Composites Part B 171 (2019) 87–95

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Composites Part B
journal homepage: www.elsevier.com/locate/compositesb

Properties of natural fiber-reinforced biobased thermoset biocomposites:

Effects of fiber type and resin composition
Wendi Liu a, Tingting Chen a, Ming-en Fei a, Renhui Qiu a, *, Demei Yu a, Tengfei Fu a,
Jianhui Qiu b, **
a
College of Transportation and Civil Engineering, Fujian Agriculture and Forestry University, Fuzhou, 350108, PR China
b
Department of Mechanical Engineering, Faculty of Systems Science and Technology, Akita Prefectural University, Akita, 015-0055, Japan

A R T I C L E I N F O A B S T R A C T

Keywords: Four biobased thermosets were used as matrices for manufacturing natural fiber-reinforced biocomposites with
Polymer-matrix composites (PMCs) high performance and biobased contents. The thermosets included acrylated epoxidized soybean oil (AESO),
Thermosetting resin AESO with methacrylated isosorbide (MI) as a comonomer (MI-AESO), methacrylated AESO with MI (MI-
Fibre/matrix bond
MAESO), and MI resins. Bamboo fibers (BFs) and hemp fibers (HFs) were chosen as representatives for natural
Mechanical properties
fibers in the biocomposites. The synergistic effects of fiber type and resin composition on the obtained com­
posites were revealed through analyses of characteristics of the fibers and the resins as well as measurements of
densities, flexural properties, dynamic mechanical properties, and water absorption of the composites. Results
indicated that resin composition, chemical structure, and crosslinking density of the matrices were closely
associated with the performance of the biobased thermosets and hence the resulting biocomposites. The HF-
reinforced composites achieved much superior flexural strengths, flexural moduli, and water resistance than
the BF-reinforced composites.

1. Introduction chemical composition, and mechanical strength of the fibers and hence
its reinforcing capacity on polymer matrices [10,11]. Agave fibers from
Recently, there has been a remarkable interest in developing high- different agave variety, age of the leaf, fiber position, and extraction
performance biocomposites from renewable materials for structural method were optimized for preparing high-performance biocomposites
application [1–5]. Biocomposite includes a fiber-reinforced polymer by using epoxy and poly(lactic acid) (PLA) as matrices [12]. Four
composite incorporating natural fiber (NF) as reinforcement. The common NFs from softwood, abaca, jute, and kenaf were comparatively
properties of this kind biocomposites strongly depend on the charac­ used as reinforcements for polypropylene (PP) to give different im­
teristics of NFs and polymer matrices as well as their interfacial adhe­ provements in the strength of the resulting composites [13]. Various
sion. To achieve high content of renewable resources, biobased wood fibers including wood flours, chemical pulps, and thermo­
polymers derived from natural materials including vegetable oils and mechanical pulps showed different reinforcing efficiency on PLA and PP
carbohydrates have been utilized as matrices for the biocomposites composites [14]. Similar studies also have been done on thermosetting
[6–8]. However, both NFs and biobased resins have their respective matrices including unsaturated polyester (UPE) and vinyl ester [15–18].
challenges that need to be addressed. The critical issue for developing biocomposites is the weak fiber/matrix
NFs can be extracted from the stems, leaves, or seeds of various interfacial bonding originated from the hydrophilic fibers in contrast
plants via mechanical, chemical, or their combined methods [9]. NFs with the hydrophobic matrices, which can be alleviated by surface
possess many attractive merits such as high specific strength and chemical modification for the fibers [19,20]. The reaction degree of the
modulus, abundance, biodegradability, and low cost. The quality of NFs fibers with modifiers is significantly influenced by the fiber character­
is closely related to several factors including plant species, harvesting istics that regulate the accessibility of the modifiers. In our previous
stage, and extraction method, which determine the morphology, work, four commercial bamboo fibers (BFs), i.e., bamboo particles,

* Corresponding author.
** Corresponding author.
E-mail addresses: [email protected] (R. Qiu), [email protected] (J. Qiu).

