Materials Science and Engineering B 132 (2006) 7073

The study on compatibility of polymer matrix resins with liquid oxygen

Ge Wang
a,
, Xiaodong Li
a
, Rui Yan
b
, Suli Xing
a
a
College of Aerospace and Materials Engineering, National University of Defense Technology, Changsha, Hunan 410073, PR China
b
Department of Remanufacturing Engineering, Armored Force Engineering Institute, Beijing 100072, PR China
Abstract
Liquid oxygen (LOX) polymer composite tank is very important in the development of next generation of launch vehicles. To study LOX
compatible polymeric matrix resins, three kinds of epoxy resins were studied. LOX impact test was used to evaluate polymers compatibility
with LOX. Thermogravimetric analysis was used to analyze polymers oxidation. It seemed that polymers with better anti-oxidation properties,
characterized by lower oxidation weight gain, lower weight loss and lower ash point, behaved better LOXcompatibility. Fourier transforminfrared
attenuated total reection spectroscopy conrmed the chemical reactions during the LOXimpact process on the surface of polymers were similar to
the oxidation reaction in gaseous oxygen (GOX) at high temperatures, which indicated the chemical mechanism of LOX compatibility of polymers
was just oxidation reaction. In this way, two new epoxy resins with desirable LOX compatibility were acquired by modication.
2006 Elsevier B.V. All rights reserved.
Keywords: Liquid oxygen; Compatibility; Oxidation; Polymers; Modication
1. Introduction
Future launch vehicles, such as reusable launch vehicles and
expendable launch vehicles, need to minimize the gross lift-off
weight for lower costs to orbit and increase payload capabili-
ties. One of the most crucial issues being considered is durable,
lightweight, cryogenic polymer composite propellant tanks. Liq-
uid oxygen (LOX) has been one of the most important propel-
lants nowadays, the preparation of LOXpolymer composite tank
is critical to the success of future launch vehicle programs.
Typically, most polymers and their composites are easily
ignited in the presence of oxygen, and are considered not suitable
in the oxygen application. The only few polymers known com-
patible with LOX are some uorocarbon such as polytetrauo-
roethylene, polychilrotriyoroethylene, and uoroethylene, etc.
In LOX systems they are usually used as seals, gaskets, lubri-
cants, etc. [4]. But they are not t for LOX composite tank.
Therefore, the development of LOX compatible polymer matrix
resins have to deal with the compatibility of polymer matrix with
LOX rst [13].
Epoxy resins, with many advantages, have been widely used
in many cryogenic elds. Cyanate ester, another high perfor-
mance matrix resin, can be self-polymerized to form a unique
structure-triazine ring, which was reported to be compatible with

Corresponding author. Tel.: +86 731 4574129; fax: +86 731 4573165.
E-mail address: wangge72@21cn.com (G. Wang).
LOX [5]. For both cryogenic properties and LOX compatibil-
itys sake, epoxy resin and cyanate ester were co-cured in the
study. The co-cured compounds LOX compatibility and their
anti-oxidation properties were studied, and some efforts were
made to modify resins for better compatibility with LOX.
2. Experimental
2.1. Materials
Three kinds of epoxy (acyclic, bisphenol F, and bisphenol
A) were co-cured with cyanate ester, and the resulted co-cured
compounds were named as AcC, BFC, and BAC, respectively.
For modication, bisphenol A epoxy and cyanate ester were
co-curedtogether witha kindof antioxidant or a kindof activator,
and the co-cured compounds were named as BAC-1 and BAC-2,
respectively.
For oxygenation treatment, BAC and its modied com-
pounds, BAC-1 and BAC-2, were exposed to oxygen gas (GOX)
at 150

