Radiation resistance of epoxy oligomers and prospects of creating new epoxy-

oligomer based materials for space structures

V.P. Laricheva
FSUE Karpov Institute of Physical Chemistry
Russia, Kaluga Region, Obninsk
E- mail: fci@karpovIPC.ru



Abstract
Such a property as radiation resistance of hardened epoxy oligomers can be controlled because it
essentially depends on the structure of the initial epoxy oligomer and used hardener. In addition,
radiation resistance of epoxy-based composite materials depends on the type of the used filler. As
proved by the available data, composite materials containing carbon fillers can reach 50-100 ? Gy
radiation resistance. Epoxy oligomers belong to the class of radiation resistant materials.
The yield of radiation cross-linking is not high. Therefore, radiation-induced cross-linking of
conventional epoxy oligomers is not reasonable. In this case modification of oligomers with unsaturated
compounds is required. This process is used by our research group to obtain long-lived prepregs. These
prepregs contain the components of different radiation sensitivity, and epoxy oligomesrs prove to be the
most suitable radiation-resistant binder components.


Epoxy matrix-based compositions make the main part of the polymeric composite
materials used in space construction. Epoxy binders possess high adhesion to reinforcing
fibres, low shrinkage and cohesion strength in the hardened state. The demand in these products
is increasing due to a favorable combination of good physico- mechanical characteristics and
high radiation resistance.
In most cases a change of the material performance properties in concrete operation
conditions is taken as a technical criterion of radiation stability assessment. The most important
technical criteria include such basic mechanical characteristics as breaking, bending and shear
strength, electric parameters (dielectric permeability and conductivity), optical and
thermophysical properties. These properties are determined by the force of intermolecular
interaction between the atoms of neighboring macromolecules and mobility of the molecular
segments depending on the processes in the polymers exposed to radiation (destruction,
oxidation, gas evolution) [1].
Our data on the change of physico- mechanical properties [2-4] were compared with the
values obtained by the other authors [5-6] for irradiated epoxy compositions hardened with
various agents. A conclusion was made that radiation resistance of hardened epoxy oligomers is
determined by radiation resistance of the used hardener. It is well demonstrated by gas
evolution studies of epoxy oligomer samples hardened with various agents (Table 1).

Table1. Composition and quantity of gases (%) evolved from -irradiated materials at dose 5 MGy

Content, %
Composition
G
Mol./
100eV ?
2
? ?
4
?
2
?
6
? ? ? ?
2
C
4
?
10
Amine Acetone NH
3
Resin E-41 0.147 49.5 2.8 0.5 43.3 3.1 - - 0.5 -
Hardeners:
Methaphenylene-
diamine (MPhD)
Hexamethylene-
diamine (HMD)
Maleic anhydride
(MA)
Phthaleic anhydride
(PhA)

0.05

5.15

2.1

0.015

70.5

22.8

-

-

0.5

-

-

-

-

-

-

-

-

-

10.5

74.0

-

-

88.8

26.0

4.5

-

-

-

5.0

0.92

-

-

-

-

-

-

13.2

70.0

-

-
Resin E-41
hardened by:
Methaphenylene-
diamine

Hexamethylene-
diamine
Maleic anhydride

Phthaleic anhydride


0.12


0.28

0.4

0,09


68.5


51.8

8.7

47


2.7


4.7

1.1

-


2.8


1.0

-

-


30.0


28.4

28.5

17


2.8


2.2

63.0

36


0.7


3.4

-

-


-


-

-

-


0.5


0.8

-

-


-


-

-

-
G radiation-chemical yield of gaseous products

As it becomes obvious from Table 1, the highest radiation yield of gases is observed
during radiation exposure of hexamethylene diamine. Accordingly, the yield of gaseous
products is the highest during irradiation of hexamethylene diamine-hardened resin E-41. The
lowest yield of gases is in irradiated phthaleic anhydride which is also evident from Table 1.
And thus, the yield of gases in resin E 41 hardened with phthaleic anhydride is the lowest as
well. As follows from Table 1 destruction of the hardened epoxy resin occurs in the aliphatic
chain of hexamethylene diamine, and therefore, a lot of butane and amines are present in the
gaseous products. It is important to pay attention to the yield and composition of gaseous
products during radiation exposure of the resin hardened with maleic anhydride. In our opinion
the content of gases increases because the quantity of maleic anhydride required for resin
hardening is four times higher than that of HMD or MPhD. At the same time the content of
gases is enriched with carbon oxide and dioxide due to destruction of the hardener chain. All
these conclusions should be taken into account in the course of developing epoxy resin-based
radiation-resistant composite materials.
Occurrence of the radiation-induced cross-linking and destruction processes was proved
by our works [2-4] through comparison of the strength characteristics of irradiated epoxy
compositions hardened with different chemical reagents. Any of the two processes can be
dominant depending on the hardener type. A cross- linking process dominates in the
compositions hardened with phthaleic anhydride and methaphenylene-diamine. If maleic
anhydride is used as a hardener both processes are equally probable, and structural changes
under irradiation are due to double bond break- up in the hardener bridge. Destruction processes
dominate in the compositions hardened with hexamethylene-diamine due to the break of
methylene chain in the hardener.
As regards radiation resistance, the investigated hardening agents and, consequently,
hardened resins can be arranged in the row as follows [2, 6]:

