Composites: Part A 82 (2016) 1–7

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Composites: Part A
journal homepage: www.elsevier.com/locate/compositesa

Soybean oil-based thermosets with N-vinyl-2-pyrrolidone

as crosslinking agent for hemp fiber composites
Wendi Liu a, Tingting Chen b, Tianshun Xie a, Renhui Qiu b,⇑
a
College of Material Engineering, Fujian Agriculture and Forestry University, Fuzhou 350002, PR China
b
College of Transportation and Civil Engineering, Fujian Agriculture and Forestry University, Fuzhou 350002, PR China

a r t i c l e i n f o a b s t r a c t

Article history: Soybean oil-based thermosets from acrylated epoxidized soybean oil (AESO) with a highly reactive vinyl
Received 8 July 2015 monomer, N-vinyl-2-pyrrolidone (NVP), as crosslinking agent to replace styrene (St) were formulated for
Received in revised form 23 November 2015 the fabrication of hemp fiber composites. The theoretical miscibility of NVP–AESO and St–AESO systems
Accepted 24 November 2015
were discussed based on the group contribution method. The AESO resin with 30 wt% NVP exhibited a
Available online 30 November 2015
slightly higher viscosity than the counterpart with St, while the maximum curing temperature of the for-
mer was considerably lower than that of the latter. The composites from 20 wt% NVP resin gained com-
Keywords:
parable mechanical properties and higher glass transition temperature (Tg) to the composites with 30 wt
A. Thermosetting resin
A. Polymer-matrix composites (PMCs)
% St. Further increase in NVP usage to 40 wt% resulted in the composites with higher tensile strength, ten-
B. Rheological properties sile modulus, flexural strength, flexural modulus, storage modulus, and Tg of 29.6%, 22.4%, 22.5%, 20.6%,
B. Thermomechanical 21.6%, and 47.2%, respectively, when compared to those of the St-based composites.
Ó 2015 Elsevier Ltd. All rights reserved.

1. Introduction been considered as a volatile organic compound (VOC) and a haz-

In recent years, with the development of transgenic technology
in soybean breeding, the global production of soybean oil has con-
tinuously increased and reached about 45 million tons in 2013,
which has greatly driven the utilization of soybean oil in industrial
fields such as coatings and printing inks, adhesives, lubricants and
plastics [1]. Soybean oil, consisting of esters of glycerol with three
long-chain fatty acids, also has been extensively utilized for the
production of bio-based polymers through various chemical mod-
ification methods [2,3]. Among various modified soybean oil
derivatives, acrylated epoxidized soybean oil (AESO), synthesized
from the reaction of epoxidized soybean oil with acrylic acid, has
been commercially available and widely employed in developing
thermosetting resins for fiber-reinforced composites [4–6]. How-
ever, AESO is highly viscous at room temperature and hence a reac-
tive diluent (RD) is required for forming a mixture with low
viscosity for wetting reinforcing fibers. What’s more, the C@C
bonds in AESO have low reactivity and cannot freely move around
for crosslinking with each other due to the molecule mobility con-
straints. Styrene (St) is a traditionally preferred RD for vinyl ester
and unsaturated polyester resins and can crosslink efficiently with
AESO for producing AESO-based thermosets [7]. However, St has
⇑ Corresponding author. Tel.: +86 591 83789337; fax: +86 591 83715175.
E-mail address: renhuiqiu@fafu.edu.cn (R. Qiu).
ardous air pollutant (HAP). Other analogous vinyl monomers such
as methyl methacrylate, vinyl toluene and divinylbenzene, also
have been employed for maleinated AESO resins [8]. But the main
drawback is their higher costs, petrochemical-base, and potential
toxicity. The interest in developing bio-based RDs from renewable
feedstocks including vegetable oil, carbohydrate and lignin has
been increasing. The potential of using (meth)acrylated fatty acids
as RDs for various triglyceride-based thermosets has been evalu-
ated because of their availability, degradability, low cost, and low
HAP or VOC emission [9,10]. But the use of these vegetable oil-
based monomers still has the intrinsic problems including high vis-
cosity and low crosslinking degree, leading to the inferior process-
ability and thermal–mechanical properties of the resulting resins.
The cellulose-derived dibutyl itaconate and lignin-derived ethyl
cinnamate were copolymerized with AESO, respectively; however,
the resulting resins exhibited lower storage modulus and glass
transition temperature than the pure AESO resin [11]. Therefore,
further development of environmentally friendly RD for AESO
resins in an effort to reduce HAP or VOC emissions while maintain-
ing the processability and performance of the resulting composite
systems is highly desired.
On the other hand, the substitution of synthetic fibers with nat-
ural fibers for producing fiber-reinforced vegetable oil-based poly-
mer composites can further increase the bio-based content of the
ending products. Several types of natural fibers have been widely

