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SUMMARY
The lifetime of composite rocket motors is primarily a function of the mechanical properties of the
propellant, the ageing characteristics of the propellant, the grain design and the environmental conditions
endured during operational use. For double base systems, lifetime is generally determined by its stability
(stabilizer consumption). The propellant properties may degrade because of a number of different
processes, i.e. chemical, physical and mechanical. In this paper an overview will be given of techniques
currently employed in the Netherlands to predict the safelife of rocket motors, focusing on chemically and
physically induced ageing mechanisms. By combining the results of mechanical and chemical analysis,
the ageing behaviour of the propellant and dominant ageing mechanisms can be established. Knowledge
about both ageing behaviour and the ageing mechanisms are essential to predict the lifetime of rocket
motors.
In contrary to the state-of-the-art composite propellants, new energetic formulations are likely to posses
some of the inherent stability related lifetime issues as are well known for double base systems.
An impression will be given how, by the use of well proven techniques for composite as well as double
base propellants, new propellant formulations may be screened in order to evaluate the use of these new
formulation in new, higher performing and long life systems.
1.0 INTRODUCTION
The Netherlands armed forces use a variety of missile systems with solid propellant rocket motors
(e.g. AMRAAM, Hellfire, Hydra, Maverick, MLRS, Patriot, Sidewinder, Standard Missile, Stinger).
Key issues for surveillance of these missile systems are safety, reliability, timely notice of replacement
needs and costs. To support the Netherlands armed forces in maintaining its missile inventory, TNO is
working on surveillance studies for specific weapon systems as well as more experimental studies to
improve lifetime prediction techniques for solid propellants.
Lifetime of modern composite solid rocket motors is primarily a function of the mechanical properties of
the propellant, the ageing characteristics of the propellant, the grain design and the environmental
conditions endured during operational use (Figure 1).
Paper presented at the RTO AVT Specialists Meeting on Advances in Rocket Performance Life and Disposal,
held in Aalborg, Denmark, 23-26 September 2002, and published in RTO-MP-091.
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Propellant
degradation
Lifetime
For CTPB and HTPB based systems, lifetime is generally limited by a degradation of the mechanical
properties of the propellant composition. The reduction of mechanical properties may lead to crack
formation at the inner bore (loss of strain capacity), debonding at the propellant- liner-casing interface or
slump (excessive softening of the propellant, generally induced by hydrolysis type of reactions). In case of
double base systems lifetime is in general limited by the amount of stabilizer consumed. Furthermore,
since these motors are usually based on a loose charge propellant grain concept, mechanical properties are
not as critical as in the case of case bonded composite motors. Ageing of a solid propellant can be caused
by a number of processes:
chemical (i.e. oxidation, chain scissioning, stabilizer consumption)
physical (i.e. migration of liquid components of the propellant or adjacent materials)
mechanical (i.e. thermally induced stresses, shock loads, vibrations).
In this paper an overview will be given of a number of techniques employed in the Netherlands to predict
the safelife of solid propellant rocket motors, focusing on chemically and physically induced ageing
mechanisms. Emphasis is given in the understanding of the dominant ageing process. Based on the
dominant ageing mechanisms, safelife of systems can be evaluated with the help of numerical tools and
real life operational conditions that are being monitored. These techniques are not only valid for
conventional systems, but its significance will grow with the use of new and more energetic propellants.
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When necessary, the standard characterisation tests can be complemented with more detailed tests,
like gas dilatometer experiments (to study bonding agent efficiency /dewetting behaviour of the
propellant), pressurized and pre-strained low temperature tensile testing (simulation ignition pressurisation
load at low temperature), cyclic testing (damage) or bi-axial tests. Examples of a gas dilatometer
experiment and the pressurized tensile test are given in respectively Figures 2 and 3. When reaching the
age-out limits of a propellant, detailed knowledge of the properties reduces the safety factors required
while assessing the safety margins of a motor, which may significantly improve the shelf life of a system.
For example, composite propellants are strongly dependent up on the pressure [2, 3], see Figure 3.
Generally the stress capacity of propellants increase with an increase in external pressure, whereas the
Youngs modulus remains constant. Effects on the strain capacity are dependent up on the actual
propellant and the test conditions used. After a certain pressure level, no significant increase is observed
anymore and the stress capacity reaches a sort of maximum level (see Figure 4). Figure 4 shows
furthermore that the initial modulus remains constant. It is possible to test the propellant with and without
pre-strain in order to simulate a cooldown load, followed by ignition pressurization.
