brl - dtic · 2011. 5. 15. · lp-28 cd-9250, disogrin lp-29 norprene, norton ind. plastics h....
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='" OnC FILE H
MEMORANDUM REPORT BRL-MR-3800
BRL
U,) ANALYSIS OF LIQUID PROPELLANTwEXPOSED TO ELASTOMERIC MATERIALS
Wr
I JO EPHINE Q. WOJC[ECHOWSKI0 SHARON L. TAYLOR
WANDA J. O SZEWSKI DTICDECEMBER 1989 ELECTE
NOV 22 1989
APIPROVID FOR PUBLIC RELEASE; DISTRIBUTION UNLIMEP~-
U.S. ARMY LABORATORY COMMAND
BALLISTIC RESEARCH LABORATORYABERDEEN PROVING GROUND, MARYLAND
89 11 17 137
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DESTRUCTION NOTICE
Destroy this report wh n it is no longer needed. DO NOT retum it to the originator.
Additional copies of this report may be obtained from the National Technical Information Service,U.S. Department of Commerce, Springfield, VA 22161.
The findings of this report are not to be construed as an official Department of the Army position,unless so designated by other authorized documents.
The use of trade names or manufacturers' names in this report does not constitute indorsement ofany commerical product.
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UNCI ASSIFIEDSECURITY CLASSIFICATION Or T" S PAGE
REPORT DOCUMENTATION PAGE Form Approved0MB No. 0704-088
la REPORT SECURi T Y C ASS r CAT)0% lb RES'PIC'VE MARKINGSUnclassified2a. SECURITY CLASSIFICATION AUTHORiT'r 3 DISTRIBUTION /AVAILABILITY OF REPORT
2b. DECLASSIFICATION I DOWNGRADING SCHEDULE Appi oved for Public Release;Distribution Unlimited.
4. PERFORMING ORGANIZATION REPORT NUMBER(S) 5 MONITORING ORGANIZATION REPORT NUMBER(S)
BRL-MR-3800
6a. NAME OF PERFORMING ORGANIZATION 16b OFFICE SYMBOL 7a. NAME OF MONITORING ORGANIZATION(If applicable)
US Army Ballistic Rsch Lab jSLCBR-IB6c. ADDRESS (City, State, and ZIP Code) 7b. ADDRESS (City, State, and ZIP Code)
Aberdeen Proving Ground, MND 21005-5066
Ba. NAME OF FUNDING/SPONSORING 8ab OFFICE Si'MBOL 9. PROCUREMENT INSTRUMENT IDENTIFICATION NUMBERORGANIZATION (If applicable)
8c. ADDRESS (City, State, and ZIP Code) 10 SOURCE OF FUNDING NUMBERS
ELEMENT NO. NO. NO. CCESSION NO.
11. TITLE (Include Security Classification)
ANALYSIS OF LIQUID PROPELLANT EXPOSED TO ELASTOMERIC MATERIALS
12. PERSONAL AUTHOR(S)Wojciechowski, Josephine Q., Taylor, Sharon L, & OLszewski, Wanda J.
13a. TYPE OF REPORT 13b. TIME COVERED 14. DATE OF REPORT (Year, Month, Day) 15. PAGE COUNT
MR TFROM Sep88 TOAr8916. SUPPLEMENTARY NOTATION
Addendum to Feuer, H.O. Jr. et al. "Elastomer Compatibility with Liquid Propellant". Technical Report2476, USA Bel-voir Rsch, Dev & Engr Ctr, Ft. Belvoir, VA, 22060-5060, Dec 88
17. COSATI CODES 18 S,UBJJ1 TERM (Contnu .o reve(se if necessary rad identify by block number)FIELD [ GROUP [ SUB-GROUP *-,..4qui ropeuant llyroxylammonmum Ir trateFIL GRU U-GOP[
HAN Triethanolammonium NitrateTEAN Compatibility Elastomer.
