s cg 01354292
TRANSCRIPT
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UNCLASSIFIED
AD NUMBER
LIMITATION CHANGES
TO:
FROM:
AUTHORITY
THIS PAGE IS UNCLASSIFIED
ADB004012
Approved for public release; distribution isunlimited.
Distribution authorized to U.S. Gov't. agenciesonly; Test and Evaluation; MAR 1975. Otherrequests shall be referred to Edgewood Arsenal, Attn: SAREA-TS-R, Aberdeen Proving Ground, MD21010.
EA, D/A notice, 13 Oct 1977
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TECHNICAU
LIBRARY
[ A H ;
USADAC
TECHNICAL
LIBRARY
5 7 2
7757
EDGEWOOD ARSENAL
CONTRACTOR
REPORT
EM-CR-74053
(E A - 4D41)
EFFECTS
OF
ENVIRONMENTAL
AND
PROCESSING
CONDITIONS
ON
COMPOSITION AND SENSITIVITY
OF
HC
WHITE SMOKE MIX
m^ftffr
by
J.
. ankow
G.
.
McKown
March
1975
NASA NATIONAL
SPACE
TECHNOLOGY LABORATORIES
General
Electric
Company
Engineering
and
Science Services Laboratory
Bay
Saint Louis,
Mississippi
39520
Contract
No.
NAS8-27750
DEPARTMENT
OF HE ARMY
Headquarters, Edgewood Arsenal
Aberdeen Proving Ground, Maryland 21010
ETIC QUALITY
IIT6PECTKD
d
Distribution limited
to U S Government agencies
only
because
of
test and evaluation;
March
1975.
Other
requests or this
document must
be referred
o
Commander ,
Edgewood
Arsenal, ttn:
SAREA-TS-R,
Aberdeen
Proving Ground, Maryland
21010.
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Disclaimer
The
findings n this report are
not
to
be
construed
as
an
official Department of
the
Army
position,
unless
so
designated by
other
authorized
documents.
Disposition
Destroy his
report
when
it is
no longer needed. Do not
return
t to
he originator.
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P V 1
m
J
THIS
REPORT
HAS BEEN PELI^'TEC
AND
CLEARED
FOR
M&LIC.
RELEASE
UNDER
DOD
DIRECTIVE
5^J0,20
MO
NO RESTRICTIONS ARE
3 POs£b UPON
I T S
USE AND DISCLOSURE,
D I S T R I B U T I O N
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SECURITY CLASSIFICATION
OF
THIS
PAGE When Data
Bntmrmd
REPORT
DOCUMENTATION AGE
1.
REPORT
NUMBER
EM-CR-74053
READ INSTRUCTIONS
BEFORE COMPLETING FORM
2. GOVT
ACCESSION
O
3. RECIPIENT S
CATALOG
NUMBER
4. TITLE
and
Subtitle
EFFECTS OF ENVIRONMENTAL AND PROCESSING
CONDITIONS
ON
COMPOSITION
AND
SENSITIVITY
OF
HC
WHITE
SMOKE
MIX
5. TYPE
OF
REPORT
ERIOD
COVERED
Technical Report
September 1973-September 1974i
6 PERFORMING ORG. REPORT NUMBER
EA-4D41
7. AUTHOR ̂
J. F. ankow
G . .
McKown
8. CONTRACT
OR
GRANT
NUMBERf«)
NAS8-27750
MIPR B4030
9.
PERFORMING ORGANIZATION
NAME
AND ADDRESS
NASA National
Space
Technology Laboratories
General Electric Company
Engineering
and
Science Services
Laboratory
Bay
Saint
Louis.
S
39520
10 . PROGRAM
ELEMENT.
PROJECT,
TASK
AREA
t
WORK
UNIT
NUMBERS
PEMA 4932
Project 5744099
«
ONTROLLING OFFI E
N ME ND DDRESS
Commander , dgewood Arsenal
Atta:
SAREA-TS-R
Aberdeen
Proving
Ground,
MD
21010
12 .
REPORT
DATE
March
1975
13 NUMBER
OF
PAGES
25
14.
MONITORING
AGENCY
NAME
ADDRESSf//
different rom
Controlling
Office
Commander , dgewood
Arsenal
Atta: SAREA-MT-TS
Aberdeen
Proving
Ground,
MD
21010
(CPO
Mr.
.
. enderson.
71-2301)
15 .
SECURITY
CLASS,
of
hle eport
UNCLASSIFIED
15«.
DECLASSIFIC
AT I ON/ DOWN
GRADING
SCHEDULE
NA
16 . DISTRIBUTION
STATEMENT
of
thle Report
Distribution limited o
U S
Government agencies
only
because of
test
and evaluation;
March
1975.
Other
requests
or
this document
must
be
referred o
Commander ,
dge-
wood Arsenal,
Atta: SAREA-TS-R, Aberdeen
Proving Ground,
Maryland
21010.
17 .
DISTRIBUTION
STATEMENT
of
th e
ebetrmct
entered
n
Block
20 ,
f
different
rom
Report
18 . SUPPLEMENTARY
NOTES
19 - KEY
WORDS
Continue
on
everee eide
t
naceaeary
an d
dentify by block
number
Jet
Airmix process
Blending
DTA
Parr bomb calorimetry
Environmental
effects
Input
sensitivity
HC
white
moke
mix
20 . ABSTRACT
Continue on everee aide
t
necememry an d Identity
by
btock
number
A
series
of
experiments
were
performed
to
determine environmental
condition
effects
of HC white smoke mix. Temperature,
umidity level, lending rates and time
were ound o have
minimal
effect
on
input sensitivities and energy release.
