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2009 Insensitive Munitions and Energetic Materials Technology Symposium
FOX-7, an IM Ingredient Candidate – Where Are We Today?
FOX-7, an IM Ingredient Candidate – Where Are We Today?
Helena Bergman, Anna Pettersson and Henric Östmark,Swedish Defence Research Agency, FOI
Helen Stenmark and Carina Bergvall-LaitalaEurenco Bofors AB
Helena Bergman, Anna Pettersson and Henric Östmark,Swedish Defence Research Agency, FOI
Helen Stenmark and Carina Bergvall-LaitalaEurenco Bofors AB
2009 Insensitive Munitions and Energetic Materials Technology Symposium
OutlineOutlineWhy new Energetic MoleculesFOX-7 BasicsFOX-7 CrystalsFOX-7 Formulations and ApplicationsConclusions
Why new Energetic MoleculesFOX-7 BasicsFOX-7 CrystalsFOX-7 Formulations and ApplicationsConclusions
2009 Insensitive Munitions and Energetic Materials Technology Symposium
Ways to Insensitive Munitions..Ways to Insensitive Munitions..Modify the energetic material Modify the composition Modify the munition
Modify the packagingModify the ammunition depot or storage
2009 Insensitive Munitions and Energetic Materials Technology Symposium
Ways to Insensitive Munitions..Ways to Insensitive Munitions..Modify the energetic material Modify the composition Modify the munition
Modify the packagingModify the ammunition depot or storage
FOI activities
2009 Insensitive Munitions and Energetic Materials Technology Symposium
FOX-7FOX-71,1-Diamino-2,2-dinitroethyleneDeveloped at FOI in 1997--WO Patent No. 9903818Produced by EURENCO Bofors AB under licence by Swedish Government
1,1-Diamino-2,2-dinitroethyleneDeveloped at FOI in 1997--WO Patent No. 9903818Produced by EURENCO Bofors AB under licence by Swedish Government
HNO3/H2SO45-10oC
H+, H2O
H2N
H2N
NO2
NO2
88%
N NH
O O
HN NH
O O
O2N NO2
O2N NO2
FOX-7 BasicsFOX-7 BasicsLow sensitivity explosivesSimple synthesis
Low sensitivity explosivesSimple synthesis
Density (crist): 1.885 g/cm3
Heat of Formation: -32 kcal/moleSensitivity: drop weight 70 cm
(RDX 38 cm)
friction > 350 N
(RDX 120 N)
Explosion Temperature: 215 oC
(RDX 220 oC)
Detonation Pressure (calc): 33.96 GPa
(RDX 34.63 GPa)
Detonation Velocity (meas.): 8870
m/s
(RDX 8930 m/s)
H2N
H2N
NO2
NO2
N NH HN NH
O2N NO2
OO2N NO2
HNO3/H2SO4 aq NH3
SynthesisSynthesis
Crystal StructureCrystal Structure
FOX-7
Impact and Friction Sensitivity of FOX-7Impact and Friction Sensitivity of FOX-7
Sample Drop height (cm)
Friction (N)
FOX-7 (recryst., 250–355 μm) 79
FOX-7 (recryst., < 70 μm) 63 >340
RDX 38 126
FOX-7: DSCFOX-7: DSC
Temperature (oC)100 150 200 250 300 350
Hea
t Flo
w (
W)
0
10
20
30
40
50
60
1000/T1.94 1.96 1.98 2.00 2.02 2.04
ln (R
)
-1
0
1
2
3Ea
=234
kJ/mole (56
kcal/mole)
FOX-7: SSGTFOX-7: SSGT
Acceptor (FOX-7)
Donor (RDX 98/1/1)
Attenuator (PMMA)
Witnessblock
HolderDetonator
12.7 mm
38.1 mm
3.59 - 12.73 mm
38.1 mm
38.1 mm
76.2 mm
25.4 mm
5.11 mm
EXPLOSIVE DENSITY(g/cc)
AttenuatorThickness
(mm)Tetryl 1.65 8.36
HNS II 1.635 7.19
TNT 0.92*TMD 6.4
HMX 0.92*TMD 10.3RDX 0.92*TMD 9.33FOX-7 1.634 6.22
2009 Insensitive Munitions and Energetic Materials Technology Symposium
FOX-7FOX-7Small-scale gap test