http://dx.doi.org/10.1016/j.compositesa.2015.11.035
1359-835X/Ó 2015 Elsevier Ltd. All rights reserved.
2 W. Liu et al. / Composites: Part A 82 (2016) 1–7
utilized as reinforcements in St-based triglyceride composites,
such as hemp, jute, flax, and bamboo [12–15]. However, the major
scientific challenge for the composites is the weak interfacial adhe-
sion between fibers and matrices. The use of non-polar St as RD in
vegetable oil-based resins brings high hydrophobicity for the
matrices, thus generating a poor interface bonding with the hydro-
philic natural fibers. Traditional fiber surface modifications such as
acetylation and treatments with silane or peroxide have been uti-
lized to overcome this obstacle [16], but few efforts have been
attempted on the exploitation of novel St-free vegetable oil-
based resins which have intrinsically good compatibility with nat-
ural fibers.
In this work, a highly reactive vinyl monomer, N-vinyl-2-
pyrrolidone (NVP) was employed as a RD for formulating novel
St-free AESO resins for natural fiber composite application, with
the particular attention on the miscibility mechanism and process-
ability (rheological and curing behavior) of the new resins as well
as the evaluation of the resin systems for composite production
with hemp fibers in terms of the static and dynamic mechanical
properties of the resulting hemp/AESO composites. In practice,
NVP has been widely used as crosslinking agent in UV curing inks,
adhesives and coatings thanks to its inherent high reactivity, low
toxicity and chemical stability [17,18]. It was reported that NVP
is a good hydrogen bonding acceptor and has a high binding affin-
ity with several small and large molecules [19]. Therefore, the
abundant hydroxyl groups on the fibers are expected to form
hydrogen bonding or other polar–polar interactions with the
NVP-based resins, thus fabricating the hemp/AESO composites
with an improved fiber/matrix interface adhesion in comparison
with the counterparts derived from St-based resins.
2. Experimental
2.1. Materials
AESO containing 4000 ppm monomethyl ether hydroquinone as
inhibitor was purchased from Sigma–Aldrich. St (P99%, Sino-
pharm Chemical Reagent, China) and NVP (99%, stabled with
sodium hydroxide, Aladdin, China) were used as the RDs for AESO
resins. The free-radical initiator, tert-butyl peroxybenzoate (TBPB,
98%), was purchased from Sigma–Aldrich. Hemp fibers with aver-
age length 3.86 cm and average fiber fineness 7.69 dtex were pur-
chased from Sanxing Hemp Industry (China) and used as
reinforcements for AESO resins. All the chemicals were used as
received without further purification.
2.2. Preparation of AESO resins
The AESO were mixed with NVP at weight ratios of 80:20,
70:30, and 60:40 (AESO:NVP) in a beaker at 70 °C by using a mag-
netic stirrer at 100 rpm initially and the stir rotation speed was
gradually increased to 500 rpm. The stirring duration lasted for
10 min, and then the resulting mixture was cooled to room tem-
perature (r.t.). Then 2 wt% TBPB (based on the total mixture) was
added to the mixture that was further stirred for 2 min to form
the final resins. The obtained resins containing 20, 30, and 40 wt
% NVP were designed as NVP-20, NVP-30, and NVP-40, respec-
tively. Using the similar procedure, the resin systems using 0 or
30 wt% St as RDs were prepared, denoted as pure AESO or St-30,
and used as controls.
2.3. Prediction of miscibility of AESO with St and NVP
The Hansen solubility parameter theory defined that the solu-
bility parameter (d) of a substance is contributed by three types
of components from dispersion forces (dd), polar forces (dp) and
hydrogen bonding (dh), and thus expressed as Eq. (1) [20]:
d2 ¼ d2d þ d2p þ d2h ð1Þ
Hoftyzer and Van Krevelen proposed that the solubility param-
eters can be predicted (Eqs. (2)–(4)) according to the group contri-
bution method [20]:
X .
dd ¼ Fdi V ð2Þ
X 1=2 
dp ¼ F2pi V ð3Þ
X . 1=2
dh ¼ Ehi V ð4Þ
where, Fdi and Fpi are the molar attraction constant per structural
group contributed by dispersion and polar components, respec-
tively; Ehi is the hydrogen bonding energy per structural group; V
is the molar volume of the substance.
The miscibility between AESO with RD can be evaluated
through their solubility parameters since close solubility parame-
ters between resin and RD show high possibility of miscibility,
i.e., AESO and RD are more soluble in one another when their d val-
ues are close, whereas they are less similar and are immiscible
mutually [21].
2.4. Characterization of AESO resins
Differential scanning calorimetry (DSC) measurements were
performed on a STA 449 F3 Jupiter Simultaneous Thermal Analyzer
(NETZSCH, Germany). The resin sample (5–10 mg) was placed in a
standard porcelain crucible with a lid for test. The scans were car-
ried out under a nitrogen (30 mL/min) protection with a heating
rate of 10 °C/min from 25 to 250 °C. The total heat of reaction
(DH) for resin curing process was obtained from the integrated
area of the exothermic peak.
Rheological behavior was evaluated on a HAAKE MARS III rota-
tional rheometer (Thermo Electron, USA) using a PP35Ti parallel
plate (gap: 0.105 mm) at a shear rate of 10 c/s. The temperature
ranged from 25 to 100 °C at a heating rate of 10 °C/min. The tem-
perature dependence of sample’ viscosity was modeled with the
Arrhenius equation [9]:
g ¼ g0 exp ðEg =RTÞ ð5Þ
where g is the viscosity (mPas), g0 is the prefactor (mPas), Eg is the
activation energy for the viscous flow (kJ/mol), R is the ideal gas
constant (8.314 J/(Kmol)), and T is the absolute temperature (K).
2.5. Preparation of hemp/AESO composites
Hemp fibers were carded for forming the randomly orientated