1.2 0.5
Stress
dV/V
1.0
P.R. 0.4
0.6
0.2
0.4
0.1
0.2
0.0 0.0
0.0 0.1 0.2 0.3 0.4 0.5 0.6
strain [-]
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1.5
ambient
2 MPa
1.0
stress [MPa]
0.5
0.0
0 10 20 30 40 50 60
strain [%]
Figure 3: Propellant Properties with and without Pressurization Loading.
2.0 16
max stress
1.8
modulus 14
1.6
12
1.4
10
maximum stress
1.2
initial modulus
1.0 8
0.8
6
0.6
4
0.4
2
0.2
0.0 0
0 1 2 3 4 5 6 7
pressure [MPa]
Figure 4: Maximum Stress and Initial Modulus versus External Pressure for
an AP/HTPB Propellant (Test Conditions: 50 mm/min @ 20 C).
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At TNO, small propellant samples of 0.05 0.2 grams are used for an accurate determination of the sol
content. This makes the sol/gel determination a powerful tool in determining ageing gradients at free or
bonded surfaces of a propellant grain. Due to ageing processes the amount and the composition of the sol
generally change. Examples of the sol-content as a function of accelerated ageing time at 60 C for two
typical air-to-air missiles with respectively an AP/HTPB and an AP/CTPB based propellant are given in
Figure 5. The reduction in sol-content of the HTPB propellant correlated very well with a reduction in
strain capacity and an increase in strength, caused by oxidative ageing, whereas the CTPB propellant is
less prone to oxidation. By further chemical analysis of the Sol (antioxidant content, plasticizer content,
etc.), the dominant ageing process can be determined.
8,0
7,5
7,0 AP/CTPB
Sol [%]
AP/HTPB
6,5
6,0
5,5
0 50 100 150 200
Ageing time [days]
A change in sol content of the propellant will lead to a change in mechanical properties of the propellant,
as there is a direct relation between the sol content, cross-link density of the binder and the mechanical
properties [3]. This relation between Sol content, cross-link density and mechanical properties is
illustrated in Figures 6 and 7. Figures 6 and 7 give experimental results of propellants with different
crosslink densities. These propellants were prepared using different isocyanate levels (NCO-OH ratio).
A distinct relationship is obtained between the initial modulus, maximum strain, maximum stress and the
sol content for this AP/HTPB propellant. By increasing the NCO-OH ratio of a propellant, the crosslink
density will increase. A similar effect occurs due to oxidative ageing, whereas hydrolysis will cause the
crosslink density to decrease.
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SOL
Sol content [%] 10% max stress 0,9
0,8
Stress [MPa]
9%
0,7
0,6
8%
0,5
7% 0,4
0,8 0,82 0,84 0,86 0,88 0,9
NCO-OH ratio [-]
max strain
60 M odulus 5,4
50
Modulus [MPa]
4,4
Max strain [%]
40
3,4
30
2,4
20
10 1,4
0 0,4
0,8 0,82 0,84 0,86 0,88 0,9
NCO -O H ratio [-]
For double base propellants, life is generally limited by its thermal stability (risk for run-away reaction
and/or gas cracking). The thermal stability can be assessed by an assessment of the remaining stabilizer
content or by means of isothermal storage tests (IST). Although double base systems generally age-out
due to long-term thermal instability effects, also a reduction in molecular weight of the NC and NG
molecules is known to occur, leading to a reduction in mechanical properties. The reduction in Mc can
very well be assessed by means of GPC.
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In the draft STANAG 4581 [5] ageing is performed with a propellant block (140 x 90 x 40 mm) that is
stored in a sealed box at a temperature of 60 C during resp. 13 and 26 weeks. After ageing, the test
samples are prepared as indicated in Figure 8. This method of ageing is expected to predict the bulk
properties of an aged propellant grain. In order to be able to establish possible gradients in the STANAG
block, the sampling plan as defined in [5] was complemented with measurements to asses possible
gradients in the propellant properties (see Figure 8). From the middle of the block, 3 JANNAF samples are
prepared. From one side an additional JANNAF sample is made, and from the other side a rectangular
propellant sample is produced that can be used for chemical analysis (profile measurements).
Profile measurement
L = 140 mm
B = 90 mm
H = 40 mm
Figure 8: STANAG 4581 (Draft) Block with 4 JANNAF Samples and Chemical Analysis Sample.
The section used for ageing profile determination is indicated.
Some of the results of the comparative study are given in Figures 9 and 10. In Figure 9, the normalised
maximum strain is plotted as a function of the normalised sol content for the propellant aged at 60 C
according to method 1 (JANNAF sample ageing). In Figure 10, normalised sol content and normalised
shore A are given as a function of the distance (depth) below the surface for propellant aged for 13 weeks
at 60 C according to Method 2. Sol content is determined at the location indicated in Figure 8. Sol profile
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measurements show that after 13 weeks ageing the inner part of the STANAG block hardly changed
(normalised sol content still equals one), but towards the edge the normalised sol decreases to 0.87.
