Lessons Learned in Service Life Prediction

Edmund K. Liu and Richard K. McCamey

Propellant Technology, Engineering, GencorpAerojet, P.O. Box 13222, Sacramento, CA 95813-6000, USA 053·99

Abstract: Service life of rocket motors has been of interest to the military. This is increasingly important today as
there is a desire to extend the useable service of rocket motors beyond their initial design life. One
important aspect of service life prediction is the ability to determine the age-life ofa system from subscale
testing. Subscale testing can include specimens from witness samples, motor dissections, or analog
simulations. These attempts have met with modemte success. This presentation will discuss some of the
lessons learned by the authors over the many years of tactical and stmtegic solid rocket motor aging and
surveillance efforts. The discussion will be focused mainly on the solid rocket propellant and bondline
interfaces of the rocket motor.

1. INTRODUCTION

There has been a desire to keep solid rocket motor systems for longer periods of time, particularly beyond
their original design life. To accomplish this, one must detennine if the system will still adequately perform
its desired mission. This paper will focus on the structural life of the solid rocket motor grain.
The industry has used many techniques to determine the end of service life of solid rocket motors. These
include various aspects of chemical and mechanical acceleration in the life process. The challenge has been
the accurate and realistic acceleration of chemical and mechanical mechanisms that affect the change in
properties of the solid rocket motor.

1.1 Chemical Mechanisms

Chemical mechanisms have most commonly involved acceleration at multiple temperatures (and possibly
hwnidity) to derive the kinetic laws for the changes. The Arrhenius relationship is then used to predict the
properties at another temperature (and relative humidity) and time. This bas met with much success in large
ballistic motors and in many smaller tactical rocket motors.
Chemical aging of solid rocket motors involves at least two complicated and interrelated processes:
chemical reactions and diffusion of species. Within each of these are other individual mechanisms and
changes such as:

Chemical reactions
- Postcure of polymeric binder (continued crosslinking)
- Effects of moisture on the binder, oxidizer and components
- Effects of oxygen on the binder
- Decomposition of energetic plasticizers
- Depletion of antioxidants

Diffusion
- Oxygen and moisture
- Plasticizers
- Reactive species

Ageil/g Stl/dies al/d Lifetime Extel/siol/ of Materials.

Edited by Mallinson, Kluwer Academic/Plenum Publishers, 2001 529
530 Edmund K. Liu and Richard K. McCamey

Each process may proceed independently, simultaneously or consecutively. Coupled with these are the
migration and reaction of those species. Oftentimes, industry has taken advantage of these diffusion/reaction
phenomena to achieve specific properties for the system.

Diffusion/reaction
- Migration of curatives and subsequent reactions
- Migration of bonding aids and subsequent reaction
- Diffusion of moisture and oxygen and reactions

1.2 Mechanical Mechanisms

Mechanical mechanisms for aging of solid rocket motors generally involve temperature cycling (hot and
cold) which induces stresses and strain in the grain. These mechanisms affect tactical rocket motors much
more than the larger ballistic rocket motors. Tactical rocket motors experience much wider
temperature/relative humidity storage conditions and experience varied other environmental exposures such
as active flight exposure, mobility, multiple temperature storage environments (deserts, arctic, etc.), just to
mention a few. Ballistic motors tend not to experience such varied types of exposure due to their much more
stable and narrow temperature exposures, which typically are storage environments.

1.3 Coupled Chemical and Mechanical Aging

Coupled chemical and mechanical aging presents unique challenges to the chemist/engineer for service
life prediction. This is particularly important for tactical rocket motors; however, ballistic rocket motors have
not been excluded from such effects.
This paper will focus on several examples of coupled and varied types of exposure and their resultant
effects on service life prediction.

2. LESSONS LEARNED

2.1 Chemical Kinetic Approach to Age Life PrediCtion Focuses on

DiffusionlReaction

In using the chemical kinetic approach, it is necessary to begin with the identification of both age sensitive
items and failure modes. It is only through the appropriate evaluation of this infonnation, in conjunction with
environmental loads (external forces), that one can define the approach to evaluation of service life studies
and focus on the critical life-limiting items. Figure 1 shows a typical flow diagram for service life prediction.
Typically, in the chemical kinetic approach, one performs mechanistic studies to understand the kinetic laws
of the processes that will determine the end of life. Accelerated aging is employed using multiple and
reasonable temperatures to obtain infonnation on rate constants, rate laws and activation energies for the
processes.