19. ABSTRACT (Continue on reverse if necessary and identify by block number)
The Army is investigating use of LP in large and medium caliber guns. The propellant of primary interest isLGP 1846 consisting of hydroxylammonium nitrate, triethanolammonium nitrate and water. One of theconcerns with fielding a liquid propellant system is compatibility with materials used for storage, transfer andhandling. The Belvoir Research Development and Engineering Center undertook an investigation on thecompatibility of elastomers with LGP 1846. The propellant was collected after exposure to the materialsand sent to the Ballistic Research Laboratory for analysis. It was analyzed for a change in fuel and oxidizercontent. This report is a compilation of the analysis.
20. DiSTRIBUTION/AVAILABILITY OF ABSTRACT 21 ABSTRACT SECURITY CLASSIFICATION
r UNCLASSIFIED/UNLIMITED M SAME AS RPT 0 DTIC USERS Unclassified22a. NAME OF RESPONSIBLE INDIVIDUAL 22b TELEPHONE (Include Area Code) 22c, OFFICE SYMBOL
Josephine Q. Woiciechowski (301) 278-6160 SLCBR-IB-B
DD Form 1473, JUN 86 Previous editions are obsolete SECUR!TY CLASSIFICATION OF THIS PAGE
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Tx:?c:OXLLYLEE? ELA- Y.
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TABLE OF CONTENTS
Pane
ACKNOWLEDGMENT . . . . . . . . . . . . . . . . . . . . . . . . . . v
BACKGROUND ............ ............................ a
DISCUSSION ............... ............................ 3
RESULTS ................ .............................. 4
CONCLUSIONS ............... ............................ 5
FUTURE WORK . . . . . . . . . . . . . . . . . . . . ........ .................... 13
R.E F E REN CES................................13
DISTRIBUTION .............. ............................ 15
A,,oss. on For
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iii
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Acknowledgement
We gratefully acknowledge Mr. Ronald A. Sasse for
development of the method for correctly determining the level of
strong acid impurity.
VI
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INT:EN::CNALLY LEFT BLANK.
vi
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Background
The US Army is currently investigating the use of liquid
propellants in medium and large caliber weapon systems. The
propellants that have been chosen for the current development
program are hydroxylammonium nitrate (HAN) based propellants, LGP
1845 and LGP 1846. These two propellants have the same ingre-
dients; HAN as the oxidizer, triethanolammonium nitrate (TEAN) as
the fuel and water as a diluent. The only difference between
1845 and 1846 is 1845 has 3 % more water.
In order to generate a practical system for storage and
handling of liquid propellants, it is necessary to know the de-
gree of compatibility with available materials which are likely
to be used for transfer and containment of the propellants cur-
rently under consideration. The measure of compatibility in-
cludes the effect of the propellant on the materials of contain-
ment such as swelling of elastomers, corrosion and chemical re-
actions. The storage compatibility of liquid propellants is also
determined by the degradation of the propellant by decomposition,
by the solution of ballistically undesirable ions, by solution of
materials that result in undesirable changes to the physical
properties of the propellant and/or subsequent pressure rise
within the storage container.1 -5
An elastomer and plastic compatibility program was initiated
by the US Army Ballistic Research Laboratory (BRL) in 1987. The
objective of this program was to measure the compatibility of
liquid propellant with various materials of construction by
measuring rates of decomposition and reaction under controlled
conditions. The approach taken was a three step program. The
initial step was exposure of the materials to the propellant.
Step two was analysis of materials for degradation or any
changes. Steps one and two were performed by the Materials,
1
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Fuels and Lubricants Laboratory at US Army Belvoir Research,
Development and Engineering Center.1 Step three, determination
of chemical changes to the propellant itself, was then to be
performed at the BRL. This report is a compilation of the pro-
pellant anaylsis.
In developing the list of materials to examine, Ft. Belvoir
searched the literature for elastomeric materials compatible with
ammonium nitrates. Candidate materials were chosen from the
following groups:
o Butyl Rubbers
o Chloroprene Rubbers
o Polysulfonated Elastomers
o Nitrile Rubbers (including Carboxylated and Highly
Saturated)o Some Urethanes and Thermoplastic Elastomers
o Some Fluoroelastomers
Also analyzed were materials from the collapsible tank and hose
industries.
