Document zQVJzOQ2EjeKXzd48w9Dkyg97
[ iname location) t, ^ Morgan, D. S. Moorman, St: Louis Research
DATE
:.
SUBJECT
:
REFERENCE :
. October 8, 1969
WR 69-22, CaC03 in Thiokol Sealants
TO : C. Paton - CPATO .
CC:. M. VI. Farrar - Res 1
J. R. Darby - Res 1
W. F. Waychoff - WWAYC
J. K. Lilly - JLILL
-
C. P. Farley/P. R. Graham - CFAR]
J. A. Cannon - Res 3
A. W. M. Coaker - Res 3
R. H. Mills - Res 3
N. W. Touchette- Res 3
|
j { | |
j ! 1 : . _. :
At your request an extensive evaluation of Monsanto plasticizers in Thiokol sealants filled with calcium carbonate has been completed. Testing was done accord ing to the supplied Thiokol test conditions whenever possible. Volatility measurements were done at 70C. only. Equipment problems prevented a second run at 86C. Evaluations were made with catalysts utilizing Santicizer 160 and Santicizer 902 as dispersants. The' following formulations were run:
General
LP-32 -
Plasticizer Non-coated CaC03
PHR
.
100 15 and 40
40
'
Formulation `'
' 100
(Catalyst System)
..
Lead Dioxide
'
Stearic Acid
Santicizer 160 or . . Santicizer 902
Sulfur
50 5.
45 .
15 0.1
Sample Identifications
Sample Number
1' 2 5 4 5 ,. 6 7 .8
9
10 11 12 13 14 15
Plasticizer
Control S 278 S 26l S 160 S 902 Aroclor 1260 Aroclor 1254 Chlorowax 500 HB-40
s 278 s 261 s 160
S 902 Aroclor 1260 Aroclor 1254*
Parts
.. . --
15 15 15 " 15 15 15 15 15 40 40 40 40 . 40 40
DSW 588423
STLCOPCB4093759
To: C. Paton
-2-
October 8, 1969
Sample Number
Plasticizer
Parts
16 17 18 .
19
20
* .
21
Chlorowax 500
HB 40
.
bis(4-chlorobutyl)
adipate
bis(4-chlorobutyl)
phthalate
bis(4-chlorobutyl)
adipate
bis(4-chlorobutyl)
phthalate
40 40
15 40
15 40
Sample Preparation;
_ All samples were paint milled. Catalyst additions were made
by shearing in polystyrene cups. No sample was molded for
physical testing for at least 48 hours after catalyst addi
tion. All moldings were made at 300F. for 10 minutes. Volatility samples were prepared according to the Thiokol
specification.
-" . -
Compatibility: Thiokol Miscibility Test
All plasticizers tested, except Chlorowax 500, were miscible
at levels up to l/l.
.'
Compatibility: Sheet Test
Heavy exudation was seen with HB-40 at 40 phr. '
Volatility: Thiokol Method, 1 week 70C . (Santicizer 902 Catalyst'
Table One
Sample
Plasticizer
Phr % wt. Hardness(Shore i
lost
after volatility
1 ` Control `
1.40
38
2 . S 278
15 1.90
27
3 S 261.
15 1.73
'26
4 S 160
15 . 1.98
24
5 S 902
15
1.75 .
25
6 Aroclor 1260 15 1.01 21
7
Aroclor 1254 15 1.85
. 31
'
8
Chlorowax 500
15
1.90
28
9 HB-40
15 2.87
21
10 S 278
40 2.10
15
11 S 26l 12 S 160
40 1.92 40 2.05
1? 14
DSW 588424
STLCOPCB4093760
To: C. Paton
., .
October 8, 1969
Table One (contd)
Sample
13 114
15 16 17 18
19 20 21
Plasticizer
Phr
S 902
40
Aroclor 1260
40
Aroclor 1254 .
4o
Chlorowax 500
40
HB-40
40
Bis(4-chlorobutyl)
.adipate
.15
Bis(4-chlorobutyl)
phthalate
15
Bis(4-chlorobutyl)
adipate
40
Bis(4-chlorobutyl)
phthalate
40
$ wt. lost
Hardness(Shore A after volatility
.2.17 2.02 2.04 3.28 3.34
1.64 .
1.68
18 14 21 10 16
15
14 .
2.59 1.99
5 '
5
It is obvious that the Thiokol test is much less severe than the
charcoal volatility run by Monsanto. In this Thiokol test a
1.5 x 4 x l/4 inch block is molded, placed on a sheet of metal,
and oven aged one week. Weight loss is measured but is not
totally plasticizer loss. From the above results no meaningful
differentiation can be made. At a higher temperature a more
useful set of data might be obtained particularly if combined
with fogging. As previously stated, equipment problems have
prevented further work.
