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Polymer Testing 21 (2002) 195199

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Test Method

Crack resistance test of epoxy resins under thermal shock


Shengguo Wang
a

a,*

, Qingxiu Li 1, Wei Zhang a, Hongwei Zhou

Department of Macromolecular Science, Fudan University, Handan Road, Shanghai 200433, Peoples Republic of China
Received 12 April 2001; accepted 20 June 2001

Abstract
In this study, a new test method for evaluating the crack resistance of epoxy resins under thermal shock is proposed.
A series of epoxy resins of varying toughness are tested by this method. We also study influence of geometry and
dimensions of molds on the experimental results. It is shown that crack resistance of epoxy resins under thermal shock
can be evaluated by this method. Our study also suggests that this method can be performed conveniently in laboratories
and factories so that it can be widely applied in many fields to evaluate the crack resistance of epoxy resins. 2001
Elsevier Science Ltd. All rights reserved.
Keywords: Crack resistance; Epoxy resins; Thermal shock

1. Introduction
Epoxy resins are widely used in coating, adhesive,
insulating, flooring, laminating and casting applications
because of their excellent mechanical and thermal
properties such as high strength, elastic modulus and
glass transition temperature [1]. However, they show low
resistance to crack initiation and propagation under thermal shock. Therefore, it is necessary to perform crack
resistance test under thermal shock of epoxy resins
before they are used.
Although many thermal shock tests have been
employed to evaluate the crack resistance of metallic and
ceramic materials [24], few investigations have been
focused on thermosetting resins. In some methods [5,6],
an embedded steel ring bonded by a strain gauge was
used to evaluate the internal stress of epoxy resins, but
it is not a direct way to evaluate the crack resistance of
materials under thermal shock by measuring their
internal stresses. Crack resistance testing of epoxy resins

* Corresponding author. Tel.: +86-216-564-2859; fax: +86216-564-7891.


E-mail address: wangshengguo@etang.com (S. Wang).
1
Current address: School of Forestry and Wood Products,
Michigan Technological University, Houghton, MI, USA.

is undertaken for assessment of them with regard to their


suitability for a given application, not for obtaining typical value data. Two kinds of inserts suggested by IEC
have been embedded into epoxy resins to perform thermal shock tests. This test method is not sensitive enough
to distinguish crack resistance of materials with varying
toughness, due to low stress concentration induced by
the inserts. Kojima et al. made a thermal shock test
machine to estimate thermal shock resistance of epoxy
resins [7]. This method has not been widely used due to
the special equipment and restrictive experimental conditions. Therefore, it is important to propose a kind of
method that can be performed conveniently and reflect
the crack resistance of epoxy resins under thermal shock
directly in laboratories and factories.
In this study, we propose a new test method to evaluate crack resistance of epoxy resins under thermal shock.
First, repeated thermal shock tests by the new method
were performed on epoxy resins of varying toughness to
demonstrate its feasibility. Then, we studied influence of
geometry and dimensions of molds on crack resistance
test results.
2. The crack resistance test method
In this study, we devise a series of molds including
inner cores, outer frames and underpans to evaluate the

0142-9418/02/$ - see front matter 2001 Elsevier Science Ltd. All rights reserved.
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S. Wang et al. / Polymer Testing 21 (2002) 195199

Fig. 1. Molds for crack resistance test under thermal shock. (a) Hexagon inner core. (b) Hexagram inner core. (c) Outer frame. (d)
Photo of assembly of hexagram inner core and outer frame.

crack resistance of epoxy resins under thermal shock.