C for 4 h with a ow rate of 160 ml/min, and the oxy-

genated specimen were named as BAC (O), BAC-1 (O) and
BAC-2 (O).
2.2. Anti-oxidation properties analysis
The anti-oxidation properties of the polymers were character-
ized by thermogravimetric analysis (TGA, DF-30) in an oxygen
0921-5107/$ see front matter 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.mseb.2006.02.028
G. Wang et al. / Materials Science and Engineering B 132 (2006) 7073 71
Fig. 1. ABMA LOX impact sensitivity tester.
atmosphere with the ow rate of about 80 ml/min. In the weight
loss analysis, each sample was exposed directly to oxygen until a
certain weight loss 10%was obtained. Alternately, in the weight
gain analysis, each sample was heated rstly up to 150

C from
room temperature in nitrogen with a heating rate of 3

C/min,
then the atmosphere was switched to oxygen, where the temper-
ature was hold for 4 h. It should be noted that all the samples
used here were grained to powder before testing.
2.3. LOX mechanical impact testing
The LOX mechanical impact test was performed according
to ASTM D2512-95. The overall apparatus and the striker pin
assembly are shown in Figs. 1 and 2, respectively.
In the test procedure, a plummet falls freely froma set height,
transferring a certain amount of energy to a striker pin resting
directly on the test specimen immersed in LOX. The speci-
mens are of 20 mmdiameter and 1.5 mmthickness. Twenty such
impacts have to be observed on 20 samples.
During the impact process, an audible report, a visible ash,
or burning or charring of the test specimen indicates a reaction.
The reaction sensitivities are calculated based on reaction inten-
sities. The prescript are as follows: one explode or combustion
Fig. 2. ABMA striker pin assembly detail.
(E&C) prorates 1, one explode prorates 0.9, one light prorates
0.7, one spark prorates 0.6, one char prorates 0.4.
2.4. Fourier transform infrared attenuated total reection
spectroscopy (ATR-FTIR)
ATR-FTIR spectra were recorded with a Bruker EQUINOX
55 spectrometer in the following conditions: spectral width
4000 400 cm
1
, resolution better than 0.5 cm
1
.
3. Results and discussions
3.1. LOX compatibility and anti-oxidation properties
Materials not compatible with oxygen will ignite or combust
when in contact with oxygen if subjected to some stimulin. So
the ASTM G4 committee denes oxygen compatibility as the
ability of a substance to coexist with both oxygen and potential
source(s) of ignition within the acceptable risk parameter of the
user at an expected pressure and temperature.
Among all the potential source(s) of ignition, impact source
is easy to handle and ration, so LOX mechanical impact test has
Table 1
The co-cured compounds impact sensitivity
a
in LOX
Co-cured
compounds
Reaction
frequency
b
Reaction intensity frequency Impact
sensitivity (%)
E&C Explode Light Spark Char
AcC 6/20 0 0 6 0 0 21
BFC 2/20 0 0 0 2 0 6
BAC 1/20 0 0 0 1 0 3
a
Tested at the height of 0.75 m.
b
Frequencies measured by number of reactions/number of trials.
72 G. Wang et al. / Materials Science and Engineering B 132 (2006) 7073
Fig. 3. TGA curves of co-cured compounds in oxygen at 3

C/min.
been the most widely used technique to evaluate the compatibil-
ity of materials with LOX for more than half a century. Table 1
gives the impact results of the three co-cured compounds at
the height of 0.75 m. BAC showed superior oxygen-compatible
properties to the others, and AcC showed the poorest.
According to the theory of polymers pyrolysis [6], poly-
mers in GOX absorb oxygen rstly, behaving mass gain. As the
temperature rises, they will, slowly at rst and quickly then,
oxidized and decomposed, showing mass loss. The mass gain
and mass loss characterize polymers anti-oxidation properties.
If the polymer behaves little oxygen absorption and its oxidized
decomposition temperature is high, its anti-oxidation properties
are better.
As seen in Figs. 3 and 4, among the three co-cured com-
pounds, AcC had the lowest decomposition temperature and
highest, BFC had medium decomposition temperature and oxy-
gen absorption, BAC had the highest decomposition tempera-
tures and lowest oxygen absorption. Its clear BAC had the best
anti-oxidation property. The sequences of anti-oxidation prop-
erties were just the same as their LOX compatibility.
ATR-IRspectra showninFig. 5provide chemical information
on surface of the samples after LOXimpact and GOXoxidation.
The assigning of the bands was shown in Table 2.
Compared with the original BAC (curve a), the spectra of
the sample after impact in LOX (curve b) and after oxidation in
GOX (curve c) had the similar changes: the band at 1670 cm
1
(C N) disappeared and the triazine ring band at 1365 cm
1
Fig. 4. The weight gain curves of co-cured compounds in oxygen at 150