fiber-mats with the dimension of 20  20  0.5 cm3 and then
oven-dried at 103 °C for 24 h before use. Five fiber-mats (75 g)
were separately coated with the prepared AESO resins (75 g) by
hand, and afterward the resin-mixed fiber-mats were stacked
and pressed in the chamber (20  20  0.3 cm3) of a mold at r.t.
under a pressure of 6 MPa for 5 min, making the resins wet the
fiber-mats well. Then, the hot-pressing continued at 70 °C for
5 min and then at 160 °C for 30 min under the unchanged pressure.
Finally, the mold was cooled to r.t. and then the formed composite
board was removed from the mold.
 W. Liu et al. / Composites: Part A 82 (2016) 1–7
2.6. Evaluation of hemp/AESO composites
Dumbbell specimens with a gage length of 50 mm and a narrow
section width of 10 mm were used for the tensile tests based on
ASTM D 3039-08. Rectangular specimens (80  10 mm2) were
used for the evaluations of flexural properties and impact strength
according to ASTM D 790-10 and ASTM D 6110-10, respectively.
The tensile and flexural measurements were carried out with a
CMT6104 microcomputer controlled electronic universal testing
machine (MTS Systems, USA) at a crosshead motion rate of
10 mm/min. Eight replicate measurements of the tensile and flex-
ural tests were taken. The unnotched impact strength test was con-
ducted on a ZBC-25B Charpy impact tester (MTS Systems, USA).
Five replicates were measured for the test.
Dynamic mechanical analysis (DMA) was conducted on a DMA
242 (NETZSCH, Germany) using single cantilever bending mode at
a frequency of 1 Hz. Rectangular samples (55  10 mm2) were
tested from 30 to 180 °C at a heating rate of 5 °C/min.
For evaluating the interfacial adhesion between hemp fibers
with different AESO resins, the tensile-fractured surfaces of com-
posites AESO, St-30 and NVP-30 were analyzed with a JOEL JSM-
7500F scanning electron microscope (SEM) (JOEL, Japan). The spec-
imens were coated with elemental gold film and then tested at an
accelerating voltage of 5.0 kV.
3. Results and discussion
3.1. Theoretical prediction of miscibility of AESO with RD
As shown in Fig. 1, the representative structures of AESO, St and
NVP were adopted for predicting the miscibility between AESO
with different RDs based on the group contribution method. The
predicted solubility parameters of AESO and RDs are presented in
Table 1. Three substances have an approximate dd value being a
range from 16 to 18 (MJ/m3)1/2, while their dp and dh values are sig-
nificantly different as a result of the different molecular groups
contributing to the different polar forces and hydrogen bonds.
The dp and dh values of St are 0.96 and 0 (MJ/m3)1/2, respectively,
confirming that St is a typical non-polar solvent. In contrast, NVP
has higher dp and dh values and hence the highest dtotal value when
compared to others due to the presence of C@O group and N atom
Fig. 1. Representative structures of St, NVP and AESO. (For interpretation of the
references to colour in this figure legend, the reader is referred to the web version of
this article.)
3
Table 1
Predicted solubility parameters of St, NVP and AESO.
Monomers dd [(MJ/m3)1/2] dp [(MJ/m3)1/2] dh [(MJ/m3)1/2] dtotal [(MJ/m3)1/2]
St 17.66 0.96 0 17.68
NVP 16.10 10.39 8.09 20.80
AESO 16.26 1.37 6.67 17.63
in NVP molecule. The two types of solubility parameter compo-
nents from polar forces and hydrogen bonds for AESO are in
between St and NVP since AESO is a relatively polar matrix because
of its ester, epoxy and hydroxyl groups. Both dtotal values for St and
NVP are close to that of AESO (Table 1), indicating that the two RDs
are miscible with AESO well. But St seems to be a better solvent for
AESO as the dtotal value of St is almost equal to that of AESO. This
was expected because the polar groups including C@O group and
N atom make NVP far away from AESO in solubility characteristic.
3.2. Processability of AESO resins
The major concern of developing vegetable oil-based ther-
mosetting resins for composites is processability. The changes in
the viscosity with temperature of AESO resins with or without
RD and their fitting results using Arrhenius equation are shown
in Fig. 2, indicating that the viscosity of all samples decreased
exponentially with the increase of temperature. The pure AESO
resin obtained a high viscosity of 5417 mPas at r.t. (Table 2) and
thus it is difficult for use in composite production directly, espe-
cially in liquid molding technique, where the preferable viscosity
of resins should range from 200 to 2000 mPas [8]. However, after
incorporation of RD, either St or NVP, the resulting resins achieved
a great decreased viscosity, being in the range of 40750 mPas at
25 °C (Table 2). Furthermore, the addition of AESO with 20 or 30 wt
% NVP resulted in the resins having higher viscosity than the St-30
blend, while increasing the NVP usage to 40 wt% further reduced
the viscosity of resin, reaching a value that was slightly lower than
that of the 30 wt% St counterpart. It was expected that the blend of
AESO with St showed lower viscosity than the one from NVP when
the RD usage was maintained in 30 wt% because of the higher sol-
ubility of AESO in St than that in NVP. That is, St can dissolve effec-
tively AESO and reduce the entanglement of AESO molecular
chains, making the chains move in the solvent more freely so as
to reduce the viscosity of resins.
Fig. 2. Viscosities of AESO resins with different RDs. Notes: Symbols represent
experimental data, and lines indicate the fitted curves with Arrhenius equation. (For
interpretation of the references to colour in this figure legend, the reader is referred
to the web version of this article.)
4 W. Liu et al. / Composites: Part A 82 (2016) 1–7