Figure 1. Flow Diagram for Service Life Prediction

Lessons Learned in Service Lift Prediction 531

This infonnation is further refmed to develop predictive laws to project properties of interest into a time in
the future. Coupled with this is generally an evaluation of margins of safety (considering only structural
failure and not ballistic failure), which takes into account the capability and requirements of the system.
Age life prediction generally is made up of a service life prediction component and a verification
component. Once a service life prediction is made, a verification or surveillance program is developed to
further refme the service life prediction. Generally one cycles back to the age sensitive items and failure
modes to determine if any of these may have changed as a result of aging characterization.
The kinetics of the aging process are evaluated using multiple temperatures. When solid rocket motors are
involved, the temperatures used are generally lower than those used for most chemical processes. This is done
for. safety reasons, to avoid inadvertently causing ignition or explosive decomposition of the energetic
ingredients used in solid propellants.
Often, the relative humidity is used in conjunction with temperature when the age sensitive items analysis
determines that the system is or can be sensitive to changes as a result of moisture. Many solid rocket motor
components are sensitive to moisture.
The processes within a solid rocket motor can be modeled just like typical chemical reactions. Rate
constants for the processes of interest are obtained and various rate equations are evaluated. The kinetic rate
laws can be of any form such as zero, first or second order, etc. Multiple processes may occur either
consecutively or in parallel. Once a proper fit of the data has been determined, an activation energy can be
determined using the Arrhenius relationship. A typical example is shown in Figure 2.

-4
I
-s r- In k (dayi'/%RH) vs lIT
-6 ~ E. = 19.29 kcal/mole
-1
'\,
·8
~
~

'" ""
·9
.!
-10

-II

-12
-----.- .... ..... -.-.-. ........':>
-13
"
-14
o 20 40 60 80 100 0.00280 0.00300 0.00320 0.00340

Relative Humidity, 0;'

Figure 2. Kinetics of the Aging Process are Evaluated Using Multiple Accelerated Conditions.

With this infonnation, one can then project the appropriate property as a function of time, temperature and
relative humidity. By evaluating multiple temperatures, one can easily determine if chemical mechanisms
have been inadvertently accelerated which do not reflect processes of interest or are inappropriate for the
system.

2.2 Lessons Learned From Historical Aging Programs Fall Into Two
General Categories
The authors have been involved in aging programs with solid rocket motors for over twenty years and
Aerojet has pioneered many critical technologies to aid in the service life predictive technology. One of the
major lessons learned during tlle many years of effort, of various systems evaluated and of many verification
programs performed is the need for full-scale motors.
Full-scale motors are key components of a successful aging program for two primary reasons: (I)
carton/motor bias and (2) motors contain stresses and strains while most analogs and dissected motors do not.
Typically, particularly in the earliest stages of solid rocket motor development, carton or analog data is the
only infonnation available and tllese are used to determine the service life of the rocket motor grain. As rocket
532 Edmund K. Liu and Richard K. McCamey

motors are built, one can then obtain infonnation from actual motors. Many factors can affect the differences
one sees in cartons or rocket motors and these include: polymeric system, cast geometry, motor size, flow
characteristics, variability, etc.
We have determined that variability is a key attribute that must be understood and controlled. The
following became important in evaluating margins of safety: gradients within cartons, gradients within
motors, variability in aging environments and variability within component populations.
Carton/motor bias is a critical parameter one must know to properly and accurately determine the service
life of rocket motors based on an analog aging program. Figure 3 provides some representative data which has
been obtained over many years of service life prediction activities. As one can see, there are differences
between propellant type and solid rocket motor application. Generally, propellant strength is consistent
between motors and cartons. Strain on the other hand is generally much lower within a rocket motor than that
obtained from carton data. Young's modulus for propellant in rocket motors is considerably higher tll3II that
obtained from carton data. Since bond requirements are dependent on modulus and strain a1lowables depend
on strain capability, predictions based on analogs may be optimistic compared with actual motors.

RlItiOl in Uniaxial Tensile Propertics'

(Motor/Cart...)
Motor Type Propellant Type
~ ~ __ "b_ E.,
Tactical Polyurethane 0.98 0.69 0.78 1.50
Ground Launch

Tactical CTPB 1.16 0.77 0.72 \.SO

Ship Launch

Strategic Polyurethane 0.90 0.59 0.71 1.79

Upp... SU8e

Strategic CTPB 1.19 0.86 0.86 1.30

Upp... Suge

Strategic PEGiFEFO 1.17 0.60 0.61 215

Upp... Suge

Strategic HTPB 0.97 0.76 0.87 1.41

Upper Suge

• Measured al77°F, 0.74 min -I. om: nominal maximum stress;

....: strain at nominal maximum stress; Eb: strain at break; Eo initial tangent modulus.

Figure 3. Predictions Based On Analogs May Be Optimistic Compared With Actual Motors.

