Contractor Report Brl-Cr-636

IRLR-'636 I I
CONTRACTOR REPORT BRL-CR-636

BRL
AD-A22
4
594
HYDROXYLAMMONIUM NITRATE COMPATIBILITY
TESTS WITH VARIOUS MATERIALS
- A LIQUID PROPELLANT STUDY -
(.
DTIC
EILECTE ECKART W. SCHMIDT
AUG 0 21990 ROCKET RESEARCH COMPANY
AEROSPACE DIVISION
D
OLIN
DEFENSE
SYSTEMS
GROUP
JULY 1990
APIROVED FOR PUBLIC RELEASE; DISTRIBUTION UNLIMITED,
U.S. ARMY LABORATORY COMMAND
BALLISTIC RESEARCH LABORATORY
ABERDEEN PROVING GROUND, MARYLAND
90 08 01 00%
,m -- mt
I '
NOTICES
Destroy this report when it is no longer needed. DO NOT return it to the originator.
Additional copies of this report may be obtained from the National Technical Information Service,
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Th,- findings of this mport 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 of
any commercial product.
REPORT DOCUMENTATION PAGE _
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I. AemJa- US ONLY (L=Mmumw/ ) 1. REPOST CATN j. RPIRT TYPE AMCO ATIS COVEED -
I July 1990 Final Report April 1989 thru March 1990
4. TM o AND susTaLE Hydroxylammonium Nitrate Compatibility LFUN. NG MNutERs
Tests with Various Materials -
A Liquid Propellant Study
F03A909AJOH3
DA306700
Eckert W. Schmid
7. PERFORMING ORGANWATION NAMEAS) AND ACORASS(ES) S. PERFORMING CRGANIZATION
49IICAT MUM614
Rocket Research Company
Redmond, WA 98073-0709 90R 1439
1. SPONSORINGGiMO'IOMING AGENCY NAM115) AND AOOCRSV|S) 1i.SP.NSORJNG MON rOpING
AGENCY REPORT NUMIER
U.S. Army Ballistic Research Laboratory
ATTN: SLCBR-DD-T
Aberdeen Proving Ground, MD 21005-5066
IRL-CR-636
11. SUP1I.MENTAAY NOT3S
Ronald Sasas' (COR, BRL)
Ie. IISTRI0nl I IAVAIIIIIIy IATEMiNT lb. 0STRIUTION COmu
Approved for public release. Distribution unlimited.
U. A T CT A ('a#mum 0 w#.o '.
The compatibility of hydroxylammonium nitrate ("HAN"), a key ingredient of liquid gun
propellants, with 48 different materials of construction was tested in short-term immersion
tests in constant temperature baths with obseri"n and mpisurement of gas evolution.
Test temperatures were 298 K and 338 K (25#C and 65t. Test duration was 30 days.
Materials tested included metals, plastics, ceramics, coatings, and lubricants. At the end
of the test, the gas spaces above the solutions were analyzed for gas composition.
Evolution of nitrous oxide and nitrogen was evidence of incipient decomposition in the
propeUant. The off-loaded HAN solutions were analyzed for leached metals. Based on the
rate of gas evolution, weight loss of the specimens, discoloration of the liquid, and amount
of metals leached, several materials were identified as being incompatible with 60% HAN
,soltinons._.)
(Author)
1-4UhJECT TEAM Liquid gun propellants Compatibility 1 NMUR OF PAGE5
LG?'t845-E6-t846 1P84R .. LP-4i6-f---eAS -- RN-13465-08-2 .- 1 12
H ydroxylamm
onium nitrate , 1& AX - Liquid propellants
,
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_30
17. SEOJEIY a.AsSWOATION il sicumRiy &-%SW-QVAi-3 It. SAcuNtY CLASSOICAntI0 20. UPATATKII OF ABSTPC
OF "myOr or TOS PAGE O A&STRACt
Unclassified Unclassified Unclassified UL
pm. 73S441 .J1SOO
Standard Form 29i (Nov 2,S9)
UNCLASSIFIED -'. ""
frrNTImoNAmyLaY LBFLANK.
Contents
Chapter 1 INTRODUCTION 1
1.1 GENERAL INFORMATION ...................................
1
1.2 OBJECTIVE ................................ ................... 2
1.3 SCOPE OF W ORK ............................................ 2
1.4 PROBLEM STATEMENT ................... : ............ *.. 2
Chapter 2 TECHNICAL APPROACH 3
2.1 LIQUID GUN PROPELLANTS .............................. 3
2.2 SELECTION OF PROPELLANT SOLUTIONS ........ ...... 6
2.2.1 Preparation of HAN Solutions .................................... 6
2.2.1.1 HAN Assay Analysis Methods ........................... 7
2.2.1.2 HAN Analysis for Trace Metals ........ ............... 8
2.3 SELECTION OF MATERIALS TO BE BESTED . 4 .. 0..*........ 9
2.4 EXPERIMENTAL METHODS ............... 6 .................. 10
2.4.1 Description of Test Apparatus .............................. 10
2.4.2 Selection of Test Atmosphere .. .. 6 .. ....................... 17
2.4.3 Selection of Total Immersion versus Partial Immersion ......... 18
2.4.4 Selection of Sample Size ........................ ...... .. 19
2.4.5 Selection of Sample Shape ........ ........................ 19
2.4.6 Selection of Test Duration ....................... ....... . 20
2.4.7 Selection of Test Temperatures ..................... . 21
2.4.8 Constant Temperature Bath ........................... 21
2.4.9 Measurement of Rate of Gas Evolution ............. . 23
2.4.10 Gas Evolution Data Reduction .............. 23
2.4.11 Rate of Gas Evolution as Termination Criteria ............... 24
2.5 CHEMICAL ANALYSIS OF EVOLVED GASES ................. 25
2.6 POST-TEST EXAMINATION OF SAMPLES AT END OF
COMPATIBILITY TEST ... 6................................... 26
2.6.1 Weight Change Measurements .............................. 26
2.7 ANALYSIS OF OFF-LOADED PROPELLANT. ................. 26
Chapter 3 EXPERIMENTAL RESULTS 31
3.1 PRE-TEST ANALYSIS RESULTS ........................... 31
3.1.1 HAN Assay Analysis Results ... ............................ .. 31
iii
3.1.1.1 As-Received24% HAN Solution .................... 31
3.1.1.2 Concentrated 60.8% HAN Solution ................... 31
3.2 POST-TEST RESULTS .............. ................... 34
3.2.1 Weight Change Measurements ........................... 34
3.2.2 Pressure Rise / Gas Evolution Measurements ................ 39
3.2.2.1 Gas Evolution at 298 K (25"C) ...................... 39
3.2,2.2 Comments on Data Reduction ........................ 46
3.2.2.3 Gas Evolution at 338 K (65"C) ....................... 49
3.2.3 HAN Trace Metals Post-Test Results ...................... 63
3.2.4 Gas Analysis by Gas Chromatography ..................... 64
3.2.5 Additional Gas Analysis ................................. 68
3.3 KINETIC ANALYSIS OF DECOMPOSITION RATE DATA ....... 69
3.3.1 Gas Evolution Rate Kinetic Analysis ........................ 69
3.4 SUMMARY AND CONCLUSIONS ............................. 70
ACKNOWLEDGMENT ......................................... 71
References .....................................................
. 72
Figures
Figure 2.1: Distribution by Type of Materials ............................... 9
Figure 2.: HAN Compatibility Test Apparatus, Schematic .................. II
Figure 2.3: Loading of Ampules with HAN Solution under an Inert
Atmosphere ........................ 14
Figure 2.4: Compatibility Test Ampule Loaded with Sample and HAN Solution .15
Figure 2.5: Hermetically Sealed Compatibility Test Apparatus (RRC Model) .. 17
Figure 2.6: Constant Temperatum Bath with 25 Ampules Prior to 25 4C Test . . 22
Figure 2.7: Flow Rate of HAN Solutions into AAS Nebulizer ................ 29
Figure 3.1: Compatibility of Materials in 60.8% HAN at 298 K (25"C) ........ .40
Figure 3.2: Compatibility of Materials in 60.8% HAN at 298 K (25"C) ......... 41
Figure 3.5: Compatibility of Materials in 60.8% HAN at 298 K (250C) . 44
Figure 3.7: Compatibility of Materials in 60.8% HAN at 338 K (65"C) ........ 51
Figure 3.10: Compatibility of Materials in 60.8% HAN at 338 K (659C) ........ 54
Figure 3.11: Compatibility of Materials in 60.8% HAN at 338 K (65'C) ....... 55
Figure 3.12: Compatibility of Materials in 60.8% HAN at 338 K (650C) ....... 56
Figure 3.13: Compatibility of Materials in 60.8% HAN at 338 K (659C) ....... 57
Figure 3.14: Compatibility of Materials in 60.8% HAN at 338 K (65"C) ....... 58
Figure 3.15: Compatibility of Materials in 60.8% HAN at 338 K (65"C) ....... 59
Figure 3.16: ARRHENIUS Plot of Gas Evolution Rates ................... 70
iv
Tables
Table 2.1: Comparison of AAS and ICP Detection Limits ......... .... 28
Table 3.1: AN Acceptance Test Results ........................ 32
Table 3.2: Analysis of Concentrated HAN Solutions ........................ 33
Table 3.3: Weight Change of Test Specimens at 298 K and 338 K (25 and 656C) .35
Table 3.4: Gas Evolution at 298 K (25"C) ................................
47
Table 3.5: Gas Evolution Rate at 298 K (25"C); In Order of Decreasing Gas
Evolution ..................................................
49
Table 3.6: Gas Evolution at 338 K (65"C) ................................. 60
Table 3.7: Gas Evolution at 65"C; In Order of Decreasing Gas Evolution Rate .62
Table 3.8: Gas Evolution Rates of HAN Blanks ................................. 63
Table 3.9: Summary of Metals Analysis by Atomic Absorption ............... 65
Table 3.10: Summary of Gas Analysis ..................................... ... 66
Table 3.11: Kinetic Rate Analysis of Gas Evolution Rates ................. 69
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Avalability Codes
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INTENTONALLY LEFT BLANK.
Chapter 1
INTRODUCTION
1.1 GENERAL INFORMATION
This is the final report on a contract that was awarded to Rocket Research Company
(RRC), in the Aerospace Division of the Defense Systems Group of Olin Corporation, by the
United States Army Ballistic Research Laboratory (BRL), Aberdeen Proving Grounds as the
result of a competitive procurement in response to solicitation DAAD05-89-R-5453. The BRL
Contracting Officer's Representative was Mr. Ronald A. Sasse'.
The research program involved the testing of candidate materials of construction for
compatibility with the key ingredient of liquid gun propellants, namely concentrated aqueous
solutions of hydroxylammonium nitrate, NH 30H + NO3 - (HAN). Materials included metals,
alloys, plastics, and lubricants.
Rocket Research Company has been actively involved in compatibility testing of materials
of construction with rocket propellants such as hydrazinium nitrate solutions in water and
hydrazine. Hydrazine Is a hydronitrogen compound similar to hydroxylamine. Hydrazinium
nitrate is an acidic salt as is hydroxylanmmonium nitrate. The RRC propellant compatibility test
effort has continued for over twenty years and storability data are now available on several
nitrate propellant blends in contact with various materials of construction. The tankage system
of a liquid propellant gun is similar to tankage systems for energetic monopropellants for rocket
propulsion. The extreme temperatures encountered in the liquid propellant gun breech are
similar to temperatures encountered in rocket engines. It is from this related experience
background with liquid rocket monopropellants that RRC has approached the liquid gun
propellant materials compatibility question.
1.2 OBJECTIVE
The objective of this final report is to provide all information necessary to document the
progress made by the contractor in comparison to the goals established in the work plan and the
contract statement of work. It is a further objective of this report to assemble the vast amount of
data generated during the contract in an easily accessible "user-friendly" format. The format
should be such that the user will quickly obtain information about the acceptability or
incompatibility of a candidate material of construction.
1.3 SCOPE OF WORK
The purpose of this contract was to determine the effect of various materials of
construction, including metals, alloys, plastics, and greases on liquid gun propellants (LOP). One
hundred tests had to be performed on one ingredient of the LOP-1845 or LGP-1846 propellant
called lydroxylammonium nitrate, NH3OHNO 3 (HAN). These 100 tests were performed on 48
Government-furnished (GFE) materials and two controls (HAN without any additive) at two
different temperatures, 298 K (25'C) and 338 K (65C). Pressure rise during the 30-day tests was
monitored daily as an indication of compatibility. Post-test samples were examined for signs of
corrosion and some of the off-loaded propellant was analyzed for leached metals. The gas space
above the samples was analyzed for chemical composition of the gases formed. This gas
composition information can be useful to interpret the mechanism of incompatibility.
1.4 PROBLEM STATEMENT
There are two concerns about the compatibility of materials of construction with liquid gun
propellant ingredients. The first is the effect of the corrosive medium on the material, causing
possible loss of structural integrity. The second is the effect of contaminants leached from the
material of construction on the storage stability of the propellant. The test program conducted
here addressed both concerns.
"-2-
Chapter 2
TECHNICAL APPROACH
Forty-eight (48) Government-furnished (OFE) materials and two blanks (hydroxyl-
ammonium nitrate solution only, no material specimen inserted) were tested at two different
temperatures for periods of 30 days and the rate of gas evolution was measured. At the end of
the test, if sufficient gas had evolved, the nature of the evolved gas was determined by gas
analysis. The propellant off-loaded from the test tube was analyzed for leached metals (if the
material was a metallic material) and the specimens were examined for weight change and
changes in appearance.
2.1 LIQUID GUN PROPELLANTS
Liquid gun propellants currently under consideration consist of concentrated aqueous
solutions of hydroxylammonium nitrate and triethanolammonium nitrate. The corrosive
properties of this solution make it necessary to conduct careful materials compatibility eval-
uations. The solutions are ionic (though not fully ionized due to the high salt concentration),
mildly acidic, contain both oxidizing and reducing species, and would therefore be expected to be
reactive with a large number of materials.
Composition of Liquid Gun Propellants, For actual applications, two slightly different
liquid gun propellants are being considered: BRL-1845 and BRL-1846. These propellants have
been historically called BRL-1845 and BRL-1846 but are now also called Liquid Gun Propellant
LGP-1845 and LQP-1846. In the context of the work reported here, the two designations (BRL
and LGP) are used interchangeably.
Nominal compositions of LGP-1845 and LGP-1846 were given in a physical properties
report published by BRL (Reference 1).
LGP-1845 consists nominally of
63.23 wt.-% hydroxylammonium nitrate
19.96 wt.-% triethanolammonium nitrate
16.81 wt.-% water
"3"
When expressed in terms of molarity instead of mass percent, LGP-1845 has the following
nominal composition:
9.62 M hydroxylammonium nitrate
1.38 M triethanolammonium nitrate
13.64 M water
LGP-1846 consists typically of
60.79% hydroxylammonium nitrate
19.19% triethanolammonium nitrate
20.02% water
or, in terms of molarity of the solution:
9.09 M hydroxylammonium nitrate
1.30 M triethanolammonium nitrate
15.93 M water
There is currently no existing military specification for these propellants. Until such a
specification is issued, deviations of +/- 0.5% by weight from the nominal compositions have
been considered acceptable for testing and contracting procurement purposes. The maximum
amount of free acid allowed is recommended at 0.1%.
The materials compatibility of these two LGP propellants is essentially identical. The
contract statement of work required the contractor to use aqueous HAN solutions containing
from 57 to 63% by weight HAN. The nominal HAN concentration used in this study was 60.8%
HAN which is equivalent to a 12.2 molar solution and identical to the nominal HAN content in
LGP-1846.
Similar propellants previously developed by the U. S. Navy, such as the NOS-series, also
included hydroxylammoniurn nitrate, but only few previous materials compatibility investigations
are published on those propellants (Reference 2).