0,50
0,00
0,50 0,60 0,70 0,80 0,90 1,00 1,10
Normalised Sol [-]
1,1 SOL
1,0
0,9
0,8
0 10 20 30 40
Depth (mm)
Figure 10: Normalised Shore A and Sol vs Distance of Free Edge (See Figure 8)
for Propellant Aged at 60 C according to Method 2.
Combining the results of Figures 9 and 10 shows that the strain capacity at the free edge of the STANAG
block after 13 weeks ageing at 60 C will be approximately 60 % of the maximum strain at the middle of
the block. Lifetime prediction based on samples cut from the middle of the STANAG block would
overestimate the strain capacity at the free surfaces of a propellant bore by 67 %, thereby overestimating
the actual safelife and potentially leading to dangerous situations. Although the gradient in a naturally
aged rocket motor is expected to be less prominent [6], Method 1 may be used as a more conservative
approach for determining propellant properties at free surfaces.
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An example of the use of environmental data and experimental propellant data is shown in Figure 11.
During a mission in Northern Africa, the temperature was measured in the storage facility and the
ammunition transport containers. Measurements started up on departure, so the effect of transport to
Africa was monitored as well. The ammunition arrived in Africa approximately 9.5 weeks after start of
the measurements. The rockets were transported back to The Netherlands approximately 16 weeks later
(at 25 weeks). In Africa, the missiles and rockets were stored in an earth covered bunker, reducing the
temperature fluctuations during the stay. After arriving in and before departing from Africa some high
temperature peaks occurred. This is caused by the fact that the ammunition containers were placed on the
quay exposed to direct sunlight.
As an example, Figure 11 shows the effect of the mission on the lifetime of a double base rocket motor.
For double base propellants, the amount of stabiliser consumed is an important parameter for lifetime
evaluation. By means of Heat Flow Calorimetry (HFC), an Arrhenius based relation between storage
temperature and stabiliser consumption for the double base propellant of the rocket was established.
This relation in combination with the measured environmental conditions was used to predict stabiliser
consumption due to the out of area mission. The result is shown in Figure 11 (stabiliser content at the start
of the measurements has been set to 100 %). Especially the periods at high temperature show to
significantly affect the stabiliser content.
60 100
50
99
40
Stabiliser content [%]
98
temperature [ C]
30
20 97
10
96
0
95
-10
-20 94
0 5 10 15 20 25 30 35
time [w eeks]
Figure 11: Storage Temperatures and Predicted Stabiliser Depletion of Double Base Rocket
Systems during an Out-of-Area Mission in Northern Africa.
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Because this mission was relatively short and storage conditions can be considered as relatively mild
(earth covered bunker) the stabilizer depletion remained limited. However, based on the experimental
determined relation between storage temperature and stabiliser consumption it can be concluded that the
consumption of stabiliser because of this mission is about 4.5 times higher then in case of depot storage in
the Netherlands.
Whereas these propellants generally behave very well in terms of their intended need, they may posses
reduced shelf life compared to their conventional equivalents. Due to their energetic nature, often they
combine the conventional composite propellant failure modes (oxidative ageing, hydrolysis) with the
double base stability issues. In addition, humidity effects and hygroscopicity of some of its ingredients
might aggravate the ageing behaviour.
A wide variety of propellant additives have been tested in this manner. Table 1 gives an overview of some
typical results using the new oxidiser HNF, showing that by a proper choice of ingredients significantly
improved stability values can be reached.
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The processes leading to thermal degradation of energetic binder systems and new oxidisers is generally
characterised by high activation energies. For example for HNF, an activation energy of approximately
150 KJ/mole is obtained. Under the assumption that the decomposition of HNF is a first order reaction,
the gas production, G, in the VST would follow from G = rT t . The time at different temperatures to
produce a set amount of gas may be used to calculate the activation energy, Ea, from the degradation
Ea / ( RT )
process with the equation rT = A e . The time has been determined at 60, 80 and 90 oC to produce
3 ml gas per gram of HNF, showing an activation energy of approximately 150 KJ/mole [7]. This data can
used to estimate the time to generate 3 ml/g gas during normal storage conditions, i.e. at 20 oC. This is
respectively 712 and 610 years for two different grades of HNF (respectively HNF-P and HNF-C),
confirming the thermal stability of the material.
