IRLR-'636 I I

CONTRACTOR REPORT BRL-CR-636

BRL AD-A224 594

HYDROXYLAMMONIUM NITRATE COMPATIBILITYTESTS WITH VARIOUS MATERIALS- A LIQUID PROPELLANT STUDY -

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DTICEILECTE ECKART W. SCHMIDT

AUG 0 21990 ROCKET RESEARCH COMPANYAEROSPACE 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,U.S. Department of Commerce, 5285 Port Royal Road, Springfield, VA 22161.

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 ofany 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 MNutERsTests with Various Materials -

A Liquid Propellant Study F03A909AJOH3DA306700

Eckert W. Schmid

7. PERFORMING ORGANWATION NAMEAS) AND ACORASS(ES) S. PERFORMING CRGANIZATION49IICAT MUM614

Rocket Research CompanyRedmond, 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 LaboratoryATTN: SLCBR-DD-TAberdeen 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 gunpropellants, with 48 different materials of construction was tested in short-term immersiontests in constant temperature baths with obseri"n and mpisurement of gas evolution.Test temperatures were 298 K and 338 K (25#C and 65tý. Test duration was 30 days.Materials tested included metals, plastics, ceramics, coatings, and lubricants. At the endof 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 thepropeUant. The off-loaded HAN solutions were analyzed for leached metals. Based on therate of gas evolution, weight loss of the specimens, discoloration of the liquid, and amountof metals leached, several materials were identified as being incompatible with 60% HAN,soltinons._.) (Author)

1-4UhJECT TEAM Liquid gun propellants Compatibility 1 NMUR OF PAGE5LG?'t845-E6-t846 1P84R .. LP-4i6-f---eAS --RN-13465-08-2 .- 1 12

H ydroxylamm onium nitrate •, 1& AX - Liquid propellants , ___)_r________W_ _30

17. SEOJEIY a.AsSWOATION il sicumRiy &-%SW-QVAi-3 It. SAcuNtY CLASSOICAntI0 20. UPATATKII OF ABSTPCOF "myOr or TOS PAGE O A&STRACt

Unclassified Unclassified Unclassified ULpm. 73S441 .J1SOO Standard Form 29i (Nov 2,S9)

UNCLASSIFIED -'. ""

frrNTImoNAmyLaY LBFLANK.

Contents

Chapter 1 INTRODUCTION 11.1 GENERAL INFORMATION ................................... 11.2 OBJECTIVE ................................ ................... 21.3 SCOPE OF W ORK ............................................ 21.4 PROBLEM STATEMENT ................... : ............ *.. 2

Chapter 2 TECHNICAL APPROACH 32.1 LIQUID GUN PROPELLANTS .............................. 3

2.2 SELECTION OF PROPELLANT SOLUTIONS ........ ...... 62.2.1 Preparation of HAN Solutions .................................... 6

2.2.1.1 HAN Assay Analysis Methods ........................... 72.2.1.2 HAN Analysis for Trace Metals ........ ............... 8

2.3 SELECTION OF MATERIALS TO BE BESTED . 4 .. 0..*........ 92.4 EXPERIMENTAL METHODS ............... 6 .................. 10

2.4.1 Description of Test Apparatus .............................. 102.4.2 Selection of Test Atmosphere .. .. 6 .. ....................... 172.4.3 Selection of Total Immersion versus Partial Immersion ......... 182.4.4 Selection of Sample Size ........................ ...... .. 192.4.5 Selection of Sample Shape ........ ........................ 192.4.6 Selection of Test Duration ....................... ....... . 202.4.7 Selection of Test Temperatures ..................... . 212.4.8 Constant Temperature Bath ........................... 212.4.9 Measurement of Rate of Gas Evolution ............. . 232.4.10 Gas Evolution Data Reduction .............. 232.4.11 Rate of Gas Evolution as Termination Criteria ............... 24

2.5 CHEMICAL ANALYSIS OF EVOLVED GASES ................. 252.6 POST-TEST EXAMINATION OF SAMPLES AT END OF

COMPATIBILITY TEST ... 6................................... 26

2.6.1 Weight Change Measurements .............................. 262.7 ANALYSIS OF OFF-LOADED PROPELLANT. ................. 26

Chapter 3 EXPERIMENTAL RESULTS 313.1 PRE-TEST ANALYSIS RESULTS ........................... 31

3.1.1 HAN Assay Analysis Results ... ............................ .. 31

iii

3.1.1.1 As-Received24% HAN Solution .................... 313.1.1.2 Concentrated 60.8% HAN Solution ................... 31

3.2 POST-TEST RESULTS .............. ................... 343.2.1 Weight Change Measurements ........................... 343.2.2 Pressure Rise / Gas Evolution Measurements ................ 39

3.2.2.1 Gas Evolution at 298 K (25"C) ...................... 393.2,2.2 Comments on Data Reduction ........................ 463.2.2.3 Gas Evolution at 338 K (65"C) ....................... 49

3.2.3 HAN Trace Metals Post-Test Results ...................... 633.2.4 Gas Analysis by Gas Chromatography ..................... 643.2.5 Additional Gas Analysis ................................. 68

3.3 KINETIC ANALYSIS OF DECOMPOSITION RATE DATA ....... 693.3.1 Gas Evolution Rate Kinetic Analysis ........................ 69

3.4 SUMMARY AND CONCLUSIONS ............................. 70ACKNOWLEDGMENT ......................................... 71References ..................................................... . 72

Figures

Figure 2.1: Distribution by Type of Materials ............................... 9Figure 2.: HAN Compatibility Test Apparatus, Schematic .................. IIFigure 2.3: Loading of Ampules with HAN Solution under an Inert

Atmosphere ........................ 14Figure 2.4: Compatibility Test Ampule Loaded with Sample and HAN Solution .15Figure 2.5: Hermetically Sealed Compatibility Test Apparatus (RRC Model) .. 17Figure 2.6: Constant Temperatum Bath with 25 Ampules Prior to 25 4C Test . . 22Figure 2.7: Flow Rate of HAN Solutions into AAS Nebulizer ................ 29Figure 3.1: Compatibility of Materials in 60.8% HAN at 298 K (25"C) ........ .40Figure 3.2: Compatibility of Materials in 60.8% HAN at 298 K (25"C) ......... 41Figure 3.3: Compatibility of Materials in 60.8% HAN at 298 K (25"C) ......... 42Figure 3.4: Compatibility of Materials in 60.8% HAN at 298 K (25"C) ......... 43Figure 3.5: Compatibility of Materials in 60.8% HAN at 298 K (250C) . 44Figure 3.6: Compatibility of Materials in 60.8% HAN at 338 K (65"C) ......... 50Figure 3.7: Compatibility of Materials in 60.8% HAN at 338 K (65"C) ........ 51Figure 3.8: Compatibility of Materials in 60.8% HAN at 338 K (65"C) ......... 52Figure 3.9: Compatibility of Materials in 60.8% HAN at 338 K (65"C) ......... 53Figure 3.10: Compatibility of Materials in 60.8% HAN at 338 K (659C) ........ 54Figure 3.11: Compatibility of Materials in 60.8% HAN at 338 K (65'C) ....... 55Figure 3.12: Compatibility of Materials in 60.8% HAN at 338 K (650C) ....... 56Figure 3.13: Compatibility of Materials in 60.8% HAN at 338 K (659C) ....... 57Figure 3.14: Compatibility of Materials in 60.8% HAN at 338 K (65"C) ....... 58Figure 3.15: Compatibility of Materials in 60.8% HAN at 338 K (65"C) ....... 59Figure 3.16: ARRHENIUS Plot of Gas Evolution Rates ................... 70

iv

Tables

Table 2.1: Comparison of AAS and ICP Detection Limits ......... .... 28Table 3.1: AN Acceptance Test Results ........................ 32Table 3.2: Analysis of Concentrated HAN Solutions ........................ 33Table 3.3: Weight Change of Test Specimens at 298 K and 338 K (25 and 656C) .35Table 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 GasEvolution .................................................. 49

Table 3.6: Gas Evolution at 338 K (65"C) ................................. 60Table 3.7: Gas Evolution at 65"C; In Order of Decreasing Gas Evolution Rate .62Table 3.8: Gas Evolution Rates of HAN Blanks ................................. 63Table 3.9: Summary of Metals Analysis by Atomic Absorption ............... 65Table 3.10: Summary of Gas Analysis ..................................... ... 66Table 3.11: Kinetic Rate Analysis of Gas Evolution Rates ................. 69

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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 theUnited States Army Ballistic Research Laboratory (BRL), Aberdeen Proving Grounds as theresult of a competitive procurement in response to solicitation DAAD05-89-R-5453. The BRLContracting Officer's Representative was Mr. Ronald A. Sasse'.

The research program involved the testing of candidate materials of construction forcompatibility with the key ingredient of liquid gun propellants, namely concentrated aqueoussolutions 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 materialsof construction with rocket propellants such as hydrazinium nitrate solutions in water andhydrazine. Hydrazine Is a hydronitrogen compound similar to hydroxylamine. Hydraziniumnitrate is an acidic salt as is hydroxylanmmonium nitrate. The RRC propellant compatibility testeffort has continued for over twenty years and storability data are now available on severalnitrate propellant blends in contact with various materials of construction. The tankage systemof a liquid propellant gun is similar to tankage systems for energetic monopropellants for rocketpropulsion. The extreme temperatures encountered in the liquid propellant gun breech aresimilar to temperatures encountered in rocket engines. It is from this related experiencebackground with liquid rocket monopropellants that RRC has approached the liquid gunpropellant materials compatibility question.

1.2 OBJECTIVE

The objective of this final report is to provide all information necessary to document theprogress made by the contractor in comparison to the goals established in the work plan and thecontract statement of work. It is a further objective of this report to assemble the vast amount ofdata generated during the contract in an easily accessible "user-friendly" format. The formatshould be such that the user will quickly obtain information about the acceptability orincompatibility of a candidate material of construction.

1.3 SCOPE OF WORK

The purpose of this contract was to determine the effect of various materials ofconstruction, including metals, alloys, plastics, and greases on liquid gun propellants (LOP). Onehundred tests had to be performed on one ingredient of the LOP-1845 or LGP-1846 propellantcalled lydroxylammonium nitrate, NH3OHNO 3 (HAN). These 100 tests were performed on 48Government-furnished (GFE) materials and two controls (HAN without any additive) at twodifferent temperatures, 298 K (25'C) and 338 K (65C). Pressure rise during the 30-day tests wasmonitored daily as an indication of compatibility. Post-test samples were examined for signs ofcorrosion and some of the off-loaded propellant was analyzed for leached metals. The gas spaceabove the samples was analyzed for chemical composition of the gases formed. This gascomposition 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 gunpropellant ingredients. The first is the effect of the corrosive medium on the material, causingpossible loss of structural integrity. The second is the effect of contaminants leached from thematerial of construction on the storage stability of the propellant. The test program conductedhere addressed both concerns.

