounds)

61,772 1,100 102.328

MIC + 10 w/ booster (5 rounds)

61,210 1,107 4.632

MIC w/ booster

(4 rounds)59,968 1,107 5.026

Acceptable action times!

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Electric DetonatorsCurrent

^^^^^^Lead Styphnate

+ _

Transfer Charge –

Lead Azide

Output Charge (RDX, HMX)

+ _

^^^^^^

Output Charge

(RDX, HMX, CL-20)

DAHA

New

DAHA = Cyclophosphazene

Silver 5 - Nitrotetrazolate

NEW TRANSFER CHARGES

NEW INITIATING MIX

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STATIC FIRING RESULTS

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NOL-130 Stab mix:Lead styphnateBarium nitrateLead azideTetrazeneAntimony sulfides

Metal or paper seal

Transfer charge:Lead azide

Output Charge:

RDX, HMX

Metal cup

Current Stab Detonator Design and Composition

Dia.= 0.2 - 0.65 cm

Length = 0.4 - 1.3 cm

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New Stab mix:Sol-gel booster coatedNanolaminate Components: Aluminum,Ferric oxide, titanium, zirconium

New Transfer Charge Candidates:ENTA C5NT

5-AZIDO-3-NITRO[1,2,4]-TRIAZOLE, CU1,5-DIAMINOTETRAZOLE,

PERCHLORAMIDES

Output charge

GREEN STAB DETONATOR

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Characterization Tests – FrictionSERDP & NSWC Compounds

CODE

CANDIDATE

NO-FIRELEVEL

(gms)

MIN. FIRE LEVEL

(gms) 13A1 Copper (II) 5-nitrotetrazole 55 65 15A KBFNP 20 30 17A 5-Azido-3-nitro-[1,2,4]-triazole, Cu * 2075 >2075 17A 5-Azido-3-nitro-[1,2,4]-triazole, Cu # 975 1000 19A Nitramino-diazido-triazine, Rb 850 900 19A Nitramino-diazido-triazine, Cs 175 200 28A 1,5-Diaminotetrazole, Cu complex 100 110 28A 1,5-Diaminotetrazole, Fe complex 40 50 29A DAATO 3.5 2075 >2075 NLS GY90022 40 50

Samples were dried at 65ºC for >2 hrs and stored in desiccator until run unless otherwise indicatedJulius-Peters Small BAM

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Characterization Test – Impact SERDP & NSWC Compounds

CODE

CANDIDATE

IMPACT (J)

13A1 Copper (II) 5-nitrotetrazole 0.057±0.006 15A KBFNP * 0.009±0.002 17A 5-Azido-3-nitro-[1,2,4]-triazole, Cu * 0.015±0.002 19A Nitramino-diazido-triazine, Rb * 0.012±0.003 19A Nitramino-diazido-triazine, Cs * 0.013±0.003 28A 1,5-Diaminotetrazole, Cu complex * 0.011±0.003 28A 1,5-Diaminotetrazole, Fe complex # 0.013±0.002 29A DAATO 3.5 # 0.085±0.025 NLS GY90022 0.025±0.001

* Temp=62ºF RH=32% # Temp=62ºF RH=49%

Samples were dried at 65ºC for >2 hrs and stored in desiccator until run unless otherwise indicatedBall Drop Method, Bruceton Analysis

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Characterization Test – Strong Ignition (10kpsi Screening)

CODE

CANDIDATE

LOADING PRESSURE

(kpsi)

AVERAGE CHARGE DENSITY

(g/cm3)

AVERAGE DENT IN Al

BLOCK (mils)

13A1 Copper (II) 5-nitrotetrazole 10 1.440 13.2 15A KBFNP 10 1.626 0.8 17A 5-Azido-3-nitro-[1,2,4]-triazole, Cu 10 1.421 2.3 19A Nitramino-diazido-triazine, Rb 10 1.810 0.8 19A Nitramino-diazido-triazine, Cs 10 2.026 0.5 28A 1,5-Diaminotetrazole, Cu complex 10 1.412 16.8 28A 1,5-Diaminotetrazole, Fe complex 10 1.465 27.0 29A DAATO 3.5 10 1.203 0.0 LA RD1333, LN 40148 10 3.119 37.3

Samples were dried at 65ºC for >2 hrs and stored in desiccator until run unless otherwise indicated

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Characterization Test – Strong Ignition

CODE

CANDIDATE LOADING PRESSURE

(kpsi)

AVERAGE CHARGE DENSITY

(g/cm3)

AVERAGE DENT IN Al

BLOCK (mils)

5 1.26 9.0 10 1.38 22.6 20 1.53 31.7

13A1 Copper (II) 5-nitrotetrazole

40 1.77 29.0 5 1.18 25.0

10 1.33 23.7 20 1.52 14.7

28A 1,5-Diaminotetrazole, Cu complex

40 1.69 7.7 5 1.28 35.3

10 1.40 40.3 20 1.52 37.7

28A 1,5-Diaminotetrazole, Fe complex

40 1.63 23.3 5 2.62 27.7

10 2.99 33.7 20 3.18 39.0

LA (RD-1333)

40 3.55 46.3

Samples were dried at 65ºC for >2 hrs and stored in desiccator until run unless otherwise indicated

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Expected Payoff

• Development of environmentally friendly formulations and manufacturing processes

• Significantly reduce generation and

release of toxic materials

• Reduce or eliminate range contamination

• Positive impact on ammunition life cycle cost

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Green Medium Caliber Ammunition

Program Summary Environmental issues are numerous and diverse

Systematic approach developed to address specific issues on DoD wide system level

Elimination of toxic heavy metals being addressed

Plan in place to address all contaminants in major ammunition components

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Chemical Acronyms/Names • (ENTA)1,1-(N,N-ethylenedinitramino)-3,3,5,5- tetraazidocyclotriphosphazene

• (C5NT) Copper(II) 5- nitrotetrazolate

• (DAHA) 1,1-diamino-3,3,5,5,7,7- hexaazidocyclotetraphosphazene

• (RDX) – Royal Demolition Explosive – cyclotrimethylene-trinitramine

• (HMX) – High Melting Explosive – cyclotetramethylene-tetranitramine

• (CL 20) - Hexanitrohexaazaisowurtzitane

Documents

ENERGETIC MATERIALS CO. 1/24 INVESTIGATING ALTERNATIVE ‘GREEN’ PRIMARY EXPLOSIVES John Hirlinger US Army ARDEC Mounted & Dismounted Infantry Munitions