the fourth annual conference on han-based liquid … · 2011-05-13 · special publications...

SPECIAL PUBLICATIONS BRL-SýP- 7

SNti

THE FOURTH ANNUAL CONFERENCEON HAN-BASED LIQUID PROPELLANTS

VOLUME I

N

MAY 1989,, JUO 1

APPROVED FOR PUBLIC RELEASE; DISTRIBUTION UNLIMITED.

U.S. ARMY LABORATORY COMMAND

BALUSTIC RESEARCH LABORATORYBEFI N PROV!NG GROUND, MARYLAND

Reproduced FromBest Available Copy

DESTRUCTION NOTICE

)est roy t2is report when it Is no longer needed. DO MY -rr- t to t-rigin'tor.

" •ditional copies of this report may be obtained from the National Tedl-nicalInformation Service, U.S, Departrent of Ccxrnerce, Springfield, \VA 221bi.

The findings of this report are not to be construed as an official Departmentof the Army position, unless so designated by other authorized docunmnts.

The use of trade names or -manufacturers' nales in this rewort dces not con-st.itute indorseient of any carmercial product.

Reproduced FromBest Available Copy

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4. PERFORM!NG OFGANIZATION REPORT NUMBER(S) S MONITORING ORGANIZATION REPORT NUMBER(S)

BRL-SP-77 , VOLUME I

6a. NAME OF PERFORMING ORGANIZATION 6b. OFFICE SYMBOL 7a. NAME OF MONITORING ORGANIZATION(If applicable)

US Armiy Ballistic Rsch Lab SLCBR-IB6c. ADDRESS (City, State, and ZIP Code) 7b. ADDRESS (City, State, and ZIP Code)

Aberdeen Proving Ground, MD 21005-5066

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11. TITLE (Include Security Classification)THE FOURTH ANNUAL CONFERENCE ON HAN-BASED LIQUID PROPELLANTS (VOLUME I)

12- PERSONAL AUTHOR(S)(editor) Josephine 0. Wojciechowski

13a. TYPE OF REPORT 13b. TIME COVERED 14. DATE OF REPORT (Year, Month, Day) 15 PAGE COUNT

SP FROM TO

16. SUPPLEMENTARY NUTATION

17. COSATI CODES 18 SUBJECT TERMS (Continue on reverse if necessary and identify by block number)

FIELD GROUP SUB-GROUP Liquid Propel!ant HAN Compatibility Physical PropertiesHydroxylammonium Nitrate TEAN ProductionTriethanolammonium Nitrate Combustion Stability

19. ABSTRACT (Continue on reverse if necessary and identify by block number)

"This report contains the abstracts arid viewgraphs of the pipers presented at the BRL's Fourth AnnualC(mference on I IAN-Based Liquid Propellants.

20 7oST7--7, ;20N /AVAILABILITY OF ABSTRACT 21 ABStRACI SEC.URITY CLASSIFICATION

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Josephin. Q, Wojciechowski (3011 278--6160 1 SI.,CBR-IB-13DO Form 1473, JUN 86 Previous editions are obsolete SECURITY CLASSIFICATION OF THIS PAGE

TABLE OF CONTENTS

, NTRODUCTION------------------------ 1

LIQUID PROPELLANT FAIL-SAFE CRITERIA PROGRAM9 \Stanley GriffaTid Gerald Doyle -- ----------------------- -- "- ----------- 3

AN OVERVIEW OF THE THERMAL REACTIVITY OF SUBSTITUTED AMMONIUMNITRATES' V.R. Pai Verneker, S.C. Deevi and C.K. Law - - - 24

IMPACT SENSITIVITY OF HAN-BASED LIQUID MONOPROPELLANTS;I. Stobie, B.D. Bensinger and J.D. Knapton - --------- 40

QUANTITATIVE ANALYSIS OF HAN-BASED LIQUID PROPELLANTS.Dr. H.J. de Greiff -.-.----------------------- ----- ----- 53

AN OVERVIEW OF THE U.K. APPROACH TO THE CHARACTERIZATION ANDCLASSIFICATION OF HAN-BASED LIQUID PROPELLANT LP101.S. Westlake --..---- ------------ 64

POSSIBLE TEST METHODS TO STUDY THE THERMAL STABILITY OFHYDROXYLAMMONIUM NITRATE BASED LIQUID GUN PROPELLANTS5 P.F.Bunyan andS..Westlake--- -- 74

HYDRODYNAMIC THEORY OF LIQUID PROPELLANT DYNAMICS;\ J.W. Hausand F. Chung-Yau - ------------------------------- 102

IONIC ASPECTS OF THE DECOMPOSITION OF HAN SOLUTION/.W.S. Koski -.-..... . - 115

REACTION KINETICS OF HAN, TEAN AND WATER MIXTURES USING APERSONAL COMPUTERJ A.K. Macpherson and A.J. Bracuti - - - - 116

ELECTRICAL IGNITION OF HAN-BASED LIQUID PROPELLANTS: G.Klingenberg, H.J. Frieske and H. Rockstroh ...... - -117

THE BURNING RATE OF JiAb-BASED LIQUID PROPELLANTS: THE EFFECTSOF HAN CONCENTRATION D0i BURIJING RATES ,S'. Vosen --------- 131

STUDY OF THERMAL DIFFUSIVE-REACTIVE INSTABILITY IN LIQUID -PROPELLANTS: THE EFFECTS OF SURFACE TENSION AND GRAVITY. R.C.Armstrong and S.B. Margolis ----------------------------- 154

THE RESPONSE OF AN LP TO HEATING AT HIGH PRESSURE. orR.A. Beyer ---------------------------------------------- 155

By

Dtstribution/

Preceding Page Blank Avali bility Codei . . Avail and/o-r

Dist Specaln

TABLE OF CONTENTS (Cont.)

EQUATION OF STATE ANP THERMODYNAMIC PROPERTIES OF THE HAN-TEAN1/"/WATER SYSTEM. J. Frankel, W. Scholz and J.F. Cox 179

"•PHYSICAL PROPERTIES OF LIQUID PROPELLANTS: MEASURENENTS OFSHEAR VISCOSITY, VOLUME VISCOSITY AND DENSITY;, J. Schroeder,C.S. Choi and Y.T. Lee ------------------- --------------- 195

'THE SOLUBILITY OF GASES UNDER PRESSURE IN LIQUID PROPELLANTS-S. Murad and P. Ravi ------------------------------------- 222

;COMPATIBILITY OF ELASTOMERIC MATERIALS WITH HAN-BASED LIQUIDPROPELLANT 1846. G. Rodriguez, H.O. Feuer and A.R. Teets - 245

/NTHE INFLUENCE OF METAL IONS ON THE STABILITY OF LIQUID GUNPROPELLANTS CONTAINING HAN. Dr. R. Hansen ---------------- 273

SELECTION CRITERIA FOR METALS AND PLASTICS AS CONSTRUCTIONMATERIALS FOR LONG TERM PRESSURE-TESTING APPARATUS ON LIQUIDPROPELLANTS (LPS). Dr. E. Backof ------------------------- 284

COMPATIBILITY STUDY WITH 60% HAN SOLUTION. 0. Briles andL.S. Joesten --------------------------------------------- 309

iv

INTRODUCTION

"The US Army is currently investigating the use of lii•ri'dpropellants kLPs) in large and medium caliber guns. These LPsare characterized by the use of hydroxylammonium nitrate (HAN) astheir oxidizer. On 30 August - 1 September 1988, the FourthAnnual LP Conference on HAN-Based Liquid Propellant Structure an.4Properties was held at the BRL.with Dr. Walter F. Morrison asGeneral Chairman..<-The papers presented at this highly successful

2•conference were given by people from academia, industry, andother government agencies.

This report is a compilation of the abstracts and viewgraphsof these papers where available. The final program is includedin appendix A and a list of attendees in appendix B.

\- .\

LIQUID PROPELLANT FAIL-SAFE CRITERIA PROGRAM

The use of Liquid Propellant (LP) as a replacement for solid propellants in someapplications -requires complete and extensive characterization of these new propellantsystems in order to establish fail-safe criteria. The fail-safe criteria program is designedto provide information to relate propellant composition and condition with performance.Prolonged aging effects on LP will be determined in order to recommend storagecontainers for long-term storage of LP. Analytical methodology is currently beingestablished to monitor the LP during storage as well as during production to providenecessary and reasonable specifications for LP.

The phase of the program which is now in progress has dealt with (1) reviewing.recommending and developing applicable analytical methods for monitoring the LPbefore, during and after storage; (2) determining physical properties requircd for thisstudy; (3) initiating and monitoring pressure-time studies as a function of temperature,composition, impurities and ullage; (4) utilization of the pressu-re-time studies todetermine degradation products, rates of pressure build-up and rates of formation ofdegradation products: (5) establishing which components or degradation products arethe best indicators of propellant utility or instability; (6) determining which impurities ordegradation products or combinations are most detrimental to the propellant stability and(7) establishing long-term storage container design based on pressure-time study data.

Preceding Page Blank

3

LIQUID PROPELLANT FAIL-SAFECRITERIA PROGRAM

STANLEY GRIFF

GERALD DOYLE

GEO-CENTERS, INC.LAKE HOPATCONG, N.J.

WILLIAM SEALSARDEC, PICATINNY ARSENAL

DOVER, N.J.

AUGUST 1988

OBJECTIVES

1. DLIVELOP ANALYTICAL METHODOLOGY FOR

MONITORING THE LP.

2. DETERMINATION OF PRESSURE BUILD-UP FOR

STORAGE CONTAINER DESIGN.

3. SELECTION OF VARIABLES TO SUBJECT THE LPTO DURING STORAGE.

4. COORDINATION OF BALLISTICS AND RELATED

TESTING.

GOALS

1. LIFETIME AND SAFETY FACTORS FOR LP UNDER

STORAGE CONDITIONS.

2. EFFECT OF CONTAMINANTS AND OTHER

VARIABLES.

3. ESTABLISH SPECIFICATIONS FOR LP.

4. ESTABLISH RATES, KINETICS AND

DECOMPOSITION MECHANISMS.

5. FLAGS FOR ESTABLISHING CONDITION OF LP.

6. ANALYTICAL METHODOLOGY FOR MONITORING

LP DURING STORAGE.

7. APPLICABILITY OF ANALYTICAL METHODOLOGY

FOR QC OF LP DURING PRODUCTION.

8. EFFECT OF LP COMPOSITION ON BALLISTICS.

LIQUID GUN PROPELLANT COMPOSITION

THE LIQUID PROPELLANT (LP) FORMULATIONSSELECTED FOR EVALUATION ON THE FAIL-SAFECRITERIA PROGRAM WERE LP 1845 AND LP 1846.TYPICAL COMPOSITIONS OF THESE LP'S ARE LISTEDBELOW:

LP1845 LP1846

HYDROXYLAMMONIUM NITRATE (HAN) 63 61

TRIETHANOLAMMONIUM NITRATE (TEAN) 20 19

WATER 17 20

ANALYTICAL MONITORING TECHNIQUES

Component Recommended

HAN IC-sensitive to small variations

TEAN IC-sensitive to small variations

H20 Titration

Nitric acid Titration

Metals IC-all TM+ 2 in one run; TM+ 3

method being coordinated withWaters

AN, EAN, DEAN IC

Gas Phase degradation GC-Two column methodproducts

Liquid Phase LC-method beingdegradation products coordinated with Waters

LP with 2% Ammonium Nitrate

•..-- "-:- " "TEANT ..

HAN as IINO3

14

4j

.r--

"-4

LP with Trace Ammonium Nitrate

TlEA N

. .A N a -• IIN 0 3

'4J

VU

T4-ri

TITRATION CURVES -FIRST DERIVATIVE

2000

Li

900 -1

-I-I

44

0 10 1'5 20M i nu tes

ION CHROMATOGRAM - STANDARDS(SAMPLES 1/5000 DILUTION)

W)

200

150

fli1 ~ol l i" CI)

H i nu t es

ION CHROMATOGRAM - METAL STANDARDSTM+2 0.5 TO 1.0 PPM

_ 0

rfi

150

ICIO

"I •h iJ• IltP1I i n~u t~es

ION CHROMATOGRAM - LP 1846 FOR TM1/10 DILUTION

METALS ANALYSIS OF LP 1846 (LP-2 & LP-3)BY ICP

Metal LP-2, ppm LP-3. ppmIron <0.09 2.06Chromium 0.74 0.40Copper <0.18 <0.17Nickel 0.88 0.34Cobalt <0.09 <0.09Lead <0.87 <0.87Tin 3.06 3.03

Iron by polarography: 0.31(Fe+ 3 )

00, 1210 ISO

*-OD, 6

ID,4

OD, 8bo ID, 2

2~p

.4 - - - ----- 80)

0 )D,12 6 3.0[L), 10

Notu: All diimeunsionsare in mm

PRESSURE - TIME STUDY APPARATUS

] !4

COMPOSITIONAL ANALYSIS OF LP 1846BEFORE AND AFTER EXPOSURE AND RATE

OF DECOMPOSITION AS A FUNCTION OFTEMPERATUREAND NITRIC ACID AT

65% ULLAGE

LP1846 Temp,°C %HAN %HNO3 Days Rate

LP-2** 59.3 0.440.44%HNO3 25 59.7 0.48 136 0.10.44%HNO3 50 58.4 0.74 116 2.00.44%HNO3 65 57.7 1.18 48 8.5

Note: All rates are final rates in mmHg/day.**-Initial composition (LP-2: Lot # ABY87FS2CO13).

COMPOSITIONAL ANALYSIS OF LP 1846BEFORE AND AFTER EXPOSURE AND RATE

OF DECOMPOSITION AS A FUNCTION OFTEMPERATURE AND IRON AT

65% ULLAGE

LP1846 Temp,°C %HAN %HNO3 Days Rate

LP-3** 59.4 0.032.1ppmFe 25 60.0 0.12 120 07.25ppmFe 25 59.9 0.14 120 02.1ppmFe 50 59.8 0.23 120 07.0ppmFe 50 59.5 0.28 120 0.4249.9ppmFe 50 58.4 0.80 70 9.0

Note: All rates are final rates in mmHg/day.**-Initial composition (LP-3: Lot # 1846-01).

20

• 10EE 50ppin Fee

13 50 p pm C u

• 25ppm Fe

25ppm Cu

5ppT Fe

0 20 40 60 80 100 120 140

Time, days

RATE AT 50 0C FOR LP 1846IRON VS COPPER

17

30

20

Co

0)

EE 1% HNO 3

n,

10

10 0. 5%0 HN03

_•_...ecf 5 ýpp m Fe

2ppni Fe

0 10 20 30 40 50

Time, days

RATE AT 65 0C FOR LP 1846IRON VS NITRIC ACID

PRESSURE BUILD-UP IN STORAGECONTAINERS HOLDING LIQUID PROPELLANT

CONTAMINATED WITH NITRIC ACID

LP1846 Type TempC Pressure, psig/yr

0.44% HNO3 25 0.71

0.44% HNO3 50 14.1

0.44% HNO3 65 60.0

0.54% HNO3 65 45.1"

0.98% HNO3 65 94.6

* -Denotes current rates from pressure-time studies

that are still in progress.


CONTAMINATED WITH IRON

LP1846 Type TempC Pressure, psig/yr

2ppm Fe 25 0

2ppm Fe 50 0

2ppm Fe 65 21.2*

7ppm Fe 25 0

7ppm Fe 50 3.0

7ppm Fe 65 56.5*

25ppm Fe 50 29.6*

50ppm Fe 25 0.1*

50ppm Fe 50 63.5

* - Denotes.current rates from pressure-time studies

that are still in progress.


CONTAMINATED WITH COPPER

LP1846 Type TempPC pressure, psig/yr

25ppm Cu 50 19.8"

50ppm Cu 25 0.1*

50ppm Cu 50 35.3

- Denotes current rates from pressure-time studiesthat are still in progress.

II

PROGRAM STATUS

1. Analytical methods have been selected formonitoring the LP during storage.

2. Preliminary pressure-time screening studies ofLP1846 are nearing completion.

a. Preliminary data has provided patterns ofdecomposition and effects of variouscontaminants.

b. Data reduction Is i~i progress to establishpressure build-up during long-term storage.

FUTURE PLANS

1. Samples of LP 1845 and LP 1846 from currentproduction lots wili be tested.

a. Pressure-time screening studies will beconducted.

i. Clarification of current pressure-time

studies.

ii. Effect of other variables and contaminants.

iii. Effect of inhibitors.

b. Initiation of long-term storage studies.

i. Correlation of data from pressure-timestudies with data from Ing-term storagestudies.

(a) Establish liquid propellant

specifications.

(b) Establish kinetics.

(c) Establish decompositionmechanism.

ii. Comparison of ballistics from exposed andunexposed samples.

Ill. Determination of propellant lifetime andother safety considerations.

4th ANNUAL CONFERENCE ON HAN-BASED LIQUID PROPELLANTSTRUCTURE AND PROPERTIES

US ARMY BALLISTIC RESEARCH LABORATORYABERDEEN PROVING GROUND, MD

30 AUG - 1 SEP 88

Title of Paper An Overview of the Thermal Reactivity of Substituted

Ammonium Nitrates

Presentation Time Request 30 (min)

Type of Paper: Progress; Summary; X State-of-art; Other

Speaker's Name Dr. V. R. Pai Verneker Phone Number( 3 01) 247-0700

Affiliatioii/address Martin Marietta Laboratories,1450 South Rollings Rd.

Baltimore, MD 21227

Co-author(s) name(s) S. C. Deevi and C.K. Law, Univ. Of California, Davis, CA 95616

ABSTRACT (Use reverse side if necessary)

The importance of alkyl and aryl substituted ammonium nitrates as energetic materialsstems from the fact that both the fuel and oxidizer groups are present within themolecule. An indepth study has been carried out (a) to evaluate the relativethermal stability with increase of substitution on the central nitrogen atom,(b) to examine the thermal stability of the substituted ammonium nitrate due tothe confijurational stability of the cation, (c) to investigate the role of basicityof the central nitrogen atom on the thermal stability of the ammonium nitrate and(d) to establish a unified mechanism of thermal decomposition process for the

substituted ammonium nitrates. Our results based on a variety of thermoanalyticaltechniques coupled with mass spectrometry revealed that the thermal stabilitydecreases with increase of methyl substitution in the case of mono-,di, and tri-methylammonium nitrates. Tetramethyl ammonium nitrate exhibited high thermal stabilityas compared to the mono-, di- and tri-methyl ammonium nitrates due to the configurat;,nalstability of the compact tetramethyl ammonium ion. The overall decomposition processin the case of mono-, di- and tri-methyl ammonium nitrates involves dissociation

of the nitrate via proton transfer. Proton transfer process has been shown to occur asin the case of hydroxyl ammonium perchlorate. We present an overview of the thermalbehavior of substituted ammonium nitrates and present a unified picture of thed(icomposition of ammonium nitrates.

