r I

AD-764 365

HYDRAZINE IMPURITY SURVEY

G. L M. Christopher, et al

United Aircraft Research Laboratories

H1
[ Prepared for:---

Air Force Rocket Propulsion Laboratory

June 1973
-- 2

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REPORT TITLE

Hydrazine Impurity Survey

4 DESCRIPTIVE NOTES (T7yp of "pot and Inclusive date*)
Phase I Special Report
5 AUTHOR(S) (Lost none. flrt new initial)

Christopher, G. L. M., and Brown, C. T.

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AFRPL-TR-73-24
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This document approved for public release; distribution unlimited.

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Air Force Rocket Propulsion Laboratory

:#E:wards Air Force Base
13 ARSTRACT

A study of the amowirts of specif±'c contaminants present in propellant

grade (.Ml Spec) hydrazine obtained from a number of users has been carried
out. A tctal of twventy-four samples from twelve user groups was analyzed.
7he contaminants examined included Tisrticulate materials, organic impurities,
water, carbon dioxide, metals and clioride. The level of particulate con-
tamination, the particle size distribution and approximate identification of
chemical types were established by appropriate techniques. Vaejor metal con-
taminants were determined by atomic absorptV.on and trace metal contaminants
were determined by emission spectroscopy. Other contaminants were assayed by
gas chromatographic, ultraviolet spectrosccpic or colorimetric techniques.

DD ,.1473 . ... .Unclassified

Security Classification
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LINK A LINK S LINK C
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~~KEY
10ft05-
OL!_
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WT
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ROLK
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WT_ ROLEI

M,!onopropellant Hydrazine
Contaminants
Physical A.pnalysis
Chemical Analysis

Hydrazine Impurity Survey

II

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DD 1473 (BACK) I
j..I~'-Secuarity Clessiffication
AFRPL-Ti-T3-24

HIYDRAZINE IMPURITY SURVDY I

ty

G. L. 1!. Christopher

and

C. T. Brown

Phase 1

June 19T3

7-his doclinent, approved for plablic release; distributiorn-

unlimiited.

A3ir Force Pocket Propulsion Laboratoxy

Director of' Science and Technology
Air Force 'Systens ron-aand
United State-- Air Force
Edwards, California 93523
 AFRPL-TR-73-2h

FOREWORD

This work was done at the United Aircraft Research Laboratories, E;

Hartford, Connecticat, for the Air Force Rocket Propulsion Laboratory
Phase I of Ccntrac. F04611-73-C-0019. The work was carried out during Jhe
period January 1, 1973 through 'larch 0, 1)73.

[-- Uork under Phase I of the Contract F04611-73-C-0019 was perforned under
rthe direction of Dr. G. L. ,.1Chrit topher, Principal Investigator, with the
assistance of Dr. G. Golden, Chiel, Analytical Chemistry, Mr. William Lasko,
Chief, flattrials Analysis, and Dr. C. T. Brown, Chemical Sciences.

This work was conducted under technical management of Captain Ronald J.

r i-eetin, AFRPL (LIDP) with tnte special cognizance of Captain Charles Mastroronico,
AFRPL (LKDP). The contracting officer is G. M. Plock of Edwards Air Force Base,
Edwards, California.

Publication of this report does not constitute Air Force approval of the
reports' findings or conclusions. It is published only for the exchange aud -

stimulation of ideas.

Ronald J. !feetin. Captain USAF

Project Enp-ineer

Iq
I 72
L-

2-U
 AYIRPL-R-73-24

ABSTRACT

V_
F. A study of the amounts of specific contaminantL. present in propellant

grade (iL Spec) hydrazine obtained from a number of tsers has been carried
out. A total of twenty-four samples from twelve user g-oups was analyzed.
The cntaninan4s examined included particulate materials, organic impurities,
-

I
water, carbon dioxide, metals and chloride. The level of particulate con- 2]
6anination, the particle size distribution and approximate identification of
cherieal types were established by appropriate techniques. ITa r metal con-
taminants were determined by atomic absorption and trace meta'. contaminant.
were determined by emission spectroscopy. Other contaminants iere assayed Ey I
gas chromatographic, ultraviolet spectroscopic or colorimetrio techniques. -

=
I

LI' ii
AFRPL-TR-73-2h
I
T!ABLE OF CONTEUTS I
-o Page

FORWARD ii

ABSTRACT iii I
TABLE OF CONTETS iv

LIST OF TABLES v

LIST OF FIGURES vi

SECTION I - Introduction 1

SECTION II - Experimental Program 2

Analytical Procedures for Nonfilterable impurities 3

Analytical Procedures for Filterable Impurities

SECTION III - Experimental Results 5 1

Chemical Analysis of Nonfilterable Impurities 9

Chenic'l and Physical Analysis of Filterable Impurities 10

SEC"TION IV - Summary and Conclusions 13

REFERENCES 15

APPENIDIX A 16

-TABLES I- XI

FTGURS 1 - 22

iv
 AFRPL-TR-73-24

LIST OF TABLES

II TABLE I Gas Chromatographic Analyses of Hydrizine Contaminants

[ TABLE I Aniline Content of Hydrazine Samples

TABLE III Particuilate, NVR and Ash in Hydrazine Samples

TABLE IV Major Metals and Chloride in Hydrazine Samples

TABLE V Trace Metals in Hydrazine Samples Submitted for Impurity Srvey-

Semiauantitative. (Emission Spectroscopy)

-I TABLE VI Particle Size Distribution

TABLE VII Results of Spectral Scan Analyses

TABLE VIII Results of Spectral Scan Analyses

TABLE T-X

TABLE X

TABLE XI
Results of Spectral Scan Analyses

Results of Spectral Scan Analyses

Results of Spectral Scan Analyses

I
I:

