OLIDT C.

CROPELLNY
Sq GN TDE

CLEVELAND S.WATERMAN

4 ~AUGUST1916i

ONMAORAY1y
loCNypuol

~fl APPROVED FOR PUBLIC RELEASE

DISTRIBUTION UNLIMITED

.3 AIR FORCE ROCKET PROPULSION LABORATORY

DIRECTOR OF SCIENCE AND TECHNOLOGY
AIR FORCE SYSTEMS COMMAND
EDWARDS, CALIFORNIA 93523 *

. . . ... .I
 UNC LASSIFIE D
SECURITY CLASSIFICATION OF THIS PAGE (Whon 0.t. Entered)
DOCUENTAION
AGEREAD INSTRUCTIONS
REPORT DOUETTINPG EFOIPE COMPLETING FORM

AFRL-T-76392. GOVT ACCESSION NO. 3. RECIPIENT'S CATALOG NUMBER

_7ILandSu e We
ttvr gRC 6EIO

SSOLID PROPELLANT AGING STUDIE(

7. AUTHOR(#)
'40--R

IrV Robert C. oley

'-L Cleveland 2S.fWaterman 1sat Lt, USAF
9. PERFORMING ORGANIZATION NAME AND ADDRESS 10. PROGRAM ELEMENT, PROJECT, TASK

IAir Force Rocket Propulsion Laboratory/MK

Edwards AFB, CA. 93523
AREA &WORK UNIT NUMB.aRS

Ii. CONTROLLING OFFIC~E NAME AND ADDRESS

1 14. MONITORING AGENCY NAME & ADDREES(II differenti trot" Controlling Office) 15. SECURITY CLASS. (of Ihla report)

AUNCLASSIFIED AJ
15. ECL ASSI F1CATION7DOWN GRADING
___________________________________________ __________SCHEDULE_____

16. DISTRIBUTION STATEMENT (of this Report)

Approved for publtic release; distribution unlimited

17, DISTRIBUTION STATEMENT (of the aimtrmcl entered In Block 20, It different from Report.)J

IS. SUPPLEMENrARY NOTES

2 19. KEY WORDS (Continue on reverse side If nec essary and idenltfy by block number)

I-ITPI3

0. ABSTRACT (Continue on reverse side If neceaeary end identify by block number)

Since 1972 AFRPL. has been building up an In-H-ouse capability for aging solid
propellants. By November of 1974 the facilities had expanded to the point
where full scale aging of propellants could be performed. A tchree-year plan)
for the accelerated aging of 17 different solid propellant formulations was
prepared. The aging conditions include elevated temperatures and2 humidity.
Data has been compiled but no analysis of this data hias as yet been
accomplished.

DD JAN 73 J473 ED '1ION OF 1NOV 65 is ouisDJETE NLSSFE

I SECURITY CLASSIFICATION OF THIS PACE (When Dole Entered)

72
o'/
 TABLE OF CIONTENTS

Preface .. . . . . .. . . . . .. . . .1.. . . . . .

Surmnmary and Conclusions ......... I......

Introduction...................................................... 2

Experimental Details ........ ...... ......................... 5

References...................................... ................ 18

Appendix I
GacIoFEngineering Maintenance Responsibilities................. ....... 20
Appendix II
Accid~nt at TestArea 1-21................................ ......... 22
Appendix III
Generaland Detailed Test Schedule. .. .. .. .... .... .... ...... .... .......... 25
Appendix IV
.. . .. .. .. ... . ... . .. ....... .28
.. .. .. ... ..
Propellant Ingredients Being Aged

j .,

iv

~C 4--
 I ILLUSTRATIONS

F1,gure Page

1. Environmental Chamber Specifications..................... . 6

2. Propellant- Block and Individual Tensile Specimen .......... 8
3. Specifications of the Instron Test Apparatus.................. 10
4;.4. Details of the Scheduling Process'........................ I
'~ 15. General Test Plan.........................13
6. Engineering Request for JANNAF Sample Preparation .. .. .. .... 14
7. Engineering Request for JANNAF Sample Testing .. .. .. .. .. ..... 1

A..
 PRE FACE

This technical report summarizes the work done on the In-House Propellant Aging
Program at the AFRPL between I November 1974 and 30 June 1976, No previous
technical reports have been published on this program.

The authors -wish to acknowledge those people who proved Invaluable to the
development of an aging capability at the AFRPL. MSgt. Louis Franks, TSgt.
Rex Thompson and Mr. Kelley Palmer were responsible for planning and over-
seeing the necessary construction of the facility. They also had the difficult task
of day-by-day maintenance of the environmental chambers and cutting the samples.
The actual aging of the propellants is only a part of the task. An important part
is samnple testing, and Mr. Tom Chew has done an excellent job at this.

SUMMARY AND CONCLUSIONS

Since 1972, the AFRPL has been building up an In-House capabilIty for aging solid
propellants. This initial work involved 'he selection of a site for the activities
and the procurements of equipment that would make accelerateu Qging of propel-
lant possible. This equipment consisted mostly of environmental chambers tlhat
could store propellant for long periods of time at constant humidity and tempera-
ture. By November of 1974, the facilities had expanded to a point where full bcale
aging of propellants could occur.