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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 differenttemperatures for periods of 30 days and the rate of gas evolution was measured. At the end ofthe test, if sufficient gas had evolved, the nature of the evolved gas was determined by gasanalysis. The propellant off-loaded from the test tube was analyzed for leached metals (if thematerial was a metallic material) and the specimens were examined for weight change andchanges in appearance.

2.1 LIQUID GUN PROPELLANTS

Liquid gun propellants currently under consideration consist of concentrated aqueoussolutions of hydroxylammonium nitrate and triethanolammonium nitrate. The corrosiveproperties 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 bereactive with a large number of materials.

Composition of Liquid Gun Propellants, For actual applications, two slightly differentliquid gun propellants are being considered: BRL-1845 and BRL-1846. These propellants havebeen historically called BRL-1845 and BRL-1846 but are now also called Liquid Gun PropellantLGP-1845 and LQP-1846. In the context of the work reported here, the two designations (BRLand LGP) are used interchangeably.

Nominal compositions of LGP-1845 and LGP-1846 were given in a physical propertiesreport published by BRL (Reference 1).

LGP-1845 consists nominally of

63.23 wt.-% hydroxylammonium nitrate19.96 wt.-% triethanolammonium nitrate16.81 wt.-% water

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When expressed in terms of molarity instead of mass percent, LGP-1845 has the followingnominal composition:

9.62 M hydroxylammonium nitrate1.38 M triethanolammonium nitrate

13.64 M water

LGP-1846 consists typically of

60.79% hydroxylammonium nitrate19.19% triethanolammonium nitrate20.02% water

or, in terms of molarity of the solution:

9.09 M hydroxylammonium nitrate1.30 M triethanolammonium nitrate

15.93 M water

There is currently no existing military specification for these propellants. Until such aspecification is issued, deviations of +/- 0.5% by weight from the nominal compositions havebeen considered acceptable for testing and contracting procurement purposes. The maximumamount of free acid allowed is recommended at 0.1%.

The materials compatibility of these two LGP propellants is essentially identical. Thecontract statement of work required the contractor to use aqueous HAN solutions containingfrom 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 inLGP-1846.

Similar propellants previously developed by the U. S. Navy, such as the NOS-series, alsoincluded hydroxylammoniurn nitrate, but only few previous materials compatibility investigationsare published on those propellants (Reference 2).

Effects of Metal Ion Contamination on Thermal Stability of Liquid Gun Propellants. Forpractical applications of liquid gun propellants it is imperative that the propellants be storableunder field condctions (-40 to +160F). Both storage stability and thermal stability of HANsolutions and liquid gun propellants are adversely affected by the presence of transition metalions. Transition metal ions are readily leached from the surface of incompatible materials incontact with the propellant. RRC has observed this phenomenon on numerous occasions withhydrazine and hydrazinium salt solutions which act similar to aqueous hydroxylammoniumnitrate solutions.

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Lack of storage stability would slowly degrade the liquid gun propellant to a point where theimpetus no longer meets tiie required performance criteria. A reported laboratory test in whicha 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 evolutionaccompanying such obvious incompatibility might burst storage containers overpressurization.Insoluble corrosion products or evaporation residues formed as the result of decomposition andcorrosive 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 inthe injection passage prior to injection into the breech or before the liquid chatgi 4njection cyclein 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 arebeing taken:

1. The propellant ingredients and all liquid gun propellants are procured to a specificationwhich limits the amount of tolerable contamination in the starting product. Acceptancetests will be conducted to verify compliance of loaded liquid gun propellants with theprocurement specification.

2. As a second precaution, all materials coming in contact with liquid gun propellants arecarefuilly screened in a materials compatibility test program to assure that no transitionmetal ions (or any other metal ions) are leached from the materials of constructionduring storage or operation of the liquid propellant gun.

It is for the second reason that the just completed testing program was proposed and acontract was awarded. In addition to metals leached from inorganic materials, other species canbe 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 causethe 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 authorsthat the presence of transition metal ions adversely affected the thermal stability and storabilityof the mixtures (References 4 ,5 6 and 7).

initially these tests had been conducted with LGP-1845 and LGP-1846 which consists ofhydroxylammonium 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 assumedthat other transition metal ions might have similar effects. In general, and again in agreementwith observations made at Olin Rocket Research with hydrazine propellants, elements with

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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 lessactive. 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 tobe tie propellant component that was predominantly responsible for adverse reactions withmetals. 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 inan effort to isolate the cause of materials incompatibility with LOP and in order to parallel theHAN/water studies done here. It is not anticipated that much could be learned from such astudy. More could be learned by studying HAN/water first as was done here. The effect of thepresence 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 shownthat the reaction of Fe3+ is electrocatalytic while the reaction of Cu2 + is not (Reference 11).The reason for the strong catalytic activity of iron is the ease with which it changes its state ofoxidation between the trivalent and the bivalent state. In HAN solutions, Fe3 + is reduced byhydroxylammonium ion to Fe2 + and the Fe2 + is re-oxidized to the trivalent state by the nitrateion. 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 afterseveral years of storage. Even after a short time, the performance of the propellant would bedegraded to a point where it would not longer meet the specification. Gas evolved during thisperiod may rupture the tank. The time to rupture of sealed glass vials has been used as a testmethod 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 valencechange 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 andgreatly 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% hydroxylammoniumnitrate with a nominal concentration of 60.8% (12.2 molar). This is similar to the HANconcentration in LOP-1846, with the TEAN portion replaced by additional water.

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Hydroxylammonium nitrate was commercially available as 24% aqueous solution (4.8molar) from Southwestern Analytical Chemicals in Austin, TX. The 24% solution is easilyconcentrated 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 perCFR 49. The more concentrated 60% (12.1 molar) solution is neither cap-sensitive nor is itpositive in the card gap test at zero cards (Reference 14). Experimental quantitieq of 85% HANsolutions 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 requiredat least 4 L of the 60% solution. Reserve solution was also prepared for those tests that mighthave to be terminated after 1 day or 7 days, requiring a substitute material to be placed in testwith 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 theapproximate 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 orpotentiometric 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 assayanalysis of HAN solutions is substantially easier than the analysis of LGP-1845 or LGP-1846since only two instead of three ingredients are involved. For the analysis of ternary LOPpropellants, other bases have to be used as titrants (Reference 17).

Olin Chemicals, a major proposed future producer of HAN solutions, uses an automatictitrator 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 usedan acidimetric titration with 1-N sodium hydroxide and thymolphthalein indicator. This methodhas the disadvantage that it will not recognize HAN solutions that are deficient in free nitirc acidand 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). Thismethod 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 theadvantage that also small deviations of nitric acid deficiency can be recognized. This methodrecommends 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 with0.2 M to 0.3 M NaOH solution.

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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 thecontract is free from contaminant metal ions that could jeopardize the success of the entire testseries. Therefore, the procured 24% solution as well as the concentrated 60% solution has beenanalyzed for trace contamination of heavy metals. The main objective of the analysis was toanalyze for iron, copper, nickel, and chromium to verify the absence of these metals inconcentrations 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 orLGP-1846, RRC used the following product specification in the procurement of 24% HANsolutions, as do other contractors:

Hydroxylammoniumn nitrate content 24% minimum, 25% maximum

Sum of all heavy metals (Fe, Cu, Cr, Ni etc.) 5 ppm maximumpH 2.5 to 3.0Total other contaminants (e.g. ammonium nitrate) 1.0% maximumFree nitric acid 0.1% maximumcolor colorless, clear

The supplier was asked to supply a batch analysis with the shipment of the chemical. Thesupplier stated that their product has typically the following properties:

Hydroxylammonium nitrate content 24.I %pH 3 to4Free nitric acid (stabilizer) less than 0.01 molarAluminum less than 0.2 ppmSulfate less than 10 ppmBarium less than 0.1 ppmChloride less than 10 ppmIron less than 0.2 ppmSum of calcium and magnesium less than 10 ppmAsh less than 10 ppmColor colorless, clear

Our results of HAN analysis are given in Paragraph 3.1.1.

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2.3 SELECTION OF MATERIALS TO BE TESTED

The selection of materials to be tested was not the responsibility of the contractor under thecurrent 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 MATERIALMATERIALS 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 arethe tank, the propellant lines, tho shutoff valve, the shuttling piston in a regenerative liquidpropellant gun, and the injector nozzles, In addition, propellant management devices (bladders,diaphragms, pistons) separate the pressurant gas and the propellant. At the beginning of thecontract, emphasis was on materials that would be in contact with mixed propellants. During alater contract period, other materials were added that may be used in chemical plants whereHAN is manufactured end mixed with TEAN.

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As was indicated in the proposal (Reference 22), it was anticipated that sufficient materialfor 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 couponfor before-and-after side-by-side photography should the appearance change as the result of theexposure. 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 monthsand were used "as received" (except for cutting them to uniform size). No additional cleaningwas done with any of the samples.

It is important to maintain traceability as to the origin of the material for the sake ofreproducibility. For instance, it may be desirable to conduct future testing on similar or evenidentical materials (e.g., using HANJIEAN/H20 blends instead of HAN solutions) and makecomparisons. The results might differ slightly if materials from different vendors or batchnumbers 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 makeprocess 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 rarelydocumented 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 asign of materials incompatibility and the rate of gas evolution was a measure of the degree ofincompatibility. It was of interest to determine the nature of the evolved gases to makedeductions about the probable cause of decomposition and possible effects of products on thematerials exposed to the vapor phase alone.

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HAN COMPATIBILITY TEST APPARATUS

RUBBERSEPTUM

~~ REMOVABLE

CONSTANT FISLI

TEMPERATURE INSULATION

BATH (NOTTO SCALE) - M

.60%-HANSOLUTION

~ MERCURYMANOMETER

MATERIAL-SPECIMEN

-- CATCHIPAN

Figure 2.2: HAN Compatibility Test Apparatus, Schematic

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Borosilicate glass (Pyrex) was chosen for the compatibility flasks. In this regard, hundredsof compatibility tests at RRC have been carried out using Pyrex flasks and the rate of gasevolution in the control flasks is always very low. The control flasks will be from the same batchof ampules as those used for the materials compatibility tests.

The ampules came from the supplier in a cleaned condition. The ampules were similar toampules 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 thematerials sample. The connection to the U-gauge was then made with a fused glass seal usingstandard glass blowing techniques. The U-tube gauges were pre-assembled and cleaned withlaboratory detergent (e.g., Alconox), rinsed with distilled water, and dried prior to attachingthem to the ampules.

In most cases, the ampules were attached to the U-gauge with the sample already in placeinside the ampule. In a few cases, the apparatus could be assembled first and the skinny samplecould be slid +!,rough the narrow neck of the assembled apparatus. Also, all oil and greasesamples could be injected after the apparatus was already completely assembled. Extreme carehad to bu taken to prevent scorching the sample while the glass blowing was in progress. Thiswas a comparatively simple operation since RRC's standard compatibility apparatus has to besealed with a glass blowing torch while the sample and the propellant is already in place. Havinghigh-energy propellant in immediate vicinity of a glass blowing torch and red hot molten glassrequires additional safety precautions which were not necessary in this program.