Effects of Metal Ion Contamination on Thermal Stability of Liquid Gun Propellants. For
practical applications of liquid gun propellants it is imperative that the propellants be storable
under field condctions (-40 to +160F). Both storage stability and thermal stability of HAN
solutions and liquid gun propellants are adversely affected by the presence of transition metal
ions. Transition metal ions are readily leached from the surface of incompatible materials in
contact with the propellant. RRC has observed this phenomenon on numerous occasions with
hydrazine and hydrazinium salt solutions which act similar to aqueous hydroxylammonium
nitrate solutions.
-4-
Lack of storage stability would slowly degrade the liquid gun propellant to a point where the
impetus no longer meets tiie required performance criteria. A reported laboratory test in which
a 3-month exposure of LOP-18 46 to a piece of copper foil resulted in reduction of HAN concen-
tration from 60.33% to 49.12% is described in Reference 3. Excessive gas evolution
accompanying such obvious incompatibility might burst storage containers overpressurization.
Insoluble corrosion products or evaporation residues formed as the result of decomposition and
corrosive attack might clog injector flow passages or foul spark plugs in the ignition system.
Lack of thermal stability might also result in premature ignition of liquid g ?ropellants in
the injection passage prior to injection into the breech or before the liquid chatgi
4
njection cycle
in a regenerative gun is complete. Such instability could also make the propellants more sus-
ceptible to adiabatic compression initiation.
In an effort to guarantee storage =J thermal stability, two common safety measures are
being taken:
1. The propellant ingredients and all liquid gun propellants are procured to a specification
which limits the amount of tolerable contamination in the starting product. Acceptance
tests will be conducted to verify compliance of loaded liquid gun propellants with the
procurement specification.
2. As a second precaution, all materials coming in contact with liquid gun propellants are
carefuilly screened in a materials compatibility test program to assure that no transition
metal ions (or any other metal ions) are leached from the materials of construction
during storage or operation of the liquid propellant gun.
It is for the second reason that the just completed testing program was proposed and a
contract was awarded. In addition to metals leached from inorganic materials, other species can
be leached from nonmetallic materials that would interfere with proper operation of the gun.
Organic tar or resin residues on the sliding surfaces of the regenerative gun piston might cause
the piston to jam or particulates on the injection valve seat might cause the valve to leak.
However, no analysis for leached organics was conducted under the program described hem.
During the development of liquid gun propellants it became apparent to various authors
that the presence of transition metal ions adversely affected the thermal stability and storability
of the mixtures (References 4 ,5 6 and 7).
initially these tests had been conducted with LGP-1845 and LGP-1846 which consists of
hydroxylammonium nitrate (HAN), triethanolammonium nitrate (TEAN), and water. Copper,
irt i, and nickel ions were found to be the most dele.terious contaminants and it was assumed
that other transition metal ions might have similar effects. In general, and again in agreement
with observations made at Olin Rocket Research with hydrazine propellants, elements with
-5-
incomplete d- shells in their electronic structure are catalytically most active. Zinc or cadmium,
although they are also transition group elements, have completely filled d-shells and are less
active. Conversely, cadmium has a stabilizing effect for hydrazine solutions.
Of the two salt ingredients in LGP-1845 and LOP-1846 propellant, the HAN was found to
be tie propellant component that was predominantly responsible for adverse reactions with
metals. Therefore, additional studies were carried out with HAN solutions at other organi-
zations to isolate the effect and avoid any interference by TEAN (References 8,9 and 10 ).
There do not seem to be any plans to study materials compatibility with TEAN/water system in
an effort to isolate the cause of materials incompatibility with LOP and in order to parallel the
HAN/water studies done here. It is not anticipated that much could be learned from such a
study. More could be learned by studying HAN/water first as was done here. The effect of the
presence of TEAN on the overall corrosion phenomena has not yet been studied in detail.
Reactions of copper and iron ions in HAN solutions were studied in detail and it was shown
that the reaction of Fe3+ is electrocatalytic while the reaction of Cu
2
+ is not (Reference 11).
The reason for the strong catalytic activity of iron is the ease with which it changes its state of
oxidation between the trivalent and the bivalent state. In HAN solutions, Fe
3
+ is reduced by
hydroxylammonium ion to Fe
2
+ and the Fe
2
+ is re-oxidized to the trivalent state by the nitrate
ion. If sufficient iron leaches from an incompatible material of construction that was inad-
vertently built into the storage tank, it is quite possible that the propellant will be expended after
several years of storage. Even after a short time, the performance of the propellant would be
degraded to a point where it would not longer meet the specification. Gas evolved during this
period may rupture the tank. The time to rupture of sealed glass vials has been used as a test
method to measure compatibility of LOPs with materials of construction (Referonce 12).
Copper Cu 2+ ion, on the other hand, although it does not undergo the multiple valence
change as easily as iron, catalyzes the production of nitric oxide NO during propellant decom-
position. In the presence of air, NO converts to N02 which reacts with the propellant and
greatly enhances thermal decomposition, thus rendering the propellant less stable.
2.2 SELECTION OF PROPELLANT SOLUTIONS
2.2.1 Preparation of HAN Solutions
Testing was to be performed in solutions containing from 57 to 63% hydroxylammonium
nitrate with a nominal concentration of 60.8% (12.2 molar). This is similar to the HAN
concentration in LOP-1846, with the TEAN portion replaced by additional water.
-6-
Hydroxylammonium nitrate was commercially available as 24% aqueous solution (4.8
molar) from Southwestern Analytical Chemicals in Austin, TX. The 24% solution is easily
concentrated in a Rotavapor under partial vacuum in a water bath not exceeding 45C
(Reference 13). The 24% HAN solution is shipped as a CorrosiveLiquid N.O.S. - UN1760 per
CFR 49. The more concentrated 60% (12.1 molar) solution is neither cap-sensitive nor is it
positive in the card gap test at zero cards (Reference 14). Experimental quantitieq of 85% HAN
solutions have been shipped under an Oxidizer (N. 0. S.) UN1479 49CFR 173.153(B)(1) desig-
nation (Reference 15).
Filling at least 100 flasks with 40 mL of HAN solution during the current contract required
at least 4 L of the 60% solution. Reserve solution was also prepared for those tests that might
have to be terminated after 1 day or 7 days, requiring a substitute material to be placed in test
with fresh solution.
2.2.1.1 HAN Assay Analysis Methods
If one assumes the HAN solutions are pure, then the easiest way to quickly measure the
approximate HAN concentration is by density or refractive index. Also an accurate determi-
nation of HAN assay can be made by acidimetric titration with KOH or NaOH and visual or
potentiometric end point indication. Initially, HAN assay titrations were performed at U. S.
Army laboratories using KOH solutions in ethanol as the titrant (Reference 16). The assay
analysis of HAN solutions is substantially easier than the analysis of LGP-1845 or LGP-1846
since only two instead of three ingredients are involved. For the analysis of ternary LOP
propellants, other bases have to be used as titrants (Reference 17).
Olin Chemicals, a major proposed future producer of HAN solutions, uses an automatic
titrator to analyze not only for HAN assay, but also for free nitric acid in the finished product
(Reference 18), but unfortunately such an instrument was not available for HAN assay deter-
minations during the current program and titration with visual wid point indication with an acid-
base indicator was used instead. A previous Bff., contractor (References
19
and 20 ) had used
an acidimetric titration with 1-N sodium hydroxide and thymolphthalein indicator. This method
has the disadvantage that it will not recognize HAN solutions that are deficient in free nitirc acid
and have excess free amine.
Therefore, an alternate method for titrimetric HAN assay was recommended by the U. S.
Army BRL Contracting Officer's Representative after start of the contract (Reference 21). This
method adds a known amount of nitric acid to the sample to be analyzed prior to its titration.
The nitric acid is then subtracted when the results are calculated. This method has the
advantage that also small deviations of nitric acid deficiency can be recognized. This method
recommends the addition of a known amount (1 to 4 mL) of 0.25 M to 0.30 M nitric acid to a
solution of 28 grams of LGP or HAN solution in 40 mL distilled water, mixing, and titrating with
0.2 M to 0.3 M NaOH solution.
-7-
2.2.1.2 HAN Analysis for Trace Metals
It is imperative to verify that the batch of HAN solution prepared at the beginning of the
contract is free from contaminant metal ions that could jeopardize the success of the entire test
series. Therefore, the procured 24% solution as well as the concentrated 60% solution has been
analyzed for trace contamination of heavy metals. The main objective of the analysis was to
analyze for iron, copper, nickel, and chromium to verify the absence of these metals in
concentrations greater than 5 ppm. The analysis methods are described in more detail in Par.
2.7.
In the absence of a military specification (MIL SPEC) for the procurement of HAN or
LGP-1846, RRC used the following product specification in the procurement of 24% HAN
solutions, as do other contractors:
Hydroxylammoniumn nitrate content 24% minimum, 25% maximum
Sum of all heavy metals (Fe, Cu, Cr, Ni etc.) 5 ppm maximum
pH 2.5 to 3.0
Total other contaminants (e.g. ammonium nitrate) 1.0% maximum
Free nitric acid 0.1% maximum
color colorless, clear
The supplier was asked to supply a batch analysis with the shipment of the chemical. The
supplier stated that their product has typically the following properties:
Hydroxylammonium nitrate content 24.I %
pH 3 to4
Free nitric acid (stabilizer) less than 0.01 molar
Aluminum less than 0.2 ppm
Sulfate less than 10 ppm
Barium less than 0.1 ppm
Chloride less than 10 ppm
Iron less than 0.2 ppm
Sum of calcium and magnesium less than 10 ppm
Ash less than 10 ppm
Color colorless, clear
Our results of HAN analysis are given in Paragraph 3.1.1.
-8-
2.3 SELECTION OF MATERIALS TO BE TESTED
The selection of materials to be tested was not the responsibility of the contractor under the
current contract. The 48 different materials tested were Government Furnished Equipment
(GFE) samples. The 48 materials included metals, coatings, ceramics, plastics, and lubricants.
The statistical distribution of the types of materials tested is illustrated in Figure 2.1.
DISTRIBUTION BY TYPE OF MATERIAL
MATERIALS TESTED UNDER CONTRACT DAAD05-89-C-0052
LUBRICANTS (16.7%)-
METALS (33.3%)
PLASTICS (20.8%)
CERAMICS (8.3%) COATINGS (20.8%)
Figure 2.1: Distribution by Type of Materials
The main system components expected to be in long-term contact with the propellant are
the tank, the propellant lines, tho shutoff valve, the shuttling piston in a regenerative liquid
propellant gun, and the injector nozzles, In addition, propellant management devices (bladders,
diaphragms, pistons) separate the pressurant gas and the propellant. At the beginning of the
contract, emphasis was on materials that would be in contact with mixed propellants. During a
later contract period, other materials were added that may be used in chemical plants where
HAN is manufactured end mixed with TEAN.
-9-
As was indicated in the proposal (Reference 22), it was anticipated that sufficient material
for at least three test coupons of each material would be provided by the contracting agency:
one for the 298 K (25"C) test, one for the 338 K (65*C) test, and one to keep as a control coupon
for before-and-after side-by-side photography should the appearance change as the result of the
exposure. Unfortunately, insufficient material was available such that before-and-after side-by-
side photographs could not be taken on those samples where corrosive attack was visible.
GFE materials were received in three different shipments over the course of four months
and were used "as received" (except for cutting them to uniform size). No additional cleaning
was done with any of the samples.
It is important to maintain traceability as to the origin of the material for the sake of
reproducibility. For instance, it may be desirable to conduct future testing on similar or even
identical materials (e.g., using HANJIEAN/H20 blends instead of HAN solutions) and make
comparisons. The results might differ slightly if materials from different vendors or batch
numbers were used. It is suggested to procure a supply of identical material now for future tests,
and making the vendor names and batch numbers part of the test record. Many vendors make
process changes, but maintain the same brand name or trademark on that product. Most ven-
dors are quite generous in supplying free no-cost evaluation samples, but such samples are rarely
documented by manufacturing date and batch number.
2.4 EXPERIMENTAL METHODS
2.4.1. Description of Test Apparatus
A schematic of the test apparatus and the constant temperature bath is shown in Figure 2.2.
The apparatus consisted of a 50-mL borosilicate glass ampule to which was attached a mercury-
filled U-gauge for measuring the pressure of the evolved gases. Gas evolution was taken as a
sign of materials incompatibility and the rate of gas evolution was a measure of the degree of
incompatibility. It was of interest to determine the nature of the evolved gases to make
deductions about the probable cause of decomposition and possible effects of products on the
materials exposed to the vapor phase alone.
- 10-
HAN COMPATIBILITY TEST APPARATUS
RUBBER
SEPTUM
~~ REMOVABLE
CONSTANT
FISLI
TEMPERATURE
INSULATION
BATH (NOT
TO SCALE) -
M
.60%-
HAN
SOLUTION
~ MERCURY
MANOMETER
MATERIAL-
SPECIMEN
-- CATCH
IPAN
Figure 2.2: HAN Compatibility Test Apparatus, Schematic
-II1-
Borosilicate glass (Pyrex) was chosen for the compatibility flasks. In this regard, hundreds
of compatibility tests at RRC have been carried out using Pyrex flasks and the rate of gas
evolution in the control flasks is always very low. The control flasks will be from the same batch
of ampules as those used for the materials compatibility tests.
The ampules came from the supplier in a cleaned condition. The ampules were similar to
ampules used for medicinal injection fluids. The ampules were taken from the sealed box,
inspected visually for cleanliness, and used without additional cleaning, just prior to inserting the
materials sample. The connection to the U-gauge was then made with a fused glass seal using
standard glass blowing techniques. The U-tube gauges were pre-assembled and cleaned with
laboratory detergent (e.g., Alconox), rinsed with distilled water, and dried prior to attaching
them to the ampules.
In most cases, the ampules were attached to the U-gauge with the sample already in place
inside the ampule. In a few cases, the apparatus could be assembled first and the skinny sample
could be slid +!,rough the narrow neck of the assembled apparatus. Also, all oil and grease
samples could be injected after the apparatus was already completely assembled. Extreme care
had to bu taken to prevent scorching the sample while the glass blowing was in progress. This
was a comparatively simple operation since RRC's standard compatibility apparatus has to be
sealed with a glass blowing torch while the sample and the propellant is already in place. Having
high-energy propellant in immediate vicinity of a glass blowing torch and red hot molten glass
requires additional safety precautions which were not necessary in this program.
Following the glass blowing, the assembled apparatus was evacuated and tested for leaks
with a Tzsla coil in a darkened room. Any pinholes in the fused glass joints could thus be
identified before the apparatus was filled with propellant. The evacuation also served to remove
any condensation in the flask caused by the preceding glass blowing operation. The two
openings (the rubber septum port and the open end of the manometer) were covered with
temporary rubber septums and the ampules were then stored in ambient air or in the glove box
under argon until they were ready to be filled with HAN solutions. The remaining steps were
carried out in an argon-filled glove box to eliminate ambient air (see Par. 2.4.2 Selection of Test
Atmosphere).
The design of the ampule/manometer combination used at RRC was modified from that
used by a previous BRL contractor such that the septum port was now coaxial with the ampule
and the syringe needle would now reach clear to the bottom of the ampule without having to
snake around bends in the apparatus. This design is superior because it avoids accidental
smearing of liquid on the walls in the vapor space of the apparatus.
-12-
The liquid was injected into the assembled apparatus (already containing the materials
specimens) through a capillary syringe needle from a graduated syringe. This allowed accurate
dispensing of exactly 40 mL of the HAN solution. Figure 2.3 shows the process of loading the
ampules in a glove box.
The capillary needle was inserted through the septum port (prior to attaching a rubber sep-
tum) and reached all the way to the bottom of the ampule for dispensing the liquid. Care was
taken not to smear any uquid on the wall when retracting the syringe needle. All this was done
in a glove box under argon. The time at which the liquid was admitted to the sample was the
starting time of the 30-day experiment at 298 K (25'C) since ambient temperature was not much
different from the constant temperature bath. For the 338 K (65'C) tests, the samples would
spend a few days at ambient before the constant temperature bath was heated to 338 K (650C)
and the 30-day count was started.