MARTIN MARIETTA LABORATORIEC

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30 AUG - 1 SEP 88

Title of Paper IMPACT SENSITIVITY OF HAN-BASED LIQUID MONOPROPELLANTS


Type of Paper: X Progress; Summary; State-of-art; Other

Speaker's Name Irv Stobie Phone Number(30]) 278-6154

Affiliation/address Ballistic Research Laboratory SLCBR-IB-B,

Aberdeen Proving Ground, Md. 21005

Co-author(s) name(s) Bruce D. Bensinger John D. Knapton


IMPACT SENSITIVITY OF LIQUID MONOF'ROPELLANTS

I.C. Stobie, B.D. Bensinger, J.D. Knapton

Ballistic Research LaboratoryAberdeen Proving Ground, MD. 2100.. 5-5]066

A Technoproducts drop weight tester was used to evaluateimpact sensitivity of four liquid monopropellants; OTTO II, NOS365, LP 1B4., LP 1344', LP 1945, and LF 1946. The monopropellantswere evaluated for impact sensitivity at ambient temperature andat temperatures in ei-'cess o+ 0O degrees C with energi es at andbeloj 100 kg-cm. Four additional propellarnts, (LGP 1561, LGF165,4 LOP 1798, and LOP 2:) were evaluated with increaseddiaphragm thicknesn to stLtdy ti-ie drop weight sensitivity of thepropellants at higher energy Values using a technique developedby Pri nceton Ccmbustion Research Lab r-atory (F'CRLR) . Thepropellants were all relatively inseni ivc, to i mpact at ambienttemperatures and the hydroxya1 ammori ium nit-ate based propellantssensitivity increased slightly at te:m peratures u,_p to 50 degrees.The impact sensitivity of OTTO II increased dramaitical lv as a{Unc-i on oXf i ncreased tEii-:perat.urc. The pr.:?.-ent test-s, agreed withthe F'CRL me-Ithod usi J nq ig -- and LFP 1 45 at h ih or enerov1 evel. The e-f'ct of weater content o-f the LGP propeu llants wasnot measurabil ustilng the PCRL mihehod.

Reproduced From

Best Available Copy

40

IMPACT SENSITIVITY

OF HAN-BASED

LIQUID MONOPROPELLANTS

Irvin C. StobieBruce D. BensingerJohn D. Knapton

BALLISTIC RESEARCH LABORATORY

VgWtS June U

41

CIO)

oo 00~

0 z 00u 0~U

High Rate Mechanical Response

Drop Weight Mechanical Properties Tester

FRAME

HEIGHT ADJ

AND RELEASEI

"WEIGHT CAGE

RAM

GUIDE . -

SAMPLE FORCE GAGE

BASE

ifI

I

ii4

NCORMi= L- FD<3FYL. N I TRATEr

SOURCE 50-% POSITIVEkg cm

ASTM D 2540 8.4

Mason et al. 17.3

BRL, 1982 12.8

BRL, 1986

(90% - 99.9%)

GC - Iso propyl nitrate

45

OTT-,---- I 1 34-77 Nov 1976

NITRATE ESTER - DESENSITIZED - STABILIZER

. 7-; -- 7) kg cm - Mason, Ribovich, Weiss, Bureau of Mines

O -- 2765P a THI OOL., Lot 240

HAN - IPAN

Iu- [g cm Smith et al.. NSWC

"1I .g cm Cruice., Hazards Research Corp.

I .. 1"-r+ t5 THIOKOL, Lot 244

HAN - TEAN

1I2 kg cm - Cruice, Hazards Rese071" h Corp.

L. F=-.1 -e46P NOS, Lot 50-3

HAN - TEAN + 3 % Water

AMBIENT MONOPROPELLANT DROP WEIGHT TESTS

PROPELLANT REFERENCE TEST PRESENT STUDY50% IGNITION 50X IGNITION

(kg-cm) (kg-cm)

OT0 II 8.5-70 98

NOS-365 >100 98

LP 1845 152 33 0@100

LP 1848 --- >100

47

ELEVATED TEMF=ERATU<E TESTS

PROPELLANT TEMPERATURE 50 % IGNITION

0C kg cm

Otto-II ambient 98

34 - 54 5 52

NOS-365 ambient 98

34 - 49 93

LP 1845 ambient (73 %- 100)

37 - 57 88

LP 1846 ambient 100

1- 5- 96

LP 1846 SENSITIVITY CONDITIONED LESS

THAN 82 DEGREES C

TEST NOS. TEMPERATURE ENERGY POSITIVE(degree C) (kg-cm) RESULTS

18 JUNE 51-57 54-62 100 2/498 1/196 1/180 1/1

20 JUNE 1-5 22 100 0/5

20 JUNE 8-15 44-48 100 1/194 2/292 2/49o 0/2

49

TEMPERATURE SENSITIVITY OF OTTO II

TESTS ENERGY TEMPERATURE POSITIVE(kg-cm) (degrees C) RESULTS

1-5 96-100 38-40 3/5

6-10 80-92 38-45 4/5

11-15 68-74 35-45 4/5

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00 ~

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Dr. Hans Joachim de Greiff

Fraunhofer-Institut f~r Chemische Technologie (ICT)

Joseph-von-Fraunhofer-Stral3e

P.O.Box 12 40

D-7507 Pfinztal 1 (Berghausen)

Phone: (0721)4640-321

Telex: 7 826 909 ict d

Telefax: (0721)46 40-111

Quantitative Analyses of HAN-Based Liquid Propellants

Abstract

This paper deals with quantitative analyses of HAN-Based monopro-

pellants, in particular following stability tests. In the case of

the propellant LP 1846, the compounds hydroxylamine nitrate and

triethanolammonium nitrate are determined as the primary com-

pounds, while free nitric acid and ammonium nitrate are consid-

ered as decomposition products.

As a determination method, potentiometric titration with water as

solvent has been selented, using as apparatus a Metrohm

"Titroorocessor 636" with a combined glass electrode as an

indicator.

The propellant components were to be quantified by simultaneous/

titration in a sample. Therefore, the pK values of the different

prooellant components have been measured before starting the

analytical work. HAN and AN had to be converted to derivates

(acetoxim and formaldoxim) to enable the separation of the

compounds.

As for triethanolammonium nitrate containing propellants such as

LP 1846, AN can be titrated after steam destillation due to the

nonvolatility of the free triethanolamine.

53

"Table 1

Dissociation constants KA as well as relevant pKA- and pKB valuesin a number of propellant components in aqueous solution at 20 *C.

No. Propellant Components KA pKA pKBmol x dM- 3

1 Hydroxylammonium nitrate(HAN) + formaldehyde-- > formaldoxime 0.245 x 10-1 1.61 12.56

2 Hydroxylammonium nitrate(HAN) + Acetone-- > Acetoxime 0.191 x 10-1 1.72 12.45

3 Ammonium nitrate (AN) +formaldehyde -- >hexamethylene tetramine 0.141 x 10-5 5.85 8.32

4 Hydroxylammonium nitrate(HAN) 0.733 x 10-6 6.135 8.035

5 Triethanol ammonium

nitrate (TEAN) 0.112 x 10-7 7.95 6.22

6 Ammonium nitrate (AN) 0.331 x 10-9 9.48 4.69

7 Isopropyl ammoniumnitrate (IPAN) 0.138 x 1010 10.86 3.31

Determination of the pK value by potentiometric titration in

accordance with the Henderson-Hasselbalch equation:

pH = PKA - log(Cacid/Calt).

If the concentration of the acid is equal to that of the salt,

the logarithmic term then becomes zero, and pK is equal to pH.

Ammonium salts react with t3r-aldehyde to form the very weak base

hexamethylen tetramine

4 NH3 .HN03 + -- N4 (C.-. H " HO + HNO3,

Aldoxime or acetoxime ',, ,htained from hydroxylammonium nitrate

with formaldehyde or a(,et.)iie:

112NOH.HNO3 I H2C:NOH + H20 + HNO3,

H2 N()H -HNO3 4 ( CH:i . ,( (C1bi )C-NOH + H20 + HNO3

.) J)

Eg�Ai... Iletrohm Titroproze�sor 6�

EiLQ�L2i

Sean, Di'txllationt after Stroblein

F~ig. 3 1 Scheme of the Steam Distillation Unit

(1) Inlet connection for the Sample, (3) Electric boiler.,(4) Drop Separator, (6) Condenser, (7) Distilling -flask,

(8) Receiver.

57

.261MLDI Y V(STRRT )/IL e.80e PH

1 2 3 4 S 6 7 8 9 te 11 12 13 14I I I I I I I I I I I I I II I g

-I

ROUrIME 0 101# 6704 PH(INIT) 2.248 V(TEL)ML 0.?e21 V'ML 0.146 PH(M) 3.61e

DATE 17.12.87 NAME teaTrt i (i

8.2SML/DIV V(START)/ML 0.080

161

ROUTINE 0 101# 6704 PHi(INIT) 2.248 Y( TE)IML. e.702I V/ML 0.146 PHtM) 3.610

DATE 17.12.87 NAME 1',i.irtini

BUR.1 V/ML 5.0 ROUTINE 0 101TEMP/C 22.0 REAGENT U. )M KO01, aqueous, LitrisolKIMET D 8.8 TITER I. UUI ,MPD VAR 8.8 ELECTRODES I (retrohm) combineJ rmicro pHissSTART V/ML 0.808 ciLctrole (type T)STOP PH 100l808 SAMPLESTOP V/ML S.000 563.6m,; dilution (= 16. Ž2g propeLtant)' wereSTOP 0 EP 9.0 adieJ with l0mi 1,0 dand titrated.PRUSE/S 0.0EP-CRIT 5.0 REMARKSADD V/ML 0.000 Determination of the concentration of nitricEP-W LIMI 0.080 acid (Hinj ) in liquid propellant.PH LIM2 14.000 HNU)= 2.?0106

Fig. 4: Analysis of LP 1846: Determination of freenitric acid: Titration curve (top) and 1stderivative (bottom)

0.26MLeDIV V4STRRT)e'L 8.60 PH

1 2 3 4 S 6 p Is 11 12 I3 14

(r)

2

ROUTINE 0 lot0 170 PH( IIT) 1.418 V(TE)/ML 3.476I V/ML 2.184 PH(M) 5.8482 V/ML 2.547 PH(IM) 18.163

DARTE 5.11.87 NAME !v-rtini

Fig. 5: Analysis of LP 1846: Simultaneousdetermination of HAN and TEAN bysubstitution titration: Titration curve.Here: 1) Determination of HAN after acetoxime

formation by the addition of acetone2) Determination of TEAN

59

*.2SML/DIYV V(START)-ilL 0.066

ROUTINE 0 1010 170b PH(INIIT) 1.410 V(TE)-'ML 3.4761 V/ML 2.184 PH(M) 5.8482 V/ML 2.547 PH(M) 10.163

DATE 5.11.87 MAME Mj rt in i

BUR.1 V/ML 5.9 ROUTIME 0 lotTEMP/C 23.8 REACEMIT U.5n VUH, ,queous, TitrisolKIMET D 8.8 TITER 1 .LvUMPD VAR 8.0 ELECTRODES I (MetrohM) comoined micro pUl glassSTART V-PML 8.088 electrude (L.ype T)STOP PH 100.088 SAMPLESTOP VYML S.008 0 S&. I1m dilutiorn'(= I'o.5&wl propellant) vereSvOP # EP P.0 ujded with IUiul hiu dnd 5nll acetone and titi'atej.

PAUSE/S 0.8EP-CRIT 5.8 REMARKSADD V/ML 0.889 oJeter•mi.ition oi Lne concentrution of hydroxyl-EP-W LIMI 8.088 o~iizoni umni ,aJte (,Hl ') ani triethb.nolaminoniuw-PH LIM2 14.888 nliLrite (frbd) in liquid piopeliant.80as= J/.u.&;l ThAN 17. 15ý

Fj._6:" Analysis of LP 1846: Simultaneousdetermination of HAN and TEAN by

substitution titration: ist derivative.

Here: 1) Determination of HAN after acetoximeformation by the addition of acetone

2) Determination of TEAN

60

V(SLDI .START)-efL s.see PH

1 2 3 4 S 'd S P to It 12 13 14

ROUTIINE 0 181*17192 PH( IIIT) 6.791 V( TE)/ML 2.88ap

I V/M'L 0.680 PH(Il 5.16S

DATE 19.03.88 NAME Martirni

e.SeML'tJ1v V(START)'flL e.0ee

ROUTINE le18* 17102 PH(INIT) 16.781 V(TE)/ML 2.088p1 V'-ML 8.688 PH(M) 5.1165

DATE 18.83.88 NAME ýIarzini

BUR.1 V-ilL 18.8 ROUTINE 0 101T*LMP/L 23.5 REAGENT J.O5m hC1, aqueous, iTitri.EolKINET D 8.8 TITER 0 - ') ) --

* MPD VAR 8.8 ELECTRODES 1 (v~jetrohzi) comuLined MiCrO Ph GlaSSSTART V'ML e.000 e~lectrode (type T)STOP PH 10e.e00 SAMPLj~STOP V'ML 10.008 105.m pure liquid propellant were ad~ded withSTOP * EP P.0 ?5m1 Fehliný; 1, 25M1 Fehlin,, 11, 2'51i1 i-O2PAUSE/S e.0 3ii-tiled in titr.ted. 0

EP-CRIT 5.8 REMARKS Y:eceiver: ',Crl 4ýo Ooric .ýcidADD V'ML 8.889 3)etermirnation of th-~e ýO cortitiur, of' j1:7.nofliuTEP-W LIMI 8.000 n"Lrite )i. miIrpe1:.PH LIM2 14eO A*N 20105

Fig. 7: Analysis of LP 1846: Titration of Ammoniain diluted boric acid with 0.05 N hydrochloric acid,Titration curve (top) and 1st derivative (bottom)

6 1

I4

i.O fl•DIV VSIASST i'N.. S.O.S PM

S 1 • 4 S ' 7 5 P 16 Ii IZ

II

ROUTIME 0 261S 217 "(IMIT) 1.431 V(TE)/MIL P.L741 V-ML e.?7 P4 ,.043 * 426,27 ol MAk # "0O3 a 58,99 1 (MAN*FN0 3 )

DATE 31.16.94 IANC jea

Fig. 8: Analysis of NOS-365:Simultaneous determination of HAN, IPAN andAN by substitution titration:Here: Determination of HAN after formation ofacetoxime by the addition of acetone

02

0 , 141SMOIV WIST0I1T IM 96411 OP5

It ise Is c t

ROUTJINE 10 21? PHI INIT) S.445 V(WTIE)elL S.0441I VML 1. set PH 7.3112 Veft 3. 6.3 PH P.P40 A 2.074 ml 126.64 04g IPAN • 17,53 It PAN

DATE 31.10.04 I f.[ a

NUR.2 VsI*L I0.0 RO4JTINE 1 261TENP,,C 24.0 GCAGEMT 0.5 A NIOH wIBr. TitrisolK ItICT D •.0 TIT:R 1 000nPD VAR 0.0 CLCCTRODci 2 ku-btnlorF0 Glaselktrode Me'roahaSTkRT VrIML 6.000STOP PH 196.0•0 SAMPLC 722.6 ag NOS 365 # 10 01 ,';uifo ('.An-Sest. ISTOP V-,. 10.660 * 5 ml Formaldehyd 37STOP 4 EP 0.0 . 406,9 at NH4 N03 Lsg. (*.43'% ag 0 *PUSCCS 6.6EP-CRIT S.0 REMARKS*D0 VMflL *.PooEP-lJ LIIt 6.0e0P14 LIMZ 14.060

1.00tL/e1V V(START)-L 0.1. .0

41 4

ROUTINE 0 10 21? P9IIIHlT) 6.466 ¥VOiT")•. S.8S"

vm. 1.1eP PH 7.111S 426 27 mg (WAN+HN0 3 ) A S8,99 I (ANX*HNO 3 )SV;I. I3.80i PH P.P40 2 2,074 l AI 126,64 mi IPAN

I 317.3 1 PAPDIATC 31.10.04 nWI ja

Fig. 9: Analysis of NOS-365:Simultaneous determination of HAN, IPAN and AN bysubstitution titration: Titration curve (top)and Ist derivative (bottom).Here: 1) Determination of AN after the

addition of ammonium nitrate at aknown quantity and the addition offormaldehyde (formation of hexamethylenetetramine)

2) Determination of IPAN

63

An Overview of the U.K. Approach to the Characterisation and

Classification of the HAN-Based Liquid Propellant LP1O1.

S Westlake.

Royal Armaments Research and Development Establishment.Powdermill Lane, Waltham Abbey, Essex EN9 lAX,

(United Kingdom).

HAN-Based liquid propellant LPIO1, is currently beingconsidered by the U.K. for use as a liquid propellant forguns. This paper summarises the initial assessment of LP1O0for this use. It covers work connected with the manufactureand assay of the propellant and the assessment of itsstability and compatibility with other materials it's likelyto come into contact with during manufacture, storage anduse. This paper will briefly outline some of the methods usedii- this assessment.

COPYRIGHT D CONTROLLER HMSO, LONDON 1988

014

1. Introduction.

2. Manufacture.

3. Compatibility and Stability.

4. Hazard Assessment.

5. Conclusions.

6. Refe-ences.

7. Figure 1.

65

Problems have been encountered in finding a suitable methodfor assaying the propellant. It is very difficult to analyseHAN in the presence of TEAN. Chromatographic and titrimetricmethods have been tried, but in both cases the results werenon reproducible. The reaction between HAN and benzaldehydewas the basis of both methods.

NHsOH÷NOs- + CeHaCHO ------ > CeHaCH=NOH + H20 + HNOs

In the titrimetric method the liberated nitric acid istitrated against ethanolic potassium hydroxide. In thechromatoghraphic method the liberated water is detected bygas chromatography. It is believed that the reaction ofbenzaldehyde with HAN does not go to completion, hence thenon reproducible results observed.

At the moment the propellant is blended by weight. The watercontent of the propellant is then determined by gaschromatography or Karl Fischer.

This situation is obviously not ideal and effort is beingmade to find a suitable method. However we have been assuredthat there has been good reproducibility between the blendsthat have been manufactured to-date.

The density, viscosity and refractive index of each blend ismeasured. Inorder to determine the effect of slightcompositional changes on these parameters several smallbatches of modified composition have been made. These areshown in Table 1. along with their measured density,viscosity and refractive index.

COMPOSITION DENSITY R.I. VISCOSITY%HAN %TEAN %WATER 20oC 240C -16 -10 0 10 20

oc

63.2 20.0 16.8 1.4555 1.4676 43.5 32.2 22.1 15.3 12.4

64.7 20.5 14.8 1.4748 1.4723 58.2 42.5 25.3 18.3 13.8

61.7 19.5 18.8 1.4409 1.4730 38.5 26.0 19.3 14.7 11.8

61.2 22.0 16.8 1.4482 1.4669 45.0 30.5 21.7 15.7 12.8

65.2 18.0 16.8 1.4624 1.4670 37.3 29.3 18.5 13.0 9.0

TABLE 1.

The different compositions represent propellants that areoutside the specification limits and cover the variation ofHAN/TEAN ratio at constant water and of water at constant

66

1, Intyndnntion.

LP101 is currently being assessed by the U.K. as a liquidpropellant for guns, with the emphasis being on its ultiieteuse as a tank gun propellant. The U.S. havy spent many yearsresearching the possibilities of using liquid propellants forboth artillery and tank guns and have produced several viablepropellants. LP101 is equivalent to American tPG 1845, buthas been given a U.K. designation for specification purposesand to avoid confusion with propellant of U.S. origin. LikeLPG 1845, LP101 is a solution of Hydroxylammani, .t nitrate(HAN) and triethanolammonium nitrate (TEAN) iD uster.

