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ABSTRACT: As a new biobased epoxy resin system, sites under the optimized conditions. The ESO–TA–MFC
epoxidized soybean oil (ESO) was cured with tannic acid composites showed the highest tan d peak temperature
(TA) under various conditions. When the curing conditions (61 C) and tensile strength (26.3 MPa) at an MFC content of
were optimized for the improvement of the thermal and me- 9 wt %. The tensile modulus of the composites increased
chanical properties, the most balanced properties were with increasing MFC content and reached 1.33 GPa at an
obtained when the system was cured at 210 C for 2 h at an MFC content of 11 wt %. Scanning electron microscopy ob-
epoxy/hydroxyl ratio of 1.0/1.4. The tensile strength and servation revealed that MFC was homogeneously distrib-
modulus and tan d peak temperature measured by dynamic uted in the matrix for the composite with an MFC content of
mechanical analysis for the ESO–TA cured under the opti- 9 wt %, whereas some aggregated MFC was observed in the
mized condition were 15.1 MPa, 458 MPa, and 58 C, respec- composite with 11 wt % MFC. V C 2010 Wiley Periodicals, Inc.
tively. Next, we prepared biocomposites of ESO, TA, and J Appl Polym Sci 120: 273–278, 2011
microfibrillated cellulose (MFC) with MFC contents from 5
to 11 wt % by mixing an ethanol solution of ESO and TA Key words: biofibers; nanocomposites; renewable
with MFC and subsequently drying and curing the compo- resources
TABLE I
Optimization of the Curing Temperature and Time for ESO–TA with an Epoxy/Hydroxyl Ratio of 1.0/1.0
Curing Curing Tan d peak Tensile strength Tensile modulus
temperature ( C) time (h) temperature ( C) (MPa) 6 r (MPa) 6 r
TA1.4–MF11) were also prepared in a similar man- tains a mixture of related compounds. Also, it is
ner to that used for ESO–TA1.4–MFC5. supposed that all of the three hydroxyl groups of
the pyrogallol (1,2,3-trihydroxybenzene) moiety of
TA are hard to react with the epoxy groups of ESO.
Measurements Therefore, the curing temperature, curing time, and
Fourier transform infrared (FTIR) spectra were epoxy/hydroxyl ratio of the ESO–TA systems were
recorded on a Shimadzu FTIR 8100 instrument optimized. The curing temperature and time were
(Kyoto, Japan) by the attenuated total reflectance changed over the range of 150–230 C and 1–5 h,
method. Thermomechanical analysis (TMA) was respectively. The epoxy/hydroxyl ratio was changed
conducted on a MAC Science (Yokohama, Tokyo, over the range from 1/0.6 to 1/1.4 on the basis of
Japan) TMA 2000S instrument at a heating rate of the oxirane oxygen content (6.7 wt %) of ESO and
10 C/min under a nitrogen atmosphere. The 5% the hydroxyl value (68 g/equiv) of TA, as calculated
weight loss temperature was measured on a Shi- from the structure shown in Figure 1. Because the
madzu TGA-50 thermogravimetric analyzer at a FTIR absorption peak at 840 cm1, characteristic of
heating rate of 20 C/min under a nitrogen atmos- the epoxy ring, which was observed for ESO, disap-
phere. Dynamic mechanical analysis (DMA) of the peared even for the cured material with an epoxy/
rectangular films (length ¼ 40 mm, width ¼ 5 mm, hydroxyl ratio of 1/0.6, we could not evaluate the
thickness ¼ 1.5 mm) was performed on a Rheolo- optimized ratio by means of FTIR spectroscopy. We
graph Solid (Toyo Seiki Co., Ltd., Tokyo, Japan) believe that some homopolymerization of ESO
with a chuck distance of 20 mm, a frequency of 1 occurred for the epoxy-rich mixture by a catalytic
Hz, and a heating rate of 2 C/min. Tensile testing of action of TA. Table I summarizes the tan d peak
the rectangular plate (length ¼ 40 mm, width ¼ 5 temperature corresponding to the glass-transition
mm, thickness ¼ 1.5 mm) was performed at 25 C temperature (Tg) measured by DMA and the tensile
with an Autograph AG-I (Shimadzu). The span strength and modulus for the ESO–TA with an ep-
length and testing speed were 25 and 10 mm, oxy/hydroxyl ratio of 1.0/1.0 cured at 150–230 C for
respectively. Five specimens were tested for each set 2 h or cured at 210 C for 1–5 h. When the curing
of samples, and the mean values and the standard time was 2 h, the maximal tan d peak temperature
deviation (r) were calculated. The morphology of (57 C), tensile strength (12.7 MPa), and tensile mod-
the composites was observed by field emission scan- ulus (409 MPa) were obtained at 210 C. When the
ning electron microscopy (FE–SEM) with a Hitachi curing temperature was 210 C, curing for 2 h
S-4700 machine (Hitachi High-Technologies Corp., showed the highest tan d peak temperature and ten-
Tokyo, Japan). All samples were fractured after sile strength and modulus. These results indicate
immersion in liquid nitrogen for about 30 min. The that the control of curing temperature and time was
fracture surfaces were sputter-coated with gold to very important for the biobased epoxy curing system
provide enhanced conductivity. containing aliphatic and sugar-based moieties with
relatively low heat resistance. Consequently, condi-
tions of 210 C and 2 h were selected for the curing
RESULTS AND DISCUSSION of ESO–TA. Table II summarizes the results of DMA
and tensile testing for the ESO–TA with an epoxy/
Optimization of the curing conditions of ESO–TA
hydroxyl ratio of 1.0/0.6–1.0/1.4 cured at 210 C for
The chemical formula for commercial TA is often 2 h. The tan d peak temperature measured by DMA
given as C76H52O46 (Fig. 1). However, in fact, it con- increased with decreasing epoxy/hydroxyl ratio
Figure 2 Tensile properties of ESO–TA1.4–MFC Figure 3 FE–SEM images of the fractured surface of
composites. ESO–TA1.4, ESO–TA1.4–MFC9, and ESO–TA1.4–MFC11.
TABLE III
Properties of ESO–TA1.4 and ESO–TA1.4–MFC with Various MFC Contents
CTE
(105 K1)
Sample 5 wt % loss Tan d peak Tg from
abbreviation temperature ( C) temperature ( C) TMA ( C) a1a a2b