Studies on the Effect of Ageing on a range of UK Polymer Bonded Explosives



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Studies on the Effect of Ageing on a range of UK Polymer Bonded Explosives Philip Cheese, Peter Barnes, Michael Sharp DOSG Ron Hollands and Ian Murray BAE Systems Nigel Davies and Peter Jemmet RMCS Shrivenham

Ageing and Insensitive Munitions Many cast PBXs have very good IM properties when pristine - low sensitiveness and explosiveness Ageing is known to affect the mechanical properties of the polymeric matrix of castcured PBXs There is a need to establish that the IM capability of cast PBXs is not compromised during service life

UK programmes on ageing of cast PBXs Accelerated ageing of cast PBX samples to simulate 20 years service life. Mechanical, chemical and hazard testing of aged and control samples What changes? By how much? Does this change compromise IM? Environmental trials on PBX-filled munitions

Explosives studied Composition Nominal Formulations (%m/m) RDX Aluminium HTPB Plasticiser (isocyanate cured) ROWANEX 1100 88 -- 5 7 ROWANEX 1400 66 22 5 7 Rowanex 1100 is BAE Systems explosive of choice for future artillery and general purpose systems Rowanex 1400 is an optimised blast explosive

Ageing programme for environmentally conditioned Rowanex 1400 samples Step Environmental Conditions 1 31 days at 71 C 2 169 days B3 cycling (diurnal cycle 33-71 C) 3 Transport Vibration (Def. Stan. 00-35; 2hr per axis, 2g sinusoidal sweep) 4 10hr vibration per axis ((Def. Stan; 00-35 -0.4g 2 /Hz, 20-2000Hz) 5 Thermal Shock (Def. Stan. 00-35; +70 to -55 C, transfer time 3-5min, 10 cycles) Represents nominal 20 year service life Radiography indicates no change in frequency of voids between control and aged test pieces

Test Regime for Control and Aged Samples of ROWANEX 1400 Test or Method Specification or Reference Antioxidant level STANAG 4581 Sol / Gel QinetiQ/FST/LP033918 / STANAG 4581 Moisture content Memo dated 30/03/2004 Dynamic mechanical analysis STANAG 4540 Surface hardness From guidelines given in BS 903-A26:1995, ISO 48:1994 and BS 903-A57:1997, ISO 7619:1997, LP043948. Tensile testing STANAG 4506 Heat flow calorimeter STANAG 4582 Tube test - internal ignition version EMTAP No.35 Tube test -Fuel fire version EMTAP No.41 Tube test -Electrically heated version EMTAP No.42 Large scale gap test EMTAP No.22 Additional Non-standard Tests Test method Additional Diagnostics or Tests Dynamic mechanical analysis Ultrasonic analysis, SEM Chemical Analysis GC-MS, Thermal Analysis (DSC, TGA), IR Spectroscopy Instrumented Gap Test

Chemical and mechanical test results for environmentally conditioned samples Test Notes Conclusions Soluble Fraction Results distribution greater for aged samples Antioxidant Levels Slight Reduction on Ageing Moisture content Karl Fischer method and weight loss on vacuum heating No Significant Changes Shore A Surface Hardness No Significant Changes

Dynamic Mechanical Analysis (DMA). 0.6 Unaged 2-9 Unaged 2-10 Aged 3-9 Aged 3-10 0.5 0.4 0.3 0.2 tan_delta ( ) [ ] 0.1 0.0-150.0-100.0-50.0 0.0 50.0 100.0 Temp [ C] Small increase in modulus between about -80 and -50 o C Glass transition temperature remains unchanged at -95 o C.

Tensile Test results, Comparison of Maximum Stress Level 0.7 0.6 Control Aged 0.5 0.4 0.3 0.2 0.1 0-40 C 20 C 60 C Relatively small changes at low and ambient temperature Reduced maximum stress and modulus, increased strain capability

Max load before failure at 60 C 0.05 Max Load / kn 0.04 0.03 0 1 2 3 4 5 Age / months Significant increase in the strength of the PBX over the first month of ageing, presumably due to the continuing cross-linking reaction. Elasticity also increases on ageing

Compression Testing Load / kn 2 1.5 1 0.5 Unaged Aged 1 mth at 60oC Aged 2 mths at 60oC Aged 3 mths at 60oC Aged 4 mths at 60oC 0 0 2 4 6 8 10 Displacement / mm Little variation in the load required to cause plastic deformation as the material ages. Homogeneity of filler dispersion within the matrix would account for the slight variations in compression resistance.