| ,
LIa

V:
 AFRPL-TR-73-24

LIST OF FIGURES

FIGURE 1 Hydrazine Impurity Analysis

FIGURE 2 Gas Chromatograph

FIGURE 3 Chromatographic Separation of Hydrazine Impurities

FiGURE 4 Chromatographic Separation of Hydraine Impurities

FIGURE 5 Chromatographic Separation of Hydrazine Impurities

FIGUME 6 Chromatographic Separation of Hydrazine Impurities

FIGURE 7 Chromatographic Separation of Hydrazine Impurities

FIGURE 8 Atomic Absorption Spectrometer

FIGURE 9 Emission Spectrograph

FIGURE 10 Electron Probe Ticroanalyzer

FIGURE 1 A1R-900 Scanning Electron Microscope

It FIGURE 12

FIGURE 13

FIGURE lh
Optical Photr icrographs of Particulates from Hvdrazine Samples

Optical Photomicrographs of Particulates from Hydrazine Samples

Optical Photonicropraphs of Particulates from Hydrazine Samples

FIGURE 15 Optical Photonicrographs of Particulates from Hydrazine Samples

FIGURE 16 Electron Bean Scan Ana&ysis of the "Glassy" Particulate Shown in

Sample 5

FIGURE 17 Electron Beam Scan Analysis of a Trpical Agglomerate Particulate

FIGURE 18 Electron Beam Scan Ai.alysis of a- Tvpictl !etallic Particulate

FIGUPE 19 Scanning Electron Microscope - Sample 9

FIGURE 20 Scanning Electron Mlicroscope - Sample 12

FIGURE 21 Scanning Electron Microscope - Sample 14

FIGURE 22 Scanning Electron Tlcroscope - Sample 22

I vi
 AFRPL-TR-73-24 - = I

SECTION I

INTRODUCTION

Problens associated with catalyst contamination effects in catalytic de-

composition engines using hydrazine-based propellant systems are encountered
throughout the industry. The loss of catalytic activity as a function of bed
size, duty cycle and total propellant mass flow throughout the life of the engine
can be caused by spallation, sintering, crystallite forsation, or true catalytic
poisoning. The latter factor has been shown to be responsible for many instances
of failure of long life engines. Impurities in hydr~zine are the most probable
cause cor thesp poironing effects; however, a systematic study of these effects
as a function of specific contaminants with varying concentrations has yeL to
F be performed.

In order to effect such a study, which is the purpose of the present con-
tract, it is necessary to define the nature sad concentration levels of con-
taminants most prevalent in hydrazine. These contaminants can be introduced
during the hydrazine manufacturing process, during handling and transfer of
v hydrazine ar by reaction of hydrazine with container materials. 41

This special report is a summary of a survey of the amount and nature of

contaminants found in hydrezine as supplied by a large number of users, both
government and industrial.

1 1
 AIr'PL-TR-73-24

SETION II

WEXPRIF!ITAL PEOGRAMi

The experimental program for the Air Force Rocket Propulsion Laboratory
(AFTIPL) Hydrazine Impurity ',urvey consi:,ted of both chemical and physical
analyses of impurities contained in twenty-four samples from twelve user groups.
A complete list of the suppliers is included in Appendix A along with the sample
designations for each container received.

The analytical scheme (Figure l) was designed to determine the level of

soluble impurities incl]i.ing water, carbon dic.ide, aniline, monomethyl hydrazine
(m-.y), msyme t Ical dimethyl hydrazine (UIW)M), isopropyl alcohol (1PA and
chloride. in .adition, the amounts of metallic iipourities i ere determined.
L Particulate matter oas also examined after filtration of the hydrazine samples.
Particle size distribution, qualitative chemical analysis for the elements
present, and particle morphology ,were determined.

in most cases samples ;ere received in both one quart snd one-half pirt
glass bottles. Each bottlc was numbered in the order in which it was received.
iere two sample numbers are listed together, both were the same composition
[ front the same lot from a si nle supplier. They represent different bottles of I
otherwise identical materials.

The sample handling procedures were as foliows,:

Sanples for Chronatorramhic Analysis:

Approximately 250 ml (1i ut. ) of hydrazine sample received in glass

bottles with polyseal closure, was transferred, through an air-lock, into a
dry-box purged with dry nitrogen. Cleaned and dried 50 ml septum bottles
euuipped with "11ininert" valves were already contained in the d-Y box.
These valves are all teflor with 0-Ping seals and are fitted with septums and

chromatographic samples. After 24 hours of conditioning, the samrple bottle

was opened, part of the contents was transferred to a septum bottle and the-
closure valve was inserted. The filled septum bottle was removed through
the air lock and served to provide samples for chromatographic analysis of 4

H2 0, C02 , UDMH, - and isoprcjpyl alcohol.

a3'les for
- Chemical
- - Analvsis
- of Metallic Materials and Determination
of Particulates:

The outside surface of the glass bottle conteining approximately 1000 ml

(I qt.) of a hydrazie sample was carefully washed to remove any particulate
material. Special attentibn was given to the region of the bottle necx and
the closure. This hydrazine was used for determi-nation of particulates, non-
volatile residue, metals, chloride and ariline.

2
 AtRPL-TR-72-24

1. ANALYTICAL PROCEDURES FOR NONFILTERABLE IMPURITIES

For convenience the impurities analyzed in this survey have been divided
into two groups; filterable and non-filterable impurities. In the latter case
there was a further s-itdivision into metallic and non-metallic izpurities. The
metallic impurities were analyzed after filtration an4 eve--ration of a large
(500 mL) sample of hydrazine (Figure 1). In addition to wu. above,-parameters
such as non-volatile residue (INVR) and ash were determined in an attempt to
differentiate between materies with high boiling points and inorganic residues.
A brief statement of the nature of the type of impurities determined is indicated
F below:

H20, C02 , UDNN, 12.2, Isopropyl Alcohol: These compounds were determined-
by gas enromatograpny. Tnroug tne use $1 two chromatographic columns in series, -

H2 0, C02, UDM, 1 and Isopropyl Alcohol were determined simultaneously. Since

well-defined chromatographic peaks are produced by water with each column, two
independent measurements of water were obtained with each sample of hydrazine
injected into the system. n all cases samples were analyzed in duplicate.

Chloride: Chloride was determined co.orietrically after evaporation of

a hydrazine aliquot to dryness. A small amo-unt of :TaOl was added before evapora-
d,"ion to ensure retention of chloride.

Aniline: -niline ifas determined by ultra-violet spectrophotometry.

Non-Volatile Residae (IZR): DuDlicate samples of filtered hydrazine of

250 ml volume were evaporated to small volume in Teflon beakers. Contents of
the beakers were transferred to weighed platinum crucibles (using small Lmounts
of pure, filtered isopropyl alcohol for rinsing the beakers) and further evaporated
a syrupy residue. This residue was then heated for 1 hour at 1050 C in an oven.
Trnw. residue eight was used as a measure of nVR.

Ash: The materials in the crucibles from the IJVR determination were
-heated to 650'C for one hour to destroy any organic residues present. The
-.. . -ths
. treatmt. reet ui.-vut...e inorganic sub-
--stances.

Trace Vetals: A semi-quantitative neasurement of trace elements present

in the hydrazine was carried out by the use of emission spectrography on one
of the ash residues. Elements found to be present in sufficiently large
quantities (major metallic impurities) were determined on a quantitative basis.

IU'ajor Mletallic rurities: These elements were determined by atomic

absorption using a solution prepared from one of the ash residues. A more
-detailed discussion of the analytical procedures is given in the folowing
--
sections of the report.

= 3 z
ArFRFL-TR-7 3-2h

a. Gas Chromatography

The gas chiomatographic Procedure for the analysis of water, carbon

dioxide, monomethyl hydrazine, unsymmetrical dimethyl hydrazine and isopropyl.
alcohol was based on the use of a dual column chromatograph. The chromatographic
equipment is illustrated in Figure 2. The chromatograph may be operated using
two detectors simultaneously or in series with two columns to give added versa-
tility in difficult separations. The response of e-ch detector is disuplayed
independently.

Liquids or gases may be introduced into the unit through a heated inlet
by mears of preciiion syringes for separation, qualitative identification, or
auantitative meastrements. Alternatively, gases may be admitted from static
or dynamic system., via a solenoid-operated gas sampling valve.