.
Physical Testing:
100$ Modulus, Tensile and Elongation were determined on all
samples.. Readings were taken initially and after three and
seven days immersion in water at 70WC. The immersed samples
were simply wiped off and tested. Any absorbed water was not
lost prior to the test.
'
. .
For this work readings were made on samples prepared' from both
Santicizer 160 and Santicizer 902 catalyst pastes. Results are
shown in Table Two. From these results the following points are
to be considered:
--
1. A general trend is noticed in which modulus decreases with
immersion time, tensile increases and elongation also increases.
This result would indicate a fair amount of water is retained
and is aiding in lower modulus. The tensile would ordinarily
be lower. Its increase may be caused by an orientation
. phenomenon.
-.
) f
OS\N 588425
v
STLCOPCB4093761
To: C. Paton
October 8, 1969
2. A slight difference is seen between catalysts.. Santicizer
902 pastes seem to give generally lower tensile and elongation
but higher modulus. A consistant exception occurs when HB-40
.or Santicizer l60 is the rubber plasticizer.
.
3. No system tested showed exceptional water resistance.
Santicizer 278 and Chlorowax 500 appeared to be the least
affected.
.
. '.
Water Sensitivity
Water sensitivity was run on the samples with the following
results:
',
Sample
Plasticizer
Catalyst
1 Control
2 S-27&
`
5 S-261
' 4 S-160
5 S-902
6 Aroclor 1260
7. Aroclor 1254
8 Chlorowax 500
9 HB-40
10 S-278
11 S-261
12 S-160
13 S-902
14 . Aroclor 1260
15 Aroclor 1254
16 Chlorowax 500
17 HB-40
18 Bis 4-chlorobutyl
adipate
19 Bis 4-chlorobutyl
phthalate
20 Bis. 4-chlorobutyl
adipate
21 Bis 4-chlorobutyl
phthalate
S-l60 S-160 S-160 S-l60 S-l60 S-l60 S-l60 S-160 S-160
s-160
S-l60 S-l60 S-160 S-l60 S-l60 S-160 S-l60
.
S-160
S-160
,S-l60
S-l60
Solids Lost
0.4l 0.35 0.32 -0.28 0.38 0.28 0.28 0.36 0.38 0.28 0.34 0.36 0.43 . 0.32 0.38 0.39 0.60
0.40
0.53
0.51
0.29
fo H20 Absorbed
0.86
1.06
1.43 1.14 1.14 1.10 1.04 1.01 1.09 0.99 0.96 1.45 0.90 0.60 0.73 1.17.
. 0.68
1.59
1.56
1.89
1.23
DSW 588426
STLCOPCB4093762
k-
i
To: C. Paton
Sample
Plasticizer
1 2 3 4. 5 6 7 8 9 10 11 12 13 14 15 16 17 18
19
20
21
Control
S-278
S-26l
S-l60
.
S-902
Aroclor 1260
Aroclor 1254
Chlorowax 500
HB-4Q
S-278
S-26l
S-l60
S-902
Aroclor 1260
Aroclor 1254
Chlorowax 500
HB-40
Bis(4-chlorobutyl)
adipate
Bis(4-chlorobutyl)
phthalate
Bis(4-c hiorobu ty1)
adipate
Bis(4-chlorobutyl)
phthalate .
October 8, 1969
Catalyst
# Solids Lost
% h2o . Absorbed
S-902
S-902 . S-902 S-902 ' S-902 S-902 S-902 . S-902 S-902 S-902 S-902 S-902 S-902 S-902 S-902 S-902 S-902
0.80 0.4l 0.48
0.47 0.29 0.29 0.35 0.71 0.57
0.35 0.39 0.39 0.53 0.54
0.59 (0.93) 3.30 ,
S-902 S-902
, "'*
O.52 -
0.40
S-902
0.94
- S-902
0.33
` 1.20 . 1.00
1.20 2.05 0.96 0.78 1.09 1.29 1.22 . . 2.05 2.07 2.74 2.23 1.25 1.51 v (1.45) 0.93
2.72
2.31
6.12
1.82
It is interesting to note that, with few exception, less weight is lost with a plasticizer than without. This observation would he consistant if the plasticizer coats the CaCC>3 in the formulation and thus reduces its water solubility. Little difference is seen with catalyst changes and no plasticizer is seen which is truly outstanding. Santicizer 278 again appears superior at higher levels.