Prior to the start of this project U.K. experience withliquid propellants had been concentrated on packaged systemsand confined to very specialist use. The gun propellant beingproposed was unlike any propellant currently in service usein the U.K. and so a programme was set up to establish itscharacteristics and suitability for service use. The U.K. hadaccess to a certain amount of U.S. data, but as LP101 wasmanufactured in the U.K., using ingredients from Britishsuppliers, it was necessary to characterise the propellant,as made, to ensure that LP1O1 was indeed comparable toLPG 1845.

Royal Ordnance were contracted to manufacture the propellantand to determine its compatibility with other materialslikely to come into contact with it.

S.tManufacture.-

LP101 is a solution of hyroxylammonium nitrate (HAN) andtriethanolammonium nitrate (TEAN) in water. The TEAN ismanufactured from Triethanolamine and nitric acid andpurified by crystallisation. The HAN is currentlymanufactured by a chemical method,(which is commercial-in-confidence ) and supplied as a 40X solution in water.However, HAN, from an alternative supplier, is in the processof being assessed. This HAN is supplied as a 24% solution.The HAN from both suppliers requires concentrating beforeblending. Concentration takes place under vacuum and thetemperature is not allowed to exceed 60oC. This requires avacuum of about 5mm of mercury to remove the last few percentof water and still keep the temperature below 80oC.

The HAN and TEAN are blended together and the percentage ofwater adjusted to give a suitable propellant.

67

HAN/TEAN ratio. This was to determine the effect a variationfrom specification had on these physical properties.

The refractive index varied linearly with water content butnot with the HAN/TEAN ratio in the range studied. The lowtemperature viscosity increased markedly as water contentdecreased but only slightly as the TEAN is increased. Thedensity varies linearly with respect to TEAN but is nonlinear with respect to water. The density variation is showngraphically in figure 1.

Density and refractive index are now being used to monitorthe blending process.

It is known that the stability of HAN based propellants isseriously affected by metal ion contamination, particularlyiron and copper. Therefore each batch of propellant has beenscreened for iron using atomic adsorption. The results areshown in table 2.

ppm wt/wt

Blend No: Copper Iron

2 0.03 0.3

4 0.10 0.4

5 N.D. 0.3

6 0.17 0.3

Table 2.

I.- nountibilix and Stability,

As part of the propellant assessment programme a testprocedure has been developed to screen all materials that arelikely to come into contart with the propellant duringmanufacture, storage and life.

Candidate materials are initially checked for possible severeincompatibility using a splash and immersion test. A fewdrops of propellant are placed in contact with the candidatematerial so that the surface is just wetted. Observations aremade over one hour. If no rapid reaction or r.•nompositionoccurs then more propellant is added such that the sample isjust submerged. The test is examined after a further hour,after 5 hours, 24 hours and 7 days. All observations arerecorded.

68

If no rapid reaction or decomposition occurs the test inrepeated at 800C. These tests can warn of severeincompatibility and screen materials for short term exposureand accidental contact.

Materials under consideration for long term contact aresubjected to further tests to establish their long termcompatibility. In this test aging is accelerated by usingelevated temperatures. Most monopropellants are inherentlythermally unstable and give rise to gaseous p-roducts whenheated. This decomposition can be catalysed by contaminationor contact with foreign material.

The test to establish long term stability compares gasevolution of propellant in contact with candidate material,when held at an elevated temperature, with that of controlsamples. The gas evolved is monitored for up to 6 monthsusing a pressure transducer and the temperature of the testis 690C. This temperature was the lowest temperature atwhich measurable levels of gas could be detected from thecontrol samples. On completion of the test the propellant isanalysed for dissolved and particulate matter and thecandidate materials are tested for any changes in physicalproperties. Full details of both the short and long termstability tests are given in reference 1 and 2.

These tests are not totally satisfactory. They are notgeneral enough to detect all types of incompatibilityreaction; for example a non gas producing reaction or onewith an initial induction period. However virtually allreactions are accompanied by heat generation. A test methodhas been developed using heat flow calorimetry to determineif the propellant is thermally stable. This test will show ifany treatment of the propellant, such as heating or contactwill a suspect material, has affected its chemical stability.Full details of the test are given in reference 3 and will bedescribed in the following paper.

The test has also been used to screen the batches ofpropellant that have so far been manufactured. Goodcorrelation has been found between iron content and thermalstability, as demonstrated by this method.

An example where gas generation can be misleading wasobserved during some work designed to measure the rates ofgas evolution from samples of LP101 heavily contaminatedwith metal ions (reference 4 ). Samples of LP101 containing0.5 g/litre of CU2* were heated at 50, 80 and 700C for up to4 days. The sample heated at 700C gave an initial gasevolution rate of 1.48 cc/hour. This steadily decreased andafter 3 days the rate had reduced to 0.67 cc/hour. After 4days the sample "boiled off" and the contents of thecontainer were ejected with some violence. This experimentgave strong indication that the reactions taking place duringthe decomposition of LPIOI are not simple. It is obvious thatthere are at least two different reactions occurring in thiscase. 69

A a... HAxd s mmmnt.

A. part of the qualification procedure, a new propellantneeds to be screened to establish whether or not it is acandidate for inclusion in UN Class 1, ie whether it needs tobe treated as an explosive or not. This screening is requiredfor transport and storage purposes. It was hoped that LP101,if suitably packaged, would not fall into this category andbe classed as non explosive. In order to establish this LP1O1was subjected to UN series 1 and 2 tests. These tests aredescribed in detail in reference 5 but are described brieflybelow:-

BAH 50/60 Steel Tube. Propellant is placed in a steel tube of50mm i.d. and 60mm external diameter and subjected to thedetonative shook from a 50g Debrix 13 high explosive boosterand a No 8 aluminium concave-based detonator in series 1 and2 respectively. The number and size of the tube fragmentsdetermines whether the propellant is class 1 or not.

Koenen Steel Tube. Propellant is placed in a 24mm diametersteel tube of 70mm length, closed at one end with an orificeplate. The tube is heated and in consecutive tests theorifice is reduced until fragmentation of the tube occurs.The size of the orifice that causes fragmentation determineswhether the propellant is class 1 or not.

The results of these tests classified the propellant as UNClass 1. These tests do not allow for differentiation betweenhigh explosive (1.1) or propellant (1.3) so the propellantwas given a temporary 1.1 classification.

Results from further testing using the Large Sealed VesselTest (reference 6) indicated that hazard division 1.3 wasappropriate for LP101. The next series of tests (reference 7)confirmed this for the proposed method of packing. The singlepackage test showed that, if confined in a 5 litre rigidpolythene, narrow recked screw top containers, explosion didnot propagate in the package and surrounding packages wouldnot be endangered.

LP1O1 was finally given a 1.3L classification i.e. Propelltantto be stored and transported separate from other propellants.Isolation is necessary because of the corrosive and oxidativenature of LP101.

70

r.1_ Cannnmnigns_

Manufanture.

The method of manufacture of LP1O1 has been fairly wellestablished, but problems in assaying the propellant havebeen encountered. Work in this area is about to commence andit is hoped that a full assay method should be available inthe near future. Refractive index or density measurementare being used for monitoring the blending procedure.

Compatibility and 9t tv.ijL

The splash and immersion test, gas evolution test and heatgeneration test are currently being used to screen materialsfor use with LP1O1. The information from all these tests areused when making a sentencing decision.

Hazard Assessment.

UN series 1 and 2 tests and supporting tests have classifiedLP10 as 1.3L. This only applies to propellant stored in 5litre lots or less and in the specified packaging. Furthertesting will be required before the propellant can betransported or stored in bulk containers.

71

1. D. Sutton. Royal Ordnance R&D Centre, Westcott Report.RO(W)/LTM/LPG/STT. May 1987.

2. D. Sutton. Royal Ordnance R&D Centre, Westcott Report.RO(W)/LTM/LPG/MLTT. May 1987.

3. P.F. Bunyan. RARDE Memorandum 4/88, 1988.

4. N. Lynch. Royal Ordnance R&D Centre, Westcott.D. Sutton. Internal Memorandum LST-IM-1/88. Feb. 1988.

5. Recommendations on the Transport ofDangerous Goods, Tests & Criteria, FirstEdition. United Nations PublicationST/SG/AC.1O/11, 1988. Part 1.

6. Explosives Hazard Assessment, Manual ofTests, SCC No 3, MOD, Waltham Abbey 1972.

7. Recommendations on the Transport ofDangerous Goods, Tests & Criteria, FirstEdition. UN Publication ST/SG/AC.1O/11,1986. Test 6 (a).

72

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73"

Possible Test Methods to Study The Thermal Stabilityof Hydroxylammonium Nitrate Based Liquid Gun Propellant

P F BunyanS Westlake

Royal Armament Research and Development Establishment,Powdermill Lane, Waltham Abbey, Essex EN9 lAX,

(United Kingdom).

The effect of contamination of a hydroxylammonium nitratebased liquid gun propellant with various metal ions has beenstudied using the techniques of heat flow calorimetry,thermogravimetry and a simple time to pressure burst test.All three tests showed a destabilising effect of dissolvedcopper and iron on this propellant. The three approaches arecompared and their relative merits and disadvantages arediscussed. It is concluded that heat flow calorimetry wouldprovide the most suitable method for detailed compatibilitystudies, while a pressure burst test could be used forroutine surveillance checks.

N.B. This document Js intended to support a verbalpresentation to be given at the 4Lh Annual Conference onHAN-Based Liquid Propellants, Structure and Properties at theBallistiso Research Laboratory, Aberdeen Proving Ground,Maryland. It reproduces the information reported in RARDE

Memorandum 4/88, but includes some additional results thathave been gathered since that Hemorandum went to press.

COPYRIGHT (DCONTROLLER HMSO, LONDON 1988

74

1 Introduction 3

2 Laboratory Work 4

2.1 Heat Flow Calorimetry 42.2 Thermogravimetry 82.3 Time to Pressure Burst Test 6

3 Discussion and Conclusions 8

4 References 9

5 Symbols and abbreviations 9

Tables 1-3

Figures 1-3

Annex A Sample Preparation Procedures

75

75

1 INTRODUCTION

Following several years of investigation into the use ofliquid gun propellants in the USA, a programme of work hasrecently commenced in the UK to develop a gun systememploying a liquid monopropellant based on Hydroxylammoniumnitrate (HAN).

This material is unlike any other propellant currently beingused in British service and it can be expected to behavedifferently from conventional solid gun propellants based onNG/NC/nitroguanidine.

It has been reported that the stability of this class ofpropellant deteriorates if contaminated with trace quantitiesof certain metal ions, particularly iron and copper (Ref 1).

When left in contact with many metal components commonlyfound in gun systems, this type of propellant has been found,by experience, both to corrode the metal surface and to takemetal ions into solution in appreciable quantities (up toseveral hundred ppm).

In order to investigate the effect of various treatments onthe propellant (age, temperature, contact with othercomponents of the gun system etc) it is necessary to havemethods of measuring the decomposition rate of thepropellant. In the case of conventional single, double andtriple base solid gun propellants, this has usually been doneby measuring the rate of stabiliser consumption eitherdirectly (eg by quantitative chromatographic determination ofstabiliser degradation products) or indirectly (eg bymeasuring the time delay before brown fumes are visible as inthe heat test).

Since HAM based propellants contain no stabiliser, thesetraditional tests are obviously of no use and alternativemeans of characterising them are required.

Tests are needed to fulfil 2 reqdirements:

a. Requirement 1

A reproducible, discerning, sensitive test to measurethe effect on stability of various forms ofcontamination quantitatively, to provide information tohelp with the selection of suitable Oonstructionmaterials for guns and storage vessels, is to performthe role that accelerated ageing followed byquantitative stabiliser analysis currently fulfils forconventional gun propellants.

b. Requirement 2

A quick stability check to be used as an indication of

76

useful li~fe remaining and to give early warning ofcontamination with incompatible materials. This toot maybe qualitative but it must be simple to perform and useinexpensive, universally available equipment, ie toperform the role that Abel's heat test currently fulfilsfor conventional solid gun propellants.

2 LABORATORY WORK

2.1 Heat Flow Calorimetry

2.1.1 EauiDmant and Material.

Heat generation was monitored using an LKB 2277microcalorimeter ("bioactivity monitor"). Its instrumentationand detection principle are described in reference 2.

Samples were contained in 3cm3 glass ampoules and sealed withTeflon lined rubber seals (LKB part no. 2277-303). Data wererecorded using the microcomputer logging system describedpreviously (Ref 3).

A sufficiently large sample of the liquid propellantdesignated LP101 was obtained from a single batch ofexperimental propellant (batch 2) to enable all experimentsin this investigation to be completed on the same material.(LP101 is a British copy of the US propellant LP1845. It isan aqueous solution of HAN and triethanolammonium nitrate[TEANJ)

Analytical reagent grade metal nitrate salts were used toprepare contaminated propellant samples.

2.1.2 Zxnerimentation and Results

Samples containing known concentrations of metal ions wereprepared by adding the appropriate metal nitrate salt to themixed propellant, or to aqueous solutions of its components(HAN or TEAN).

Heat generation was measured by fbllowing the experimentalprocedure described in Annex A.

Heat evolution rates after 3 hours at 770C associated withvarious treatments of the propellant are shown in Table 1.

2.1.3 Ohnervatinns and Remarks

Iron

It can be seen that the presence of trace quantities ofdissolved iron causes a large increase in the heat generationrate of the propellant. The effect appears to be a linearfunction of concentration under the conditions investigated(Fig 1).

77

The presence of copper also causes a large increase in theheat generation rate of the propellant. The effect is again alinear function of concentration and the rate is about anorder of magnitude greater than for a similar concentrationof iron.

Nickel

The presence of nickel increased the heat generation rateslightly, but the effect was far smaller than that seen witheither iron or copper.

Aluminum

It can be seen that aluminum has very little effect on heatgeneration rate from the propellant when in solution comparedwith other metals investigated. (However, this propellant isknown to be very incompatible with solid metallic aluminum)

Chromium

The presence of chromium increased the heat generation rateslightly, but the effect was far smaller than that seen withiron or copper.

Silver

It can be seen that the presence of silver had very littleeffect on the heat generation rate given by the propellant.

Propellant Components

No heat generation was detected from aqueous solutions ofTEAN whether contaminated or not.

Aqueous solutions of HAN can be seen to be exhibiting asimilar enhancement in their heat generation rate whencontaminated by iron or copper as was seen with the intactpropellant when similarly treated.

It would appear that the heat gen6ration enhancement observedis the result of a reaction between the HAN and the metalions. TEAN appears to neither react with the metal ionsitself, nor to influence their reaction with HAN.

LPAOI - Blend 4

When heat flow calorimetry was performed on a new batch ofpropellant (blend 4) it was found to be generating abouttwice as much heat as the original blend 2. It was shownsubsequently that the new propellant contained a traceimpurity of about 1.5 ppm of iron, compared with the 0.5 ppmpresent in the old propellant (Ref 5). This finding isconsistent with the higher heat generation rate reportedhere.

78

2.2 Thermogravimetrv

2.2.1 Eauipment and Materials

Weight loss curves were recorded using a Mettler TG50thermobalance.

Samples were contained in 150 uI alumina crucibles (Mettlerpart no. ME 24124)

2.2.2 Experimental and Results

Propellant samples containing known concentrations of metalions were prepared by weighing in the appropriate metalnitrate salt.

Weight loss curves were recorded on propellants containingdifferent contaminants using the experimental procedure andconditions described in Annex A. A typical weight loss curvefor an uncontaminated sample is shown in figure 2. All curveswere of this general shape, but with the step tending to bedisplaced to lower temperatures when the sample wascontaminated.

A summary of the temperature at which a 50% reduction ofweight had occurred for each treatment is shown in table 2.

2.2.3 QOservations and Remarks

It can be seen that a significant reduction in the meantemperature of 50% weight loss could be demonstrated if 10runs each of uncontaminated propellant and either 5 ppm (orgreater) of iron contamination or . ppm (or greater) ofcopper contamination were considered.

The resuilts are not quantitative, but agree qualitativelywith the HFC results as follows:

a Copper and iron appear to cause thermal instability.

b The effect of copper is greater than that of ironfor similar concentrations.

2.3 Time to Preanure Burnt Teet

2.3.1 Rouioment and Materials

Liquid propellant samples were sealed in 3cm3 glass ampoules,identical with those used for the HFC tests (LKB part no.2277-303).

7()

An elevated temperature was maintained in the sample using anelectrically heated, cylindrical, aluminium block with20xlOOmm cylindrical holes cut into the plane surface tocontain the samples (Fig 3). Isothermal temperature controlof the block was achieved with an AEI platinum resistancethermometer controller. All experiments reported here wereperformed at a block temperature of 1180C.

2.3.2 Experimentation and Results

The pressure required to rupture the ampoule cover was foundby sealing distilled water inside the glass ampoules andincreasing the temperature slowly. Rupture of the sealsoccurred between 160 and 1700C, implying a bursting pressureof between 6 and 8 atmospheres (Ref 3).

Time to pressure burst was recorded by monitoring, with apotentiometric chart recorder, the voltage from athermocouple embedded in a cork bung used to seal thecylindrical hole in the heating block containing the sampleampoule. When a pressure burst occurred, the bung was forcedout of the hot block and the thermocouple cooled, causing adeflection on the recorder.

Details of sample preparation and experimental procedure aredescribed in Annex A.

Pressure burst times for propellant samples contaminated in a

variety of ways are summarised in Table 3.

2.3.3 Qbs•. .- U. ,.

It can be seen that contamination of the propellant withcopper and iron causes a large decrease in time to pressureburst while nickel, aluminum, chromium and silver have littleor no effect.

Duplicate results are variable, as would be expected from the6 to 8 atmosphere variation in rupture pressure of theseempoules. However, the effect due to contamination withtraces of iron and copper is sufficiently pronounced to beseen above random variation, even on single results.

As with the TGA test, the results are not quantitative, butagree qualitatively with the HFC results.

80)

3 DISCUSSION AND CONCLUSIONS

All three types of test show the destabilising effect oftraces of certain metals in solution on this type ofpropellant and agree qualitatively on the ranking order ofmagnitude of effect of those metals.

The HFC method gives the most sensitive, discerning andreproducible information of the three, is quantitative andoperates at a temperature closer to that which the propellantis likely to encounter during manufacture and use than theother two. It would therefore appear to be an acceptabletechnique for performing sophisticated tests to allowdecisions about suitable construction materials to be usedfor storage vessels and gun systems etc (Requirement 1).However, the equipment is expensive, requires a skilledoperator and carefully controlled laboratory conditions andis not widely available. It would not appear practicable touse it as a quick, cheap, simple surveillance check.

The time to pressure burst test gives semi-quantitativeinformation and the results are too variable to be used forexact work. However, it requires simple, cheap, universallyavailable equipment and little training. This type of testcould thus fulfil the need for a quick stability test(Requirement 2).

The thermogravimetric method does show a decrease instability caused by copper and iron contamination and agreesqualitatively with the other two tests. It would therefore beconceivable to employ such a test as a stability check forthese types of propellants. However, it shares thedisadvantages of the HFC test of requiring carefullycontrolled laboratory conditions, expensive equipment and askilled operator, without offering the advantages ofmeasuring any single recognised feature of the decompositionreaction quantitatively. It 4- therefore not proposed topursue this approach any f,•rther.

Future work will concentrate on employing the HFC testdescribed here to study the effect on thermal stability ofvariou3 treatments of HAN-based liquid propellents.