Gas concentrations in the part per million to part per hundred range may
be determined. Isothermal or programmed temperature modes of operation up to
hoo 0 c yield sufficient vapor pressures to allow samples with boiling points
over 500 0 C to be analyzed. Provisions have been made to allow zrapping of
separated fractions for infrared identification.

In the course of the chromatographic work, it was found that Tbe columns
specified in the military specifications (Fefs. 1 1 2) -ere not sufficient for
commlete separation of all the filtered impurities noted above.

A Pas Lhromatographic colum system was developed consisting of two separate

column- of two sections each. In one system a section containing Carbowax LOO
(polyethylene glycol 400) liquid phase is followed by a section containing Dcwfax
9119 (nonyl phenyl polyethylene glycol ether). The second system ccntains a Porapat-.
PS section followed by a section containing Dowfax 9N19. NH4, C02 , H20 and I.I
are resolved on the first system and 11H 3 , C02 , H2 0, !PA, and UDt.I on the second.
The Carbowax 400 column described in the military specification (Fef. 1) voz1
not resolve LWI!-IPA and H20.4-4i; the Dcwfax 9119 column described in the military
specificatons (il'f It:
e±±eM nu~~
U~ ;j--i. 1FAt epuaations.

The three primary gas chromatographic column- used were,--

A - one meter x 1/4" length containinF 33' Carbo;wa;x hoG (polyethylene glycol
It00) on 90/100 mesh Anakrom 1B (Anakrom B used in the military specification is
no longer available);

B - 6 ft x 1/4" length containing lO% Dowfax 9119 (nonyl phenyl polyethylene

glycol ether) on 60/c9 mesh T6 '(Teflon V used in the military specification is
no longer available);

C - 6 ft x 1/4" length containing 50/80 mesh ?orapak PS.

All colurmns were made of 316 or 321 stainless steel. The carrier gas was heli m,

4
 iA

4 AFRPL-TR-73.-2

and the flow rate was set to 80 ml/mmn. These columns were tested and u. ed in
a Beclman GC 72-5 with two hot wire thermal conductiity detectors and heated
inlets. With this system two independent chromatographic systems were seA up
to facilitate more rapid total analysis. The procedure used in the military
specificat'ons (Refs. 1 & 2) was followed and gave satisfactory results. The
procedure is as follows:

1) Condition columns at 150&C for 4 hrs with 50 mlimin He flow V

2) Column temperature for analysis - 110 0 C; He flow rate - 80-120 mL/in

3) Detector and inlet temperature - 1500 C

4) Saturate colunns by injecting 3 successive 10 microliter samples of

propellant. (If more tan 30 minutes elapse between elution of the hydrazine
and the next injection, re-saturate the column with a 10 microliter injection
of hydrazine.

5) Using a clean, dry 10 m,.croliter syringe, carefully fill and set

plunger to 3 microliters, -ipe tip wth tissue without touching the open end
of the needle. Quickly inject the sample into the instrument and irmediately
withdraw the needle.-

First temts to accomplish component separation were made using the

military specification methods per se. Figures 3 and 4 show typical chromato-
grams usirn; these methods. It can be seen that the Carbowax 400 co!umn did not
senarate UD.9i-rPA and hi20-1t and the Dowfax 9119 coiumn did not separate I 2 0-UD i
.d .'Sfll-IPA. From the separation data obtained or, these zolumns it was concluded
that some advantage might be rained by using these two columz.s in series. This
p;:ocedure gave better results as can be seen on the chromatogran in Figure 5;
however, UD:i and IPA are not se-rated. Porapak PS (co!mn C) resolves C02 ,
H2 0 and IPA from the hydrazines. 11 2 4 , 12-21 and LUIRf elute from this column
~t he in hat
1 ordr ~ 1 tab* t I 'Ih.
of elution for the hydrazines is the reverse of that obtained using eolumns A
and B. Since column B gave ,he sane h 2 0-IPA elution order Rs column C and gave
clean sharp peaks, the approximate length necessary to place elution time for C

IPA ahead of the UDU.i was cal-ulated from retention data. This calculation
indicated a length of 6 ft for column C which when combined with column A,
resulted in the chromatogram shown in Figure 7. These column systems have
proven ,alaable in analyzing many propellant samples which were found to con-
tain frcn <0.01 w/o to over i w/o of these various components.

The cobination of columns R and C (Figure 7) was used for the analys.s
of all impurity components with the exception of MI.%, which was analyzed using
a combination of columns A and B (Figure 5).
AFRPL-TR-73-24

Standards were prepare. by adding weighed amounts of each impurity specified

above to weighed hydrazine samples and extrapolating the results to determine the
original amounts of these constituents in the hydrazine by calculating peak height
ratios.

b. bltraviolet Spectroscopy

Aniline in hydrazine was determined by ultraviolet spectroscopy ising a

lodel. 1l Cary Recording Spectrophotoneter, set at 28T microns. The alsorbance
of aniline in the samples was measured against doubly distilled vater in a 3.5
c zell. Standards containing known arounts of aniline in doubly distilled water
were used for calibration. This calibration resulted in a factor of one (1)
absorbance unit per 90 microgrons aniline/ml of a st lution which was -'iluted by
a factor of 100. This absorb:-nce X(90) x (100) is equivalent to ppr aniline in
the original- sam-le.

c. Colorimetric Analysis for Chloride

Hydrazine samples were analyzed for chloride using a portion of the samples
retained (unfiltered) for chrortographic and aniline analysis (Figure 1).
Dulicate ten milliliter samnles were taken and analyzed according to 07T1
method D512-67 (Ref. 3). This pr3cedure is a colorinetric nethod basec or the
reaction of chloride ion with a Mixture of ferric arzonium sulfate and mercuric
thiocyanate to form the colored ferric thiocyanate complex. Absorbance is
measured at 460 milimicrons and compared to staendards coataining krnown a=ounts
of chloride.

d. Chemical An alysis of !eetalic Impurities

letallic impurities were determined in hydrazine after determination of

the non-volatile residue, Samples heated to 650*C were analyzed for both major
and runor metallic impurities by atomic absorption md emission spe..troscopic
procedures. In the former case the heated samples were dissolved in KC. and
diluted to 10 ml with delonized water using atomic-absorption procedures election
of the liquid samples into a flame containing fuel and oxidizer appropriate to
the prticular metal impurity in question. The major impurities analyzed in
this fashion included sodium, iron, chromdum, nickel, zinc and cadmium. The
atomic absorption apparatus is a Perkin-Elmer 1i1odel 303 shown in Figure 8.

Minor metallic impurities were analyzed using ash sample #'2 from each
filtrate. These filtrates were evaporated in two portions for determination
of NIR and subsequently ashed for analysis of major metallic impurities by
atomic aosorption and minor metallic impurities by emission spectroscopy. A
Jarrel Ash-Ebert Uark IV, 3.4 meter spectrograph was used for the latter analysis.
This instrument is illustrated in Figure 9.