Mercury was introduced into the U-gauge manometer to fill both legs of the manometer to
half their length. This gave a maximum readable pressure range once the gas evolution stated.
The mercury used was vacuum degassed and filtered through a pinhole prior to use. This was
necessary not only to eliminate contaminants, but also to obtain a clean meniscus that is needed
for accurately measuring the pressure to t0.1 mm with a cathetometer,
Finally, a new rubber septum was placed on the septum port to seal it gas tight. After this
final stop, the loaded and tightly sealed ampules were removed from the glove box and inserted
into the constant temperature bath. Figure 2.4 shows a completely assembled compatibility test
ampule ready to be inserted into the constant temperature bath. Those ampules inserted into a
338 K (65'C) bath experienced some initial pressure rise from the thermal expansion of the gas
in the vapor space ("ullage") alone. This slight overpressure was not vented due to the difficulty
in re-connecting the septum tightly, the risk of suffering pressure loss during the 30-day test, and
inadvertent introduction of air while the pressure of the 65'C warm sample Is vented to ambient
pressure. The initial travel of the mercury due to ullage warm-up thus reduced the travel
remaining for the test before gas would bubble though the low portion of the U-manometer at
the end of the test.
- 13-
RUA,
4g
i~Ii
Flpre ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~~~* 2.:Laigo
9
mueswt A ouinudetnIetAmshr
,2u i..14 -
(
I::
. I
-
Ii
?L'
*

*
A b.
*
*
-I
* '.
FIgure 2.4: Compatibility Test Ampule Loaded with Sample and HAN Solution
15 -
The amount of gas evolved during the 30-day observation period was calculated from the
ullage volume of the flask, the pressure read from the manometer, and the temperature and was
reduced to standard conditions (Standard Temperature and Pressure - STP). The total volume
of several of the flasks was determined by filling with water and weighing. The flasks were all
constructed as identical as possible and flask-to-flask variations of total volume were held at a
minimum. All manometers were filled to approximately the same mercury level at the beginning
of the test. The ullage volume ,vas calculated from the total internal volume minus the volume
of liquid loaded into the ampule (40 cm
3
). The sample itself did not occupy much volume and
was ignored.
The length of the U-gauge was 34 cm from top to bottom of the U. The full scale range was
300 mm Hg corresponding to a gas evolution of approximately 16 cm
3
STP at 338 K. A widened
section like a small funnel at the top of the open end of the U-gauge allowed gases to escape in
the event of unintended overpressurization without spilling the mercury on the bench top or the
floor. A catch pan was placed under the U-gauges to catch mercury spillage in the unlikely event
of overpressure or glass breakage.
The vapor pressure of the HAN solution is lower than that of water and is similar to but
somewhat higher than that of LOP-1846, i.e. approx. 12 mm Hg at 298 K (25"C) and 89 mm Hg
at 338 K (65"C). It is part of the total pressure measured. The partial pressure of the vapor (the
pressure reading at the beginning of the 30-day test period) was subtracted from the pressure
read on the manometers prior to the calculation of the amount of gas formed. Minor
fluctuations of the constant temperature bath temperature would cause vapor pressure
fluctuations on the manometer. The bath temperature was kept constant to within +_ 0.1 'C in
order to prevent pressure fluctuations.
Since the flasks and U-gauge manometers were open ended, the readings fluctuated with
the ambient barometric pressure. The ambient barometric pressure was read each day when the
samples were reati and entered in the test log for future data reduction. This mode of testing
with open-ended U-gauges has the disadvantage that it is sensitive to ambient pressure
fluctuations, whereas other materials compatibility test methods are independent of ambient
pressure fluctuations if the U-gauge is hermotically sealed under vacuum and not exposed to
atmospheric pressure fluctuations (Reference 23). Admittedly, the open-ended U-gauge ampules
are easier to build and to fill and are perfectly adequate for tests where high rates of gas
evolution must be expected. Their use is perfectly acceptable for initial compatibility testing
where high accuracy is not required, but for those samples that show slow rates of gas evolution,
it should be followed by long-term tests using hermetically sealed ampules like the one shown in
Figure 2.5. The RRC-type apparatus is preferred for long-term compatibility testing with
samples that have low rates of gas evolution.
-16-
task
Figure 2.5: Hermetically Sealed Compatibility Test Apparatus (RRC Model)
- 17-
2.4.2 Selection of Test Atmosphere
It is known that oxygen from ambient air can react with some of the materials in an acidic /
strongly ionic solution and it may adversely affect the test results. When attempting to determine
the solubility of oxygen in HAN solutions, it behaved anomalous since it apparently slowly reacts
with the hydroxylammonium ion to produce nitrous oxide (Reference 24).
It is also known that nitric oxide, should it form through the decomposition of hydroxyl-
ammonium nitrate, would become oxidized by oxygen to form nitrogen dioxide which would
react with HAN, thus escaping analysis in the gas phase. Also, some oxygen may form during the
decomposition of HAN solutions and if the ampules were not carefully freed from air to start
with, one could not discern between oxygen formed from HAN reactions or oxygen present as a
contaminant.
For these reasons, the tests were conducted under an atmosphere of argon. The glove box
was purged with argon for several hours prior to loading and the absence of oxygen was verified
by GC analysis of a grab sample taken from the glove box atmosphere. A large weather balloon
was inflated inside the glove box to displace the previous atmosphere and to minimize the
volume that needed to be purged. The ampules, the material specimens, the degassed
hydroxylammonium nitrate solution, and the mercury were all placed into a glove box and
purged with argon. The ampules were purged with argon, loaded with hydroxylammonium
nitrate solution, and sealed with a rubber septum inside the glove box to prevent exposure to
atmospheric oxygen. If the ampule initially contains only argon, it will then be possible to
analyze for formed nitrogen, oxygen, or nitric oxidein the gas space above the sainple at the end
of the test.
However, argon and oxygen are difficult to separate on the molecular sieve column unless
the gas chromatograph oven is cooled to below room temperature. It was thought to be advanta-
geous to conduct the tests under a helium atmosphere instead of an argon atmosphere. For the
very first series of 25 samples, helium instead of argon was used initially in the glove box to fill
the ampules under an inert gas atmosphere. However, the rubber septums had an excessively
high permeability to helium and the tests had to be abandoned and re-started after replacing the
helium with argon (see Paragraph 3.2.2.1). Helium is not recommended for tests where rubber
septums are used as seals. It was noted during tests at other organizations where seals for pres-
sure gauges in HAN propellants were evaluated for compatibility and permeability that helium
had the highest permeability of all gases under consideration (Reference 25).
2.4.3 Selection of Total Immersion versus Partial Immersion
In order to maximize the possibility of detecting adverse reactions between the material and
the liquid gun propellants, the entire samples were immersed in the liquid. This is in analogy to
compatibility testing done by other organizations on LGP-1846.
- 18-
There have been rare incidents where corrosion in the vapor phase above the liquid level
was more severe than in the liquid itself. This can be caused by interaction of the liquid with the
atmosphere above the liquid, resulting in a more corrosive environment than either liquid or
vapor by itself. The current test method would not detect such types of corrosion.
It was noted that many of the materials coupons submitted for testing had a small hole
drilled into one end, as if the samples were intended to be suspended from a wire such that only
the lower portion was immersed in the liquid propellant. However, since no detailed instructions
were given with the samples, the coupons were totally immersed in the propellant same as the
other materials that did not have pre-drilled holes in them.
2.4.4 Selection of Sample Size
Most of the materiai specimens supplied by the contracting agency were small enough to fit
through the 8-mm inner diameter neck of the ampules without further cutting. It appeared that
many of the GFE samples provided by the contracting agency were cut by another government
contractor to dimensions of 1 inch length by 1/4 inch thickness. These coupons were easily
loaded into the ampules. Other materials submitted by the contracting agency for testing were
oversize and had to be cut to size. Yet other materials, laminated multi-layer composites,
coating materials, or glass ceramic coatings on a steel flange, could not be cut to size and had to
be returned untested.
It was desirable to use as large a sample as possible in order to obtain measurable rates of
gas evolution during the 30-day observational period. Therefore, provided that the material
supplied was of sufficient width, the coupons were cut 65 mm length and 8 mm width, which is
short enough to be completely immersed in the 40 mL of liquid, but long enough to provide a
sufficient surface area (e.g. 11.9 cm
2
with a 1-mm - 0.04 inch thick flat coupon) to generate
mieasurable gas evolution and metals leaching for those materials of marginal compatibility.
Samples that were cut to size at RRC from larger stock were weighed and measured, cleaned
with 2-propanol, dried, and bagged and sealed in polyethylene bags until ready to be used.
2.4.5 Selection of Sample Shape
The REP did not prescribe the sample shape and previous reports on BRL- sponsored
compatibility testing with LGP-1846 were not specific with regard to the sample shape (or even
the sufface area) of the specimens used. It was noted that many of the materials coupons
submitted for testing had a small hole drilled into one end, as if the samples were intended to be
suspended from a wire such that only the lower portion was immersed in the liquid propellant.
However, since no other instructions were given, the samples were used as-received and totally
immersed in the propellant.
- 19-
Also, some materials coupons were coated with a coating, but the coating did not extend
over the entire area of the coupon or the small hole, leaving some underlying metal exposed.
The current method of testing unfortunately exposed the entire coupon, the coated and the
uncoated area of the coupon. Future tests should use coupons were the entire surface area is
uniformly coated.
It would be simplest to work with rectangular shaped flat coupons that are easy to machine
or, in the case of elastomers, could even be cut to size with a scissors. However, in testing liquid
rocket propellant material compatibility, it has become common practice to use dogbone-shaped
tensile specimens per ASTM E8 which can be used for determination of tensile strength and
yield at break. There exists an ASTM specification for static immersion testing of unstressed
materials with dinitrogen tetroxide N204 (Reference 26). This method should be adapted with
some modifications for future materials compatibility testing with HAN solutions where not only
materials chemical interactions, but also mechanical
1
properties are studied. Another related test
method for elastomers is ASTM D-471 (Reference 27) which has been used by the United States
Army Belvoir Research, Development & Engineering Center for testing the compatibility of
elastomers with LGP-1846 (References
2 8
and 29). This method can be combined with measure-
ment of gas evolution and components leaching in future tests.
2.4.6 Selection of Test Duration
The test duration was 30 days , as prescribed by the solicitation RFP Scope of Work Par.
3.3.1. This duration is short in comparison to immersion tests commonly conducted with similar
liquid rocket propellants. The accuracy of prediction from the short-term exposure test
described here with liquid gun propellants is poor in comparison to the accuracy derived from
the materials compatibility data base accumulated as the result of lengthy (2 to 20 years) testing
with liquid rocket propellants. The tests now completed with HAN solutions and similar tests
with complete mixtures of LGP-1846 can therefore be considered only as preliminary screening
tests. It is recommended that they be followed up with longer tests using only those materials
that are identified as compatible as the result of the current screening tests.
The test duration should be long enough that initially transient phenomena (induction peri-
ods, passivation) have stabilized by the time the test is completed. Conversely, it should be short
enough that no valuable test time is wasted on incompatible materials which would most likely
have to be eliminated in the next round of testing anyway.
A large number of ampules had to be opened and analyzed within a short time at the end of
the 30-day test. Analysis of the first batch of 25 ampules should be completed before the next
batch has to be pulled. Therefore, the test starts were staggered by several weeks. This allowed
sufficient time to complete the analysis of the first group before the second group of 25 ampules
had to be opened.
- 20-
2.4.7 Selectloa of Test Temperatures
The two test temperatures were selected in accordance with the requirements spelled out in
Par. 3.3.4 of the RFP. For the first groups of 2 times 25 ampules, the temperature of the
constant temperature baths was allowed to be anywhere between 24 and 26"C, as long as it was
kept constant to within t_0.1"C. Because some of the testing extended through the summer
months, and the ambient temperature in the laboratory rose above 24'C, a water cooling coil was
inserted into the water bath.
For the second group of 2 times 25 ampules, the temperature of the constant temperature
baths was allowed to be anywhere between 64 and 66'C, as long as it was kept constant to within
+.O.1'C. RRC selected 65'C as the nominal test temperature.
There have been efforts by other investigators to test materials compatibility and thermal
stability of liquid gun propellants at temperatures above 65'C using a slightly different
experimental technique (Reference 30). It would have been of interest to compare their results
with the results from the program described here.
2.4.8 Constant Temperature Bath
A typical 298 K (25'C) constant temperature bath setup is shown in Figure 2.6. The use of
water as the bath fluid was perfectly acceptable for 25'C tests. For the 338 K (65'C) tests, water
evaporation was retarded by covering the surface of the liquid with styrofoam chips. The water
level in the 65"C bath was adjusted every few days. Forced convection circulation was achieved
by stirring motors with propellers on a single shaft. Temperature gradients in the baths were
thus kept at a minimum. Condensation in U-gauge tuoes was prevented by keeping the U-
gauges warm by wrapping a removable insulation blanket around the bath (although they were
not at exactly the same temperature ,s the sample ampule).
-21-
Pik*
l~J
At least 25 ampules were placed together in one bath (per RFP requirement Par. 3.3.4).
Each group of 25 ampules included one control without a material specimen in it. Previous
investigators have also placed the ampules in the constant temperature bath such that only the
sample ampule was at constant temperature and the U-gauge portion with the mercury was
outside the bath, subject to ambient conditions as it was in the current test series. This method is
acceptable since the vapor pressure of the solution is very low and condensation of the water in
the upstream leg of the U-gauge is minimal. For the high-temperature tests at 338 K (65"C), the
temperature of the U-gauges was very close to that of the baths due to conduction and radiation.
An insulation blanket was wrapped around the entire bath while no readings are being taken.
The baths were placed on a rotary table ("lazy Susan") which allowed all four sides of the
bath to be viewed so that the U-gauges could be read without having to move the cathetometer.
2.4.9 Measurement of Rate of Gas Evolution
The experiment consisted of measuring the gas pressure as a function of time. In accor-
dance with Par. 3.3.3 of the RFP, the pressures were read at least once per day (excluding
weekends or holidays), and more often if warranted by the extent of reaction. Care was taken to
ensure that pressures were recorded near the end of the workday on Fridays and on days pre-
ceding legal holidays. Also, pressures were read at the beginning of the workday on Mondays
and on days after legal holidays.
Pressures were read using a cathetometer with a nonius vernier scale. When the stirrer
motor was turned off to eliminate vibrations of the mercury column while the readings were
taken, pressure could be read to _O.l mm Hg with this instrument. The cathetometer was
calibrated against a length standard (block gauge) traceable to the National Institute of
Standards and Technology. The standoff distance between the cathetometer and the mercury
manometers was typically 30 cm. This was close enough to avoid parallax errors. The catheto-
meter was aligned to true vertical with the aid of a spirit level.
