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NASA
CONTRACTOR
NASA CR-1384
REPORT
OS
CO
19960326 095
AN INVESTIGATION OF
THE BASIC PROPERTIES OF
IRRADIATED POLYETHYLENE
MEMORY MATERIALS
by Presto?z Keusch, Donald Greer, and John Rozembersky
!
Prepared by
RAI RESEARCH CORPORATION
Long Island City. N. Y.
for Langley Research Center
DEPARTMENT OF DEFENSE
PLASTICS TECHNICAL EVALUATION
PfCTiNNY ARSENAL, DOVER, N. J.
SEPTEMBER 19f9
DISCLAIMS! NOTICE
THIS
DOCUMENT
IS
BEST
WHICH
REPRODUCE
DO
LEGIBLY.
OF
NOT
NASA CR-1384
FOREWORD
The work described in this report was performed
during the period 31 May 1967 to 31 July 1968 under
Contract No. NAS1-7335 with the National Aeronautics and
Space Administration.
The authors wish to acknowledge the valuable
guidance of Dr. David E. Bowker, Technical Officer,
during the course of the contract.
We also wish to acknowledge the helpful
discussions with Mr. Vincent P. D'Agostino, Vice PresidentResearch, R A I
Research Corporation.
iii
TABLE OF CONTENTS
Pags
ABSTRACT
1. o
"l.l
2 .0
2.1
2.2
2.2.1
2.2.2
2*. 2.2.1
2.2.2.2
2.2.2.3
2.2.2.4
2.2.2.5
2.2.2.6
2.2.3
2.3
2.3.1
3.0
3.1
3.2
3.2.1
3.2.1.1
3.2.1.2
3.2.2
3.2.3
3.2.4
3.2.5
3.2.6
3.2.6.1
3.2.6.2
3.2.6.3
3.2.6.4
. . .xi
INTRODUCTION
History
1
2
THEORY
5.0
6.0
6.1
6.2
6.3
6.4
6.5
6.6
7.0
REFERENCES
87
8.0
LIST OF SYMBOLS
90
APPENDIX I
93
APPENDIX II
APPENDIX III
74
79
. . ' ]-jg
80
Memory
Processing.
80
*80
Uses
Future Work
'.'.'.'.'.'.'.'.'.'&1
RQ
102
INFRARED SPECTRA
104
vi
LIST OF TABLES
p
age
Table
1
2
3
4
5
6
30
33
43
47
52
vii
70
LIST OF ILLUSTRATIONS
Figure
1
Page
SCHEMATIC DIAGRAM OP MEMORY CONCEPT
FOR DEPLOYMENT
.
18
18
35
37
s+s2 VS. r
/ FOR POLYETHYLENES UNDER
T
STUDY. . . . .T. /. .
.38
40
7
8
9
10
11
16
. .42
42
12
13
14
15
OF
51
57
59
Vlll
Page
MODULUS OF ELASTICITY AT l40C. OF
GULF 5555 FILM VS. DOSE WITH THICKNESS
AS A PARAMETER
60
17
18
76
19
20
94
21
97
22
98
99
100
101
23
24
25
26
27
106
28
29
Ix
Page
30
31
32
33
ABSTRACT
CThis report describes the work done and
conclusions arrived at in an investigation of the basic
properties of irradiated polyethylene memory materials.
The properties affecting crosslinking, the main factor
which determines the memory in polyethylene, were
investigated using different commercial polyethylene
materials.
These conditions
Finding
It was
xii
Research Corporation
INTRODUCTION
The purpose of this contract,
NAS1-7335J
is to
were concerned with the memory or "deployment" characteristics of the material, while most of the molecular properties were concerned with the crosslinking characteristics
of the polyethylene when irradiated with high energy
electrons.
crosslinking characteristics were determined since crosslinking is the factor that gives the polyethylene its
elastomeric properties or "memory" for self-deployment.
The approach undertaken was to initially investigate in house a large number of commercially available
polyethylene films and resins and, based on their molecular
and mechanical properties, and their availability, to
select from this collection a representative number of them
to be used in further studies of the effect of molecular
properties on crosslinking and memory.