Significant
findings
were;
gross
sublimation
of hexachloroethane from
stored
samples;
large
nho-
mogeneities
in he blended
samples;
and
inconsistencies
n
impact
sensitivities of all
samples
compared
to
previous results.
D D 5
ORM
AN
73
1473
EDITION
OF NOV
65
S
OBSOLETE
UNCLASSIFIED
SECURITY
CLASSIFICATION
OF
THIS
PAGE
When
Data
Entered
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PREFACE
The work described n his
report
was authorized under Edgewood
Arsenal
MIPR
Num-
ber
B4030, RON 81-4-B4030-01-F4-W5, AMCMS
4932.05.4099.0.
It
was performed at
the NASA National Space Technology Laboratories
NSTL)
or
he Edgewood Arsenal Resi-
dent
Laboratory EARL)
nd
NASA-NSTL y
he
General
Electric
Company
under
Contract
No. AS8-27750.
Reproduction
of
this
document in whole or n
part is
prohibited
except with
permission
of
th e Commander,
dgewood
Arsenal,
Attn:
SAREA-TS-R, Aberdeen
Proving
Ground,
Maryland
21010;
however,
DC
s authorized o reproduce he
document
for United States
Government purposes.
The
use of
trade names n
this report does not
constitute
n
official endorsement
or
approval
of the
use
of
such
commercial
hardware
or
software.
his
report
may
not
be
cited or purposes of
advertisement.
The
nformation
n
his
document
has
not been cleared or release
o
he
general
public.
SUMMARY
A program was conducted o determine sensitivity
and
energy
release
of
HC
white smoke
mixes prepared under a
variety
of environmental
nd blending
conditions.
The
effects
of
temperature,
umidity,
mixing
rate
nd
ime
on
moisture
content,
nitiation
sensitivity,
homogeneity,
utput energy nd reaction mechanism were nvestigated.
Impact
sensitivity,
thermal stability, electrostatic
sensitivity,
hemical
analysis,
ifferential hermal analysis,
and Parr bomb
calorimetry results
are
reported
on samples prepared
within he ollowing
matrix
of
conditions:
• emperatures
of 24°C
and 41°C
• elative
humidity
of 35,
5,
nd
90
percent
• wo
blending
times
•
hree sampling
imes
•
our
HC mix compositions
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EFFECTS
OF
ENVIRONMENTAL
AND
PROCESSING
CONDIT IONS
ON
COMPOSIT ION
AND SENSITIVITY
OF
HC
WHITE SMOKE
MIX
1.0
NTRODUCT ION
1.1
bjective,
The
objective
of this
work
s
o provide he
ollowing
nformation for HC
white
smoke
mix
compositions:
• o
determine the
effect of
humidity
and
temperature on
absorption
of moisture
during
blending
by
he Jet Airmix( Process.
•
o
determine he
relationship between
moisture
content
and
nitiation sensitivity.
•
o
determine
the
effect
of
mixing
rate
and
time
on
he
composition
and
homoge-
neity
of
the mixture.
• o
examine
changes
n
reaction processes
by
determination
of
th e
thermal
decom-
position and
output
energy variations
with
hexachloroethane concentration.
1. 2 uthority.
his
work
was
authorized
by
Technical
Work Request
EA-4D41, ated
September 1973,
s
amended
on
21
June
1974.
1.3 Background.
HC white
smoke
mix
is
a
commonly
produced
pyrotechnic
composition
used
or numerous
signal applications
n
he
U S
Army.
The
mix
nominally contains
46.
5
percent
ZnO,
4.5
percent
hexachloroethane,
nd
9.
0
percent
aluminum
powder
by
weight,
although
small
adjustments
n
these
percentages
are permitted
to
control burning rate
and
ignition
characteristics.
The
reaction
of
H C
smoke
mix s presumed
o
nvolve
ormation of aluminum
oxide and
zinc
chloride,
hich
hydrolyzes
n air
to
orm a
dense
aerosol,
nd small amounts of
free
carbon.
The
percentage
composition
of the
mix
s
not
n
simple
stoichiometric
ratios,
nd
a
complex reaction s predicted that
s
approximated
by
the equation
2A1
+
7ZnO
+ 2C
0
C1 _-^A1_0
0
6ZnCl_
3C O
+
C +
ZnO Eq.
1)
2
6
3
An
excess
of
the
diluent
(coolant)
zinc oxide s
noted.
he carbon
monoxide
and
some of
the
carbon
formed
s expected to
combine
with atmospheric oxygen
at
he temperature
of
the reacting mass.
2
The nput
sensitivity
and output
energy
of
HC smoke
mix
has
been
determined,
result-
ing in
an
assignment
of Class
2
fire hazard) for
the
bulk composition.
The
classification
data
shows
evidence of
the
rather
nert
nature
of
the
standard
mix toward
all
normal
modes
of
initiation,
nd both
starter
and first
fire nitiators are
required
n
end-item usage. An
extensive
evaluation
program
has recently
been
concluded
that
provided data
for
safety
cer-
tification
of
Jet
Airmix blending of HC
smoke mix n
quantities up to 2170
pounds.
