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19th International Symposium of Ballistics, 7–11 May 2001, Interlaken, Switzerland SPHEROIDAL PROPELLANT STABILIZER STUDIES
A. Gonzalez1 and H. Shimm2
1 St. Marks Powder, A General Dynamics Company, P.O. 222, St. Marks, FL 32355 2 ARDEC, U.S. Army, Picatinny Arsenal, New Jersey 07806 The stabilization effectiveness of diphenylamine, ethyl centralite and arkadit IIis being evaluated in spheroidal propellant formulations ranging from 0 to 35%nitroglycerin. German stability, stabilizer depletion rates, pH, NO2/NO3 ionchromatography and microcalorimetry are being used to assess stabilizer effec-tiveness.
In a joint effort sponsored by the U. S. Army Mortar Program Management Office; the U.S. Army Research Development and Engineering Center (ARDEC) and St. MarksPowder are evaluating the performance of various stabilizers in spheroidal propellants.
A matrix of nine propellant formulations is being extensively analyzed to evaluate and compare the stabilizing effects of three stabilizers. Results to date are presented here.
Three basic propellant formulations were selected, and each was manufactured with the three selected stabilizers for a total sample matrix of nine propellants. The three for-mulations selected are: I. Single baseII. Low nitroglycerin double base deterredIII. High nitroglycerin double base undeterred Each of the three formulations was stabilized with diphenylamine (DPA), ethyl cen- The nominal compositions for each of these three formulations are summarized in “Table 1”. The sample matrix nomenclature used through out this report is depicted in“Table 2”.
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Table 1. Nominal compositions of propellants formulations EVALUATION TESTS
The sample matrix is being subjected to a battery of tests to evaluate the stabilization properties of the three stabilizers for the varying formulations. The tests are being con-ducted at ARDEC, NSWC–Crane and/or St. Marks Powder.
Tests conducted and summarized here include: German Heat Tests – A reference test for propellant stability.
– Salmon Pink Time (135°C. for single base and 120°C. for double base samples).
– Time to Explosion at (135°C. for single base and 120°C. for double base samples).
Stabilizer Depletion Rate – Stabilizer depletion rates are being measured at 65°C.
over a period of 12 weeks.
Microcalorimetry – Heat flow microcalorimetry measurements are being made at 50°,65.5° and 80°C.
To date, tests have been completed on the DPA and EC stabilized samples (ID, IID, IE and IIE). Evaluation of the high nitroglycerin undeterred samples is partially completed,and evaluation of the akardit stabilized samples is planned for 2001.
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Spheroidal Propellants Stabilizer Studies German Heat Tests
Salmon pink test results are shown in “Table 3”. All samples tested exceeded the 300- minute minimum explosion time criteria.
Stabilizer Depletion Rates
Stabilizer depletion rates at 65.5°C for the DPA and EC stabilized samples were mea- sured for a period of 12 weeks at St. Marks Powder and ARDEC. The St. Marks Powderresults are summarized in “Figures 1 and 2”. ARDEC results show similar depletion rates.
Figure 1. 65.5°C stabilizer depletion rates for the single base formulation – samples IDand IE.
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Figure 2.65.5°C stabilizer depletion rates for low the NG, deterred double base formula-tion-samples IID and IIE.
DPA is reported as the combined total of DPA and daughter products using the for- DPA = DPA + .854 NNDPA + .790 (2nDPA + 4nDPA) Values were normalized to % using the formula: Normalized % Stabilizer = Stabilizer (t)/Stabilizer (to) * 100% Analyses were conducted using high-pressure liquid chromatography (HPLC). pH and NO3/NO2 Ion Concentrations
Samples conditioned at 65.5°C storage were subjected to pH, and NO2 and NO3 ion concentration analysis. Samples were stored for eight weeks at 65.5°C and analyzed atweeks 0, 1, 2, 3, 4 ,6 and 8.
All samples were held and analyzed for pH at the same time. The procedure was adap- ted from an NSWC-Crane method for testing pH of propellants after accelerated agingstorage. The samples were ground to increase surface area and extracted with deionizedwater for 24 hours. The pH was taken directly from the water/propellant slurry.
No differences in pH were noted for the EC and DPA stabilized high NG formulations.