6
 AFRPL-TR-73-2,,,4

2. MIALYTICAL PROCEDUPES POR FILTERABLE IMPURITIES

Insoluble impurities were characterized after filtration from hydrazine

as follows.

a. Optical microscopy for particle size distribution and particle

morphology.

b. Electron probe analysis for the elements present in specific

particles.

c. Scanning electron microscopy to determine the topographic&L t

features of selected particles.

Particulates from hydrazine samples were collected by 1iltration through a

Teflon filter medium, which retained particles larger than 5 microns (p). Using
the procedure in M.L-P-26536 the particulate residues were lifted from a one-
quarter section of the filter medium by a stripping technique and optically
photographed. The strippings were then coated with a thin layer (several hundred
Angstroms) of pure graphite and subjected to Electron microprobe analysis.
L Stripnings from an unused filter were treated in the smie manne- and served as
a blanh.control specimen.-

-The site distribution of the pe ticulatis xemoved from the hydrazine samples
were obtained by photographing at IOOX, five randomly chosen fields of the re-
mainin6 3/4 section oi, the filters containing the particles from 500 ml. of
hydrazine sample. 711.e particles in the size ranges 6-10u, 1I-2511, 26-50p, 51-
100p and >100p were counted in each field and the data reduced and reported as
particles ter 100 ml. hydrazine. The area of each field was 1.015 cm2 and the
total Ailter area- was 9.62 cm2 .

The Electron Probe T4icroanaJyzer (Figure lO) was used -o qualitatively

determine the elements present in the various particulate types found in each
sampla. This instruent combines techniques from electron -nicroscnpyend X-rav y-
- spectrescopy in one instrument to achieve exacting analysis in the micro range.
With this instrument it is possible to, make direct chemical analysis of a sample
approximately one nicron2 in area and o-.e micron in Iepth, representing approxi-
mately one micro-microgram of material. The test is nondestructive and the
v sample may be retained for further experimentation.

The Electron Probe Ificroanalyzer employs an electron optical system using t

two magnetic lenses which produce an electron focus of approximately one micron-
in diameter. This focused electron bea is used to excite characteristic X-rays
from the specimen. The X-rays are then sorted by means of curved crystal spectro-
* graphs, and presented on recorders or scalers as- in conventional X-ray spectro-
scopy. This instrument provides both qualitative and quantitative information
of the elemental composition on any specimen area from I to 200 microns, from
atomic ni=,ber 5 (boron) up through the remainder of the periodic chart.
4-,

-. .... .
AFJPL,-TR-73-24

Selected particles from some of the hydrazine samples were also examined
using a Scanning Electron Microscope (JSM)(Figure 11) in order to determine
their topographical features. The AM-900 Model
0 SE14 has a magnification range
from 5X to 100,OOOX, and a resolution of 250A.

)
rJ I

-I

- J

-t
g A

8
 AFRPL-TR-73-24 "

SECTIONI III

EXPERIMENITAL RESULTS

K The experimental results of the hydrazine survey are presented below.

The chemical analysis and partculate analysis are presented in separate
sections; however total particulates are included in the chemical analysis
section.
R$ J
I. CHE1(CAL AIIALYSIS OF 11011-FILTERABLE IMPUPJTIES

The results of chromatographic analysis of twenty-four hydrazine samples

are surnpadzed in Table I. - Water content varied considerably from 0 3 to 1.0
weight percent, while carbon dioxide levels were found to be in the ranige 0.1
to 0.6 percent., Io detectable amounts of UD:.i (<0.01 percent) were fouind in
any of the samples. Nine (9) samples were found to contain from 0.01 to 0.08
percent INZI',and four (h) of these nine (9) also contained 0.02 to 0.0h percent
IPA. The 121Y. and IPA are probably present as result of successive use of
containers and plumbing for 12M and hydrazine followed by inadeauate cleaning
v-th IPA,- which in turn may not be thoroughly eliminated before use.

The results of analysis for aniline (the third major impurity in hydra-
zine) are summarized in Table I1. Aniline levels are remarkably constant and
range from 0.17 to 0.36 percent. Aniline is used in the hydrtzine -purification
step during manufacture of the latter and the data reflects the fact that a
fairly consistant fraction of aniline remains in the troduct. -

The- non-volatile residue (11VR) and ash levels found i the hydrazine
samples ate summarized in Table III. The non-volatile resi.due reflects the
presence of high boiling corpouands. Aniline has a relativel-y low vapor pres-
sure at the evaporation temperature of 105°C. It is also probable that products
resulting from the interaction of C02 with hydrazire also have relatively low
vapor pressure at this temperature. The 1TVR is believed to contain such materials -'
in addition to y hydr_ ne 'hydr chloride normally pre-ent in the hydrazine.
kt terpts to utilize infrared xpectroscopy for demonstrating the presence in
:1111R of compounds derived from hydrazine, CO2-and FICI-vere unsuccessful.

The ssh samplev were aral :zel 'or b-th major metalli' irurities and for
metals present in trace quantities. '--e ,-,xP s of thes analysrs are s,'maxized
in T.able !V and V. The major metallic impurities include sodium, iron, chromium,
nickel, zinc and cadmium. The quantities of sodium and iron were in general in
the range .04 to 0.5 ppm which is about in order of magnitude greater than the
other "major" impurities. Iron, chromimx and nickel are probably from the stain-
less steels used in containers, transfer tubing and valves, and may be present
either in soluble form or as compoiients of particulates.

-- L J
AFRPL-TR-7 3-24

Sodium may be introduced as a constituent of soluble salts that are

introduced by exposure of hydrazine to the atmosphere, however the majority of
the sodium content is probably present due to the use of sodium hydroxide in
the manufacturing process for neutralization of hydrochloric acid and chlorine.
The hydrochloric a:id is a product end the chlorine a reactant in the Manu-
facturing process.

'Thechloride levels found in the samples (Table IV) are quite large con-
pared to th _ metals and range from 0.3 to 4.6 ppm. These levels are such that
they are much greater than the sum of all the metal concentrations. These
results indicate that chloride is associated with either hydrazine, anmonia
or possibly aniline in addition to its association with sodium or other retallic
ions. The major portion of chloride is probably introdrc-J duri,g the manu-
facturing process as hyd&'hlorLc aci I as noted above.

q-1t foJmation of nPitrogenous bases with hydrochloric acid also nay ac'count
for -....high levels of lIVP since these salts would not be volatile at the tem-
perature used in the test. These materials would volatilize at the high tempera-
-ure (6500 C) used for determining the ash content and the large differences
observed Tetween IVR and ash are thus explained. Aln -a similar manner, -the
interaction between nydrazine and CO- could lead to a salt-like produwt which
also could have a relatively low vapor pressur_ and therefore produce a high

2. CHErMCAL ANlD PHYSiCAL ANALYSIS OF FIL-UALE 2p.I7nTIES

The particulate level in each sample is summarized in Table III along zith
the results for non-volatile residue end ash. The particulate levels ranged
from a trace (<0.1 ppm) to as high as 2.2 ppm in sample 23-24. In most cases
the observed particulate level was below 0.4 ppm. The particulates were examined
to determine Particle size distribution, chemical elements present and particle
morphology.

a. FaUtel Size Distribation

Particle size distribution data for twel'e (12) samples is smmrized in

Table VI. The size distribution is such that in cases where a large nizaber of
particles was found, the majority -ere less than 25 microns in size. With the
exception of samples 23-24, very few particles greater than 50 microns were
present. The particle size distribution was determined from random samples as
previously described. The samples could only be analyzed as received so-the
size distribution and the total particulate count (Table ITS) will not necessarily
reflect actual particle levels in a given drum unless the contents were thoroughly
stirred and samples "ere taken before any settling could occur.