2.4.10 Gas Evolution Data Reduction
The volume of the ampule and the attached glass tubing was measured at the beginning of
the test series by filling on apparatus with water and weighing. The internal volume of the dry
apparatus without mercurM vas 78.29 mL. Subtracting 40.00 mL for the volume of the HAN
solution and neglecting the volume occupied by the test specimen, leaves an ullage volume of
38.29 mL. Earlier investigators had once proposed the following formula for calculating the
amount of gas evolved in the course of the test and reducing it to standard temperature and
pressure (STP):
- 23 -
V = [Vo (Ti/P 1) (P2/T 2)]A -[V (Ti/P 1) (Po/T 2)]
where:
V = volume of gas produced, STP
V
o
- initial "gas volume" (measured)
Ti = standard reference temperature, 273 K
P
1
- standard reference pressure, 101 kPa - 760 mm Hg
P2 - current pressure (barometric pressure + manometer reading)
T2 - current bath temperature, K
P
o
i initial pressure (barometric pressure + manometer reading)
This equation is in error since it does not sufficiently account for the fixed volume ("ullage")
of the glass apparatus and its increase due to movement of the mercury. Instead, the following
equation was used:
V=(T o/P o) IV2 (PT 2) - V 1(Pl /T1) ]
where:
V - volume of gas produced, STP
To - standard reference temperature, 273 K
P
0
- standard reference pressure, 101 kPa = 760 mm. Hg
P2 - current pressure (barometric pressure + manometer reading)
T2 - current bath temperature, K
V2 - ullage, corrected for travel of mercury
P I initiel pressure (barometric pressure + manometer reading)
Ti = initial temperature on day zero
V I = initial ullage on day zero
2.4.11 Rate of Gas Evolution as Termination Criteria
Unscheduled Termination. Safety considerations dictated that the following gas evolution
rates serve as termination criteria as defined in Pars. 3.3.6.2 and 3.3.6.3 of the RFP:
1. Any solution that generated more than 3 cm
3
(STP) of gas in one day was declared
reactive and testing was terminated.
2. Any solution that generated more than 7 cm
3
(STP) of gas in 10 days at 25C was
declared reactive and testing on it was terminated at that time.
Fortunately, none of the sample solutions "fumed off' as the result of progressive contamination
and self-acceleration of the decomposition reaction.
-24-
The materials furnished by the U. S. Government Contracthig Agency were assured to be
"intrinsically safe", that is, they were assured not be self reactive or hypergolically reactive with
the HAN solution. Therefore, test tube screening or materials compatibility screening on the
Differential Scanning Calorimeter (DSC) or Accelerating Rate Calorimeter (ARC) was not re-
quired. As a standard safety precaution, screening of new candidate materials should be con-
ducted before enclosing them in a closed container together with any nitrate-containing mono-
propellants. The same precautions must be taken for HAN-based liquid gun propellants. It
appears that for some of the lubricants and greases tested during the current program, DSC or
ARC data were not yet available.
2S CHEMICAL ANALYSIS OF EVOLVED GASES
Other investigators have discovered the evolution of nitrogen and nitrous oxide as the result of
incompatibility of HAN/TIEAN solutions with metals (References 16, 19 and 20). Traces of
oxygen were expected because the HAN solution would initially typically contain some dissolved
air, although it was attempted to minimize the dissolved air by keeping the freshly concentrated
60% HAN solution in tightly closed bottles under a blanket of argon.
The evolved gases were analyzed in a gas chromatograph using argon as the carrier gas. Using
argon instead of helium as the carrier gas made it possible to detect small oxygen peaks that
otherwise would have been difficult to separate from the argon peak if helium was used as the
carrier gas. As specified in Par. 3.3.5 of the RFP, only species comprising more than 5% by
volume of the final volume (including the approximately 10 mL ullage argon that was initially in
the apparatus) needed to be determined.
Some materials that are now shown to be incompatible resulted in such high rates of gas evolu-
tion that the full scale range of the manometer was exceeded in a few days. This was particularly
true for several tests conducted at 338 K (65"C). Gas samples were drawn through the rubber
septum into a gas-tight syringe and immediately injected into a gas chromatograph. Some
contamination due to air intrusion into the needle while moving it the short distance from the
test ampule septum to the GC port was inevitable using this method, in spite of the fact that the
syringe and the needle was purged with sample gas several times prior to injection into the GC
port. There was sufficient gas in the ullage to perform duplicate analyses on most samples.
Hydrogen, nitrogen and oxygen were analyzed on a 1.80 m x 6.2 mm (6 foot by 1/4 inch)
molecular sieve (Linde 5A) column and nitrous oxide and carbon dioxide were analyzed on a
1.50 m x 6.2 mm (5 foot by 1/4 inch) Porapak Q column. Several gas chromatographs with both
thermoconductivity and flame ionization detectors (FID) were available to support this program.
Since the off-gasses did not contain organic compounds, it was not necessary to use the FID. The
FID does not result in substantial improvement of sensitivity for nitrogen compounds.
- 25 -
The peaks were identified at the beginning of the program by measuring the retention times of
synthetic mixtures spiked with known amounts of hydrogen, helium, oxygen, nitrogen, carbon
dioxide, and nitrous oxide. When using argon as a carrier gas, the response for helium and
hydrogen is much higher than for the other gases.
Nitrogen dioxide was not found by either GC or visual observation. Evolution of nitrous oxide
fumes is typical for reaction of HAN solutions with materials containing copper. The red-brown
color of this evolved gas would have been sufficient early warning that a reaction is taking place.
In accordance with instructions in Par. 3.3.6.1 of the RFP, such specimens would have been
immediately terminated and no further testing would have been required.
2.6 POST-TEST EXAMINATION OF SAMPLES AT END OF COMPATIBILITY TEST
2.6.1 Weight Change Measurements
Upon early termination or at the end of the test period, a final pressure reading was taken and a
gas sample was drawn for gas analysis (see Par. 3.2.4). After completion of the gas analysis,
which would typically take less than a day, the rubber septum was removed and the mercury was
removed from the U-gauge with vacuum suction tube. The ampule was opened at the neck, the
HAN solution poured out into a marked sample bottle, the material specimen taken out, rinsed
with distilled water, and examined for visual appearance while still wet. The samples were then
dried and weighed. The weighed samples were placed in polyethylene plastic bags, heat-sealed
and packaged for shipment to the contracting agency for further examination.
2.7 ANALYSIS OF OFF-LOADED PROPELLANT
The following analyses were applied only to those material specimens that contained metals. No
metal ion leaching was analyzed for polymer and grease samples that do not contain inorganic
fillers. Some greases and anti-seize compounds contain molybdenum disulfide. In those
instances, one would want to analyze for molybdenum in the off-loaded propellant.
It was one of dte possible objectives of the future study to derive kinetic equations that will allow
prediction of the rate of metals leaching at different environmental temperatures. In order to
derive such equations, the rate of metal solubilizing has to be measured at at least two different
temperatures. After the rates are obtained, the logarithm of the rate can be plotted in an
ARRHENIUS graph versus the reciprocal absolute temperature. Extrapolations can be made to
other temperatures assuming that the mechanism is the same over a wide range of temperatures.
-26-
It would be desirable to measure the metal concentratiovi continuously throughout the 30-day
duration of the experiment just like the rate of gas evolution is measured by taking daily data
points. Instead, the metal concentration wa. analyzed only at tho cginaing and at the end of the
30- day immersion experiment. The only other alternative would be to use a very large
experimental setup of the order of 200 mL liquid where the withdrawal of a 10-mL sample does
not appreciably change the surface area: liquid volume ratio.
Candidate methods for the analysis of leached metals include atomic absorption spectroscopy
(AAS), emission spectroscopy with conventional arc emission excitation sources, and inductively
coupled plasma (ICP) emission spectroscopy. Each of these methods has its advantages and
limited shortcomings and to a certain extent the various methods complement each other.
For ICP as well as AAS analysis, the off-loaded HAN solutions have to be diluted to reduce their
viscosity to that of the standards in order to avoid errors caused by different nebulizer efficiency.
In either method, the necessity to dilute the sample causes a loss of threshold detectability of the
metals to be analyzed by more than one order of magnitude. Dilution may also be advisable for
safety reasons to prevent accumulation of very concentrated HAN in the nebulizer.
In results reported by other investigators, metal contaminations in off-loaded LOP-1846 and 13-
M HAN solutions after 1 to 13-week exposure to metals ranged from 0.6 to 43,000 ppm. In this
range of metal concentrations, AAS is perfectly adequate and ICP is not needed, The improved
sensitivity of ICP Is only needed in the analysis of leached metals that have a very low rate of
corrosion. ICP was used mainly for analysis of the received 24% HAN solution to certify that It
did not contain an excessive amount of dissolved metals to start with.
A Perkin Elmer Model 1100B AAS spectrometer with a large number of lamps for different
groups of elements was used on this program. Table 2.1 gives a summary of the lamps on hand,
the elements that can be analyzed with these lamps, and the detection limit for each element in
the as-analyzed solutions in comparison to detection limits with an ICP instrument.
-27 -
Table 2.1: Comparison of AAS and ICP Detection Limits
Detection Limit, ppm
Element AAS I CP *
Al 1 0.01
B 13 0.01
Ca 0.15 0.01
Co 0.12 0.003
Cr 0.08 0.006
Cu 0.08 0.002
Fe 0.1 0.01
K 0.5 1.0
Li 0.05 0.02
Mg 0.01 0.01
Mn 0.5 0.002
Mo 0.7 0.01
Na 0.1 0.02
Ni 0.15 0.01
Pb 0.2 0.02
Si 2 0.04
V 2 0.002
Zn 0.02 0.002
* Thermo Jarrel Ash ICAP 61 Spectrometer at AmTest, Redmond
Igor metals analysis by AAS, a sample of the off-loaded propellant was diluted 1:1 with
distilled water in a volumetric flask, filled to volume with distilled water and analyzed. If the
aaalyte concentration was so high that it was out of the range of the instrument, an aliquot was
diluted once again to bring the concentration down into the range of the instrument.
For achieving an optimum detection sensitivity, it was attempted to dilute the off-loaded
HAN solutions as little as necessary. However, viscosity effects initially prevented reproducible
results when using HAN concentrations above 30%.
In an effort to quantify viscosity effects on AA nebulizer performance, the time required to
mipirate solutions containing different concentrations of HAN into the AA nebulizer were
measured. The results are shown in Figure 2.7.
-28 -
EFFECT OF VISCOSITY ON ATOMIC ABSORPTION ANALYSIS
ARF DATA. 10 OCT 1989
0.15
0.14 -
0.13
0.12
0.11
C3
0.08
0.007
0.08
0.05- I I I
0 20 40 80
HAN CONCENTRATION IN WATER. WT.-%
Figure 2.7: Flow Rate of HAN Solutions into AAS Nebulizer
As can be seen in this illustration, the analyte flow rate (and consequently the AA
absorption signal) varies over a factor of 0.5 from HAN concentrations between 60 and 0 %.
Thus, if standard solutions for calibrating the AAS were made up in water and undiluted 60%
11AN was aspirated, the results could be off by a factor of two. In order to avoid the viscosity
effects, the standards were made up in 24% HAN solution, and the off-loaded post-test solutions
were also diluted to close to 24% HAN. In this way, viscosity effects were eliminated.
- 29 -
IMMMNToNALLY LEFT DLANK.
30
Chapter 3
EXPERIMENTAL RESULTS
3.1 PRE-TEST ANALYSIS RESULTS
3.1.1 HAN Assay Analysis Results
3.1.1.1 As-Received 24% HAN Solution
A sample of the as-received 24% HAN solution was analyzed by both ICP and AAS to
verify its compliance with the procurement specification. Table 3.1 shows the results of the ICP
and AAS analysis in comparison to the spec requirements. Sample A was the as-received
solution. Sample B was the same solution, but spiked with 200 ppb iron and submitted for
analysis at the same time, but without providing knowledge of the iron addition to the analyst.
This served as a double check on the accuracy of the iron analysis. Iron was the most likely
contaminant and one of the contaminant that would be most deleterious to the type of testing
that was planned with the 24% HAN solution.
As can be seen in Table 3.1, the ICP and AAS analysis at RRC agreed with the batch
analysis provided by the supplier, Southwest Analytical Chemicals. The material was meeting
the specification and was therefore accepted for the subsequent concentration step. The highest
concentration of any cation was sodium with 1.27 ppm. There is currently no specification limit
for sodium except that the total metals cannot exceed 5 ppm.
3.1.1.2 Concentrated 60.8% HAN Solution
The 24% HAN solution was concentrated in a rotavapor in several batches to just slightly
above 60.8% HAN. Several batches analyzed initially at 64.9% HAN. The batches were com-
bined in a large bottle, mixed, titrated for assay, and adjusted with distilled water to arrive at the
desired nominal HAN concentration.
-31-
Table 3.1: HAN Acceptance Test Results
Property SWAG Spec. SWAG Batch
Analysis AmTnt AmTlet AmTeat RRO RRC
%bywt %bywt loP lop Detectlon byAAS Deteocton
or ppm or ppm ppm ppm Umht, ppm Umli
Sample A Sample B"ppni Sample A ppm
Assay, %HAN 24+1 . 1% 24.50%
Ntirlo Add, molar 0.01 0.006
Ash,ppm -1O <10
Sulfate, ppm <10 <10
Ohloride, ppm 4
Ag, ppm v L 0.01
Al, ppm 40.2 <0.1 0.039 - 0.01
As, ppm 0,055 L 0.03
B, ppm 0,151 0.235 0.01
Be, ppm .<0.1 0.1 0,011 0,011 0.003
Be, Ppm L L 0.007
Ct, ppm 0,332 0,462 0.01 L 0.15
Oa+Mg, ppm .10 0
Od, ppm L L 0.002
Co. ppm L L 0,003
Or, ppm 0,008 0,009 0.006 L 0.08
Ou, ppm 0,004 L 0.002 L 0.08
Fe, ppm q0.2 0.03 0,053 0.1M' 0,01 L 0.1
H9, ppm L L 0.01
K. ppm L L I
U, ppm L L 0.02
Mg, ppm 0,067 0,099 0.01 L 0.01
Mn, ppm L L 0.002
Mo, ppm L L 0.01
Na, ppm 1,24 1.27 0.02
NI, ppm L L 0.01 L 0.1
P. ppm L L 0.05
Pb, ppm L L 0.02
8, ppm 1.5 1.5 0.1
Sb, ppm L L 0.02
So, ppm L L 0.03
SI, ppm 0,376 0.489 0,04
Sn, ppm L L 0.02
Sr. ppm 0,004 0,004 0.003
T1, ppm L L 0.01
TI, ppm L L 0.03
Y. ppm L L 0.002
V. ppm L L 0,001
Zn, ppm 0,054 0,049 0,002
L - at or below detecton limit
Samnple B spilked with 200 ppb iron
-32-
The concentrated solution was again analyzed for iron which is the contaminant of primary
concern. The results are shown in Table 3.2 in comparison to the iron concentration in the
original 24% solution. As expected, the iron concentration in the solution increased as the result
of concentrating the solution. However, the ratio of iron increase is the same as that of the
volume decrease. This proves that no additional iron was inadvertently introduced during the
concentrating step. The same was true for magnesium and calcium.
Table 3.2: Analysis of Concentrated RAN Solutions
Contaminant RRC Results (AAS) Ratio Sundstrand Results
Metal Original Concentrated after: (Reference 18)
ppm 24% HAN 60.8% HAN
before 24% HAN 60% HAN
Concentr.
Fe 0.08 0.2 2.8 <0.5 <0.5
Mg 0.07 0.2 3.0
Ca 0.14 0.47 3.4
Ni 0.14 0.4 1.4
- 33 -
3.2 POST.TEST RESULTS
3.2.1 Weight Change Measurements
Table 3.3 gives a summary of the weight changes observed as the result of immersion in
60.8% hydroxylammonium nitrate. This table is subdivided in two portions, one on the 298 K
(25'C) tests, tho other on the 338 K (65'C) tests.
The samples in Table 3.3 are arranged by sample number. Sample numbers above 70 were
already pre-assigned to the specimens by other BRL contractors when they arrived at RRC. It
appears the same sample numbers were used by other BRL contractors and It was considered
best to keep these numbers instead of assigning new numbers. The numbers are not in an
uninterrupted sequence. Missing numbers therefore do not represent missing samples. It may
be more convenient to arrange the samples in alphabetical order by material name or group
them by the type of material. This was done in a database which will be provided to the
contracting agency in computer-readable form. A partial printout of the database showing the
materials samples arranged by material name and grouped by type of material is shown in
Appendix A.
Sample numbers 1 through 21 were assigned by RRC to a group of mostly nonmetallic
materials that was submitted for testing after the program had already started. These materials
were in irregular shapes and had to be cut at RRC to fit into the apparatus.