Following the glass blowing, the assembled apparatus was evacuated and tested for leakswith a Tzsla coil in a darkened room. Any pinholes in the fused glass joints could thus beidentified before the apparatus was filled with propellant. The evacuation also served to removeany condensation in the flask caused by the preceding glass blowing operation. The twoopenings (the rubber septum port and the open end of the manometer) were covered withtemporary rubber septums and the ampules were then stored in ambient air or in the glove boxunder argon until they were ready to be filled with HAN solutions. The remaining steps werecarried out in an argon-filled glove box to eliminate ambient air (see Par. 2.4.2 Selection of TestAtmosphere).

The design of the ampule/manometer combination used at RRC was modified from thatused by a previous BRL contractor such that the septum port was now coaxial with the ampuleand the syringe needle would now reach clear to the bottom of the ampule without having tosnake around bends in the apparatus. This design is superior because it avoids accidentalsmearing of liquid on the walls in the vapor space of the apparatus.

-12-

The liquid was injected into the assembled apparatus (already containing the materialsspecimens) through a capillary syringe needle from a graduated syringe. This allowed accuratedispensing of exactly 40 mL of the HAN solution. Figure 2.3 shows the process of loading theampules 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 wastaken not to smear any uquid on the wall when retracting the syringe needle. All this was donein a glove box under argon. The time at which the liquid was admitted to the sample was thestarting time of the 30-day experiment at 298 K (25'C) since ambient temperature was not muchdifferent from the constant temperature bath. For the 338 K (65'C) tests, the samples wouldspend 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 tohalf 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 wasnecessary not only to eliminate contaminants, but also to obtain a clean meniscus that is neededfor 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 thisfinal stop, the loaded and tightly sealed ampules were removed from the glove box and insertedinto the constant temperature bath. Figure 2.4 shows a completely assembled compatibility testampule ready to be inserted into the constant temperature bath. Those ampules inserted into a338 K (65'C) bath experienced some initial pressure rise from the thermal expansion of the gasin the vapor space ("ullage") alone. This slight overpressure was not vented due to the difficultyin re-connecting the septum tightly, the risk of suffering pressure loss during the 30-day test, andinadvertent introduction of air while the pressure of the 65'C warm sample Is vented to ambientpressure. The initial travel of the mercury due to ullage warm-up thus reduced the travelremaining for the test before gas would bubble though the low portion of the U-manometer atthe end of the test.

- 13-

RUA, 4g

i~Ii

Flpre ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~~~* 2.:Laigo 9mueswt 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 theullage volume of the flask, the pressure read from the manometer, and the temperature and wasreduced to standard conditions (Standard Temperature and Pressure - STP). The total volumeof several of the flasks was determined by filling with water and weighing. The flasks were allconstructed as identical as possible and flask-to-flask variations of total volume were held at aminimum. All manometers were filled to approximately the same mercury level at the beginningof the test. The ullage volume ,vas calculated from the total internal volume minus the volumeof liquid loaded into the ampule (40 cm 3). The sample itself did not occupy much volume andwas ignored.

The length of the U-gauge was 34 cm from top to bottom of the U. The full scale range was300 mm Hg corresponding to a gas evolution of approximately 16 cm 3 STP at 338 K. A widenedsection like a small funnel at the top of the open end of the U-gauge allowed gases to escape inthe event of unintended overpressurization without spilling the mercury on the bench top or thefloor. A catch pan was placed under the U-gauges to catch mercury spillage in the unlikely eventof overpressure or glass breakage.

The vapor pressure of the HAN solution is lower than that of water and is similar to butsomewhat higher than that of LOP-1846, i.e. approx. 12 mm Hg at 298 K (25"C) and 89 mm Hgat 338 K (65"C). It is part of the total pressure measured. The partial pressure of the vapor (thepressure reading at the beginning of the 30-day test period) was subtracted from the pressureread on the manometers prior to the calculation of the amount of gas formed. Minorfluctuations of the constant temperature bath temperature would cause vapor pressurefluctuations on the manometer. The bath temperature was kept constant to within +_ 0.1 'C inorder to prevent pressure fluctuations.

Since the flasks and U-gauge manometers were open ended, the readings fluctuated withthe ambient barometric pressure. The ambient barometric pressure was read each day when thesamples were reati and entered in the test log for future data reduction. This mode of testingwith open-ended U-gauges has the disadvantage that it is sensitive to ambient pressurefluctuations, whereas other materials compatibility test methods are independent of ambientpressure fluctuations if the U-gauge is hermotically sealed under vacuum and not exposed toatmospheric pressure fluctuations (Reference 23). Admittedly, the open-ended U-gauge ampulesare easier to build and to fill and are perfectly adequate for tests where high rates of gasevolution must be expected. Their use is perfectly acceptable for initial compatibility testingwhere 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 inFigure 2.5. The RRC-type apparatus is preferred for long-term compatibility testing withsamples 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 determinethe solubility of oxygen in HAN solutions, it behaved anomalous since it apparently slowly reactswith 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 wouldreact with HAN, thus escaping analysis in the gas phase. Also, some oxygen may form during thedecomposition of HAN solutions and if the ampules were not carefully freed from air to startwith, one could not discern between oxygen formed from HAN reactions or oxygen present as acontaminant.

For these reasons, the tests were conducted under an atmosphere of argon. The glove boxwas purged with argon for several hours prior to loading and the absence of oxygen was verifiedby GC analysis of a grab sample taken from the glove box atmosphere. A large weather balloonwas inflated inside the glove box to displace the previous atmosphere and to minimize thevolume that needed to be purged. The ampules, the material specimens, the degassedhydroxylammonium nitrate solution, and the mercury were all placed into a glove box andpurged with argon. The ampules were purged with argon, loaded with hydroxylammoniumnitrate solution, and sealed with a rubber septum inside the glove box to prevent exposure toatmospheric oxygen. If the ampule initially contains only argon, it will then be possible toanalyze for formed nitrogen, oxygen, or nitric oxidein the gas space above the sainple at the endof the test.

However, argon and oxygen are difficult to separate on the molecular sieve column unlessthe 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 thevery first series of 25 samples, helium instead of argon was used initially in the glove box to fillthe ampules under an inert gas atmosphere. However, the rubber septums had an excessivelyhigh permeability to helium and the tests had to be abandoned and re-started after replacing thehelium with argon (see Paragraph 3.2.2.1). Helium is not recommended for tests where rubberseptums 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 heliumhad 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 andthe liquid gun propellants, the entire samples were immersed in the liquid. This is in analogy tocompatibility testing done by other organizations on LGP-1846.

- 18-

There have been rare incidents where corrosion in the vapor phase above the liquid levelwas more severe than in the liquid itself. This can be caused by interaction of the liquid with theatmosphere above the liquid, resulting in a more corrosive environment than either liquid orvapor 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 holedrilled into one end, as if the samples were intended to be suspended from a wire such that onlythe lower portion was immersed in the liquid propellant. However, since no detailed instructionswere given with the samples, the coupons were totally immersed in the propellant same as theother 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 fitthrough the 8-mm inner diameter neck of the ampules without further cutting. It appeared thatmany of the GFE samples provided by the contracting agency were cut by another governmentcontractor to dimensions of 1 inch length by 1/4 inch thickness. These coupons were easilyloaded into the ampules. Other materials submitted by the contracting agency for testing wereoversize 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 tobe returned untested.

It was desirable to use as large a sample as possible in order to obtain measurable rates ofgas evolution during the 30-day observational period. Therefore, provided that the materialsupplied was of sufficient width, the coupons were cut 65 mm length and 8 mm width, which isshort enough to be completely immersed in the 40 mL of liquid, but long enough to provide asufficient surface area (e.g. 11.9 cm 2 with a 1-mm - 0.04 inch thick flat coupon) to generatemieasurable 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, cleanedwith 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- sponsoredcompatibility testing with LGP-1846 were not specific with regard to the sample shape (or eventhe suf•face area) of the specimens used. It was noted that many of the materials couponssubmitted for testing had a small hole drilled into one end, as if the samples were intended to besuspended 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 totallyimmersed in the propellant.

- 19-

Also, some materials coupons were coated with a coating, but the coating did not extendover 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 theuncoated area of the coupon. Future tests should use coupons were the entire surface area isuniformly coated.

It would be simplest to work with rectangular shaped flat coupons that are easy to machineor, in the case of elastomers, could even be cut to size with a scissors. However, in testing liquidrocket propellant material compatibility, it has become common practice to use dogbone-shapedtensile specimens per ASTM E8 which can be used for determination of tensile strength andyield at break. There exists an ASTM specification for static immersion testing of unstressedmaterials with dinitrogen tetroxide N204 (Reference 26). This method should be adapted withsome modifications for future materials compatibility testing with HAN solutions where not onlymaterials chemical interactions, but also mechanical1properties are studied. Another related testmethod for elastomers is ASTM D-471 (Reference 27) which has been used by the United StatesArmy Belvoir Research, Development & Engineering Center for testing the compatibility ofelastomers 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 similarliquid rocket propellants. The accuracy of prediction from the short-term exposure testdescribed here with liquid gun propellants is poor in comparison to the accuracy derived fromthe materials compatibility data base accumulated as the result of lengthy (2 to 20 years) testingwith liquid rocket propellants. The tests now completed with HAN solutions and similar testswith complete mixtures of LGP-1846 can therefore be considered only as preliminary screeningtests. It is recommended that they be followed up with longer tests using only those materialsthat 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 shortenough that no valuable test time is wasted on incompatible materials which would most likelyhave 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 ofthe 30-day test. Analysis of the first batch of 25 ampules should be completed before the nextbatch has to be pulled. Therefore, the test starts were staggered by several weeks. This allowedsufficient time to complete the analysis of the first group before the second group of 25 ampuleshad to be opened.

- 20-

2.4.7 Selectloa of Test Temperatures

The two test temperatures were selected in accordance with the requirements spelled out inPar. 3.3.4 of the RFP. For the first groups of 2 times 25 ampules, the temperature of theconstant temperature baths was allowed to be anywhere between 24 and 26"C, as long as it waskept constant to within t_0.1"C. Because some of the testing extended through the summermonths, and the ambient temperature in the laboratory rose above 24'C, a water cooling coil wasinserted 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 thermalstability of liquid gun propellants at temperatures above 65'C using a slightly differentexperimental technique (Reference 30). It would have been of interest to compare their resultswith 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 ofwater as the bath fluid was perfectly acceptable for 25'C tests. For the 338 K (65'C) tests, waterevaporation was retarded by covering the surface of the liquid with styrofoam chips. The waterlevel in the 65"C bath was adjusted every few days. Forced convection circulation was achievedby stirring motors with propellers on a single shaft. Temperature gradients in the baths werethus 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 werenot 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. Previousinvestigators have also placed the ampules in the constant temperature bath such that only thesample ampule was at constant temperature and the U-gauge portion with the mercury wasoutside the bath, subject to ambient conditions as it was in the current test series. This method isacceptable since the vapor pressure of the solution is very low and condensation of the water inthe upstream leg of the U-gauge is minimal. For the high-temperature tests at 338 K (65"C), thetemperature 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 thebath 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 (excludingweekends or holidays), and more often if warranted by the extent of reaction. Care was taken toensure 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 Mondaysand on days after legal holidays.