10
 AFRPL-TR-73-24 ,

b. Chemical Analysis and Morphology

The spectral analysis of the particulater in all twenty-four samples

analyzed are sumarized in Tables VII through XI. The analyses are segregated
according to the general type of particulate found. These types include:

(i) Agglomerates: Dark in appearance and apparently composed of

multipie components (size: 5-l00p); two basic sub-types:

A. Low-melting variety (sintered when exposed to electron bean)

B. Stable variety (unchanged when exposed to electron beam)

(2) Glassy Plates: Large, flat and similar in appearance to thin

sheets of rviica (size: 20-100p., generally 100-30011).

(3) Netallics: Small metallic chips (&ize: 20-l00u).

Rcpresentation photomicrographs of the particulates are illustrated in

Figures 12 through 15. The three general types of particles are labeled in
Figure 12. Also included is identification of 2etlon filaments which were-
SJ transferred from the filters used to trap the rarticulates.
specific analysis was -o
performed for oxygen, nitrogen or carbon. Experi-

ence with the analytical characteristics of small particulates, however, does

indicate that the agglomerates and glassy plates would be oxygen-inch. The
major metal elements observed suggest the presence of metal oxides, sand and 71-
clays. Electron beam scan photographs of repres..ntativt particles of each type
of contaminant are illustrated in Figures 16, 17 and 18 for a glassy plate phase,-
a stable agglomerate particle and ametallic particle respectively. It is apparent
from these photos that the "glassy" plates contain primarily potassium and
silicon, while the agglomerates are silicon and iron and the metals are probably
particles of pure iron.

Particulates were also examined using the Scanning Electron Microscope

(SEM) to determine their topographical features. The particles were generally
plat.-like or rough textured, irregularly shaped.

Figure 19 shows particles from Sample 9 (Bell Aerospace, S/IN 929). A few
flat particles, (9A) and a few granular particles, (9B) were observed. The
majority of the particulates from this sample were of rough, irregular shape
similar to those shown -n C & D.

Figure 20 shows particles from Sample 12 (China Lake, 2037). The parti-
culates are about equally divided between the irregularly shaped particles shown
in A and B and those with a more block-like shape as in C & D.

11f
 AFRPL-TR-.73-24

In Figure 21 are particles from Sample 14 (JPL, H-3155). Two rather un-
usual types of particles are shown in A & B. This type was not observed in the
other samples reported here. Sharply cleaved and irregularly shaped plate-like
particles were also observed and are shown in C & D, respectively.

Particles from Sample 18 (Sundstrand, H-110) are shuwn in Figure 22. They
consist of the typical plate (A & B) and rough textured, irreg,.'arly shaped (C &
D) particles.

LA

:
FA I

iii
zj
--
A

1-i

= 12
 AFRPL-TR-73-2'
It
SECTION IV

SUMMARY AND CONCLUSIONS

From the data presented in the preceding section of this report several
general observations may be made regarding the nature of impurities found in
the twenty-four samples analyzed.

The major soluble, non-metallic impurities in hydrazine are water, carbon

dioxide, aniline and chloride. The amount of aniline was remarkably constant
in all the samples analyzed. It is evident that this contaminant is present in
the manafactured hydrazine and is not introduced by handling or exposure. Water
and carbon dioxide are introduced by exposure to air. The variations in the
levels of carbon dioxide and water are such that they constitute a good measure
of tI- -:.,csure of the specific samples to the atmosphere prior to receipt for --
analysis at UARL. The range of concentrations of carbon dioxide and wattEr,
which are 0.1 to 0.6 percent and 0.3 to 1.0 pereent respectively, are not
large when one considers the large affinity of hydrazine for these constituents.
Chloride concentrations, which ranged from 0.3 to 1.6 ppm, are much larger

than the sum of the metallic ion concentrations. Of the major metallic :ons -
sodium, chromium, iron and nickel - sodium and iron are th nost concentrated
Iron, nickel and chromium are probably introduced by reaction of hydrazine witi
the stainless steels used for containers and associated plumbing. The sodium
is primarily introduced during the manufacturing process when sodium hydroxide
is used to neutralize the hydrochloric acid produced as a product along with
hydrazine. The chloride which is introduced from the hydrochloric acid in this
process must be present, not only as metallic chloride salts, but also in corn-
bination with hydrazine, ammonia and possibly aniline.

The non-volatile residue (IlVR) is a result of high boiling constituents

such a; aniline anA reaction products of hydr-.zine with carbon dioxide, and
chloride. All of these salt-forming compounds have boiling points greater thaai
thvporation temperature of I" " z - th , 0Cue .. ..
i ash samples.

The ash samples are primarily metallic residues; principally Iron and sodium.

These metallcs may be present in solutio n as hydrazine complexes,-or in the form

of small particulates less than 5 icrons in size.

71e remaining non-metallic soluble impurities are monomethyl hydrazine

(1-4,, unsymmetrical dimethyl hydrazine (U.MH) and isopropyl alcohol (IPA).
UDMT was not present in any significant amounts in any of the samples analyzed.
11 and IPA were found in nine and four of the samples axalyzed respectively,
and are probably the result of successive use of containers and plumbing for
hydrazine and 1I-M and subsequent cleaning of these containers with IPA, accompanied
with insufficient flushing of the IPA. Proper cleaning pro tedures should mini-
mize these problems.

13
 AFRPL-TR-73-2h

An additional and major problem in propellant contamination is the pre-

sence of insoluble particulate materials. Although the vast majority of these
particles are less than 25 microns in size, they are still large enough to
cause plugging in the small fuel lines used for propellant delivery to small
thrust engines. In many cases the maximum particle size was less than 10 microns,
but these particles would still cause clogging in the catalyst bed itself unless
line filters of less than 10 microns capability are used in the fuel lines.
The types of particles analyzed were found to be very similar to metal oxides,
sand, clay and individual metallic particles (basically iron). The sand and
clay are'probably introduced from air suspended dirt during exposure of the
hydrazine to the environment. Some of the sodium may also be from this source.

1etal oxides and metallic particles are probably introduced as stainless

steel corrosion products (due to exposure to oxygen when containers are epty)
and as metal chips from galled threads on container fittings.