https://doi.org/10.1016/j.compositesb.2019.04.048
Received 28 November 2018; Received in revised form 15 March 2019; Accepted 29 April 2019
Available online 30 April 2019
1359-8368/© 2019 Elsevier Ltd. All rights reserved.
W. Liu et al. Composites Part B 171 (2019) 87–95

mechanical pulps, chemical pulps, and original bamboo fibers, were (Fig. 1) [47]. Results revealed that these resins had high renewable
treated with N-methylol acrylamide, respectively, to impart the BFs contents, superior processability and mechanical properties, and hence
surface with C¼C bonds for crosslinking with UPE resins [21]. It was demonstrated great potential for use in fiber-reinforced composites.
found that the improvements in the mechanical properties of the Therefore, in this study, two high-strength NFs with different origins, i.
BF/UPE composites were dependent on the different chemical reactivity e., hemp fibers (HFs) and bamboo fibers (BFs), were incorporated into
of the four BFs with NMA. However, few work has been done on these biobased thermosets to fabricate biocomposites with performance
comparing the reinforcing effects of different NFs on the biocomposites competing those of petroleum-based counterparts. Both bamboo and
using biobased polymers as matrices. hemp are fast-growing plants, and the generated BFs and HFs have
Concerning polymer matrices from natural feedstocks, vegetable oils particularly high specific strength and modulus compared with other
such as soybean oil, castor oil, palm oil, linseed oil, and sunflower oil NFs [48,49]. The densities, flexural properties, dynamic mechanical
have been intensively employed in formulating thermosets including properties, and water absorption of the resulting NF-reinforced biobased
epoxy, polyurethane, and UPE due to their good availability and high thermoset biocomposites were comparatively studied to correlate the
degree of functionalization possibility [22–27]. The main challenges for properties of the biocomposites with characteristics of NFs and resin
using these thermosets in fiber-reinforced composites are the high vis­ composition of matrices.
cosity and low crosslinking density derived from the three long-chain
fatty acids and low reactivity of triglycerides. Therefore, curing agents 2. Experimental
with a low molecular weight and stiff structure, such as anhydrides [28,
29], isocyanates [30,31], and styrene [32,33], are necessary for the 2.1. Materials
resins, but most of which are toxic and petroleum-based. Among various
vegetable oil products, acrylated epoxidized soybean oil (AESO) has HFs (Cannabis sativa L.) were purchased from Sanxing Hemp Industry
been commercially available and utilized in fiber-reinforced composites (Anhui, China). BFs extracted from green bamboo (Dendrocalamopsis
[34,35]. The epoxidation and acrylation of soybean oil generate the oldhami Munro) were provided by Fujian HBS Chemical Technology
AESO with reactive double (C¼C) bonds; hence the AESO can (Fujian, China). AESO (inhibitor: 3500–4500 ppm monomethyl ether
self-polymerize and co-polymerize with other monomers to form ther­ hydroquinone), methacrylic anhydride (MAA, 94%, inhibitor: 2000 ppm
mosetting resins. The use of comonomers such as styrene could signifi­ topanol A), 4-(dimethylamino)pyridine (DMAP, 99%), and tert-butyl
cantly enhance the mechanical properties and processability of the peroxybenzoate (TBPB, 98%) were purchased from Sigma-Aldrich
AESO resins, which motivated the development of biocomposites from (Shanghai, China). Isosorbide (98%) was purchased from Thermo
styrene-AESO resin and NFs [36–38]. Petroleum-based monomers Fisher Scientific (Shanghai, China). All the chemicals were used without
including N-vinyl-2-pyrrolidone, isophorone diisocyanate, and bifunc­ further purification.
tional isocyanates were incorporated into hemp fibers (HFs)-reinforced
AESO composites to improve their crosslinking degree and hence me­ 2.2. Formulation of biobased thermosets
chanical properties [39–41]. However, they would reduce the sustain­
ability of the obtained biocomposites. Biobased reactive diluents from Four kinds of biobased resins were formulated for composite prep­
natural materials including fatty acids, carbohydrates, and lignin were aration as our previous work [47]. As given in Fig. 1, the synthesis
synthesized as styrene replacements for the formation of environmen­ processes were briefly described as follows.
tally friendly AESO resins with high biobased content [42–45]. For
instance, a lignin-derived monomer, i.e., methacrylated eugenol (ME), (1) AESO: Pure AESO without reactive diluents was used for
was synthesized for co-polymerizing with maleinated AESO; the results comparison.
showed that the mechanical properties and glass transition temperatures (2) MI-AESO: Solid isosorbide and DMAP were suspended in MAA in
of the copolymers increased with the increase of ME content [46]. a round bottom flask. The molar ratios of isosorbide to DMAP and
Previously, a rigid monomer, i.e., methacrylated isosorbide (MI), MAA to isosorbide were 1:0.05 and 3:1, respectively. The reac­
was formulated from isosorbide and methacrylic anhydride (MAA) for tion was performed in an ultrasonic water bath with a power of
use in co-polymerizing with AESO to form a biobased thermoset (MI- 80 W at 60 � C for 12 h. After the reaction, the resulting solution
AESO); the obtained MI-AESO resin was then modified with MAA to was purified with 0.5 mol/L NaOH, saturated NaHCO3 and water,
graft more C¼C bonds on AESO through the reaction between the hy­ and then dried over MgSO4 to form methacrylated isosorbide
droxyl and epoxy groups of AESO and the anhydride groups of MAA, (MI). The obtained MI was blended with AESO at a weight ratio of
forming a resin (MI-MAESO) with an improved level of unsaturation

Fig. 1. Synthesis routes of biobased thermosets.