The geometry of the molds is shown in Fig. 1, D of
hexagram inner cores are 7, 5, 4 cm, respectively. D of
hexagram inner core is 7 cm. D of outer frame is 8 cm.
Epoxy resins are cast into the space between the inner
core and the outer frame. Thickness of the specimen is
5 cm. If the specimen is too thin, it will easily crack,
and if the specimen is too thick the changing temperature
conditions in the specimen will be different. The groove
shown in Fig. 1 is used for keeping the same thickness
of specimens.
Thermal stresses will be set up due to the differences
in the thermal expansion (or contraction) of epoxy resins
and steel molds. The stresses loaded at the tip of the

Fig. 2. Stresses loaded at the tip of epoxy specimen tested by


hexagram inner core.

epoxy specimen constrained by hexagon inner core and


outer frame are shown in Fig. 2. These three stresses
cause the specimen crack at their tip. This kind of loading mode belongs to the cleavage or tensile-opening
mode [8]. Thermal stresses can be expressed as follows:
saET

(1)

Where
a
E
T

is difference of thermal expansion coefficient


between epoxy resin and steel
is modulus of epoxy resin
is the change of temperature

From Eq. (1), we can see that a is determined by . Due


to crack initiation and propagation relating to a, changing temperature of epoxy resins could control the cracking. This is the principle of the method. In this study,
the thermal shock temperatures are 50C and 18C,
which can be attained easily in many laboratories and
factories.

S. Wang et al. / Polymer Testing 21 (2002) 195199

3. Materials and experiment procedures


3.1. Materials
Molding epoxy compounds used for this study are
composed of epoxy resin, curing agent, accelerator and
toughening agents, The epoxy resin is diglycidylether of
bisphenol A with a trade mark name DER331. The curing agent is methyl hexahydrophalic (MeHHPA) and the
accelerator is benzyl dimethylamine (BDMA).The
toughening agents are dibutyl phthalate (DBP), C1214
glycidyl ether (Epodil748), poly ethylene glycol (PEG),
carboxyl-terminated
poly
(butadiene-acrylonitrile)
copolymers (CTBN), ZR rubber (a commercial rubber
purchased from Tsinghua university), respectively. The
neat epoxy resin compounds without modification are
tested as control systems. The neat epoxy compounds are
fabricated with 88 parts of curing agent, 0.14 parts of
accelerator per 100 parts of resin by weight, while the
modified epoxy compounds have added toughening
agents.
3.2. Sample preparation
The molds including outer frames and inner cores are
cleaned and mopped with acetone, then put into an oven
at 80C for 45 min. The molds are taken out, coated with
mold release agent, constrained with bolts and put into
the oven at 140C for 2 h to make the release agent form
a membrane on the molds. After that the molds are taken
out of the oven and cooled to a lower temperature about
90C. Epoxy resin compounds are cast into the space
between the inner core and outer frame and the epoxy
specimens in molds put into the oven for curing. The
curing procedure is as follows: 3 h at 90C, 2 h at 110C,
1 h at 130C and then 12 h at 140C.
3.3. Crack resistance test under thermal shock
The epoxy resin samples in molds are taken out of the
oven at 140C and immediately flushed with water at
0C for 3 min. They are then put into a refrigerator with
a temperature of 18C. After 3 h, we take the molds
out and observe whether the samples crack or not. If a
specimen cracks it is not subjected to the thermal shock
cycle. The rest of the specimens are put into the oven at
50C for 2 h. Then they are taken out and examined for
whether or not they have cracked. A thermal shock test
cycle includes 18C for 3 h and 50C for 2 h. The
number of specimens for each epoxy compound is 5, if
a specimen cracks the percent of crack is 20%, and so
on. Thermal shock testing continues until all the specimens crack.