However the single base samples showed distinct pH differences between the EC andDPA stabilized samples. Likewise the NO2 anion concentration (measured by chromato-graphy) showed a marked difference of NO2 presence between the DPA and EC stabilizedsingle base propellants.
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Spheroidal Propellants Stabilizer Studies “Figures 3 and 4” depict the pH and NO2 comparison for the single base propellants.
The DPA stabilized formulation shows higher pH and lower NO2 concentration as com-pared to the EC stabilized formulation. The pH drop and the presence of increased levelsof NO2 should be considered negative stability indicators.
Figure 3. pH shift as a function of 65.5°C storage time for the single base formulation.
Figure 4. NO2 ion concentration as a function of 65.5°C storage time for the single baseformulation.
NO3 analysis did not yield conclusive results for the single base samples, and the dou- ble base sample results were skewed by the presence of NG, which interfered with NO2and NO3 quantification.
Microcalorimetry provides a measure of the total heat generation rate of a material.
Propellant chemical stability is determined by the rates of denitrification reactions of ni-trate esters. If these denitrification reactions are the predominant source of heat genera-tion in aging propellant, then microcalorimetry can provide a good indication of relativestability.
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Extensive heat flow microcalorimetry analyses are being conducted by NSWC-Crane Division. Heat generation rates are being measured at 50°C, 65.5°C and 80°C, to gatherinformation about the relative stability of the samples.
Microcalorimetry measurements for the single base samples ID and IE show similar heat flows at 50°C. The 65.5°C tests show the DPA stabilized sample (ID) has a lower rateof heat generation for the first 10 weeks. After approximately 10 weeks the heat genera-tion curves for samples ID and IE intersect, and the EC stabilized sample shows a lowerrate of heat generation at 65.5°C. Results at 80°C show similar trends as those at 65.5°C.
The low nitroglycerin deterred samples (IID and IIE) show almost equivalent heat ge- neration rates at the three temperatures tested (50°C, 65.5°C and 80°C.).
“Figures 5 and 6” depict the total heat generation as a function of time at 80°C. for the otal Ener
Figure 5. Total energy released at 80°C. As a function of time for the single base samplesID and IE.
otal Ener

Figure 6. Total energy released at 80°C. As a function of time for low nitroglycerindeterred samples IID and IIE.
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Spheroidal Propellants Stabilizer Studies CONCLUSIONS
All data on the stabilizer test matrix evaluation is not available. As testing is ongoing, no definitive conclusions have yet been drawn. However from the available data the following observations and preliminary conclu- In multiple sampling of all formulations, the EC stabilized samples demonstrate alower Salmon pink time than their DPA stabilized counterparts.
With the exception of the microcalorimetry test, all of the stability indicators evalua-ted (salmon pink time, pH, ion chromatography and stabilizer depletion rates) point toDPA as more suitable for single base formulations than EC. No conclusions are drawnfrom the microcalorimetry results of samples ID an IE, as further interpretation andanalyses are required.
For the low NG deterred formulation (samples IID and IIE) the stability indicatorsevaluated do not show significant differences between the stabilization effects of DPAand EC.
Work is ongoing to complete the testing of the sample matrix described in “Table 1”: Completion of the high nitroglycerin and akardit samples (IA, IIA, IIIA, IIID andIIIE) evaluation is planned for 2001.
Ballistic evaluations will be conducted with selected samples.
Future areas of planned work include an evaluation of the effects of potassium flash suppressants (KNO3, K2SO3) on the chemical stability of single and double base propel-lants.