Table 2
Calculated Arrhenius parameters of AESO resins with different RDs.

Resins g (mPas) (25 °C) g0 (mPas) Eg (kJ/mol)

5
Pure AESO 5417.15 ± 193.00 2.12  10 48.31
St-30 55.73 ± 3.28 2.47  101 13.37
NVP-20 743.75 ± 66.76 4.84  104 35.52
NVP-30 170.88 ± 5.75 4.45  103 26.09
NVP-40 39.76 ± 2.90 6.07  102 15.93

As shown in Table 2, the activation energy (Eg), representing the

required energy for resins flowing with the increased temperature,
showed the highest value for pure AESO resin due to its long
molecular chain and high molecular weight. It was obvious that
the addition of RD into AESO increased the flowability and thus
reduced the Eg values of the resins. However, NVP showed lower
ability than St to reduce the Eg value when comparing St-30 to
NVP-30 resins. This is attributed to the polar groups of NVP that
might form hydrogen bonding or other polar–polar interactions
with those of AESO, which constraints the mobility of the resin sys-
tem and thus increases the viscosity and Eg value of the resins [22].
But this problem can be tackled by further increasing the NVP
usage since both viscosity and Eg value decreased with the increase
in NVP usage. The more NVP usage means the less AESO content in
the blends, which would result in the lower viscosity and activa-
tion energy because AESO has a significant higher molecular
weight than NVP.

