Volume Change of Hycar OR=15 Compounds on Immersion A. E. Juve B. S. * * and
GarvoyfJr.
The 8. F. Goodrich Company, #ran,
Effect of Softeners
Ohio
#iura 4 through 7 illustrate the effect of Merent tvpes of softeners on volume change. With dibutyl phthalate, which is soluble and relatively volatile, the volume change and heat logs P--- at high temperature are nearly the 881118. At room temr re some of the softener is extracted. Tricresyl phhs is less volatile and shows the same extract. Here
sr t is show0 that the change in volui pounds of Hycar OR-I5 dwends o T perature of immersion, the softener in compound, and the type of test s ecimen. The shrinkage, and to a less extent, the welling of a commercial article cannot be accurately phtricted from standard laboratory tests because of this dependence on immersion conditions.
I
..._
.-
#
E volume change of products made from synthetic rubbers when immemd in oil is the resultant of a complex set of fsctom. The object of thia study waa to m u r e and illustrate the effect of the temperature of immersion,the tm of softener in the comwund. and the size and shaoe of
1
&testspecimen.
A series of comwunds of Hvcar O R 1 5 was used. The reciw are given id Table I. &om each compound Btsndsrd A. C. S. tensile sheets were cured 40 minutea at 310' F.and thick sheeta (3 X 3 X 0.376 inch) were cured 45 minutea at 310' F. Immersion test specimens were die cut from these sheete aa foUows: 1 X 0.125 X 0.080 inch, 1 X 2 X 0.080 inch, and 0.5 X 0.5 X 0.376 inch. Immersion tea& were run 1,2,7, 14,and 28 days at room temperature, at loOO and at 149' C. All compounds were tested in Univis 40. Change in volume (1) was measured on each size specimen,and d w m eter hardness waa measured on the 0.5 X 0.5 X 0.325 inch specimen. In addition, heat lass in air at the 881118 tempxatures and Soxhlet extraction with hexane in 48 houm were measured on each compound. The complete data are given in Tables 11, III, and IV.
FIGURE
.
I 2
1 t
?
.I
28
MrS IUYLRIDN I N UNIVlS 4 0
u2
MIS IMMERSION IN UNIVIS 60
Wed of Temperature of Immersion The effect of temperature of immersion is illustrated by Figures 1, 2, and 3. In Figure 1 the change in volume of compounds A and C is shown,wing standard 1 X 2 X 0.080 inch specimens at Merent temperatures. Figure 2 gim the eane relation for the 0.5 X 0.5 X 0.375 inch specimens. In figure 3 the resulte obtained with the thick specimens of compounds E and H are shown. It is apparent that at higher temperatures the change in volume is not only faster but is usually greater. With thicker specimens these Merenw me more pronounced. The amount of swelling decreases after reaching a maximum, particularly at 149' C. This is due to stflening of the compound by heat.
Figures 1 to 3.
Effect of Temperature of Immersion on Volume Chnnge
1316
Novantmr, 1942
***
INDUSTRIAL A N D ENGINEERING CHEMISTRY
******
1317
by a comparison of compound A (Figure 2) with compound E (Figure 3). The heat loss of the compounds with d 8 e m t softenera at 100' C. and at 149' C. is shown in Figure 8. The change in durometer hardnem of three of the compounds when immersed is shown in Figure 9. With the volatile softener the hardening is faater.
Effect of Sire and Shape of Test Specimens
The influence of the ratio of a m to volume is shown in Figure 10. The resdta are for the thick specimen and the standard specimen. The results with the third specimen are too close to these with the standard specimen to justify the extra c u m . These c u m show considerable diEerence for the two DLlf
Figures
I Y Y L R Y O l IN "WYlL
40
4 to 7. Effect of Softeners on Volume Change
h M * 1. Reelpa A
1w
1.6 1.6 5
B
C
D
E
F
100 1w 100 100 100 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 6 6 6 6 6 a6 a6 26 2s a6 20 a0
as ... ...... . . . ..ao.. .. ...... ... ... ... ... ......... . . . . . . . . . . . . ao ...