3
Results
of
this
project
yielded
no
evidence
of
hazardous
situations
due
o
nitiation
stimuli
evels
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found
n
he blending
process,
nd
showed critical detonable)
mass-diameter
of
the
mix to
be
greater than 500 pounds
at
3
eet
diameter even
under
severe
conditions of energy
nput.
However,
ccidents
nvolving production of
HC smoke
mix
have
been reported. It has been
specifically
determined
hat
the
presence
of
moisture
n the composition can
be
potentially
hazardous.
4
A
otal
moisture
content
greater
than
0.6
percent by weight
has
been observed
to
be
extremely dangerous,
nd
t
is postulated
hat
a decomposition process
nvolving chlo-
ride
on
s
responsible.
The acidic
chloride
solution probably catalyzes reaction
of
the
aluminum
metal;
i.e. cts
as
an
etchant
to
expose
resh
aluminum
surfaces hat
can react
with
water
in a
highly
exothermic
manner:
2A1
3H
2
0 -Al
2
0
3
3H
2
Eq.
1A)
The hydrogen, eleased interstitially, s n intimate contact with the
other
mix compo-
nents. At
the
elevated
emperature
of
the
nitiation,
reduction
of
the
hexachioroethane
could be
effected:
H
0
C
0
C
1
-HC1 CJHC1
tc.
(Eq.
B)
1
6
5
The
acid
ormed promulgates urther
reaction
resulting
in
production
of highly lamma-
ble partially hydrogenated
chlorocarbons
and
hydrogen
gas. The
sensitivity
of these
pro-
ducts
o nitiation by electrostatic,
hermal,
or
electromagnetic stimuli s obvious.
It is known that a least one previous accident involved extended blending of HC smoke
mix under hot, humid environmental conditions,
nd nitiation mechanisms such as that
postulated
are
suspect.
The
present
study
was
undertaken to determine
he nfluence
of
environmental
and
processing
parameters
with
respect
to
safety
of
HC
smoke
mix
manu-
facturing
operations.
A factor
that
potentially
could create
abnormally
high
hazard
levels
s
he
sublimation
rate
of hexachioroethane. The
cubic crystalline orm of
this
compound
exhibits
sublima-
tion pressure
of
1.6mm
at
41°C.
* Thus
significant
removal
of this
constituent
rom
mix-
ture,
articularly
during
blending,
s expected even at normal
ambient temperatures.
It is
easonable o
assume
hat the
reaction
process will
depend
on the
constituency of
the mix.
For
he
case
with
no
zinc oxide present, he ollowing reaction is
expected:
2A1
C
0
C
1
-2A1C1
0
2C
Eq.
2)
A
composition
with excess
aluminum
might
ollow
the
equation:
2A1 3ZnO C
0
C
1
_
—
Al
O.
3ZnCl
+
2C
(Eq.
)
2
6
3
Finally,
otal absence of hexachioroethane permits only
the well-known
thermite-type
reaction:
2Al+3ZnO
* A 1
+3Zn
Eq.
4)
—
o
*
For
hexachioroethane
cubic
form), og
P(mm) -
8.731
2677/T(°K)
6
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An
investigation
of the
reaction
energy
depending on hexachloroe
thane concentration
was
attempted
o
determine whether his
situation could be
a
relevant safety actor.
2.
0 TECHNICAL
APPROACH
Experiments
were
performed
or
determination
of chemical
analysis
and
nput
sensiti-
vities
of
HC
smoke batches
blended within a matrix
of
environmental
and
process
parame-
ters. Blending
of
standard
formula
HC
moke
mix
was accomplished
n
bench
mode l Jet
Airmix
TM)
blender,
etails of
which
have
been described
previously.
Four
hundred
gram
batches were blended
n the mixer under a
variety of
conditions, s
ollows:
•
emperatures of 24° + 3°C
and
41°
+ 3°C
• elative
humidities
of 90
+
5% , 5
+
5 5
+ 5
•
lending
repetitions of
five
5)
and two
2)
two-second blend/four-second pause
sequences.
Appropriate
sample
sizes were
removed
rom
he
blender
and
packaged
n sealed
containers
(polyethylene
bags)
o
aid
n
preservation of the
original
material
condition.
6
i
Impact
sensitivity, thermal
stability
and electrostatic
sensitivity
tests were
per-
formed
on
each of the samples.
Chemical analysis was accomplished
as
ollows:
7
•
etermination
of moisture
content
by a
desiccation
method .
• etermination of
chemical
composition; a known quantity of
the
mixture was eluted
with sopropyl alcohol
and
filtered. The
residue
was dissolved
n
nitric and
hy-
drochloric
acid
solutions and he
resulting
solution
diluted
to one
liter. Aliquots
were urther
diluted
and
ntroduced
nto
a
Perkin-Elmer Model
403 atomic
absorp-
tion
spectrometer
fitted
with appropriate
amps.
The
percentages of zinc
and
aluminum
were
determined
by
comparison
o known
standards;
he percentage
of
hexachloroethane
was
determined
by
difference.