Once the facilities were in place and operating, a 6tandard procedure for utilizing
the capabilities had to be formulated, This procedure includes the timely insertion
of propellant 'ato the environmental chanmbers along with the subsequent
extraction and testing. Coordination of all facilities and personnel had to be
effected. This technical report summarizes how this task was accomplished.
Now that the capability and procedures have been established, future reports will
contain the actual aging data.

1,,,
,.-.
 INTRODUCTION

During the early 1970's, hydroxy terminated polybutadiene (HTPB)

propellants graduated from laboratory curiosities to leading conte.,ders for future

solid rocket motors. The two primary composite propellant systems with which
HTPB is competing are carboxy terminated polybutadiene (CTPB) and
polybutadiene - acrylic acid - acrylonitrile (PBAN). The latter two systems have
been in use since the 1950's and are well characterized with a massive amount of
aging data available (reference #1). No matter how favcrably HTPB may compare
in regards to cost, processing, and initial mechanical properties, the available
aging data and experience with PBAN and CTPB propellants are important
criteria t.. systems personnel and prime contractors. In order to lend credence
to the AF'RPL's contention that HTPB is ready for applications, aging capability
must be established.

The years of experience necessary for establishing that capability iL lacking.

However, accelerated aging has indicated (references 42 aid #3) the superior
aging characteristics of HTPB propellants. Later in this report, the dang.r of
"overinterpretation or raisinterpretation of accelerated aging data will be pointed
out.

It is the objective of this report to review the efforts which have led to the
development of the capability to perform an aging study at the AFRPL and to
review the types of propellants currently being aged. The reason for performing
aging studies at the AFRPL is to eliminate comparison problems among different
facilities by having a central facility to age and test propellants under identical
conditions.

The equipment and experim--ital procedures will be discussed in detail in a

subsequent section of this report. I' essence, the AFRPL has developed the
capability to age propellants under a variety of condit,.ons. In addition to bunkers
and storage rooms for long-term, anmbier t aging, chambers are available for
storing under a variety of temperature/hunmidity conditions.

It is an understood fact that many problems exist in aging propellants in

cartons. Primarily, the correlation of carton sample data to dissected motor
sample data has been relatively poor (reference #4). This is particularly true for

! ', .. . . . . . .
S.Ilarge meters where the exothermi~c cure reaction can produce up to 9°0F higher
temperatures in ,;he center of the grain during cure. The temperature differential
results in different propellant properties. One way around this problem i½
s toh
e

determine the temperature gradient across the grain during cure and then to cure
cartons at the required temperatures to correspond to certain sections of the motor.
An additional problem with carton aging is that flow lines are introduced during
casting and the physical properties (as well as burn raie) will vary with these lines.
The flow (and thus properties) can be different in cartons and motors, and in
different parts of a motor.

Reproducibility of test methods is another problem associated with interpreta-

tion of aging data. This inr;1c.-es such factors as: sample containers (e. g., unlined,
foil-lined, lined with insulation/liner as per motor); means of preparing JANNAF
specimen (e. g., stamp, mill, Class A., 3, or C); time from cutting to testing and;
control of humidity and temperature in the Instron Chamber. These reproduci-
bility problems sometimes result in data sc erratic that aging trends are obscured
by data scatter. The problems are compounded to an insurmountable degree if
one tries to make facility-to-facility comparison of aging trends. This latter fact
is ,, strong Justification for having one central facility for azing and testing propel-
lants under identical conditions.
Accelerated aging methods and dat. interpretation have always been
questionable. The attempts to perform aging studies at elevated temperatures and
project age life at a lower temperature ignores the probability of having reactions
which occur at one temperature but are of no consequence at a lower temperature.
A major step towards resolving this question has been the work of Layton (reference
#2 and #5) which entails gathering chemical aging data along with mechanical
property aging data at different temperatures to assure linear changes in both.
If, for instance, a linear plot is obtained for gel content vs.log time at tempera-
tures up to 1500F and linear plots are obtained for some property (e. g., stress)
over the same temperature range, it may be assumed that the same aging
mechanism is applicable over that range. Therefore, a simple Arrhenius
relationship may be used to derive a rate constant from dp/dt k/t and predict
property changes (dp) over a time period (dt).

A practical problem encountered in predicting age life (even assuming a

knowledge of temperature effects) is the uncertainty of cyclic effects. An ICBM
3

i•. • -••',,•<•
.,,•• •'•,,':
j- •, '"":••.• •"'•.,.,'j~•.•
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 may see a relatively constant temperature whereas a tictical missile is exposed
to a varied temperature history. Davis and Nelson (reference #6) have shown for
an HTPB propellant that total time at an elevated temperature is the important;

factor and the same degree of damage occurs regardless of whether the exposure
for that time period is continuous or intermittent.

One final environmental aging condition to be considered is humidity. Most

motors have weather seals. However, some are open to moisture and others
suffer punctures of weather seals. It would be valuable to know the effect of
moisture and one objective of this In-House effort is to determine that effect.