Pressures were read using a cathetometer with a nonius vernier scale. When the stirrermotor was turned off to eliminate vibrations of the mercury column while the readings weretaken, pressure could be read to _O.l mm Hg with this instrument. The cathetometer wascalibrated against a length standard (block gauge) traceable to the National Institute ofStandards and Technology. The standoff distance between the cathetometer and the mercurymanometers 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 ofthe test series by filling on apparatus with water and weighing. The internal volume of the dryapparatus without mercurM vas 78.29 mL. Subtracting 40.00 mL for the volume of the HANsolution and neglecting the volume occupied by the test specimen, leaves an ullage volume of38.29 mL. Earlier investigators had once proposed the following formula for calculating theamount of gas evolved in the course of the test and reducing it to standard temperature andpressure (STP):

- 23 -

V = [Vo (Ti/P 1) (P2/T 2)]A -[V (Ti/P 1) (Po/T 2)]

where:V = volume of gas produced, STPVo - initial "gas volume" (measured)Ti = standard reference temperature, 273 KP1 - standard reference pressure, 101 kPa - 760 mm HgP2 - current pressure (barometric pressure + manometer reading)T2 - current bath temperature, KPo 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 followingequation was used:

V=(T o/P o) IV2 (PT 2) - V 1(Pl /T1) ]

where:V - volume of gas produced, STPTo - standard reference temperature, 273 KP0 - standard reference pressure, 101 kPa = 760 mm. Hg

P2 - current pressure (barometric pressure + manometer reading)T2 - current bath temperature, KV2 - ullage, corrected for travel of mercuryP I initiel pressure (barometric pressure + manometer reading)Ti = initial temperature on day zeroV 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 evolutionrates 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 declaredreactive and testing was terminated.

2. Any solution that generated more than 7 cm 3 (STP) of gas in 10 days at 25C wasdeclared reactive and testing on it was terminated at that time.

Fortunately, none of the sample solutions "fumed off' as the result of progressive contaminationand 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 withthe HAN solution. Therefore, test tube screening or materials compatibility screening on theDifferential 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. Itappears that for some of the lubricants and greases tested during the current program, DSC orARC 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 ofincompatibility of HAN/TIEAN solutions with metals (References 16, 19 and 20). Traces ofoxygen were expected because the HAN solution would initially typically contain some dissolvedair, although it was attempted to minimize the dissolved air by keeping the freshly concentrated60% 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. Usingargon instead of helium as the carrier gas made it possible to detect small oxygen peaks thatotherwise would have been difficult to separate from the argon peak if helium was used as thecarrier gas. As specified in Par. 3.3.5 of the RFP, only species comprising more than 5% byvolume of the final volume (including the approximately 10 mL ullage argon that was initially inthe 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 particularlytrue for several tests conducted at 338 K (65"C). Gas samples were drawn through the rubberseptum into a gas-tight syringe and immediately injected into a gas chromatograph. Somecontamination due to air intrusion into the needle while moving it the short distance from thetest ampule septum to the GC port was inevitable using this method, in spite of the fact that thesyringe and the needle was purged with sample gas several times prior to injection into the GCport. 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 a1.50 m x 6.2 mm (5 foot by 1/4 inch) Porapak Q column. Several gas chromatographs with boththermoconductivity 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. TheFID 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 ofsynthetic mixtures spiked with known amounts of hydrogen, helium, oxygen, nitrogen, carbondioxide, and nitrous oxide. When using argon as a carrier gas, the response for helium andhydrogen is much higher than for the other gases.

Nitrogen dioxide was not found by either GC or visual observation. Evolution of nitrous oxidefumes is typical for reaction of HAN solutions with materials containing copper. The red-browncolor 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 beenimmediately 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 agas 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 wasremoved from the U-gauge with vacuum suction tube. The ampule was opened at the neck, theHAN solution poured out into a marked sample bottle, the material specimen taken out, rinsedwith distilled water, and examined for visual appearance while still wet. The samples were thendried and weighed. The weighed samples were placed in polyethylene plastic bags, heat-sealedand 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. Nometal ion leaching was analyzed for polymer and grease samples that do not contain inorganicfillers. Some greases and anti-seize compounds contain molybdenum disulfide. In thoseinstances, 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 allowprediction of the rate of metals leaching at different environmental temperatures. In order toderive such equations, the rate of metal solubilizing has to be measured at at least two differenttemperatures. After the rates are obtained, the logarithm of the rate can be plotted in anARRHENIUS graph versus the reciprocal absolute temperature. Extrapolations can be made toother 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-dayduration of the experiment just like the rate of gas evolution is measured by taking daily datapoints. Instead, the metal concentration wa. analyzed only at tho •cginaing and at the end of the30- day immersion experiment. The only other alternative would be to use a very largeexperimental setup of the order of 200 mL liquid where the withdrawal of a 10-mL sample doesnot 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 inductivelycoupled plasma (ICP) emission spectroscopy. Each of these methods has its advantages andlimited 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 theirviscosity 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 themetals to be analyzed by more than one order of magnitude. Dilution may also be advisable forsafety 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 thisrange of metal concentrations, AAS is perfectly adequate and ICP is not needed, The improvedsensitivity of ICP Is only needed in the analysis of leached metals that have a very low rate ofcorrosion. ICP was used mainly for analysis of the received 24% HAN solution to certify that Itdid 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 differentgroups 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 inthe 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 0.01B 13 0.01Ca 0.15 0.01Co 0.12 0.003Cr 0.08 0.006Cu 0.08 0.002Fe 0.1 0.01K 0.5 1.0Li 0.05 0.02Mg 0.01 0.01Mn 0.5 0.002Mo 0.7 0.01Na 0.1 0.02Ni 0.15 0.01Pb 0.2 0.02Si 2 0.04V 2 0.002Zn 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 withdistilled water in a volumetric flask, filled to volume with distilled water and analyzed. If theaaalyte concentration was so high that it was out of the range of the instrument, an aliquot wasdiluted 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-loadedHAN solutions as little as necessary. However, viscosity effects initially prevented reproducibleresults when using HAN concentrations above 30%.

In an effort to quantify viscosity effects on AA nebulizer performance, the time required tomipirate solutions containing different concentrations of HAN into the AA nebulizer weremeasured. The results are shown in Figure 2.7.

-28 -

EFFECT OF VISCOSITY ON ATOMIC ABSORPTION ANALYSISARF 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 AAabsorption 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 viscosityeffects, the standards were made up in 24% HAN solution, and the off-loaded post-test solutionswere 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 toverify its compliance with the procurement specification. Table 3.1 shows the results of the ICPand AAS analysis in comparison to the spec requirements. Sample A was the as-receivedsolution. Sample B was the same solution, but spiked with 200 ppb iron and submitted foranalysis 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 likelycontaminant and one of the contaminant that would be most deleterious to the type of testingthat 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 batchanalysis provided by the supplier, Southwest Analytical Chemicals. The material was meetingthe specification and was therefore accepted for the subsequent concentration step. The highestconcentration of any cation was sodium with 1.27 ppm. There is currently no specification limitfor 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 slightlyabove 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 thedesired nominal HAN concentration.

-31-

Table 3.1: HAN Acceptance Test Results

Property SWAG Spec. SWAG BatchAnalysis AmTnt AmTlet AmTeat RRO RRC

%bywt %bywt loP lop Detectlon byAAS Deteoctonor 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 0.006Ash,ppm -1O <10Sulfate, ppm <10 <10Ohloride, ppm 4

Ag, ppm v L 0.01Al, ppm 40.2 <0.1 0.039 - 0.01As, ppm 0,055 L 0.03B, ppm 0,151 0.235 0.01Be, ppm .<0.1 0.1 0,011 0,011 0.003Be, Ppm L L 0.007Ct, ppm 0,332 0,462 0.01 L 0.15Oa+Mg, ppm .10 0Od, ppm L L 0.002Co. ppm L L 0,003Or, ppm 0,008 0,009 0.006 L 0.08Ou, ppm 0,004 L 0.002 L 0.08Fe, ppm q0.2 0.03 0,053 0.1M' 0,01 L 0.1H9, ppm L L 0.01K. ppm L L IU, ppm L L 0.02Mg, ppm 0,067 0,099 0.01 L 0.01Mn, ppm L L 0.002Mo, ppm L L 0.01Na, ppm 1,24 1.27 0.02NI, ppm L L 0.01 L 0.1P. ppm L L 0.05Pb, ppm L L 0.028, ppm 1.5 1.5 0.1Sb, ppm L L 0.02So, ppm L L 0.03SI, ppm 0,376 0.489 0,04Sn, ppm L L 0.02Sr. ppm 0,004 0,004 0.003T1, ppm L L 0.01TI, ppm L L 0.03Y. ppm L L 0.002V. ppm L L 0,001Zn, ppm 0,054 0,049 0,002

L - at or below detecton limitSamnple B spilked with 200 ppb iron

-32-

The concentrated solution was again analyzed for iron which is the contaminant of primaryconcern. The results are shown in Table 3.2 in comparison to the iron concentration in theoriginal 24% solution. As expected, the iron concentration in the solution increased as the resultof concentrating the solution. However, the ratio of iron increase is the same as that of thevolume decrease. This proves that no additional iron was inadvertently introduced during theconcentrating step. The same was true for magnesium and calcium.

Table 3.2: Analysis of Concentrated RAN Solutions

Contaminant RRC Results (AAS) Ratio Sundstrand ResultsMetal Original Concentrated after: (Reference 18)ppm 24% HAN 60.8% HAN

before 24% HAN 60% HANConcentr.

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 in60.8% 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 werealready pre-assigned to the specimens by other BRL contractors when they arrived at RRC. Itappears the same sample numbers were used by other BRL contractors and It was consideredbest to keep these numbers instead of assigning new numbers. The numbers are not in anuninterrupted sequence. Missing numbers therefore do not represent missing samples. It maybe more convenient to arrange the samples in alphabetical order by material name or groupthem by the type of material. This was done in a database which will be provided to thecontracting agency in computer-readable form. A partial printout of the database showing thematerials samples arranged by material name and grouped by type of material is shown inAppendix A.

Sample numbers 1 through 21 were assigned by RRC to a group of mostly nonmetallicmaterials that was submitted for testing after the program had already started. These materialswere 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 thebottom of the ampule. 9.6% by weight of the metal was lost. A sample of the same material thatwas in test at 65'C (Samplo No. 31 1B) was covered with white and yellowish sludge and actuallygained 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 toquantitatively remove the grease from the ampule after the test and separate it from the HANsolution. For oil samples, only the approximate initial volume was recorded. The surface areaused for the calculations was the internal diameter of the ampule, the interface between the twoimmiscible layers.