81

1 Klein N BRL Report No 1876, 1976.

Wellman C R

2 Wadso I Thermochimica Acta 96, pp313-325,1985.

3 Bunyan P F RARDE Memorandum 43/86, 1987.

4 Handbook of Chemistry and PhysIcs,65th. Edition, D-193.

5 Phillips M Private Communication.

5 SYMBOLS AND ABBREVIATIONS

"BAM Bioactivity Monitor

HFC Heat Flow Calorimetry

HAN Hydroxylammonium Nitrate

TEAN Triethanolammonium Nitrate

W Watts

g Grammes

ppm Parts per million (weight/weight)

82

TABIL. 1 Heat Evolution Rates of Liquid Propellants

Measured Using The Bioactivity Monitor

SAMPLE HEAT GENERATION RATE (pW/g)

LP101 (uncontaminated blend 2) 1.2

LP101 (uncontaminated blend 4) 2.4

LP101 + 8.4 ppm iron 13.2

LP101 + 19.7 ppm iron 33.4

LP101 + 50 ppm iron 96

LP101 + 92 ppm iron 171

LP101 + 100 ppm iron 208

LP101 + 3.8 ppm copper 26.8

LP101 + 8 ppm copper 70

LP101 + 100 ppm copper >1000*

LP101 + 50 ppm nickel 3.2

LPI01 + 100 ppm nickel 5

LP1O1 + 50 ppm aluminum 1.6

LP101 + 100 ppm aluminum 1.6

LP1OI + 100 ppm chromium 6.9

LP101 + 50 ppm chromium 5.0

LP101 + 100 ppm silver 2.5

LP101 + 50 ppm silver 2.2

80.3% HAN (uncontaminated) 2.9

80.3% HAN + 8.3 ppm iron 11.5

80.3% HAN + 8.8 ppm copper 55

SGenerating heat at a rate above the maximum range of theequipment. Sample removed tc prevent damage.

CONDITIONS Samples contained in zaled 3 cm3 glass ampoulesat 770c. Heat generation rate reported after 3hours.

83

16(

04m

at~4 0 to CD -4 coM+1 +1 +1 +1 +1 +5

C:0

-4 x r- 4t wDQ

0 0' r- Ul C7~ -4 CD -4 00Si14 o+1 +1 +1 +1 +1 +1

Nc 0)- CD O -4 -. C

V N4 P') 8- 04D

.9-4 II C4C

0

in 4

r 441

10 '' '4 6'N ('

= 0 D OD V; U29 a) 0 OD C . 4

C.)~q C. .- 1 -4 T - -4 ~ 10"-4 0)

>1 0

ow4 44xn 0

0 Oci) m

M w.-4$4141o- 14)4 O0 0 C)~NC) '

4) 0 04 0 ol 0 C4.4 5.4 0 5.4 0 M- 0 ccd C)

C 06 C 0

84

Time To Pressure Burst Of Liquid Gun Propellant

Contaminated With Metal Ions

SAMPLE TIME TO PRESSURE BURST (HOURS)

Uncontaminated LP1O1 45,38,35,39,41,43,48 41!

LP101 + 100 ppm iron 2,2 2!

LP101 + 50 ppm iron 3.75,3 3.375!

LP101 + 20 ppm iron 8,7.5 7.75!

LP101 + 10 ppm iron 12.5,12.5 12.5!

LP1O1 + 5 ppm iron 13,16 14.5!

LP101 + 100 ppm copper 0.5,0.75 0.825!

LP1O1 + 50 ppm copper 1,1 1!

LP101 + 20 ppm copper 4,4.5 4.25!

LP1O1 + 10 ppm copper 7,7 7!

LP1O1 + 5 ppm coppb.. 10.5,9 9.75!

LP1O1 + 100 ppm aluminum 34,32 33!

LP101 + 50 ppm aluminum 34,45 39.5!

LP1O1 + 100 ppm nickel 17,18 17.5!

LP101 + 50 ppm nickel 19,20 19.5!

LP1O1 + 100 ppm chromium 24,38 30!

LP1O1 + 50 ppm chromium 29,39 34!

LP1O1 + 200 ppm silver 37,44 40.5!

LP1O1 + 100 ppm silver 35,40 37.5!

80.3X HAN (in water) 17,17 17!

Mean value (hours)

CONDITIONS: 3g samples of propellant sealed in 3cm3 glassampoules held isothermally at 1180C

Seals burst between 8 and 8 atmospheres

85

FIG. 1

0 0. C

09-

80

0

00

+D

c~J 0 a

6 MW1) 3lVW NounIJ~oA3 IY3H

86

"FIG. 2

z8

0,0

zD

0

w

I-.

•= NIVVE JHO13M

87

C,

FIG. 3

TO RECORDER

CORK BUNG

THERMOCOUPLE

HEATED ALUMINIUM BLOCK

SAMPLE CONTAINEDIN GLASS AMPOULE

FIG. 3 PRESSUREi BURST TEST - SAMPLE CONFIGURATION

_ $8

ANNEX A

SAMPLR PREPARATION PROCEDURES

Al HEAT FLOW CALORTMETRY

1 Heat new glass ampoules and lids for 24 hours at 80oC ina vacuum oven. Store in a desiccator over P208 until readyfor use.

2 Set the BAM bath to the desired temperature and allow 24hours for the cylinder to equilibrate.

3 Adjust the output to zero volts using the potentiometeron the BAM, with thermally balanced, inert ampoules in boththe sample and reference wells.

4 When the output becomes constant, recors the blanksignal for 1 hour.

5 Subject the sample well to an appropriate, knowncalibrating power, supplied by resistive heating of thecalibration element around the sample detection zone.

6 Record the calibration signal, when constant.

7 Fill a glass sample ampoule with uncontaminatedpropellant using a Pasteur pipette. This step is to removeany source of contamination present in the ampoule assupplied.

8 Discard the uncontaminated propellant.

9 Place between 3.5 and 4g of propellant which hasreceived the treatment of interest into the sample ampouleand record the sample weight.

10 Seal the ampoule with a Teflon-lined aluminium cap.

11 Lower the ampoule into the equilibration region of theBAN cylinder. Retain the sample in this region untiltemperature equilibrium is achieved (this will take about 30minutes)

12 Lower the sample into the detection region of thecylinder and commence measurement of power output.

A2 THEROGRAVIMETRY

1 Weigh between 25 and 35mg of the sample of liquidpropellant into a clean 150ul alumina crucible (Mettlr paL'•no 24124).

2 Place on the balance pan of a calibrated Mettler TGSOthermobalance. Do not cover the crucible with a lid, sincethis would be pushed off by the foaming, decomposingpropellant.

89

3 Increase the temperature experienced by the sample from50 to 3000 C at a linear rate of 20 degrees per minute in anatmosphere of nitrogen flowing at 200 ml/minute and recordthe sample weight as a function of temperature throughout theanalysis.

4 Record the temperature at the point where the sample hadexperienced a 50% weight loss.

A3 TIME TO PRESSURE BURST

1 Clean a 3oms glass ampoule with uncontaminated liquidpropellant as for steps 7 and 8 of the HFC method.

2 Transfer 3g of treated propellant sample into the sampleampoule and seal with a Teflon-lined aluminum cap.

3 Heat the ampoule and sample to 118 0C by placing theminside a cylindrical hole drilled into a heated aluminumblock.

4 Seal the entrance to the neating block well with a corkbung containing a chromel/aluminel thermocouple.

5 Monitor the voltage from the thermocouple as a functionof time using a potentiometric chart recorder.

s When the ampoule se'l ruptures, the cork bung is blownout of the hot block allowing the thermocouple to cool down.the time to pressure burst may be deduced from the associatedpen deflection on the chart recorder.

90

0 P04

Q~ 0

A) 0

F=4 0

0)) ;14Col0 0)

0 ,0f $

'4-1l io0 P0

0) ~ 4r)~~ U-4

0 04

91

z0

- >

O LUI

0- Dw a .~

LUF- CO Wmum f- CC<0

CO

0 xwcL Z N C\

92

0)LL

0 ELJQLJ

LU)

m CC

U)<Z LECC

0 0LCoJ

LUJ LU HF-nc c: LU

z LU -J75L

0 c

0 < <>

C 0 1 C C

93

OUTPUTVOLTAGE

TIMP TEMPT, T,>T 2 T

LARGEHEAT

HEAT HEATFLOW FLOW

SAuMPLE THERMO ELECTRICDETECTOR

NOTE: HEAT FLOW IS ACTUALLY THREE DIMENSIONAL

94

DIGITAL PANELMETER (DVM)

DISPLAYMAINS AND SELECTIONOUTPUT SWITCHCONNECTIONSAT REAR SIGNAL

LIGHTS

HJ3NCED LID OVERMEASUREMENT

......... ELECTRONICSCONTROL PANEL"(CALIBRATION UNIT,CHANNEL AMPLIFIERS)

- AýAMPOULE LIYTER

MEASURING CYLINDERFLOW TUBINGINPUT/OUTPUT

FLOW TUBE SPIRALHEAT EXHANGER

"-AMPOULE (IN TEMPERATURESTABILISING POSITION)

MEASURING CYLINDER

MEASURING CUP

S~MAIN HEAT SINK

WATER BATHCCmCULATING PUMP

WATER BATH TEMPERATUREREGULATION UNIT

HINGED BOTTOM

CONNECTIONS PLATEFOR EXTERNALWATER CIRCULATOR

LEVELLINGFEET

95

AMPOULZL

DRY GASFLUSHERTUBB ]NUT -

HICAT EXCHANGOERCOIL (FOR FLOW MODE)

(SHOWN IN

MIASURINOcup

PZLTIER

HIATSM NTNbDIT

HEAASEN

96

0.0

o0+0

0

cZ0

z

0

z0-

0

S 0

0 C0

++

(t6'M'1 ) 3LVU Notufl10A IY3H

9 .7

00/L

U.-

fUJ

- Bw oz

NIVE) IHOI3M

98

Il).HtUUHUtH

CORK BUNG

j 'THERMOCOUPLE

Z /

HEATED ALUMINIUM BLOCK

SAMPLE CONTAINEDIN GLASS AMPOULE

PRESSURE BURST TEST - SAMPLE CONFIGURATION

99

U Y

__ Li:' IDI0 IDL~)I

I'I)

LY

kl-.-

F. Z i

LUILC H d LL L

Hn~ LCL ZL ID DLC0- Ld E L C L 0L CC. C

z- z C 000L o z

I o a a E a

-I++++ + +

1 00

0-4 0

E--~J2 0'

- H-ý

C)101

HYDRODYNAMIC THEORY OFLIQUID PROPELLANT DYNAMICS

J.W. Haus and F. Chung-YauRensselaer Polytechnic InstituteTroy, New York 12180-3590

1. Linearized HydrodynamicsA. Three component fluid

i) light scattering spectraii) sound absorption and

dispersionB. Chemical reactions in Equilibrium

2. Continuing ResearchA. Instabilities

i) Thermodynamicii) Chemical

B. Inhomogeneous distributionof gases

C. Thermal effe s of inhomogeneitieson instabilities

pop f e JL ýx 0. S. A r IAr/v

Arse Lra No. DAAA - -c- OZ)8

102

1. Linearized Hydrodynamic, equations for

a three-component mixture

HAN + TEAN + water

Continuity equation +

Navier-Stokes equation

Conservation of energy "-r T,.•"-T

Conservation of particle species

= V(3T

103

Parameters for three component fluid

Thermodynamic

thermal ratios: 147 1

baricentric ratios: -Kp, KpK_

Transport

viscosities: 431"+'

thermal diffusion: D-Y C -Pchemical diffusion:

D, DaChemical Reactions

relaxation times: 2' 'C

enthalpic changes:

thermodynamic:

aT c)

104

A. Three-component fluid

solution of equations via Fourier-Laplace transform methods

R.D. Mountain, J. Res. NBS A72, 95(1968).R.D. Mountain and J.M. Deutch, J. Chem.

Phys. 50, 1103(1969).J.W. Haus, J. Chem. Phys. 60, 2638(1974).

5-component vector for the thermodynamicstate variables A.

A A~

IV3 (C, i P.10

105

The probability distribution for fluctuationsis statistically independent

the functions h(Q) are Gaussian:

V~. hC))' Gxf•~

The linearized hydrodynamic equations are

written in matrix form:N(A » /'- W2)e/'VAo)

'M(k,z) is the matrix of coefficients of

the variables in N(Z,z).

det(W) is a polynomial of order 5 in z.

It contains only even orders in k.

106

The determinant of 1 has the followingroots:

2 roots are complex, these are associatedwith the propagating modes

* =,

3 roots are real, these are diffusion modes

107

I A t I I. . 1

i) Light scattering spectrum ,

structure factor is the spectral density ofdielectric constant fluctuations.

spectrum of fluctuations in the statevariables

e F VA.Yj_.

108

ii) Ultrasonics

Frequency imposed by transducer,akin to light transmission experiment

absorption: wave intensity dimisheswith distance

dispersion:"time-of-flight" afterlaunching acoustic wave

det(M) gives solution for plane-wave propagation

?(o) e

d Ism.• rs l o n 17< 0-=

Co

aLSorp to\ _

1 0 9o - C 6

B. Chemically reacting fluid near equilibrium

-tft

eigenvalues of det(M)

+ zeý T

"-r'h r-t.•L p~r(- 4s 1.,e!, ÷ ; J''i~a1

110

2. Continuing research

A. InstabilitiesI) Thermodynamic, spinodal

decomposition

liquid-gas transition

phase separation of fluid components

••< 0 •A/ •,o

II) Chemical

model: change of activation energy withpressure:

lag

k4 o~ o

4-Tre roofT o:

Fh- -, civ4a'o ev ef-$y rx st

112

Inhomogeneous distribution of gases

LS0 0o

0 o

0 0

gas is easily compressed

a. large change of volume on compressionb. hot spots. They affect. the chemical

stability.

113

CONCLUSIONS

A. Hydrodynamic theory gives a completedescription that can unify both lightscattering and ultrasonic experimentsunder a single formalism.

B. The hydrodynamic theory providesinsight into modelling instabilitiesin fluid mixtures.

C. Chemical reactions change the lightscattering spectra, especially in theforward scattering direction, and theultrasonic absorption.

D. An inhomogeneous distribution ofreaction products could be modelledwithin this formalism.

114



30 AUG - 1 SEP 88

Title of Paper Ionic Aspects of the Decomposition of HAN Solution


Type of Paper: X Progress; Summary; State-of-art; Other

Speaker's Name Walter S. Koski Phone Number( 3 01 ) 3 3 8- 74 18

Affiliation/address Department of Chemistry, The Johns Hopkins University,Baltimore, Maryland 21218

Co-author(s) name(s) none


Abstract.

HAN aqueous solutions are stable at room temperature however

application of an appropriate stimulus either thermal or chemical can

initiate the decomposition of the HAN to produce N2 0, NO, N2 , NO2 , etc.

Since HAN solutions are highly ionic it is reasonable to examine the role

that ion-molecule reactions may play in the decomposition process. It is

believed that the initial step is a proton transfer reaction from the

hydroxylammonium ion so to this end the proton affinities of NH2 OH, NH3 , H2 0

and nitric acid will be discussed and a chemical mechanistic scenario will

be developed which is consistent with the known experimental facts of HAN

decomposition.

115

4th ANNUAL CONFERENCE ON RAN-BASED LIQUID PROPELLANTSTRUCTURE AND PROPERTIES


30 AUG - 1 SEP 88

Title of Paper Reaction Kinetics of HAN, TEAN and Water Mixtures Using a

Personal Computer


Type of Paper: X Pzogress; Summary; _ State-of-art; Other

Speaker's Name A.K. Macpherson Phone Number(215)758-4105

Affiliation/address Dept. of Mech. Engg. and Mechanics, Bethlehem, PA 18015

Co-author(s) name(s) A.J. Bracuti


A program has been developed to study the reaction kinetics of gun propellantssuch as the HAN based liquids using a personal computer. These HAN based systemscan be studied using a mainframe computer but often-require long run times. Inorder to eventually model the liquid propellant guns, including the fluid flow, itwas necessary to develop a fast reacting program which would form part of the finalsystem. In addition, a reaction program which could run on a PC is convenient forinitial testing of possible fuels. The main problem with any such system is thatthe equations are stiff with ideal time steps varying from lOE-18 seconds to10E+03 seconds. Under these conditions many integration schemes become unstable.An additional problem of using a PC is that the accuracy is limited and with longruns, the atom conservation can become badly in error.

A semi-implicit time advance scheme was used to obtain stability. The timestep was varied through a prescribed regime and equations were included or eliminateddepending on the particular part of the regime in operation. By varying the timestep pattern, the accuracy could always be improved at the expense of increasedcomputer time. The equilibrium conditions were calculated using the MCVECE code.Using the equilibrium conditions, the reaction kinetic code was used to studyvarious HAN, HAN-waLer, TEAN and TEAN-Water and the results compared with availableexperimental data.

116

ELECTRICAL IGNITION OF HAN-BASED LIQUID GUN PROPELLANTS

G. Klingenberg*, H. J. Frieske**, and H. Rockstroh*

* Fraunhofer-Institut for Kurzzeitdynamik, Ernst-Mach-Institut,Abteilung for Ballistik (EMI-AFB), Weil am Rhein, FRG

** Dynamit Nobel AG, Werk Dellbr~ck, Abteilung Grundlagen undZukunftstechnik, K6in, FR G

ABSTRACT

The present paper reports on progress achieved in the studyof the electrical ignition of the hydroxylammonium nitrate (HAN)based liquid gun propellant LP 1846. The goal of the present workis to develop an igniter system suitable for regenerative liquidpropellant guns. Several igniter configurations, designed by theBallistic Research Laboratory (BRL) and the Ernst-Mach-Institute(EMI-AFB), have been tested. Voltage and current as well as thepressure histories were measured for each discharge. The electro-static field distribution was calculated by a finite element codeimplemented at Dynamit Nobel. The theoretical analysis yieldedimproved electrode designs for future testing.

1. INTRODUCTION

The discharge by an igniter system into the combustion chamberof a regenerative liquid propellant gun (RLPG) builds up the pres-sure required to set the injector piston into motion and to generatethe energy for igniting the liquid propellant (LP) thus injected.Solid propellant igniters are currently being used to initiate thecombustion in medium and large caliber RLPGs. However, the goal ofthe future RLPG development is to incorporate a liquid propellantignition system eliminating solid propellants from the logistic

train [1]. One LP used for the tests is LGP 1846, which containshydroxylammonium nitrate (HAN), triethanolammonium nitrate (TEAN),and water [2]. Since LGP 1846 is an electrolyte, primarily electri-cal ignition has been studied so far.

117T

2. EXPERIMENTAL

The ignition experiments were conducted with two different

ignition test fixture types used in the closed bomb mode.

2.1 Test Fixture No. 1

A view of the first test chamber is shown in Figure 1. It ccprises the isochoric test chamber equipped with pressure gage ancrupture disk or sapphire window and the center electrode assembl1

The test chamber volume can be preselected, via an insert, to 60.or 101 cm3.

TEST CHAMBER BODY

E GAG Kilter

L _• TEST CHAMBER

VOLUME WITH INSERTVOLUIE WITHOUT INSERT

CAVITY HOUSINQ

F.LECTOOOf WITH VENiT

CgNTEP ELEC[TRODE

/" / • •ADAPTOR

Fig. 1. EMI-AFB test chamber (first design)

118

The center electrode assembly is depicted in somewhat greater

detail in Figure 2. The principle structural features of this

S STEEL (42 CrMok V)

SNYLON

GLAS CERAMIC 914

TEFLON

PLA STIC

Fig. 2. Center electrode assembly

assembly are the center electrode, the vented outer electrode and

the base insulator. Figure 2 displays a more recent design than

Figure 1. Two igniter cavity configurations were investigated:

One, a design introduced by BRL; the other developed by EMI-AFB

(Figs. 3 and 4).

