Outgassing of epoxy resins in vacuum*

received 23 January 1967; accepted 8 May 1967

R D Brown, Senior Research Engineer, Department of Aerospace Propulsion Research,

Southwest Research Institute, San Antonio, Texas

Weight loss of three plastic materials (two glass-fibre-filled 815MPDA Epoxies and an unfilled 828-U
Epoxy) during 100 hours exposure to vacuum (10-h to 10-d torr) at 24°C were measured with a recording
electrobalance. Weight loss decreased with time, indicating that the outgassing products were absorbed
or adsorbed gases. This view is supported by results of experiments which showed that specimens
subjected to a second vacuum exposure following seven to nine days exposure to air exhibited weight
loss histories nearly identical to that of the first vacuum exposure. Also, qualitative mass spectra
indicated that the outgassing products were principally water vapour plus nitrogen, oxygen, and carbon
dioxide. By assuming the outgassing products were principally water vapour, the weight loss rates were
converted to torr litrelsec cm2 units and found to be comparable to those reported in two other
investigations of plastic outgassing in one of which a pressure rise technique was used, and, in the
other a mass spectrometer was used to measure outgassing rates.

Intraduction
This investigation was conducted in order to determine which ELECTROBALANCE I I
of two glass-fibre-filled Epoxy 8 15 MPDA materials was best -CONTROLLER 1
suited as a constructional material for a large pipe which had
to be quickly evacuated to a pressure below 10-Z torr. The
selection of the best material would significantly reduce the
pumpdown time. As it turned out, one of the materials had an SAMPLE T”EiE.jffj$ ARE T”E3’i,
outgassing rate of about one-fifth that of the other. This
difference is attributed to the fact that the material with the
lower outgassing rate had no exposed glass fibres, whereas, the
other material had numerous exposed glass fibres. The surface
area associated with the exposed fibre glass was evidently a
site for adsorption of gases over and above what would be
adsorbed on the plastic material itself.

Test apparatus and procedures

Test apparatus. The apparatus used in the weight loss experi-
ments and the accompanying gas analysis experiments is shown
B2VAL$+== PRESSURE
in Figure 1. Weight loss measurements were made with a Cahn
Model RG recording vacuum electrobalance. With the electro- ANALYZER
balance-recorder combination used in these tests, weight
changes of 0.01 milligram could be easily detected. A General
Electric Model 22 PC 110 partial pressure analyzer with a
S-kilogauss magnet, providing scanning from 12 to 90 atomic
I I
mass units, was used to analyze the outgassing products. +id 93124K
Vacuum was maintained in the electrobalance chamber by
Figure 1. Experimental test apparatus.
an I-litre per second ion pump. With this pump, pressure as
indicated by ion pump current approached 1 x 10-6 torr after
100 hours of pumping. A Scubic feet per minute, molecular was opened only to admit gases for analysis. This valve was an
sieve trapped mechanical pump was used to rough the pump ultrahigh vacuum valve of the metal diaphragm type, Granville-
chamber and tubulation to around 10 microns at which Phillips Type C. The valve between the roughing pump and
pressure the ion pump was started and the mechanical pump the vacuum system was a bellows-sealed right angle valve with
valved off. a viton seat. Except for the glass electrobalance chamber and
Vacuum was maintained at all times in the partial pressure tubes, the entire vacuum system was of stainless steel. Copper
analyzer; the valve between it and the electrobalance chamber gaskets were used to seal all flange joints.
Whis research was supported by the Atomic Energy Commission under Contract AT(26-1)_193.
This paper was presented at the AVS 13th National Vacuum Symposium, San Francisco, 25-28 October 1966.

Vacuum/volume 17/number 9. Pergamon Press Ltd/Printed in Great Britain 505

R D Brown: Outgassing of epoxy resins In vacuum

Test procedures. A typical test procedure was as follows:

(I) Suspend specimen from electrobalance beam.
(2) Tare and calibrate electrobalance.
(3) Start recording weight.
(4) Start rough pumping electrobalance chamber.
(5) Start weight loss test-“zero” time was taken as the point MATERIAL NO.3 /cc/-
at which weight reaches a maximum during the rough pumping
(because of loss of buoyancy, the specimen appears to gain
weight at the start of pumping.)
(6) Weigh specimen intermittently during IOO-hour exposure to
vacuum.
In addition to the above procedures, outgassing products
were analyzed during both early and late stages of vacuum
exposure. o.olL”-I ’ ’ ” #‘I’ I I1111111 ,111,