After completion of the test, the samples were removed from the solution, rinsed withdistilled water, and dried at room temperature. The plastic samples were not dried to constantweight. 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 % Wtmen No. TRADE NAME Wt., g Wt, g Change

Fmpm firt batch at 298K (25"C0

73 CRES-301 0.1260 0.1261 +0.0'1974 CBES-304 0.2401 0.2402 +0.04275 17-7PH (Mill annnealed) 0.1260 0.1260 +0.000

112 Haynes Alloy 255 5.5528 5.5528 +0.000113 Ferralium Alloy 255 4.6885 4.6883 -0.004120 Tristelle Alloy T5-2 3.7854 3.7855 +0.003134 Stellite #8 on 17-4PH 4.0220 4.0165 -0.137135 Stellite #6 Nicraly on 17-4 4.1025 4.0965 -0.146145 Silicon carbide PS-9242 1.6675 1.6674 -0.006

162A UCAR LW-15 on 17-4 4.8963 4.8963 +0.000163A UCAR LC-111 on 17-4 4.0817 4.0818 +0.002165A Molydag on 17-4 PH 3.3400 3.3388 -0.036166A Nitrided Tribocor 532N 14.0432 14.0432 +0.000179A Ag Plate on 17-4 PH 3.8449 3.8445 -0.010220A Sermatech GC-WC-111 17-4 PH 4.5658 4.5669 +0.024258A Tantalum coating 3.4882 3.4882 +0.000263A CRES-316 3.5930 3.5928 -0.0062C6A Tungsten weld rod 2.3667 2.3658 -0.038268A CRES-302 3.7613 3.7613 +0.000269A CRES-308 4.1095 4.1094 -0.002306A 15-5 PH 3.2069 3.2065 -0.012310A Nickel flash on 17-4 PH 3.7000 3A6975 -0.068326A Al-6061 1.3490 1.3278 -1.572351A 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)

Speci- Initial Final % Wtmen No. TRADE NAME Wt., g Wt, g Change

Pmm second batch at 298 K (25'C

2A Tefzel lining 5.3221 5.3221 +0.0003A Kynar lining 7.0136 7.0094 -0.0605A Carbon bearing 2.4353 2.4857 +2.0706A Ceramic thrust washer 0.9537 0.9537 +0.0007A Superproline 2.2142 2.2140 -0.009

17A Zirconium Zr-702 5.8194 5.8194 +0.00018A Zirconium Zr-705 4.6943 4.6943 +0.00019A Silicon carbide 8.0010 8.0005 -0.006

116A Graphitar Grade 47 1.0025 1.0028 4.0.030126A Grease 3451 2.0376129A Victrex 4800G 0.6932 0.6933 +0.014130A Victrex Gr. 4101GL20 0.7874 0.7876 +0.025146A Arlon 1160 0.7379 0.7379 +0.000147A Arlon 1260 0.8178 0.8178 +0.000156A Paxon BA 50-100 0.4790 0.4790 +0.000158A Aeroshell 17 1.50161A Rulon II 0.7983 0.7990 +0.088259A Polyvinylchloride tubing 1.3076 1.3076 +0.000311A MG 120 Silver solder 0.7536 0.6811 -9.620335A Brayco 783E Micronic 2.1 mL396A Aeroshell 14, 1.50402A 10W-30 Motor oil 2.1 mL412A SAE 50W Motor Oil 2.8 mL446A Galden D20 2.8 mL

-36-

Table 3.3 (Continued) Weight Change of Test Specimens at 298 K and 338 K (25 and 65C)

Speci- Initial Final % Wtmen No. TRADE NAME Wt., g Wt, g Change

From firt batch at 338 K (65"CL

2B Tefzel lining 5.8561 5.8557 -0.0073B Kynar lining 6.8989 6.8895 -0.1365B Carbon bearing 2,*!'67 2.9371 +0.0146B Ceramic thrust washer 0.6465 0.6465 +0.0007B Superproline 2.0844 2.0842 -0.010

17B Zirconium Zr-702 5.8742 5.8741 -0.00218B Zirconium Zr-705 4.7359 4.7359 +0.00019B Silicon carbide 8.5881 8.5878 -0.003

162B UCAR LW-15 on 17-4 4.5640 4.5619 -0.046163B UCAR LC-1H on 17-4 3.6345 3.6342 -0.008165B Molydag on 17-4 PH 3.6912 3.6889 -0.062166B Nitrided Tribocor 532N 13.9628 13.9626 -0.001179B Ag Plate on 17-4 PH 3.6719 3.6714 -0.014220B Sermatech GC-WC-111 on 17-4 4.7933 4.7925 -0.017258B Tantalum coating 3.8550 3.8547 -0.008263B CRES-316 3.5865 3.5863 -0.006266B Tungsten weld rod 2.4004 2.3991 -0.054268B CRES-302 3.9264 3.9260 -0.010269B CRES-308 4.0880 4.0828 -0.127306B 15-5 PH 3.1550 3.1545 -0.016310B Nickel flash on 17-4 PH 3.1184 3.1158 -0.083311B MG 120 Silver solder 0.6432 0.7494 +16.5326B Al-6061 1.3051 1.2777 -2.099351B 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)

Speci- Initial Final % Wtmen No. TRADE NAME Wt., g Wt, g Change

Frm second batch at 338 K (651C

73B CRES-301 0.1261 0.1260 -0.07974B CRES-304 0.2402 0.2401 -0.04275B 17-7 PH (Mill annealed) 0.1260 0.1259 -0.079112B Haynes Alloy 255 5.5527 5.5527 +0.000113B Ferralium Alloy 255 4.6883 4.6882 -0.002116B Graphitar Grade 47 1.0028 1.0037 +0.090120B Tristelle Alloy T5-2 3.7856 3.7855 -0.003126B Grease 3451 2.5800129B Victrex 4800G 0.6933 0.6923 -0.144130B Victrex Gr. 4101GL20 0,7876 0.7868 -0.102134B Stellite #8 on 17-4PH 4.0164 4.0152 -0.030135B Stellite#6 Nicraly on 17-4 4.1025 4.0929 -0.234145B Silicon carbide PS-9242 1.6674 1.6673 -0.006146B Arlon 1160 0.7372 0.7376 +0.054147B Arlon 1260 0.8172 0.8179 +0.086156B Paxon BA 50-100 0.4788 0.4788 +0.000158B Aeroshell 17 3.1531161B Rulon II 0.7990 0.7990 +0.000259B Polyvinylchloride tubing 1.2852 1.2428 -3.299335B Brayco 783E Micronic 2.1 mL396B Aeroshell 14 2.7203402B Kendall 1OW-30 Motor Oil 2.1 mL412B Valvolk.•e SAE 50W Motor Oil 2.8 mL446B Gladen D20 2.8 mL

Note:

Samples No. 73B thru 145B have boen used for a previous test at250C 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. Thereare two different formats for presentation of gas evolution curves:

1. Gas volume reduced to STP conditions (273 K, 101 kPa). The ordinate scale unit ofthese graphs is cm.

2. Gas volume reduced to STP conditions (273 K, 101 kPa) and divided by the surface areaof the specimen C'normalized by the surface area"). The ordinate scale unit of thesegraphs is cm 3/cm 2.

The rationale for using the "normalized" volume of evolved gas (units of cm3 /cm 2) ratherthan the volume itself (units of cm 3 ) should be explained here. In the course of thousands ofsimilar compatibility tests it has been found most useful to divide the amount of gas evolved bythe 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 ionsleached and causing homogeneous decomposition in the fuel is also proportional to the amountof surface area exposed. Quite often, looking at a graph containing data obtained withspecimens of different shapes such as those used during the contract, the observer forgets thefact that the specimens were not of equal shape and may draw wrong conclusions about thecompatibility of a material of construction with the liquid propellant. It was thereforerecommended that the normalized gas volume be plotted in the graphs. The ultimate raw gasvolumes (Unit cm 3 ) are listed in a separate table format in case they are needed for additionaldata reduction and pressure rise predictions at BRL.

For the control (blank) ampule, which does not have a surface area, a fictitious surface areaof 10 cm 2 was assumed which is typical for many of the specimen coupons. The number is alsoeasy for converting from one unit to the other. Use of a surface area of 1.0 cm2 for this purposewould be even more convenient, but would result in excessive distortion and shift of the blankcurves 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 graphsFigure 3.1 through 3.5 are therefore presented in one format only, the format where the directvolume is presented without division by the surface area.

- 39-

5.

• 4-

2-

0

0-

o 1 2 4 6 7 8 91213141516192021 2223262i2930TIME, DAYS iLoT, i

.-HAN/Argon Blank ,.0.CRES-,301 CRES-304S---17-7PH (Mill annnealed) Haynes Alloy 255

S4-

Z 3.

0

• 0. 1 . .

0 1 24 6 78 9121314 1516 192021222326282930

TIME, DAYS ýo 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 30

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 30TIME, 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-

E8

z 6.

4-

2-

~0-

0228 9 124131'4 s11516192021222326282930

TIME, DAYS HýE 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. 1520253TIME, DAYS FHoýsA

--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 didnot 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 agas 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 thesolid square (--i---). On the same graph are then four to five samples, such that no morethan six curves are shown on the same graph. If more than six curves were shown on the samegraph, the graph would get too "busy" and it would be difficult to trace individual curves becausemany of them may fall on top of each other. In spite of tracing no more than six curves in asingle graph, in some of the graphs the curves do still fall on top of each other simply becausethem was not much activity and the curves of the materials specimens are not much differentfrom those of the blank. This "problem" (actually, a non-problem) is only observed in the 25"Cseries. For the 65'C series, the curves diverge sufficiently such that they do not fall on top ofeach other. The 65"C curves are therefore better suited to illustrate the method of datareduction because the curves are more differentiated from each other.

The vertical scale expansion of the graphs was chosen such that it can accommodate themaximum gas evolution of the most incompatible samples, yet show enough detail of thecompatible samples. Although the apparatus can handle gas evolution up to near 20 cm3 , themaximum ordinate scale was chosen at 5 cm 3 for 250C tests and 10 cm 3 for 650C tests, which isa good compromise. Likewise, the optimum ordinate scale extension for the normalized gasevolution 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 ofrecording 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. Thesamples tested were either grossly incompatible and the full scale range of the manometer wasexceeded within less than three days at 338K (65"C) (Samples Al-6061 and SilverSolder MG 120), or the gas evolution within 30 days stayed below 5 cm 3 STP. Therefore the gasvolume graphs use 5 or 10 cm3 as an expanded scale in order to provide a good scale expansionat which differences in gas evolution become discernible. If the full scale of 20 cm 3 had beenused as the ordinate scale on all graphs, the pressure (volume) traces would all fall on top ofeach other.

The sample gas volume curves are identifiod by graph symbols in the legend at the bottomof each graph. The sample names are sometimes truncated because in the case of long samplenames not all letters would fit into the legend box. There are sufficient letters shown to allowthe unique identification of each sample. The sequence of samples is the same as that used inmost 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 assurethat none of the samples would react violently and endanger the adjacent samples when itcooked off.