Hexamethylene diamine < methaphenylene diamine < maleic anhydride < phthaleic anhydride

Depending on the hardener type, it is possible to obtain hardened compositions and non-
reinforced composite materials with radiation resistance up to 10 MGy and 100-150 MGy,
respectively [3-6, 8-9].
Rather high radiation resistance of epoxides in comparison with other resins [3] proves
the presence of numerous benzene rings which provide internal protection of polymeric
molecules. Excitation energy can be transferred either from one molecule to another or from
aliphatic to aromatic part of the molecule as in polymers [10]. Therefore, a protective action of
aromatic rings also extends to the neighboring aliphatic parts of epoxy resin structure. This can
explain an increase of radiation resistance of epoxy compositions hardened with aromatic
reagents. Radiation resistance of the reinforced composite materials increases because the
absorbed doze is distributed non-uniformly in the heterogeneous environment [11]. In practice a
dose absorbed by the resin in fibreglasses is 3 times lower than unfilled resin [8]. As shown in
papers [7-9], radiation resistance of the reinforced composite materials additionally depends on
the type of the filler used. This dependence is especially significant in black-reinforced plastics.
The authors [9] explain this fact by increasing polarity of the resin and filler during irradiation.
In our opinion high radiation resistance of black-reinforced plastics is determined, on the one
hand, by the formation of polar groups which intensify resin interaction with carbon fibres, and
on the other hand, by the presence of numerous conjugated bonds in carbon fibres participating
in radiation crosslinking reactions. Therefore, a post-hardening effect is observed in the black-
reinforced plastic products on exposure to radiation [7, 10].
The only drawback of epoxy oligomer use as the main binder component in the
composite materials with high physico- mechanical properties is associated with long hardening
time and high temperatures (150-250(? for 6-12 hours). Therefore, further numerous attempts
of epoxy oligomer curing have been made with the help of high-efficient radiation technology.
Unfortunately, all the straightforward efforts to carry out radiation curing of the well-
known epichlorhydrine and diphenylol-propane epoxy oligomers (diane resins) turned to be
unsuccessful. The reason of this failure can be understood after analyzing radiation-chemical
transformations in non-cured epoxy oligomers of various structures.
Our investigations [3-4, 7], as well as the research results of other authors [8], showed
that between the two radiation-induced processes observed in these materials crosslinking
dominated destruction irrespective of epoxy oligomer structure.
Domination of radiation crosslinking over epoxy resin destruction is proved by the
following experimental data: the loss of hard resin solubility in acetone after exposure to high
radiation dozes (Fig.1), absence of fluidity on the thermomechanical curves (Fig.2) at 5 MGy,
increase of liquid resin molecular mass [13]., etc. The yield of gel- fraction depends on the
exposure dose and initial molecular mass.


Fig.1

Solubility of solid epoxy resin E41 in acetone at different radiation dozes
20 0 0 0
30 0 0 0
40 10 2 0
44 55
45 90 10 0
50 25 10
53 30
55 85 50 0
58 80
65 -10
72 -50
75 -20
80 10
82 20
90 20
100 20
120 20
140 20
-60
-40
-20
0
20
40
60
80
100
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150
Temperature,
o
?
D
e
f
o
r
m
a
t
i
o
n
,

r
e
l
a
t
i
v
e

u
n
i
t
s
3
2
1
4

Fig.2
Thermomechanical curves of epoxy resin exposed to Co
60
gamma rays, vacuum: 1 non-
irradiated; 2 0.5 MGy; 3 3 MGy; 4 5 MGy.

Crosslinking occurs via a radical mechanism because the yields of radicals and gaseous
products are comparable [14]. A radical yield in epoxy oligomer E-41during radiation exposure
is equal to 0.33 particle/100 eV.