Inherent
experimental
accuracy
of
this
method was
calculated
to
be
better
than
three percent
of
the
composition
fo r
any
component;
.
e.,
or
the
percentages
n
tandard
HC
smoke
mix:
Aluminum + 0.
08%
Zinc Oxide
+
1.0%
H exachloroethane + 1.0%
The
nvestigation
of reaction process was accomplished
as
ollows:
•
C
smoke
mix
samples were prepared with
varied
composition
as
hown
in
table 1.
•
eighed
samples of
each
mix
were
conditioned
fo r
24
hours
at constant
tempera-
tures n desiccators
containing
H2SO4 solutions
of concentrations
appropriate or
maintenance
of
35 ,
5,
nd
90
percent
relative
humidities.
Other
samples
were
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ovendried
or
maintained at low humidity,
nd
control
samples
were taken
imme-
diately
after
blending.
Details
are given in able 2.
Samples
were
e-weighed
after
the
24
hour period to
determine
weight
loss
n
each
of
the environments.
• ifferential
hermal analysis
of
50 milligrams
of
each
sample
was performed
on
a
Fisher
Thermalyzer(
.
All
sotherms
were ecorded over the ange
rom
ambient temperature
to beyond the
melting
point of
aluminum.
•
xygen-bomb
calorimetric
measurements
were
made
on one
gram
sample
of
each
batch using
a standard Parr(TM)
bomb
calorimeter.
The
heat
of
combustion n
calories
per gram,
was
obtained
rom
he
equation;
H =
tW
e
i
6
2
6
3
Where:
t
is he
temperature
rise
W
is
the energy equivalent of calorimeter 1386)
e
is
he correction
for
heat
of
formation of
HNO
in
calories,
hich
was
used as
an
estimation
for
acidity
of
combustion
residue due o
ormation
of amphoteric metal
chlorides
e is
he
correction
for
heat
of formation of H
O
in
calories,
iven
by
14 )
x
sulfur
n
sample)
x weight of
sample in
grams)
e
is he correction for
heat of combustion of
firing
wire n
calories;
2.
3 x centimeters of chromel C wire consumed;
and
g
is he weight
of
sample n
grams
3.
0
RESULTS AND DISCUSSION
3.1 xperimental Data. Experimental results
are
given in tables
hrough
8.
3.2
iscussion of Results.
3.2.1
Input
Sensitivity
vs Mixing
Parameters.
A serious
anomaly
exists n
the
results
shown
in
table
3
or
the
mpact
sensitivity
tests.
These
results
ndicate
decomposition
in
3 9
percent of
all
ests using
drop heights
rom
. 5
to
25.4
cm and
n
59 percent
of the tests
at
25.4 cm 10-inch drop height). These
observations
contrast
strikingly
with those obtained
in
previous classification
tests
or HC white smoke mix
2
which
showed
no
apparent
reaction
at
any drop height.
Based
on the
results
of this
project, he classification
of
HC
white
smoke mix as Class
2
s highly suspected.
There does not appear
to be any
significant
correlation between
the mixing parameters
(temperature, humidity,
irmix
sequence)
nd any of
the nput
sensitivity
tests;
nternal
comparisons of the mpact sensitivity results
are
erratic.
The
mix
prepared
at
a
tempera-
ture of 41
°C and 0
percent
relative
humidity
gave some detectable evidence
of
decomposi-
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Table
1.
Composition
of
Samples
Mixture
Constituent
Composition
Mole
Composition
Rationale
Aluminum 5.0
1
Standard
Mix
Zinc
Oxide
48.6
3.6
Equation
Hexachloroethane
46.4
1.
2
Aluminum
18.6
2
No
diluent;
Hexachloroethane
81.4
1
Equation 2
3
Aluminum
10.0
2
No excess diluent;
Zinc
Oxide
46.0
3
Equation
3
Hexachloroethane
44.0
1
4
Aluminum
18.1
2
No
oxidizer;
Thermite
Zinc Oxide
81.9
3
reaction;
Equation
4
Table
2.
Conditioning
Parameters for
Samples
Relative
Humidity %
Temperature
Desiccant
Period
0
24.7°C
Drierite
(TM
CaS0
4
)
24
hours
35
24.7°C
so.
o o ;
H
SO
4
24
hours
6 5 24.7°C
35.8'Y
0
SO.
2
4
24
hours
90
30.0°C
18.6
r
i
2
S0
4
24
hours
-
40.5°C
Oven Dried 24
hours
Conti
P O l
None
Immediately
after
mixing
9
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Table
3. Test Results,Sensitivity of
Mixes
Sample
Number
Mixing Parameters Thermal
Stability
Test
Electrostatic
Sensitivity
Impact
Sensitivity
Tests*
Temp.
R.H.
No. f
Pulses
Time
Lapse
W t.
(g )
Wt.
(g )
Loss
(g )
Loss
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and high
humidity
was
ndicated,
albeit
based
upon
shallow
evidence.
The most striking
observation
was he overall nput
sensitivity
results nd the magnitude of weight loss n
the
thermal stability
test,
result
expected n view
of
the probable
extent
of
hexachloro-
ethane
sublimation from
samples
maintained
at
75°C
or
a
period
of
24
hours.
3.2.2
Variances
n
Moisture
Content
and
Chemical
Composition.