All of the propellants currently at the AFRPL were produced on various

contracts with the irnustry. A large number are under investigation because
they cover a wide burn rate range (0. Z2 to 2.1 in/sec at 1000 psia) and act as
baselines for many different systems. They also serve as means of comparing
various ingredients. For instance, the UTP propellants will give comparative
data on two different Pro-Techs and a standard antioxidant with all other factors
being identical. The ANB formulations look at the long term metal cure catalysts
effects along with a dl.fisrent antioxidant blend. The TP-H1135 is an example of a
propellat with no plasticizer or metal additives. TP-18213 will give data on
DDI as the curative. TP-H8Z19 and 8220 will give comparative data on two means
of getting to a high rate. One way has UFAP and the other transparent iron
oxide.

-4

i, j
 II EXPERIMENTAL DETAILS

At present, the propellant aging work at Test Area 1-21 breaks down into two
distinct phases. First is a two-year long period during which the propellant is
stored under a variety of environmental conditions and is sampled and tested at
predetermined intervals. Second is an indefinite period of storage during which
no testing is planned. The propellant is available for testing should any aspe3ct of
that propellant be of possible future interest. For example, the importance of
propellants containing ferric fluoride was not known at the time of their receipt at
the AFRPL. However, the effect of ferric fluoride on the aging of reduced smoke
Maverick and SRAM propellants became of concern, and therefore the ferric
-fluoride containing propellant was tested one year after being placed in the A.FRPL
inventory. The second phase is sinmple. All that is needed is a shelf on which the
propellant can be stored under ambient conditions of temperature and humidity.
Phase I requires a great deal more planning, more facilities, and more data
handling. The primary thrust of this report will be to show how Phase I was
constructed and how it can be modified to permit the easy insertion of new pro-
pellants into the two year formal period of aging.
Since the two years is not considered long in the lifetime of a propellant, an
environment that would accelerate the aging process of the propellant is required.
Thus, the six environmental chambers at Test Area 1-21 are the heart of the In-
I-louse Propellant Ajing Program. Figure 1 gives a technical description of the
chambers being used. Prior to 1972, environmental control capability at the
AFRPL was very limited. Hlumidity control was obtained by placing various salt
solutions in ovens. Varying humidity was obtained by varying the solution. The
chambers for temperature control were in the open with only a sun shade over the
top and dirt bunkers on three sides. Under these conditions it was difficult to

maintain desired environments. It was also difficult to maintain the chambers in

operable condition due to exposure to the elements. Thus, it was decided that
chambers capable of mainta'ning both temperature and humidity and stationed in an
enclosed area would be the best conditions for an aging program. This is the
arrangement being employed at Test Area 1-21.

The proper operation and maintenance of the ovens is critical to the entire
program. Years of aging could be wiped out overnight if the ovens malfunctioned.

5 . , , ,_ . .
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 For example, the temperature controller could go astray and literally bake the
propellant. Just as bad, the humidity controller could fail and drown the propel-
lant. In the early years of the program both of these fatal malfunctions occurred.
* To prevent their future occurrence, reiundant high temperature cutoffs were
installed on both the wet and dry bulb temperature controls. If either of the set
points on these redundant controllers iJ exceeded, the entire oven is shut down.
S~For
example, a very high wet bulb te riper'ature indicates that the relative humidity

is high since the wet air can no longer cool off the wick in the wet bulb temperature
sensor. To completely avoid any break in the test schedulo, one of the six ovens
is held on a stanabv basis to take ovct" the duties of any one of the other five. ovens
that malfunctions and shuts dcwn. When such a malfunction occurs, the party
responsible for effecting repairs is (Cornponent Processing, also known as Chalco,
Inc. The duties of this organization are described mnore fully in Appendix I.

The actual use of the ovens 's relatively simple. The bulk samples of propel-
lant aru ut into blocks with the rough dimensions 5 in. x 4 in. x 3 in. for a short
test serios and 5 in. x 8 In. x 3 in. for a full test series. The series will be
describrd subsequently. A sufficient number of these blocks for carrying out the
two yearsi of formal aging and testing are placed into the ovens. The blocks are
wrapped on all sides except one so that any gradient effects can be meas'ired.
The blocks are placed in the ovens so that the exposed surface faces the door of
*the chamiber. if the exposed surface of the block were to face upwards, any
collection of water on the upper surface could pool. This is, of course,undesirable.
Care is also taken to avoid stacking the blocks on top of each other so that the
physical stress on all blocks is the same. Propellant is also stored under ambient
conditions for both Phase I and Phase I. Gradient effects are considered
negligible in ambient storage. No special wrapping precautions are taken. The
propellant is stored in various bulk sizes and various types of wrapping. For the
must part, however, the propellant in ambient storage is wrapped much like that
which is placed in the ovens.
After storage comes testing. The mechanical properties testing is, at present,
limited to uniaxial Instron testing. Thus, the only treatment of the bulk propellant
necessary is the cutting, milling, and stamping of the dogbones used in Instron
testing. Throughout the program, the tolerance of the din-iensioris of the dogbones
conform to the specifications laid down for a JANNAF Class C dogbone, Vigure 2
gives these dimensions, The rough cutting is accomplished using a Blue Chip
7

ah
 4.951.02

1.00± .06

•-e I
1.00± .02

.50:L_.01

Figure 2. Propellant Block and individual Tensile Specimen

8.
Manufacturing Company circular saw. Slabs of propellant with a th•,ckness
roughly that of the finished dogbone are cut from the appropriate propellant
block. This slab is then machined with an Index Machine and Tool Company fly
spec milling machine till its thickness conforms to specifications. The final dog-
bones are then stamped from these slabs and are ready for testing. The dog-
bones derived from the propellant blocks are numbered and lettered as shown in
Figure 2. Testing on the Instron is done by triplicate runs using three dogbones
processed from the same slab. For example, the three dogbones numbered 5A,
5B, and 5C are tested at identical conditions. The data resulting from these
three dogbones is averaged for presentation.