Sample No. 31 IA, MG 120 Silver Solder, partially dissolved and formed sludge on the
bottom of the ampule. 9.6% by weight of the metal was lost. A sample of the same material that
was in test at 65'C (Samplo No. 31 1B) was covered with white and yellowish sludge and actually
gained some weight due to adhering crusts of deposits. Sample No. 5A, a carbon (graphite)
bearing, had gained 2% weight, but the appearance was unchangeL
For grease samples, only the initial weight or volume was recorded. It was not possible to
quantitatively remove the grease from the ampule after the test and separate it from the HAN
solution. For oil samples, only the approximate initial volume was recorded. The surface area
used for the calculations was the internal diameter of the ampule, the interface between the two
immiscible layers.
After completion of the test, the samples were removed from the solution, rinsed with
distilled water, and dried at room temperature. The plastic samples were not dried to constant
weight. If they contained absorbed moisture, it would show in the weight gain values in Table 3.3.
-34-
T D'Ie 3.3: Weight Change of Test Specimens at 298 K and 338 K (25 and 65C)
Speci- Initial Final % Wt
men No. TRADE NAME Wt., g Wt, g Change
Fmpm firt batch at 298K (25"C0
73 CRES-301 0.1260 0.1261 +0.0'19
74 CBES-304 0.2401 0.2402 +0.042
75 17-7PH (Mill annnealed) 0.1260 0.1260 +0.000
112 Haynes Alloy 255 5.5528 5.5528 +0.000
113 Ferralium Alloy 255 4.6885 4.6883 -0.004
120 Tristelle Alloy T5-2 3.7854 3.7855 +0.003
134 Stellite #8 on 17-4PH 4.0220 4.0165 -0.137
135 Stellite #6 Nicraly on 17-4 4.1025 4.0965 -0.146
145 Silicon carbide PS-9242 1.6675 1.6674 -0.006
162A UCAR LW-15 on 17-4 4.8963 4.8963 +0.000
163A UCAR LC-111 on 17-4 4.0817 4.0818 +0.002
165A Molydag on 17-4 PH 3.3400 3.3388 -0.036
166A Nitrided Tribocor 532N 14.0432 14.0432 +0.000
179A Ag Plate on 17-4 PH 3.8449 3.8445 -0.010
220A Sermatech GC-WC-111 17-4 PH 4.5658 4.5669 +0.024
258A Tantalum coating 3.4882 3.4882 +0.000
263A CRES-316 3.5930 3.5928 -0.006
2C6A Tungsten weld rod 2.3667 2.3658 -0.038
268A CRES-302 3.7613 3.7613 +0.000
269A CRES-308 4.1095 4.1094 -0.002
306A 15-5 PH 3.2069 3.2065 -0.012
310A Nickel flash on 17-4 PH 3.7000 3A6975 -0.068
326A Al-6061 1.3490 1.3278 -1.572
351A Steel MP35N 4.0919 4.0918 -0.002
-35-
Table 3.3 (Continued) Weight Change of Test Specimens at 298 K and 338 K (25 and 65C)
Pmm second batch at 298 K (25'C
2A Tefzel lining 5.3221 5.3221 +0.000
3A Kynar lining 7.0136 7.0094 -0.060
5A Carbon bearing 2.4353 2.4857 +2.070
6A Ceramic thrust washer 0.9537 0.9537 +0.000
7A Superproline 2.2142 2.2140 -0.009
17A Zirconium Zr-702 5.8194 5.8194 +0.000
18A Zirconium Zr-705 4.6943 4.6943 +0.000
19A Silicon carbide 8.0010 8.0005 -0.006
116A Graphitar Grade 47 1.0025 1.0028 4.0.030
126A Grease 3451 2.0376
129A Victrex 4800G 0.6932 0.6933 +0.014
130A Victrex Gr. 4101GL20 0.7874 0.7876 +0.025
146A Arlon 1160 0.7379 0.7379 +0.000
147A Arlon 1260 0.8178 0.8178 +0.000
156A Paxon BA 50-100 0.4790 0.4790 +0.000
158A Aeroshell 17 1.50
161A Rulon II 0.7983 0.7990 +0.088
259A Polyvinylchloride tubing 1.3076 1.3076 +0.000
311A MG 120 Silver solder 0.7536 0.6811 -9.620
335A Brayco 783E Micronic 2.1 mL
396A Aeroshell 14, 1.50
402A 10W-30 Motor oil 2.1 mL
412A SAE 50W Motor Oil 2.8 mL
446A Galden D20 2.8 mL
-36-
Table 3.3 (Continued) Weight Change of Test Specimens at 298 K and 338 K (25 and 65C)
From firt batch at 338 K (65"CL
2B Tefzel lining 5.8561 5.8557 -0.007
3B Kynar lining 6.8989 6.8895 -0.136
5B Carbon bearing 2,*!'67 2.9371 +0.014
6B Ceramic thrust washer 0.6465 0.6465 +0.000
7B Superproline 2.0844 2.0842 -0.010
17B Zirconium Zr-702 5.8742 5.8741 -0.002
18B Zirconium Zr-705 4.7359 4.7359 +0.000
19B Silicon carbide 8.5881 8.5878 -0.003
162B UCAR LW-15 on 17-4 4.5640 4.5619 -0.046
163B UCAR LC-1H on 17-4 3.6345 3.6342 -0.008
165B Molydag on 17-4 PH 3.6912 3.6889 -0.062
166B Nitrided Tribocor 532N 13.9628 13.9626 -0.001
179B Ag Plate on 17-4 PH 3.6719 3.6714 -0.014
220B Sermatech GC-WC-111 on 17-4 4.7933 4.7925 -0.017
258B Tantalum coating 3.8550 3.8547 -0.008
263B CRES-316 3.5865 3.5863 -0.006
266B Tungsten weld rod 2.4004 2.3991 -0.054
268B CRES-302 3.9264 3.9260 -0.010
269B CRES-308 4.0880 4.0828 -0.127
306B 15-5 PH 3.1550 3.1545 -0.016
310B Nickel flash on 17-4 PH 3.1184 3.1158 -0.083
311B MG 120 Silver solder 0.6432 0.7494 +16.5
326B Al-6061 1.3051 1.2777 -2.099
351B Steel MP35N 3.9613 3.9603 -0.025
- 37 -
Table 3.3 (Continued) Weight Change of Test Specimens at 298 K and 338 K (25 and 65'C)
Frm second batch at 338 K (651C
73B CRES-301 0.1261 0.1260 -0.079
74B CRES-304 0.2402 0.2401 -0.042
75B 17-7 PH (Mill annealed) 0.1260 0.1259 -0.079
112B Haynes Alloy 255 5.5527 5.5527 +0.000
113B Ferralium Alloy 255 4.6883 4.6882 -0.002
116B Graphitar Grade 47 1.0028 1.0037 +0.090
120B Tristelle Alloy T5-2 3.7856 3.7855 -0.003
126B Grease 3451 2.5800
129B Victrex 4800G 0.6933 0.6923 -0.144
130B Victrex Gr. 4101GL20 0,7876 0.7868 -0.102
134B Stellite #8 on 17-4PH 4.0164 4.0152 -0.030
135B Stellite#6 Nicraly on 17-4 4.1025 4.0929 -0.234
145B Silicon carbide PS-9242 1.6674 1.6673 -0.006
146B Arlon 1160 0.7372 0.7376 +0.054
147B Arlon 1260 0.8172 0.8179 +0.086
156B Paxon BA 50-100 0.4788 0.4788 +0.000
158B Aeroshell 17 3.1531
161B Rulon II 0.7990 0.7990 +0.000
259B Polyvinylchloride tubing 1.2852 1.2428 -3.299
335B Brayco 783E Micronic 2.1 mL
396B Aeroshell 14 2.7203
402B Kendall 1OW-30 Motor Oil 2.1 mL
412B Valvolk.e SAE 50W Motor Oil 2.8 mL
446B Gladen D20 2.8 mL
Note:
Samples No. 73B thru 145B have boen used for a previous test at
25
0
C and had to be re-used after Intevmediate examination
(as directed by BRL).
-38-
3.2.2 Pressure Rise / Gas Evolution Measurements
The gas evolution curves of more than 100 tests are shown in Figure 3.1 through 3.15. There
are two different formats for presentation of gas evolution curves:
1. Gas volume reduced to STP conditions (273 K, 101 kPa). The ordinate scale unit of
these graphs is cm.
2. Gas volume reduced to STP conditions (273 K, 101 kPa) and divided by the surface area
of the specimen C'normalized by the surface area"). The ordinate scale unit of these
graphs is cm
3
/cm 2.
The rationale for using the "normalized" volume of evolved gas (units of cm
3
/cm 2) rather
than the volume itself (units of cm
3
) should be explained here. In the course of thousands of
similar compatibility tests it has been found most useful to divide the amount of gas evolved by
the wetted surface area of the specimen, in the assumption that the decomposition of the mono-
propellant is mostly surface catalyzed (heterogeneous catalysis) or that the amount of metal ions
leached and causing homogeneous decomposition in the fuel is also proportional to the amount
of surface area exposed. Quite often, looking at a graph containing data obtained with
specimens of different shapes such as those used during the contract, the observer forgets the
fact that the specimens were not of equal shape and may draw wrong conclusions about the
compatibility of a material of construction with the liquid propellant. It was therefore
recommended that the normalized gas volume be plotted in the graphs. The ultimate raw gas
volumes (Unit cm
3
) are listed in a separate table format in case they are needed for additional
data reduction and pressure rise predictions at BRL.
For the control (blank) ampule, which does not have a surface area, a fictitious surface area
of 10 cm
2
was assumed which is typical for many of the specimen coupons. The number is also
easy for converting from one unit to the other. Use of a surface area of 1.0 cm
2
for this purpose
would be even more convenient, but would result in excessive distortion and shift of the blank
curves in the graphs.
3.2.2.1 Gas Evolution at 298 K (25*C)
The gas evolution measurements at 298 K (25"C) were very uneventful and the graphs
Figure 3.1 through 3.5 are therefore presented in one format only, the format where the direct
volume is presented without division by the surface area.
- 39-
5.
4-
2-
0
0-
o 1 2 4 6 7 8 91213141516192021 2223262i2930
TIME, DAYS iLoT, i
.-HAN/Argon Blank ,.0.CRES-,301 CRES-304
S---17-7PH (Mill annnealed) Haynes Alloy 255
S4-
Z 3.
0
0. 1 . .
0 1 24 6 78 9121314 1516 192021222326282930
TIME, DAYS o 2AI
--- HAN/Argon Blank --- Ferrallum Alloy 255 m Tristelle Alloy T5-2
-a- Stellite #8 on 17-4PH -'- Stellite #8 on Nicraly on 1 -&- Silicon carbide PS-9242
Figre 3.1: Compatibility of Materials in 60.8% HAN at 298 K (25T)
-40-
z 3
0
0
S4 4
2-
-1~
0 1 2 4 6 78 91213141516192021222326282930
TIME, DAYS
-- *- HAN/Argon Blank -- ,-- UCAR LW-18 onC7-4 -x1-UCAR-LC-1H ont17-4ing
-S- Molydag on 17-4 PH TuNitreded Trboor 32N A- Ag Plate on 17-4 ...PH
-14-
2-
6 1 ,2 4 6 7 8 9 12 13 14115.'1'61920 2122 23 282829 30
TIME, DAYS LPLOT147A _ -
SHAN/Argon Blank -+-Sermatech Gc-wc-1 11 on -X-- Tantalum coating
---CRES-318 Tungsten weld rod -Ar CRES-302
Figure 3.2: Compatibility of Materials in 60.8% HAN at 298 K (25C)*-
-41 -
10-
E
8
z 6.
4-
2-
~0-
0228 9 124131'4 s11516192021222326282930
TIME, DAYS HE AE
-- HAN/Argon Blank ~~sCRES-308
1* 1-.5 PH
Nickel flash on 17-4 PH -4- AI-BO1
-- Steel MP35N
iii _ _i__i__i_ TiMi DAY ii _ _... ____'. . ;m
F ue .:Co" llt f aeiasin6.% A t 9 (:C
-42
2-
0 10 152,033
TIM~E, DAYS 2POTtA]
SHAN/Arg'on Blank .. -- Tefhel lining -. "Kynar Ening "
---Carbon bearing --. Cerarmic thrust washer
Figure 3.3: Compa0l;U~ity of Materilas in 60.8% HAN at 298 K (254C)
m
- 42 -
5-
2f3-
0.
5 --
0.
0 30 i o '
TIME, DAYS IPO2A
-an- HAN/Argon Blank "'4-" Greas 351 ** Virctrium 4 -00
-G- Zitrcoiu Zr-74012 - SilAon 1160d -A- GAphona 1260 4
43-
Z 5.
0
TIME, DAYS [ ....
-i-HAN/Argon Blank --4-- Paxon BA 50-100 --w- Aeroshell 17
-- Rulon 11 --W- Polyvlnylizhlorlde tubing -A- MG 120 Sl~ver solder
5-
C~4,
3-
0
2-1
0 5 10. 1520253
TIME, DAYS FHosA
--a- HAN/Argon Blank -'*Brayco 783E Micronlo -** Aeroshell 14
-a 1 OW-30 Motor Oil --W- SAE 5OW Motor Oil -Ar- Galden 020
Figure 3.5: Compatibility of Materials in 60.8% HAN at 298 K (25*C)
-44-
Figures 3.1 through 3.5 present the gas evolution at 25C. As can be seen, most samples did
not produce much gas. The only samples found to be incompatible at 25"C were Al-6061,
Aeroshell 17 and Silver Solder M0120. The graphs are arranged such that each graph carries a
gas evolution trace for the control (blank) that was run along in the same group of 25 ampules.
The blank trace is always the first trace listed and the graph symbol for the blank is always the
solid square (--i---). On the same graph are then four to five samples, such that no more
than six curves are shown on the same graph. If more than six curves were shown on the same
graph, the graph would get too "busy" and it would be difficult to trace individual curves because
many of them may fall on top of each other. In spite of tracing no more than six curves in a
single graph, in some of the graphs the curves do still fall on top of each other simply because
them was not much activity and the curves of the materials specimens are not much different
from those of the blank. This "problem" (actually, a non-problem) is only observed in the 25"C
series. For the 65'C series, the curves diverge sufficiently such that they do not fall on top of
each other. The 65"C curves are therefore better suited to illustrate the method of data
reduction because the curves are more differentiated from each other.
The vertical scale expansion of the graphs was chosen such that it can accommodate the
maximum gas evolution of the most incompatible samples, yet show enough detail of the
compatible samples. Although the apparatus can handle gas evolution up to near 20 cm
3
, the
maximum ordinate scale was chosen at 5 cm
3
for 250C tests and 10 cm
3
for 650C tests, which is
a good compromise. Likewise, the optimum ordinate scale extension for the normalized gas
evolution was 1.0 or 2.0 c" /cm
2
for the 65 C series of tests.
Although the ampules with 300 mm H travel of the U-tube manometers were capable of
recording the formation of a total of 20 cmgas (at standard temperature and pressure - STP),
none of the gas volume evolution tables or charts shows this large an amount of gas formed. The
samples tested were either grossly incompatible and the full scale range of the manometer was
exceeded within less than three days at 338K (65"C) (Samples Al-6061 and Silver
Solder MG 120), or the gas evolution within 30 days stayed below 5 cm
3
STP. Therefore the gas
volume graphs use 5 or 10 cm
3
as an expanded scale in order to provide a good scale expansion
at which differences in gas evolution become discernible. If the full scale of 20 cm
3
had been
used as the ordinate scale on all graphs, the pressure (volume) traces would all fall on top of
each other.
The sample gas volume curves are identifiod by graph symbols in the legend at the bottom
of each graph. The sample names are sometimes truncated because in the case of long sample
names not all letters would fit into the legend box. There are sufficient letters shown to allow
the unique identification of each sample. The sequence of samples is the same as that used in
most other tables in this report (by Government supplied sample number, not shown on graphs).