3.3. Polymerization mechanism of AESO resins

The typical DSC curves of AESO resins with different RDs are
shown in Fig. 3, and their characteristic curing temperatures and
total heat of reaction are summarized in Table 3. The curing reac-
tion of pure AESO resin presented a distinct exothermic peak at
126.5 °C, corresponding to the free-radical crosslinking of active
double bonds of AESO molecules, and an unapparent peak at
169.0 °C, probably due to the homopolymerization of unreacted
acrylic acid monomers. The introduction of RD into AESO resins
essentially increased the first peak intensity, indicating that the
RD participates in the free-radical crosslinking of AESO resins and
accelerates the polymerization rate of the resulting resins. The
AESO resin blended with 30 wt% St had a much lower onset curing
temperature (Tonset) than the pure AESO resin and the counterparts

Fig. 4. Mechanical properties of hemp fiber composites with different AESO resins.
(a) Tensile properties; (b) Flexural properties; (c) Impact strength. Notes: Data were
analyzed with one-way ANOVA based on a 95% confidence interval; the groups do
not significantly differ from one another when same letter is presented at the top of
the columns.

Table 3
Characteristic curing temperatures and total heat of reaction of AESO resins with
different RDs.

Resins Tonset (°C) Tmax1 (°C) Tmax2 (°C) Tend (°C) DH (J/g)
Pure AESO 103.4 126.5 169.0 192.8 212.0
St-30 97.1 127.9 171.3 195.6 309.1
NVP-20 104.8 114.3 159.0 195.3 281.9
NVP-30 104.3 111.7 147.2 194.1 314.0
NVP-40 104.1 110.0 134.8 193.2 335.3

with NVP. This is mainly attributed to the resonance effect of ben-

Fig. 3. DSC curves of AESO resins with different RDs. (For interpretation of the
references to colour in this figure legend, the reader is referred to the web version of
this article.)
zene substituent which increases electronic flowability and induces
polarization of St monomers, thus accelerating the generation of St
radicals [23]. However, the substituent in improving free-radical
reactivity is the opposite in improving monomer reactivity [24].
 W. Liu et al. / Composites: Part A 82 (2016) 1–7 5

The benzene substituent in St is effective in stabilizing the radicals
due to the loosely held p-electrons that are available for resonance
stabilization, hence reducing the reactivity of St radicals. Therefore,
St-30 resin showed slightly higher maximum curing temperature
(Tmax1 and Tmax2) and end curing temperature (Tend) than the pure
AESO resin. In contrast, the substituent in NVP monomer is nitrogen
which is ineffective in stabilizing the radicals since only the non-
bonding electron on nitrogen is available for interaction with a rad-
ical, resulting in the high reactivity of NVP radicals [24]. This is
responsible for the lower Tmax1 and Tmax2 of NVP–AESO resins than
those of St–AESO resin. Also, the maximum curing temperatures of
NVP–AESO resins decreased with the increase of NVP usage, rang-
ing from 114.3 to 110.0 °C and 159.0 to 134.8 °C for Tmax1 and Tmax2,
respectively, when the NVP usage increased from 20 to 40 wt%
(Table 3), indicating that the higher amount of NVP resulted in
the better processability due to the high reactivity of NVP.
The DH value reflects the required activation energy of resin
curing, representing the reaction degree of resin to some extent.
The pure AESO resin obtained the lowest DH value, indicative of
its insufficient curing reaction due to the long molecular structures
and low reactivity of acrylate groups of AESO molecules. However,
the addition of RD into AESO resins increases the conversion rate of
double bonds of AESO through copolymerizing with highly reactive
RD monomer, giving rise to the crosslinking density and DH values
of the resins. Furthermore, the DH values of NVP–AESO resins
showed an increased tendency with the amount of NVP, indicating
higher NVP usage resulting in higher reaction degree (i.e. curing
degree).
Nevertheless, the impact strength of the composites was reduced
after the use of St or NVP as RD for AESO resins (Fig. 4c). For the pure
AESO composite, it might contain part of flexible AESO molecular
chains in the composite, which could function as a plasticizer to help
disperse instantaneous loading and effectively prevent stress con-
centration when the composites are loaded, thus showing superior
impact strength [27]. But this effect was eliminated after the incor-
poration of RD into the resins since RD could provide high crosslink-
ing degree for the resins and thus high rigidity and modulus for the
resulting composites, generally giving rise to the brittleness of the
composites. However, the increase in NVP usage did not change
the impact strength of the composites significantly, probably due
to the fact that the reduction in toughness of AESO matrices is com-
pensated by the reinforcements, i.e. hemp fibers, since natural fiber
plays a crucial role in improving the toughness of polymer matrices.
3.4.2. Thermomechanical properties
The temperature dependence of storage modulus (E0 ) and
damping parameter (tan d) of composites are presented in Fig. 5.
It is observed that the E’s of all composites decreased sharply along
with the increase of temperature (Fig. 5a), showing the increased
molecular mobility of polymer chain with the increased tempera-
ture. All the composites of AESO resins with RD had much higher
initial E’s at r.t. than the pure AESO composite due to the higher
crosslinking density. The initial E0 of St-30 composite was higher
than that of NVP-20 composite, while the initial E0 of NVP–AESO