2.3 Stresses In A Motor Can Be An Integral Part Of The Aging Mechanism

Another important lesson learned is the impact of motor stresses on tile aging mechanism. Typical
chemical kinetic aging occurs in a 'stress-free' environment. The importance of either motor stresses or stress
simulation on analogs is a result of the appropriate application of failure modes analysis in conjunction with
the age sensitive items. Often when motors are dissected and san>ples obtained for future accelerated aging
evaluation, the motor internal stresses on the grain are relieved and the aging data obtained may be incorrect.
The example provided in Figure 4 is one obtained from an actual motor which was evaluated for service
life. Wit1>out including motor stresses on the area of interest, one could not appropriately model the failure
mechanism which was observed in the rocket motor. Merely using chemical kinetics, including aging
mechanisms and analog san>ples provided an incomplete picture of the actual aging of the rocket motor.
The authors have also detennined that kinetic projections of rocket motors and analog cartons can be
different. The example presented in Figure 5 involved a reaction/diffusion scenario. During the aging process,
decomposition of an energetic propellant ingredient results in internal gas generation. Fonnation of cracks
was monitored in both analogs and motors. Unfortunately, t1>e service life prediction detennined by analog
aging was different from that detennined by rocket motors. The primary difference was attributed to tile web
thickness of the rocket motor, where tile grain could crack as a result of gas being generated faster than it
could diffuse through t1>e propellant grain. Subsequently, a model was developed that included the following
important infonnation: (I) rate of gas generation, (2) rate of gas diffusion and (3) lengtll of tile diffusion
pathway.
Lessons Learned in Service Life Prediction 533

Initial State Aging

Casellnsulation Adhesive I--
Sprayed &om Solvent Solution
Migration of Plasticizer From
---<~Curalivesand CatalYSQ Carried
PropeUant Through Insulation
into Insulation By Solvent
into Adhe.ive

Figure 4. Stresses In A Motor Can Be An Integral Part Of The Aging Mechanism.

Arrhenius Equation

10‫סס‬oo

Kinetic Projection
k
I Analog Cartons I
.
III
>. 10000
f'...
--'

."
'l:l
.-
U
....
.:J
1000
I
"-
.:,....r""
I-

T" I
"
~
.5
!- 100
~"
"
Kinetic Projection
1Accelerated
Aged Motors
sb
=l Motor Samples

10
I
180 160 140 120 100 80 60
Temperature, OF

Figure 5. Kinetic Age Life Predictions Can Be Different Between Motors And Analogs.

2.4 Propellant Property Gradients

Evaluation of margins of safety is one method to detennine end of useful service life of a solid rocket
motor grain. Part of this calculation involves determining the induced stresses at the bondline of the rocket
motor using the modulus of bulk propellant as one of the input properties. Extensive testing has detennined
that, in many motors (not all), significant gradients in mechanical properties can exist near the bond interface
due to chemical reactions or migration of species within the rocket motor.
The example in Figure 6 incorporates the use of these bondline gradients within the rocket motor grain.
By incorporating these gradients, the stresses can change by 10-20% and this can significantly affect tlle
detennination of the end of service life.
534 Edmund K. Liu and Richard K. McCamey

Example: 3O-year storage at 6O'F

Bond Normal Stress Shear Stress

1-
No Gradient 33.9 14.3
11 [-18%
% 16.8
With 37.6
Gradient

'r:.;;

L.
2500
:::I
-; 2000
."
co
)1 1500
'W;

:, =-
=
.. l:l
1000
9 --i)

'01"' 500

~ 0
0 0.5 1 l.S 2 2.5 3
Distance from Bond, Inches

Figure 6. Gradients At The Bondline Can Significantly Affect Thennally Induced Bond Stresses.

2.5 Environmental Load Conditions

An important aspect of accurate service life prediction is the appropriate use of induced loads, which
include environmental loads such as temperature and humidity. Service life prediction is generally performed
for a population of rocket motors under assumed load conditions. However, inaccurate estimates of these load
conditions can lead to inaccurate service life estimates. The graph in Figure 7 demonstrates this. The dotted
line represents the predictive model developed for the service life estimate for bond tensile strength as a
function of a desired temperature and relative humidity. This model was originally developed using a
measured temperature and an assumed hwnidity, in this case 70°F and 50% RH. The apparent fit, developed
with relatively short-term data, was not realized for longer aging times. As additional data was collected from
motors, it became clear that a better fit was to assume a 40% RH average exposure.
120 T ..· •..• ·· ·.. · · ·• .

o Excised Production Motors

...... 700F/40%RH

- - - 700 F/50%RH

20

o+------+------+------+------t-----+----"
o so 100 ISO 200 2SO
Age, months
Figure 7. Variability Reduces Confidence Of Prediction.
Lessons Learned in Service Lift Prediction 535