The ARDEC Surveillance Group and NSWC-Crane are acknowledged for their con- Table of Contents
  • IBS 2001 19 th International Symposium on Ballistics
  • IS01 The Ballistics of Hornussen
  • IS02 The History of Explosives in Switzerland
  • IB01 Insensitive High Energy Propellants
  • IB02 Advanced Cartridge Design for the Term-KE Round
  • IB03 High Performance Propulsion Design for
  • IB04 Ballistic Shelf Life of Propellants for Medium
  • IB05 Development and Validation of a Comprehensive Model
  • IB06 Comparison of 0D and 1D Interior Ballistics Modelling
  • IB07 Two-phase Flow Model of Gun Interior
  • IB08 Interior Ballistic Principle of High/Low Pressure
  • IB09 Factors Effecting the Accuracy of Internal Ballistics,
  • IB10 ATwo-Dimensional Internal Ballistics Model for Modular
  • IB11 Investigations for Modeling Consolidated Propellants
  • IB12 Burning Characteristics of Foamed Polymer
  • IB13 The Analysis of Gun Pressure Instability
  • IB14 Influence of Different Ignition Systems on the Interior Ballistics
  • IB15 ALeading-Detonation-Tube Ignitor and Its Firing Results
  • IB16 Functional Lifetime of Gun Propellants
  • IB17 Spheroidal Propellant Stabilizer Studies
  • IB18 Applicability of the Hydrogen Gas Erosion Theory to
  • IB19 Experimental Investigation of Heat Transfer in a 120 mm Gun
  • IB20 Analysis of ETC or Classical Manometric Closed Vessel Tests
  • IB21 Variation in Enhanced Gas Generation Rates
  • IB22 Plasma Ignition of Consolidated Propellants
  • IB23 Plasma Ignition and Combustion
  • IB24 Discussion on Emission Spectroscopy Measurements
  • LD01 Sabot Discard Model for Conventional and
  • LD02 Experimental and Simulation Analysis of Setback
  • LD03 Measurements of Muzzle Break Effectiveness
  • LD04 Transitional Motion of KE Projectile and Governing
  • LD05 Numerical Simulation of Intermediate Ballistics
  • LD06 Multistage Method for Acceleration of
  • LD07 Computation of Muzzle Flow Fields Using Unstructured
  • LD08 Modelling of Fume Extractors
  • LD09 Modeling and Simulation of the Gas Charging
  • LD10 Numerical Analysis of the Propagating Blast
  • LD11 Intermediate Ballistics Unsteady Sabot Separation:
  • LD12 Temperature and Heat Transfer at the Commencement
  • LD13 Gun Barrel Erosion: Study of Thermally
  • LD14 AStudy on the Erosion Characteristics of the Micropulsed
  • LD15 Friction and Wear Mechanism at High Sliding Speeds
  • LD16 Increasing the In-Bore Velocity Measurements
  • LD17 The Development of Composite Sabots for Kinetic
  • LD18 Structural Analysis of a Kinetic Energy Projectile
  • LD19 Joining Jacket and Core in Jacketed Steel/Tungsten Penetrators
  • LD20 Soft Recovery of Large Calibre Flying Processors
  • LD21 New Materials for Large-Caliber Rotating
  • LD22 Methodology for Hardening Electronic Components
  • LD23 Adiabatic Depressurisation of Vented Vessels
  • LD24 Solid Fuel Ramjet (SFRJ) Propulsion for Artillery
  • EB01 Transonic Aerodynamic and Scaling Issues for
  • EB02 Flight Dynamics of a Projectile with High Drag
  • EB03 Flight Test Results of the Swedish-Dutch Solid Fuel
  • EB04 Aeroelasticity of Very High L/D Bodies in Supersonic Flight:
  • EB05 ASimulation Technique for Analyzing Effect
  • EB06 The Transition Ballistic Simulation Facility
  • EB07 Acceptance Criteria for Fire Prediction Accuracy
  • EB08 On the Influence of Yaw and Yaw Rate
  • EB09 Diagnostic of the Behaviour of a Course-correction
  • EB10 The Influence of a Projectile Stability Subjected
  • EB11 Aerodynamic Aspects of a Grid Finned Projectile
  • EB12 Magnus Instabilites and Modeling for a 12.7 mm Projectile
  • EB13 Wind Tunnel Investigation of a High L/D Projectile
  • EB14 Roll Producing Moment Prediction for Finned Projectiles
  • EB15 Aerodynamic Wind-tunnel Test of a Ramjet Projectile
  • EB16 Numerical Model for Analysis and Specification