Most of the first batch of 25 samples at 298 K (25C) showed a slow pressure decreaseduring 30 days as the result of continuing loss of dissolved helium that could not be replaced bypurging with argon. Table 3.4 shows a method how this unwanted drift of the baseline can beeliminated 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 thetest). After this correction, all gas evolution numbers are positive, although most samples exceptAl-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 gasevolution with a sample of SAE 1OW-30 Motor Oil. The tests with the other samples in thesecond batch at 25C were uneventful.

Table 3.5 gives a summary of the same data, in which the samples were arranged and sortedby the rate of gas evolution. The worst cases with the highest rates of gas evolution are shownfirst. None of the samples tested at 298 K reacted vigorously enough that would have precludedtheir testing at 338 K.

3.2.2.2 Comments on Data Reduction

The raw data were not processed through a Statistical Analysis System computer programwhich would tend to smooth the curves. The up-and-down fluctuations in ampule pressurevisible 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 intothe data reduction routine on a spread sheet, there appears to be some hysteresis where theindicated ampule pressure does not Immediately adjust to changes in ambient pressure.Extensive Pacific Ocean weather fronts moving through the area and the accompanying changein barometric pressure were immediately reflected in the shape of the pressure curves. Towardthe end of the testing, when mercury tended to stick to the glass walls, the operator used a cleanglass rod to agitate the mercury column to form a nice round meniscus which could be accuratelyread with the cathetometer independently of the direction in which the mercury had lasttraveled. This Improved the smoothness of the pressure traces. The stirring of the mercury forachieving a clean meniscus was particularly necessary where some black mercury sulfide hadformed 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 closedall-glass flasks where pressure measurements can be taken tuaffected by ambient barometricpressure fluctuations.

Table 3.4: Gas Evolution at 298 K (25C)

FINAL CORRECTED RATESpeci- TRADE VOLUME FOR He LEAK OF GASmen NAME EVQLUTNo. cm3 cm3 cm /da

From first batch at 25 oC

73 CRES-301 -0.24 0.06 0.00274 CRES-304 -0.04 0.26 0.00975 17-7PH (Mill annnealed) 3.16 0.14 0.005

112 Haynes Alloy 255 -0.28 0.02 0.001113 Ferralium Alloy 255 -0.06 0.24 0.008120 Tristelle Alloy T5-2 -0.24 0.06 0.002134 Stellite #8 on 17-4PH -0.16 0.14 0.005135 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 0.007163A UCAR LC-1H on 17-4 -0.09 0.21 0.007165A Molydag on 3.7-4 PH -0.17 0.12 0.004166A Nitrided Tribocor 532N -0.37 -0.08 -0.003179A Ag Plate on 17-4 PH -0.16 0.13 0.004220A Sermatech GC-WC-111 on 17-4 PH -0.18 0.11 0.004258A Tantalum coating -0.34 -0.04 -0.001263A CRES-316 -0.04 0.25 0.008266A Tungsten weld rod 0.01 0.31 0.010268A CRES-302 -0.21 0.09 0.003269A CRES-308 -0.38 -0.08 -0.003306A 15-5 PH -0.36 -0.06 -0.002310A Nickel flash on 17-4 PH -0.22 0.08 0.003326A Al-6061 8.94 9.24 0.308351A Steel MP35N -0.19 0.10 0.003

B1 Empty ampule 0.05 0.35 0.0120 Blank 1 -0.30 0.00 0.000

-47,

TABLE 3.4 (continued) Gas Evolution at 298K (25*C)

FINALSpec. TRADE NAME VOLUME RATENo. cm3 cm3 /day

From second batch at 25 oC

2A Tefzel lining -0.3 -0.0093A Kynar lining -0.4 -0.0135A Carbon bearing -0.2 -0.0076A Ceramic thrust washer 0.0 0.0017A Superproline -0.4 -0.015

17A Zirconium Zr-702 -0.3 -0.01018A Zirconium Zr-705 -0.1 -0.00319A Silicon carbide -0.3 -0.009116 Graphitar Grade 47 -0.1 -0.003

126A Grease 3451 -0.1 -0.004129A Victrex 4800G -0.5 -0.016130A Victrex Gr. 4101GL20 -0.4 -0.013146A Arlon 1160 -0.4 -0.012147A Arlon 1260 -0.3 -0.009156A Paxon. BA 50-100 -0.3 -0.011158A Aeroshell 17 2.3 0.076161A Rulon II -0.3 -0.010259A Polyvinylchloride tubing -0.3 -0.010311A MG 120 Silver solder 2.7 0.091335A Brayco 783E Micronic -0.4 -0.012396A Aeroshell 14 -0.3 -0.009402A 10W-30 Motor Oil 0.3 0.011412A SAE 50W Motor Oil 0.1 0.004446A Galden D20 0.1 0.002

HB2 HAN\Argon Blank -0.2 -0.005Air Air Blank -0.2 -0.008Ar2 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 OnlyGas Gas

Spec. TRADE NAME Volume, EvolutionNo. Ra e

Sample cm3 cm /dayDesignation

326A Al-6061 9.2 0.308311A MG 120 Silver solder 2.7 0.091158A Aeroshell 17 2.3 0.076402A 1OW-30 Motor Oil 0.3 0.011266A Tungsten weld rod 0.3 0.010

74 CRES-304 0.3 0.009135 Stellite #6 on Nicraly on 17-4 0.3 0.009

263A CRES-316 0.2 0.008113 Ferralium Alloy 255 0.2 0.008

163A UCA. LC-1H on 17-4 0.2 0.007162A UCAP. LW-15 on 17-4 0.2 0.007

134 Stellite #8 on 17-4PH 0.1 0.00575 17-7PH (Mill annnealed) 0.1 0.005

179A Ag Plate on 17-4 PH 0.1 0.004165A Molydag on 17-4 PH 0.1 0.004220A Sermatech GC-WC-111 on 17-4 PH 0.1 0.004412A SAE 50W Motor Oil 0.1 0.004351A Steel MP35N 0.1 0.003

145 Silicon carbide PS-9242 0.1 0.003268A CRES-302 0.1 0.003310A 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 toSTP conditions (273 K, 101 kPa). The ordinate scale unit of these graphs is cm 3 .) as well asnormalized gas evolution (Gas volume reduced to SW conditions (273 K, 101 kPa) and dividedby 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 onthe top of the page and the normalized gas evolution graph ("PLOTB") is at the bottom of thepage. If the user wants to compare gas evolution of one given material to the gas evolution inthe control (blank) under the conditions of the experiment, one would look at the volume curvesat the top of the pages (PLOTA). It one war s to compare different materials with differentshapes and surface areas, the curves at the bottom of the page should be used (PLOTB). Ascan 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 3TIME, 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 30TIME, 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-

00 510 i'5 20 25 3

TIME, DAYS PT3A

1.481.2-

0 .4

TIME, DAYS

Figure 3.9: Covnpatibility of Materials in 60.8% HAN at 338 K (65"C)

53

10

1 9

ob

432

10

20r'ME, DAYS 30

Ma k Steel MP35 PLO735A120 Silver *older -*- AAJI 08,2 Nicksl fl4sh or, 17-4 PH -A, 15.5 pH

1.41.2

0.80.60.40.2

5 10....... 0 2s, 11"k,1111IIArgon i k TIMs, C)Ayq 30

MG 120,911ver sjo %Sý881 MP35N PLO7,1368ld*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

#87

TIE DY

55

10

2f 70 6

I5t4

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 30TIME, 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 threedays, aluminum 6061 and silver solder MG120 (Figure 3.10) and Aeroshell 17 (Figure 3.14). Inaddition, one case of accelerating rate of gas evolution was observed with Arlon 1160 (solidtriangle symbols in Figure 3.13).

The ultimate amount of gas evolved is tabulated in Tables 3.6 and 3.7. Table 3.6 gives thegas 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 constructionof liquid propellant guns.

Table 3.6: Gas Evolution at 338 K (65'C)

SMAX. RA ESpec. No. TRADE NAME VOL. DAYS cm /DAY

2B Tefzel lining 1.9 30 0.063B Kynar lining 2.5 30 0.085B Carbon bearing 4.4 30 0.156B Ceramic thrust washer 2.0 30 0.077B Superproline 2.1 30 0.07

17B Zirconium Zr-702 2.3 30 0.0818B Zirconium Zr-705 1.8 30 0.0619B Silicon carbide 2.9 30 0.10

162B UCAR LW-15 on 17-4 9.7 30 0.32163B UCAR LC-1H on 17-4 7.6 30 0.25165B Molydag on 17-4 PH 6.8 30 0.23166B Nitrided Tribocor 532N 1.8 30 0.06179B Ag Plate on 17-4 PH 3.5 30 0.12220B Sermatech GC-WC-111 on 17-4 PH 10.3 30, 0.34258B Tantalum coating 2.9 30 0.10263B CRES-316 2.6 30 0.09266B Tungsten weld rod 4.3 30 0.14268B CMES-302 3.0 30 0.10269B CRES-308 2.4 30 0.08306B 15-5 PH 3.2 30 0.11310B Nickel flash on 17-4 PH 6.1 30 0.20311B MG 120 Silver solder 7.5 1 7.50326B A1-6061 9.9 0.5 19.80351B 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 0.0874B CRES-304 2.1 30 0.0775B 17-7 PH (Mill annealedl 2.5 30 0.08

112B Haynes 255 Alloy 2.8 30 0.09113B Ferralium 255 Alloy 2.3 30 0.08116B Graphitar Grade 47 2.3 30 0.08120B Tristelle P.loy T5-2 2.2 30 0.07126B Grease 3451 2.4 30 0.08129B Victrex 4800G 2.6 30 0.09130B Victrex Gr. 4101GL20 2.6 30 0.09134B Stellite #8 on 17-4PH 3.7 30 0.12135B Stellite #6 on Nicraly on 17-4 4.3 30 0.14145B Silicon carbide PS-9242 2.6 30 0.09146B Arlon 1160 15.6 28 0.56147B Arlon 1260 3.2 30 0.11156B Paxon BA 50-100 2.1 30 0.07158B Aeroshell 17 4.2 4 1.05I.CIB Rulon II 2.4 30 0.08259B PVC Tubing 3.9 30 0.13335B Brayco 783n Micronic 4.0 30 0.13396B Aeroshel] 14 7.9 30 0.261)2B Kenaall IOW-30 Motor Oil -0.2 30 -0.01412B ValvoV..... SAE 50W Motor Oil -0.2 30 -0.01446B 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 ontop of the table.