0.1 0.5 I 5 IO 50 loo

TIME, HOURS
Specimens
Figure 2. Weight loss of materials 1, 2, and 3 during vacuum
The weight loss in vacuum was measured for three materials.
exposure.
The two plastic pipe materials were both composites of fibre
glass and Epoxy 815-MPDA, but their construction details
hours of vacuum exposure. In one of two tests extending
were different. These materials are designated Materials No.
beyond 100 hours, weight loss did not increase in going from
I and 2. In order to try out the apparatus, some trial specimens
100 to I IO hours and in a second test only increased 0.01 mg
were fabricated from unfilled Epon 828 cured with Agent U;
in going from 100 to 121.5 hours. In a test in which a specimen
these are designated as Material No. 3.
was retested, there was no weight loss in going from 50 to 290
Material No. 1 was a fibre glass reinforced Epoxy 815-
hours. This suggests loss of absorbed or adsorbed gases and
MPDA plastic. The distinguishing feature of this material was
not evaporation losses. Also, specimens retested after 7 and 9
the presence of numerous glass fibres projecting from one
days exposure to air had weight losses only slightly less than
surface. The material was received in the form of a 8.25 cm
for the first test (Figure 3), suggesting that during exposure to
ID x 8.90 cm OD pipe from which rectangular specimens were
cut.
Material No. 2 was a fibre glass reinforced plastic that was
received in the form of a section that had been cut from a
large diameter pipe. The pipe was of 3-layer construction; the
outer layers were of reinforced plastic, and the centre layer
consisted of thin strips of wood that had been glued together.
Rectangular specimens were cut from the plastic material on
what would be the inside of the pipe. These specimens had ci SYMBOL MATERIAL
very smooth surfaces and the fibre glass was embedded well ‘? NO.1 (FIRST EXPOSURE)
0.05
within the plastic.
z NO.1 (SECOND EXPOSURE)
Material No. 3 (Epoxy 828-U) specimens, cast and cured at ‘3
room temperature, were tested within a few days after casting.
Approximate weights, areas and volumes of the three types
of specimens are presented in Table I. 0.01 L I ’ ’ ’ ’ ’ ’ ” I I II11111 1 I1llll
0.1 0.5 I 5 IO 50 loo
TIME, HOURS
Table 1. Specimen weight, area and volume
Figure 3. Weight loss of Material No I during first and second
Material No Weight, gm Area, cm* Volume, cm” vacuum exposure (after 9 days exposure to air).
1 0.96 5.0 0.46
2 0.9 1 3.9 0.40 air the specimens reabsorbed almost the same quantity of gases
3 0.95 6.0 0.80 as was lost during the first test. Also, on admitting air after one
test, the specimen regained, in 17 hours, one-fourth of the
Test results weight lost during 100 hours vacuum exposure.
At higher temperatures Materials No. 1 lost weight much
The envelopes of weight loss data from four tests each of
more rapidly than at 24°C. During one hour in which specimen
Materials No. I and 2 are plotted in Fig. 2 along with the
tube temperature increased from 24” to 22o”C, the specimen
average of results from two tests of Material No. 3. Material
lost 0.74 mg.
No. 2 had the smallest weight loss of the two Epoxy 815
MPDA materials; throughout the 100 hour tests its weight loss
was about one-fifth that of Material No. 1. Material No. 3 Partial pressure analyzer results
had slightly less weight loss than did Material No. 1. Additional Examples of spectra obtained from Material No. 1 are shown
tests with Material No. 1 indicate the weight loss characteristics in Figures 4 and 5. In Figure 4 is shown the spectrum obtained
of that material, and the conclusions drawn from these tests after a specimen had been exposed to the vacuum for two hours.
are probably applicable to the other two materials. The background spectrum of the partial pressure analyzer,
Material No. I exhibited very little weight loss after 100 taken before the valve to the electrobalance chamber had been