C.
Table 2
IR Characteristic frequencies of chemical structures
Attribution (cm
1
)
1750 (C O)
1700 (C O)
1670 (C N)
1600 ()
1365 (N C O)
1245
1032
830
(N C O) weakened, which indicates the impact in LOX and
oxidation in GOX have the similar chemical mechanism. For
better LOXcompatibility, those chemical structures assigned by
the two bands should be avoided. After impacted in LOX, curve
d had little difference with the spectrum of BAC (O), which
indicates the inherent relationship between impact in LOX and
oxidation in GOX again.
3.2. Modication for better LOX compatibility
The correlation between the LOX compatibility and anti-
oxidation properties of polymers implied that polymers could
be modied for better LOX compatibility by improving their
anti-oxidationproperties. Since BACexhibitedsuperior oxygen-
compatibility among the studied co-curing compounds, it was
selected as the basic resin system for modication.
Two approaches had been tried. One way was adding some
antioxidant into the resin system. The other was introducing
some kind of activator into the resin system to alter the curing
process for preferable chemical structures according to ATR-IR
results. After modication, BAC-1andBAC-2showedimproved
anti-oxidation properties (shown in Fig. 3) as they had higher
decomposition temperatures than original BAC and there were
no measurable mass gains for both of them at 150

C in GOX.
Besides, BAC-1 had a higher decomposition temperature than
G. Wang et al. / Materials Science and Engineering B 132 (2006) 7073 73
Table 3
The modied co-cured compounds impact sensitivity
a
in LOX
Co-cured
compounds
Reaction
frequency
b
Reaction intensity frequency Impact
sensitivity (%)
E&C Explode Light Spark Char
BAC-1 1/20 0 0 0 0 1 2.5
BAC-2 1/20 0 0 1 0 0 3.5
BAC-1 (O) 5/20 2 3 0 0 0 23.5
BAC-2 (O) 5/20 0 0 2 0 3 14.5
a
Tested at the height of 1.0 m.
b
Frequencies measured by number of reactions/number of trials.
Fig. 5. IRspectral changes of BACduring impact in LOXand oxidation in GOX
(a) original; (b) after impact in LOX; (c) after oxidation in GOX; (d) BAC (O)
after impacted in LOX.
BAC-2, which indicated BAC-1 had better anti-oxidation prop-
erties.
The LOX impact test results of the modied co-curing com-
pounds are also better that original BAC(Table 3). The energy at
the height of 0.75 mwas not high enough to distinguish the poly-
mers because there was no reaction at all for the two modied
co-curing compounds. The impact tests were conducted at the
height of 1.0 m, which means a higher energy (98 J) of stimulin.
Even under the impact energy of 98 J, there was only very slight
reaction intensity for both modied polymers. Its obvious the
modication had achieved the goal for better LOXcompatibility.
Its believed with further studies, such as optimization of antiox-
idant or activator improvement of curing process, zero reactions
under the impact energy of 98 J could be achieved which means
LOX compatibility under most application circumstances.
To have a better insight into the effects of modications,
BAC-1 and BAC-2 specimen were oxygenated in GOX. After
oxygenated, their surface color got deeper.
The impact results of oxygenated samples showed their reac-
tion frequencies and reaction intensities got much higher than
before (Table 2). BAC-1 (O) was even worse than BAC-2 (O).
The correlation between oxidation and LOX compatibility were
validated once again.
4. Conclusion
The chemical mechanism of LOX impact and GOX oxida-
tion of polymers are similar. So polymers could be modied
by improving their anti-oxidation properties for better LOX
compatibility. Two kind of modied epoxy with desirable com-
patibility with LOX were got in this way.
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