VOLUME DAYS RATE,Specimen No. TRADE NAME cm3, STP cm3/day

326B Al-6061 9.9 0.5 19.80311B MG 120 Silver solder 7.5 1 7.50158B Aeroshell 17 4.2 4 1.05146B Arlon 1160 15.6 28 0.56220B Sermatech GC-WC-111 on 17-4 PH 10.3 30 0.34162B UCAR LW-15 on 17-4 9.7 30 0.32396B Aeroshell 14 7.9 30 0.26163B UCAR LC-1H on 17-4 7.6 30 0.25165B Molydag on 17-4 PH 6.8 30 0.23310B Nickel flash on 17-4 PH 6.1 30 0.20

5B Carbon bearing 4.4 30 0.15135B Stellite #6 on Nicraly on 17-4 4.3 30 0.14266B Tungsten weld rod 4.3 30 0.14335B Brayco 783E Micronic 4.0 30 0.13259B PVC Tubing 3.9 30 0.13134B Stellite #8 on 17-4PH 3.7 30 0.12179B Ag Plate on 17-4 PH 3.5 30 0.12351B Steel MP35N 3.4 30 0.11147B Arlon 1260 3.2 30 0.11306B 15-5 PH 3.2 30 0.11268B CRES-302 3.0 30 0.10258B Tantalum coating 2.9 30 0.10

19B Silicon carbide 2.9 30 0.10112B Haynes 255 Alloy 2.8 30 0.09129B Victrex 4800G 2.6 30 0.09145B Silicon carbide PS-9242 2.6 30 0.09263B CRES-316 2.6 30 0.09130B 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 seriesof tests to gas evolution rate data reported by other investigators (Reference 17). As can be seenfrom the data in Table 3.8, the rate of gas evolution at 338 K (65'C) was somewhat higher in thecurrent test, while the gas evolution rate at 298K (25"C) was too small to be measured in eitherstudy. This can be due to differences in experimental technique or in the purity of the rawmaterial used for the tests. Also, passivation of the surface of the glass ampules by immersingthem in HAN solution prior to the test should be considered. Although borosilicate glass infairly resistant to acid attack, some materials may leach from the glass that will catalyze HANdecomposition. If the same ampules were used for a second time, the gas evolution rate mightbe 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 solutionsremoved from metals compatibility tests had to analyzed for metals. The materials selected werethose where either gas evolution or discoloration of the solution had occurred. The oneexception referred to above is that of a lubricant, Aeroshell 17 (Sample No. 158B) which causedhigh rates of gas evolution usually not expected from a pure hydrocarbon grease. AAS analysisshowed that substantial amounts of molybdenum were leached from Aeroshell 17. It would be ofinterest to obtain the gross composition of this lubricant from the manufacturer to identify theincompatible 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 CVfý 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 ý 0V VV V vvv V

LM 0

0c0o co0 nma 0 00 000m00n 0

N 0- MU 0W1)I - 0 4.) ; ýC C ýCI!!m0 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 in0mV N V m1414e

Ný 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 thesolutions were still very viscous and aspirated into the AA more slowly than the standards madeup in clear water. The standards were made up in 24% HAN solution with the same viscosity tocompensate for viscosity effects on sample aspiration flow rate into the AAS. A few post-testsamples of off-loaded HAN solutions were analyzed for HAN-assay, but, within the accuracy ofthe manual titration method, the HAN-content was unchanged from the initial HANconcentration.

3.2.4 Gas Analysis by Gas Chromatography

Analysis of the gas space was performed with a gas chromatograph with athermoconductivity detector using argon instead of helium as a carrier gas. Two differentcolumns are being used: a 5-ft. X 1/4-in. Porapak-Q column to separate permanent gases andnitrous oxide, and a 6-ft. X 1/4-in. Linde Molecular Sieve 5A column for separation ofpermanent gases. Table 3.10 is a summary of the gas analysis results obtained. The presence ofhelium in the post-test gas analyses of the first batch tested at 25'C is an artifact. The ampuleshad been initially filled with helium, but the helium in the gas space was replaced with argonafter 11 days with the intent of replacing all the helium. At that time, the liquid unfortunatelywas already saturated with helium and the dissolved helium could not be totally removed bysimply purging the gas space with argon. The presence of residual helium which had come out ofsolution did not adversely affect the compatibility results reported here. If the helium in Table3.10 is ignored, the corrected gas compositions printed in bold type in the line below applyinstead. The response factor of the CC to helium is higher than that for the other gases whenargon 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* H2 02 N2 CO2 N2 0

First Batch at 25 oCS=- 3 U 27.4 16.5 53.9 2.2

22.7 74.3 3.074A CRES-304 61.9 12.0 26.0

31.6 68.4134A Stellite #8 on 17-4PH 54.3 11.3 27.9 6.4

24.8 61.1 14.1135A Stellite #6 on Nicraly 55.3 9.7 27.0 7.9

on 17-4 21.7 60.5 17.7162A "CAR LW-15 on 17-4 36.0 10.6 53.4

16.6 84.4326A Al-6061 4.7 14.2 0.9 12.1 68.0

Second Batch at 25 oC158A Aeroshe-T T •- 4.1 13.2 75.6 7.1311A MG 120 Silver solder 6.1 21.9 72.0396A Aeroshell 14 19.5 68.2 12.3402A 1OW-30 Motor Oil 10.2 32.2 57.6412A SAE 5OW Motor Oil 15.5 53.4 31.1HB2 HAN\Argon Blank 29.9 70.1Ar Argon Blank 25.2 74.8

First Batch at 65 oC5B Carb-n-eiriRg 2.6 40.7 2.2 54.6162B UCAR LW-15 on 17-4 2.0 32.5 2.8 62.7163B UCAR LC-IH on 17-4 1.3 39.3 T 59.3165B Molydag on 17-4 PH 1.0 41.8 T 57.2220B Sermatech GC-WC-111 on 17-4 PH 2.0 35.9 1.1 61.0266B Tungsten weld rod 2.4 60.3 T 37.3310B Nickel flash on 17-4 PH 1.4 33.6 T 64.9311B MG 120 Silver solder 1.3 20.1 78.6326B Al-6061 5.1 0.2 31.3 63.3HB3 HAN\Argon Blank 4.8 76.2 19.0Ar3 Argon 31.2 68.8T - 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 N2 C02 N2 0

Second Batch at 65 oC

73B CRES-301 4.8 72.5 22.7116B Graphitar Grade 47 T 73.1 26.9120B Tristelle Alloy T5-2 5.3 73.6 21.1126B Grease 3451 3.8 69.9 26.3129B Victrex 4800G 3.7 66.2 30.1130B Victrex Gr. 4101GL20 3.1 58.6 38.3134B Stellite #8 on 17-4PH 2.6 51.7 45.7135B Stellite #6 on Nicraly on 17-4 1.9 50.4 47.6145B Silicon carbide PS-9242 4.0 69.9 26.2146B Arlon 1160 0.5 13.3 0.9 85.3147B Arlon 1260 2.9 49.9 47,2156B Paxon BA 50-100 3.7 68.5 27.7158B Aeroshell 17 T 21.9 28.7 4-.4161B Rulon II 3.7 68.7 27.6259B Polyvinylchloride tubing 2.7 61.3 2.3 33.7335B Brayco 783E Micronic T 41.6 4.0 54.4396B Aeroshell 14 T 85.7 5.3 9.0446B Gladen D20 4.1 73.1 22.8HB4 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 thecompatibility test samples: The incompatibility of aluminum alloys with HAN solution resultedin the formation of 5.1 and 14.2% hydrogen. Hydrogen formation had not been previouslyreported in the literature. However, hydrogen formation would not be surprising since thereaction of PAN solutions with aluminum is similar to reactions of metals with acids. With bothaluminum samples tested here, no oxygen was formed by HAN decomposition and whateverlittle 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 withHAN 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 sample402A (1OW-30 Motor Oil). HAN appears to be a strong oxidizer comparable to concentratednitric acid and can effectively destroy hydrocarbon bonds in oils and greases. It may be difficultto 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 eithertemperature.

-67 -

All gas samples removed from the test at 338 K (650 C), even the blank control without amaterial sample in it, had very high nitrous oxide concentrations from HAN decomposition. Thehighest nitrous oxide concentration, 85.3%, was observed with Arlon 1160. Arlon 1160 was alsoruled 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 ofnitrogen and oxygen it is not possible to differentiate between air introduced as an artifact duringgas sampling and nitrogen and oxygen formed as the result of HAN decomposition. Isotopelabeling 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 itsoxygen 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 andwould 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 at65*C (Sample No, 412B and 402B), it was noted that the m•rcury on the ampule side of the U-gauge manometer was gradually turning black from a crust of black material forming on themercury that made it very difficult to read the meniscus. Also, black material adhered to thewall of the tubing. At the completion of the test, a "rotten egg" odor typical for hydrogen sulfidecould be noted when removing the septum. When testing the residual gas in the ampule withmoist lead acetate paper (a reagent for hydrogen sulfide), it promptly turned black in Sample412B (Valvoline SAE SOW). The paper in sample 402B did not turn black, but the odor wasnevertheless distinct. It appears that some motor oils have sulfur-containing additives(antioxidants) which become reduced by hydroxylamine (hydroxylammonium ion) to hydrogensulfide.

What makes this observation important is that the same smelly samples also had the lowestrate of gas evolution of all other lubricant samples at 65C, and no free nitrous oxide could befound with the 25"C tests. However, the 250C did show formation of carbon dioxide. Some ofthe oil additives may act as scavengers for ions which otherwise would promote decomposition ofHAN solutions.

- 68 -

3.3 KINETIC ANALYSIS OF DECOMPOSITION RATE DATA

The objective of the current study was to determine rates of propellant decomposition andrates of corrosion as a function of temperature and time. The two test temperatures chosenunfortunately were not suitable for an extended kinetic rate analysis of the data. If kinetic ratestudies 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 longerstorage durations using fundamental kinetic rate laws such as the ARRHENIUS, relationship. foractivation energy. In order to be able to extrapolate in an ARRHENIUS plot where thelogarithm of the kinetic rate is plotted against the reciprocal absolute temperature, one has tohave 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 gasevolution and metals leaching. Those materials that did evolve gas and leached metals at roomtemperature 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 ratedata 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 suitedbecause the materials are totally incompatible, the logarithm of the gas evolution rate of samplesAl-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 evolvingprocess (I. e. the slope of the straight lines) was very similar. Similar curves should be obtainedby testhig all compatible materials at two or even three and four different temperatures wellabove 298 K. Such curves then are useful for prediciting 10-year gas evolution during storage atambient temperature.

Table 3.11: Kinetic Rate Analysis of Gas Evolution Rates

Absolute Reciprocal Rate inSample Temperature Temperature RateDesignation K I/K cm3/day

Al-6061 298 0.00336 0.308 -1.1777Al-6061 338 0.00296 19.80 2.9857Silver Solder 298 0.00336 0.091 -2.3969Silver Solder 338 0.00296 7.50 2.0149

-69-

ARRHENIUS PLOT OF GAS EVOLUTION RATE

4-31338 K....... ............

• -1............... . . .... ....... ..............

4 .... .....

-07

M 2 " - .. ..... ..

-410.0028 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 orLGP-1846. It is recommended to place those materials that are shown to be compatible basedon the short-term tests described here into a future long-term storage test with continuousmeasurement of gas evolution and periodical analysis for leached metals. Other samples shouldbe tested in the stressed state. Welded samples and galvancic couples of dissimilar metals needto be tested also.

A test method should be developed that allows the testing of oversize specimens that are toolarge 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 ofthis 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 forLiquid 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 PlasmaSpectroscopy in Liquid Propellant Analysis, 1986 JANNAF Propellant Char. SubcommitteeMtg., CPIA Publ. 459 (Nov 1986) pp. 225-231, DoD Limited.