This process, a, described here, sounds very quick and sinmple. Complications,
however, can set in. The 'rery nature of the material being cut and milled make
the process hazardous and necessitates remote control of the operation. Such
precautions proved necessary when a fire and explosLon occurred on 28 March 1976
resulting in severe damage to equipment,but no injury to the personnel operating
the equipment. Appendix II contains more information on this incident.

Once the dogbones are formed, they leave the purview of Project NX since
mechanical properties testing is the responsibility of Project NE. An engineering
request (ER) written by the project engineer of Project NX accomnpanies the dog-
bones to Test Area 1-30 fcr Instron testing. The ER calls out the temperature
and cross-head speed of the Instron at which each dogbone will be tested. There
are presently two Instron testing devices in operation at Test Area 1-30.
Specifications on these devices are given in Figure 3.

To coordinate the cutting and testing of 17 different propellants cver a two-

year period requires a very large master plan. The basic tebi philosophy that
went into creating this plan is as follows: All of the propellants shall reside in
the ovens for the same length of time. That is, the number of days from insertion
into the ovens until testing shall be the same for all propellants. Therefore, the
basic test plan for all propellants put into the ovens is the same. Since the
storage, cutting, and testing facilities could not accomodate all of the propellants
at once, the schedule for insertion ol the propellant into the ovens had to be
staggered. With the 17 propellants Project NX started with, the stagger from the
insertion of the first propellant to the seventeenth propellant was over a year.
Some idea of the complexity of the master plan can now be seen since the stagger
9
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 causes different start dates for the formal two-year aging period of each
propellant. The stagger could not be made u.1iform (I.e., start a new propellant
each week) since the overlap of two schedules could cause an intolerable ,,umber
of tests to be performed in one week. A uniform stagger could also cause tests
downstream to be performed during ( irlstmas week in order to conform to the
basic test philosophy as described above. Each propellant testing schedule had
to be treated iadividually and thc earliest possible start date for insertion into
the ovens had to be determhied. A quick and simple graphical technique for
accomplishing this purpose was developed. A test plan for each propellant is slid
along a time scale drawn on a long piece of graph paper until an appropriate start
time can be determined. Information is then transferred to the graph paper con-
cerning the dates at which piopellant will be drawn from the ovens and tested.
Figure 4 shows this process in more detail. Any conflicts between propellant
schedules can be visualized as well as any test dates on holidays. Thus, the best
possible start time for each propellant can be quickly determined.

The generalized test plan that is the same for all propellants placed in the4
environmental chambers is as shown in Figure 5. The time is the number of
months from insertion into the ovens. The different ovens numnbered 1 through 6
are set at different operating conditions of constant temperature and relative
humidity. Appendix Ill contains a Standard Cutting Procedure that explains this

more fully and presents the test plan in detail as it presently stands. Oven #5 is
the stand-by oven that can take over the duties of any one of the other ovens in the
event of a malfunction.

As an example, at time point T 6 , the propellant has been in the ovens for six
months. Samples -vould be taken from ambient storage and from ovens #3 and #4.
They would be tested according to test series S,which is also called the short test
series. The engineering requests that would be generated by a propellant being
tested at time point T 6 would be as shown in Figure 6 and 7. The first ER directs
Test Area 1-Z1 personnel to extract half-blocks of propellant from the three storage

second ER directs Test Area 1-30 personnel to test these samples according to

the short test series. The day for cutting and the day for testing is called out on
the ER's so that coordination between the two groups can be obtained. The days
must also be specified so that there is a standardization of the length of time that

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 77 F 1350 1700F

Ambient Ambient
Time Humnidity 90% RH 20% RH 30% RH 50% RH Huýmid i1

TO F

TI S S S S S
T3 S S S
-T6 S __ _ _ _ _ _ _ _ _ _ _ _ _ _

ST9_ _ _ _ _ _ _ __ _ _ _ _ _ _ _ _

T12 F S S S S
T24 F S S S

S Short Test Series F - Full Test Series

Instron Test ýettings Instron Test Settings

Temp X-head Speed Temp X-head Speed

Sample No. (Deg. Far.) (in/mmr) Sample No. (Deg. Far.) __(in/min)

1:A-B. C 77 2. 0 .A. B. C 77 2.0

2ABC77 2- 4AB. C 1652-
~ABC165 2.0 5-.B- 135 Z.0
4.A, B, C -65 2.0 6:A. B. C 40 2. 0
7:.B 0 2.0
8:A. B.C -40 2. 0
Sainples 5:A, B, C are to be used as 9:A, B, C -65 2.0
backup spares and not to be 10:A.-B. C 165 0.2z_
otherwise used. 3:A, B, C -40 20. 0

Samples 2:A, B, C are to be used as

backup for above tests. If not needed
as spares, test at 770F and 2 in/min.