This
In addition, the
History
The memory effect induced In polyethylene by
in I96I.
2.0
THEORY
Prior to discussion of the theory on the experi-
This
If the material is
Consequently, the
This is accomplished by a
The whole
The
Irradiate
Anneal
Package
Hot
Cool
(Crystallize)
Cool
(Crystallize)
Heat above Tm
(Melt crystals
restore
Figure 1
Irradiation of
Radiation,
it is
E = 3vk<a>2gT
where
(1)
k = Bolczmann constant
T = absolute temperature (above Tm)
v = number of chains per unit volume
= ^ (, f^c )
Mc
0 =
N =
Mc =
Mn =
Mn
'
density
Avagadro's Number
Molecular Weight between crosslinks
Number Average Molecular Weight of chain
<a>}
<cc>
If, when
will be greater
the high molecular weight molecules which are the ones that
most readily entangle.
Equation (l) may not entirely comply to crosslinked
polyethylene.
None-
theless, equation (l) may be used as a guide to the experimental study of polyethylene memory material.
Of paramount
Furthermore,
It
1 /
PM ^
rr- \1cj, since
c
n
Mc
2.2
2.2.1
(Other reactions,
Extensive discussions
10
strength of a polymer.
Since both crosslinking and degradation occur
simultaneously in most polymers, it is the relative tendencies toward the two reactions which determine the net result
of irradiation.
11
although ionic
Furthermore,
For instance,
Fortuitously,
12
Dose
It has been found that the density of crosslinks
(2)
where MQ
(3)
c = cT
is the molecular weight of a repeat unit in a
polymer chain.
, .
gei
A cross-
13
period of time.
Molecular Weight
With the larger molecules determining when
o
where Mw is the weight average molecular weight.
If equation (2) is substituted into (4) it is
then seen that the dose just causing gelation is
M
Sel
2.2.2.3
%%
14
It has
The
It appears
It
M~
- ^
% r'
15
100
60
40
20
10
8
6
II!
1
1)
\ IV
3 4 567 10 15 20
Crosslinking coefficient 6
16
= D- - \(T)>a(T) + x(T)kc(T)
where
(6)
that:
(1) At low temperature (below ca. 110C.) crosslinking is more efficient in the amorphous region.
(2) Above ca. 125C. crosslinking in the
crystalline region is about twice as efficient as in the
17
>H
EH
1.0 -
<
EH
CO
>H
Pd
o
O
H
EH
fe
25
Figure 4
50
125
75
100
TEMPERATURE (oc.]
CRYSTALLINE
2
k (T)
K (T)
kc(T)
MTLAMORPHOUS
n
25
50
7D
100
TEMPERATURE (C.)
io
150
18
amorphous region.
2.2.2.5
tertiary hydrogen
H
i
c
I
0
ca. 0.2-6.0 (ref. 15)
Polypropylene
50
system.
This
It
As for crystaliinlty
A highly crystalline
20
2.2.3
11
where
2
+
q3(2g+T)
Gn(z) = I m(P,o)e_zPdP
21
(7)
n(P,)
ii^i-
exp[- I (i
e3e
A)2J
(8)
[T(I-T/4)
= g(2g+T)
where
eS
/4 I (Z
e8
/2) -T i(z)
(9)
2 /U
l(Z) = <L2-i_
0/TT
CO
f
J
(lO)
p
expf-d^
f -(Z e-P/2)Jd,
L
0
V =
'
F7FT
n^ '
exp
(332/4)
(T)
Consequently, with
correlated with g.
shown by Charlesby,1
It has been
M0
M0
Mn(o)
= =
q
y/Pn(o)
y
(11)
The term
23
24
(12)
where
or
mean
Li . Lr
Lo " Lo
Na
/3Mjv
(R02 >|Vx>
(13)
25
reduced up to 20 times.
schematically below:
oriented
polymer
heated to
>
T > T
Crosslinked
oriented
polymer
L
heated to
>
T ^ T.m
amorphous
polymer
L
L0 < Lj
isotropic
polymer
L II
26
II < Li
II >
3.0
EXPERIMENTAL PROGRAM
The purpose of the experimental program was
were in mind:
1. Evaluate the properties of polyethylene
material which can optimize the memory force.