-45 -
The 25"C tests served essentially as a screening test for the subsequent 65'C tests to assure
that none of the samples would react violently and endanger the adjacent samples when it
cooked off.
Most of the first batch of 25 samples at 298 K (25C) showed a slow pressure decrease
during 30 days as the result of continuing loss of dissolved helium that could not be replaced by
purging with argon. Table 3.4 shows a method how this unwanted drift of the baseline can be
eliminated by adding the same amount of gas as was lost from the control to all other specimens
(assuming they all contained the same amount of helium contamination at the beginning of the
test). After this correction, all gas evolution numbers are positive, although most samples except
Al-6061 had only a very slow rate of gas evolution at 298 K.
The second batch of samples at 25'C included mostly nonmetallic samples and lubricants.
There were only two samples that showed higher than normal gas evolution rates, Sample 158
(Aeroshell 17 Grease), and Sample 31 IA, MO 120 Silver Solder, There was moderate gas
evolution with a sample of SAE 1OW-30 Motor Oil. The tests with the other samples in the
second batch at 25C were uneventful.
Table 3.5 gives a summary of the same data, in which the samples were arranged and sorted
by the rate of gas evolution. The worst cases with the highest rates of gas evolution are shown
first. None of the samples tested at 298 K reacted vigorously enough that would have precluded
their testing at 338 K.
3.2.2.2 Comments on Data Reduction
The raw data were not processed through a Statistical Analysis System computer program
which would tend to smooth the curves. The up-and-down fluctuations in ampule pressure
visible in Figures 3.1 through 3.5 are mostly caused by barometric pressure fluctuations.
Although the barometer is read daily and corrections for barometric pressure are entered into
the data reduction routine on a spread sheet, there appears to be some hysteresis where the
indicated ampule pressure does not Immediately adjust to changes in ambient pressure.
Extensive Pacific Ocean weather fronts moving through the area and the accompanying change
in barometric pressure were immediately reflected in the shape of the pressure curves. Toward
the end of the testing, when mercury tended to stick to the glass walls, the operator used a clean
glass rod to agitate the mercury column to form a nice round meniscus which could be accurately
read with the cathetometer independently of the direction in which the mercury had last
traveled. This Improved the smoothness of the pressure traces. The stirring of the mercury for
achieving a clean meniscus was particularly necessary where some black mercury sulfide had
formed from interaction with the d6ecomposition gases (Samples 412B and 402B. See Par. 3.2.5).
-46-
It is recommended to conduct future long-termn compatibility testing in hermctically closed
all-glass flasks where pressure measurements can be taken tuaffected by ambient barometric
pressure fluctuations.
Table 3.4: Gas Evolution at 298 K (25C)
FINAL CORRECTED RATE
Speci- TRADE VOLUME FOR He LEAK OF GAS
men NAME EVQLUT
No. cm
3
cm3 cm /da
From first batch at 25 oC
73 CRES-301 -0.24 0.06 0.002
74 CRES-304 -0.04 0.26 0.009
75 17-7PH (Mill annnealed) 3.16 0.14 0.005
112 Haynes Alloy 255 -0.28 0.02 0.001
113 Ferralium Alloy 255 -0.06 0.24 0.008
120 Tristelle Alloy T5-2 -0.24 0.06 0.002
134 Stellite #8 on 17-4PH -0.16 0.14 0.005
135 Stellite #6 on Nicraly on 17-4 -0.04 0.26 0.009
.1-45 Silicon carbido PS-9242 -0.19 0.10 0.003
162A UCAR LW-15 on 17-4 -0.10 0.20 0.007
163A UCAR LC-1H on 17-4 -0.09 0.21 0.007
165A Molydag on 3.7-4 PH -0.17 0.12 0.004
166A Nitrided Tribocor 532N -0.37 -0.08 -0.003
179A Ag Plate on 17-4 PH -0.16 0.13 0.004
220A Sermatech GC-WC-111 on 17-4 PH -0.18 0.11 0.004
258A Tantalum coating -0.34 -0.04 -0.001
263A CRES-316 -0.04 0.25 0.008
266A Tungsten weld rod 0.01 0.31 0.010
268A CRES-302 -0.21 0.09 0.003
269A CRES-308 -0.38 -0.08 -0.003
306A 15-5 PH -0.36 -0.06 -0.002
310A Nickel flash on 17-4 PH -0.22 0.08 0.003
326A Al-6061 8.94 9.24 0.308
351A Steel MP35N -0.19 0.10 0.003
B1 Empty ampule 0.05 0.35 0.012
0 Blank 1 -0.30 0.00 0.000
-47,
TABLE 3.4 (continued) Gas Evolution at 298K (25*C)
FINAL
Spec. TRADE NAME VOLUME RATE
No. cm
3
cm
3
/day
From second batch at 25 oC
2A Tefzel lining -0.3 -0.009
3A Kynar lining -0.4 -0.013
5A Carbon bearing -0.2 -0.007
6A Ceramic thrust washer 0.0 0.001
7A Superproline -0.4 -0.015
17A Zirconium Zr-702 -0.3 -0.010
18A Zirconium Zr-705 -0.1 -0.003
19A Silicon carbide -0.3 -0.009
116 Graphitar Grade 47 -0.1 -0.003
126A Grease 3451 -0.1 -0.004
129A Victrex 4800G -0.5 -0.016
130A Victrex Gr. 4101GL20 -0.4 -0.013
146A Arlon 1160 -0.4 -0.012
147A Arlon 1260 -0.3 -0.009
156A Paxon. BA 50-100 -0.3 -0.011
158A Aeroshell 17 2.3 0.076
161A Rulon II -0.3 -0.010
259A Polyvinylchloride tubing -0.3 -0.010
311A MG 120 Silver solder 2.7 0.091
335A Brayco 783E Micronic -0.4 -0.012
396A Aeroshell 14 -0.3 -0.009
402A 10W-30 Motor Oil 0.3 0.011
412A SAE 50W Motor Oil 0.1 0.004
446A Galden D20 0.1 0.002
HB2 HAN\Argon Blank -0.2 -0.005
Air Air Blank -0.2 -0.008
Ar2 Argon Blank 0.1 0.002
-48-
Table 3.5: Gas Evolution Rate at 298 K (25C); In Order of Decreasing Gas Evolution
Note: 20 Worst Materials Listed Only
Gas Gas
Spec. TRADE NAME Volume, Evolution
No. Ra e
Sample cm
3
cm /day
Designation
326A Al-6061 9.2 0.308
311A MG 120 Silver solder 2.7 0.091
158A Aeroshell 17 2.3 0.076
402A 1OW-30 Motor Oil 0.3 0.011
266A Tungsten weld rod 0.3 0.010
74 CRES-304 0.3 0.009
135 Stellite #6 on Nicraly on 17-4 0.3 0.009
263A CRES-316 0.2 0.008
113 Ferralium Alloy 255 0.2 0.008
163A UCA. LC-1H on 17-4 0.2 0.007
162A UCAP. LW-15 on 17-4 0.2 0.007
134 Stellite #8 on 17-4PH 0.1 0.005
75 17-7PH (Mill annnealed) 0.1 0.005
179A Ag Plate on 17-4 PH 0.1 0.004
165A Molydag on 17-4 PH 0.1 0.004
220A Sermatech GC-WC-111 on 17-4 PH 0.1 0.004
412A SAE 50W Motor Oil 0.1 0.004
351A Steel MP35N 0.1 0.003
145 Silicon carbide PS-9242 0.1 0.003
268A CRES-302 0.1 0.003
310A Nickel flash on 1.7-4 PH 0.1 0.003
3.2.23 Gas Evolution at 338 K (65C)
The testing at 65"C resulted in some more interesting gas evolution charts. For this reason,
the charts are presented here in both formats, as plain gas evolution (Gas volume reduced to
STP conditions (273 K, 101 kPa). The ordinate scale unit of these graphs is cm
3
.) as well as
normalized gas evolution (Gas volume reduced to SW conditions (273 K, 101 kPa) and divided
by the surface area of the specimen. The ordinate scale unit of these graphs is cm
3
/cm 2.).
The graphs are arranged such that the simple gas evolution curve graph ("PLOTA") Is on
the top of the page and the normalized gas evolution graph ("PLOTB") is at the bottom of the
page. If the user wants to compare gas evolution of one given material to the gas evolution in
the control (blank) under the conditions of the experiment, one would look at the volume curves
at the top of the pages (PLOTA). It one war s to compare different materials with different
shapes and surface areas, the curves at the bottom of the page should be used (PLOTB). As
can be seen in Figures 3.6 through 3.15, there was substantially more gns evolution in the 338 K
(65C) tests than in the 298 K (25*C) tests. This was to be expected.
-49 -
10-
6-
0 510 15s 20 25 3
TIME, DAYS [!=
-U- HAN\Agon Blank -+-Ceramic thrust washer - Carbon bearing
-a- Kynar lining -X- Tsfzei lining
2-
1.4-
01
-50
10-
2-
18-
Z17-
0
0 5 10 15 20 25 30
TIME, DAYS B
-- HAN~rgon Blank - + - UCAR LW-15 on 17-4 -N*- Silicon carbide
-- Zirconium Zr-705 -N- Zirconium Zr-702 -Ar- Superproline
-5-
10
9-
00
TIME, DAYS
-a- HAN~Argon Blank + - Sermatech GC-WC-1 11 on -0*- Ag Plate on 17-4 PH
-s-Nltrddo Tribocor 532N -- Molydlag on 17-4 PH -As- UCAR LC-1 H on 17-4
1.4-
z 1.2-
0
0.2-
10~
Z7-
04-
0
0 510 i'5 20 25 3
TIME,
DAYS
PT3A
1.48
1.2-
0 .4
TIME, DAYS
Figure 3.9: Covnpatibility of Materials in 60.8% HAN at 338 K (65"C)
53
10
1
9
ob
4
3
2
10
20
r'ME, DAYS
30
Ma
k
Steel MP35
PLO735A
120 Silver *older
-*- AAJI 08,
2
Nicksl fl4sh or, 17-4 PH -A, 15.5 pH
1.4
1.2
0.8
0.6
0.4
0.2
5
10
.......
0
2s
, 11"k,1111IIArgon i k TIMs, C)Ayq 30
MG 120,911ver sjo %S881 MP35N PLO7,1368
ld*r Nicksl Ai.eoel
"Sure 3-10: CO-p-dbjUy of
flash on 17.4 PH 15.5 PH
60'8%
RM
at 338
K (65-C)
34
10
#8
7
TIE
DY
55
10
2f
7
0 6
I5
t4
00
0i~.31:Cmaiio
aeiji
60.8
U
Jat38is
6c
TIEDA6-0253
~14-
2-
.16
TIME, DAYS
-U- HAN/Argon
Blank H54 - +- Viotrex Gr. 4101GL20
- Stellite #8 on 17-4PH
-a- Stellite #6 on NMorely on 1 --- Silicon carbide PS-9242 -A- Arlon 1100
1,06-
0.4-
Figure 3.13: Compatibilty of Materials in 60.8% HAN at 338 K (63Tl)
-57--
10'
2- -
TIME, DAYS___ ____
-a- HAN/Argon Blank H64 - +-Arlon 1260-4- Paxon BA 50-100
-8- Aeroahell 17 --- Rulon 11 -A- PVC Tubing
F2-e31:Cmaiilt fMtrasI 0.%HNa 3 6C
1.4-
10-
'3-
2-
0 5 10 15 20 25 30
TIME, DAYSL4
-UR. HWAN/on Blank HB4 - +- Brayco 763E Mlcorono -W- AsroshoU 14
-9- Kondal IOW-30 Motor 01 -N- Vuivmoin. BAOW Motor ON-r-Gladon D20
0
TIME, DAYS
-~HAN/Argon Blank HB4 -~- Brayco 783E Micronic )K- Aeroahell 14
-- KendallI1OW-30 Motor Oil -44- alvoline SAE B0W Motor -zkV Gladen D20
Figure 3.15: Compatibility of Materia n 60.8% HAN at 338 K (65-C)
-59-
There were three samples that exceeded the capability of the mercury U-gauge within three
days, aluminum 6061 and silver solder MG120 (Figure 3.10) and Aeroshell 17 (Figure 3.14). In
addition, one case of accelerating rate of gas evolution was observed with Arlon 1160 (solid
triangle symbols in Figure 3.13).
The ultimate amount of gas evolved is tabulated in Tables 3.6 and 3.7. Table 3.6 gives the
gas volumes in the same sequence as the samples are listed in all other tables and on the graphs.
Table 3.7 presents the data of the 21 worst materials sorted in order of decreasing gas evolution,
highlighting the most incompatible samples first that should be avoided for further construction
of liquid propellant guns.
Table 3.6: Gas Evolution at 338 K (65'C)
SMAX. RA E
Spec. No. TRADE NAME VOL. DAYS cm /DAY
2B Tefzel lining
1.9 30 0.06
3B Kynar lining
2.5 30 0.08
5B Carbon bearing 4.4 30 0.15
6B Ceramic thrust washer 2.0 30 0.07
7B Superproline
2.1 30 0.07
17B Zirconium Zr-702
2.3 30 0.08
18B Zirconium Zr-705 1.8 30 0.06
19B Silicon carbide
2.9 30 0.10
162B UCAR LW-15 on 17-4 9.7 30 0.32
163B UCAR LC-1H on 17-4 7.6 30 0.25
165B Molydag on 17-4 PH 6.8 30 0.23
166B Nitrided Tribocor 532N 1.8 30 0.06
179B Ag Plate on 17-4 PH 3.5 30 0.12
220B Sermatech GC-WC-111 on 17-4 PH 10.3 30, 0.34
258B Tantalum coating 2.9 30 0.10
263B CRES-316
2.6 30 0.09
266B Tungsten weld rod 4.3 30 0.14
268B CMES-302
3.0 30 0.10
269B CRES-308
2.4 30 0.08
306B 15-5 PH
3.2 30 0.11
310B Nickel flash on 17-4 PH 6.1 30 0.20
311B MG 120 Silver solder 7.5 1 7.50
326B A1-6061
9.9 0.5 19.80
351B Steel MP35N
3.4 30 0.11
HB3 HAN\Argon Blank 2.2 30 0.07
-60-
Tanle 3.6 (continued)
VOLUMvE DAYS RA3E,
Spec. No. TRADE NAME cm3, STP cm /day
73B CRES-301 2.4 30 0.08
74B CRES-304 2.1 30 0.07
75B 17-7 PH (Mill annealedl 2.5 30 0.08
112B Haynes 255 Alloy 2.8 30 0.09
113B Ferralium 255 Alloy 2.3 30 0.08
116B Graphitar Grade 47 2.3 30 0.08
120B Tristelle P.loy T5-2 2.2 30 0.07
126B Grease 3451 2.4 30 0.08
129B Victrex 4800G 2.6 30 0.09
130B Victrex Gr. 4101GL20 2.6 30 0.09
134B Stellite #8 on 17-4PH 3.7 30 0.12
135B Stellite #6 on Nicraly on 17-4 4.3 30 0.14
145B Silicon carbide PS-9242 2.6 30 0.09
146B Arlon 1160 15.6 28 0.56
147B Arlon 1260 3.2 30 0.11
156B Paxon BA 50-100 2.1 30 0.07
158B Aeroshell 17 4.2 4 1.05
I.CIB Rulon II 2.4 30 0.08
259B PVC Tubing 3.9 30 0.13
335B Brayco 783n Micronic 4.0 30 0.13
396B Aeroshel] 14 7.9 30 0.26
1)2B Kenaall IOW-30 Motor Oil -0.2 30 -0.01
412B ValvoV..... SAE 50W Motor Oil -0.2 30 -0.01
446B Glade.. D20 1.9 30 r)
11.14 HAN\Argon Blank 2.2 30
61
Table 3.7: Gas Evolution at 65"C; In Order of Decreasing Gas Evolution Rate
Note: Only 27 worst samples listed here. The worst samples are on
top of the table.