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1:1 in a beaker (70 � C, magnetic stirring 500 r/min, 10 min) to in an air-conditioned oven at 50 � C for 24 h before cooling down to RT in
generate resin MI-AESO. sealed plastic bags. The dry weight (wd) of the specimens was obtained
(3) MI-MAESO: The reaction product from (2) without purification with a balance. Then, the specimens were soaked in distilled water at RT
was directly blended with AESO to form MAA-modified AESO for 24 h, and subsequently they were removed out from water, wiped
resin, i.e., MI-MAESO. The content of AESO was kept at a weight with tissue papers, and weighed to determine the wet weight (ww).
ratio of AESO to MI at 1:1 based on the theoretical yield of MI. Similarly, the specimens were soaked in a boiling distilled water bath for
The unreacted MAA in the system was expected to react with the 2 h. Afterward, the specimens were removed to distilled water at RT for
–OH and epoxy groups of AESO to graft C¼C bonds onto AESO 15 min before obtaining the ww. The water absorption rate of the spec­
molecules. The flask was placed in a water bath for reaction at imens was calculated as (ww‒wd)/wd � 100%. Three replicates were
60 � C for 6 h. After the reaction, the mixture was purified as (2) to tested for each resin and composite.
generate MI-MAESO resin containing MI, AESO, and MAA-
modified AESO. 3. Results and discussion
(4) MI: Pure MI obtained from (2) was used for comparison.
3.1. Characteristics of BFs and HFs
2.3. Curing of biobased thermosets
As shown in the digital images of the fibers (Fig. 2ab), HFs were
The obtained four resins were added with 2 wt% TBPB with a me­ basically gray, and BFs had obviously yellow feature. From the micro­
chanical stirring for 2 min, and then degassed under vacuum and scope images of the fibers (Fig. 2cd), most of HFs existed as individual
transferred to silicon molds, respectively. The molds were removed into filaments, while BFs had a large number of fiber bundles that consisted
an oven for 2 h at 120 � C and 4 h at 160 � C. After being cooled to room of several filaments. These are closely related to the different extraction
temperature (RT), the cured resin samples were then obtained from the method of the fibers. HFs were prepared by chemical method, and their
mold. non-cellulosic substances such as lignin and hemicellulose were mostly
removed by chemical reagents. By contrast, BFs were extracted by me­
2.4. Preparation of biocomposites chanical techniques with the assistance of 1,4-butanediol as a dispersant
[51]; they were mainly fiber bundles consisting of filaments that were
The biocomposites were prepared from the biobased resins and HFs adhered together by binding materials including lignin and
or BFs with a 50 wt% fiber fraction via a compression molding tech­ hemicellulose.
nique. Taking BFs and AESO as example, randomly orientated fiber-mats The distributions of fiber length, width, and length-to-width ratio of
(10 � 10 � 0.5 cm3) were prepared from BFs and then oven-dried at HFs were given in Fig. 3. The fiber length of HFs averaged 38.7 mm, and
103 � C for 24 h. The resulting fiber-mats (10 g) were evenly coated with 88% of the fibers had lengths ranging from 20 to 60 mm. The fibers
AESO (10 g) by hand, and then the resulting resin-coated fiber-mats averaged 64.6 μm in width and ranged primarily from 20 to 100 μm in
were stacked in a steel mold (10 � 10 � 0.3 cm3) at RT. The mold was width (86%). The length-to-width ratios of the HFs distributed mainly
hot-pressed under a pressure of 6 MPa at RT for 5 min, at 70 � C for 5 min, from 300 to 900, and the average length-to-width ratio was 665.5. The
and at 160 � C for 30 min. Finally, the generated composites were morphological characteristics of BFs has been reported in our previous
removed from the mold. work [51]. For comparison, the average length, width, and length-to
width of BFs were listed in Table 1. BFs had much higher fiber width
2.5. Characterization and lower fiber length than HFs, and thus the length-to-width ratio of
HFs was greatly higher than that of BFs.
Morphologies of HFs and BFs were observed by a digital camera and The chemical compositions of the fibers were evaluated in Table 1.
an optical microscope VHX-6000 Series (KEYENCE America, IL, USA). HFs had almost 90% cellulose, indicating the removal of hemicellulose
Microscope images were obtained by clamping several individual fibers and lignin by chemical reagents. The mechanically extracted BFs
with two sheet glasses. The fiber width was measured from the micro­ reserved a relatively high integrity of fiber cell wall structure, and hence
scope images, and the fiber length was tested by a digital vernier caliper. had low content of cellulose (65.6%) and high contents of hemicellulose
Four hundred individual fibers were tested. The chemical compositions (17.1%) and lignin (11.5%). Compared to BFs, HFs contained a higher
of the fibers were determined according to TAPPI (Technical Association
of the Pulp and Paper Industry) standards. The content of cellulose was
tested by nitric acid and ethanol extraction in accordance with TAPPI
T201 wd-76. The content of pentosan (hemicellulose) was evaluated by
titration based on TAPPI T223 cm-01. The content of Klason lignin was
determined according to TAPPI T222 om-11.
Densities of resins and composites were measured on an electronic
densimeter (SD-200L, Alfa Mirage, Osaka, Japan) based on the Archi­
medes method [50]. Three replicates were conducted for each sample.
Flexural properties of resins and composites were evaluated on a
CMT6104 universal testing machine (MTS Systems, MN, USA) under
three-point bending mode according to ASTM D 790–10. Five rectan­
gular specimens (80 � 10 mm2) were tested for each resin and composite
at a crosshead rate of 10 mm/min.
Dynamic mechanical analysis (DMA) was performed on a DMA 242
(NETZSCH, Selb, Germany) machine by using rectangular samples
(55 � 10 mm2) in accordance with ASTM D7028-07. The tests ranged
from 25 to 250 � C under three-point bending mode at a heating rate of
5 � C/min and a frequency of 1 Hz.
Rectangle specimens (76.2 � 25.4 mm2) of resin and composites
were used for water absorption measurement based on ASTM D570-10
in distilled water at RT and boiling water. The specimens were placed Fig. 2. Digital and optical microscope images of (a, c) HFs and (b, d) BFs.