.. .. .. .. .. .. .. .. .. .. .. .. ...... . .ao. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. HIOV O b 1 6
B* Bensothiw1di.ulsds %O
odds
8oft brown fMuos
cirnoli.htgrworoll
Q
H
I
J
K
100 1.6 1.6 6 a6
100 1.6 1.5 6 a6
100 1.6 1.6 6
100 1.6 1.6 6 a6
100 1.6 1.6 6 a6
. . . . . . . as. . . . . . . . ...... ,. . . . . . . . .20. . ..._ . . . .10. . . 6. . ._.. .
... . . . . .ao. .10. . . 16. . . .16.
the heat loss is much less than the change in volume. Coal tar is partly volatile and partly atxaotable. In thin c m the volume change curve are somewhat lower than the heat loss curves. Circa light-prow oil is volatile hut not very soluble in hexane. In an immersion fluid of similar nature, any loss of Circo oil from the compound is replaced, at Least in part, by the other oil. FsOtice is nonvolatile and only slightly soluble. Apparently it prcmotes the swelling of the compound, aa shown
Figure 8. Effect of Softeners on Heet Loss
1318
* * * ** *
INDUSTRIAL n"D
ENGINEERING CHEMISTRY
***
Vol. 34 No. 11
Tablr II. lmmnrion and Heat Lon W Time.
2 7 14 28 1 2
7 14 28
P 149'AV C. AV AT' 1.12 -2.16
3.31 0.82
a m
0
0.17 -0.17
1.24
-
-0.37 -2.27 -0.78 -4.18 -7.68
2 7 I4 28
-2.28 -2.23 -3:a7 -7.9
1 28
-2.n -0.85 -1.28 -1.08 -3.88
1
1.08
7
14
a
7
-10.8
--13.85 e:47
--11.8 9.88
-1a.a
-13.05 -13 -22.1 (7)
(n
-13.8 -14.05.
--14.25 8.07
-- 7.4 1.83 -- 7.71 - 7
--- 3.88 5.84 8.0 8.86 - 5.97
- 4.09 -14.1
--10.8 9.72
-13.3 -13.36
-1a.a
-14.7 -12.3 -17.2
1.11 -0.38 0.38 -1.08 0.34
3.35 --- s7.8 .~a -- 8.98 9.73
7.07 --- 7.07 8.84 7.9 -- 8.78
1
2
7
14 28
1
a
7
14 28
a.02 0.81 0.81
.... ....
.... .... .... .... .... .... ..r, ....
7 14 28
5.98 11.0 11.66 9.9 9.1
2.03 0
.... .... .... .... ....
..
..... .
..... ..... ..... .....
f0.31 f0.31 +o.i8 +O.E
-0.29 -0.51 -0.8 -1.07
f0.17 f0.17
-1.88 -2.21 -2.75 0
-0.28 -0.8 -0.77 -0.79 1.5 0.22 0.05 0.25 0.71 -0.15 -0.16
-
.....
..... .....
+0.8a
+o.80 +o.i6 fO.11 +0.26
-0.32 -0.48 -0.68 -0.1 -0.13 -0.21 -0.34 -0.43
. .. .. .
..... .....
-9.88
-10.6 -12.0 -12.7 -13.1
+o.aa
-1.1 -1.8 -2.1 -a.38
-o.ea
..... ..... ..... . ..... .
,,
7.8 --1a.e 8.9
AV
a/,
149' C.