VOLUME DAYS RATE,
Specimen No. TRADE NAME cm3, STP cm3/day
326B Al-6061 9.9 0.5 19.80
311B MG 120 Silver solder 7.5 1 7.50
158B Aeroshell 17 4.2 4 1.05
146B Arlon 1160 15.6 28 0.56
220B Sermatech GC-WC-111 on 17-4 PH 10.3 30 0.34
162B UCAR LW-15 on 17-4 9.7 30 0.32
396B Aeroshell 14 7.9 30 0.26
163B UCAR LC-1H on 17-4 7.6 30 0.25
165B Molydag on 17-4 PH 6.8 30 0.23
310B Nickel flash on 17-4 PH 6.1 30 0.20
5B Carbon bearing 4.4 30 0.15
135B Stellite #6 on Nicraly on 17-4 4.3 30 0.14
266B Tungsten weld rod 4.3 30 0.14
335B Brayco 783E Micronic 4.0 30 0.13
259B PVC Tubing 3.9 30 0.13
134B Stellite #8 on 17-4PH 3.7 30 0.12
179B Ag Plate on 17-4 PH 3.5 30 0.12
351B Steel MP35N 3.4 30 0.11
147B Arlon 1260 3.2 30 0.11
306B 15-5 PH 3.2 30 0.11
268B CRES-302 3.0 30 0.10
258B Tantalum coating 2.9 30 0.10
19B Silicon carbide 2.9 30 0.10
112B Haynes 255 Alloy 2.8 30 0.09
129B Victrex 4800G 2.6 30 0.09
145B Silicon carbide PS-9242 2.6 30 0.09
263B CRES-316 2.6 30 0.09
130B Victrex Gr. 4101GL20 2.6 30 0.09
It is of interest to compare the gas evolution rates of the control blanks in the current series
of tests to gas evolution rate data reported by other investigators (Reference 17). As can be seen
from the data in Table 3.8, the rate of gas evolution at 338 K (65'C) was somewhat higher in the
current test, while the gas evolution rate at 298K (25"C) was too small to be measured in either
study. This can be due to differences in experimental technique or in the purity of the raw
material used for the tests. Also, passivation of the surface of the glass ampules by immersing
them in HAN solution prior to the test should be considered. Although borosilicate glass in
fairly resistant to acid attack, some materials may leach from the glass that will catalyze HAN
decomposition. If the same ampules were used for a second time, the gas evolution rate might
be lower.
62
Table 3.8: Gas Evolution Rates of HAN Blanks
Source of Temperature, Days Gas Volume, Avn. Rate,
Data C cm
3
STP cm /day
This study 25 30 <0.1 <0.004
This study 25 30 <0.1 <0.004
This study 65 30 2.2 0.07
This study 65 30 2.2 0.07
Reference 19 25 30 <0.30 <0.010
Reference 19 25 30 <0.30 <0.010
Reference 19 65 30 0.63 0.021
Reference 19 65 30 0.60 0.020
3.2.3 HAN Trace Metals Post-Test Results
Table 3.9 gives the AAS analysis results of HAN solutions off-loaded at the end of the test.
As can be seen, substantial metal leaching has occurred with several of the coupons exposed.
Not all off-loaded propellant samples were analyzed. With one exception, only HAN solutions
removed from metals compatibility tests had to analyzed for metals. The materials selected were
those where either gas evolution or discoloration of the solution had occurred. The one
exception referred to above is that of a lubricant, Aeroshell 17 (Sample No. 158B) which caused
high rates of gas evolution usually not expected from a pure hydrocarbon grease. AAS analysis
showed that substantial amounts of molybdenum were leached from Aeroshell 17. It would be of
interest to obtain the gross composition of this lubricant from the manufacturer to identify the
incompatible additive, possibly molybdenum sulfide.
63
u4H 4H )
60 0
va 000 10 o 0 0
0 * 4* * *- *4N
V) Ln cn i
040,. N HC N0 N
v v m vco 0 0 CVf C;) M(V) 0V C;0
v 0)
00 Ln co 0 coG 0O DC) c 0 0
v V l0 0 00 ccC ON 0 000 0
V VV V vvv V
LM 0
0c0o co0 nma 0 00 000m00n 0
N 0- MU 0W1)I - 0 4.) ; C C C
I!!m
0 0 0 0 0vcoccoo CD V)0 00U 0rM CO 0
V H V-4 V S%
r* m
m 0 m * m
0 00 OV 00 00 00 000 in0
mV N V m1414e
N CV4) I":H H
*~~1 . .-. i.
aH') H 0l %0IW 0000000 n 0
w
0n
U)1 COO CO U)V *41 N 41)
HO C V) r- HW HNLr)nlV H w N
WH HH 00000000
AH oow C
4-1 H pq CD N .) 10
NH 41 1 H 1 0) 0
oU) m 0) Aco 4A M r D M VU 4i 0A
H 3 H H U- H Mi '~ 440 NNNmmm D - -
r12 d4J4H . ~H O0.64
Analysis was done after diluting the HAN solution with water 1:1, at which point the
solutions were still very viscous and aspirated into the AA more slowly than the standards made
up in clear water. The standards were made up in 24% HAN solution with the same viscosity to
compensate for viscosity effects on sample aspiration flow rate into the AAS. A few post-test
samples of off-loaded HAN solutions were analyzed for HAN-assay, but, within the accuracy of
the manual titration method, the HAN-content was unchanged from the initial HAN
concentration.
3.2.4 Gas Analysis by Gas Chromatography
Analysis of the gas space was performed with a gas chromatograph with a
thermoconductivity detector using argon instead of helium as a carrier gas. Two different
columns are being used: a 5-ft. X 1/4-in. Porapak-Q column to separate permanent gases and
nitrous oxide, and a 6-ft. X 1/4-in. Linde Molecular Sieve 5A column for separation of
permanent gases. Table 3.10 is a summary of the gas analysis results obtained. The presence of
helium in the post-test gas analyses of the first batch tested at 25'C is an artifact. The ampules
had been initially filled with helium, but the helium in the gas space was replaced with argon
after 11 days with the intent of replacing all the helium. At that time, the liquid unfortunately
was already saturated with helium and the dissolved helium could not be totally removed by
simply purging the gas space with argon. The presence of residual helium which had come out of
solution did not adversely affect the compatibility results reported here. If the helium in Table
3.10 is ignored, the corrected gas compositions printed in bold type in the line below apply
instead. The response factor of the CC to helium is higher than that for the other gases when
argon is used as the carrier gas. The results were not corrected for dhe response factor of helium.
65
Table 3.10: Summary of Gas Analysis
Sample Material Name G a s C o m p o s i t i o n , Vol.-%
No. He* H
2
02 N
2
CO
2
N
2
0
First Batch at 25 oC
S=- 3 U 27.4 16.5 53.9 2.2
22.7 74.3 3.0
74A CRES-304 61.9 12.0 26.0
31.6 68.4
134A Stellite #8 on 17-4PH 54.3 11.3 27.9 6.4
24.8 61.1 14.1
135A Stellite #6 on Nicraly 55.3 9.7 27.0 7.9
on 17-4 21.7 60.5 17.7
162A "CAR LW-15 on 17-4 36.0 10.6 53.4
16.6 84.4
326A Al-6061 4.7 14.2 0.9 12.1 68.0
Second Batch at 25 oC
158A Aeroshe-T T - 4.1 13.2 75.6 7.1
311A MG 120 Silver solder 6.1 21.9 72.0
396A Aeroshell 14 19.5 68.2 12.3
402A 1OW-30 Motor Oil 10.2 32.2 57.6
412A SAE 5OW Motor Oil 15.5 53.4 31.1
HB2 HAN\Argon Blank 29.9 70.1
Ar Argon Blank 25.2 74.8
First Batch at 65 oC
5B Carb-n-eiriRg 2.6 40.7 2.2 54.6
162B UCAR LW-15 on 17-4 2.0 32.5 2.8 62.7
163B UCAR LC-IH on 17-4 1.3 39.3 T 59.3
165B Molydag on 17-4 PH 1.0 41.8 T 57.2
220B Sermatech GC-WC-111 on 17-4 PH 2.0 35.9 1.1 61.0
266B Tungsten weld rod 2.4 60.3 T 37.3
310B Nickel flash on 17-4 PH 1.4 33.6 T 64.9
311B MG 120 Silver solder 1.3 20.1 78.6
326B Al-6061 5.1 0.2 31.3 63.3
HB3 HAN\Argon Blank 4.8 76.2 19.0
Ar3 Argon 31.2 68.8
T - Trace detected
* He dissolved in HAN solution, carried over from
previous test method.
-66-
Table 3.10 (continued)
Sample Material Name G a s C o m p o s i t i o n,
Vol. -%
No. H2 02 N
2
C02 N
2
0
Second Batch at 65 oC
73B CRES-301 4.8 72.5 22.7
116B Graphitar Grade 47 T 73.1 26.9
120B Tristelle Alloy T5-2 5.3 73.6 21.1
126B Grease 3451 3.8 69.9 26.3
129B Victrex 4800G 3.7 66.2 30.1
130B Victrex Gr. 4101GL20 3.1 58.6 38.3
134B Stellite #8 on 17-4PH 2.6 51.7 45.7
135B Stellite #6 on Nicraly on 17-4 1.9 50.4 47.6
145B Silicon carbide PS-9242 4.0 69.9 26.2
146B Arlon 1160 0.5 13.3 0.9 85.3
147B Arlon 1260 2.9 49.9 47,2
156B Paxon BA 50-100 3.7 68.5 27.7
158B Aeroshell 17 T 21.9 28.7 4-.4
161B Rulon II 3.7 68.7 27.6
259B Polyvinylchloride tubing 2.7 61.3 2.3 33.7
335B Brayco 783E Micronic T 41.6 4.0 54.4
396B Aeroshell 14 T 85.7 5.3 9.0
446B Gladen D20 4.1 73.1 22.8
HB4 HAN\Argon Blank 3.9 72.8 23.3
T - Trace detected
There are several new discoveries in the gas analysis of the gas space above the
compatibility test samples: The incompatibility of aluminum alloys with HAN solution resulted
in the formation of 5.1 and 14.2% hydrogen. Hydrogen formation had not been previously
reported in the literature. However, hydrogen formation would not be surprising since the
reaction of PAN solutions with aluminum is similar to reactions of metals with acids. With both
aluminum samples tested here, no oxygen was formed by HAN decomposition and whatever
little oxygen was found was mostly due to air introduced by the sampling technique.
'The other surprise was the high carbon dioxide concentration when testing lubricants with
HAN solutions. The highest carbon dioxide concentration, 75.6%, was observed in sample 158A
(Aeroshell 14). The second highest carbon dioxide concentration, 57.6%, was found in sample
402A (1OW-30 Motor Oil). HAN appears to be a strong oxidizer comparable to concentrated
nitric acid and can effectively destroy hydrocarbon bonds in oils and greases. It may be difficult
to find a lubricant that is not affected and additional work in this area may be required.
Aeroshell 14 was also found to be incompatible based on the rate of gas evolution at either
temperature.
-67 -
All gas samples removed from the test at 338 K (65
0
C), even the blank control without a
material sample in it, had very high nitrous oxide concentrations from HAN decomposition. The
highest nitrous oxide concentration, 85.3%, was observed with Arlon 1160. Arlon 1160 was also
ruled out for future use because of the high rate of gas evolution at 338 K.
Nitrogen and some oxygen are also formed as decomposition products. In the case of
nitrogen and oxygen it is not possible to differentiate between air introduced as an artifact during
gas sampling and nitrogen and oxygen formed as the result of HAN decomposition. Isotope
labeling would be useful to differentiate the two sources of nitrogen and oxygen.
In the control ampules that were filled with dry argon, there was only a trace of air, but its
oxygen to nitrogen ratio had changed somewhat, as if nitrogen had diffused out of the rubber-
septum sealed ampules preferentially. Nitrogen has a lower molecular weight than oxygen and
would be expected to diffuse faster than oxygen.
3.2.5 Additional Gas Analysis
In the case of two motor oil samples, Valvoline SAE 5OW and Kendall IOW-30 tested at
65*C (Sample No, 412B and 402B), it was noted that the mrcury on the ampule side of the U-
gauge manometer was gradually turning black from a crust of black material forming on the
mercury that made it very difficult to read the meniscus. Also, black material adhered to the
wall of the tubing. At the completion of the test, a "rotten egg" odor typical for hydrogen sulfide
could be noted when removing the septum. When testing the residual gas in the ampule with
moist lead acetate paper (a reagent for hydrogen sulfide), it promptly turned black in Sample
412B (Valvoline SAE SOW). The paper in sample 402B did not turn black, but the odor was
nevertheless distinct. It appears that some motor oils have sulfur-containing additives
(antioxidants) which become reduced by hydroxylamine (hydroxylammonium ion) to hydrogen
sulfide.
What makes this observation important is that the same smelly samples also had the lowest
rate of gas evolution of all other lubricant samples at 65C, and no free nitrous oxide could be
found with the 25"C tests. However, the 250C did show formation of carbon dioxide. Some of
the oil additives may act as scavengers for ions which otherwise would promote decomposition of
HAN solutions.
- 68 -
3.3 KINETIC ANALYSIS OF DECOMPOSITION RATE DATA
The objective of the current study was to determine rates of propellant decomposition and
rates of corrosion as a function of temperature and time. The two test temperatures chosen
unfortunately were not suitable for an extended kinetic rate analysis of the data. If kinetic rate
studies are conducted properly at two temperatures well above the normal storage temperature,
far enough apart from each other, it is possible to extrapolate to higher temperatures or longer
storage durations using fundamental kinetic rate laws such as the ARRHENIUS, relationship. for
activation energy. In order to be able to extrapolate in an ARRHENIUS plot where the
logarithm of the kinetic rate is plotted against the reciprocal absolute temperature, one has to
have at least two data points. At the two temperatures chosen for the current contract,
insufficient activity was observed at the lower temperature to allow accurate measurement of gas
evolution and metals leaching. Those materials that did evolve gas and leached metals at room
temperature were those that are obviously incompatible and therefore are of no further interest.
It would have been of interest to obtain pairs of gas evolution rate data or metals leaching rate
data for materials that are of interest and are considered compatible for all practical purposes.
33.1 Gas Evolution Rate Kinetic Analysis
Just to illustrate the principle, although the two examples chosen are not ideally suited
because the materials are totally incompatible, the logarithm of the gas evolution rate of samples
Al-6061 and Silver Solder MG120 are tabulated in Table 3.11 and plotted in Figure 3.16.
As can be seen from the two lines in the graph, the activation energy of the gas evolving
process (I. e. the slope of the straight lines) was very similar. Similar curves should be obtained
by testhig all compatible materials at two or even three and four different temperatures well
above 298 K. Such curves then are useful for prediciting 10-year gas evolution during storage at
ambient temperature.
Table 3.11: Kinetic Rate Analysis of Gas Evolution Rates
Absolute Reciprocal Rate in
Sample Temperature Temperature Rate
Designation K I/K cm3/day
Al-6061 298 0.00336 0.308 -1.1777
Al-6061 338 0.00296 19.80 2.9857
Silver Solder 298 0.00336 0.091 -2.3969
Silver Solder 338 0.00296 7.50 2.0149
-69-
ARRHENIUS PLOT OF GAS EVOLUTION RATE
4-
31338 K
....... ............
-1............... . . .... ....... ..............
4
.... .....
-07
M 2 "
- .. ..... ..
-41
0.0028 0.0029 0.003 0.0031 0.0032 0.0033 0.0034
RECIPROCAL TEMPERATURE, I1/K
UAl-6061 ~'~Silver Solder MG1 20
Flgure 3.16: ARRHDNRS Plot of Gas Evolution Rates
-70-
3.4 SUMMARY AND CONCLUSIONS
The tests described here have shown that some materials are not compatible with 60%
HAN solutions and therefore, most likely, also are not suitable for use with LGP-1845 or
LGP-1846. It is recommended to place those materials that are shown to be compatible based
on the short-term tests described here into a future long-term storage test with continuous
measurement of gas evolution and periodical analysis for leached metals. Other samples should
be tested in the stressed state. Welded samples and galvancic couples of dissimilar metals need
to be tested also.