_--_- .• .-- T

:ý 16

VOLUME :1.9cm3

Fig. 3. BRL type igniter cavity

119

VOLUME 1.9cm 3

Fig. 4. EMI-AFB type igniter cavity

The cavity volume was 1.9 cm3 in both cases. During the course of

the experiments,the vent diameters were narrowed from 2 to 1.6 mm

thus improving the confinement of the liquid propellant fill.

2.1.1 BRL Igniter Configuration

The study commenced with one of the BRL type [(] configurations

(Fig. 3) according to the request of the contracting agency. The

design tested at EMI-AFB is characterized by its cylindrical cavity

and the fact that the center electrode ends well below the insu-

lator's upper edge.

2.1.2 EMI-AFB Igniter Configuration

Figure 4 shows the igniter configuration designed at EMI-AFB.

The cavity is circular rather than cylindrical; in addition, the

center electrode protrudes further upward into the cavity.

120


A special test chamber has been designed and built at EMI-AFB

(Fig. 5). This chamber includes sapphire windows for monitoring the

ignition process by optical techniques and a measuring port for

S, ELECTRODE

ELECTRODE WINDOW

Fig. 5. EMI-AFB test chamber (second design)

recording the pressure or temperature history. The fill volume of

20 cm 3 can be reduced by appropriate inserts. In our current

experiments a volume of 6.7 cm3 was used. Various electrode con-

figurations can be built into the chamber. The configurations

tested so far include plate, sphere, and needle electrodes (Fig. 6).

The maximum pressure is limited to 60 MPa by the rupture disk.

Fig. 6. Basic electrode configurations

121

3. SAMPLE RESULTS

3.1 BRL Igniter Configuration

Tests were conducted with the test fixture number 1 using both

the 101 and 60 cm3 volumes. In the latter tests the vent diameters

were 2.0, 1.8, and 1.6 mm, respectively; some of the data measured

are summarized in Table 1. Note, that the maximum pressure is

determined by the rupture disk to pmax = 16 MPa.

Table 1.. Tests of BRL igniter cavity; chamber volume: 60 cm3

Test Vent Volume Current Voltage Power Energy Pressure IgnitionNo. Orifice of LP I U P E Pmax Delay

Diam.[mm] [cm I [A] [Volt] [kW] [Joule] [MPa] IrMs

1 1.6 1.9 132 1700 192 79 16.4 1.6

2 1.6 1.9 147 1660 225 88 15.1 1.6

3 1.8 1.9 128 1600 184 101 16.5 2.9

4 1.8 1.9 127 1620 184 94 16.0 2.8

5 1.8 1.9 130 1660 193 91 15.9 2.9

For a vent diameter of 2.0 mm, the ignition characteristi-s

was poor. In several cases there was no ignition of the LP. In

other cases s,.bstantial amounts of LP were expelled prematurely

into the test chamber. The shortest ignition delays were obtained

with the higheit confinement of 1.6 mm vent diameter. Generally,

the reproducibility of the tests was unsatisfactory. A possible

explanation for this will be given in the theoretical section.

In view of the above results the subsequent tests with the

chamber volume of 101 cm 3 were performed using the 1.6 mm vent

diameter exclusively (Table 2). The scatter of the ignition delay

is not really improved.

122

Table 2. Tests of BRL igniter ca-vity; chamber volume: 101 cm 3

Test Vent Volume Current Voltage Power Energy Pressure IgnitionNo. Orifice of LP I U P E Pmax Delay

Diam.3

(mm] [cm 3 [A] (Volt] [kW] [Joule] [MPa] [ms]

6 1.6 1.9 140 1560 200 85 9.0 1.7

7 1.6 1.9 130 1650 194 63 12.0 1.3

8 1.6 1.9 145 1580 208 78 12.5 1.0

9 1 6 1.9 153 1560 210 84 9.5 2.2

10 1.9 133 1650 195 60 8.5 1.9

3.2 EMI-AFB Igniter Configuration

The EMI-AFR cavity configuration is essentially a geometrically

compressed version of the BRL design. The basic idea was to produce

an even spacing in the field lines centered at the tip of the inner

electrode. It was assumed that this would ensure improved ignition

behavior. Sample results of these experiments are summarized in

Table 3. When compared with the data of Table 1, less electrical

energy is required to achieve sustained ignition with the EMI-AFB

configuration. Also, the ignition delay is significantly reduced.

Table 3. Tests of EMI-AFB igniter cavity; chamber volume: 60 cm 3

Test Vent Volume Current Voltage Power Energy Pressure IgnitionNo. Orifice of L? I U P E Pmax Delay

Diam.3 [o(mm] [CM I [A] [Volt] [kW] [joule] [MPa) [ms]

11 1.6 1.9 180 1500 215 66 11.6 1.2

12 1.6 1.9 175 1550 225 62 11.5 1.2

13 1.6 1.S 170 1550 215 56 12.5 1.1

14 1.6 1.9 180 1700 250 59 11.5 0.9

15 1.6 1.9 170 1500 220 68 12.0 1.2

123


This design permits the investigation of both conductive andnon-conductive LPs, by generating either a plasma through an arc

discharge or by electrochemical initiation. The following anode-

cathode configurations have been tested so far: (1) plate-plate,

(2) sphere-plate, (3) needle-plate, and (4) sphere-sphere.

Preliminary results indicate that at the selected electrode

distance of 7.2 mm the configuration (3) yields an arc discharge

but no ignition. Comparatively, the other configurations gave

electrochemical ignition. However, extremely long and inconsistent

ignition delays were observed. Generally, ignition took place well

after the current had been shut off (30 ms - 1.5 min). The investi-

gation of the physical and chemical processes involved by optical

means, starting with high-speed camera recordings, has begun.

4. CALCULATION OF ELECTRICAL FIELD

The calculation of the electrical field between the electrodes

was made by means of a finite element code for the electrostatic

case. This work was carried out for the BRL and EiI-AFB igniter

cavity configurations. In addition, a modified version is proposed

aiming at an optimal field distribution.

The calculated field lines for the BRL and EMI-AFB configu-

rations are drawn in Figures 7 and'8. The spaces or segments

between individual field lines are numbered 1 to 11. The segment

sizes were chosen for convenience. Figure 9 depicts the change of

electrode surface areas and the segment volume versus the segmentnumber. No distinct differences are seen for the center electrode

surface area curves (Fig. 9 A). Comparatively, the outer electrodesurface area curves are characterized by the existence of a maximum.

The maximum surface for the BRL configuration is to be found at

segment number 4, that for the EMI-AFB type at segment number 8

124

SEGMENT 3

2

6

7

9

10

11

Fig. 7. Field lines calculated for BRL type igniter cavity

2)

7, ,

9

Fig. 8. Field lines calculated for E:MT-AFB type. Lgniter cavity

EVALUATION FROM PREDICTED FIELD LINESEMI TYPE IGNITER CAVITY- RL TYPE IGNITER CAVITY

A

20 CENTER

EMI ELECTRODE

I SURFACEL, AREA4

BRL< 10

2 3 4 5 6 7 8 9 10

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Lu

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C

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z SEGMENTSD o x..X\ X-/ /e

Lu NS10 Xx "73RL

wp

2 3 6 1b

SEGMENT NUMBER

Fig. 9. Electrode surface area and volume of segments versussegment number for BRL and EMI-AFB type igniter cavities

(Fig. 9 B). The corresponding volume curves, whose maxima are at

segments numbers 4 and 9, respectively, are shown in Figure 9 C.

126

Ignition is expected to be favored in the vicinities of the

minima of the curves in Figure 9. That is, for the BRL design

there are two such regions, one at the inner electrode in seg-

ments 2, 3, 4, the other at the outer electrode in segments 8, 9,

10 (Fig. 7). Contrarily, the EMI-AFB design has only one such

favored region, namely in segments 2, 3, 4 for both electrodes

(Fig. 8).

The points made above suggest that an optimized cavity geo-

metry should feature both an even spacing of the field lines and

a narrow surface/volume minimum at or near the tip of the center

electrode. Figure 10 shows such a configuration, obtained from the

computer calculations. The corresponding surface area/volume versus

segment number curves are drawn in Figure 11.

10

*11

Fig. 10. Field lines calculated for optimized version ofigniter cavity

127

EVALUATION FROM PREDICTED FIELD LINES

I OPTIMIZED IGNITER CAVITY I

30-

CENTERELECTRODE

z- 2 0 SURFACEAREA

wI--

w

2 3 4 5 6 7 8 9 10

30-

z 20 OUTERELECTRODE

w SURFACEAREA

-j lo-w

2 3 4 5 6 7 8 9 `10

"30

I-

: 20

_> VOLUMEOFSEGMENTS

,• 10

2 3 4 5 6 7 8 9 10

Fig. 11. Su.td.ce area and volume of segments versus segmentnumber for optimized version of igniter cavity

128

5. CONCLUDING REMARKS

Although it is tempting to speculate on the connection between

the experimental data in Tables 1 and 3 and the theoretical results

in the last section, we prefer to wait for the test results of the

modified chamber. We do not expect to find a simple connection

between the electrostatic field line distribution and the ignition

behavior. In reality, a non-uniform time-varying electrical field

develops in the liquid propellant charge interacting with the

electrolyte.

Our scepticism is reinforced by the preliminary results ob-tained with the EMI-AFB test fixture (Section 3.3). Apart from the,

unsurprising, occurrence of an arc discharge for the needle-plate

geometry, the ignition delays did not seem to follow any pattern.

However, it may well be that electrode surface uniformity plays a

more important role than previously appreciated. In this case, the

conventional finishing procedure will prove to have been inadequate.

The extreme scatter of the ignition delays indicates that factors

other than the basic electrochemistry may come into play.

ACKNOWLEDGEMENT

The authors would like to acknowledge that the research work

reported in this paper has been made possible through the support

and sponsorship of both the Ministry of Defence of the Federal

Republic of Germany and the U.S. Government through its Ballistic

Research Laboratory via its European Research Office as well as

through the inhouse funding of the Dynamit Nobel AG. Also, the

authors would like to thank Messrs. 0. Wieland and R. Roschig for

their assistance in this work.

129

REFERENCES

[1] J. DeSpirito, J. D. Knapton, and I. C. Stobie, "Progress onElectrical Ignition of Liquid Gun Propellants for Applicationin Regenerative Liquid Propellant Guns", Proceedings of the24th JANNAF Combustion Meeting, Monterey, CA, October 1982.

[2] W. F. Morrison, J. D. Knapton, and G. Klingenberg,"Regenerative Injection Liquid Propellant Guns", Journal ofBallistics, Vol. 8, No. 3, July 1985, pp. 2026-2060.

13 0


US ARMY BALLISTIC RESEARCH LABORATORYABERDEEN PROVING GROUND. HD

30 AUG - 1 SEP 88

Title of Paper The Burning Rate of HAN-Based Liquid Propellants: Fhe Effect

of HAN Concentration on Burning Rates


Type of Paper: __ Progress; Summary; X State-of-art; Other

Speaker's Name Steven R. Vosen Phone Number(4l_) 294-3434Affiliation/address Sandia National Laboratories

Livermore, CA 94550

Co-author(s) name(s)ABSTRACT (Use reverse side if necessary)

Propellants being considered for use in liquid propellant (LP) guns consist of astoichiometric mixture of the salts hydroxylammonium nitrate (HAN) and triethanolammoniumnitrate (TEAN) in water. The flame structure at pressures of less than 34 MPa has been shown1

to consist of a HAN decomposition reaction followed by a TEAN decomposition reaction. Theburning rate of the propellant has been shown to be limited by the decomposition rate of HAN, tothe extent that HAN decomposition may occur in the absence of TEAN. One implication of this isthat it may be possible to sustain a "fume-off' in which HAN decomposes (releasing 20% of theheat of reaction), resulting in a highly explosive mixture. In an attempt to better understand theinitial reactions which occur during LP combustion, previous experiments were conducted onHAN-water mixtures which have the same HAN concentration as does LP. This provides onewith information on the initial reactions which occur in an LP flame and also closely approximatesthe burning rate of the propellant.

To obtain more information on the HAN decomposition reaction as it occurs in a flame, aseries of experiments will be conducted on HAN-water mixtures of varying concentrations atvarious pressures. Specifically, HAN-water concentrations of 13, 11, 9, 7 and 5 molar will beconducted at pressures of 6 MPa to 34 MPa. (For comparison, LP 1846 is 9.1 molar HAN andbums at these pressures during the ignition of LP guns.) The mixtures will be contained in astrand burner while undergoing combustion at approximately constant pressure (less than 1%pressure increase duiing combustion) and will be observed by shadowgraph photography. Thiswill provide information on the importance of HAN decomposition on the burning rates of LP, onthe presence of drops in the region above the decomposing liquid, and on the stability of the liquid-gas interface. In addition, the relationship between HAN concentration and pressure on thedecomposition rate will be indicative of the importance of condensed phase reactions in thedecomposition of HAN.

* This work is sponsored at Sandia National Laboratories by a cooperative research and development program funded

by the Department of Energy and the Department of Army.

1 Vosen, S. R. "The Burning Rate of HAN-Based Liquid Propellants." To appear in the Twenty-second(International) Symposium on Combustion, also in the Twenty-fourth JANNAF Combustion Meeting, October1987.

131

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US ARMY BALLISTIC RESEARCH LABORATORYABERDEEN PROVING GROUND. MD

30 AUG - 1 SEP 88

Title of Paper Study of Thermal Diffusive-Reactive Instability in LiquidPropellants: The Effects of Surface Tension and Gravity


Type of Paper: __ Progress; Summary; X State-of-art; Other

Speaker's Name Robert C. Armstrong Phone Number(415) 294-2470

Affiliation/address Sandia National Laboratories

Livermore, CA 94551

Co-author(s) name(s) S. B. Margolis


We have extended previous work by considering a thermal and pressure dependenceto the reaction dynamics. We predict that, in addition to the well-known cellularinstabilities first found by Landau, pulsating instabilities will be found associated withflame interaction with the thermal and pressure (hydrodynamic) fields. These resultsare found in the limit of small gas-phase density and are related to similar resultsfound for solid propellants. As a consequence of this discovery, it is predicted thatthere are regimes of instability under conditions that would have been predicted stableby previous work. Entirely different behavior is found for a relatively dense gas phase.We predict a separate new mechanism for instability that is a direct interactionbetween convection cooling of the flame and the thermal field's ability to restore itselfvia thermal diffusion.

it becomes evident from this and previous work that many regimes of instability inliquid propellant combustion are possible and even likely. Some direction fromexperiment is necessary to make the best use of theoretical effort. We will discussthe ways in which stability analyses can be used to interpret liquid propellantexperimental data for the purpose of uncovering which of the proposed mechanisms ofinstability are present in physical systems.

This work sponsored at Sandia National Laboratories by a cooperative research anddevelopment program funded by the Department of Energy and the Departmert ofArmy.

154

Title of Paper: The Response of an LP to Heating at High Pressure

Presentation Time Requested: 15 min.

Type. of Paper: Progress

Speaker's Name: Richard A. Beyer

Affiliation: US Army Ballistic Research LaboratorySLCBR-IB-IAPG, MD 21005-5066

A series of experiments has been performed with the goal ofunderstanding the rate and phenomenology of the energy release ofdrops of a liquid monopropellant when subjected to hot, high pressureflows. The propellant studied was TLP 1846.

The studies to be reported has involved the application ofincreased pressure, up to 4000 psi (28 MPa). Although incomplete,several interesting observations have been made. The primarydiagnostic has been high speed photography. Drops have been heatedeither by placing them in electrically heated regions while suspendedon 10 um diameter carbon fibers, or by directly heating the wireholding them. In the first case, helium gas was used to maximizethermal conductivity to the drops and to maintain good visualizationof event. Over a range from 2000 to 4000 psi, the drops were found tappear quiescent for a time up to 500 msec, with no change intransmission (the liquid is transparent until reactions begin) ordiameter; they then gassify in a time on the order of 1 millisecond.The evolved gases are relatively transparent. Any light emissionwould probably not be detected. If a drop is similarly suspended afew drop diameters from a heating wire, the time to drop gasificationis shorter, as expected, and results in a cloud of high opticaldensity gas. This difference suggests that significant liquid phasereactions are taking place in the first case.

Drops have also been studied by directly heating the suspendingwire. In studies with fine (25 um) diameter wires, there appears tobe an important pressure effect on behavior. In all cases the evolvegases are very dense. At pressures below a threshold which is near1500 psi (10 MPa), gases evolve from the contact point of the wirewith the drop for up to ten milliseconds or more, and the processstops if the current is turned off to the wire. Above the apparentthreshold the gasification of the drop is rapid (ca. 1 msec) andirreversible; in events where the drop was thrown from the wire bymotion upon heating, the drop gasified rapidly while free at higherpressures, but merely emitted a small puff of gas and then stabilizeduntil leaving the field of view (several msec) at lower pressures.Studies are under way to determine if this threshold is as sharp aspreliminary work indicates.

Studies into the mechanism of drop ignition are also of interestThese have been pursued by placing a s'rnewhat larger drop (1 mm dia.)on 22 ga. nichrome wire. Imaging of emitted light shows that a flameis present in the gas phase well away from the wire, suggesting thatthe drop completely gasifies and then ignites and burns as a premixedgas phase flame. Present efforts are to identify and time resolve themission from this flame to identify possible roles of the various LPcomponents.

155

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>- F- > :LU 2 l. CL CDCID W- U-) F-V )

cr- _-rLUIu LUL >: Lii LiiI

2: 2: C) ~c * U ) ( -'

190

2 L, D

LZo ! u

-4•o

4.'+

V/v0

EG UATior,. O f- CT/-rT fb-,/ etqA-?~r •PM'E-E /,JoCL-

191

U-,

~f-) LUJ

CDD

C3-

LU-

= LIJ

L-4

CZ)C

CD

U-LL)

Bes zvialeCp

-4

LLJL

CD

LDLL

CCD

LUU-, LOLUJ: : LC:

LU J CO (VI' L

Lj - ':: 'j L

u~~C (OIU -4C- L UJ ::: 1.

LU.c

ZD __ -

LLU)

J LLJ /7'LJ'~ d

I,)- LU- J-4L) -J~

LU V)Q Z:

LLJ~L LU C

*~~ + ~r~II LU__ ' 0 <

-~ Z +

>U ,7-1,Z

-4 c~>

_ t.