Environmental Temperature Humidity

Chamber No. Setting Setting__

1 77 0 F 907o RH
2 135OF 20% RH
3135SF 30% RH
4 135 0 F 50%1/ RH
6 170OF Ambient. (at present)
Chamber No. 5 is held in reserve in the event of failure of one of the other
C'' chambers.
Figure 5. General Test PlanI

,, = 10
 ENGINCERING R$QUEST OT

01o THRWt

P rop ellantNE A g in~g 305 908 N

5U@JECT CP
JANNAF SAMPLE PREPARATIONI

ER~

)Propellant Batch Day Oven I Block Propellant Time

Name Number Gilt #Size Name Point

UTX-144ZO 5/3 Monday 4 Short HT

TX-1420Mnday3 /2 Shrt6
LTX-14420 5/2 Monday 3 Short 11 T6

UTX-14420 5/2 Monday Ambient Short H T

Figure 6. Engineering Request ior JANNAF

Sam,-ile PreparationI

14
-XIEYOfMW 5 fEPLA69i HPI. FOýAiO.4 O4Ak 70, ýb4ICH WIZL~. USKID
OCT 72

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 TDAT

0ATE[ REQUIRED AK R~: MR4C

UM$ER
- Progellant. A.4ing 305908 NX
*SUBj~t7 PATS COMPLETE COPIES TO:
SA NNA F SAMPLE~ TESTING

E R.

Propellanit Batch Day Oven Test Time Sol

Name Number Tested #Series Po int Gel.

TTX-14420 5/3 Mon 4 Short T6 ___

UT- O5/2 Tue, 3,1, and Short T6

_________ mbient

SHORT TEST SERIES FULL TEST SERIES

Sample No. Temp. X-head Speed Sample No. Temp. X-head Speed
(Deg. Far.) (in/min) (Deg. Far. ) (in/min)
i:A. B.C 77 2.0 1:A, B, C 77 2.0
Z:A. B. C 77 2.*0 4:A, B, C 165 2.0
3:A, B, C 165 2.0 5:A, B, C 135 2.0
4:A, B. C -65 2.0 - :A
RB, C 40 2.0
B 0A 2.0
Sampl1.s 5:A, B, C are to be used as backup 8:A, B, C -40 2.0
spares and are not to be otherwise used. 9:A, B G -65 2.0
1 O:A, B, G 165 0.2
3.A. B.CG -40 -o 200
Samples 2:A, B, C are to be used as backup
spares for above tests. Ifnot needed as
spares, test 77'F and 2 in/mn..

Figue 7.Enginieering Request for JANNAF Sample Testing

AFRFL
FO MaPL ACES RPL FORM 0 -6,, AA 70, bIIHM WIRLL, 8USE 0S!
OCT 72 "
 a sample spends between its extraction from the ovens and its testing. Samples
stored in oven #4 would lose the moisture gained from storage in the high
temperature - high humidity environment of oven #4. The loss of moisture would
cause a change i.i nmeasured mechanical properties. To circumvent this change,
propellant from oven #4 is cut in the woQrning and tested in the afternoon. It is not
possible to maintain such a schedule with all of the chambers because of man-
power and facility limitations. The cutting/testing schedule that is followed for

the ovens at their present settings is as follows for propellants extracted and cut
on some day D:

Storage Days for

Condition Testing

ambient D+l to D+4 71

oven #•1 D+l
oven #2 D+l
oven #3 D+1
oven #4 D
oven I D+I

Another standardizaticn of procedure implemented in this program is what

to do in case one of the large blocks (approximate dimensons 5 in. x 8 in. x 3 in.
takeni from ambient storage for a full (30 dogbone ) test s -ries is not large enough
to provide all the dogbones necessary. The simplest procedure is to renumber
the dogbones , e.g., designating slab 4 as slab 7 even though It comes between 3
and 5. This procedure simplifies matters for the Instron testing phase. The
actual steps are as follows:

No. of Dogbones Original Slab No. Redesignated Slab No.

27 2 10
24 6 9

This way the less important parts of the full test series are eliminated.
The example ER shown in Figure 7 will result in 36 dogbones being tested.
Each one of thtse dogbones generates nine numbers upon testing which means that

this ER will reduce about 13 lbs of solid propellant 324 numbers. During the two-
year formal aging period, a single propllant will cause around 3300 new numbers J
to come into the world. ror the propellant now on hand at Test Area 1-21, around