Determination
of
the
percentage
moisture
n
batches of
HC smoke mix
was
nconclusive, ue
primarily o the
experimental method desiccator)
employed
nd
the overwhelming
interference
of hexachlo-
roethane
sublimation
on
sample
weight
losses with
time.
As shown
in
table
5,
pproximate-
ly
one
percent
loss
n
weight
of all
samples was observed
within
period
of 72
hours
and
the
loss
rate
continued
until he experiment
was erminated after 15
days.
The average
weight
loss
rate
was 0.
21
jf
04
percent-per-day
over the
period
of
observation,
even
in
the
closed
vessel conditions
of
the desiccation
method.
̂
An
attempt was made
o
obtain
percentage
moisture
content
of
the samples by extrapo-
lation of the weight loss/time
data backward
to
time
zero.
It
was assumed that
sublimation
of
the
hexachloroethane
would
proceed
at
a
constant
rate
and
hat
moisture
oss
would
cease
after some nitial period of time. Nonlinear variations n the
oss/time
curve near
time
zero could
be attributed to
the loss of
moisture.
Straight-line
extrapolation of
the curves
from
regions
of
constant loss
rate
o
zero time
would
yield
the percent weight
loss not attri-
butable
o sublimation;
i.e.
he
percent
of
moisture n he original sample.
These
attempts
were eventually abandoned for
the ollowing reasons:
•
t
was
required
to use
several
different desiccators
n he
experiment,
nd
weight
losses
or
both
water
and
hexachloroethane
are
expected to
be strongly
dependent
on
the
physical
characteristics,
e.g. ightness
of
cover
and percent
of desiccant
expended,
f
a
particular desiccator
system.
This situation
was n fact
observed
during the
experiment.
•
here
s
no
reason
to believe
that
sublimation
rate
from
a
10
gram
sample
would
be constant, articularly at
the
start
of
the experiment,
ince
material-air
and
material-material nterface partition
functions
would
be different.
•
he desiccators were opened
periodically
for
weighing of samples nd consequently
the closed system environment
was
altered.
• everal
samples
were maintained
n each
desiccator,
nd complex
partition
func-
tions,
po n
which
weight
loss
rates
depend,
ould
be
nvolved.
Despite
the
failure o
obtain
reliable moisture content
information, he
weight
loss
mea-
surements
provide
valuable
gross sublimation
rates
or
he
xachloroe
thane
rom
HC smoke
mix
under
semiconfined
conditions.
The
chemical
analysis
data shown
n
table
appears
o be
inconsistent
in
several
ways:
•
he
variation
in percentage
composition
for
samples
aken from
a
particular
batch
at different
times s much
larger
than
both
the
expected
effect and he
inherent
analytical
reliability.
The
expected
variation
would be
due
entirely
to
changes
n
moisture
content
with
sampling time,
which
effect
should
not
exceed
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For
a given mixture ormulation,
here
s
ittle or no significant difference n
he
heats
of combustion
or
samples conditioned
under
various
humidity
environments,
nd
nearly
all
such
results are within
he
standard deviation expected or a single value. The
only
no-
table
exceptions
o
this general observation occur in he results or
samples
oven-dried or
24 hours
at
41 °C .
Comparison
of values or this conditioning with data rom all
other
simi-
lar
samples s shown
in
table 6.
It is
noted hat the comparison or
Mixture
s
based
on
a
single
data
point
at
a
different
pressure
value
nd
s
considered
o
be
unreliable.
There does
not
appear
o be
any
significant
rend
in he
observed
percentage
differences.
It
s possible
hat the
differences
are
due
o
combustion
properties
of
material
emaining
after
sublimation of
hexachloroethane
rom
he
oven-conditioned sample,
ut this should
show
a
greater effect for Mix
1
since he
percentage
of
HC s higher.
The
effect
of
the
diluent
ZnO)
may
be
seen
in
he
results
shown
in
able
7.
Mixes
and
3
both
how
H
values significantly lower than hat
of
Mix
3,
ince
he
latter
contains
no zinc oxide. At
1
atmosphere,
equation
1)
ndicated probable
ormation
of zinc chloride
rather than ZnO.
However,
t high
pressures
of
oxygen,
ully oxygenated
products
are
anticipated;
i.e. :
ZnCL
30 (20 atm) ZnO + C1_0 (etc.)
The net result
is
hat
th e
original
zinc
oxide
does
not contribute o he heat of
reaction
observed
and calorie-per-gram
quantities
are educed n
mixtures
containing that consti-
tuent.
Caloric
and
DTA)
measurements
on
Mix
4 containing only aluminum nd zinc oxide
were
difficult o obtain. Heat
from
his hermite-type eaction s iberated so apidly
hat
sample crucibles,
hermocouples,
nd other parts
of apparatus
were
destroyed.
Conse-
quently he measurements on
this
material
were
seriously
curtailed.
As
expected,
he ob-
served value
or
heat of
reaction
for Mix
4
s
equivalent
to hat obtained
or
oven-conditioned
(excluded
HC)
Mix
3; the reason
for
a
low
value for oven-dried Mix may
be
due o
he
high-
er pressure
used
n hat
experiment.
In general, Differential Thermal Analysis results on a given mixture under various
environmental
conditions
do not
exhibit
large
variations.
DTA results rom able
8,
om-
bined n
bands,
re
compared
to
values
obtained
or he
Aluminum
powder and
hexachloro-
ethane constituents n
he
igure on page 18. Zinc oxide does
not
produce
isotherms in the
temperature ange
of
interest.)