4. Klein, N., and C. R. Wellman: Reactions Involving tho Thermal Stability of AqueousMonopropollants, BRL Report No. 1876, U. S. Army Ballistic Research Laboratory, AberdeenProving Ground, MD (May 1976).

5. Messina, N. A., and N. Klein: Thermal Decomposition Studies of HAN-based LiquidMonopropellants, 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 PropellantsContaining HAN, in: Fourth Annual Conference on HAN-Based Liquid Propellants, BRLSpecial Publications BRL-SP-77, Vol.I, p. 273-283 (May 1989).

7. Klein, N.: Preparation and Characterization of Several Liquid Propellants, TechnicalReport ARBRL-TR-02471, U. S. Army ARRADCOM Ballistic Research Laboratory, AberdeenProving Ground, MD (Feb 1983).

8. Decker, M. M., et al.: Presence and Removal of Trace Transition Metal Ions inHydroxylammonium Nitrate (HAN) Solutions, CRDC-TR-84062, Chemical Research andDevelopment Center, Aberdeen Proving Ground, MD (Dec 1984),

9. Ward, 1. R., and M. M. Decker. Presence and Removal of Trace Transition Metal Ionsin Hydroxylammonium Nitrate (HAN) Solutions, CRDC-TR-8501, Chemical Research andDevelopment 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 InternationaleJahrestagung 1984, pp. 167-180 (1984).

12. Backof, E.: Selection Criteria for Metals and Plastics as Construction Materials forLong-Term Pressure-Testing Apparatus in Liquid Propellants, in: Fourth Annual Conference onHAN-Based Liquid Propellants, BRL Special Publications BRL-SP-77, Vol.I, p. 285-308 (May1989).

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 above15. Letter by Thiokol Elkton Div. to BRL dated 7 February 199016. 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 HydroxylammoniumNitrate, 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, ContractDAAD05-86-C-0168, Appendix B (Aug 1987).

20. Briles, 0. M., and L. S. Joesten: Compatibility Study with 60% HydroxylammoniumNitrate (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, Draftof 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 SpecialPublication BRL-SP-73 (March 1988), AD-A194679.

25. Backof, E.: Selection Criteria for Metals and Plastics as Construction Materials forLong-Term Pressure-Testing Apparatus in Liquid Propellants, in: Fourth Annual Conference onHAN-Based Liquid Propellants, BRL Special Publications BRL-SP-77, Vol.1, p. 285-308 (May1989).

26. Standard Practice for Static Immersion Testing of Unstressed Materials in NitrogenTetroxide, 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-BasedLiquid 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 RocketPropellants, Fraunhofer Institut fuer Treib- und Explosivstoffe, Pfinztal-Berghausen, WestGermany, Interim Reports No. 1, 2, and 3 (1987); AD-A190686, AD-A190687, and AD-A190688.

- 73 -

INIVTONALLY LM BLANK.

74

-4

Appendix A

SAMPLE PRINTOUT FROM H,.N COMPATIBILITY DATA BASE

-,75.

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No of No ofQqka Organization capie QrOnnk9n

Office of the Secretary of Defense 1 DirectorOUSD(A) US Army Aviation ResearchDirector, Live Fire Testing and Technology ActivityATTN: James F. O'Bryon Ames Research CenterWashington, DC 20301-3110 Moffett Field, CA 94035-1099

2 Administrator I CommanderDefense Technical Info Center US Army Missile CommandAMTN: DTIC-DDA ATrN: AMSMI-RD-CS-R (DOC)Cameron Station Redstone Arsenal, AL 35898-5010Alexandria, VA 22304-6145

1 CommanderHQDA (SARD.TR) US Army Tank-Automotive CommandWASH DC 20310-0001 AMTN: AMSTA-TSL (Technical Library)

Warren, MI 48397-5000CommanderUS Army Materiel Command 1 DirectorATTN: AMCDRA-ST US Army TRADOC Analysis Command5001 Eisenhower Avenue ATTN: ATAA.SLAlexandria, VA 22333-0001 White Sands Missile Range, NM 88002-5502

Commander (CW. *MY) 1 CommandantUS Army Laboratory Command US Army Infantry SchoolATTN: AMSLC-DL ATMN: ATSH-CD (Security Mgr.)Adelphl, MD 20783-1145 Fort Benning, GA 31905-5660

2 Commander (umiahi. s.y) I CommandantUS Army, ARDEC US Army Infantry SchoolATMN: SMCAR-IMI.I ATTN: ATSH-CD-CSO-ORPicatinny Arsenal, NJ 07806-5000 Fort Benning, GA 31905-5660

2 Commander 1 Air Force Armament LaboratoryUS Arnmy, ARDEC ATTN: AFATL/DLODLATTN: SMCAR-TDC Eglin AFB, FL 32542-5000Picatinny Arsenal, NJ 07806-5000

Aberdeen Proving GroundDirectorBenet Weapons Laboratory 2 Dir, USAMSAAUS Army, ARDEC ATTN: AMXSY-DATTN: SMCAR-CCB.TL AMXSY-MP, H. CohenWatervliet, NY 12189-4050 1 Cdr, USATECOM

AMrN: AMSTE-TDCommander 3 Cdr, CRDEC, AMCCOMUS Army Armament, Munitions AMTN: SMCCR-RSP-A

and Chemical Command SMCCR-MUATTN: SMCAR-ESP-L SMCCR-MSIRock Island, IL 61299-500 Dir, VLAMO

ATI: AMSLC.VL.DCommanderUS Army Aviation Systems CommandATTN: AMSAV-DACL4300 Goodfellow Blvd.SL Louis, MO 63120-1798

77

No. of No. ofCo±ie OraiQto OR6 ranizatio

Cmdr, US Army Armament, Rsch, I CommanderDevelopment & Engr Center US Army Biomedical Research and

ATTN: Develpment LabSlCAR-TDC (2 COPIES) ATTN: SCRD-UBG-0, MAJ SmartSliCAR-AEE-B, D. Downs Fort DetrickSMCAR-AEE-BR, W. Seals Frederick, MD 21701-5010

A. BeardellPicatinny Arsenal, NJ07806-5000 1 Commander

Naval Ordnance Station3 Commander ATTN: P. Skahan, Code 2810G

US Army Armament, Rach, Indian Head, MD 20640Development & Engr Center

ATTN: SMCAR-FSS-DH, Bldg 94 1 AFAL/RKPAJ. Feneck ATTN: CPT M. HusbandR. Kopmann Edwards AFB, CA 93523-5000J. Irizarry

Picatinny Arsenal, NJ 2 Director07806-5000 Jet Propulsion Lab

ATTN: Tech Library. Director Dave Maynard

Benet Weapons Laboratory 4800 Oak Grove DriveUS Army Armament, Rich, Pasadena, CA 91109

Development & Engr CenterATTN: SMCAR-CCB, Frankel 1 Sandia National LaboratoryWatervliet, NY 12189-4050 ATTN: Dr. Steve Vosen

Combustion Research Facility3 Commander Livermore, CA 94550

US Army Belvoir RD&E CtrATTN: STRBE-WC Calspan Corporation

Tech Library (Vault) B-315 ATTN: Tech LibrarySTRBE-VU, H. Feuer PO Box 400STRBE-VL, G. Farmer Buffalo, NY 14225

Fort Belvoir, VA 22060-56062 General Electric Ord Sys Div

2 Commander ATTN: J. Mandzy, OP43-220US Army Research Office J. ScudiereATTN. SLCRO-CB, D. Squires 100 Plastics Avenue

SLCRO-E, D. Mann Pittsfield, MA 01201-3698P.O. Box 12211Research Triangle Park, NC 1 General Electric Company

27709..2211 Armament Systems DepartmentATTN: D. MaherBurlington, VT 05401

78

No. of No. of

1 IITRI 2 Thiokol CorporationATTN: Library Tactical Operations10. W. 35th St Elkton DivisionChicago, IL 60616 ATTN: R. Biddle

R. BrasfieldOlin Chemicals Research P.O. Box 241ATTN: David Gavin Elkton, MD 21921-0241P0 Box 586Chesire, CT 06410-0586 2 Southwest Research Institute

ATTN: Bill HerreraOlin Corporation Nollie SwynertonATTN: Dr. J. Leistra 6220 Culebra Road24 Science Park San Antonio, TX 78284New Haven, CT 06511

2 GeoCenters, Inc4 Olin Corporation ATTN: Gerry Doyle

ATTN: Ken Woodard Stanley GriffDave Cawfield 762 Route 15 SouthSanders Moore Lake Hopatcong, NJ 07866Ronald Dotson

PO Box 248 2 DirectorCharleston, TN 37310 CPIA

The Johns Hopkins Univ.5 Olin Rocket Research ATTN: T. Christian

P.O. Box 97009 Tech LibraryATTN: Dr. E. Schmidt Johns Hopkins RoadRedmond, WA 98073-9709 Laurel, MD 20707

2 PEI Associates, Inc. 1 U. of MD at College Park11499 Chester Road ATTN: Professor Franz KaslerATTN: M.L. Taylor Department of Chemistry

M.A. Dosani College Park, MD 20742Cincinnati, OH 45246

1 U. of Missouri at ColumbiaSundstrand Aviation ATTN: Professor R. ThompsonOperations Department of Chemistry

ATTN: Mr. Owen Briles Columbia, MO 65211PO Box 7202Rockford, IL 61125 1 Princeton Combustion Rsch

Laboratories, Inc.

1 Veritay Technology, Inc. ATTN: N.A. MessinaATTN: E.B. Fisher 4275 US Highway One North4845 Millersport Highway Monmouth Junction, NJ 08852P0 Box 305 1 University of DelawareEast Amherst, NY 14051-0305 Dept of Chemistry

ATTN: Professor Thomas BrillNewark, DE 19711

79

, I..

No. of

Dr. Hans-Juergen FrieskeDynamit NobelWaitherstrasse 805000 Cologne 80 FRG

2 George CookPeter HenningRARDEFt. HalsteadSevenoaks, Kent TN14 7BTEngland

2 Paul BunyanSally WestlakeRARDEPowder Hill LaneWaltham AbbeyEssex, England 1 AX

2 Fraunhofer-Institut fuerTreib-und Explosivutoffe

ATTN: Dr..R. HansonDr. F. Volk

D-7507 Pfinztal-BerghausenFRO

1 Dr. H. SchmidtBundesministerium der

VortoidigiongRue V11-4Postfach 13285300 Bonn 1FRG

I. G. KlingenbergFraunhofer-Institut fuer

Kurzzoitdynamik Ernst-Mach-Institut

Abteilung fuer BallistikHauptstrasue 18D-7858 Wail am RheinFRG

80

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DEPARTMENT OF THE ARMY IIlMCroow N-0I I' POSAGEU.S. Aimy Ballistic Ruaoch'Labo,4Wry 'I• " "' NECEMARYATTN: SLCBR-DD-T ,IF MAIIAbrdoen Provinl Ground, MD 2101 -5D6 IN THE

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