V,16

_____ _____
_____ __ *
 50, 000 numbe'.s will be presented ro the project engineer over the three years
required for testing all of the propellants. This is around 50 numbers per day,
seren days per week, for three years. Keeping track of all these numbers can lead
to problems. This problem is compounded by the fact that even though the pro-
gram has been in progress for a year, the numbers have only recently started
coming in. Thus, the project engineer immediately has to contend with approxi-
mately 10, 000 numbers. Therefore, the meth'-ds that will be employed to handle
the data are cnly just beginning to make themselves known. The techniques to be
used for cataloging the data will be greatly influenced by the data acquisition system
used in conjunction with the Instron. This syster. has not yet been flnali:e.i nor
is there any firm date for its completion. Ultimately', a computerik'd system will
have to be employed. Presently, a hard copy computer cutput is received by the
project engineer from the personnel at TETP responsible for data reduction. The
output consisits almost entirely of numbers with little alphamerl, information on it.
This puts the burden on the project engineer to identify the orig~n of the numbers as

:1
to propellant name, dogbone number, storage condition, and length of time at the
storage condition. Project NE, Mechanical Properties Testing, is nmaking progress

in this direction. Meanwhile, this information must be extracted from the hand-
writtcn data sheets generated at the time the tests are performed. This unfortunate
method of gathering is a result of the temporary system presently being used in
conjunction with the Instron.

17

id
 REFERENCES

1. F. R. Mayo, "The Chemistry of Aging of Hydrocarbon Binders in Solid

Propellants," OPIA Publication 262, Feb 75.
2. L. H. Layton, "Chemical Structural Aging Studies on an HTPB Propellant,"
Thiokol Corporation, Report #AFRPL-TR-75-13, Apr 75.
3. "Develowment of HTPB Propellants for Ballistic Missiles," Thiokol Report
#AFRPL-TR-75-.Z3, May 75.
4. S. J. Bennett, "'Carton/Motor Sample Correlation." Thiokol Corporation,
Report TWR-7304, Dec 73.
Propellants." Thiokol Corporatic-"., Report IIAFRPL-TR.-74-16, Jun 74.
6. R, T. Davis and J, M. Nelson, "Prediction of Tactical Propellant Service
.uiie,' CPIA Publication 11253, Papoi; pres~ented at Feb 74 meeting of S
JANNAF Structure and Mechanical Ilehavior Working Group Meeting.

LI18/19I
 ,'I
APPENDIX I

C14ALCO ENGINEERIING MXAINTENANCE RESPONSIBILI TIES

Cb:alco is responsible for performing the following tasks on a periodic maintenance •

basis for Environmental Chambers #1,.42, #3, and #4. .
Chambers #1 and #2 (Tenney Chambers)

44Ma intenance Requirements F~requency i

Check condition of wicks .for proper Weekly "

operation

Inspect fan and motor Monthly

Check for unusual vibration or noise Monthly

inspect water system

Change w icks
Monthly

Monthly
J
Inspect wiring, heaters, insulation,, Monthly
I'i
and connections
120

Change water filter Quarterly

Clean motor fan and housing exterior Quarterly

Clean heaters and control equipment Quarterly

Clean water chambers, lines, coils, Semi-annually '
trays and float valve
- b.sis for'Environmental Chambers #1,,#2, #3, and,#4.

The mTaintenance requirements for chambers #3 and #4 (Missi-mer Chambers) ar,'

as above except for the deletion of the last requirement to clean the humidification
equiprnent (water chambers, lines, coils, etc. ) on a semi-annual basis.

Environmental Chambers #1 and #Z, manufactured by Tenney Engineering, have

experienced considerable difficulties over the past year. Repairing the chambers
required extensive component replacement and modification of the chamber cir- .•
cuitry. Stated below is a history of the repairs muade on these two chambers. .

Chamber #Z

15 April 1975 Controller failed. New controller

from Trenney received defective...
Reordered replacement. ;

23 April 1975 Replaced recorder

 15 May 1975 Replaced controller

17 June 1975 C ontroller failed:

40 Juae 1975 Replaced controller

7 October 1,975 Replaced sensor and controller

8 October 1975 Repla,ced' soleno.id valve (SV-l)

7 November 1975 Replazed. compressor and expansion

valve

12 November 1975 InsiP;Uled service valves for

,frigeration system
24 February 1ý9,76 Completed mod.ification to control and
refrigeration system consisting of:

Replaced I each solenoid valve with 2

each solenoid valves (SV-4 anu SV-ll)

Replaced 2 each capillary tube

assemnblies with filter driers

Replaced 1 each constant pressure

valve

Installed 30 amp line circuit breakers

Installed 2 each heater relays

Installed I each 1 Amp circuit breakers

Installed 2 each i5 Arnp circuit

breakers

Installed Z30 VAC transformer

Chamber f#1

29 October 1975 Replaced controller

211

hi

Y.,.>,.***
 JL

APPENDIX II

.-1 ACCIDENT AT TEST AR.EA 1-21

On 28 Mar.74 at 1045 hours, a flre and explosion occurred in Bldg 8582, ;: oom
B, S6lid Prdpejlant M~iling and Cutting Facility.

2. Two operators were present;'MU1gt Louis A.. Franks and Mr. Kelley N. Palmer.
No injuries occurred.

3. The incident occurred while remotely cutting an eight pound piece of TP-
H819 propel] 4nt (about X 7," X 4") into one-half inch slabs with a band saw.
MSgt Franks loticed a ian'ie near the band saw table in the region of the saw
blade. After ne had stepped back from the protective window, an explosion
occurred. The TP-H8219 specimens being cut at the AF RPL were relatively
new samples that were entering an aging program. This propellant c'ontains
ultrafine ammonium perchlorate (20%6), iron oxide (1%), 90 micron ammmonium
perchlorate and 6 micron ammonium perchlorate. A Class II explosive
classification resulted from AFRPL test on compositions similar to TP-H8219.