The
following
observations
can
be
made:
•
catter of
data
appears
o
be
governed
more by
sample
nhomogeneities nd
heating rates han o
differences n
experimental parameters.
The heating
rate
used
in
the
DTA
analyses was
25°C per minute, nd would
appear
o be
signifi-
cantly
oo
high.
•
hermograms
of
oven-dried
41°C)
samples
appear o be
simpler
han those of
th e
humidity-conditioned materials,
ndicating
the
complexity ntroduced
by
he
presence
of
hexachloroethane
in
the
atter.
The
expelling
of
HC
from
sample
during
he
course
of
a
DTA
analysis complicates he spectrum
by
causing
signifi-
cant
base line drift. The
presence
of
water in all samples
except
those hat
were
oven-conditioned
is
indicated
by
the
100°C
sotherms.
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Table 7.
Calorimetry
and
Weight
Loss Data
Number
of
Trials
Number
of
Results
Conditioning
(24 H r)
Pressure
(ATM)
Cal/gm
(Average)
(
+
Std
Dev)
Acidity**
24
our
Weight
Loss
MIX
4
2
(Immed. fter
Mix)
20
827+2
0.55
-
3 2
RH
20
826.5+0.1
0.47
1.41
5
2
RH
20
831+9
0.90
*0. 51*
2
2 20 861+49
0.50
*1.22%
2
2
RH
20
840+20
0.50
1.31
3
2
24 hr
at
41°C°C
20 804+29 0.00 49.415%
MIX 2
4
(Immed. fter Mix)
15
2,100
+ 1 80
3.15
4
3
RH
20
2,377+45
1.65
1.14
9
2
35* RH
20
2,132+2 3.38
0.93
f
;
3
2
65*
RH
15
2,100+240
1.66
0.77
r
:
6
2
90*
RH
15
2,510+54
1.85
0.89
r
4
1
24 hr
at
41°C°C
1
3,402+?
0.20 68.40*
MIX 3
3
(Immed.
fter
Mix)
1,294+70 3.07
2
2
0*
RH
1,241+22
4.15
2.oi
(
;
3
2
RH
1,263+50
3.47
i.08
(
;
2
2
65^ H
1,264+53
4.23
0.5591
2
2
90^
RH 1,299+7
3.8
2.48
r
;
3
3
24
hr at
41°C°C
1,050+85
*
0.72
49.85*
MIX
4
3
3
(Immed.
fter Mix)
1
1,100+16
0.00
-
*
Different hexachloroethane
ot
used.
**
Ml standard alkali 0.
0725N)
o titrate calorimeter residue.
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Table 8.
Summary
Date, DTA °C)
Mix
Conditioning
Endo
therms
1
2
3
4
5
I
RH
35',
RH
65' , H
90', RH
105°F 0',
RH
Immed.
fter
Mix
667.61
684.83
682.50
660.50
640.08
86.49
90.33
89.00
95.50
92.31
103.99
110.08
106.25
112.81
176.43
191.33
182.75
172.88
191.18
682.05
693.83
714.50
671.25
687.03
683.93
2
RH
35% RH
6 5%
RH
90
p
; H
105°F
RH
Immed. fter Mix
697.22
653.56
647.00
683.50
603.67
672.78
99.30
96.31
92.50
92.50
92.78
124.30
110.00
115.50
132.28
205.60
168.56
178.75
196.13
201.67
178.53
712.22
673.06
680.25
700.00
664.17
692.28
3
RH
$591 H
6 5%
RH
90
f
#
RH
105°F 0° /
H
Immed. fter
Mix
648.75
671.47
678.00
663.67
669.80
689.96
99.50
104.78
81.00
91.45
104.25
103.67
164.38
171.72
184.25
171.67
183.20
666.25
681.72
692.75
680.92
698.55
727.25
Aluminum
%
665.89
-
—
690.54
Hexachloroethane
—
92.57
112.64
182.59
—
Zinc
Oxide
Based
on Handbook of
Chemistry:
decomposes
at
>1800 C
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00
ALUMINUM
HEXACHLO-
ETHANE
OVEN
MIX
3
OTHER
OVEN
MIX
2
OTHER
OVEN
MIX
OTHER
m
100
- y
A
TEMPERATURE, C
5
600
I
1
W77?m
wmm
7
Summary
of DTA esults
Temperature of
Endotherms
-
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•
Isothermal
behavior was observed n he region of 530
o
C-ß00°C
only or oven-
dried
Mixes nd
3 and
for
Ü Ü
percent
U I
samples
of Mix
3. This
esult may
be
attributed
o
mproperly obtained thermograms
or
o
peculiar
sample
behavior.
The
possibility
hat
the
sotherms
are
due
o
presence
of
A1/II
O/C
l
reaction
products eqs.
1A,
IB) cannot be proven
rom
he
existing data. Possible
eaction
products
and
known
sotherms
are:
A1C1 6H
00°C
Decomposition)
AiCl
78°C
Sublimation)
Al (OH )
00°C
Decompositon)
•j
C
C l
r
62 °C Boiling
point)
— o
83°C Melting
point)
732°C (Boiling
point)
None of these
temperatures
correspond o he
anomaly
observed.