506
R D Brown: Outgassing of epoxy resins in vacuum

18 ly absorbed or adsorbed gases sucn as water vapour, oxygen,

nitrogen, and carbon dioxide. Evaporation or degradation of
I
ANALYZER BACKGROUND the plastic in Material No. 1 accounts for but a negligible
ANALYZER PRESSURE portion of the outgassing products-this is indicated by the
absence of peaks at higher m/e values (30 to 90).
5 X IO-’ TORR
There was some concern that heavier molecules might be
‘; ATTENUATOR X IO-lo
leaving the specimens and condensing on chamber walls before
reaching the partial pressure analyzer. However, when a
Material No. 1 specimen was heated to 220°C numerous
peaks were obtained at m/e values in the range of 30 to 90, as
shown in Figure 5. This shows that enough heavier molecules
could reach the analyzer to produce sizeable peaks even though
all surfaces between the specimen tube and analyzer were at
room temperature. The numerous peaks at higher m/e values
recorded in the 220°C spectrum undoubtedly resulted from
evaporation of the plastic in the specimen material.
. MATERIAL NO. I Spectra of Material No. 2 were very similar to those of
2 HOURS EXPOSURE Material No. l-no peaks at high m/e values were observed.
18 ANALYZER PRESSURE A typical spectrum of Material No. 2 is shown in Figure 6.
I I X IO+ TORR

d $i.Y-~;~~y;:;4 py::ND

Figure 4. Background spectrum and spectrum of Material No 1

at 2 hours exposure
MATERIAL NO. 2
32 HOURS EXPOSURE
16 17 16 ANALYZER BACKGROUND ANALYZER PRESSURE
ANALYZER PRESSURE 1x10-6 TORR
I 1 7X10-9 TORR
ATTENUATOR IO-‘0
CHAMBER PRESSURE
17 I X IO-4 TORR
J ATTENUATOR IO-9

ATTENUATOR X IO-‘0
Figure 6. Background spetrum and spectrum of Material No 2
cat 32 hours exposure.

One curious feature of all the spectra is the relatively large

Figure 5. Spectrum of Material No 1 at 220°C.
size of the 16 peak in conjunction with a negligible 32 peak. It
can only be surmised that the 16 peak is the sum of a number
of ions such as CHf resulting from methane and 0+ resulting
from water vapour, carbon monoxide, oxygen, and carbon
dioxide. All of these are typical of the background gases found
in an operating partial pressure analyzer.

opened, is shown at the top of Figure 4. From Figure 4, it can Discussion

be seen that at two hours exposure the spectrum of Material
No. 1 contained only six peaks of any consequence: 16, 17, 18,
27, 28, and 44. Though no attempt was made to determine
the exact composition of the outgassing products, it is pre-
sumed that the aforementioned peaks result from water vapour
(HaO+, HO+), nitrogen (N8+, N+, N,++), oxygen (OS+, Of,
Oaf+) and carbon dioxide (C08+, CO+, O+).
The results of the partial pressure analyses indicate that, at
room temperature and in vacuum ranging from lo-$ to 10-6
torr, the outgassing products from Material No. 1 are principal-
The experimental results provide a measure of the outgassing
rate of Epoxies 815 and 828 which should be of interest to
designers of vacuum chambers. In addition, the results show
that at room temperature the gases evolved from these plastics
come principally from gases adsorbed on or within the plastic
material. This supposition is supported by the fact that in two
tests, weight loss rates were almost identical for the first
vacuum exposure and the second vacuum exposure after the
specimens had been exposed to room air for 7 and 9 days. All
these findings are in accord with the results of other investiga-