_~~C >~,I~i

-~ --~C":

19 ep o u ed F o

BetAvialeCp

Vt)

$-4

-4

C) 0

-- 4 -2- N - r-, -4 -4 OD.ý ~ r-ý CD>< r- r- 00 co C N a\ aN Cz CD a) --4

ý. _ -zr - zr -z' -:r Uf" ) N ' U(N

LAJI-

4.,)

CD ) >-

- LU

M *L I-- * * . * * - C

t4D , --- C=: UNI 00C -4) I'D r.- r- CO

COJ 0 O \0 KO-4aN 10 -r -4co \0 U4i CDr> \0 \0 %In 110 L(Ný UN' UNý UN # -T -z m~ VDL)

LLU LAJzX LU I

.4 cr- CCCC C) 3m

I- Lco LU) LUCD cn -j

C)

=) CD(ni CD )

\O L?) LfD C:)

-4- >J

z V4) LI,M (-.4 r- UNs \O iUr% ONý CI-. --4 r-. r- 0r1 '-

0...- * ft * * * * U.JJ iC>< ON ON U4 -4 (N NO ý UN UN rl CD ý- m a. LU

LU , ( N 1.1 -.2 \O0 -- CD C(N r-- U"N \0 2-W CU *:--4 N lZ re't ON UrN CD -T r- CD (N4 -4C D -J :Z

U- Ln CD )c:: (n CD

*u M CD

= :Z- LU

cLLw LU L c

OfD crz cCD1 -

W~ CD C-) CD CZ) CD CD CDý CD CD CD CDz CD) CD CD CD CZ) CD CD CD CD CD

UNLf% CD UN, CD UNl CD UN) CD U"% CD-- - (i (N4 r f t --Ij -- UN

194

Physical Properties of Liquid Propellants:

Measurements of Shear Viscosity, Volume Viscosity and Density

J. Schroeder , C.S. Choi , Y.T. Lee

Department of Physics

Rensselaer Polytechnic Institute

Troy, NY

J. Frankel

Watervliet Arsenal

Watervliet, NY

Supported in part by U.S. Army, Watervliet Arsenal, Grant No. DAAA

22-85-C-0218.195

P-s .- LVOT

-Wkl1d Bellows

I

Tapered Bross RingTube

Pressure Vessel

Tube Holde

Thermocouple

2.2

P 16

The density ' can be obtained from the

following equation

M4

where M is the mass of fluid in the bellows, f is

the fluid density at temperature T and atmospheric

pressure, Ao is the bellows cross-sectional area

at reference temperature T0 and atmospheric pres-

sure. Cý is the linear coefficient of compres-

sibility of stainless steel, '1P- Y" is the change0

of bellows length. The bellows cross-sectional

area A is determined by calibration with distilled

water.

197

400-

y 5.7002 + 1.4140e-2x RA2 = 1.000

40" 300"NX

"200

w 100

Water at 27C

00 10000 20000 30000

PRESSURE(psi)

198

661

a o-

AIIoM30+

100000*

KnaptonLP84 LP1 845

10000

__1000

0.-I

0o Our Data

U- 100

10 I0 ~Messina "

-80 -60 -40 -20 0 20 40

TEMPERATURE(C)

2(00

1.8

LP1845

1.7

-• "- 27CS. 47C

-m 1.6 •U- -14C4,- -32C

in-zw

1.4

0 10000 20000 30000 40000 50000 60000

PRESSURE(psi)

201

0.3

LP1845

7C

0.2 27C

> -14C

0.1

-32C

Costatino(25C)0.00 20000 40000 60000 80000

PRESSURE(psi)

202

Vlcswwtpe Tube moletClew* Plug

t LVDT

Viscometer Tube

Ir Tapered Broas RkviKeI-F Spacer

2 03

TEMP(K)

300 280 260 240

1000

LP1845

C-

100

t)0

10

1 0 ...- I '" ' " I , , * , , * . ..

0.0032 0.0034 0.0036 0.0038 0.0040 0.0042

1/TEMP(1/K)

20/4

Viscosity measurements

Viscosities of LP1845 as a function of temperature and pressurewere measured by a high pressure falling slug viscometer ofsimiliar design as that descrived by R.J. Mclachlan1 ). To detect thefalling time exactly a linear variable differential transformer(LVDT)was used. The viscosity r' of the liquid at a given temperature andpressure for a right circular cylinder of radius r falling vertically fora distance of L in a tube of radius R, is proportional to the fallingtime T of the slug and is given by the equationl), 2)

T(p I-p2)r 2 g ((R 2+r 2 )ln(R/r)-.(R 2 -r2 )2)Ti - 2L(R 2 +r2)

where p, and P2 are densities of the slug and liquid respectively, and

g is the acceleration due to gravity. In deviations of above equationend effects have been neglected and it can be simplified as

r = c (pt-P 2)T

where c is the proportionality constant. The proportionality

constant was determined experimentally by using Brookfieldviscosity standard fluid(50.5 cp, 0.960 g/ml at 25 C). Allmeasurements for calibration were made at constant temperaturewithin 0.1 C and atmospheric pressure. Special attention was paid tocleanliness of the viscometer and removal of air bubbles in theliquid. Viscosity measurements of LP1845 were performed atvarious temperatures and pressures. To reduce the experimentalerror, the falling time was measured at least six times at samecondition. The results are shown in the table.

205

Table. Viscosity of LP-1845Temperature Density * Viscosity

(C) (g/ml) (cp)25.0 1.4515 11.3313.4 1.4596 15.034.9 1.4657 20.36-2.8 1.4712 28.65

-13.6 1.4786 56.74-21.2 1.4846 70.12-28.0 1.4893 161.66

*Extrapolated value from N.A. Messina et. al 3)

o. Reference

1) R.J. Mclachlan, Journal of physics E; Scientific Instruments, 1976,

vol.9, p391-394.

2) J.B. Irving and A.J. Barlow, Journal of physics E; Scientific

Instruments, 1971, vo14, p232-236.

3) N.A. Messina et. al., Preceedongs of the 21st JANNAF Combustion

Meeting, vol.11, CPIA Publication 412, Oct. 1984, p515.

20(

1000

LP1845

7C

-140

S1 OC-7

100

Ep)0

27C

100 10000 20000 30000 40000 50000 60000

PRESSU RE(psi)

207

1000

LP1845

-17C

S100

(I)

Cl7C

270

10.0001 .001 .01

1/PRESSURE(I/psi)

208

SF~iLLOUIN SCATTERING SYSTEM WITH STABLE $-PASSFA13RY-PEROT ANTERFEROMETEP

POWER MIT"SAMPLE Jm musj mS

14NHOLE ISPATIAL FILTERI

(OLAN.THOMPSOANALYZER PAISMBEMSLT

PAR~OREFLECTOR /

WfL~TIAC / POLARIZATWIO- ~ -d SCREEN.1 ROTATOR

FA Y PE O 2 / A R -E OMIFARYEORS 00"FROME

RETRO-REFLECTOR

AvA

SPECTRUM' .

L4 ANALYZER

APEATURESTOP ARGO"N-'oWI SER

SINGLEPM. TUSEM(r-FW 130 MODUETALON :

I- - II-- -- -- - --- IfpHOTON L' DATA ACOUISITION AND I

-1COU~nTERI ISTABULAZTION SYSTEM 1

n QU)

44 >

z oz +

) ;:4 4

0 0-4

-~~~1 0 4H ~

E-4 C I 0~-~ ~ H ~~z

E4-4 )~~~b0-4

0 Z Q ~ n

U)P-4

nimm nI AvI "S' "/V-V V i :

la.. 0( / ,- e ,

-- *

o° 9 / ..

U ; " ..- 0 ._

C•

° 9

- ..0

I1

0 x

U-3 Li.

.Jm

L..1L&.

em -

.4b

("I"

Ilk..

N83

N8

0 lid

a~ at

_~ C.)

AY01

1 3O

RAYLEIGH - BRILLOUIN

LIGHT SCATTERING

I= 0Cp '- < p 2 > + -1,El2 <Ac >

Density Fluctuations:

:- Concentration flucutatirbns:

[De termi ne f r om Ul t r asonic 11IHyper sonic Measurements

Measurement of this quantity as a function of T, P or Concentrationwill allow the study of the critical point of phase separation. RayleighLinewidth becomes very narrow, and .Rayleigh line becomes vey.inten. Henc, s y stability of Binary fluid mixtures.

214

p

Co

00

j~4ýcuD

U-;S 'in."vl-WPW

21

x 4

Lr) X4

(A 40 x 44

X 44

X44

c x

C)x 44

o RbCl 43

0~216

*Vs(-9 GHz)/ q

A Vs (1OMHz) pd

U'4(&( 9GWz)/

a/ ~;3o'E

=IR .2

moi l j 1.,-.l 1 1-1 'fo 16= am ww26028 3wl'

Tepeatre(K

2 17

00

0

0 ae

CSS

em bmmN4.

-~218

BRILLOUIN SCATTERING AT HIGH PRESSURE

V = AvAd/2

"C AXIS

. .. -- ~2n V2=

FIG. 4

14~ Z~4. -I4 .

~--~ LL JC7

/ /n

~~0/ Uj

/U :7w

CC 2 21~ 3 S~W

un/

THE SOLUBILITY OF GASES UNDER PRESSURE

IN LIQUID PROPELLANTS

S. MURAD / P. RAVI

UNIVERSITY OF ILLINOIS

CHICAGO

AUGUST 1988

222

ABSTRACT

A corresponding states correlation has been developed for thesolubility of pure gases and mixtures In LGP 1846, a HAN basedliquid propellant (1]. For nitrogen, methane, xenon, krypton, andargon, and their mixtures the correlation can be used to estimategas solubilities for pressures upto 100 MPa in the temperature range258 < T < 303 K. The correlation is in satisfactory agreement withall available experimental data for these systems. Dissolved gasesare expected to significantly effect many physical and chemicalproperties of liquid propellant systems.

223

INTRODUCTION

Aqueous solutions of hydroxyl ammonium nitrate (HAN), andaliphatic amine nitrates (AAN), posses excellent potential for use ashigh performance liquid propellants. One such propellant beingactively considered is LGP 1846, which consists of 60.79, 19.19, and20.02 weight percent of HAN, triethanol ammonium nitrate (TEAN),and water, respectively. [2]. The physical properties of thesepropellants are needed to model their behavior in the gun, wherethey can be under high pressures, and in contact with combustiongases. Since such gases can in general be expected to be soluble tosome extent in the propellants, there is a need for a reliable methodfor predicting such solubilities, especially under high pressures.Dissolved gases are known to significantly affect many physical andchemical properties of aqueous solutions.

The corresponding states theory is a powerful tool for predictingthermodynamic and transport properties of fluids. However, theconditions that must be satisfied for the simple correspondingstates principle to be valid are only obeyed by simple molecules likepure argon , krypton, and xenon [3]. In this paper we extend thesimple corresponding states theory to include more complexsubstances that do not satisfy these conditions. This has beenaccomplished by replacing the critical parameters (usuallytemperature and volume) generally used in corresponding states, bytwo adustable parameters. These parameters can be obtained fromvery limited experimental data. The technique used is similar inspirit ID the shape factor method which has been widely used topredict thermodynamic and transport properties for a wide range ofsubstances [4,5].

THEORY

The solubility of a gas in a liquid can be conveniently estimated viaits fugacity. At equilibrium the fugacity of any component i must beequal in both the gas and liquid phases [6],

f(G) =(L)f =fI (1)

The fugacity in the gas phase can usually be estimated usinggeneralized corresponding states charts,which are widely available[7], although if necessary it can be directly obtained from therelationship

(G) P PRTIn( 1-)= --- (2)

where R is the universal gas constant, T the temperature, P thepressure, Yi the mole fraction of i In the gas phase, and Vi the partialmolar volume of i. The integral in eqn. (2) can be evaluated using asuitable equation of state. For the more common substances, suchequations of state are available [8].

For the liquid phase the fugacity can be estimated from [9],

Pf (L)= ;jxtHisexp *-V)dP)

i RT (3)

where Hs is the Henry's constant in the solvent, ;1 the activity

coefficient, and xi the mole fraction of I in the solution. When xi-> 0

(in practice less than 0.1), ; 1-> 1. Since we expect our solubilities to

be rather low, and assuming Vi to be independent of pressure (anassumption generally acceptable up to 100 MPa), eqn. (3) can besimplified to

225

f(L) W 0 Pv) (4)

From eqns. (1) & (4), the solubility of the gas can be estimated as

(G) 0 vxi = f /i i exp (-) (5)

(QThus in addition to fi , to predict the solubility of gases in liquid

0propellants, data is needed on His and Vt. In the next section wedescribe how these can be estomated using corresponding states.

RESULTS

The fugacity of component i In the gas phase can be obtained usinggeneralized corresponding states tables or charts, e.g., thoseprovided in Lewis and Randall [7]. For pure gases,

(f/P)P"' = (f/p)o[(f/P)l] (6)

where (f/P)°and (f/P)1 are generally given as a function of reducedtemperature and pressure, and w is the Pitzer acentricity factor [9].For mixtures , one can generally make the assumption of idealmixing , especially when the constituents of the mixture havesimilar chemical structure. In such cases the fugacity of componenti in a mixture is given by

226

f(C) PurMf =yf (7)

To test the accuracy of this generalized corresponding statesmethod for fugacity for the gases of interest to us, we alsocalculated fugacities using the rigorous definition of eqn. (2), usingaccurate equations of state. Both the methods showed excellentagreement. For mixtures we used a revised Redlich - Kwongequation [10] with eqn. (2).

Henry's constants for gases in solvents can be estimated fromsolubility data at atmospheric pressure and eqn. (5).

Hi1s = P/x()

(Qsince at low pressures fi -> P and PV i/RT -> 0. Experimental data onthe solubility of various simple gases in LGP 1846 has beenmeasured recently by Koski [11]. We have used this data to obtain ageneralized correlation for Henry's constant,

H = -206.7 + 3.992 T -0.0126 T , (9)

where H1s= H°/I3 and T'- T/ 1,. Values of ',i and Pi for various gasesin LGP 1846 are given in Table 1. Figure I shows a comparison ofvalues for Henry's constants from the corresponding statescorrelation given by eqn (9), and the available experimental data. Ascan be seen, the correlation represents the data quite accurately.

There are no experimental measurements available for Vi of thegases studied here in LGP 1846. However experimental data is

available for V, in water and other concentrated aqueous electrolytesolutions. Eqn. (2) applied to the solubility oi gases in water andlelectrolyte solutions leads to the expression

W 0x _x = H iss exp{ "[iE (10O)SES 0 RTX1 H R,W

An examination of experimental data [12,131 on gas solubilities inwater, and aqueous electrolyte solutions at pressures between 0.1

and 60 MPa, clearly shows that although xi /xi is a function oftemperature, it is independent of.pressure. From the form of eqn

(10), this can only be possible if V 's-_V1,.w. We have extended this

result to LGP 1846 and approximated Vi data in water as V1 for these

gases in LGP 1846. Such "experimental data" for Vi was then fittedto a generalized corresponding states correlation,

* .V -0.0156 + 33.26T , (11)

where Vi=V1 Pi/RTi and T TPi/CsTi

Here Pf and T, are the critical pressure and temperature of i, and Csis the cohesive energy density of LGP 1846, originally introduced byScatchard and Hildebrand in developing the regular solution theory[6]. Since water is the only volatile substance in LGP 1846 attemperatures of interest to us, this would essentially be the value

for water. Figure 2 shows a comparison of Vii values predicted usingthe corresponding states correlation of eqn. (11), and availableexperimental data [12,13]. In view of the relatively largeuncertainties in such experimental measurements, the correlation isquite satisfactory.

228

The solubility of gases under pressure can now be obtained by usingeqn (5). The fugacity in the gas phase can be obtained using thecorrelations available in the literature (see eqns 6 and 7). TheHenry's constants required in eqn (5), can be obtained from thecorrelation developed here (eqn 9), and the partial molar volumes

from eqn (11). Experimental data is not available for the solubility

of gases in liquid propellants, at high pressures. It is therefore not

possible to test our method for liquid propellants. However, limited

data is available on gases in aqueous solutions such as sodium

chloride. In Figure 2A we have compared results obtained using thetechnique outlined above with experimental data for N2 in aqueous

sodium chloride [12]. The results confirm the general validity ofassumptions we have made for a wide range of pressures.

The results for five pure gases ( Ar, Kr, Xe, NT2 and cH 4 ).are shown in

Figures 3 to 7. The solubility increases with pressure, but the rateof increase of solubility with pressure decreases with increasingpressure. The solubility also increases with temperature at low andmoderate pressures, but it appears that there may be an inversion inthis temperature dependence at high pressures (around 100 MPa).Although, this inversion is within the estimated accuracy of ourpredictions, it is clear, that the temperature dependence ofsolubility varies considerably over the pressure range 0 to 100 MPa.The behavior of xenon is somewhat different from that of the othersimple gases. This is because the critical temperature of xenon is289.7 K, which is close to the ambie•it temperatures studied here.

The solubility of simple gas mixtures in LGP 1846 is shown inFigures 8 and 9 for N(-I 4, and Ar-cH 4 , respectively, for three

composition.•. The solubility of the mixture as a function ofpressure increases as the mole fraction of the component with thehigher critical pressure increases. The solubility of the Ar-cl-i 4

mixture does not vary much with composition, as the criticalpressures of the two are very close to each other, although there

seems to be an inversion in the composition dependence at around700 atm. This again is within the estimated accuracy of ourpredictions. The pressure dependence of the solubility is similarand the temperature dependence is expected to be the same as for

229

the pure gases. Similar results are obtained for Ar-N, and Kr-cH 4mixtures.

CONCLUSIONS

We have developed a technique for predicting solubilities of gases inLGP 1846. This technique could be extended to other aqueouselectrolyte solutions, and work is currently in progress to enablesuch an extension. All the correlations used are based on thecorresponding states principle, which has been found to be a verypowerful method for such predictions by us and others [4,5]

ACKNOWLEDGEMENTS

The authors would like to thank Prof. W. Koski, for supplying hisexperimental results prior to publication. This research wassponsored by the U. S. Army Ballistics Research Laboratory (J. 0.Wojoiechowski, technical monitor). The authors would like to thankE. Freedman, N. Klein, C. Leveritt, W. Morrison, and J. Wojciechowski,for their helpful comments and encouragement. Computing Serviceswere provided by the University of Illinois Computer Center.

230

REFERENCES

I1. Decker, M.M., Freedman, E., Klein, N., Loveritt, C.S., andWojciechowski, J.Q., "HAN-Based Liquid Propeliants :PhysicalProperties*, Ballistic Research Laboiatory, Technical Report (1988).2. Klein, N.,. 'Liquid Propellants for use in Gun - A Review', Rept.BRL-TR-2641, U.S. Army Ballistic Research Laboratory, AberdeenProving Grounds, Maryland, 1983.3. Reed,T.M., and Gubbins, K.E., OApplied Satistical Mechanics".McGraw Hill, New York, 1973.4. Rowlinson, J.S., and Watson, l.D, Chem. Eng. Sdi., 24, 1565, 1969.5. Brucks, M.G., and Murad, S., Chem. Eng. Commun., 40, 345, 1988.6. Prausnitz, J.M., Llchtenthaler, R.N., and Azevedo, E.G., *MolecularThermodynamics of Fluid Phase Equilibria%, Prentice Hall, NowJersey, 1986.7. Lewis, G.N., Randall, M., Pitzer, K.S., and Brewer, L.,"Thermodynamics', McGraw Hill, 1961.8. Reid,R.C., Prausnitz, J.M., and Poling, B.E., 'The Properties ofGases and Liquids", McGraw Hill, New York,1986.9. Ref. 6, Page 87.10. Prausnitz,J.M., and Chueh, P.L., 'Computer Calculations for High-Pressure Vapor - Liquid Equilibriag, Prentice 1140, New Jersey,'1968.11. Koski, W., private communications, 1987.12. O'Sullivan, T.D., and Smith, N.O, J. Phys. Chent., 74, 1480, 1970.13. Gardiner, G.E., and Smith, N.O., J. Phys. Chem., 76, 8, 1972.