3.2.4 General Discussion.
The results
obtained
n
this
experiment
showing
marked dif-
ferences
rom those
obtained previously
may
be a unction
of
he purity
differences n
a-
boratory
samples
prepared rom
chemically
pure components
and
technical
grade
commer-
materials
used
n
the
manufacturing
process.
It is possible
that technical
grade ma-
terials
would
produce
less
sensitive
mixes
han
that
prepared
from
pure
components,
s
observed,
ut
this
phenomenon
would
not
be
expected. The
absence
of
gross
moisture
absorption
by
the
mixes
prepared rom
chemically
pure components may
not
relate o
the
same effect in plant
material. It
is feasible
that
impurities
n
the
hexachloroethane
or the
other components
could
contribute significantly to absorption of
moisture.
These
effects
cannot
be
completely
determined
by
the
results of
this
experiment.
The choice
of
HC
white
smoke mix and
he
Jet
Airmix blender
as
subjects or this
study
of
environmental
effects
an d reaction processes was
prompted
by he
current
interest
n
he
products.
However,
t
devolved
hat this
selection
was
ll-advised.
The reactions of
the
hexachloroethane-based pyrotechnics
are
apparently quite
complex
and
deduction of
reaction
mechanisms
are
difficult.
Furthermore,
he
sensitivity
of
the
normal
mix
o
nput
energy
tests
s
such
that
slight variations
dependent
on
environmental
or
other
parameters
cannot
be readily
detected.
Other
objections relate
o he
quality
of
technical grade
materials and
th e
difficulty
n achieving
satisfactorily homogeneous
blending
of
semi-solid,
lutinous
hexa-
chloroethane.
The
use
of
the
Jet
Airmixer
or
these
studies was
also
unfortunate. Sample
exposure
times
o
environmental
conditions
s
so
brief
and
mixing
energy
so
ow
that
little effect
on
the
mixes s
expected. It s
nteresting
o
speculate what results
may
have been
obtained
had
a
mechanical mixer
been
used with blending
times of
several
minutes rather
han
a ew
seconds.
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Cl
Cl
1
1
Cl
- c - C
-
1
i
Cl
Cl
Since
ree radical
reactions
usually obey
apparent
high
order
kinetics,
ast
re-
action
nvolving he
reactive aluminum
metal and uch
radicals
or
ons
may
be
possible.
The
high
enthalpy of formation of most
aluminum
salts
act o
avor
this ype of
reaction.
Possible reactions
nvolving
free
radical
catalysis
are
shown below:
h
l
Cl
Cl—-Cl -
c
c \
I
Cl Cl
Cl
c
2
ci-+ci
Jc- ci
3
—
4
ci
10
t
Cl
3d* +
l—A1C1
0
+ heat
Etc .
Similar
electrophilic
and nucieophilic
mechanisms would be
possible
f
ionization
schemes
are mportant.
4.
0
FINDINGS AND CONCLUSIONS
4.1
Summary
Findings.
a. mpact
sensitivity
data obtained from HC smoke mix
differ radically rom
pre-
vious
results
and from interpretation
of
the
Class
2
designation
fo r
he bulk
material.
b . ublimation of
hexachlo roe
thane
rom
HC
smoke
mixes
s significant
under
any
of
the
conditions
studied,
ven under
conditions
of
semiconfinement. Complete
loss occurred when openly
stored
fo r 24
hours
at
41°C.
c. ross nhomogeneities were ound for HC smoke
ormulations
prepared
n
he
bench
mode l
Jet
Airmixer.
d . vidence
was
obtained
hat
absorption
of
moisture
occurs
under
the
conditions
studied;
however,
uantitative
evaluation of
moisture
content
was
nconclusive.
e.
o
contributions
o
nput sensitivity or output
energy
were
ound
rom blending
or
storage
n
humid environments
or
from
variances
n
mixing
times.
f.
eaction
mechanisms were
ndeterminant,
nd changes
thereto
with
concentra-
tion
of hexachloroethane were not
proven
with
certainty.
g.
TA
and
Parr
bomb
calorimetry
d id
not
provide
readily
nterpre
table,
seful
results.
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4.2 Conclusions Refer o Paragraph 3.2.4).
a.
he present Class hazard classification or bulk
IC
smoke mix does
no t
correlate
with
he overall results of this
experiment;
n
error
exists
n one or
the other.
b.
here s ittle influence of moist atmosphere
or
moderately high
temperatures
on he
sensitivity
of HC smoke mix; results were consistently nconsistent
with
prior work.
f k
c.
ixing
rates
and imes,
r
blending procedure,
sed
or
he
Jet
Airmixer, may
not produce an adequately
homogeneous
HC
smoke
mix.
d.
ublimation
of
hexachloroethane
rom
HC smoke
mix occurs
at
normal
ambient
temperatures.
Mix sensitivity as a function of lost HC s nconclusive.
e.
Reaction
process/mechanism
determinations were
nconclusive.
5.0
RECOMMENDATIONS
The
ollowing
recommendations
are
made:
•
study should
be
made
o determine suitability of end
tems
prepared rom
material blended
n
pneumatic
mixers.
•
he classification of bulk
HC
smoke
mix
should
be
eexamined.
#N.
The
sensitivity
of
HC smoke mixes o all normal modes of initiation should be
investigated, ncluding dependency
on
hexachloroethane concentration.
