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Akatsuka 2001
Akatsuka 2001
Akatsuka 2001
www.elsevier.nl/locate/polymer
Abstract
Inorganic ®llers are widely used for epoxy resins to improve mechanical and thermal properties. However, inorganic ®llers may
unexpectedly affect the curing reactions of such epoxy resins. In our present study, in¯uences of inorganic ®llers on the curing reactions
of phenol novolac epoxy resin (EPN) initiated with boron tri¯uoride ethylamine complex (BF3MEA) are detailed. The gel times of epoxy
resins containing alumina (Al2O3) ®llers were longer than those of corresponding un®lled epoxy resins, indicating that Al2O3 ®llers delayed
the curing reactions of epoxy resins. Mechanisms were proposed and in¯uences of aluminum hydroxide (Al(OH)3), silica (SiO2), and
aluminum ¯uoride (AlF3) ®llers were also described. q 2001 Elsevier Science Ltd. All rights reserved.
Keywords: Epoxy resin; Curing reaction; Inorganic ®ller
1. Introduction 2. Experimental
Fig. 1. Curing reaction scheme of epoxy resin initiated with boron tri¯uoride ethylamine complex.
2.3. Curing reactions and gel time measurement with the mixture of EPN, BF3MEA, and Al2O3-a ®ller into
the oil bath whose temperature had already be stabilized. At
Typically, a mixture of EPN (50 g) and BF3MEA (0.5 g) that time, the gel times of the mixtures were also deter-
was placed in a stainless steel beaker and heated to 1008C mined. For example, the curing reaction of the mixture of
while being stirred mechanically. The temperature was kept 100 weight parts of EPN and 1 weight part of BF3MEA
at 1008C, dried Al2O3-a ®ller (35 g, 15 vol.%) was added to containing 15 vol.% Al2O3-a ®ller at 1708C proceeded
the beaker slowly for 20 min. Then, the mixture was stirred rather slowly and the gel time was 21 min. In contrast, the
for another 20 min. It was poured into a glass test tube with a curing reaction of the un®lled epoxy resin system under
glass bar and cured in an oil bath attached to a gel timer, similar conditions proceeded very rapidly and the gel time
which make the glass bar turn round slowly and give the gel was 3.4 min, which is approximately 6 times faster than that
times as the times when the glass bar stop. In this paper, gel of the former epoxy resin system.
times were the average of two samples. When the initial weight ratio of BF3MEA with respect to
EPN was increased, the curing reactions of the epoxy resin
system proceeded more rapidly. As shown in Fig. 3, the gel
3. Results and discussion times of Al2O3-a ®lled and un®lled epoxy resin systems
were close to 4.5 and 2.5 min, respectively, at 1708C as
3.1. In¯uences of alumina ®llers on curing reactions of the initial weight ratio of BF3MEA increased. It was also
phenol novolac epoxy resin initiated with boron tri¯uoride observed that the presence of Al2O3-a ®ller delayed the
ethylamine complex curing reactions of the epoxy resin system. On the other
hand, when the initial weight ratio of BF3MEA with respect
Curing reactions of EPN initiated with boron tri¯uoride to EPN was decreased, the curing reactions of the epoxy
ethylamine complex (BF3MEA) containing an alumina
(Al2O3) ®ller were carried out by dipping the test tube ®lled Table 1
Shapes, average diameters and LOI values of alumina (Al2O3) ®llers
Fig. 4. Scheme of possible chain-transfer reaction of growing species with Al-OH groups remaining in the alumina ®ller.
As expected, the gel time was longer if the LOI value was 3.3. In¯uences of inorganic ®llers on curing reactions of
higher. The expected gel times of this system which give the phenol novolac epoxy resin initiated with boron tri¯uoride
curve in Fig. 7 were estimated by following assumption. ethylamine complex
From the result of Fig. 3, the shift amount of the curve to
the direction of higher BF3MEA content was approximately Inorganic ®llers besides alumina ®ller also delayed the
0.5 phr, when the 15 vol.% Al2O3-a ®ller (LOI: 0.215 %) curing reaction under similar conditions. The gel times of
was used. Assuming that the shift amount was in proportion EPN/BF3MEA (100/1, ratio of weight parts) system contain-
to the LOI value of the corresponding Al2O3 ®ller, the ing 15 vol.% crystalline silica (cryst-SiO2) ®ller and fused
expected gel time of the 15 vol.% Al2O3 (LOI: L%) ®lled silica (fused-SiO2) ®ller were 4.4 and 4.6 min, respectively,
system with 1 phr of BF3MEA was equal to the gel time of at 1708C. These were longer than that of the corresponding
the 15 vol.% Al2O3-a ®lled system with C phr of BF3MEA epoxy resin system, but close to the value of the shortest gel
given by following equation: time in the Al2O3 systems. The result indicated that the
chain-transfer reaction occurred quite slowly with the Si-
C 1 1 0:5{
0:215 2 L=0:215}
OH groups which generally remain in the SiO2 ®ller. The gel
All gel times estimated were very close to the curve in Fig. 7, time of EPN/BF3MEA (100/1, ratio of weight parts) system
which supported both proposed mechanisms.
Fig. 6. Gel times of epoxy resin mixtures of phenol novolac epoxy resin
Fig. 5. Gel times of epoxy resin mixtures of phenol novolac epoxy resin (EPN) and boron tri¯uoride ethylamine complex (BF3MEA) at 1708C.
(EPN) and boron tri¯uoride ethylamine complex (BF3MEA). Effects of Effects of aluminum hydroxide (Al(OH)3) ®ller (O: Al(OH)3 ®lled
reaction temperature (V: 1508C, B: 1708C). phr: weight parts per 100 system, B: un®lled system). phr: weight parts per 100 weight parts of
weight parts of EPN. EPN.
M. Akatsuka et al. / Polymer 42 (2001) 3003±3007 3007
4. Conclusions