Table 2. Temperature dependence of radiation yield and gas composition in resin E-41
Content, %
DOSE,
MGY
Radiation
temperature, ?
G /molecule
100 eV
?
2
? ? ? ?
4
? ?
3
? ? ? ?
3
0.5 -176 0.052 70.4 28.9 0.4 -
0.5 20 0.1 45.1 50.5 2.6 -
0.5 120 0.48 9 32.8 1.7 35.8
9.18 20 0.13 37.4 48.2 4.9 4.0

. A process of radical formation is proved by the ESR data, where the spectra of
oligomer E-41 and diphenylol-propane are identical (Fig. 4).





Fig.4. ESR spectra: 1 - diphenylol-propane; 2 epoxy resin E-41; 3 propylene oxide; 4 -
epichlorhydrine

Based on these data and gas evolution values (Table 1) we can assume that radicals 1; 2 and 3
participate in the crosslinking process.

Crosslinking is also possible due to epoxy group opening with atomic hydrogen generated
simultaneously with radical 1 formation. With opening epoxy rings radical (4) can be formed and
involved in further crosslinking reactions.

? ?
2
- ? ? -? ?
2
-? - + ? ? ?
2
- ? ? -? ?
2
-? -
\ /
? OH
(4)


This process accounts for increasing the number of hydroxyl groups during radiation
exposure. Destruction reactions, isomerization of epoxy groups into carbonyl groups and formation of
hydroxyl groups are observed simultaneously with crosslinking reactions.
Temperature dependence of gaseous yield and composition, presence of acetone and other
heavy masses in gaseous products (Table 1) and decreasing intensity at 1420 cm
-1
(benzene ring-
related ? ?
2
? groups) prove the occurrence of the destruction process.
Isomerization of epoxy groups into carbonyl ones and low radical yields are the main reasons
that explain inefficiency of crosslinking during radiation exposure of the conventional epoxy
oligomers.
According to the studies made by our researchers and other scientists, complete curing (or
crosslinking as accepted in radiation chemistry) of epoxy oligomers with the formation of spacious
structures occurs at 6-10 MGy depending on the initial molecular mass, which is hard to justify from
economical point of view. The products arising from this process are fragile. Conventional hardening
agents were mixed with epoxy resins to accelerate a curing reaction, but without any noticeable result.
Radiation sensitivity of epoxy oligomers can be changed in a desirable way due to the presence
of two functional groups (epoxy and hydroxyl) in the oligomer molecules.
On the contrary, modification of epoxy oligomers through epoxy groups makes it
possible to increase radiation sensitivity of the materials and to decrease a dose of radiation
curing from 15 ? Gy to 0.01 MGy.
At present radiation-cured compositions (0.01-0.02 MGy) of epoxy oligomers are based
on acrylic and methacrylic binders or epoxy acrylates preliminary obtained by acrylation or
methacrylation of epoxy oligomers, where epoxy group opening is caused by the chemical
initiators of acrylic and methacrylic acids. However, the use of such binders does not provide
any possibility to develop a radiation technology that can compete with a conventional
thermochemical process of composite material production. The materials based on these binders
have low heat resistance characteristics (100-110(C) and, therefore, cannot be used in extreme
operation conditions.
The Italian scientists [15] concentrate on the compositions containing di- and tri-
functional epoxy oligomers combined with strong salts of oneic- like acids. Oneic salts intensify
cation polymerization during radiation exposure. The best results were obtained for epoxy
composition mixtures with polysulphone and polyester ketone copolymers.
Canadian, American and Japanese researchers are following the same direction. At
present we are also investigating one-phase radiation curing of the components suitable for
copolymerization with modified epoxy oligomers. We have already obtained test samples of the
composite materials with 230-260(C heat resistance.

Table 3. Physico-mechanical characteristics of black-reinforced plastic produced via radiation
technology based on fibber UKN-P/5000 and heat resistant binder


Characteristics

Parameters
Density, g/cm
3
1.5
Glass transition temperature,
?
? 259
Ultimate tension, MPa 1470 100
Ultimate interlayer shear strength 57 5


In our opinion a combination of radiation-resistant epoxy oligomers with unsaturated
compounds can be promising for radiation technology of long- lived prepregs [16]. As it
becomes evident from Table 4, the characteristics of the composite materials based on such
prepregs are higher than those of the conventional products. Prepregs obtained by radiation-
chemical procedures have a one- year shelf- life or even more, depending on the composition. A
process for manufacturing prepregs that we propose makes it possible to eliminate the use of
solvents and to obtain end compositions with 200-260? heat resistance.