In general it appears that many of the contaminant problems inelud ng

particulate sand and clay, 1,4 and IPA, may be minimized by more stringent
cleaning and handling procedures. The presence of iron, cbh'cmium and nickel
-indicate that better procedures for passivation of stainless steels must be
developed to ensure mininal dissolution of these materials.

144

Lk-
I - -_ -_ ---- -- -- -- -- - - - - - - - - - -
 AFRP.L-TR-73-24

BUFREICES

1. ~IML-P-27402B, flay 27, 1969.

2. MIL-P-27hoA, fay 20, 1969.

3. ColoriMetric Determination of Chloride Ion., ASTM Method D512-67 Annual

Book of ASV- Standards, Part 23, pp. 21-26, 1972.

Ii 1

15 =15
AFRPL-TR-73-24~

H(U
0
CQ' 2-1
Cri0 0H
-z

H
0'q
I4

NI tr\

_-: InI CU!

-- -e Iq
0. o H
coI

- 4-)

4-1. 4-'' '

ci ci 4.4 j a -

o
-. !4

04C ci
H~ 0~ f-4
a) >4
+)00
vi
I-4
I
+Z5'
Co.- 0
-
)r-
4C
H

F00
4 "f -w 0 H
AFRPL-TR-73-.24

CVI
cI.n
%0 0
0--. cr1 m \0tl-
01n -1 H1

cu

I ko I
_rt I~-.Z cu m c'. 01

*rff

0e -

ri~ .1 r tO' gw

E-4 o

00 z -

41 0
a ~0i4 C)4 00

Of 4f O i40,

034344- 0~:
9h 4)0 '0C1
r>o C4 >b 9

- 17
 to~ H - mcuc

H C~jC'4 (. i Ci(M c 'i I

C

00

(0.

001%
El-
% C%\
 AFRPL-TR-73-24
Table I

GAS CHROMATOGRAPHIC ANALYSES OF

hYDRAZflJE C0flTANIAI1TS

[ UARL SAMPLE H20 CO2 M UDMH IPA

I.D.# USER I.D. %(Wt.) %

!t3 ROCKET RESEARCH if-1799 0.5 0.2 <0.01 <0.01 <0.01

- 5,6
7,8
10,11
12,13
SHELL
CHINA LAU
BELL
CHINA L.KE
H-4670
H-2002
S/N 929
2037
0.4
0.6
0.5
1.0
0.2
0.5
0.3
0.3
0.08
<O.01
<0.01
<0.01
<0.01 <0.01
<0.01 <0.01
<0.01
<0.01
<0.01
<0.01
14,15 JPL H-3155 0.3 0.2 <0.01 <0.01 <0.01
17,18 SUIDSTRANID 11-110 0.3 0.3 0.03 <0.01 <0.01
19,20 CHINA LAKE Lot 681 1.0 0.4 <0.01 <0.01 <0.01
K. 21,22 CHINA LAKE 1-3139 o.6 0.5
o.4
<0.01
<0.01
<0.01 <0.01
<0.01 <0.01
23,24 CHINA lAM H-3456 0.9
-25,26 CHINA LAIM H-794- 0.6 0.6 <O.01 <0.01 <0.01
27,28 CHINA LAKE H-2604 0.7 0.6 <0.01 <0.01 <0,01
4 LOC=1-ED A 3937 0.3 0.4 -<0.01, <0.01 <0.01
16 SHELL H-4903 0.4 0.5 <0.01 <0.01 <0.01
29,30 ROC-:ETDYiIE PRA Tank #5 0.5 0.1 o.04 <0.01 O.04
31,32 EDWARDS Drum 3103 0.4 0.2 0.04 tt,.01 0.02
33,34 EDWARDS 11-1993 o.4 0.2 0.02 <0.01 0.02
35,36 EDUARDS Drum 2763 0.3 0.2 0.01 <0.01 0.02
37,38 TRW None O.h 0.2 0.02 <0.01 <0.01
140 1AI. STAOD. 4313 0.7 0.5 <0.01 <0.01 <0.01
41 H1. ST ITD. 2556 0.4 0.6 <0.01 <0.01 <9o0l
46,47 EDWARDS Drum 1810 0.3 0.5 0.06 <0,01 <0.01
148,49 ROCKYf 1ri1. APS. DODX 17074 0.4 0.2 <0.01 <0.01 <0.01
l 50,51 ROCKY 1.101. ARS. DODX 17067- 0.3 0.5 0.03 <0.01 <0.01

V I=

tiq
 AFRPL-TR-73-24

Table II
F

M1Tfi1iTE CONTENT OF HYDRAZINE S39PLES

F1
r!
ANILINE
LAPL I.D./# USER SAMPLE I.D.

1,3 ROCKET RESEARCH H-1799 0.27+.02

q,6 SHELL H-4670 0.28
7,8 CHriA LAKE H-2002 0.33
iO,!i BELL S/11 929 (,.26
12,13 CHINA LAKE 2037 0. 36
14,15 JPL H-3155 0.17
17,18 SiJDSTRAID H1-110 0.26
19,20 CHINA LAUE Lot 681 0.31
21,22 CHI.1 LAKE H-3139 0.3h
23,2h CHINA LAKE H-3456 0.36
25,26 CHINA LAKE 1-794 0.34
27,28 CHINA LAKE H-2604 0.33
4 LOCKHEED A 3937 0.30
16 - SHELL H-4903 0.23
29,30 ROCmylTDY ?1,At ank 5
PE 0.25
31,32 EDWARDS -Drum 3103 0.30
33,34 EDWARDS N-1993 0.29
35,36 EDWARDS Drum 2763 o.24
37,38 TRW Ilone 0.32
4HA!I. STAND. 4318 0.32
41 HAIl. STAND. 2556 0.27
46,47 EDWARDS Drum 1810 0.27
48,49 ROCKY MI. AIRS. DODX 17074 0.31
50,51 ROCKY "TM. ARS. DODX 17067 0.2-

Vf --
'u

I=
 ¢. I

Table i II

PAhRTICULA-TE, lIVE A111 ASH Ill HYDRAZINE SAkPLES

M;
rR ASH
PAT1ICTJAE'S (10osOC) (65 0 C)
tJARL I.D.# USER SAMPLE I.D. ppm ppm DnM

1,3 ROCKET RESEARCH H-1799 0.2 8.8 1.8

5,6 SIMLL H-467) 0.3 3.0 2.0
7,8 CHINA UE H-2002 0.1 12.2 1.9
10,11 BELL S/11 929 0.3 21.0 <i.0
12,13 CHINA LAKE 2037 0.3 9.5 3.6
14 ,15 JPL 1-3155 <0.1 13.2 <1.0
17,18 S,,IDSTPRL:D H-Iio 0.2 19.4 1.7
19,20 CHITIUA LAIM Lot 681 0.3 32.4 1.0
2 1-3,39 <0.1 12.5 <I.0
23,24 CHIITA LAKE 11-3456 2.2 24,5 1.0