4. An AFRPL group closely inspected the site on 2 Apr 74. Physical evidence
showed that the block of propellant being cut burned without detonation. The
cenflagration caused substantial but repairable damage to the band saw. A cutting
exhaust duct,4 inches I. D. with 0. 125 inch walls connected to the band saw with a
t-wo-inch flexible line, e:ploded scattering large metal fragments throughout the
cell. Another more or less simultaneous explosion occurred under a vacuum
holding plate on an adjacent milling machine blowing the vacuum plate against the
ceiling. The milling machine was also in repairable condition after the incident.
7he cutting cell door was blown off and the door of an adjacent cell pulled off,
with damage to lower hinges.

5. Damage was sustained by the band saw, milling machine, exhaust duct, a
small vacuum pump, two doors and electrical wiring. Estimated cost of damage
4 wva s:

a. Band saw $ Z80.00

b. Milling machine 300.00
c. Exhaust duct 700.00
d. Vacuum pv np 100.00
e. Doors 350.00
f. Electric *. & cleanup 3,410.00

TOTAL $5,140.00

6. The incident was probably initiated with a fire caused by friction between the
saw blade and the propellant. An examination of a piece of propellant that had
been previously cut cff the block that was involved !n the incident showed that
extensive deformation and smearing of the aluminum particles had occurred. Thus,
galling between the large aluminum particles (90 micron) and the saw blade could
have created sufficient local heating to cause ignition. Burning particles from
22 i:
the burning propellant were swept into the cutting exhaust duct igniting an
accumulation of finely divided propellant in an approximately ten-foot horizontal
duct section. The propellant particles in the duct exploded. By an undetermined
process,a spark also ignited finely divided propellant powder accumulated in a
cavity under a vacuum holding plate on the milling machine bed. The ensuing
explosion ripped the vacuum holding plate off the machine.

7. Several recommendations were made by the investigators for propellant

cutting operations in the future. These recommendations were primarily involved
with prevention of propellant particle accumulations and ease of cleaning and
inspection of the equipment.

a. Replace the band saw with a large circle saw. This was suggested
because Mhe band saw is a more complex device that is difficult to clean and has
a large number of places where entrained propellant particles can be subjected to
pinching and friction. Particularly, particle entrapment between the driving
wheels and the saw blade appeared to be an ignition hazard.

b. Use a tungsten carbide tipped saw blade. Gallinxg between large aluminum
part-cles (90 micron) in the propellant and a slightly dulled saw blade appeared a
probable Lgnition source for this incident. Use of tungsten carbide cutters, which
are not readily dulled from cutting aluminum,could reduce the amount of local
heating during cutting. Cutting speed did not stand out as a factor ir. this incident
but should be controlled to less than 1000 feet 'per minute.

c. Design the particle exhaust system so that the inlet at the cutter is not
reduced to less than fifty percent of area of the primary exhaust duct. This
design feature will keep the air velocity and mass flow in the exhaust duct maxi-
accumulating in the
mized. Such conditions should aid in keeping particles from duct
I. D. terminating at
duct. The system before this incident used a four inch
the cutter with a two inch I. D. flexible hose.

d. Minimize horizontal exha'st duct sections to less than two feet and
eliminate dead air spaces in connections where particulate material could accumu-
late . An explosion occurred in a long horizontal duct section where propellant
dust from the cutting operation had settled out. If the exhaust duct was constructed
so that it rose at a steep angle to a high point and then fell at a sharp angle to the
dust collector, buildup of particulate in the duct would be lessened. Also, the
duct in use has horizontal connections for accessory equipment with dead air
spaces about one foot long at right angles to the duct flow between the duct and
shut off valves. Such dead air zones that would be efficient particle collectorb
should be eliminated.

e. Flush cutting exhaust duct with high pressure nitrogen each day following
cutting oaerations. By flushing higE/pressure nitrogen through smnall lines
installed in the rising portion of the exhaust duct after each day of cutting operation,
dangerous buildup of fine propellant particles would be avoded. Direct observation
of the duct interior for inspection would be desirable.

f. Use lightweight conductive material for construction of the exhaust duct.

