Cryogenics 45 (2005) 450–454

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Cryogenic properties of SiO2/epoxy nanocomposites

C.J. Huang a, S.Y. Fu a,b,*
, Y.H. Zhang a, B. Lauke b, L.F. Li a, L. Ye c

a
Cryogenic Materials Division, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100080, China
b
Institute of Polymer Research, Hohe Str. 6, 01069, Dresden, Germany
c
School of Aerospace, Mechanical and Mechatronic Engineering, Centre for Advanced Materials Technology (CAMT),
The University of Sydney, Sydney, NSW 2006, Australia

Received 26 August 2004; received in revised form 5 February 2005; accepted 10 March 2005

Abstract

SiO2/epoxy nanocomposites were prepared using diglycidyl ether of bisphenol-F (DGEBF) type epoxy and tetraethylorthosilicate
(TEOS) via the sol–gel process. Silica nanoparticles were collected after burning off the matrix resin and the silica nanoparticles were
observed using TEM. The cryogenic tensile properties at 77 K and thermal expansion coefficient of the nanocomposites were stud-
ied. The tensile properties at room temperature were also given to compare with the cryogenic tensile properties. The fracture sur-
faces were examined with scanning electron microscopy (SEM). The effects of silica nanoparticle content have been studied on the
cryogenic tensile and thermal properties of the nanocomposites. In addition, the dependence of the glass transition temperature on
the silica nanoparticle content has also been examined.
Ó 2005 Elsevier Ltd. All rights reserved.

Keywords: Epoxy resin; Tensile properties; Thermal expansion; Low temperature

1. Introduction epoxy resins are always desired for cryogenic application

Epoxy (EP) resins have been widely employed in
cryogenic engineering fields. Since normal epoxy resins
would readily crack at low temperature, it is important
to select appropriate epoxy resins as adhesives in super-
conducting apparatus [1–3]. For example, relatively
tough epoxy namely diglycidyl ether of bisphenol-F
(DGEBF) as the main ingredient [4] has been chosen
as adhesive for cryogenic application in HT-7U super-
conducting Tokamak apparatus. Moreover, direct
dispersion of nanoscale silica fillers in the resin formula-
tion [5] has also been developed for improving the frac-
ture toughness. Furthermore, high cryogenic mechanical
properties and low thermal expansion coefficient of
*
Corresponding author. Tel.: +86 10 6265 9040; fax: +86 10 6256
4049.
E-mail address: syfu@cl.cryo.ac.cn (S.Y. Fu).
[6,7].
Inorganic–organic hybrid materials by the sol–gel
process have received considerable attention in the past
decade [8–12]. Usage of the sol–gel process can rela-
tively easily obtain homogeneous nanocomposites with
good dispersion of nanoparticles in polymer matrices
when compared with direct dispersion method. As a
result, the mechanical and physical properties of the
inorganic–organic hybrid materials can be easily im-
proved by the introduction of a low content of inorganic
nanofillers using the sol–gel process [13–15].
In the present study, SiO2/epoxy nanocomposites
were prepared using the bisphenol-F type epoxy resin
(DGEBF) and tetraethylorthosilicate (TEOS) as the
organic and inorganic sources, respectively. The inor-
ganic phase was incorporated into epoxy resin by the
sol–gel process. The cryogenic tensile properties and ther-
mal expansion coefficient of the silica/epoxy nanocom-
posites were investigated in detail. The fracture surfaces