2. Obtain a material which has good strength for
handling at ambient conditions.
3. Obtain a material which can have 100$ recovery
and with manageable shrinkage.
The above investigations were to be done using
only commercially obtainable materials.
two problems were encountered,
At the outset
(l) On commercially
27
The high
The
usim
The branching
28
It was then
Additionally,
The
,
,
,
,
low density
low density
low density
high density
**
29
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30
properties (of the four materials chosen for the study) had
on the crosslinking-memory properties, the following were
studied on the materials after crosslinking:
1. Gels - for crosslinking efficiency.
2. Modulus of Elasticity above the Tm at l4oC. to measure the memory force.
3. The Memory - to actually test the memory effect.
4. Shrinkage - to determine the dimensional
stability of the memory material.
The experimental procedures and results of the
above studies will be described in the following sections,
but before this is done a description of the production of
the experimental, crosslinked materials will be given.
The materials to be described were used throughout the
entire program.
3.2.1
3.2.1.1
32
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33
ro
o
o
vo
w
ft
H
rH
rH
H
P-.
g
H
CO
the material.
The
To
minimize the degrading effect of oxygen the sample irradiations were carried out in sealed polyethylene bags which
were purged with nitrogen.
/
/
o
CO
1
1
CO
EH
o
w
1-H
w
>
Oi
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^
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[i<
3
H
<D
OH
H
K
W
P-,
CO
CO
35
J
<=C
En
^-i
In
addition, the solvent was changed at the 24th and 48th hour
to insure efficient extraction.
4> gel
A gel dose
The more
5555
Super C
3328
6003
A temperature of
36
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00
K
w
p
Is
p
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cu
CO
1 *
w
p
K
E-"
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p
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p
w
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rn
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00
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p
w
C3
^s
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(iNSOHad) 130
37
o
m
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CvJ
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tn
in
in
to
IT)
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p.
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-p
n
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fa
H
.=1-
in
co
CM
t-
o
CVJ
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i
38
co
o
CM
polyethylene.
The sample
The
A schematic
c
2 cm.
heated, folded
specimen
Final Sample
39
460
'
Figure 9
400 '
300 -
/
H
~"
GQ
CU
,"
0-"
rT~]
'
200
o/
v7
.-"
tp
oy
Super C
3328
//
NOTE:
^
/
r4Q
^
J
O--
'/
- / mE?
^7
~-t
SSS^
P'" ,to
//
100
/ /
/
/.
"' S4
S'
.'
/
/
.-'s"
100
DOSE
40
200
(MRADS)
300
This is shown in
The oven
Once
restoring moment of the memory force is thickness dependentsince the outer radius of a thick folded sample will be in a
greater state of strain than a thin one.
41
Sample
Vertica
'HP
( )
Figure
MIIIKLE RECOVERY,
TIOTOGRAPH
42
Table 3
Memory vs. Dose with Thickness as a Parameter
for the Materials under Study
Material
Gulf 5555
Dose
(Mrads)
11
12
21
32
54
58
85
PER-CENT REOOVEKY
Thickness (mils)
14
7
1.5
92
100
100
<90
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
14
22
100
100
100
100
100
100
14
22
100
100
100
100
100
100
Thickness (mils)
1.25
7
Super C
73
12
21
32
100
90
54
58
85
100
96
100
100
Thickness (mils)
1
7
Phillips
3328
21
32
54
22
96
91
100
100
100
100
Thickness (mils)
1.5
USI NA 107
11
21
32
54
8"5
96
100
100
100
100
Thickness (mils)
6
12.5
1
Phillips
6003
11
21
32
54
85
95*
100*
97
100
100
98*
95*
98
83*
84*
100*
88*
100
100
100
22
100*
85*
100*
100*
100
USI NA 107
Gulf 5555
DuPont Super C
Phillips 3328
Phillips 6003
The role the USI NA 107 film had in this evaluation
in conjunction with dimensional stability problems will
presently be discussed.