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W. Liu et al. Composites Part B 171 (2019) 87–95

Fig. 3. Distributions of (a) fiber length, (b) width, and (c) length-to-width ratio of HFs.

that of traditional UPE resin with 40 wt% styrene (styrene-UPE). How­

Table 1
ever, a higher viscosity was observed for MI-AESO resin compared with
Morphologies and chemical compositions of HFs and BFs.
the AESO resin with 30 wt% styrene (styrene-AESO), which is due to the
Fibers Average Average Length- Chemical compositions (wt%) higher viscosity of MI than styrene (0.7 mPa⋅s) [52].
length width to-width
Cellulose Pentosan Klason The curing process of all the resins including styrene-UPE initiated
(mm) (μm) ratio
lignin by TBPB exhibited two maximum curing temperatures (Tmaxs), which
BFs 22.81 150.00 199.96 65.60 17.10 11.50 reflects the co-polymerization and homo-polymerization of the resin
HFs 38.74 64.58 665.48 89.31 6.12 1.64 systems. The Tmax1s and Tmax2s of both MI-AESO and MI-MAESO resins
were slightly lower than those of styrene-UPE resin. However, MI-AESO
and MI-MAESO resins had slightly lower Tmax1s and comparable Tmax2s
content of cellulose and lower contents of lignin and hemicellulose.
than styrene-AESO resin. Similar Tmax1s and Tmax2s were seen for the MI
and styrene-UPE resins. It is concluded that the resins in this study
3.2. Processibility of biobased thermosets showed comparable and even superior processibility than the typical
styrene-UPE resin for the preparation of fiber-reinforced composites.
The rheological and curing behaviors of the biobased thermosets
were investigated in details in our previous work [47]. For briefly 3.3. Densities of biocomposites
demonstrating the processibility of the thermosets in fiber-reinforced
composites, the viscosities and curing temperatures of the thermosets The densities of the cured thermosets had close relationship with
and their counterparts were given in Table 2. Compared to pure AESO their resin compositions (Fig. 4). Cured AESO resin had the lowest
resin, both MI-AESO and MI-MAESO resins showed significantly reduced density among all the resins due to its insufficient crosslinking degree
viscosities because of the addition of MI as a reactive diluent. The vis­ caused by low unsaturation degree. AESO molecules with long aliphatic
cosities of MI-AESO, MI-MAESO, and MI resins were much lower than chains lead to a long average molecular distance between crosslink
points, which would reduce the compactness of the cured AESO. By
Table 2 contrast, MI monomer has a bicyclic ring structure that results in short
Viscosities and curing temperatures of biobased thermosets. molecular distances between crosslinks and provides stiffness for the
Resins Viscositya (mPa⋅s) Curing temperaturesb (� C) cured MI, thus contributing to the highest density of MI resin [54]. The
combination of MI with AESO generated the cured MI-AESO resin with
Tmax1 Tmax2
an improved density than AESO due to its increased crosslinking degree.
AESO 4789 124.2 167.8 However, increase in unsaturated level for AESO due to MAA modifi­
MI-AESO 151 116.6 172.3
MI-MAESO 186 117.5 172.1
cation did not significantly change the density of MI-MAESO resin when
MI 12 121.0 183.3 compared to MI-AESO resin.
Styrene-AESO [39] 56 127.9 171.3 The introduction of NFs into the biobased thermosets generated the
Styrene-UPE [53] 375 122.0 180.1 biocomposites with lower densities than their corresponding cured
a
The viscosity was measured on a rotational rheometer (30 � C). resins (Fig. 4). This demonstrates that the compact structure of resins
b
The curing temperatures were obtained by DSC analysis at a heating rate of was destroyed by fibers and voids were generated within the bio­
10 � C/min. composites. The densities of BF composites were much lower than those