F7 .
25,26
27,28
2
29,30
31,32
CHITTIA LPKE
CHINA LAKE
T_CIKEED
ROCUETDYE
EWDAPDS
-794
H2604
A 3937
PEA Tank P5
Dru-m 3103
0.2
<0.1
0.13
0.35
0.25
9.0
7.8
15.9
h6.9
17.9
<1.0
<1.0
<1
1.0
<1
33,34 EDWAP.AD H-1993 <0.1 20.9 <1
S35,36 EDWARDS Drum 2763 <0.1 17.9 <1
., 37,38 TR lione <0.1 28.5 <I
01A1.4.STAUD. 4313 0.11 11.3 <
41 11A. STAIID. 2556 0.37 18.7 <!
4h,47 E-WARD Drum 1810 <0.1 10.5 1-
DX 170 7h <0.1 U 6i
48,49 ROCKY tI. ARS.
5 r0,51iCjVf
fil. ABS. DODX 17067 0.1i 13.0 <I

Iz

f/JR
 -L m cm m CY :rYr -7 Ml-~ fnr.-'2q.
..-

vt -

14~- -ifc

C ~ 0 0 0l

ci %0

Ul 4 CA 0 0 0 0 0

0 .4i 0. W%. en ma U raN c 7 W

0~~ ~ m t-U 0v 0 0 0r 0, 0- 0 cc
.44

g- .4 . 04 U% 0J %D It 0
m V% t'S e ' r4w

4" 1 L a

C'.4 0 A
140 ca '.0 _r ~
%0 4 .4

bf

- ~ L5C L4~
 v c 0

0 a cii't

VC2ii
01 01 0

'.4 vC;
~ ~

: ::i
0 c 01 %D -- U
C, ci 0 0u '.

0
2 0
ci 0 0 .4
-~ i ~~ ~c ~~
ci .0i
ci 'coi ~0ii ~~~C?
0 C ~ 0
) '4~
0
, v'.
ci ci c-C

UN4 0 C-4 u1
0. 01 01
V 0
a 0
v .p .; . ci 0 c-
v 0 C; c 0 CY
;
cc'~ ci % 0 ci 0o coit * c ) i c

C?) go 0i
t .'' 0 000 0 t- C ci~ 0
0 0

vi'. 0 Or
c C 01 - 0 CO 01 CVi

L'i C . cif
%* toc

V~~ *, V V 't 9 < q

ci 0q 9

0i 01 44 :
0 0-
OOJ~'. ri '1 -1-

-. 0

cu r
cl0 C ci .
P.
4c4 C; C; C; C
"t
oi rI. I
73 v V 01 - 0-~ <;

Or~ CQ
cnD
4'. - ~ -~
0
40

CV M f co t
AFFL-TR-73-21j

TABLE VI

Particle Size Distribution (Particles/100 ml)

Size Range (in icrons)rcl

UA
L Samle i
I.D.# User I.D. 6-I0 11-25 26-50 51-100 >100 ,

!,3 Rocket Research H-1799 23 7 2 0 0

:

5,6 Shell H-4670 32 13 10 1 0

7,8 China Lake H-2002 3 11 2 1 0

10,11 Bell S/IN 929 31 14 5 0 1

12,13 China Lake 2037- 11 3 2 1 1

14,15 JPL 11-3155 10 3- 2 0 0

17 ,18 Sundstrand H-110 21 10 7 1 0

19,20 China Lake Lot 681 3 5 1 0 0

21,22 China Lake H-3139 3 20 0 0

23,24 China Lake 11-3456 SO 40 32 17 10

25,26 China Lake 11-794 - 10 6 1 0 0

27,28 China Lake I-2V:-J4 13 6 2- 1 0

L
 AFRPL-TR-73-24 4

Table VII

Results of Spectral Scan Analyses

Particle Nuuber Elements Observed

Sample 2e Analyzed Major Minor .

11o. 1 Glassy Plates 3 Fe,K,Ti,Si A1,Mn

Metallic 1 Fe 1n

Agglomerates: Stable 2 Fe,Si,Ca,P,K Cr,S,IliAl

11o. 5 Glassy Plates 2 K,Si,Fe,Al Ti ,Mg

Agglomerate: Unstable 1 Fe,Cl Si,Na

Agglom-rate: Stable I K,Si,Fe,Ti AlCa,Cl,Mg

Small-Orange Fluorescent 1 Si ,Cl Ca,Ti

io. 7 Glassy Plates 2 Si,Fe,K,Ti Al

Metallic -Fe lInCr

Agglomerates: Stable 2 Fe,CaSi l,K,I.Ig

Agglomerates: Unstable 2 Cl,Fe-,Si II&,Ca,

:o1.23 Agglomerates : Unstable 2 Si,Fe,Cl Ca,AI,K,Cr

Metallic 1 Fe Ti,A1,C2 Si,Ca

Glassy Plates 2 K,Fe,Si,Ti Al,Ca,Cr

Agglomerates: Stable 2 Fe,K,Si,Ca AlTi

Control Oxide Particle 1 Ti Al

P

Particles : Unstable 3 Si ,Ca,CI,Ti K,S

Ut

- -ifi
 AFRPL-TR-73-24

Table VIII

Results of Stectral Scan Analyses -

(Fig. 13)
Ilumber Elements Observed
Sample Particulate Type Analyzed or Minor

:lo. h Agglomerates: Stable 2 Ca PSi

Glassy Plate 1 Si --

.ietallic 2 Fe,CI Cr,Cl

IA
ao. 16 Agglomerates: Stable 1 Ca Si,Ca

Agglomerates: Unstable 2 l,Fe,Si,Ca Mg f_,t

Glassy Plate 2 K,Fe,Si Ti AlMg,Ca

NO. 19 Agglomerates: Unstable hCa,A!,K,Cl Si ,S,1o ,Ca

Metallic 1 Fe,Crli --

Io. 25 Agglomerates: Stable 4 Ca.Si,Fe Fe,CdK,C2,AI

Agglomerates: Unstable 1 Ca FeSi

41
 ArRPL-TRx-73-24J

Table IX

Results of Spectral Scan Analyses

Number Blerents Observed

Sam!e Particle Type Analyzed Major inor

11o. 9 Agglomerates: Stable 3 CaFe,Si Cr,Fe,Ca,Al

Agglomerates: Unstable 3 Si,Ca,Fe,Cr Fe,Al,Mgj

11o. 12 Glassy Plate 2 Fe,Cr,KSi, Ti

Al,Ca

Agglomerates: Stable i CaFe Si

Agglomerates: Unstable 2 Ca,P,Cl Fe ,Cr,Ca

14 Agglomerates: Stail e 1 Ci,Fe,Ca Cr,Si

No.