231

Table

GAS. 10"3

Nitrogen 1.52 3.220

Methane 1.64 1.220

Xenon 2.64 0.373

Krypton 1.99 0.566

Argon 1.74 1.350

232

FIGURE CAPTIONS

Fig. 1: The calculated (eqn. 9) and experimental values of Henry'sconstants; calculated, * experimental.

Fig. 2: The calculated (eqn. 11) and experimental values of partialmolar volumes; - calculated, * experimental.

Fig. 2A: The calculated and experimental solubilities of nitrogen in1 m aqueous sodium chlorid( calculated, a experimental (12].

Fig. 3: The estimated solubility of argon in LGP 1846; _._ 30,--- 15, __ 0 Deg. C.

Fig. 4: The estimated solubility of krypton in LGP 1846; ---25,

0 Deg. C.

Fig. 6: The estimated solubility of xenon in LGP 1846 at 30 Deg. C.

Fig. 6: The estimated solubility of nitrogen in LGP 1846; 30,--- 15, __ 0Deg. C.

Fig. 7: The estimated solubility of methane in LGP 1846; . 30,--- 15, -_0 Deg. C.

Fig. 8: The estimated solubility of nitrogen-methane mixture in LGP1846 at 30 Dog. C; - 75, - 50, _._ 25 mole% methane.

Fig. 9: The estimated solubility of argon-methane mixture in LGP1846 at 30 Dog. C. _._ 75, --- 50, - 25 mole% methane.

233

110

100"

90

H°

80 II

70-

60

53-159I I I I•

90 110 130 150 170 190 210

T

FIG. 1

234

0.120

0.1150

0.105

V

0.100

0.095

0.090

0.085

0.0801I I

0.0'030 0.0032 0.0034 0.0036 0.0038 0.0040

T

FIG. 2235

0.0022

0.0016,9"o-

0.0013-

0. 0 003

0.00074

0.00014

0 20 40 60 so 100

FIG. 3

2,36

0.0030

0.0025

0.0020

x

0.0015

0.0010

0.00051 II I ;

0 20 40 60 80

P (MPR)

237

0.0038

0.0033-

0o0o 28-

0.0023-

xS

0.0018.

0.0013-

0.0008-

0.0003-10 20 40 60 80 100

P (MPA)

FIG. 4238

0.0041

0.0036

0.0031

0.0026

x

0.0021

0.0016

0.0011

0.0006

0 20 40 60 80 100

P (MPR)

FIG. 5239

0.0018

oSS

0.0015 /'-Sf

0.0012 - /

X /°°

0.0009/

/5/

/ oo°/

I,'!/ S#

0.0 006-X''/

1/,"

0.0003 X5

,/5

0.0000 1 -,.

0 20 40 60 80 100

P (MPR)

FIG. 6240

0.0026

77

7 ,I

II-

0 .0021 "*/ ,I

/ 'S

/ -5/ o

V-V -

/ /5-

/ •

0-0016-

0.0011-5

,D

g V

FI .

241

//a'aI'a

• f"I

0.0006

p T T l

0 20 40 50 80 100

P (MPR)

• FIG. 7-- 241

C .0025

C .0022

C .00 19

C .00 16

C .0013 ."

0.0016 -

0 2 4. ,0 80 10

p pP

O . 80 0 P Blank

243 7

C *L1IJI I - 50 20 40* 7O8 OP {I"P )

pF I . 8Pecdn7a. l~

'!, " 24

0.0025

0.0022-

0.0019,

0.0016

x0.0013

b .ooilo

0.0007

0.0004

0.0001 ,

0 20 40 60 80 100

P (MPR)

FIG. 9244

COMPATIBILITY OF ELASTOMERICMATERIALS WITH HAN-BASED

LIQUID PROPELLANT 1846.

BY

GUMERSINDO RODRIGUEZ *

HENRY 0. FEUERALAN R. TEETS

U,S, Army Belvoir RD & E CenterFort Belvoir, VA 22060-5606

AUGUST 1988

Presented at the 4th Annual Conference on HAN-Based LiquidPropellant Structure and Properties, Ballistic ResearchLaboratory, Aberdeen Proving Grounds, MD 21005-5066

245

ELASTOMERS COMPATIBILITY WITH LIQUID PROPELLANT

G. Rodriguez, H.O. Feuer and A. R. Teets

Rubber and Coated Fabrics Research Group,Materials, Fuels and Lubricants Directorate

U.S. Army Belvoir Research, Development and Engineering Center,Fort Belvoir, VA 22060-5606

ABSTRACT

The Advanced Ballistic Concepts Branch of the BallisticResearch Laboratory, BRL, tasked the Rubber and Coated FabricsResearch Group of the Belvoir RD&E Center, BRDEC, to study thecompatibility of various elastomers with liquid propellant 1846.

In order to generate a practical system for the handling andstorage of liquid propellants a group of thirty seven elastomericcompositions were evaluated for compatibility with liquidpropellant. All the materials tested were selected because theywere either currently being considered for use in fuels or waterhandling equipment. In addition the materials were further selectedon the basis of resistance to alkalies due to the composition ofthe liquid propellants currently in use. The measurements to assesselastomer compatibility with the liquid propellant includedswelling of the elastomers, change in hardness, discoloration andretention of tensile strength, modulus and ultimate elongation.

246

CTJ, XO

W xO

w co a:

FýW H

-L -UF ýC

CH a: za m

F-- 2J U)Q) ZMOa<m. CCml-

CO c UJ r. C z F 0 00 c

CZ F- M o < M W L -

F-- = M C: F- -

~ZZOO~H. ZI U.

2470j j

TABLE 1

IdS rHTML FOR-COMPATIBILITY WITH LIQUID PROPElLANT.

SLASTOMERS

A. HIGHLY SATURATED NITRILE RUBDER TEST CODE

1. NBR-2 [LP-1)

B. NITRILE RUBBER

1. NBR-8 [LP-2 J2. NBR-9 (LP-3]3., 1203-F60-R2, RADIAN (LP-4J4. VT-380 {NBR/PVC), RADIAN CLP-5]5. BJLT M-40, UNIROYAL [LP-6)6. OZO-HA-0221, {70%NBR/30%PVC), UNIROYAL [LP-7]

C. CARBOXYLATED NITRILE RUBDER

1. XNBR-2 [LP-8]2. XNBR-3 CLP-9]3. XNBR-6 CLP-1 0

D. POLYCHLOROPRENE RUBBER

1. CR-i (LP-1.112. CR-2 (LP-12J

E.* FLUOROELASTOHERS

1. VITON-1 [LP-13)2. VYTON-2 (LP-14)3. REEVES S/4616, (GUM) (LP-15)4. FLURAN F-5500-A NORTON IND. PLASTICS [LP-16]

F. ETHYLENE-PROPYLENE RUBBER

1. REEVES 4601, (GUM) [LP-17 J2. REEVES 4594, (GUM) (LP-1B]

G. THERMOPLASTIC ELASTOMERS

1. THP-l, ALCRYN R1201 B-70A [LP-19 J2. THP-3, ALCRYN R1101 B70 [LP-20)3. THP-4, MONSANTO GEOLAST [LP-2 1)4. THP-5, MOBAY TEXIN 355DR (LP-22)5. THP-6, MOBAY TEXIN 480 AR [LP-2 3)6. THP-7, GAFLEX (LP-2417. THP-8, SANTOPRENE, 201-55 [LP-25j

248

8. THP-9, SANTOPRENE, 101-64 [LP-26]9. THP-10, SANTOPRENE, 101-73 [LP-27]10. CD-9250, DISOGRIN (LP-28)11. NORPRENE, NORTON IND. PLASTICS [LP-29]

H. POLYURETHANES

1. PU-i, UNIROYAL, Vibrathane 5004 rLP-30]2. PU-2, UNIROYAL, Adiprene CM (LP-31]3. TSE-E-34-94, TSE INDUSTRIES, MILLATHANE LLP-32]

I. SYNTHETIC RUBBER

1. 3130 TREAD [LP-33]2. KRATON 1650, ILC DOVER (LP-34]3. ATL-644-30, AERO TEC LABORATORIES, INC. LLP-35]4. GOODYEAR COLLAPSIBLE TANKS GUM [LP-36]

J. HALOGENATED BUTYL

1. PE 100A027, ILC DOVER Inc. [LP-37]

249

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272

The Influence of Metal Ions on the Stability

of Liould Gun Prooellants Contalnino HAN

Dr. R. Hansen

FRAUNHOFER-INSTITUT FURCHEMISCHE TECHNOLOGIE

(FR GERMANY)

ABSTRACT

In HAN-based liquid gun propellants (LP 1846), HAN (hyd-roxylammonium nitrate) is the chemically sensitive com-ponent. Traces of metal ions are capable of acceleratingits decomposition rate. To assess the stability andstorage life of the propellant and the effects of metal-lic impurities, the buildup of pressure was studied inrelevant propellant samples.'

The experiments to determine the lifetime of LP 1846were carried out in sealed containers at a temperatureof 90 OC (194 OF). The metal ions were added to thepropellant at different concentrations. As a relativemeasure for assessIng efficacy in each case, we usedeither the time up to tho bursting of the containers orobservation of the pressure through time, with a sub-sequent component analysis.

273

Table 1: The influence of 100 ppm metal ions on the storage life

of LP 1846 in ampoules at 90 °C (194 OF)

LP 1846 (Lot 49 - 1)

Metal ions Decomposition time Relative decomposition time

in days in %

Fe 3 3,5 3,9Ni2+ 80,7 88,9Co2+ 73,0 80,4Cu2+ 15,2 16,7

Hg2+ 64,1 70,6

W + 94,2 103,7M06+ 62,6 68,9Mn2+ 88,0 96,9

All' 78,5 86,5Ce'÷ 82,6 91 ,0

Pb + 87,0 95,8

Ag 83,4 91,9

Mg ?+ 87,3 96,1Cr'+ 90,7 99,9Fe + 3,5 3,9

Ti+ 59,6 65,6

V4+ 11,9 13,1

Zn2+ 81,8 90,1

Cdl+ 78,1 86,0

B'+ 77,3 85,1Pd ' 31,4 34,6

Zr4+ 92,2 101,5

Sn2+ 83,6 92,1

Bi' +49,3 54 , 3

274

Table 2: Comparison of the relative decompoaltion times of

LP 1846. Accelerated storage tests in glass ampoules at

90 4C. Metal Ion concentrations in 2, 5, 10, 100 ppm

Relative decomposition time in %

Metal ions 2 5 10 100

W6+ 115 120 103 104Zr-+ - 98 100 102

Cr'+ - - 92 100

Mn2+ 106 102 101 97Mg2 + - 98 95 96Pb2+ 92 88 87 96

Snl+ 103 98 100 92

Ag+ 101 99 93 92

Ce+ 103 98 80 91

Zn 2 99 100 84 90Ni 2 105 97 (75) 89

Al'+ 101 88 80 87Cd=* 96 94 80 86

B)+ 102 97 96 85

C02+ 100 99 (71) 80

Hg2+ 98 100 102 79

Mo' -' - 98 69

Ti-4 109 95 (69) 66

Bit' 93 100 93 54

Pdz+ - 65 51 35

Cu"' 73 59 48 17

71 59 40 13

Fe ' 55 36 24 4

Fel 57 31 20 4275,

Table 3: The influence of Iron and copper

compounds on the storage life of

LP 1846 in ampoules at 90 OC

Additive Decomposition time

in days

86,6

10 pp. Fe-ions 17,4

Ferrocene (10 ppm Fe's) 22,0

10 ppm Cu-ions 41,6

Copperphtalo- 84,5

cyanine (10 ppm Cua)

27(

r-4V U1

lii 10 01

Li in

in u

uU~o

va 00 0

q - 26 -@ ~ 0

004 ~ ~ Li-4-00277

Table 5. The influence of stabilizers on the

decomposition of LP 18416 containing10 ppm iron ions. Decomposition timesIn days at 90 OC

stabilizer iron : stab. iron : stab.1 :1 1 : 10

in moles in moles

Svi thout stabilizer 17 ,1 17,14

Turpinal SL 19,8 25,0(Dequest 2010)

Turpinal D 2 34,2 2 5(Dequest 2000)

Reomet 19,7 18,

NI'-Disalloyloyl- 18,5 19,2hydrazine

Dequest 20141 29,2 47,4

Dequest 2060 S 18,3 11,8

c,a'-Dipyridyl - 19,2

278

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283

FRAuNHOFFR-INSTITUT

FUR TREIB- UND EXPLOSIVSTOFFEJ

Selection Criteria for Metals and Plastics asConstruction Materials for Long Term Pressure-Testing

Apparatus on Liquid Propellants (LPs)

Dr. E. Backof

4th ANNUAL CONFUSNCK ON HRAIN.IAD LIQUID PROPWLLANTSTRUCIURE AND PROPERTI&S

US A•IU IBALLZSTIC RESEARCH LABORATORYABERDEEN PROVING GROUND.D ND

30 AUG - SI? SI88

Abstract

The Paper describes the testing and selection ofmetallic and non-metallic materials for application inpressure-testing apparatus to determine the life term ofHAN-based liquid propellants (LPs). Metallic materialsare'necessary for pressure sensors and non-metallic mate-rials for sealing of the testing apparatus. Selectioncriteria for the metals are their corrosion-resistingquality and their capacity to Influence or restrict thechemical stability of the LP. Selection criteria for thesealing materials are their impermeability to gases, de-formation under strain and compatibility with the LPused. The testing apparatus is being used at the presenttime.

WiUth~ f tfmm lt July, 1l01u will catvytSflOW fM

IRAUN4OPER-INSIT1UT 1"RCHEMISCHIE TICHNOLOGIE (ICT)

P.O. tx Is 400.1?W PflaW I ¶(Uletghswsfi)Phoe (:21) 4 0-0Telex : 7F414 lot dTownf (am) 44640.111

284

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LLLJ

4-

CL.IbC

4-

Li U 4-9-4

rLU W

Ir 0

L-uL

285

011 Pressure sensor

Seating 12ring12x8x2mm

40

0 12

Test arrangement for pressure measure=ments on liquid propettants

286

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(.,,): . -L ,, 3) C u --

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C C)

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aJ •J,.LV .•0-o

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r.0-

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288

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00%____

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Table 1 (oont.inued-1):

The lnfluensoe of metals and alloys on the &wmloalstability of LP 18116. Accelerated storage te.t

in apoules at 90 1C (194 OF).

Metal/Alloy Decomposition Relative

time in days decomposition

I_ Itime in%Copper 1,6 2,3

Zinc 69,2 100,9

Titanium 42,0 61,2

Tantalum " 47,5 61,2

Chromium 23,4 34,1

Molybdenum 47,8 69,7Tungsten 34,4 49,7

Manganese 73,5 108,6

Iron 1,0 1,5

Cobalt 55,6 81,0

Nickel 56,8 82,8

Aluminium 73,0 106,0

Silicon 57,0 83,1Tin 45,0 65,6

Lead 74,0 107,9

Antimony 4,0 5,8

net, possibly polluted

290

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a) m.- CI-l 4- V CU

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V)4Jco V) CL4-'C 4-) (U ) )

c, W ~ N L -"4-CU~V.4 E %0 (n M

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0- 30() CO- CL.4-0 C:)G OG)0Cu_

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=N a4-1 4- OV

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293

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0 -0-

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- _ Liu-I 6 0 0.0 o..E-u ____________ -

295

Tabl. 3: The influence of sealing materials on thechemical stability of LP 1846. Acceleratedstorage test in glass ampoules at 90 OC

(194 OF)

Sealing material Relative decomposition time in

in contact with LP in gas space

- (original LP) 100 100

EPDM 7r2 23,9

FPM (Viton) 21,6 21,9

NBR 23,8 22,1

VMQ 51,7 71,6

EP 7,5 25,5

296

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0 C:

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29733

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4- U% 4-J=3 a)~

4- -'

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L t,_

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u L C)

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(D ,_ r 4-J (L - ,--4

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299

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(3.

VI)

"-0

4-J

4- (1r0 I

=3s

4-J CL oE x

QE 0

a) I 0.GI) I, o

F-2 -,--Q m

C'I

300

Table 4•i The permeation coefficients

of sintered PTFE (Hostaflon,

manufactured by Hoechst AG)

at room temperature in

accordance with DIN 53380

Gas Material: PTFE (Hostaflon)

TF 17400 TFM 1700

air 100 80

02 250 160

N2 80 60

CO2 700 450

He 2100 1700

Water vapor 0.03 0.03

A . Ap -day m2 bar

301

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4) 0

0k. O- L

C0S0 r- 4

0~4~4 00 0

.&.) 0 1 C~) Nrf --ci a 0

06 06 0:P

H0 0 0 0).C

LO1

co 4) CIO

302

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0 co 0atlV) CVJ 0

0) 4-

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*4)4

00'

c0 0

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0o6 ('3

0 0 0 0 '

* n -Op

r-4 aA 0 0

* ,.. ~03C-

100 90 75 50 25 00C100 - g I

C

10

02 C02

1 N2

oil

0,01 -2,6 2,8 3,0 3,2 3,4 3,6 3,8 4,0 4,2 10":4rExponential temperature dependency of the permeation coefficients Pof PCTFE (Voltalef 300)

P In cmmm / sa(cm Hg)

3 04

I- a 14

0el 0*I 4) -

0 0 anO*V, N Nn

Q4 ) CO 0 0LAI 0 gý U 0

o00 0 0 0-

A' F-4 0 0 9

4 %.0 0

"N 0-4 la CLa P- 0 0CL

e 1i09 tt- o 0W0 3 oA CV 0%

in r4 a %

04 4).0 9 )0 a

x0305

0

L) (

L--

-- -I

-- -

00

CLC0'

CL

CIO L^ (n*

00

o- -P- - W4.

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0. 4.0 0icu c r- z

306

LLULL 0

4- ( - ,-= -0-- %..1.-

4-J U CU .. -

E D C- 4-1 -E•L-O. . (n P

4' CYQ 0 w 3-C V" ,--. 40J L_C/-.• • o) cn• 4-J CD 4--J

0)o 0_ - 'COCl) I+- CLCD C: w,

M. L .,-I * 4-'4- • ----J 4._ .4-J 4-J,

m C .0• 4-- E

0 (n 4-- MD L.- (n)a) CO a) 0 L.) C

U)'--- E 1-- .,-4Vo C ( LL w) 4.- • X

E-,• 14--- C w C" -004-J n 1o4-J 0 CO

C/) (nOO

a_ 0 co wo---,•OE- 4-1 x C

4-- 0DX 0)CD C0')

•--0 U_ -r- 4a) C -f.• .--

4-- CDm

I -4- -Cw CIO )C o,

n = w. cu00. o= _ 4-- 10 - 4 0- 4 E ( --

CO 0 w -- - a4-Q )-J C'-4-D0=

4-- U W E c 'n0)

0 M1 0 W' 4 , -J I-- C:o -7 co .-. ,"

E E aU 4-0 (U (n E UJ

aD- (n --

307

a)

Li

a-

C. > C:)1ajLn L.)E

ý1: CEo 3cLj

a)aL. C

'308

Compatibility Study With 60% HAN Solution

By

Owen M. BrilesLeonard S. Joesten

Sundstrand Energy SystemsRockford, Illinois 61125

Unit of Sundstrand Corporation

Work Performed forDepartment of the Army

USA LABCOM/Ballistic Research LaboratoryAberdeen Proving Ground, MD

Contract No: DAA D05-86-C-0168

Presented at 4th Annual Conference on HAN-Based Liquid Propellant30 August - 1 September 1988Ballistic Research Laboratory

The materials tested and referenced throughout this report are not of Sundstrand manufacture and were supplied to Sundstrandby the United States Army or directly purchased by Sundstrand.