3.15 2.87 0.94 0.77 0.87
HL
-- 1.28 1.23 -- 00.91 .U
-
0.6'
-13.3
-1a.7 -12.1
-11.06 -11.4 -12.9 -18.1 -12.75
-o.w
-10.4
- a m
-0.07 -0.09 -0.15 -0.28
-0.25
-0.03 -0.1 -0.29
-
Compound D -10.2 -11.8 -18.1 -13.7 -14.1 Cornmound E , 4.57
-13.6
-13.4 -13.1 -13.1
-
0.9
- 0.88 0.69 5.14 --- 4.09 2.81 -
-10.9
-12.4
-1a.s
-1a.a
-11.7
-la
-2.69 -6.21 -5.w 5.1
-
-- 7.96 9.17
-1a.s -13.7 -13.8
-11.76 -11.56 -11.8
-
--5.07 4.7
1.37 -2.47 -3.m -3.09 -2.88
6.25 -6.71 -7.42 -7.72 -7.49
-5.81 --6.87 -6.64
-0.84 0.84 -a.35 -3.08 4.10
-
-10.4
-6.84
-12.8
8.84 -12.a5 -12.15 -1a.06
2.01 a --- m4.95 -- 4.88 5.06
5.8 --- 8.8 8.37 -- 8.84 8.84
Compand H 9.69 f 0.12 9.88 0.12 9.21 0.2 f0.17 9.1 0.m f0.25 8.07 2.69
10.1 10.5 9.as
+o.oa
-0.12 -0.11
-6.09
-6.w -7.55 -8.15
Comnound
~
I
HL
Compound B -10.8 -10.8 +o.w -12.5 +om -18.9 fO.17 -13.6
-0.82
..... ~~. ..... .... . .. .. .~... . . ..... ..... ..... ..... .... r ' : t . 2 L < L .: ..... -~ ..... ........ ... ,. :;:, .....
, T ~ .
In. Sample 1W. c.
-- 0.10 0.27 -- o.aa 0.14 - 0.74
-0.88
-0.98
11.95 12.7 11.95 11.5 11.1
..... ..... ..... .....
AV
Compound A + O X 3.34 +0.35 3.84 fO.18 1.61 +om 0.87 fo.25 0.11 +0.28 f0.28
-1.8 -1.99
-12.8
0.73 -1.12 0.46 -7.3 -3.26
HL
-1.01 -1.35 -2.83 -3.09 -3.9
-0.8
1
14 28
0.02
-11.05 -18.46
-1.08 0
7
-0.28
4.3
14 28
a
0 -0.18 -0.a3
-11.9
-13.8 -13.9
R.T.
-o.ea
-1a.o
4 0 . 7 (1) -14.86 -21.5 (7)
8.8
AV
x
R.T. AV
a/*
x
AV
1.M
88mPlS 149' C.
AV
1.84 2.51
1.87 1.87 0.81 1.81 0.76 0.75 0.61 -0.88 -0.38
I/. In.
100'0.
2.31 8.48 2.89 1.89 1.82
a.78 a.88 3.25
-- 8.39 -- 8.75 8.W - 7.28 8.77 -10.17 -10.16 -10.96
-11.1 i10.0
-4.8
-8.09 -8.81
Compound C
-12.2
-1a.e
-0.37 0
4.8 4.ia 1.84 1.84 7.78 (7)
6.a3 0.42 (7) 5.37 5.8 118.9
--
0
2
-
0
x a x 0.080
1
*/a X 1 X 0.080 In. Sample
$!::I
+o.ia
f0.11 f0.23
-10.4 -12.0 -12.4 -13
---
Compound I c0.07 3.78 4.56 +0.09 5.27 C0.13 4.71 +0.11 +0.20 4.28
---
Compound 3 2.57 3.0 c0.04 3.2 +O.l2 2.6 +0.09
f0.04 +0.08 +O.M f0.04 +O.M
--- 2.15
Compound K. 1.7 1.76 1.52
-- 0.82 -- 0.34
type of, specimen. Where the compounds swell, the change in volume is sloyer and the curves seem to approach
-
0.3
-- 4.66 6.88 7.5a --11.5 8.88
1.16 1.41 1.45 0.47 1.7
-1.81 -3.13 -8.73 -2.96
1.02 1.27 0.87
-3.52 3.88 -8.4a
0.87 1.0 0.78
-0.43
-a m
-
-8.69
--9.43 9.49 -- 8.m 7.74 -11 -11.0 -11.7
-
1.37 -2.44 -3.5 -4.08 -4.08
--
0.48
.8 -- 7 8.18
--
6.7 -- 86.15 .0 -- 8.18 6.95
1.35 1.83 1.48 0.7 1.48
1.98 -- 4.41 1.51 -- 4.9 6.33
-- 4.28 3.78 -- 6.89 8.84 - 5.81
1.48 1.84 1.87 1.19 2.28
2.48 3.2 4.86 4.77 8.94
8.76
9.01
0.71 --- 0.74 0.84 0.74 -- 0.78
-- a.18 4.24 3.99 5.32 --- 4.53
-- 55.37 .3 -- 4.83 5.0 - 4.57
-- 8.83 9.81 - 9.88 9.76 - 9.77