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moduli than BF composites. The properties of composites are correlated

to the properties of fibers and its interface bonding with matrix when the
same resin was used. The strength of lignocellulosic fibers is majorly
contributed by cellulose. The higher cellulose content in HFs gives
higher strength for the fibers and hence its composites. Meanwhile, the
higher length-to-width ratio for HFs provides more efficient stress
transfer in fiber/matrix interface. By contrast, BFs had higher contents
of lignin and hemicellulose than HFs. These non-cellulosic materials that
covered on the surfaces of fibers would impede the wetting of resins on
the fibers and thus generate inferior interface in the BF composites,
which results in an ineffective stress transfer from matrices to fibers
[55].
Composition of resin matrix was another crucial factor affecting the
Fig. 4. Densities of biobased thermosets and their biocomposites with BFs and properties of composites. The lowest flexural strength and flexural
HFs. Note: The data were analyzed with one-way ANOVA based on a 95% modulus were achieved for AESO resin with the highest flexural strain,
confidence interval. There is no significant difference between any two groups which is resulted from its low crosslinking density and long molecular
when they have same letter at the top of the columns. The letters mean the same chains. This led to similar results on the flexural properties for both HF
in the following figures.
and BF composites from AESO, i.e., HF/AESO and BF/AESO composites
had much lower flexural strengths and moduli than other composites.
of HF composites when same resin matrix was used. The fiber-matrix Compared to AESO resin, significant increases in flexural strength and
interfacial adhesion is the main factor affecting the void contents and modulus were observed in MI-AESO resin. This is because the added MI
thus compactness of the composites. The large amount of non-cellulosic provides an improved crosslinking density and stiff structure for the
materials on BFs surfaces would result in a poor interfacial adhesion resin. But the flexural strain of the resin was dramatically reduced.
between BFs and resins such that voids are generated at the interface of Similar situation for MI-AESO resin also occurred in BF/MI-AESO and
the composites. Furthermore, the densities of HF composites were sta­ HF/MI-AESO composites. Furthermore, MI-MAESO resin achieved
tistically comparable between different resin systems, showing that the significantly higher flexural strength and modulus than MI-AESO resin
effect of resin composition on the densities of the composites was thanks to the improved unsaturation level of AESO molecules after MAA
weakened by that of HFs. As for BF composites, BF/MI composite had a modification. However, the strengthening effect in MI-MAESO relative
much lower density than other three composites that had comparable to MI-AESO resin was not seen for their composites, i.e., the flexural
densities. The higher density of MI resin might have a higher volume properties of MI-AESO and MI-MAESO composites using the same fibers
shrinkage during curing, which results in an insufficient wetting of MI were statistically comparable. In addition, the self-polymerized MI resin
resin on fluffy BFs and hence an inferior fiber-matrix interface bonding had much lower flexural strength than MI-MAESO resin due to its lower
of the composite. crosslinking density as a result of the incomplete crosslinking network
[54]. During the self-polymerization of MI, once one C¼C bond of MI
3.4. Flexural properties of biocomposites molecule polymerizes, the other unreacted C¼C bond in the molecule
would be locked in the network. The locked C¼C bond with limited
The flexural strengths, flexural moduli, and flexural strains of the mobility might remain in the network such that the network with many
thermosets and their composites with HFs and BFs were shown in Fig. 5. unsaturated sites would be formed. This results in the formation of an
Overall, HF composites had significantly higher flexural strengths and incomplete network in the cured resin. However, isosorbide with a

Fig. 5. (a) Flexural strength, (b) flexural modulus, and (c) flexural strain of biobased thermosets and their biocomposites with BFs and HFs.