Air gap test
Small-scale gap test
Air gap testName Density Distance
(50% probability point)
TNT 1.51 g/cm3 (91% of TMD) 34 –
35 mm
FOX-7 1.72 g/cm3 (91% of TMD) 35 –
37.5 mm
Composition B 1.59 g/cm3 (91% of TMD) 60 –
62.5 mm
H. Östmark et al. Int. Det. Symp. (1998)R. Adolfsson et al. FOI-R-0668-SE (2003)
Name Density Distance
(50% probability point)
FOX-7 1.63 g/cm3 (86% of TMD) 6.2 mm
TNT 1.53 g/cm3
(92% of TMD) 6.4 mm
RDX 1.66 g/cm3
(92% of TMD) 9.3 mm
FOX-7: Ignition Temperature (Wood’s metal bath)
FOX-7: Ignition Temperature (Wood’s metal bath)
Temperature of metal bath [ C]
210 220 230 240 250 260 270
Tim
e to
reac
tion
[s]
0
50
100
150
200
250
No reaction when T < 215oC(RDX ignites at 220°C)
FOX-7: KOENEN TEST (Steel sleeve test)
FOX-7: KOENEN TEST (Steel sleeve test)
Type “F”
reaction at nozzle plate diameter 6 mmRDX explodes at nozzle plate diameter 8 mm
FOX-7: Compatibility by HFCFOX-7: Compatibility by HFCPolymer Ea (J/g/week) Cab (J/g/week)CAB (BF900) 0.38 -0.38 Estane 0.27 -0.26 GAP (SNPE) 2.57 -0.44 HTPB (R-45 HT) 1.89 3.89 HTPB (Krasol LBH) 0.24 0.13 Viton 0.10 0.03 Isocyanate H12MDI 0.70 0.41 Plasticizer Butyl-NENA 1.07 0.16 K-10 0.41 0.44
2ba
ababEEEC
Incompatible:C>20 J/g/week
Slightly Incompatible:10 J/g/week
<C<20J/g/week
Compatible:C<10 J/g/week
2009 Insensitive Munitions and Energetic Materials Technology Symposium
FOX-7 Cylinder testsFOX-7 Cylinder tests
detail image
Pcj (Gpa)
E0 (kJ/cc)
A (Gpa)
B (Gpa)
R1 R2 w
27.9 8.663 998.6 8.78 4.93 1.12 0.40
Data for FOX-7 + 1.5 w% wax, δ
= 1.756 g/cc The detonation velocity was estimated to 8.335 ±
0.025 mm/μs;
A Cheetah calculation, BKWC, gave a velocity of 8.266 mm/μs, which is in good agreement with the experimental value.
2009 Insensitive Munitions and Energetic Materials Technology Symposium
FOX-7FOX-7
Candidate for ingridients in BoostersShape Charge warheadsHigh performance warheadsRocket and gun propellants
Particle size and particle quallity is very important for sensitivity and processing properties
Candidate for ingridients in BoostersShape Charge warheadsHigh performance warheadsRocket and gun propellants
Particle size and particle quallity is very important for sensitivity and processing properties
250 µm250 µm250 µm250 µm
2009 Insensitive Munitions and Energetic Materials Technology Symposium
NSF 110 (20 –
40 µm) is the smallest particle size available which also gives a relatively low bulk density, < 0.6 g/cm3 according to Hall measurements. Below, a SEM-photo with a1000 times magnification is shown together with a particle size distribution measured by Malvern is shown.
2009 Insensitive Munitions and Energetic Materials Technology Symposium
NSF 120 (50 –
100 µm) gives a bulk density of approximately 0.7 g/cm3 according to Hall. The picture shows a 200 times magnification of the particles and a particle size distribution measured by Malvern.
2009 Insensitive Munitions and Energetic Materials Technology Symposium
NSF 130 (100 –
200 µm) gives a bulk density of approximately 0.85 g/cm3. The SEM photo is a 70 times magnification and the particle size distribution is a Malvern measurement.