In examining the results of the material study, Ft. Belvoir
determined that nitrile, nitrile/polyvinylchloride blends, poly-
chloroprenes, fluoroelastomers, halogenated butyl, and ethylene-propylene elastomers performed satisfactorily. Carboxylated
nitriles, polyurethanes, and thermoplastic elastomers either
totally failed or showed sufLicient reduct-on in properties to
label them unacceptable for use with LP.
2
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Discussion
The materials tested were conditioned in the propellant for
several different time periods: 7, 14, 28, 42 and 70 days at
70 +/- 40 F. Samples of propellant were collected at the end of
each immersion time. This collection of samples was submitted to
the BRL for analysis. The original propellant, LGP 1846 Lot No.
ABY86JG2001, was also analyzed prior to exposure to any material
for comparitive purposes.
The current assay analytical technicue for LP 1846 is
aqueous titration.6 Samples were titrated on a Brinkman In-
strument Model 672 Titroprocessor and Metrohm 665 Dossimat.
Aqueous sodium hydroxide (NaOH) base was used with an approximate
0.25 molarity. Sample sizes were approximately 0.30 grams.
Fifty mL of distilled water and 2 mL of acetone were added to
each sample. The acetone reacts with HAN to form an oxime and
nitric acid and is then titrated with base. Two end points are
obtained, one for nitric acid and the other for TEAN. At least
two replicates of each sample were analyzed and eight replicates
of the control sample were analyzed. The NaOH base was prepared
and standardized several times throughout the analysis.
Analysis of several samples showed little change from the
control and it was decided that the longest exposure times
available for each sample would be analyzed first. If no change
relative to the control was evident, intermediate exposure time
samples would not be analyzed. This reduced the workload
significantly while not affecting the results.
The strong acid impurity was also determined on the control
sample. Strong acid impurities could cause decomposition of the
LP over extended periods of time. The control had 0.lq wt%
excess strong acid, an acceptable level for this investigation.
3
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Sasse developed a new spiked method for measuring excess
strong acid in LP nat replaces previous BRL methods in use. It
was suggested that 1 to 4 mL of 0.25 M HNO 3 be added to 20 mL of
LP diluted with 40 mL of water. Such a small acid addition al-
lows a typical "S" slope titration curve to be developed which is
necessary to determine an end point. The sample is titrated with
0.24 M strong base. The method is accurate to below 0.01 weight
% excess acid in LP.
Results
Results of the control analysis are shown in Table 1.
Values reported are individual analyses.
Table 1. Titrimetric Analysis of LP 1846 Lot No. ABY86JG2001
Wt% HAN Wt% TEAN HAN/TEAN
61.0002 20.6333 2.9564
61.0807 20.2917 3.0101
61.0429 20.7880 2.9365
61.1214 20.5543 2.9736
61.0911 20.3975 2.9950
61.0206 20.7433 2.9417
60.9387 20.8026 2.9294
61.1557 20.6610 2.9600
Average 61.06 20.61 2.96
Standard
Deviation 0.07 0.18 0.028
4
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A list of the materials surveyed is provided in Table 2 with
appropriate designations. Analytical results for these designa-
tions are listed in Table 3. The result reported in Table 3 is
the average of two to four actual titrations for each sample.
The average and standard deviation of all 100 numbers in Table 3
is given.
Conclusions
Over 90 % of the values listed in Table 3 are within two
standard deviations for both weight % HAN and weight % TEAN.
Therefore, there is no statistical basis for claiming chemical
reactions of HAN and TEAN. This is not to say that the pro-
pellant was not affected as some of the samples showed evidence
of change by color and precipitation. Indepth analysis is
required on the LP samples of the best material sample
candidates.
Future Work
Examination of the most promising material candidates is
planned at temperature extremes. Indepth propellant analysis
will be made at that time to include gas products.