Acoustic Analysis Velocity of Sound = 1666ms -1 - has remained constant for the samples tested Height of Reflected Signal / mm 32 30 28 26 24 22 20 0 1 2 3 4 5 6 Age / mths Signal attenuation is reduced with age. Less energy lost to elastic polymer as X-linking increases

ATR/IR Transmission ATR Data Transmission Data C-H polymer 4000-1 Urethane peak @ 1737cm 3600 3200 2800 2400 2000 C-H RDX 1600 1200 800 400 100 90 80 70 60 50 40 30 20 10 0 0 Transmission / Reflectance Wavenumber / cm-1

IR Peak Ratios 1.4 1.2 Urethane/C-H RDX Urethane/C-H polymer Ratio 1.0 0.8 0.6 ATR 0.4 0.2 Transmission 0 0 1 2 3 4 Age / Months Intensity of urethane peaks is reduced with age Can be explained by the formation of allophanate groups?

Vacuum Stability Carried out in accordance with STANAG 4147 Samples heated at 80 C for 10 days Pressure / mbar 600 500 400 300 200 100 Tube 1 Tube 2 0 0 2 4 6 8 10 Time / days

Large Scale Gap Test Sample Median gap (mm Perspex) Median Gap (Gpa) Control 33.5 4.38 Aged 33.9 4.29 LX-14 54.4 1.70 Rowanex 1100 44.8 2.50

Tube Test - Internal Ignition Control 8 no ignition 2 burned, no burst Aged 3 no ignition 4 burned, no burst 3 burst, no fragmentation

Tube Test - Fuel Fire Control 4 burst, no fragments 6 deflagration, maximum 4 fragments Aged 3 burst, no fragments 7 deflagration, maximum 4 fragments

Conclusions for Rowanex 1400 Chemical and physical properties change with age These changes are not sufficient to compromise IM capability Values measured can be used as bounds for intelligent surveillance programmes

Environmental Trials on PBXfilled Munitions BAE Systems has carried out risk reduction programmes on a range of ROWANEX 1100 filled projectiles, in readiness for anticipated UK MOD orders for IM compliant ammunition systems: L15 155mm L31 105mm HE 4.5 IA/IM Naval Ammunition

155mm L15 Projectiles Bounce to Defence Standard 00/35, Test M11, duration 6 x 5 minutes Modified AOP-34 vibration regime (AS90), 205minutes duration low frequency at axial and traverse, and 44 minutes duration high frequency at axial and traverse 2.1m drop to Defence Standard 00/35, Test M5, two drops per shell All At 46 C

155mm L15 Projectiles 155mm L15 Cold Bounce 155mm L15 Cold Drop No evidence of cracking, exudation or dusting

105mm L31 Projectiles Sixty shell conditioned; thirty at 46 C and thirty at +63 C 2.1m drop to Defence Standard 00/35, Test M5, two drops per shell Loose cargo bounce to STANAG 4370, AECTP- 400 Method 406, duration 2 x 10 minutes 7 days B3 Diurnal Cycling to STANAG 2895 All fired without incident at pressures up to 400MPa

4.5 IA/IM Naval Ammunition 15 rounds were conditioned at 18 and +49 C packed in N36 containers/n6 crate Logistic vibration to Defence Standard 00-35, Test M1 for 6 hours Restrained cargo shock to Defence Standard 00-35, Test M3 Multiple free fall to Defence Standard 00-35, Test M5; two from 1.5m while cold and one from 2.1m while hot Horizontal impact to Defence Standard 00-35, Test M5 B2 Diurnal cycling for 91 days (equivalent to 3 years service) and 231 days (equivalent to 10 years service) C1 Diurnal cycling for 14 days Free fall to Defence Standard 00-35, Test M5, either 1m, 1.5m or 2.1m Ship vibration to AECTP Edition 1, Method 401 Underwater shock to Defence Standard 00-35, Test M3 Free fall to Defence Standard 00-35, Test M5, 0.5m

4.5 IA/IM gun firings After completion of the three year environmental regime five rounds were fitted with L106 fuzes and gun-fired without incident. After completion of the ten year environmental regime five rounds were filled with NC23 fuzes and gun-fired without incident.

Conclusions for Rowanex 1100 Extensive accelerated ageing has failed to induce any apparent failure in Rowanex 1100 filled shell Aged shell proven to be safe for gun launch Although mechanical properties undoubtedly change with time, there is no reason to suspect that this could compromise the excellent IM characteristics of the formulation

Questions?