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unique bicyclic ring would provide large stiffness for the MI resin, which improved crosslinking degree, stiffness, and thermal resistance of
explains its improved flexural modulus and decreased flexural strain MI-AESO resin contributed by MI monomer. HF/MI-MAESO composite
when compared to MI-MAESO resin. For the BF or HF composites from showed significantly higher E0 and Tg than HF/MI-AESO composite due
MI resin, they achieved comparable flexural properties with those from to the enhanced crosslinking degree of MI-MAESO resin resulted from
MI-AESO and MI-MAESO resins. This reveals that the reinforcing effects MAA modification for AESO. This seems to be contradicted with the
of fibers surpass that of the increased matrix properties for the flexural properties of the composites that were not significantly affected
composites. by MAA modification, which demonstrates that the enhanced cross­
linking density of resin matrix has a more significant influence on the
properties of the composites under vibration condition and at evaluated
3.5. Dynamic mechanical properties of biocomposites temperature. HF/MI composite had the highest E0 and Tg among all the
composites because of the superior stiffness and thermal stability of MI
The DMA curves and their characteristic results of the BF- and HF- resin. Moreover, the tan δ curves of the composites from MI-MAESO and
reinforced biobased thermoset composites were given in Fig. 6 and MI resins presented a shoulder peak at the temperatures around 220 � C,
Table 3. The storage modulus (E0 ) curves for all the composites showed a which might be related to the occurrence of phase separation from MI
dramatically reduced trend with the increasing temperature due to the self-polymerization.
improved molecular mobility. The glass transition temperature (Tg) of
the composites is usually determined from the maximum peak on the
damping parameter (tan δ) curve. Excluding the Tgs of BF/MI and HF/MI 3.6. Water absorption of biocomposites
composites, both BF and HF composites had much higher initial E’s and
Tgs than their corresponding resin matrix, indicating the reinforcing The water absorption of biobased thermosets and their bio­
effects of NFs on polymer matrices. The lower Tgs of BF/MI and HF/MI composites were measured by immersing samples in distill water at RT
composites than MI resin might be resulted from the lower thermal for 24 h and boiling water for 2 h (Fig. 7). The water uptake rate (WRT
stability of NFs than MI resin. The non-cellulosic polysaccharides such as and W100) of AESO resin at RT and 100 � C were only 0.45% and 1.44%,
hemicellulose and pectin of NFs were the main compositions that start to respectively, which is associated with the large amount of non-polar
degrade with the increased temperature [56]. Furthermore, HF com­ components such as fatty acid chains on AESO molecules. MI resin
posites exhibited significantly higher E’s in all the temperature range had a WTR of 0.87% and a W100 of 3.27% due to the presence of ester
and slightly higher Tg than BF composites, which confirms a higher groups on MI molecules, which were much higher than those of AESO
reinforcing efficiency of HFs than BFs. resin. The combination of AESO and MI did not significantly affect the
Regarding the effect of resin composition, the E’s and Tgs for the WRT and W100 of the obtained MI-AESO resin when compared to AESO
composites with the same fibers had the order of AESO < MI- resin, while MI-AESO resin had lower WRT and W100 than MI resin. MAA
AESO < MI-MAESO < MI, which was in line with those of the resin modification for AESO resulted in a dramatic increase in W100 for MI-
matrices. Taking HF composites as example, HF/AESO composite had MAESO resin than MI-AESO resin, which is due to the reaction be­
the lowest E0 and Tg due to the low crosslinking density of AESO. The tween the anhydride groups of MAA with the –OH and epoxy groups of
crosslinking density (ve) calculated from DMA analyses according to the AESO. The consumption of –OH groups would reduce the water ab­
rubbery elastic theory are also given in Table 3 [47]. The incorporation sorption of AESO, while the conversion of epoxy groups into ester groups
of MI into AESO greatly increased the E0 and Tg of the composites from might increase the water absorption of AESO since ester groups are more
4.12 to 6.26 GPa and 55.7–96.4 � C, respectively. This is attributed to the sensitive to water than epoxy groups. The latter might be more

Fig. 6. DMA curves of biocomposites from biobased thermosets with BFs and HFs. (a) Storage modulus of BF composites; (b) Storage modulus of HF composites; (c)
Damping parameter of BF composites; (d) Damping parameter of HF composites.