2009 Insensitive Munitions and Energetic Materials Technology Symposium
0%
10%
20%
30%
40%
50%
60%
70%
80%
90%
100%
04 35 739
04 36 753
08 07 038
>75µ
150-75µm
300-150 µm
>300µm
NSF 140 (250 –
350 µm) is the largest particle size available at present. This quality has a bulk density of approximately 0.95 according to Hall. The SEM photograph is 70 times magnification and sieving results for a couple of batches are shown a long side.
2009 Insensitive Munitions and Energetic Materials Technology Symposium
•
Eurenco Bofors AB has produced nerly 1000 kg (7 kg batches, 1 to 3per day) of FOX-7 in its own pilot plant
•
Molar yield 80 % for nitration step•
Very small particle size has caused problems to wash the filter cake. A separate washing step has been introduced to obtain pure product
•
HPLC-purity is more than 99 % for washed product
•
Eurenco Bofors AB has produced nerly 1000 kg (7 kg batches, 1 to 3per day) of FOX-7 in its own pilot plant
•
Molar yield 80 % for nitration step•
Very small particle size has caused problems to wash the filter cake. A separate washing step has been introduced to obtain pure product
•
HPLC-purity is more than 99 % for washed product
Scaling up of FOXScaling up of FOX--77
2009 Insensitive Munitions and Energetic Materials Technology Symposium
Insensitive Formulations and Applications
Insensitive Formulations and Applications
Pressed ExplosivesPressed ExplosivesPressed FOX-7/wax (97.8/2.2 wt%)Investigated as an explosive for use in shape charge applications
Pressed FOX-7/wax (97.8/2.2 wt%)Investigated as an explosive for use in shape charge applications
A. Helte et al. 23rd Int Symp on Ballistics, Spain
(2006)A. Helte et al. FOI-R-1780-SE
(2005)
Pressed ExplosivesPressed Explosives
Jet straightness
Jet velocity
Fragmentation timeFOX-7 > Comp B
Jet straightness
Jet velocity
Fragmentation timeFOX-7 > Comp B
Penetration (ARMOX 300S)FOX-7 230 mm (2.9 cal) Comp B 265 mm (3.3 cal)
Penetration (ARMOX 300S)FOX-7 230 mm (2.9 cal) Comp B 265 mm (3.3 cal)
A. Helte et al. 23rd Int Symp on Ballistics, Spain
(2006)A. Helte et al. FOI-R-1780-SE (2005)
2009 Insensitive Munitions and Energetic Materials Technology Symposium
FOF-2FOF-2FOX7 (255-350mm)
50 wt%
FOX7 (< 70mm)
20 wt%PolyGlyN
21wt%
Butyl-NENA
5 wt%H12MDI (Desmodur-W)
4 wt%
DBTDL
0.03 wt%
Tg = -35°CThermally stable at 65°C (14 days)
FOX7 (255-350mm)
50 wt%FOX7 (< 70mm)
20 wt%
PolyGlyN
21wt%Butyl-NENA
5 wt%
H12MDI (Desmodur-W)
4 wt%DBTDL
0.03 wt%
Tg = -35°CThermally stable at 65°C (14 days)
Small-scale slow cook-offSmall-scale slow cook-off
100100--400400°°CCHeating rate: 3.3Heating rate: 3.3°°C/hourC/hour
RDX/TNT 60/40RDX/TNT 60/40
TTcookcook--offoff
207207°°C (Type I reaction)C (Type I reaction)
FOFFOF--22
TTcookcook--offoff
220220°°C (Type V reaction)C (Type V reaction)
Small-scale slow cook-off -
ResultsSmall-scale slow cook-off -
Results
2009 Insensitive Munitions and Energetic Materials Technology Symposium
A New Explosives Formulation -
FOF-5A New Explosives Formulation -
FOF-5
FOX-7 (238µm)
38.1 %FOX-7 (32µm)
25.4 %HMX (22 µm)
16.5 %Energetic binder
20%PolyGlyN
7.2 %GAP 7.2 %Butyl-NENA
3.6 %H12
MDI (Desmodur-W)
2.0 %DBTDL
FOX-7 (238µm)
38.1 %FOX-7 (32µm)
25.4 %HMX (22 µm)
16.5 %Energetic binder
20%PolyGlyN
7.2 %GAP 7.2 %Butyl-NENA
3.6 %H12
MDI (Desmodur-W)
2.0 %DBTDL
Slow Heating (Slow Cook-Off)Slow Heating (Slow Cook-Off)