A test method should be developed that allows the testing of oversize specimens that are too
large to fit through the 8-mm neck of the currently used apparatus.
ACKNOWLEDGMENT
The laboratory work in this program was carried out by Mr, Alan R. Fields. His support of
this program is highly appreciated.
References
1. Decker, M. M., E. Freedman, N. Klein, C. Leverltt, and J. Q. Wojciechowski: HAN-
Based Liquid Propellants: Physical Properties, BRL-TR-2864 (1987), AD-A 195246, N89-10180,
CA 110, 117754
2. Cruice, W. J., and W. 0. Soals: Reclassification and Grease Compatibility Studies for
Liquid Propellants, Hazards Research Corp., Rept. ARAED-RR- 86020 (Dec 1986), 30 p., AD-
A175188.
3. Decker, M, M., N. Klein, and C. Leveritt: The Use of Inductively Coupled Plasma
Spectroscopy in Liquid Propellant Analysis, 1986 JANNAF Propellant Char. Subcommittee
Mtg., CPIA Publ. 459 (Nov 1986) pp. 225-231, DoD Limited.
4. Klein, N., and C. R. Wellman: Reactions Involving tho Thermal Stability of Aqueous
Monopropollants, BRL Report No. 1876, U. S. Army Ballistic Research Laboratory, Aberdeen
Proving Ground, MD (May 1976).
5. Messina, N. A., and N. Klein: Thermal Decomposition Studies of HAN-based Liquid
Monopropellants, Proceedings, 22nd JANNAF Combustion Mtg., CPIA Publ. 432, Vol. 1, pp.
185-192 (1985), AD-A165503, AD-D600778.
-71-
6. Hansen, R.: The Influence of Metal Ions on the Stability of Liquid Gun Propellants
Containing HAN, in: Fourth Annual Conference on HAN-Based Liquid Propellants, BRL
Special Publications BRL-SP-77, Vol.I, p. 273-283 (May 1989).
7. Klein, N.: Preparation and Characterization of Several Liquid Propellants, Technical
Report ARBRL-TR-02471, U. S. Army ARRADCOM Ballistic Research Laboratory, Aberdeen
Proving Ground, MD (Feb 1983).
8. Decker, M. M., et al.: Presence and Removal of Trace Transition Metal Ions in
Hydroxylammonium Nitrate (HAN) Solutions, CRDC-TR-84062, Chemical Research and
Development Center, Aberdeen Proving Ground, MD (Dec 1984),
9. Ward, 1. R., and M. M. Decker. Presence and Removal of Trace Transition Metal Ions
in Hydroxylammonium Nitrate (HAN) Solutions, CRDC-TR-8501, Chemical Research and
Development Center, Aberdeen Proving Ground, MD (Jan 1985).
10. Decker, M. M. et al.: Transition Metal Reactions in HAN-Based Monopropellants,
Proceedings, 22nd JANNAF Combustion Mtg., CPIA Publ. 432, Vol. 1, pp. 177-184 (1985), AD-
A165503, AD-D600777.
11. Klein, N.: Liquid Propellant Stability Studies, Proceedings, ICT Internationale
Jahrestagung 1984, pp. 167-180 (1984).
12. Backof, E.: Selection Criteria for Metals and Plastics as Construction Materials for
Long-Term Pressure-Testing Apparatus in Liquid Propellants, in: Fourth Annual Conference on
HAN-Based Liquid Propellants, BRL Special Publications BRL-SP-77, Vol.I, p. 285-308 (May
1989).
13. Biddle, R. A.: Concentration of HAN Solutions, Final Report, Contract DAAD05-84-
M-6657, Morton Thiokol Inc. Elkton, MD (1985).
14. Same as Reference above
15. Letter by Thiokol Elkton Div. to BRL dated 7 February 1990
16. Decker, M. M., and E. Freedman: Analysis of HAN-based Liquid Monopropellants,
Proceedings, 22nd JANNAF Combustion Mtg., CPIA Publ. 432, Vol. 1, pp. 173-176 (1985), AD-
A165503, AD-D600776.
17. Decker, M. M. N. Klein, and E. Freedman: Titrimetric Analysis of Liquid Propellants,
1986 JANNAF Propellant Char. Subc. Mtg., CPIA Pubi. 459, p. 233- 242 (Nov 1986).
18. Geenty, F. 0.: Titrimetric Determination of Nitric Acid and Hydroxylammonium
Nitrate, Olin Chemicals, Research Center, Analytical Department., CAM. 10-86 (1 Aug 1986).
19. Briles, 0. M., and L. S. Joesten: Experimental Analysis of Hydroxylammonium Nitrate
(HAN) on Sample Materials, Sundstrand Corp., AER-2813, Final Report, Contract
DAAD05-86-C-0168, Appendix B (Aug 1987).
20. Briles, 0. M., and L. S. Joesten: Compatibility Study with 60% Hydroxylammonium
Nitrate (HAN) Solution, in: Fourth Annual Conference on HAN-Based Liquid Propellants,
BRL Special Publications BRL-SP-77, Vol.d, p. 309-326 (May 1989).
21. Sasse', R. A.: Analysis of Hydroxylammonium Nitrate Based Liquid Propellants, Draft
of Analytical Procedure, Personal communication (15 June 1989).
22. Schmidt, E. W.: Tests on Liquid Propellants Program, Rocket Research Company, 89-
P-1308 (6 Mar 1989).
-72-
23. Schmidt, E. W.: Materials Compatibility Test Method, RRC-TP-0632 (1988).
24. Koski, W. S.: Solubility of Gases in LP-1846, in: The Third Annual Conference on
HAN-Based Liquid Propellants, E. Freedman and J. Q. Wojciechowski (Editors), BRL Special
Publication BRL-SP-73 (March 1988), AD-A194679.
25. Backof, E.: Selection Criteria for Metals and Plastics as Construction Materials for
Long-Term Pressure-Testing Apparatus in Liquid Propellants, in: Fourth Annual Conference on
HAN-Based Liquid Propellants, BRL Special Publications BRL-SP-77, Vol.1, p. 285-308 (May
1989).
26. Standard Practice for Static Immersion Testing of Unstressed Materials in Nitrogen
Tetroxide, ASTM F359-82.
27. Rubber Property - Effect of Liquids, ASTM D-471.
28. Feuer, H. 0., 0. Rodriguez, and A. R. Teets: Elastomer Compatibility with Liquid
Propellant, ARDEC Report 2476 (Dec 1988).
29. Rodriguez, G., H. 0. Feuer, and A. A. Teets: Compatibility of Elastomeric Materials
with HAN-Based Liquid Propellant 1846, in: The Fourth Annual Conference on HAN-Based
Liquid Propellants, BRL Special Publication BRL-SP-77, Vol. I, p. 245-272 (May 1989).
30. do Greif, H. J.: Process for Assessing the Stability of HAN-Based Liquid Rocket
Propellants, Fraunhofer Institut fuer Treib- und Explosivstoffe, Pfinztal-Berghausen, West
Germany, Interim Reports No. 1, 2, and 3 (1987); AD-A190686, AD-A190687, and AD-
A190688.
- 73 -
INIVTONALLY LM BLANK.
74
-4
Appendix A
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04 I(Of 04 04 04'.4.40
-A30 -
No of
No of
Qqka Organization
capie QrOnnk9n
Office of the Secretary of Defense 1 Director
OUSD(A) US Army Aviation Research
Director, Live Fire Testing and Technology Activity
ATTN: James F. O'Bryon Ames Research Center
Washington, DC 20301-3110 Moffett Field, CA 94035-1099
2 Administrator I Commander
Defense Technical Info Center US Army Missile Command
AMTN: DTIC-DDA ATrN: AMSMI-RD-CS-R (DOC)
Cameron Station Redstone Arsenal, AL 35898-5010
Alexandria, VA 22304-6145
1 Commander
HQDA (SARD.TR) US Army Tank-Automotive Command
WASH DC 20310-0001 AMTN: AMSTA-TSL (Technical Library)
Warren, MI 48397-5000
Commander
US Army Materiel Command 1 Director
ATTN: AMCDRA-ST US Army TRADOC Analysis Command
5001 Eisenhower Avenue ATTN: ATAA.SL
Alexandria, VA 22333-0001 White Sands Missile Range, NM 88002-5502
Commander (CW. *MY) 1 Commandant
US Army Laboratory Command US Army Infantry School
ATTN: AMSLC-DL ATMN: ATSH-CD (Security Mgr.)
Adelphl, MD 20783-1145 Fort Benning, GA 31905-5660
2 Commander (umiahi. s.y) I Commandant
US Army, ARDEC US Army Infantry School
ATMN: SMCAR-IMI.I ATTN: ATSH-CD-CSO-OR
Picatinny Arsenal, NJ 07806-5000 Fort Benning, GA 31905-5660
2 Commander 1 Air Force Armament Laboratory
US Arnmy, ARDEC ATTN: AFATL/DLODL
ATTN: SMCAR-TDC Eglin AFB, FL 32542-5000
Picatinny Arsenal, NJ 07806-5000
Aberdeen Proving Ground
Director
Benet Weapons Laboratory 2 Dir, USAMSAA
US Army, ARDEC ATTN: AMXSY-D
ATTN: SMCAR-CCB.TL AMXSY-MP, H. Cohen
Watervliet, NY 12189-4050 1 Cdr, USATECOM
AMrN: AMSTE-TD
Commander 3 Cdr, CRDEC, AMCCOM
US Army Armament, Munitions AMTN: SMCCR-RSP-A
and Chemical Command SMCCR-MU
ATTN: SMCAR-ESP-L SMCCR-MSI
Rock Island, IL 61299-500 Dir, VLAMO
ATI: AMSLC.VL.D
Commander
US Army Aviation Systems Command
ATTN: AMSAV-DACL
4300 Goodfellow Blvd.
SL Louis, MO 63120-1798
77
No. of
No. of
Coie OraiQto OR6 ranizatio
Cmdr, US Army Armament, Rsch, I Commander
Development & Engr Center US Army Biomedical Research and
ATTN:
Develpment Lab
SlCAR-TDC (2 COPIES) ATTN: SCRD-UBG-0, MAJ Smart
SliCAR-AEE-B, D. Downs Fort Detrick
SMCAR-AEE-BR, W. Seals Frederick, MD 21701-5010
A. Beardell
Picatinny Arsenal, NJ07806-5000 1 Commander
Naval Ordnance Station
3 Commander
ATTN: P. Skahan, Code 2810G
US Army Armament, Rach, Indian Head, MD 20640
Development & Engr Center
ATTN: SMCAR-FSS-DH, Bldg 94 1 AFAL/RKPA
J. Feneck
ATTN: CPT M. Husband
R. Kopmann
Edwards AFB, CA 93523-5000
J. Irizarry
Picatinny Arsenal, NJ 2 Director
07806-5000
Jet Propulsion Lab
ATTN: Tech Library
. Director
Dave Maynard
Benet Weapons Laboratory
4800 Oak Grove Drive
US Army Armament, Rich, Pasadena, CA 91109
Development & Engr Center
ATTN: SMCAR-CCB, Frankel 1 Sandia National Laboratory
Watervliet, NY 12189-4050
ATTN: Dr. Steve Vosen
Combustion Research Facility
3 Commander
Livermore, CA 94550
US Army Belvoir RD&E Ctr
ATTN: STRBE-WC
Calspan Corporation
Tech Library (Vault) B-315 ATTN: Tech Library
STRBE-VU, H. Feuer PO Box 400
STRBE-VL, G. Farmer Buffalo, NY 14225
Fort Belvoir, VA 22060-5606
2 General Electric Ord Sys Div
2 Commander
ATTN: J. Mandzy, OP43-220
US Army Research Office
J. Scudiere
ATTN. SLCRO-CB, D. Squires 100 Plastics Avenue
SLCRO-E, D. Mann Pittsfield, MA 01201-3698
P.O. Box 12211
Research Triangle Park, NC 1 General Electric Company
27709..2211
Armament Systems Department
ATTN: D. Maher
Burlington, VT 05401
78
No. of
No. of
1 IITRI
2 Thiokol Corporation
ATTN: Library
Tactical Operations
10. W. 35th St Elkton Division
Chicago, IL 60616 ATTN: R. Biddle
R. Brasfield
Olin Chemicals Research P.O. Box 241
ATTN: David Gavin Elkton, MD 21921-0241
P0 Box 586
Chesire, CT 06410-0586 2 Southwest Research Institute
ATTN: Bill Herrera
Olin Corporation
Nollie Swynerton
ATTN: Dr. J. Leistra 6220 Culebra Road
24 Science Park San Antonio, TX 78284
New Haven, CT 06511
2 GeoCenters, Inc
4 Olin Corporation ATTN: Gerry Doyle
ATTN: Ken Woodard Stanley Griff
Dave Cawfield 762 Route 15 South
Sanders Moore Lake Hopatcong, NJ 07866
Ronald Dotson
PO Box 248 2 Director
Charleston, TN 37310 CPIA
The Johns Hopkins Univ.
5 Olin Rocket Research ATTN: T. Christian
P.O. Box 97009 Tech Library
ATTN: Dr. E. Schmidt Johns Hopkins Road
Redmond, WA 98073-9709 Laurel, MD 20707
2 PEI Associates, Inc. 1 U. of MD at College Park
11499 Chester Road ATTN: Professor Franz Kasler
ATTN: M.L. Taylor Department of Chemistry
M.A. Dosani College Park, MD 20742
Cincinnati, OH 45246
1 U. of Missouri at Columbia
Sundstrand Aviation ATTN: Professor R. Thompson
Operations Department of Chemistry
ATTN: Mr. Owen Briles Columbia, MO 65211
PO Box 7202
Rockford, IL 61125 1 Princeton Combustion Rsch
Laboratories, Inc.
1 Veritay Technology, Inc. ATTN: N.A. Messina
ATTN: E.B. Fisher 4275 US Highway One North
4845 Millersport Highway Monmouth Junction, NJ 08852
P0 Box 305 1 University of Delaware
East Amherst, NY 14051-0305 Dept of Chemistry
ATTN: Professor Thomas Brill
Newark, DE 19711
79
, I..
No. of
Dr. Hans-Juergen Frieske
Dynamit Nobel
Waitherstrasse 80
5000 Cologne 80 FRG
2 George Cook
Peter Henning
RARDE
Ft. Halstead
Sevenoaks, Kent TN14 7BT
England
2 Paul Bunyan
Sally Westlake
RARDE
Powder Hill Lane
Waltham Abbey
Essex, England 1 AX
2 Fraunhofer-Institut fuer
Treib-und Explosivutoffe
ATTN: Dr..R. Hanson
Dr. F. Volk
D-7507 Pfinztal-Berghausen
FRO
1 Dr. H. Schmidt
Bundesministerium der
Vortoidigiong
Rue V11-4
Postfach 1328
5300 Bonn 1
FRG
I. G. Klingenberg
Fraunhofer-Institut fuer
Kurzzoitdynamik Ernst-
Mach-Institut
Abteilung fuer Ballistik
Hauptstrasue 18
D-7858 Wail am Rhein
FRG
80
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............................ .....-.... FOLD HERE-------------------------- -----------------
DEPARTMENT OF THE ARMY IIl
MCroow N-0I I' POSAGE
U.S. Aimy Ballistic Ruaoch'Labo,4Wry 'I " "' NECEMARY
ATTN: SLCBR-DD-T ,IF MAII
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IN THE
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POSTAGE WILL BE PAID BY ADDRESSEE
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ATTN" SLCBR-DD-T
Abcrdeen Proving Ground, MD 21005-9989
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