3.4. Evaluation of AESO resins for composites

3.4.1. Mechanical properties

For evaluating the influence of the novel RD, i.e. NVP, for AESO
resins on the properties of natural fiber composites, the composites
from pure AESO resin and its blends with 30 wt% St and increasing
content of NVP (20 to 40 wt%) were made with hemp fibers. Fig. 4
indicates the composites of AESO resins added with RD had much
higher tensile and flexural properties than that of pure AESO resin.
The incorporation of 20 wt% NVP into AESO resin increased greatly
the tensile strength, tensile modulus, flexural strength, and flexural
modulus of the composites by 22.62%, 23.08%, 47.27%, and 42.75%,
respectively, compared to the pure AESO composite; and the com-
posite of NVP-20 also obtained statistically comparable tensile and
flexural properties with those of traditional St-based (30 wt% St)
AESO resin. This confirms that NVP could be an effective St alterna-
tive for developing St-free AESO resins in terms of the mechanical
properties of their composites with hemp fibers, which might be
explained by: (1) NVP molecules with highly reactive N-vinyl
groups would accelerate the free-radical polymerization of NVP–
AESO system such that the cured resins with a high crosslinking
density generate, leading to the excellent mechanical properties
of the resulting composites; (2) A stronger fiber/matrix interface
between hemp fibers and NVP-based resins might be obtained
through the formation of hydrogen bonding or polar–polar interac-
tions between the hydroxyl groups of fibers and the polar groups
(particularly the C@O groups and N-groups from NVP) of the resins
[25], which will be further discussed in Section 3.4.3. In addition,
the mechanical properties of the composites can be further tailored
by adjusting the usage of NVP for AESO resins. Increase in the NVP
content to 40 wt% resulted in the NVP-40 composite having the
tensile strength, tensile modulus, flexural strength, and flexural
modulus of 82, 2612, 100, and 6717 MPa, respectively. These are
even as high as those of the hemp fibers reinforced St-based unsat-
urated polyester composite (tensile strength 75 MPa, flexural Fig. 5. DMA curves of hemp fiber composites with different AESO resins. (a) Storage
strength 110 MPa, and flexural modulus 6400 MPa), as reported modulus; (b) Damping parameter. (For interpretation of the references to colour in
in our previous study [26]. this figure legend, the reader is referred to the web version of this article.)
6 W. Liu et al. / Composites: Part A 82 (2016) 1–7
Fig. 6. SEM images of tensile-fractured surfaces of hemp/AESO composites. (a) Pure AESO composite; (b) St-30 composite; (c) NVP-30 composite.
composites increased as the increase of NVP usage, and hence both
NVP-30 and NVP-40 composites exhibited higher initial E0 than St-
30 composite. The aromatic planar ring structure of St explains the
great E0 of St-based composites, yet the high reactivity of NVP and
strong interface bonding between fibers and resins are responsible
for the superior modulus of NVP-based composites.
Glass transition temperature (Tg) was determined by the peak
position of tan d curve of the composites (Fig. 5b). All the tan d
curves showed a single peak, i.e. glass transition, indicating that
there is no phase separation in these composites. The Tg of neat
AESO composite cannot be detected by DMA measurement run-
ning from 30 to 180 °C, showing that its Tg was lower than 30 °C
due to the low crosslinking density of AESO. It was reported that
the Tg of pure AESO resin was approximately 35 °C, depending on
the acrylation level of epoxidized soybean oil, which was higher
than its composite with hemp fibers in this study, probably as a
result of the incorporation of fiber reinforcements further reducing
its crosslinking degree [28]. The Tg of NVP–AESO composites
increased greatly as a function of NVP content, i.e., increase in
NVP content from 20 to 40 wt% increased the Tg from 60.97 to
77.05 °C, which were much higher than that of St-30 composite