Table 4. Physico- mechanical characteristics of carbon plastics on the basis of prepregs
obtained by different technologies
Characteristics
Prepreg obtained by
radiation technology
Prepreg obtained by
thermochemical
technology

Density, g/cm
3
1.52 1.5
Ultimate tensile strength, MPa 984 700
Youngs modulus, GPa 221 140
Ultimate strength at interlayer shear, MPa 70 55
Ultimate strength at static bending, MPa 1250 1250
Elastic modulus at static bending, GPa 141 125
Ultimate compression strength, MPa 1050 700
Heat conductivity factor, kcal/m ? 0.52 0.63


Alongside with our team, the scientists of Canada, Italy and Japan made a great contribution
into this field of research. According to Canadian researchers, a 50 kW-accelerator facility
increases the output of the end composite materials 50 times as compared with the autoclave
facility. It is significant that accelerator and autoclave costs are practically the same. Electron
beam accelerators with 10 MeV energy provide 21- mm electron penetration through the
material [17].

Advantages of the radiation technology include
- low-temperature and solvent-free accomplishment of the process;
- short time of curing;
- high productivity;
- a possibility to replace bulky ovens with hard-to-maintain isothermal heating conditions by
more convenient electron beam accelerators;
- a possibility to control desirable variation of the end composite material characteristics due to
radical copolymerization of specially selected components;
- to control a substrate or a filler;
- unlimited time of binder storage.
In this work a mixture of conventional epoxy oligomers and unsaturated compounds is
used to obtain new compositions by the method of radical copolymerization. These materials
are promising for construction applications (in particular, for polymeric equipment) in extreme
operation conditions due to high heat resistance (> 200C) and radiation stability (> 10 ? Gy).
We would like to invite other companies and organizations for cooperation in this field.
The Branch of Karpov Institute in Obninsk has various types of radiation facilities including the
WWR-c reactor; two locally protected 0.7 MeV accelerators equipped with conveyor belts
(suitable for manufacturing prepregs) and a 10 MeV chamber-type accelerator, which can be
used for producing 3.5x1.5m items of 25 mm thickness. Available Co-60 sources can provide
radiation intensity of 1000 rad/s, if recharged.

References
1.Charlesby A. Jadernye of radiation and polymers. ? . Publishing house of the foreign
literature 1962,183,429, 469, 472.
2. Bakaeva V. P., Egorova Z. S., Karpov V. L. // Plastmassy (Russian Journal). 1967. ? 9.
3. Laricheva (Bakaeva) V. P. // Epoxy resins and radiation. M. NIITEKHIM. 1976.
4. Laricheva V. P. Radiat.Phys.Chem.(2007),doi:10.1016/j.radphyschem.2007.02.033
5. Colichman E. L. Strong J. D., 1957. Effect of gamma-radiation on epoxy plastics. Mod. Plast.
35, p.180-188
6. Birkina N., Neverov A., Bocharnikov V. Mech. Polym.3, 476-482
7. http:// glossary. Hobbyarea.ru/1.8/index.php/term/1,1261.xhtml
8. Welikovsky, Plastmassy 1971, ? 9, pp..44-45
9. Seo K. S. Fornes, Gillbert, Memory J. of Polymer Physics 26, 245-255 (1988)
10. Kaplan I. G., Plotnikov V.G., High Energy Chemistry 1967,1, 5
11. Popova K.V. Abstracts of reports of 3-rd All- Union meeting Influence of ionizing
radiation and light on heterogeneous systems Kemerovo, 1982
12. Bakaeva V.P., Egorova Z.S., Karpov V.L. // Proceedings of the USSR Academy of
Sciences. 1966. 170. ? 4.
13. Meleshevich A.P. Radiation chemistry of epoxy compounds. Kiev, Naukova Dumka, 1989.
14. Blumenfeld L.A., Voevodskiy V.V., Semyonov A.T. Use of Electron Spin Resonance in
Chemistry, Publ. House of USSR Academy of Sciences, Novosibirsk, 1962, p.
15. Alessi et al.11
th
Tihany Symposium on radiation chemistry, 2006, august, p8;15;67
16. Laricheva V.P., Korotky A.F. HIGH Energy Chemistry2008 42, ? 1, pp23-26
17. 15.Saunders C.B. Radiat.Phys. Chem.1994 .V.46, ? 4-6. pp991-994