309

Abstract

A Hydroxylammonium Nitrate/Materials Compatibility Study wasconducted for the Ballistic Research Laboratory in 1967. Fifty-onematerial specimens were exposed to 60 percent hydroxyl-ammonium nitrate solution for 30 days at 250C, and 48 materialspecimens were exposed to 60 percent hydroxylammonium nitratesolution for 30 days at 650C. Material specimens were examinedat the end of the exposures, and gas evolution was monitoredduring the exposures. Gaseous species were identified andanalyzed. The test procedures will be described and test resultspresented.

310

Introduction

PROBLEM:

There is limited information available on material resistance toHAN solutions and on the stability of HAN solutions when incontact with various materials.

OBJECTIVE:

Develop and demonstrate a test method whereby materialsresistance to HAN and HAN stability can be simultaneouslyevaluated.

311

HAN Solution

"* 2.8M solution procured from Southwest Analytical

"* Concentrated to 60% (wt) by vacuum distillation

Analysis of HAN Solution

Test As Received After Concentration

Assay, % by wt. 23.7 61.7

Iron, ppm < 0.5 < 0.5

Copper, ppm < 0.3 <0.5

Chromium, ppm < 0.5 < 1.0

Nickel, ppm 0.4 1.4

Cobalt, ppm < 0.3 < 0.5

Zinc, ppm 0.1 0.4

312

Test Specimens

* Purchased (5mm x 5mm x "Imm)

Tantalum, 99.9%

Iron, 99.99 + %

Nickel, 99.98%

Aluminum, 7075-T651

Stainless Steel, 316

Chromium, 99.99 + 0/o

Copper, 0o

* Supplied by the Army

58 Material specimens (including metal and plastic coupons,and metal couporns with metallic and nonmetallic coatings).

313

Specimens Tested

Sample No. G.E. No. Description

1 & 54 Tantalum2 Iron3 & 55 Nickel4 & 56 7075 Aluminum5 & 57 316SS6 & 58 Chromium7 - Copper8 & 59 4 Teflon 05-026®9 & 60 5 Teflon 05-002D

10 & 61 6 Nylon 05-03711 & 62 7 Polyamide 05-03612 & 63 9 17-4PH13 & 64 13 Poco Graphite ACF-10QE2€14 & 65 21 Everlube 620C on 17-4®15 & 66 22 Nibronze on 17-416 23 Metco 309N5-3 on 17-4®17 & 67 24 Metco 505 on 17-4®18 & 68 25 Nedox SF2 on 17-4®19 & 69 26 HI-T-Lube on 17-420 & 70 28 K-Ramic SCA1002 Coating on?21 & 71 29 Vespel SP-210 (15% Graphite)6

22 & 72 30 Vespel SP-211D®23 & 73 31 Torlon 7130024 & 74 33 Vespel SP-21®25 - Blank-A26 & 75 41 Vespel SP-211®27 & 76 42 Vespel SP-22028 & 77 43 Vespel SP-1®

78 - Blank-C29 & 79 44 UDEL Polysulfone P-170030 & 80 46 Nylasint MA®31 & 81 47 Zytel 101L®32 & 82 48 Zytel 70G43L®33 & 83 49 Rynite 530m34 & 84 50 Hytrel 7245635 & 85 51 Torlon 4275®36 & 86 53 Jessop Alloy 2037 & 87 54 Jessop Alloy 27638 & 88 55 303SS39 & 89 72 Teflon 55450-3®40 & 90 77 Fluorocarbon 3341 & 91 78 Fluorocarbon PEEK42 & 92 79 Stellite 21 Weld Rod®43 & 93 83 CrB2 on 17-444 & 94 84 Hard Chrome on 17-445 & 95 86 Kennametal K602046 & 96 89 Kennametal K801®47 & 97 91 Tiolube 1175 cn 17-448 & 98 100 Rynite SST-356

48 & 99 102 Hostalen 102m50 - Blank-B51 & 100 105 K-Barb52 & 101 110 Nitronic 5053 & 102 111 Haynes 718®

103 Blank-D

314

Test Vessels

* Glass ampule with attached manometer

* Specimens placed in ampule before assembly

* HAN solution added, mercury added, and vessels sealed inArgon atmosphere

315

Reaction Test Vessel

SEPTUM PORT---" 10MM GLASS TUBING

50ML AMPULE

HAN•

SOLN/

MERCURYwlJ MANOMETER

316

Phase I Testing

* 25 ± 0.20C constant temperature bath

0 48 Vessels with specimens/2 blanks

* Record pressure daily

0 Terminate after 30 days, or if pressure increase exceeds3cm-Hg/day

Phase 11 Testing

* 65 ± 0.20C constant temperature bath

0 48 Vessels with specimens/2 blanks

* Record pressure daily

* Terminate after 30 days, or if pressure increase exceeds3cm.,Hg/day

3117

Gas Evolution Rates

"* Daily manometer readings

"* Pressure readings converted to standard cc's of gas produced:

Vc - (TJPO) [V2 (P2/T2) - V, (P,/T,)Jwhere: Vc = Corrected Volume (gas)

V2 = Uncorrected Volume (gas)

V, = Initial Volume (gas)

T2, P2 = Temperature and PressureMeasurements

T,, P, = Initial Temperature and PressureT^/PQ = Standard Temperature and Pressure

"* A statistical analysis system (SAS) program was used tocalculate and graph results.

3 18

HAN Outgassing650C

30

28

26-

"24-

S22-

U 20-

a 180m 1 6

POCO-GRAPHITEACF-10QE2

(n<~ 14

w 120m 10

2 NEDOX MFS8

-j0 6

24 NYLON 05-037

2 EVERLUBE 620C--- • "17-4PH

0 POLYAMIDE

0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30

DAYS OF TEST

319

Gas Analysis

* Gas samples taken via syringe through rubber septa if >0.3 cc

gas produced

* Analysis performed by gas chromatography

320

Gas Evolution Ratesand Gases Produced at 25*C

Days Volume of Gas Produced AverageSample Sample in cc Rate,

No. Material Test N, NO Total cc/Day

1 Tantalum 30 - - <0.30 <0.010

2 Iron 9 4.09 11.53 15.62 1.7363 Nickel 30 0.39 0.46 0.85 0.0284 7075 Aluminum 30 0.54 0.54 1.08 0.0365 316SS 30 - - <0.30 <0.010

6 Chromium 30 - - <0.30 <0.0107 Copper 9 4.98 14.52 19.50 2.1678 Teflon 05-0261 30 - - <0.30 <0.0109 Teflon 05-0020 30 - - <0.30 <0.010

10 Nylon 05-037 30 - - <0.30 <0.01011 Polyamide 05-036 30 - - <0.30 <0.01012 17-4PH 30 - - <0.30 <0.01013 Poco Graphite® 30 0.63 0.40 1.03 0.03414 Everlube 620C® 30 - - <0.30 <0.01015 Nibronze 30 2.8 2.31 5.11 0.17016 Metco 309N5-3® 2 - - 4.13 2.06517 Metco 505® 30 7.25 17.62 24.87 0.82918 Nedox SF2® 30 0.24 0.16 0.40 0.01319 HI-T-Lube 30 - - <0.30 <0.01020 K-Ramic 30 - - <0.30 <0.01021 Vespel SP-210® 30 - - <0.30 <0.01022 Vespel SP-211D®I 30 - - <0.30 <0.01023 Torlon 71300 30 - - <0.30 <0.01024 Vespel SP-21® 30 - - <0.30 <0.01051 K-Barb 30 - - <0.30 <0.01052 Nitronic 50 30 - - <0.30 <0.01053 Haynes 718® 30 - - <0.30 <0.01025 Blank-A 30 - - <0.30 <0.01026 Vespel SP-211® 30 - - <0.30 <0.01027 Vespel SP-220 30 - - <0.30 <0.01028 Vespel SP-1® 30 - - <0.30 <0.01029 UDEL Polysulfone 30 - - <0.30 <0.01030 Nylasint MA® 30 - - <0.30 <0.01031 Zytel 101L® 30 - - <0.30 <0.01032 Zytel 70G43L® 30 - - <0.30 <0.01033 Rynite 5300 30 - - <0.30 <0.01034 Hytrel 7245® 30 - - <0.30 <0.01035 Torlon 4275® 30 - - <0.30 <0.0103S Jessop 20 30 - / -- <0.30 <0.01037 Jessop 276 30 - - <0.30 <0.01038 303SS 30 2.47 0.80 3.27 0.10939 Teflon 55450-3® 30 - - <0.30 <0.01040 Fluorocarbon 33 30 - - <0.30 <0.01041 Fluorocarbon PEEK 30 - - <0.30 <0.01042 Stellitý.-, 21® 30 - - <0.30 <0.01043 CrB, 30 - - <0.30 <0.01044 Hard Chrome 30 - - <0.30 <0.010

45 Kennametal K602r 30 - - <0.30 <0.01046 Kennametal K801® 30 0.21 0.38 0.59 0.19747 Triolube 1175 30 - - <0.30 <0.010

48 Rynite SST-35® 30 - - <0.30 <0.01049 Hostalen 1020 30 - - <0.30 <0.01050 Blank-B 30 - - <0.30 <0.010

32.

Gas Evolution Ratesand Gases Produced at 650C

Days Volume of Gas Produced AverageSample Sample In cc Rate,

No. Material Test N2 N2O Total cc/Day

54 Tantalum 30 5.77 4.17 9.94 0.33155 Nickel 30 1.01 0.36 1.37 0.04656 Aluminum 6 2.20 5.50 7.70 1.28357 316SS 12 2.91 2.83 5.74 0.47858 Chromium 30 1.46 0.57 2.03 0.06859 Teflon 05-026® 30 3.96 2.65 6.61 0.22060 Teflon 05-0020 30 5.80 8.23 14.03 .46861 Nylon 05-037 30 2.05 0.63 2.68 0.08962 Polyamide 05-036 30 0.73 C.23 0.96 0.03263 17-4PH 30 0.84 0.25 1.09 0.03664 Poco Graphite' 30 6.89 18.57 25.46 0.84965 Everlubco 620C® 30 1.71 0.71 2.42 0.08166 Nibronze 1 0.74 1.31 2.05 2.0567 Metco 505® 1 6.07 14.73 20.80 20.8068 Nedox SF-20 30 4.37 2.96 7.33 0.24469 HI-T-Lube 30 2.99 1.72 4.70 0.15770 K-Ramic 4 1.78 8.36 10.14 2.53571 Vespel SP-210 0 30 1.05 0.30 1.35 0.04572 Vespel Sp-211DO 30 1.15 0.33 1.48 0.04973 Torlon 71300 30 0.94 0.28 1.22 0.04174 Vespel SP-210 30 0.88 0.21 1.09 0.03675 Vespel SP-211® 30 .077 0.25 1.02 0.03476 Vespel SP-220 30 1.64 0.82 2.46 0.08277 Vespel SP-10 30 0.81 0.22 1.03 0.03478 Blank-C 30 0.61 0.16 0.77 0.02679 UDEL Polysulfone 30 0.72 0.19 0.91 0.03080 Nylasint MAI 6 2.37 6.33 8.70 1.45081 Zytel 101LO 30 0.97 0.27 1.24 0,04182 Zytel 70G43L® 30 0.89 0.15 1.04 0.03583 Rynite 5300 30 0.52 0.13 0.65 0.02284 Hytrel 72450 30 2.51 0.72 3.23 0.10885 Torlon 42750 30 0.63 0.15 0.78 0.02686 Jessop 20 30 0.60 0.18 0.78 0.02687 Jessop 276 30 2.70 1.41 4.11 0.13788 303SS 30 2.59 1.37 3.96 0.13289 Teflon 55450-3D 30 0.24 0.15 0.39 0.013110 Fluorocarbon 33 12 4.30 5.87 10.17 0.84891 Fluorocarbon PEEK 30 0.65 0.13 0.78 0.02692 Stollite 210 30 0.51 0.13 0.65 0.02293 CrB2 14 2.24 6.97 9.21 0.65894 Hard Chrome 30 1.00 0.27 1.27 0.04295 Kennametal K6020 30 0.96 0.44 1.40 0.04796 Kennametal K801® 15 3.75 9.80 13.56 0.90497 Tiolube 1175 30 2.53 1.34 3.87 0.12998 Rynite SST-35 0 17 4.49 12.48 16.79 0.98899 Hostalen 1or 30 0.72 0.19 0.91 0.030

100 K-Karb 30 2.90 1.96 4.86 0.162101 Nitronic 50 30 0.95 0.22 1.17 0.039102 Haynes 71801 30 0.78 0.20 0.98 0.033103 Blank-D 30 0.56 0.16 0.72 0,024

322

Specimen Examination

"* Test vessels opened, specimens washed and dried

"* Specimens weighed (wt. changes recorded), and visuallyexamined

323

Specimen Examinations, 25 0C

Sample Wt. Before, Wt. Aftar,No. Description gms gms

1 Tantalum 0.4251 0.4245

2 Iron 0.2040 Disintegrated

3 Nickel 0.2188 Dissolved

4 7075 Aluminum 0.0725 0.0443

5 316SS 0.2035 0.2028

6 Chromium 0.1852 0.1851

7 Copper 0.2190 Dissolved

8 Teflon 05-026® 0.4428 0.4428

9 Teflon 05-0028 0.5297 0.5308

10 Nylon 05-037 0.3310 0.3393

11 Polyamide 05-036 0.3693 0.3703

12 17-4PH 2.0022 2.0026

13 Poro Graphite® 0.421o 0.4099

14 Everlube 620CO 1.7668 1.7667

15 Nibronze 1,9124 1.7577

16 Metco 309N5-30 2.2978 1.999(Coating Gone)

17 Metco 505® 2.6021 2.4130

18 Nedox SF20 1.9302 1.8638

19 HI-T-Lube 1.9192 1.9038

20 K-Ramic 1.7657 1.7655

21 Vespel SP-2100 0.3258 0.3276

22 Vespel SP-211DO 0.3369 0.3387

23 Torlon 71300 0.2386 0.2396

24 Vespel SP-21® 0.3363 0.33815- K-Barb 0.2973 0.3036

52 Nitronic 50 1.9106 1.9106

53 Haynes 7180 2.3438 2.3437

25 Blank-A - -

26 Vespel SP-211® 0.3318 0.3329

27 Vespel SP-22e 0.3580 0.3591

28 Vespel SP-1® 0.3128 0.3141

29 UDEL Polysulfone 0.2955 0.2961

30 Nylasint MAO 0.2112 0.2357

31 Zytel 101L® 0.2491 0.2631

32 Zytel 70G43LO 0.3246 0.3322

33 Rynite 5300 0.3733 0.3734

34 Hytrel 72450 0.1962 0.1968

35 Torlon 4275® 0.2387 0.2401

36 Jessop 20 1.8598 1.8602

37 Jessop 276 , 3.4406 3.4404

38 303SS 2.0420 2,0285

39 Teflon 55450-30 0.5183 0.5187

40 Fluorocarbon 33 0.5557 0.5558

41 Fluorocarbon PEEK 0.2471 0.2478

A2 Stellite 21"' 1.4531 1.4531

43 CrB, 1.8120 1.8110

44 Hard Chrome 1.8400 1.8397

45 Kennametal K6021 3.8297 3.8294

46 Kennametal K801® 6.0968 6.0609

47 Tiolube 1175 1.9458 1.9447

48 Rynite SST-35® 0.2721 0.2742

49 Hostalen 1020 0.2655 0.265450• Blank-B - -

324

Specimen Examinations, 65 0 C

Sample Wt. Before, Wt. After,No. Description gms gms

54 Tantalum 0.4254 0.4249

55 Nickel 0.1859 0.1857

56 7075 Aluminum 0.0697 0.0358

57 316SS 0.2015 0.2004

59 Chromium 0.1873 0.1872

59 Teflon 05-0260 0.4350 0.4352

60 Teflon 05-0028 0.5316 0.5331

61 Nylon 05-037 0.4087 0.4264

62 Polyamide 05-036 0.3237 0.3247

63 17-4PH 1.8115 1.8122

64 Poco Graphite® 0.4669 0.4492

65 Everlube 620CO 1.9498 1.9479

66 Nibronze 2.3115 2.1489(Corroded)

67 Metco 5050 2.7061 2.5614

68 Nedox SF-20 1.9855 1.9243

69 HI-T-Lube 1.9385 1.9240

70 K-Ramic 1.9501 1.9500

71 Vespel SP-1100 0.3354 0.3372

72 Vespel SP-211DO 0.3958 0.3972

73 Torlon 71300 0.3018 0.3028

74 Vespel SP-210 0.3899 0.3918

75 Vespel SP-21 I 0.4028 0.4040

76 Vespel SP-220 0.4182 0.4192

77 Vespel SP-10 0.3718 0.3732

78 Blank-C - -

79 UDEL Polysulfone 0.2606 0.2610

80 Nylasint MAO 0.2072 0.1997

81 Zytel 101L. 0.2799 0.2221(Cracked)

82 Zytel 70G43L® 0,3585 0.3586

83 Rynite 530M 0.3466 0.3466

84 Hytrel 7245® 0.2183 0.2154

85 Torlon 4275® 0.2988 0.3003

86 Jessop 20 1.8773 1.8778

87 Jessop 276 3.7662 3.5857

88 303SS 2.1353 2.1312(Dark)

89 Teflon 55450-3® 0.5652 0.5657

904 Fluorocarbon 33 / 0.5299 0.5298

91 Fluorocarbon PEEK 0.2882 0.2908

92 Stellite 21® 1.5565 1.5564

93 CrB2 2.0173 2.0083(Flaking)

94 Hard Chrome 2.0114 2.0111

95 Kennametal K602m 4.2569 4.2564

96 Kennametal K801® 6.8260 6.7622

97 Tiolube 1175 1.7228 1.7208

98 Rynite SST-35® 0.3011 0.2988

99 Hostalen 102V 0.2943 0.2943

100 K-Karb 0.2874 0.2976

101 Nitronic 50 2.1129 2.1130

102 Haynes 718® 2.5248 2.5246103 BlInK-D - -

325

Discussion and Conclusions

1. The test method provides a very sensitive method to measurepropellant stability at the same time material compatibility isbeing determined.

2. Iron, copper and Metco 309N5-3® were the most reactive.These plus 11 other materials exceeded the 3-cm/day limit.None of the reactions were considered vigorous.

3. Temperature had a definite effect on reaction rate. Only 11 of51 materials tested at 250C produced measurable quantities ofgas. All tests (including blanks) produced measurable amountsof gas at 650C.

4. N. and NO were the only gaseous species produced. TheN)1N20 ratio was < 1.0 for reactive materials and above 3.0 fornonreactive materials.

METALS

5. Chromium, 17-4PH, Jessop 20, Stellite 21®, KennametalK606®, Nitronic 50, Haynes 718®, and hard chrome platingperformed well.

NON METALS

6. Polyamide, Vespel®, Torlon®, Udel, Rynite®, Hytrel®, Hostalen®and some Teflons/Zytels® performed well.

COATINGS

7. Everlube 620C® and Tiolube 1175 dry film lubricants performedwell.

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