507
R D Brown: Outgassing of epoxy resins in vacuum
tions in which gas evolution from plastics was studied. In the
other investigations cited here, different experimental tech-
niques were employed, and, consequently, a comparison of
results is of interest.
Markley, Roman, and Vosecekl measured the outgassing
rates of several epoxies and rubbers. Their data were taken
by measuring the rate of pressure rise in a closed volume.
Figure 7 presents both sets of data: Markley, Roman and
I I T -7-r
- BROWN
----- MARKLEY ET AL
I I
._
1
J
.^^
0.1 I .o ICI IUU
TIME, HOURS
Figure 7. Outgassing rates of epoxy resins.
Vosecek’s’ outgassing data for Epoxy 828 cured with three
different agents and for the present data two glass-fibre-filled
Epoxy 815MPDA materials and Epoxy 828-U. There seems
to be reasonable agreement between the two sets of data
considering the fact that two different epoxies and several
different curing agents are involved. The only apparent
difference in the two sets of data is in the slope of the out-
gassing rate curves. For Material No. 1 and for Epoxy 828-U,
the outgassing rate decreased more rapidly than for the 828
Epoxies used by Markley, et all. In the case of Material No. 1,
the decrease in outgassing rate can be attributed to the
additional surface area provided by the glass fibres. During
exposure to room air, these fibres would absorb gases in
addition to those adsorbed or absorbed by the plastic material
itself. This additional gaseous matter would be rapidly lost
during the early stages of vacuum exposure; with continued
vacuum exposure, the weight loss rate would approach that of
the base material.
Grossart* has reported another disadvantage of exposed
glass fibres on plastic laminates. He reports that about three
per cent of the fibres in glass cloth were hollow and provided
leak paths through the laminate. The presence of hollow glass
fibres in the materials tested in this work was not suspected at
the time the work was done. Their presence in a laminate
material could serve to increase outgassing rate by providing
an easy escape path for gases emanating within the material.
This effect would be most pronounced in the case of Material
No. 1 which had numerous exposed glass fibres.
In the case of the 828-U Epoxy, the initial rapid weight loss
may be attributable to the fact that this material was cured at
10-4 I--mrTym
- BROWN
-- THIEME
j_
POLYSTY ROL
lo-8 *
0.1 1.0 IO 100
TIME, HOURS
Figure 8. Comparison of our measurements with those of Thieme.
room temperature, and weight loss experiments were started a
few days after the plastic had been formulated. The plastic
pipe materials may have been cured at higher temperatures
and, in any event, were much older.
Comparable outgassing rates have been reported by Thiemez
for four plastic materials: Pertinax, Plexiglas, Polystyrol, and
Teflon, see Figure 8. Thiemez used a mass spectrometer both
to indicate total pressure and to quantitatively identify the
gaseous species. He found that the principal gases given off
by the various materials were as follows: Pertinax, HzO;
Plexiglas, H,O and CO; Polystyrol, H,O, N,, CO, Op, and
CO,; and Teflon, NI, CO, CO,, and 0,.
Outgassing rates comparable to those reported here have
been reported for two other epoxies by Daytot9, see Table 2.
Conclusions
The fact that outgassing rates obtained with the recording
microbalance closely approximate those obtained by pressure
rise and mass spectrometer techniques indicates that the
microbalance techniques is suitable for outgassing rate
measurements, In fact, the simplicity of the microbalance
R D Brown: Outgassing of epoxy resins in vacuum

Table 2. Outgassing rates of epoxy resins as reported by Dayton‘ by the fact that in each of two tests with Material No. 1, the
weight loss was nearly the same for the initial vacuum exposure
Outgassing rate,
torr litre/sec cmp and for subsequent vacuum exposure made after the specimen
had been exposed to room air for seven or nine days. Also, the
Vacuum Vacuum decrease in weight loss with time indicates that the source is
exposure exposure
Plastic 1 hr 4 hr adsorbed or absorbed gases. With evaporation, the weight loss
Epoxy resin 200 at any fixed temperature would not change with time.
(24 hr 95 uer cent humidity) 1.1 x lo-5 -
Finally, the experimental results strongly indicate the
Epoxy resin 200 importance of maintaining surface area at a minimum in any
(outgassed+ hr dry nitrogen) 2x10-s -
vacuum system. This is especially important if the system is to
Eppon, Shell Oil Co. 4x10-s 8.5 x lo-’
be repeatedly subject to readily adsorbable gases (such as are
present in ordinary air) between pumpdowns.
technique makes it especially attractive for measuring out-
gassing or evaporation rates.
On the basis of the outgassing measurements, it is concluded References
that Material No. 2 (free from exposed glass fibres) is more ‘F Markley, R Roman and R Vosecek, Outgassing Data for Several
suitable for vacuum applications than Material No. 1 (with Epoxy Resins and Rubbers for Zero Gradient Synchrotron, Tram 8 A VS
exposed glass fibres). Nat Vat Symp and Second International Congress, 1961, pp 78-85.
* G Thieme, Vacuum, 13 (4), April 1963, 137-143.
At room temperature, partial pressure analyzer results show a G S Grossart, The Vacuum System of Nimrod, Third International
that the outgassing products from both materials were princip- Vacuum Congress, 1965, Vol I, Pergamon Press (Oxford), 1967, pp 87-110.
ally absorbed or adsorbed gases such as water vapour, nitrogen, ’ B B Dayton, Relations between Size of Vacuum Chamber, Outgassing
Rate, and Required Pumping Speed, Trans 6 A VS Nat Vat Symp, 1959,
oxygen, and carbon dioxide. This conclusion is also supported Pergamon Press (Oxford), 1960, pp 101-119.

509