(52.34 °C). This further implies that NVP was a good RD for AESO
resins in terms of the thermal stability of the hemp fiber compos-
ites. Furthermore, the peak intensity and area of the tan d curve
indicate the damping behavior of composite under vibrating condi-
tions [29]. Although the peak intensity of tan d of St-30 composite
was comparable with that of NVP-40 composite, the peak area
under the tan d curve was higher for all NVP–AESO composites
due to the broadening feature, confirming the better damping abil-
ity of NVP-based composites. The broader peak also shows the
wider distribution of chain types and molecular weights, probably
due to the high reactivity of NVP radicals leading to the enhanced
probability of radical initiation, propagation and termination reac-
tion and hence generating the different regions with different
degrees of crosslinking.
3.4.3. Interfacial adhesion
For the SEM image of fractured surfaces of neat AESO compos-
ite, it is apparent that the fibers are mostly fractured at the fiber
root and some indistinct fiber/matrix interfaces are observed, indi-
cating a good interfacial adhesion between fibers and matrices
(Fig. 6a). This is probably due to the polar groups of AESO mole-
cules, especially the hydroxyl groups, which may form hydrogen
bonding with the hydroxyl groups of hemp fibers. But the integrity
of AESO matrix is disturbed and the scalelike matrices are torn
apart with the breaking of fibers (Fig. 6a). These suggest that the
failure of the composites is partly plastic-deformed as a result of
the toughness effect of uncured AESO molecules, as discussed in
the section for the improvement of impact strength of composites.
After the addition of non-polar St as a RD, however, the obtained
St–AESO resin is more hydrophobic and hence incompatible with
the hydrophilic hemp fibers when compared to the pure AESO
resin. This can be evidenced by the fact that large amounts of deep
and smooth grooves resulted from the pull-out of fibers are
observed in the SEM image of St–AESO composite (Fig. 6b). In con-
trast, regarding NVP–AESO composite, the fiber/matrix interface is
indistinct, the fractured surface is fairly flat, and most of fibers are
fractured at the fiber root (Fig. 6c), indicative of a superior interface
adhesion. This interface seems to be stronger than that of pure
AESO composite since almost no fibers are pulled out in the
NVP–AESO composite, which may be due to the highly polar NVP
molecules giving rise to the polarity of the resulting resins and thus
making the resins more compatible with hemp fibers. Further-
more, in contrast with the pure AESO composite, NVP–AESO com-
posite shows a relatively integrated matrix, indicating that the
cracks in the composite might propagate in a planar manner due
 W. Liu et al. / Composites: Part A 82 (2016) 1–7
to the high stiffness and modulus resulted from high crosslinking
density of NVP-based resin.
4. Conclusion
The St-free soybean oil-based thermosetting resins were suc-
cessfully formulated by using NVP as crosslinking agent for use in
hemp fibers reinforced composites. It is concluded that the
NVP–AESO resins can be an available alternatives to the traditional
St-based AESO resin because, (1) the new resins have comparable
rheological behavior and lower curing temperature and reaction
heat compared to the St–AESO resin; (2) the hemp fiber composites
from NVP-based resins obtained superior static and dynamic
mechanical properties due to the high reactivity of NVP monomers
and the improvement of interfacial adhesion between fibers and
NVP-based matrices.
Acknowledgments
This research was supported by the funding from Fujian Agricul-
ture and Forestry University (Grant No. 1122YB019), the National
Natural Science Foundation of China (Grant Nos. 31070495 and
31250007), the Department of Science and Technology, Fujian Pro-
vince, China (Grant No. 2013H6005), and the State Administration
of Forestry, China (Grant No. 2014-4-41).
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