I
1`
- /-
DSW 588427
* STLCOPCB4093763
To: C. Paton
.. ...----- -----
October 8, 1969
Samples
-. '
`
./
/
`
'
/Hardness Shore A
\
i
` ;' After Molding
'
S-902 Catalyst"
S- 160 Catalyst
- js
(S902) After Volatility from Table One
1 . 42 2 26
3 29 4 28
5 51 6 ' 26
7 55 8 51
9 51 10 17 11 10 12 .18 15 21 14 23 15 22 16 14 17 10 18 26
19 19 20 9 21 12
38
27 29 50
31 28
33 28 28 16 12 18
17 24
21
12 '
11 24
20 10 12
38
27 ^26
1/24
^25 t-21
31 28
./
21-^
15
13 14
1184^//
' 21
V^-1160 /'
15 l4i/
5 5
The above hardness data again indicates that very slight
differences exist between S-902 and S-160 catalyst pastes.
It is interesting to note that the hardness after molding ,
is generally higher than the hardness after volatility.
At low plasticizer levels little change is seen with
Santicizer 278, Aroclor 1254, or Chlorowax 500. At higher
levels the preceding are again very similar. This indicates
that the plasticizer is very permanent (S278 and Chlorowax
500) or quite volatile (Aroclor 1254 and S-26l and S-902 at
higher levels). Medium volatility plasticizer results show
that the volatility test was less severe than the molding
cycle.
.
All samples .have shown' good heat and light stability. If we may be of further service please call.
Time: 120 hrs ds
A. . Morgan D. S. Moorman
DSW 588428
STLCOPCB4093764
S-160 Cat.
Sample
1 2 3 4 5 6 *7
8 9 10 11 12 13 14 15 16 17 18 19 20 21
Plasticizer
A
Control
110
S-273
58
S-261
69
s-160
83
S-902
75
Aroclor 1260
87
Aroclor 1254
94
Chlorowax 500
82
HB-40
81
S-278
37
S-261
40
S-l60
53
S-902
38
Aroclor 1260 Aroclor 1254
52 41
Chlorowax 500
22
HB-40
23
Bis(4-chlorobutyl)adipate 71
" " phthalate 35
" " adipate 27
" " phthalate 26
100* C
112 60 66 70 68 78 84
771 72 34 35 41 42 58 43 27 26 64 34 25 25
B
86 60 57 64 69 66 770 51 63 31 33 28 333 45 38 21 23 47 37 19 22
A
181 155 134 153 129 125 121 121
90 79 104 104 96 98 99 79 81 92 88 56 72
Tensile C
B
230 200 164 228 206 148 143 167 142
77 106 114 121 142 134
95 39 78 111 58 74
228 197 170
175 192 161 150 171 114
81 102
85.3 122 139 157
77 86 71 103.7 51.4 69.4
A
353 633 386 333 349 209 176 246 133 309 365 433 579 323 476 819 586 163 539 319 533
Elong. C
506 823 543 630 706 373 316 489 333 459 643 626 729 573 736 941 673 236 773 466 766
B
623 833 653 599 719 513 473 570 233 526 663 593 826 659 836 936 803 279 823 503 749
DSW 588429
STLCOPCB4093765
S-902 Cat
Sample
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 13
19
20
21
Plasticizer
Control S-278 S-261 S-160 S-902 Aroclor 1260 Aroclor 1254 Chlorowax 500 HB-40 S-278 S-261 S-160 S-902 Aroclor 1260 Aroclor 1254 Chlorowax 500 HB-40 Bis(4-chlorobutyl)
adipate Bis(4-chlorobutyl)
phthalate Bis(4-chlorobutyl)
adipate
Bis(4-chlorobutyl) phthalate
100/6 Modulus(PSl)
3 days
7 days
Fresh 70"c.ln HaO 70"c.in HaO
108 82 ' 79 73 97
104 111
85 65 43 22 30 42 50 42 30 18.7
112 69 67 58 75 78 80 70 6l 31 21 22 44 52 45 30 25
.
92 44 57 49 64 112 75 6l 53 29 17 23 35 44 42
23 25
,
18.7
47
42
43 33
28
33 18
15
39 27
23
Tensile (PSI)
37
Fresh days
days
187 138 105 176 117 141 138 138
94 69 59 86 83 95 89 77
55
284 144 120 193 101 133 153 154 114
63 77 97 118
123 136
92 68
265 103 119 180 107 110 164 147 123
72 65 94 125 156 122 83 62
52 106
107 79
109 72
82 60
56
65 59
44
Elongation (Percent)
37
Fresh
days
days
369 256 209 426 139 198 214
315 229 233 559 706
373 386 418 603 559
636 396 336 729 213 292 349 506 376 389 819 819 613 593 680 803 699
659 523 449 806 323 319 456 543 506 446 909 970 766 799 689 849 640
559
493
616
543 566
656
534 793
353
24i
386
383
DSW 588430
STLCOPCB4093766