The loss in
When
This,
It is
44
This
Memory
Test
v
v
Measured restoration
angle
^^^___
True restoration
angle, l80
a) Extrusion induced interference with memory phenomenon
Memory
Test
>
180
r\
45
3.2.5
The two
materials chosen were the Gulf 5555 (1.5 mil) and the
U.S.I. NA 107 (1.0 mil).
46
Table 4
Dimensional Stability of Films of Different Orientation
upon Completion of a Memory Cycle
Dose
(Mrads)
11
21
32
54
85
200
GULP 5555
% Change
Transverse
Extrusion
Direction* Direction**
-40
-22
-17
-12
-6
-6
NA 107
% Change
Extrusion
Transverse
Directi on* Direction**
+14
+13
+8
+5
+7
+9
+5
-20
-9
-8
-4
-7
+ 10
+10
+9
+5
Two
The results of
On the other
47
Wrinkling and
It has been
This second
An alternative
3.2.6.1
Gels
As discussed in Section 2.2.2 the main factors
Based on gel
In order to conclusively
As can be seen
from the MWD curves the Gulf 5555 which crosslinks best
does have the narrowest MWD.
X
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cc
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52
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3.2.6.2
Modulus of Elasticity
As has been shown In Section 2.1 of the theory
This
Memory
Despite the fact that the "memory" force of the
Phillips 6003 is higher than the others it cannot be considered to be the material possessing the best memory
properties.
53
Dimensional Stability
It is seen that dimensional stability is directly
In summary, the
54
to follow.
55
4.0
in further detail.
were determined:
Stress-strain curve - for uncrosslinked material
at ambient temperature.
Stress-strain curve - for material crosslinked to
90 Mrads at l4oC.
The modulus of elasticity vs. dose with thickness
as a parameter at l4oC,
The modulus of elasticity vs. temperature with dose
as a parameter above 110C.
4.1.1
e)
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57
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n^k
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4.1.2
The
~~
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E-
W
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59
3
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60
This
MQ\
Modulus-Temperature Study
The modulus of elasticity of 1.5 mil Gulf 5555
Below the T
62
material.
- consequently rendering
The moduli
To
4.2.1
Equilibrium Lengths
As discussed in Section 2.3 of the theory, there
are three lengths to contend with in dealing with crosslinked oriented polymers.
63
Table 6
Modulus of Elasticity vs. Temperature for Gulf 5555
In Extrusion and 'rransverse Dlrec tions
Dose
(Mrad)
E//
(psixl03)
(psixlo3)
-70+2
7o.519.2
73.0+20.2
-30+2
40.3+10.4
41.5+8.9
25t3
31.0+1.0
48.0+11.0
110+3
2.39^0.78
2.540.57
110+3
13
1.47+-0.24
2.11+0.54
110+3
214.5
3.32+0.22
4.23+0.05
130+3
91
.284+.027
0.255t.162
l4o3
13
.0841.006
0.016+.002
l4o3
85
0.230+.009
0.213+.015
l4o3
297
0.441+.003
175+3
91
0.187+.041
(oc)
64
0.l89.128
transverse direction
A
extrusion direction
85-91 Mrad dose level
300 Mrad dose level
13 Mrad dose level
0.1
0.06
-100
Figure 17
-60
-20
20
60
TEMPERATURE (oC.)
100
140
65
180
irradiated.
(LJJ)J
(LJJJ)
sample at
l4oC., with the original cold length being 1 in. to 1.5 in.
Additionally, the new crystalline equilibrium length was
measured at room temperature.
direction.
Mrad
58
85
4.2.2
LjjAlU
1.01^.005
1.02*.02
1. OS1.005
1.03*.005
IIl/LI
Crystallinity
In order to fully characterize the polyethylene
Table 7
Lengths Relative to Unheated State of 1.5 Mil
Gulf 5555 Film in Extrusion Direction
in Hot and Cold States vs. Dose
Dose
(Mrad)
Lengths at l4oC.