  • EB17 Numerical Ricochet Calculations of Field Artillery Rounds
  • WM01 Active Protection Against KE-Rounds and
  • WM02 Multiple Explosively Formed Penetrator
  • WM03 Barnie: A Unitary Demolition Warhead
  • WM04 Experimental and Numerical Studies of Annular
  • WM05 Shaped Charge Warheads Containing Low Melt
  • WM06 Comparing Alternate Approaches in the Scaling
  • WM07 Effect of Fragment Impact on Shaped
  • WM08 Breakup of Shaped-Charge Jets: Comparison
  • WM09 Application of Overdriven Detonation of High
  • WM10 Relative Performance of Anti-air Missile Warheads
  • WM11 ARetrospective of the Past 50 Years of Warhead Research
  • WM12 Time-Reversed, Flow-Reversed Ballistics Simulations:
  • WM13 TNT Blast Scaling for Small Charges
  • WM14 ANovel Approach to the Multidimensional Nature
  • WM15 Fragmentation Properties of AerMet® 100 Steel in
  • WM16 Using a Numerical Fragmentation Model to Understand
  • WM17 Dual Mode Warhead Technology for Future
  • WM18 Steerable Hitiles Against TBM Warheads
  • WM19 The Design of Small-Calibre Tandem Warhead against Tank
  • WM20 Application of Loose Powder Liner Shaped Charges
  • WM21 Lasers for AP-Mine Neutralisation
  • WM22 AReactive Mine Clearing Device: REMIC
  • WM23 The Measure of Jet “Goodness” M.E. MAJERUS, R.M. COLBERT
  • WM24 Some Improvements into Analytical Models of Shaped
  • WM25 Role of Texture in Spin Formed Cu
  • WM26 Predicted and Experimental Results of Shaped
  • WM27 The Design and Performance of Annular EFP’s
  • WM28 Explosively Formed Penetrators
  • WM29 Analytical Code and Hydrocode Modelling
  • WM30 The Contribution to the Optimization of Detonation
  • WM31 Variational Principle for Shaped Charge Jet Formation
  • WM32 The Effects of Finite Liner Acceleration on Shaped-Charge
  • WM33 Investigation of Several Possibilities to Disturb
  • WM34 Further Analytical Modelling of Shaped Charge
  • WM35 Shaped Charge Jet Break-up Time Formula Confirmed
  • WM36 Computer Simulation of Shaped Charge
  • WM37 Determination of Dynamic Tensile Strength of Metals
  • WM38 Coupled Map Lattice Model of Jet Breakup
  • WM39 The Indeterminacy of the Outgoing Flow of Two
  • WM40 Electromagnetic Control of the Shaped-charge Effect
  • WM41 Aero Stripping from a Water Jet
  • WM42 Photoinstrumentation for Warhead Characterisation
  • WM43 APractical Method to Determine Poisson's Ratio
  • VM01 The Development of a Physical Model of Non-Penetrating
  • VM02 Advanced Multiple Impact Endgame Model Against Ballistic
  • VM03 Assessment of Shaped Charge Jet Mitigation,
  • VM04 Analysis of Active Protection Systems: When ATHENAMeets
  • VM05 Numerical Modeling of a Simplified Surrogate Leg
  • VM06 Numerical Head and Composite Helmet Models
  • VM07 The Testing of the Tank Fire Control Systems Accuracy
  • VM08 Methodology for Predicting Ballistic Shock Response
  • VM09 Major Issues Affecting Characterisation and Modeling
  • VM10 Digitization of Witness Pack Plates
  • VM11 Lightweight Passive Armour for Infantry Carrier Vehicle
  • VM12 Lightweight Transparent Armour Systems
  • VM13 Non-KKV End Game Kinematic Plan of Anti Tactical Ballistic
  • VM14 Defeating Active Defense Systems by Double-
  • VM15 AComparative Evaluation of Personnel Incapacitation Methodologies
  • VM16 Behind Armour Blunt Trauma for Ballistic Impacts on Rigid Body Armour
  • VM17 Soap and Gelatine for Simulating Human Body Tissue:
  • VM18 Sphere Penetration into Gelatine and Board
  • VM19 AComputer Program to Assess the Effectiveness of Shotgun
  • VM20 Creams for Protection Against Skin Burns in Explosions
  • TB01 Whipple Shields Against Shaped Charge Jets
  • TB02 General Overview of Capability in the Simulation
  • TB03 Analytical Model to Optimize the Passive Reactive
  • TB04 Approximating the Ballistic Penetration