0011-2275/$ - see front matter Ó 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.cryogenics.2005.03.003
 C.J. Huang et al. / Cryogenics 45 (2005) 450–454
of tensile samples were examined with scanning electron
microscope (SEM).
2. Experimental
The materials used in this study were diglycidyl ether
of bisphenol-F (YDF-175, Kukdo Chemical Ind. Co.,
Korea) as epoxy matrix, and polypropylene glycol
diglycidyl ether (PPGDE) (PG-207, Kukdo Chemical
Ind. Co., Korea) as plasticizer and diethyl toluene dia-
mine (DETD) (ETHACURE-100, Albemarle Co.,
USA) as hardener, and tetraethylorthosilicate (TEOS)
(A.R. Beijng Chemical Co., China) as precursor, and
ammonia solution (A.R, Beijing Chemical Co.) as cata-
lyst and acetone (A.R. Beijing Chemical Co., China) as
solvent.
The epoxy resin/silica nanocomposites were prepared
via the following steps. Firstly, epoxy resin, ammonia
and acetone were mixed and stirred (tagging solution
A). At the same time, acetone and TEOS in a volume
ratio of 10:2 were mixed and stirred for 2–3 min (tagging
solution B). Then the two solutions (A and B) were
mixed and stirred for 2–4 h at ambient temperature. Sec-
ondly, the mixture was degassed in order to get rid of the
more acetone, ammonia and H2O, then the plasticizer
and the curing agent were added to the above mixture.
The resulting mixture was stirred for about 20 min at
ambient temperature. The mixture was impregnated into
the preheated mould in an oven. Then the samples were
gelled at 78 °C for 24 h and post-cured at 135 °C for
12 h. The tensile samples were prepared according to
the recommendation of ASTM D638-96. Then the spec-
imens were stored in a drying oven for mechanical test-
ing. The tensile properties were obtained using a Reger
mechanical tester with a 10 kN load cell and a crosshead
speed of 2 mm/min. The tensile testing was performed at
both room temperature (RT) and liquid nitrogen tem-
perature (LNT, 77 K). The low temperature was
achieved by dipping clamps and samples in a liquid
nitrogen filled cryostat.
Fig. 1. TEM observation of silica nanoparticles obtained from (a) 2 wt.% and (b) 4 wt.% silica/epoxy nanocomposites.
451
The thermal expansion coefficient of epoxy and silica/
epoxy nanocomposites was measured by the strain
gauge method. It is well known that relative change in
length DL/L of strain gauge could be detected electri-
cally by the relationship DL/L = (1/Ks)DR/R, where
DR/R is the relative change in the electrical resistance
of strain gauge, Ks is the gauge factor. In our measure-
ment, 350 X strain gauges were bonded to the surface of
the epoxy and nanocomposites so that the strain gauge
and the epoxy or nanocomposites have the same strain
when the temperatures vary. The strain DL/L of the
strain gauge was recorded from room temperature
(298 K) to liquid nitrogen temperature (77 K). Conse-
quently the mean thermal expansion coefficient of epoxy
and silica/epoxy nanocomposites could be obtained by
the following relation:
1 DL
a¼
T RT
T LNT L
where a is the thermal expansion coefficient, TRT and
TLNT denotes room temperature (298 K) and liquid
nitrogen temperature (77 K).
Dynamic mechanical properties were measured with a
PE-7 thermal analysis instrument at an oscillation fre-
quency of 1 Hz. And the data were collected from

150 °C to 100 °C at a scanning rate of 5 °C/min. The
glass transition temperatures (Tg) could be determined
by Dynamic Mechanical Analysis (DMA). In the DMA,
the glass transition temperature is defined as the tempera-
ture where the sample exhibits a dramatic change in
mechanical and damping behavior with increase of tem-
perature when connected to an oscillation displacement.
The Tg could be obtained by the peak of the diagram tan r
vs temperature curves. Here the loss factor tan r is the
ratio of loss modulus to storage modulus. The loss modu-
lus vs temperature and storage modulus vs temperature
can be directly got by the DMA testing.
Silica/epoxy nanocomposites were burned in an elec-
tric muffle furnace for 2–3 h at 620 °C. The ashes were
collected after burning off the epoxy matrix and the
silica nanoparticles (Fig. 1) were observed using
452 C.J. Huang et al. / Cryogenics 45 (2005) 450–454