For these high energetic materials, a clear link between quality and thermal stability is shown. Figure 12
shows the effect of purity on the stability of the HNF produced (expressed in gas production in a VST test,
90 oC). The purity of the HNF produced directly affects the purity of the propellant.
Figure 12: VST of Improved HNF Grades from APP vs. US Patent Values at 90 C.
Another technique to determine the stability of propellant mixtures is the isothermal storage tests (IST).
Test samples are stored at a constant temperature and endo-/exothermic reactions are being measured by
measuring the energy flow as a function of time. By comparing the results at different temperatures, either
at constant energy production or at the onset of characteristic decomposition modes (e.g. double base
propellants go into autocatalyses) the activation energy of the decomposition process can be determined.
Based on isothermal storage tests (70, 60, 50 and 40 C), a preliminary evaluation of the activation energy
of the degrading process has been made for a HNF/HTPB propellant. The activation energy came close to
the observed values for HNF (approx. 135 150 KJ/mole).
Similar high activation energies are also shown for the more energetic binder systems. Reference [8]
for example gives typical numbers for GAP based propellants using GAP-A, TMETN, and BTTN as
plasticizers, giving activation energies of typically 120 130 KJ/mole in the 70 80 oC temperature range.
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Screening of possible propellant ingredients and early identification of possible life issues is a necessity
when looking at the introduction of the new ingredients. Small scale tests can be used to identify possible
ageing mechanisms (VST, IST, TG/DTA, DSC, .). Together with the ability to use of numerical
modelling techniques, allows for the assessment of the life of such systems.
5.0 CONCLUSIONS
In order to be able to assess the current state and the projected lifetime of a propellant, knowledge of both
the mechanical and the chemical changes is essential to understand and quantify the ageing processes
(dominant ageing mechanisms).
When predicting rocket motor lifetime based on accelerated ageing, special care must be taken with
respect to sample geometry and ageing conditions. A combination of different ageing techniques may be
used to get a complete overview of the ageing behaviour of the propellant. By combining the results of
chemical and mechanical analysis, possible drawbacks of a chosen ageing method can be accounted for.
Using the method described in the draft STANAG 4581 to asses the life of rocket motors,
may overestimate the actual safety margins of a rocket motor, potentially yielding an unsafe situation.
Complementing the method currently described with sol-measurement to account for possible surface
effects may overcome this effect.
Sol measurements, using samples of 0.05 0.2 grams of propellant, allow for an accurate assessment of
the mechanical properties (and safety margins) in interface layers.
Monitoring of environmental conditions is essential to assess the current state of ammunition that was
deployed during missions to hot areas. Missiles specific knowledge of these conditions allow for
prioritisation of usage of these missiles when they return to their storage depots.
When evaluating the ageing behaviour of new energetic propellant compositions, a combination of
composite propellant ageing aspects (reduction in mechanical properties) together with thermal instability
problems is often shown. A combination of DB and composite propellant techniques is required to fully
assess the life issues at hand. When combining the ageing parameters of these new compositions with
operational (temperature) monitoring data, reliable life predictions of such new energetic systems can be
made. Such life predictions will become necessary to fully exploit the possibilities of these new propellant
types.
6.0 ACKNOWLEDGEMENT
The presented work is supported by the Dutch Ministry of Defense.
7.0 SYMBOLS
A pre-exponential coefficient
Ea Activation Energy
G Gas production
Mc Average molar weight
R gas constant
T Temperature
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8.0 REFERENCES
[1] AGARD Advisory Report 350: Structural Assessment of Solid Propellant Grains, Report of the
Propulsion and Energetic Panel Working Group 25, Dec. 1997.
[2] Fitzgerald, J.E., Hufferd, W.L., Handbook for the Engineering Structural Analysis of Solid
Propellants, CPIA Publ 214, May 1971.
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[4] Christiansen, A.G., Layton, L.H., Carpenter, R.L., HTPB Propellant Ageing, AIAA 80-1273, 1980.
[6] Cunliffe, A.V., Davis, A., Tod, D., Ageing and Life Prediction of Composite Propellant Motors,
87th AGARD PEP Symposium, 1996.
[7] Keizers, H.L.J., Heijden, van der, A.E.D.M., Vliet, van, L., Welland-Veltmans, W.H.M., Ciucci, A.,
Developments on HNF-based High Performance and Green Solid Propellants, ESTEC, NL, ESA
Green Propellant Symposium, June 2001.
[8] Bohn, M.A., Ageing and Service Time Period Assessment of Novel Solid Rocket Propellant
Formulations containing CL-20, AP and Energetic Plasticizers, 28th Int. Pyrotechnics Seminar,
Adelaide, Australia, Nov. 2001.
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