The duct in use was constructed of one-eighth inch thick stainless steel with heavy
flanges at duct connections. This mass of metal contributed to the physical damage
23
 AA

in the cell when the duct exploded. Lightweight construction should not impair
operation of the duct and would lessen damage to surrounding equipment due to
impact of heavy metal fragments.

g. Construct vacuum plate on milling machine with attached hinges so that

the plate can be readily lifted for cleaning vacuum cavity under plate. The vacuum
holding plate on the milling machine had many bolts to keep it in place and maintain
a vacuum seal. Accumulated propellant material under the plate made possible
the explosion that lifted off the plate. By use of an Inset 0-ring gasket and
positioning pins below the vacuunm plate, bolting would not be necessary as the
vacuum pressure would hold the plate down. By lifting the plateeasy access to
the vacuum cavity for clean up would be obtained. Since dropping the plate could
be hazardous to an operator, use of a hinged mechanism on the plate would reduce
that possible danger.

h. Remove stored propellant from adjacent cell. Four hundred pounds of

Class II propellant was stored in the cell adjacent to the chamber where the
explosive incident occur-.,d. The lower hinges of the storage cell door were
damaged and the door was forced open. Although the contents of the cell were
undisturbed, a large fire could have occurred had the stored propellant become
involved.

i. An Air Force Rocket Propulsion Laboratory representative should be

sent to industrial facilities for assessing the r'elative merit of their propellant
rations versus that of the AFRPL. Thiokol at Huntsville, Alabama
has not had a fire durirtg propellant cutting in the last ten years. Thiokol's :
facility should be a good candidate for obtaining improved cutting procedures.

"V.
Ire

Z4I
 APPENDIX III

GENERAL AND DETAILED TEST SCHEDULES

Time Propellant
Point Typo

I H Cut one whole block of propellaut taken from ambient

o storage and mark as usual. Place half-blocks ini
Environmental Chambers as follows:

Chamber No. of Half-Blocks

#1 77'F/90% RH 5

#2 135°F/Z0% RH 5

#3 135°F/30% RH 6

I#4 135°F/50% RH 5

#6 170 0 F/Arnbient 3

T A Cut and mark one full block from. ambient storage, No

o blocks are to be put in Environmental Chambers.

'1 1/2 H PRemove half-block

one and from Environmental Chambers 3
and 4. Cut mark as usual.

i TI H ~ 3, 4, andone
Rem-ove 6. half-block
Cut and mark< Environmental
fromas usual. Chambers 1, 2,

T3 H Remove one half-block from Environmental Chambers 1, 2,

3, 4, and 6. Cut and mark as usual. Remove one half-
block from ambient storage. Cut and mark as usual.

T3 1. Remove one half-block from ambient storage. Cut and

mark as usual.
Remove one half-block fro -HEnvironmental Chambers 3, 4,
and 6 and one half-block from ambient storage. Cut and
mark as usual.

T6 A Remove one half-block from ambient storage., "ut and

mark as usual.'

T H Remove one half-block from Environmental Chambers 1 and

2. Cut and mark as usual.

251

.Ilia
 Time propellauit

T1 2 H1 ereove one 'whiole block,from gnbient storage and one

half-block from Environmental Chambers 1, 2, 3, and 4.
. Cut and mark as usual.
.T Remove, one whole block from ambient storage. Cut and
-mari. as usual.-

T H Remove one whole block from ambient storage and one

half-block from Environmental Chambers 1, 2, and 3.
Cut and mark as usual.
TA Remove one whole block from ambient storage. Cut and
mark as usual.

Type 1-1 propellant is stored in the Environmental Chambers as well as under

conditions of ambient temperature and humidity.
Type A propellant is stored only under conditions of ambient temperature and
humidity.

44

26
I'. i
 7--

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- , - - - - - - - -- - - -- - - -. - - - .
0

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LA LO in ;0 9 D

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 APPENDIX IV

PROPELLANT INGREDIENTS BEING AGED

POLYMERS

HTPB hydroxy terminated polybutadiene

CTPB carboxy terminated polybutadiene

FBAN polybutadiene - acrylic acid - acrylonitrile terpolymer

R-45M a free radical produced I-TTPB

Butarez -HTS a lithium ini-tiated HTPB with secondary hydroxy groups.

CURING AGENTS

tDDI dimer acid diisocyanate

IHDI hexamethylene dlisocyanate

IPDI Isophorone 1-11-ocyanate

TDI toluene diisocyanate

PLASTICIZERS

DOA dioctyl adipate

FlOronite
IDP

Stan-Pete
isodecyl pelargonate

a polybutene
a hydrocarbon oil

CURE CATALYSTS /SUPPRESSOR~S

DBTDL, dibutyl tin dilaurate

BA benzllic acid
Cr Cl., chromium trichlorlde

ZnO zinc oxide

LA linoleic acid
Fe (AA.) 3 ferric acetyl acetonate

28
BONDING AGENTS

HX-752 propylene imine adduct of iaophthalic acid

TEPAN reaction product of tetraethylei-e pentamine and

acrylonitr ile

TEPANOL reaction product of TEPAN and glycidol

STABILIZERS
DT 11 d itert iarybutyl hydroquinone

Ager ite White di!-beta - naphthyl -p-phenylened iarnine

PBNA phenyl -beta -naphthylamine

Plastinox 711 di(tridecyl) thiodiproplonate

AOZ246 2-Z'-methylene-bis(4-methyl-6-t-butyl phenol)I

Pro-Tech 6402 a Chemical System Division (UTC) ingredient

Pro-Tech 3102 a Ghev-ilcal System Division (UTC) ingredient

S sulfur

UDP- 36 N-phenyl-N - cyclohexyl-p-phenylene diarnine

OXIDIZERS

AP ammonium perchlorate
B-MX cyclotetramethiylenietetranitramine

F UEL
AlI alumi-inumn

29 1