The apparent data scatter around the model can be easily explained by variations in the two major load
parameters, temperature and humidity. The equation used is representative of a single temperature and
humidity environment for the entire exposed life of the rocket motor. Unfortunately, this is never the situation
as rocket motors can experience significant variations in temperature and humidity exposure. This is
particularly true for tactical rocket motors and, to a lesser extent, ballistic boosters. The lesson learned was the
need for accurate temperature and humidity exposure records for rocket motors, otherwise, assnmed
conditions can result in an inaccurate prediction of service life.
Part of the service life prediction methodology is the verification of the model(s) being developed. The
best way to provide accuracy and to improve/refine the prediction is to use full-scale assets as represented in
Figure 8. Unfortunately, this is often difficult on large ballistic boosters. Large boosters present significant
cost issues as these assets are very expensive. Also, the large boosters present dissection challenges, handling
of large segments, storage issues and ultimately disposal of large quantities of propellant. Tactical rocket
motors are generally more abundant and of lower cost per asset. The problem posed here is whether the motor
will be representative of the entire population of thousands of motors, particularly as tactical rocket motors
experience multiple environmental exposure. This varied environmental exposure can affect the accuracy of
the service life estimate.

Development ProductionIDeploymentlStorage

LaboratorylMotor
Analogs

· Screening Evaluation
· Formulation Variables
· Processing Variables
· Aging Variables
· Aging Trend Assessment
· Accelerated Condition
· Real-Time
· Aging Mechanisms
· Special Studies
· Age Life Prediction
· Variability Analysis
· Preliminary Structural
Assessment
Full-Scale Moton
(plug and/or Dissect)
· Complete Characterization
· Compare with Lab Analogs
· Within-Motor Variability Excised Samples
· Between-Motor Variability andNDE
· Aging Trend Confmnation
· Update StructuraVBallistic . Field Motor Verification
Assessment . Update StructuraVBaIlistic
· Size Bias Confmnation Assessment

Figure 8. FuII-Scale Motors Are Key Components For Verification Of Service Life.

A method to obtain more accurate estimates of service life is to understand, control and/or incorporate as
much variability information as reasonably possible and available, as illustrated in Figure 9. 111ere are many
sources of variability and many of these are listed. Incorporation of these variability factors into the models
developed will ultimately result in more accurate estimates of service life for a specific population of rocket
motors.

3. SUMMARY

The desire to keep rocket motors beyond their original design life has presented some interesting
challenges to chemists and engineers. Some of the lessons learned presented here include:
- Full-scale motors are key components of a successful aging program.
The aging program must take into account carton/motor bias and should simulate motor stresses in the
laboratory.
Accurate assessment of gradients in propellant properties is critical to margins of safety determination.
Accurate and correct environmental exposure of the rocket motor must be modelled.
Understanding variability in the propellant and at its bond interfaces leads to accurate assessment of
service life.
536 Edmund K Liu and Richard K. McCamey

Raw MatcrW. • • AsiOl • Ac. Ufe Prcdjcljon

• Polym.r • ClwnbcrDry TIDI. • Testing • Motor_Mot..

• MW DiJlribution • Time Between Drying • SIO.... • Predictive ECflIlion
• Functionslily IDdLining TCDlpcrlture • Actual Stong. Conditions
• Malcrial Moisture Content • Insulation Moisture • SlOng. Hwnidily
• Liner Formul.tion Vlriobl. Content • AslctTypc
• No Adjuslmcllt for • Insulation Thickness • Aslct Grldi.nls
Equival.nt Weight • T CDlpcrlture During • SIR..

• Weighing Voria1>ilily Lining Component

• Other Raw Material • R.lative Hwnidily
Con..minalcs During Lining
• Liner Moi.ture Content
• Liner Thicknes.
• Procure lime
• Lin.r Hold lim. Prior
to Cut
• S.... of Cure II
().TIDI. Testing
• Testing Vlriobilily
• Conllminltion

Figure 9. Understanding /Controlling Variability hnproves Accuracy Of Service Life Predictions.

REFERENCES
McCarney, Richard K. and Liu, Edmund K.S., 1996, CP-586, Methodology and Techniques for Determining Service Life
ofSolid Rocket Motors, AOARD PEP Syrnposiwn on "Service Life of Solid Propellant Systems", Athens, Greece.
McCarney, Richard K, Lessons Learned on Solid Rocket Motor Aging Programs, AlAA/ASAME/SAEIASEE 33'd Joint
Propulsion Conference, Aging and Surveillance Workshop II, Seattle, WA, July 6-9,1997.
Veil, P.w., Landuk, 1.0. and Svob, OJ., Experimental Evaluation of As-Processed Propellant Grains, 1. Propulsion, Vol.
I, No.6, p. 494-497.
PW. Veil, Experimental Evaluation of As-Processed Propellant Grains, AlAA/ASMElSAE 20'" Joint Propulsion
Conference, Cincinnat~ OH, June 11-13, 1984, Paper 84-1293.