  • TB05 Sensitivity of ERA-boxes Initiated by Shaped
  • TB06 ANumerical Investigation of Top-Attack Submunition
  • TB07 Protective Power of Thick Composite Layers
  • TB08 The effect of matrix type on the ballistic and
  • TB09 Size Scaling in Ballistic Limit Velocities for Small
  • TB10 Reference Correlations for Tungsten Long Rods
  • TB11 Oblique Plate Perforation by Slender Rod Projectiles
  • TB12 Tungsten into Steel Penetration Including
  • TB13 On the Behaviour of Long-Rod Penetrators Undergoing
  • TB14 Penetration Comparison of L/D=20 and 30 Mono-bloc
  • TB15 Definition and Uses of Rha Equivalences for Medium
  • TB16 Analytical Model of Long Rod Interaction
  • TB17 Penetration of APProjectiles into Spaced Ceramic Targets
  • TB18 Behavior and Performance of Amorphous and Nanocrystalline
  • TB19 Kinetic Energy Projectiles: Development History,
  • TB20 Kinetic Energy KE Ammunition for Medium Calibre
  • TB21 Multirole APFSDS-T Expanding the Traditional
  • TB22 Penetration Mechanics of Extending Hemicylindrical Rods
  • TB23 Evaluation of Replica Scale Jacketed Penetrators
  • TB24 Replica Scale Modelling of Long Rod Tank Penetrators
  • TB25 High Velocity Jacketed Long Rod Projectiles Hitting
  • TB26 The Penetration Process of Long Rods into Thin
  • TB27 Oblique Penetration in Ceramic Targets
  • TB28 The Influence of Penetrator Geometry and Impact
  • TB29 Observations on the Ratio of Impact Energy to Crater Volume
  • TB30 Cavity Shape Evolution During Penetration
  • TB31 Instrumented Small Scale Rod Penetration Studies:
  • TB32 AParameter that Combines the Effects of Bend
  • TB33 The Effects of Stress Pulse Characteristics on the Defeat
  • TB34 Penetration Efficiency of Tungsten Penetrators
  • TB35 Shock Reduction Power of Different
  • TB36 Cavity Expansion Theory Applied to Penetration of Targets
  • TB37 Development and Validation of a Dwell Model
  • TB38 Glass Ceramic Armour Systems for Light
  • TB39 Ballistic Resistance and Impact Behaviour
  • TB40 Dynamic Fragmentation of Alumina with Additions
  • TB41 Influence of Liners on the Debris Cloud Expansion
  • TB42 Mass Efficiency of Aramid Composites Depending
  • TB43 Numerical Fragmentation Modeling and Comparisons
  • TB44 Fragment Impact on Bi-Layered Light Armours
  • TB45 Penetration Analysis of Ceramic Armor with Composite
  • TB46 Ballistic Limit of Fabrics with Resin
  • TB47 Finite Element Design Model for Ballistic Response
  • TB48 Numerical Simulations of Dynamic X-Ray Imaging
  • TB49 Perforation of Spaced Glass Systems by the 7.62 mm
  • TB50 The Development of the Glass Laminates
  • TB51 Model of the Wood Response to the High Velocity of Loading
  • TB52 Terminal Ballistics of EFPs – ANumerical Comparative
  • TB53 An Experimental Investigation of Interface Defeat
  • TB54 Cutoff Velocity in Precision Shaped Charge Jets
  • TB55 Performances and Behaviour of WCu-pseudo-alloy
  • TB56 AComputational Method of Fast Simulating Full-physics
  • TB57 Numerical Simulation of the Performance
  • TB58 Study of Spin-compensated Shaped Charges
  • TB59 Jet Perturbation by HE Target
  • TB60 Evaluation of High Explosive Parameters
  • TB61 Combination of Inert and Energetic Materials
  • TB62 Interaction Between a Metallic Reactive Armor
  • TB63 Numerical Simulation of Shape Charge Jet Interaction
  • TB64 A3D Modelling Study of the Influence of Side
  • TB65 Effect of Multiple and Delayed Jet Impact and Penetration
  • TB66 Hydrocode Modelling of High-velocity
  • TB67 The Effect of Obliquity and Conductivity on the Current
  • TB68 Taylor Impact Experiments of Electrified Copper
  • Source: ftp://ftp.wargamer.com/pub/TechSpec/Armor%20Plate%20Penetration%20Theories/International%20Journal%20of%20Ballistic%20Studies%20Symposium%202001/Ib17(147.pdf


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