Agglomerates: Unstable 3 Ti,Ba.Cl,Ca, Fe,SI,S,

Fe,co-,K,P CI,A1,Cr

Metallic 1 --

;Io. 38 Glassy Plate 1 Si -

Agglomerates: Stable 2 Ca,Fe Si,Cr

A
Aglomerates: Unstable 3 03,e,,

I -a

-- I-2

Li
 AFRPL-TR-73-24

Table X
Results of SDectral Scan Analyses "
(Fig. 14)

N{umber Elements Observed

Sample Particulate y-e Analyzed Major Minor
2
410. 21 Agglomerates: Stable 2 Ti,Ca,Si CaFe

Agglomerates: Unstable 3 Ca,KCI Si,Fe,Ti,K

No. 27 Agglomerates: Stable ! Si

Agglomerates: Unstable 3 Ca,Pe,A1,Cl, Si,KCd,S,

LSiK Cl,Fe

bo. Z9 Agglomerates: Stable 1 Si,CaFe Al

Agglomerates: Unstable 2 Ca,Ci Fe,S,X,CI

:A
Metallic 2 Fe ,Si Si Ca

-1o. 31 Agglomerates: Stable 2 Fe ,Kgi,Ti Ca, g

:I
Agglomerates: Unstable 2 K,Fe,Ti,Si

LJ
M4etallic 1 Fe,Si K,Ca-Ti

[ io. 40 Agglomerates: Stable 1 Mg,Ca Fe

Agglomerates: Unstable 3 Ca,CI,K K,S

no. hi Agglomerates: Stable 2 Fe,Ca,KSi K,Ti.

Agglomerates: Unstable i Ca,Fe,Si K

Metallic 2 Fe,Cr 'i,Ca

 AFRPL-TR-73-24

A
Table XI

Results of Spectral Scan Analyses

(Fig. 15)

Number Elements Observed

Sample Particle T d j Minor

'No 33 Agglome-ates: Stable 3 Fe,Si,K,Ti, A1,Ti,K

Al

Metallic 2 Fe,Si,K Ti,A1

No. 35 Agglomerates: Stable 3 Fe,Cr,A1,S, Cr,Ca,li,

Si,K Al,Ti

Metallic 2 Fe,Si,K A1,Ti,Si-

No. 37 Agglomerates: Stable 3 Ca,Fe --

Agglomerates: Unstable 2 Ca,Cl,Fe,Si --

Io. 46 Agglomerates: Stable 1 Cr Si,ve,Cl

Agglomerates: Unstable 1 Si Al,ClCa

Metallic 3 SiFjFe ,K,Ca, -4[r,

i ,AII--

:io. 48- Agglomerates: Unstable 2 Al,Si -- >

Metallic 3 Fe,A1,K,Si Ca,Ve

-1o. 50 Agglomerates: Stable I Ca S

Agglomerates: Unstable 3 S,Cl,CaSi CIAl

4 1etllic 1 Al --
 71

AFRPL-TR-73-24
Ft FIG. 3

CHROMATOGRAPHIC SEPARATION OF HYDRAZINE IMPURITIES

(COLUMN A - lm x 1/4 IN. OD 33% CARBOWAX 400 ON 90/100 MESH ANAKROM AB)

-r.~

-A I

IL + I

r 0 - a

i .- 1

TIME (MIN

S0 2 4 6 8 10

; - TIME (MIN)
AFRPL-TR-73-24.FG21

FI.

0
AFRPL-TR-73-24 FIG. 3

CHROMATOGRAPHIC SEPARATION OF HYDRAZINE IMPURITIES

(COLUMN A - lm x 1/4 IN. OD 33% CARBOWAX 400 ON 90/100 MESH ANAKROM AB)

[3
I4

Nz -

UZ

0/
" 0i

0 28

0 I 2 TIM
4 WIN)
6 8 10 - ;

TIME (MINI
AFRPL-TR-73-24 - __ ~ - ~ -- FIG. 4

ICHROMATOGRAPHIC SEPARATION OF HYDRAZINE IMPURITIES

(COLUMN B - 6 FT x 114 IN., 00 10% DOWFAX 9N9 ON 60/80 MESH T6)

zz

0 2 -4 t 8 1

I - pI
77
TIME (MIN)
AFRPL-TR-73-24

CH-ROMATOGRAPHIC SEPARATION OF HYDRAZINE IMPURITIES

(COLUMN A4-B)

0 0 2 1

TIE(MN
AF9PL-TR_73_24 FIG. 6

.CHROMATOGRAPHIC SEPARATION OF HDRAZINE IMPURITIES

(COLUMN C - 6 FT x 1/4 IN. OD 50/80 MESH PORAPAK PS)

iLi
C14
0
r-,ij

Ii I p
0 2 4 6 8 10 -

TIME (MIN)
F,
AFRPL-TR-73-24 -FIG. 7

CHROMATOGRAPHIC SEPARATION OF HYDRAZINE IMPURITIES

(COLUMN B +C)

NN

0 2 0 2 1

TIME VAIN)
 AFRPL-TR-73-24 FIG. 8

- C

It
cr

co
 AFRPL-TR-73-24 FIG. 9

I EMISSION SPECTROGRAPH

II

'0
AFRPL-TR-73-24 FIG. 10

rc
I-i

Irw4 uLq ,
Iw

04

- I
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C,

04
 AFRPL-TR-73-24FG.1

II

a. '

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CLEl
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cco Z- A <I0
tU C l

0-0

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cro
CL
0-
00

C, Cr

0L <
z1
AFRPL -TR .73-24 FIG. 13

OPTICAL PHOTOMICROGRAPHS OF PARTICULATES FROM 14YDRAZINE SAMPLES

SAMPJ.E 4 (LOCKHEED - DRUM A -3937) 0ipj~

SAMPLE 16 (SHELL - DRUM H .4903) ___

 FIG. 14
AI-RPL-TR -73 - 24
OPT ICAL PHOTOMICROGRAPHS OF PARTICULATES FROM HYDRAZINE SAMPLES

It--

SAMPLE 29 (RALOCEDNE TANK NO.S5)56)

 -/-7 '

AFRPL-.TR-73-24 FIG. 15
OPTICAL PI-OTOM ICROGRAPHS OF PARTICULATES FROM HYDRAZINE SAMPLES

- Ar

AA

IWI
[
"~~~~ SAMPLE 3 (EDWARDS~fl-DRUM -19934) i APE3 EWRSDU 73

SAMPL 45 RO~K
M~f.-DOX--10741SAIMPLE S0 (ROCKY MiTN.-DODX 17067) I
 AFRPL-TR-73-24 FIG. 16

<I
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La... .-
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cc
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wY .H.
LO - --. .
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ci-w

-J

<J

<D

Zn

zi
m~

LUJ

346
AFRPL-TR-73-24
FIG. I8

CLI

0I
LU

CO,

I- -

F caI I

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C.,
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F-O
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II
111

L CL

wir

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At

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K4Z<
AFRPL-TR-73-24 FIG. 20

L[

0-z

V. !
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AFRPL-TR-73-24 FIG. 21

.9 <

Ln

0c

I-
C)

CD

44z
AFRPL-TR-73-24 FIG. 22

ca co

CLU
li A

0cc

[Z 0- 0
cc

(0

to

A 0
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-
FI

1- V