Quantities of
HC white smoke mix
should
not
be stored
n
open or
semiconfined
containers or more han
a few
hours.
The
entire
scenario
of HC
smoke
mix
life
cycles
should be
nvestigated
o deter-
mine
he
nfluence of hexachloroethane
sublimation.
Techniques should
be
developed
for
detection of
chloride on n
aw
materials
and
n
th e
mixing
process.
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REFEREN ES
1. yrotechnic
Mix
Formulary
and
End Item
nformation, eapons Development
and
Engineering
Laboratories,
hemical
Process Laboratory, dgewood
Arsenal,
Mary-
land, 970;
drawing
number
B-143-1-1.
2.
E-MTSD-R-035,
yrotechnic
Hazards
Classification and
Evaluation
Program,
hase
I,
ontract
NAS8-23524,
May
1970.
3.
A-FR-4D21, dentification and
Evaluation
of
Hazards
Associated with
Blending
of
HC
White
Smoke Mix by Jet
Airmlx
Process,
dgewood Arsenal,
Maryland, 974.
4.
ngineering Design
Handbook,
Military
Pyrotechnic
Series
Part 1,
heory
and Appli-
cation, AMC
P
706-185,
186, 187, nd -189, evision 1967.
5.
angerous
Properties
of
Industrial
Materials,
.
rving Sax,
econd
Edition, 963 .
6 .
epartment
of
the
Army
Technical Bulletin
700-2, 9
May
1974, hapters
and
5.
7.
ATR,
Application
of
Explosive
Test Technology
o
Determine Pyrotechnic Hazard
Classification, 974, n
preparation.
GENERAL
BIBLIOGRAPHY
1. dgewood Arsenal, lectrostatic
Hazard Evaluation of Pneumatic Dispersive
Mixing
Operation,
inal
Report
EA-FR-1HOX,
973.
2.
S
Army
Munitions Command ,
Military Chemistry and Chemical Agents,
echnical
Manual
TM3-215,
963 .
3.
ational
Bureau
of
Standards, recision
Measurement
and
Calibration-Heat,
BS
Special Publication
300,
ol, ,
970.
4.
dgewood
Arsenal, yrotechnic
Hazards Classification
and
Evaluation
Program,
hase
m,
egments
1-4,
nvestigation
of Sensitivity
Test
Methods
and
Procedures
or
Pyro-
technic
Hazards
Evaluation
and
Classification,
inal
Report
GE-MTSD-R-059,
971.
5.
MC
385-100
Safely Manual,
pril 1970 revised
4
January 1974, lectrostatic Hazard
Evaluation of Pneumatic Dispersive
Mixing
Operation,
A-FR-1HOX ,
0 June 1973.
23
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DISTRIBUTION
LIST
Addressee
o.
f
Copies
Commander
U S Army Armament
Command
ATTN:
Safety
Office
Rock
Island
Arsenal
Rock
Island,
L
61201
Commander
Picatinny
Arsenal
ATTN:
Safety Office
Dover,
J
07801
Commander
Pine Bluff
Arsenal
ATTN:
Safety
Office
Pine Bluff,
R
71601
Commander
Frankford Arsenal
ATTN:
Safety
Office
Bridge
and
Tacony
Streets
Philadelphia, A 19137
Commander
Rocky Mountain
Arsenal
ATTN :
Safety Office
Denver,
O
80240
Director
National
Aeronautics
and
Space
Administration
ATTN :
Safety Office
Washington, C 20546
Director
NASA
National
Space Technology Laboratories
ATTN: Safety Office
Bay
St.
Louis,
MS
39520
Commander
Edgewood Arsenal
ATTN :
SAREA-MT-C
SAREA-MT-TL
SAREA-SA
SAREA-TS-L
SAREA-TS-R
Aberdeen Proving
Ground, MD
21010
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Commander
U S
Army
Armament
Command
ATTN: AMSAR-MT CPT
Lewis)
Rock
Island
Arsenal
Rock
Island,
L 61201
Chairman
Department of
Defense
Explosives
Safety Board
Forrestal
Building,
GB-270
Washington,
C
20314
Commander
U S
Army
Materiel
Command
ATTN:
Safety
Office
AMCSA-BC
COL Aaron)
5001
Eisenhower
Avenue
Alexandria,
A
22333
Office
of
th e Project
Manager
for
Munition
Production Base Modernization
and
Expansion
ATTN: AMCPM-PBM-E
Mr.
ybacki)
U SA
Materiel
Command
Dover, J 07801
Director
U S
Army
Ballistics Research
Laboratories
ATTN: Safety
Office
Aberdeen Proving Ground,
MD
21005
Director
Defense
Research
&
Engineering
Pentagon
Washington,
C
20310
Record Copy
Commander
Aberdeen
Proving
Ground
ATTN:
STEAP-AD-R/RHA
APG-Edgewood Area, ldg E5179
Aberdeen
Proving
Ground,
MD
21010
Administrator
Defense Documentation Center
ATTN:
Accessions
Division
Cameron
Station
Alexandria,
A
22314
Director
of
Procurement
ATTN:
Contracting
Officer's
File
Aberdeen Proving Ground,
MD
21010
25
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30/31
-
8/19/2019 s Cg 01354292
31/31