5
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Table 2. Material Designators
A. Highly Saturated Nitrile Rubber
LP-l NBR-2
B. Nitrile Rubber
LP-2 N-BR-8LP-3 NBR-9LP-4 1203-F60-R2, RADIANLP-5 VT-380 (NBR/PVC), RADIANLP-6 BJLT MI-40, UNIROYALLP-7 OZO-HA-0221 (70% NBR/30% PVC), UNIROYAL
C. Carboxylated Nitrile Rubber
LP-8 XNBR-2LP-9 XN BR-3LP-10 XNBR-6
D. Polychioroprene Rubber
LP-11 CR-iLP-12 CR-2
E. Fluoroelastomers
LP-13 VITON-1LP-14 VITON-2LP-15 REEVES S/4646, (GUM)LP-16 FLURAN F-5500-A NORTON IND. PLASTICS
F. Ethylene-Propylene Rubber
LP-17 REEVES 4601 (GUM)
LP-18 REEVES 4594 (GUM)
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Table 2. (cont) Material Designators
G. Thermoplastic Elastomers
LP-19 THP-1, ALCRYN R1201 B-70ALP-20 THP-3, ALCRYN R1101 B70LP-21 THP-4, MONSANTO GEOLASTLP-22 THP-5, MOBAY TEXIN 3550RLP-23 THP-6, MOBAY TEXIN 480 ARLP-24 THP-7, GAFLEXLP-25 THP-8, SANTOPRENE, 201-55LP-26 THP-9, SANTOPRENE, 101-64LP-27 THP-10, SANTOPRENE, 101-73LP-28 CD-9250, DISOGRINLP-29 NORPRENE, NORTON IND. PLASTICS
H. Polyurethanes
LP-30 PU-1, TSE INDUSTRIES, MILLATHANE HT-TIOLP-31 PU-2, TSE INDUSTRIES, MILLATHANE HT-R5LP-32 TSE-E-34-94, TSE INDUSTRIES, MILLATHANE
I. Synthetic Rubber
LP-33 3130 TREADLP-34 KRATON 1650, ILC DOVERLP-35 ATL-644-30, AERO TEC LABORATORIES, INC.LP-36 GOODYEAR COLLAPSIBLE TANKS GUM
J. Halogenated Butyl
LP-37 PE 100A027, ILC DOVER INC.
K. Miscellaneous
LP-38 SANTOPRENE aged 7 days at room temp.LP-39 REEVES S/4616 aged 7 days at room temp.
7
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References
1. H.O. Feuer, Jr., G. Rodriguez, and A.R. Teets, "ElastomerCompatibility with Liquid Propellant", Technical Report 2476, USABelvoir Research, Development and Engineering Center, FortBelvoir, VA, December 1988.
2. M.M. Decker, E. Freedman, N. Klein, C.S. Leveritt, and J.Q.Wojciechowski, USA Ballistic Research Laboratory, AberdeenProving Ground, MD, and 0. Briles and L. Joesten, SundstrandCorporation, "Compatibility Assessment of HAN-Based Liquid Pro-pellants", CPIA Pub. 470, pp 119-125, Proc. 1987 JANNAF Propel-lant Characterization Subcommittee Meeting, Laurel, MD, October1987.
3. K.A. Lavin, "Material Compatibility Testing Results", LetterReport from GE Company, Ballston Spa, NY, June 1987.
4. R. Hansen, E. Backof, and H.J. de Greiff, "Process forAssessing the Stability of HAN-Based Liquid Propellants", 1stInterim Report on Contract DAJA45-86-C-0056, Fraunhofer-InstitutFuer Trieb-und Explosivstoffe, Pfinztal-Berghausen, FRG, February1987.
5. O.M. Briles and L.S. Joesten, "Experimental Analysi- ofHydroxylammonium Nitrate (HAI) on Sample Materidis", Final Reporton Contract DAAD05-86-C-0168, Sundstrand Corporation, Rockford,IL, August 1987.
6. M.M. Decker, E. Freedman, N. Klein, C.S. Leveritt, and J.Q.Wojciechowski, "Titrimetric Analysis of HAN-Based LiquidPropellants", BRL-TR-2907, USA Ballistic Research Laboratory,Aberdeen Proving Ground, MD, March 1988.
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