Il/ALI
L
T
Lengths at 23C,
L
TLIIl//L
I
11
0.795
0.59
18
0.800
30
0.823
0.78
54
0.857
0.87
85
0.883
0.89
106
0.916
110
0.89
150
0.83
200
0.962
297
0.953
67
0.94
20
An important
What
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68
(16)
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rH cn-=t vo tco oo co co m inco
vo
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70
close tolerances.
4.3
Environmental Tests
A number of environmental tests were performed
as follows:
Modulus hysteresis
Memory hysteresis
Thermal shock
Thermal degradation
Blocking
In general, the results of the tests were
successful with no appreciable loss of mechanical properties
or memory on the first four tests.
71
It was found
Weight
72
A weight was placed over the samples and the system was
heated to l4oC. for 1 hour.
pulled
The degree of
73
5.0
The effect of
l-v 2
2Et
cr
R(l-v )
\I
'
v t
2 R2
(17)
-t, 0
2Et
cr
or
(18)
3z{l-v2)i
t = 3u(l-v )UR
cr J
2E
74
Additionally, based on
follows:
"Experiments with thin spherical shells subjected
to uniform external pressure show that buckling
occurs at pressures much smaller than that given
by equation (17)
"(ref. 23)
"Because of the greater likelihood of geometrical irregularities, and their greater relative
effect, the critical stresses actually developed
by such members usually fall short of the
theoretical values by a wider margin than in the
case of bars... The critical stresses or loads
indicated by any one of the theoretical formulas
should, therefore, be regarded as an upper limit,
approached more or less closely according to the
closeness with which the actual shape of the member
approximate the geometrical form assumed...."
75
0.001
RADIUS (FEET)
76
10
100 ^
Figure 19 THEORETICAL SPHERE SKIN THICKNESS
TO WITHSTAND SOLAR PRESSURE VS
TEMPERATURE WITH RADIUS AS A
PARAMETER
/
/ /
RADIUS (ft.)
4000
0.001
100
-80
-60
-40
-20
0
20 40
TEMPERATURE (C)
77
60
100
120
140
160
0.1176 x 10
-k
78
6.0
is given.
6.1
Crosslinking Properties
With the following factors affecting crosslinking
In addition,
79
6.2
Mechanical Properties
The mechanical properties of the crosslinked
It was
Memory
The memory of a number of initial materials
Processing
It had been found that complete (100$) restoration
80
If the material
They are:
Uses
Based upon the strength of the crosslinked poly-
Of even greater
at l4oC. would need a thickness of only 3.5 mils corresponding to a weight of 4,000 lbs. and a sphere of
6 ft. radius need only weigh
0.36 lbs.
81
Another
Conse-
82
6.6
Future Work
Areas still not fully Investigated that require
should be undertaken to
The
> T
>
m*
84
The
This needs to
85
86
7.0
REFERENCES
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
87
16.
17 =
18.
19.
20.
21.
22.
23.
Ibid. p. 518.
24.
25.
26.
27.
28.
29.
30.
31.
88
32.
33.
34.
35.
36.
37.
38.
39.
89
8.0
LIST OF SYMBOLS
Boltzmann constant.
k (T)
k (T)
a
n
c
n
m(P,o)
n
q
q
Beam intensity.
L0
LR
M.
MtT
w
Avagadro's Number
OD
Io
Optical density = In j
OD
P OX
P (o)
R
_ 2
R0
Absolute temperature, K.
<cc>
ea
'n
\,x(T)
Density, gm./cc.
CT
Stress, psi.
92
A schematic diagram
The molecular
The technique
It must be emphasized
that in using GPC to determine the molecular weight distribution of polymers that the conditions used must be exactly
the same as those used to determine the calibration
34,35
curve.
93
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95
*c_j
19:
M.
^ h.M.
M
(20)
^hi
96
106
T
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Figure 21
Analysis Conditions:
Solvent: 1,2,4-Trichlorobenzene
\\
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28
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32
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(23)
102
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k
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