197

4. Results and discussion


4.1. The feasibility of the test method
The crack resistance of basic epoxy compounds without modification and epoxy compounds containing 10
parts CTBN, PEG, Epodil 748, DBP by weight per 100
parts epoxy resin under thermal shock is shown in Fig.
3. We can see that the more to the right the crack line
lies, the better is its crack resistance. The effect of toughing agents on crack resistance is as follows:
CTBNPEGEpodil748DBP0, which can be
explained by their toughening mechanisms. The increase
in crack resistance of CTBN modified epoxy resins is
the best because of the capability of the added elastomer
to separate out as a discrete phase while curing. This
can arrest crack propagation to a great extent when the
materials undergoes fracture by disturbing the applied
stress over the whole bonded area [9]. Hydroxyl groups
on both ends of PEG react with epoxy resin so that PEG
incorporates into networks by forming a block structure
and increases the flexibility and mobility of networks,
which makes it easier to dissipate stresses loaded on the
specimens. Epodil 748 is a kind of reactive diluent or
toughening agent, containing only one epoxide group
capable of reacting with the curing agent. It reduces the
functionality and crosslink density of the system and,
therefore, improves the crack resistance of epoxy resins.
DBP is a kind of non-reactive diluent or toughening
agent, incapable of reacting with epoxy or curing agent.
It only reduce viscosity of systems and has little effect
on improving crack resistance.
In this study, we also investigated the influence of
CTBN amounts on crack resistance of epoxy resins
under thermal shock. The amounts of CTBN were 1, 5,
10, 15, 20, 30 parts by weight per 100 parts epoxy resin.
The results are shown in Fig. 4, where it is apparent
that the higher the amount of CTBN the better the crack
resistance. This can be explained by the definition of
crack resistance. A materials crack resistance is defined
by its ratio of toughness to yield stress, KIC/sy. The
higher the CTBN amount, the higher the toughness and
the lower the yield stress [10]; hence, the higher crack

Fig. 3.

Crack resistance of neat and toughened epoxy resins.

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S. Wang et al. / Polymer Testing 21 (2002) 195199

Fig. 4. Crack resistance of epoxy resins toughened by varying


amounts of CTBN.

Fig. 5. Crack resistance of epoxy resin tested by varying


dimensions of hexagram inner cores.

resistance of epoxy resins. However, crack resistance of


epoxy resins toughened by 5 and 10 parts CTBN is the
same. This may be due to insufficient number of test
specimens which could be solved by changing from 5 to
10 test specimens.
From the results obtained, we can see that this kind
of method can be used conveniently to evaluate crack
resistance of epoxy resins with varying toughness under
thermal shock.

by the same outer frame and different dimensions of


inner cores 7, 5 and 4 cm are shown in Fig. 5. We can
see that epoxy specimens become difficult to crack with
decrease of the inner cores dimension. In the next study,
we will investigate the relationship between the results
tested by small and large size inner cores.

4.2. Influence of geometry and dimensions of molds on


experimental results

As demonstrated by the experimental results, the thermal shock test method proposed by us is suitable for
evaluating crack resistance of epoxy resins and other
thermosetting resins. This kind of method can be
manipulated conveniently and needs no special equipment. Although there are some problems in this method,
for example, the number of thermal shock cycles of
CTBN toughened epoxy resins is 24 (equal to 5 days)
so that the testing process is too long, this method are
still practicable in many fields and these problems could
be overcome by selecting suitable size and geometry of
molds. In the next study, we will continue improving this
test method for further and wider applications.

There are two kinds of inner cores used in this study:


hexagon and hexagram, the angles at the tips of the hexagon are twice that of the hexagram. Thermal shock test
results for epoxy compounds which are formulated by
90 parts of MeHHPA, 10 parts of ZR rubber, 6 parts of
PEG400 and 0.14 parts of BDMA per 100 parts of resin,
tested with hexagon and hexagram inner cores of the
same size are shown in Table 1. The epoxy specimens
with the same formulation all fracture within 4 cycles
when using hexagram inner core, while none fractures
within 4 cycles when using the hexagram inner core.
This suggests that the angle of the tip of the inner core
greatly influences the results.
The influence of the dimensions of the inner cores on
experimental results has also been investigated. Crack
resistance results of the same epoxy compounds tested
Table 1
Crack resistance of epoxy resin with the same formulation
tested by hexagram and hexagon inner cores

Cycle

Hexagon

0
1
2
3
4

20%
60%
60%
80%
100%

Failure Percent
Hexagram
0%
0%
0%
0%
0%

5. Conclusions

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