transmission electron microscope (TEM, JEM-200CX).
The results obtained from the TEM micrographs
showed that the average particle size was less than
100 nm for the case of 2 wt.% silica and the average par-
ticle size was about 200 nm for the case of 4 wt.% silica.
The particle size distribution can be obtained from the
data for the particle sizes evaluated from the TEM
micrographs of silica particles. And the size distribution
showed a narrow range (not presented). The fracture
surfaces were examined by scanning electron micros-
copy (SEM, Hitachi S-450). Before SEM observation,
the fracture surfaces were cleaned with alcohol and
coated with a thin gold layer to improve image quality.
3. Results and discussion
3.1. Tensile properties
The effects of silica content on the tensile properties
of epoxy nanocomposites are illustrated in Table 1
and Fig. 2, where the silica content ranges up to
4 wt.%. In principle, a higher silica content could be
achieved in the SiO2/epoxy composites. However,
increase in the silica content would lead to increase
Table 1
The effects of silica content on the tensile strength and failure strain of
silica/epoxy nanocomposites
Sample SiOl Tensile strength, rB
code contents (MPa)
(wt.%)
77 K
1 0 72.7 ± 4.5
2 2 84.6 ± 0.9
3 4 102.5 ± 3.4
7
Ambient Temperature
6 Cryogenic temperature (77 K)
Young's modulus (GPa)
in silica particle size during the sol–gel process. Large
size particles would have a negative effect on mechanical
properties of the composites. Moreover, a further
increase in the silica content would bring about the in-
crease in the viscosity of the epoxy, which is not desired
for vacuum pressure impregnation (VPI) process in
cryogenic application. At ambient temperature, a slight
enhancement of the strength was observed when the
silica content was 2 wt.%, while the strength was
slightly decreased by the addition of 4 wt.% silica
nanoparticles. This phenomenon has also been observed
for other nanocomposite systems [16,17]. However, it
is interesting to note that at low temperature, the com-
posite strength increased significantly with the increase
of silica nanoparticle content (see Table 1). This is
mainly because the silica/epoxy interface adhesion
strength has been greatly improved at low temperature
due to the compressive stress which must be over-
come during loading at the interface caused by the
different thermal expansion behaviors between silica
nanoparticles and epoxy resin. Moreover, it can be seen
in Table 1 that the composite strength at low tempera-
ture was much higher than that at ambient tempera-
ture. This was due to the fact that both matrix
strength and silica–epoxy interface adhesion strength
at low temperature were higher than that at ambient
temperature. Both matrix strength and silica–epoxy
interface strength make positive contribution to the
composite strength. As expected, the modulus has been
improved by the addition of silica nanoparticles at both
Failure strain, eB (%) ambient and low temperatures and the modulus at low
temperature was much higher than that at ambient tem-
perature (Fig. 2). The failure strain at ambient tempera-
298 K 77 K 298 K
47.5 ± 1.5 1.6 ± 0.1 6.5 ± 2.4 ture has been greatly enhanced by the addition of silica
50.2 ± 0.8 1.8 ± 0.15 16.5 ± 1.6 nanoparticles while the failure strain at low temperature
46.2 ± 0.8 2.3 ± 0.1 15.2 ± 2.1 was slightly improved by the addition of silica nanopar-
ticles. It is well known that for an engineering material,
crack propagation would proceed along the weakest
paths in the material. At ambient temperature, the
cracks would propagate along both matrix and particle-
matrix interfaces, the improvement in the failure strain

is then likely attributed to the inhibition of the crack

5 propagation during tensile loading by the silica nano-
particles. However, at cryogenic temperature (77 K),
4 the matrix becomes more brittle, cracks would more eas-
ily occur in the matrix than at ambient temperature. Be-
3
cause the particle-matrix interface adhesion becomes
2
much stronger at cryogenic temperature, the cracks in
the composites would propagate mainly along the weak-
1 er matrix routes, thus the particles would play a less
role in resisting the propagation of cracks. It was then
0 observed that the failure strain at cryogenic temperature
0 2 4 was slightly improved by the introduction of silica nano-
Silica content (wt%)
particles. Furthermore, it was observed that the failure
Fig. 2. The effect of silica content on the YoungÕs modulus of silica/ strain at low temperature was much lower than that at
epoxy nanocomposites. ambient temperature. This observation can be easily
 C.J. Huang et al. / Cryogenics 45 (2005) 450–454 453