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Table 3
DMA parameters of biocomposites from biobased thermosets with BFs and HFs.
Samples E0 at 30 � C (GPa) Tg (oC) ve � 103 (mol/m3) [47]

Resins Composites Resins Composites Resins

BF HF BF HF

AESO 0.30 2.41 4.12 – 53.8 55.7 16.0

MI-AESO 1.96 4.76 6.26 75.6 94.1 96.4 75.2
MI-MAESO 2.13 5.59 7.16 94.9 105.7 107.1 83.3
MI 2.74 6.79 8.75 142.2 132.4 138.0 59.7

Fig. 7. Water uptake rates of biobased thermosets and their biocomposites with BFs and HFs. (a) 24 h immersion at room temperature (23 � C); (b) 2 h in boiling
water (100 � C).

significant than the former, hence leading to the increased water ab­ composites. (3) BFs were basically fiber bundles that consist of filaments
sorption of MI-MAESO resin. binded together by non-cellulosic substances. The fine filaments in BFs
Both BF and HF composites had much higher WRTs and W100s than linked with each other would form a connected hygroscopic route for
the resins due to the incorporation of highly hydrophilic NFs. The WRTs the penetration of water, i.e., water molecules penetrate into the com­
of the BF composites from AESO, MI-AESO, and MI-MAESO were sta­ posites through the microgaps between the filaments in the fiber bundles
tistically comparable, which were much lower than that of BF/MI [58].
composite; however, the W100s of all the BF composites were not
significantly influenced by resin composition. This indicates that BF/MI 3.7. Comparison of biocomposites with their counterparts
composites showed higher water absorption rate at RT due to the high
WRT of MI resin. But this effect might be overlapped by the high hy­ HF/MI-MAESO composite was selected as a representative for
drophilicity of BFs when the water absorption of BF/MI composites comparing with its counterparts (Table 4). Excluding glass/styrene-
approaches equilibrium at evaluated temperature. As for the water ab­ AESO composite, all the composites prepared from same HFs as re­
sorption of HF composites, HF/MI composite had the highest WRT and inforcements were referenced to precisely compare the effects of resin
W100, while the WRTs and W100s of HF/AESO composite were the lowest; matrices on the properties of composites. According to the USDA that
both WRTs and W100s of HF/MI-AESO and HF/MI-MAESO composites defines the biobased content of a material as the weight ratio of biobased
were comparable with each other. It is concluded that resin composition carbon in the material [59], AESO is considered to be 86% renewable
has a higher effect on the water absorption of HF composites than that due to the presence of allyl groups, and NFs were 100% biobased.
on BF composites. This is contributed by the high hydrophilicity of BFs Therefore, the biobased contents of the composites were determined in
that has a more significant effect on the water absorption of the com­ Table 4. Overall, the HF/MI-MAESO composite achieved greatly higher
posites than resin composition. This also resulted in greatly higher WRTs flexural strength, flexural modulus, and Tg than other HF/AESO com­
and W100s of BF composites than HF composites as explained by the posites with different reactive diluents, which is attributed to the high
following reasons. (1) HFs had a much higher content of cellulose and usage of MI, modification of AESO, and the stiffness structure of MI.
relatively less contents of hemicellulose and lignin than BFs (Table 1). However, the biobased content of the HF/MI-MAESO composite was
Hemicellulose is the most hydrophilic components in NFs, hence comparable with those of HF/styrene-AESO and HF/NVP-AESO and
contributing to higher water absorption of BFs than HFs [57]. (2) As slightly lower than that of HF/TMI-AESO composite. NVP is a highly
aforementioned, the poor interfacial adhesion of the BF composites reactive monomer, thus leading to the superior properties of
would provide more opportunities for the entrance of water into the HF/NVP-AESO composite than HF/styrene-AESO composite [39]. TMI

Table 4
Comparison of properties of HF/MI-MAESO composites with its counterparts.
Composites Reactive diluent (wt%) Flexural strength (MPa) Flexural modulus (GPa) Tg (oC) Biobased content (%) References

HF/MI-MAESO 50% MI 136.5 9.9 107.1 79 this study

HF/styrene-AESO 30% styrene 82.4 5.5 52.3 80 [39]
HF/NVP-AESO 30% NVPa 90.6 6.1 68.5 80 [39]
HF/TMI-AESO 15% TMIb 116.6 7.9 89.5 87 [41]
HF/styrene-UPE 40% styrene 139.3 8.7 134.7 50 [53]
Glass/styrene-AESO 50% styrene 205.5 9.0 – 22 [60]
a
NVP refers to N-vinyl-2-pyrrolidone.
b
TMI refers to 3-isopropenyldimethylbenzyl isocyanate.