2.8 --- 3.95 5.6 -- 5.17 8.26
3.63 --- 3.88 3.25 -- 2.83 2.98
9.82 -11.1 -10.85 -10.85 -10.85
-- 2.86 -- 3.63 5.75 8.13 - 3.35
-- 1.77 1.77 -- 0.71 1.29 - 0.77
++ ++
fO.29 f0.30 +0.19
+0.04 +0.09
0.88
-6.05
-7.18 -8.11 7.46
F
-9.8
ComDound G 6.a 5.95 +om f0.M 8.0 +0.08 8.82 9.6 -0.07
+o.m
1.14 1.14 1.2 0.1
-10.8
-12.1 -12.6
9.01
-0.22
8.22 8.41 7.73 8.8
-
- 9.41 -10.6
-10.4 -10.35 -10.~5
Relation of Frdon Affecting Volume Change
It has been mentioned that heat hadening causea a drop in the same limiting value. When the compounds shrink, the change in volume is slower. Furthermore, the shrink^@ is the amount of swelling after the maximum has been reached, not so great for the thicker specimen aa for the thinner one, . that some softeners caused increased swelling, and that other softenerscause shrinkape and further hardening due to lo88 of probably because of the low permeability of the Hycar OR softener by evaporation and extraction. In Figure 11 the after the plasticizer is extracted. solid linea indicate actual changes in volume and the broken This indicates that the shrinkage of an article having a small ratio of area to volume will not be so much aa one with a linea indicate the theoretical change if various factors were eliminatad. The space between the lines indicatesthe magnilarge ratio. This is of considerable practical intereat Since tude of the Werent d e c k . most laboratory testa are run on thin specimens.
***
Nmmber, 1942
******
lNDUSTRIAL AND ENGINEERING CHEMISTRY
1319
I
W+
c o u ~ l l oA , I
.,
gvrTl WYRX~O
'- 94%
x
B
6
7
Mll
rnR us=UT. YP.
H
S -
I 2
A
28
Y I Y Y f I S l D N lY W l V 6 40
Figure 9. Effect of Softeners on Durometer Hardness
Table 111. The, Days
Room Temp.
Durometer Hardnus e h r Imm.rrlon Room 1W'C. 149°C. Temp. lWoC. 149O C.
-Compound
ea 68
a
7 14 28 0rii.l
1 2 7 14 28
70 69
70
69
A m
en en
63 62
2 7 14 28
";i""" 2 7 14 28
A-
..
e4
88 66
88
79 87
68 67
71 78
67 67
- ..
69
88
76
..
69 72
69
67 66 62 62 66
ea e4 ea
..
69
70 72 72 72
-64 .. 67 70
7 2 '
71
..
38 67 68
( i -
66
4 o m p o u n d R?--.
72 73
..
e4
.74 76 77 61 77 83 - - - C o m p o u n d E82
ea
011
..
78 73 73 77 78 p o u n d
..
en
67 89
.
88
..
26
66
70 68 83 A m p o u n d F -
7a 77
82 84 87
S9
69
61 69
Bo 69
..
64 67 89 70 73
..
73 78 78 84
66 72 77 83 86
Effect
..
kp/&Ratio
on Volume
I
69
73
7a
78
84
ii
76
78
en
83
A B C D E F Q H I
1i:1 13.1 13.1 13.1 13.1 13.1 13.1
J
::fi1 10.1
8.6
K
1.49 18.20 16.96 14.m 8.41 14.76 10.37 3.19 4.91 4.2i
2.66
Litentun Cited (1)
Figure I O .
A. S. T. M.St.nda& on Rubber Pmducb D371-1oT (1941).
c1
-
&.a
-TILE
=Tc!sE
Figurell. Effectofseveral FdctorsonVolumeChanges~ Due to Irnmenioh in Univis 40 at 100"
c.