understood from the SEM micrographs of the frac- 7

ture surfaces of the samples as shown in Fig. 3. The
fracture surfaces of the samples at low temperature are 6
much smoother than that at ambient temperature (see
5

CTE (x10-5K-1)
Fig. 3). Since smooth fracture surfaces correspond
to lower failure strain, thus the failure strain at low 4
temperature must be lower than that at ambient
temperature. 3

2
3.2. Thermal expansion coefficient and glass transition
temperature 1

Fig. 4 shows the average coefficient of thermal expan- 0

sion (CTE) from 298 K to 77 K of the nanocomposites as
a function of silica content. It can be seen that the intro-
duction of silica nanoparticles dramatically reduced the
CTE. This is because silica nanoparticles have much
lower CTE than epoxy resins do. The reduction in the
CTE by the addition of silica nanoparticles is desired
for cryogenic application.
The effect of the silica nanoparticle content on the
glass transition temperature (Tg) was exhibited in Fig.
5. It is clearly shown that the addition of silica nanopar-
ticles by the sol–gel method has enhanced the glass tran-
0 2 4
Silica content (wt%)
Fig. 4. The effect of silica nanoparticle content on the average
coefficient of thermal expansion from 298 K to 77 K.
sition temperature (Tg). The increase in Tg is likely
attributed to a loss in the mobility of chain segments
of epoxy resin resulting from the silica nanoparticle/
matrix interactions. This observation is the same as for
silica/PA 6 nanocomposites [16].

Fig. 3. SEM photographs of (a) neat epoxy at ambient temperature, (b) neat epoxy at 77 K, (c) 2 wt.% silica/epoxy nanocomposites at ambient
temperature and (d) 2 wt.% silica/epoxy nanocomposites at 77 K.
454 C.J. Huang et al. / Cryogenics 45 (2005) 450–454
100 4wt% SiO2/EP
80 2wt% SiO2/EP
neat EP
Tg (0C)
60
40
20
0 [3] Chen Q, Gao B, Chen J. Properties of impregnation resin added
Fig. 5. The glass transition temperature of neat epoxy and silica/epoxy
nanocomposites.
4. Conclusions
The cryogenic tensile properties and thermal expan-
sion coefficient of silica/epoxy nanocomposites prepared
by the sol–gel process have been studied. The results
showed that the tensile strength at cryogenic tempera-
ture has been significantly enhanced by the addition of
a low content of silica nanoparticles while the strength
at room temperature was almost insensitive to the addi-
tion of silica nanoparticles. As expected, the modulus at
both ambient and low temperatures increased with the
increase of silica content. The tensile strength and mod-
ulus at low temperature are much higher than that at
ambient temperature. The failure strain at low tempera-
ture was slightly enhanced by the addition of silica
nanoparticles yet the failure strain at room temperature
was obviously improved by the addition of silica nano-
particles. The fracture surfaces were examined by scan-
ning electron microscopy (SEM) to explain the
observation of the failure strain. The average coefficient
of thermal expansion from 298 K to 77 K was obviously
reduced by the addition of silica nanoparticles, which is
desired by cryogenic application. In addition, the glass
transition temperature has been enhanced by the addi-
tion of silica nanoparticles.
Acknowledgement
This work is funded by the Key Research Program
of Beijing City Science and Technology Committee
(No. H020420020230). S.Y. Fu is grateful to the support
of the Alexander von Humboldt Foundation, Germany.
L. Ye gratefully acknowledges the support of K.C.
Wong Education Foundation, Hong Kong.
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