First test (inert fuze)
Type V response (fire)
Second test (HNS II-based fuze)
Type IV response (deflagration)
Composition B Type I response (detonation)
First test (inert fuze)
Type V response (fire)
Second test (HNS II-based fuze)
Type IV response (deflagration)Composition B Type I response (detonation)
Fast Heating/Fuel Fire (Fast Cook-Off)Fast Heating/Fuel Fire (Fast Cook-Off)
Blast pressure (max 160 Pa) and no significant heat radiation
Type IV response (fire)
Debris (fuze) recovered at > 24 meters from test stand
Type IV response (deflagration)
Composition B Type I response (detonation)
Blast pressure (max 160 Pa) and no significant heat radiation
Type IV response (fire)
Debris (fuze) recovered at > 24 meters from test stand
Type IV response (deflagration)
Composition B Type I response (detonation)
Bullet ImpactBullet Impact
Debris (fuze) recovered less than 15 meters from test stand
Type V response (fire)
Composition B Type I response (detonation)
Debris (fuze) recovered less than 15 meters from test stand
Type V response (fire)
Composition B Type I response (detonation)
A Potential IM Explosive?A Potential IM Explosive?•
FOF-5 is a cast-cured explosive based on FOX-7 and HMX with the same performance (calc.) as Composition B (RDX/TNT 60/40).
•
Initial IM testing of ammunition containing FOF-5 -
results:
•
FOF-5 is a cast-cured explosive based on FOX-7 and HMX with the same performance (calc.) as Composition B (RDX/TNT 60/40).
•
Initial IM testing of ammunition containing FOF-5 -
results:
Slow Cook-Off Fast Cook-Off Bullet ImpactFOF-5(Batch No. 1)
Fire (1st test)Fire/Defl (2nd test)
Deflagration Fire
Composition B Detonation Detonation Detonation
2009 Insensitive Munitions and Energetic Materials Technology Symposium
Composite propellantsComposite propellantsFOX-12/RDX and FOX-7/HMX based compositions
Energetic binder
FOX-12/RDX and FOX-7/HMX based compositionsEnergetic binder
Temperature (K)
2000 2200 2400 2600 2800 3000 3200 3400
Forc
e (J
/g)
800
850
900
950
1000
1050
1100
1150
1200
FOX-7 based propellantFOX-12 based propellant
Pressure (MPa)
20 40 60 80 200 40010 100
Burn
rate
(mm
/s)
20
40
60
80
200
400
600
10
100
FOX-12 based propellantJA 2XM 39
y=0.81P0.90
( )
y = 0.09P1.32
y = 3.82P0.73
2009 Insensitive Munitions and Energetic Materials Technology Symposium
N
NO2
NO2
H2N N NH2
O
H
NH2-+
H2N NO2
NO2H2N
NO2
NH2
NO2
NH2
H2N
O2N
N
N
NO2
O
O2N
NH2H2N
N
N
N
H
NO2
H
O
Low Sensitivity Explosives HELow Sensitivity Explosives HE
TATB
LLM-105
NTO FOX-7
FOX-12
2009 Insensitive Munitions and Energetic Materials Technology Symposium
ConclusionsConclusionsFOX-7 is very insensitive. FOX-7 makes it possible to produces low sensitivity
charges with high performance, as
exemplified by the shaped charge and 40mm small caliber examples. The availability of more and better characterized particle sizes will enable an easier development of new low sensitivity, high performance applications.
FOX-7 is available in large quantities
FOX-7 is very insensitive. FOX-7 makes it possible to produces low sensitivity
charges with high performance, as
exemplified by the shaped charge and 40mm small caliber examples. The availability of more and better characterized particle sizes will enable an easier development of new low sensitivity, high performance applications.FOX-7 is available in large quantities