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W. Liu et al. Composites Part B 171 (2019) 87–95

is a bifunctional isocyanate that can concurrently crosslink with the C¼C [10] Pickering KL, Efendy MA, Le TM. A review of recent developments in natural fibre
composites and their mechanical performance. Composites Part A 2016;83:
bonds of AESO and react with the –OH groups of both AESO and HFs;
98–112.
hence, the HF/TMI-AESO composite with only 15 wt% TMI gained [11] Fuqua MA, Huo S, Ulven CA. Natural fiber reinforced composites. Polym Rev 2012;
significantly improved flexural properties and Tg than HF/styrene-AESO 52(3):259–320.
and HF/NVP-AESO composites, and had the highest biobased content [12] Zuccarello B, Zingales M. Toward high performance renewable agave reinforced
biocomposites: optimization of fiber performance and fiber-matrix adhesion
among all the composites [41]. Furthermore, the HF/MI-MAESO com­ analysis. Composites Part B 2017;122:109–20.
posite had comparable flexural strength, higher flexural modulus, but [13] Bledzki A, Franciszczak P, Osman Z, Elbadawi M. Polypropylene biocomposites
lower Tg than the typical HF/styrene-UPE composite; a slightly higher reinforced with softwood, abaca, jute, and kenaf fibers. Ind Crops Prod 2015;70:
91–9.
flexural modulus was also seen for the HF/MI-MAESO composite when [14] Peltola H, P€aa
€kk€
onen E, Jetsu P, Heinemann S. Wood based PLA and PP
compared to glass/styrene-AESO composite. These confirm that the composites: effect of fibre type and matrix polymer on fibre morphology,
prepared HF/AESO composites in this work had great potential to dispersion and composite properties. Composites Part A 2014;61:13–22.
[15] Du Y, Wu T, Yan N, Kortschot MT, Farnood R. Pulp fiber-reinforced thermoset
replace their analogues such as petroleum-based UPE composites polymer composites: effects of the pulp fibers and polymer. Composites Part B
because of their high renewable nature. 2013;48:10–7.
[16] Lila MK, Saini GK, Kannan M, Singh I. Effect of fiber type on thermal and
mechanical behavior of epoxy based composites. Fibers Polym 2017;18(4):806–10.
4. Conclusions [17] Qiu R, Liu W, Li K. Investigation of bamboo pulp fiber-reinforced unsaturated
polyester composites. Holzforschung 2015;69(8):967–74.
Biocomposites with superior performance and high renewable con­ [18] Liu W, Qiu R, Li K. Effects of fiber extraction, morphology, and surface
modification on the mechanical properties and water absorption of bamboo fibers-
tents were successfully produced from natural fibers and biobased
unsaturated polyester composites. Polym Compos 2016;37(5):1612–9.
thermosets. The characteristics of fibers and resins and their interfacial [19] Karger-Kocsis J, Mahmood H, Pegoretti A. Recent advances in fiber/matrix
bonding played important roles in the properties of the resulting com­ interphase engineering for polymer composites. Prog Mater Sci 2015;73:1–43.
posites. The composites from HFs achieved greatly higher physical [20] Zhou Y, Fan M, Chen L. Interface and bonding mechanisms of plant fibre
composites: an overview. Composites Part B 2016;101:31–45.
properties, mechanical properties, and water resistance than the com­ [21] Liu W, Xie T, Qiu R, Fan M. N-methylol acrylamide grafting bamboo fibers and
posites from BFs due to its higher cellulose content, length-to-width their composites. Compos Sci Technol 2015;117:100–6.
ratio, and superior interfacial adhesion with resins. The resins with [22] Mustapha SNH, Rahmat AR, Arsad A. Bio-based thermoset nanocomposite derived
from vegetable oil: a short review. Rev Chem Eng 2014;30(2):167–82.
stiffness structure and higher crosslinking density, i.e., MI-AESO, MI- [23] Jian XY, An XP, Li YD, Chen JH, Wang M, Zeng JB. All plant oil derived epoxy
MAESO, and MI, resulted in significantly higher mechanical strength thermosets with excellent comprehensive properties. Macromolecules 2017;50
and modulus as well as Tg for the corresponding composites when (15):5729–38.
[24] Jian XY, He Y, Li YD, Wang M, Zeng JB. Curing of epoxidized soybean oil with
compared to the flexible AESO resin. However, fiber characteristic had a crystalline oligomeric poly (butylene succinate) towards high performance and
more profound effect on the water absorption of the composites than sustainable epoxy resins. Chem Eng J 2017;326:875–85.
resin composition. In summary, the produced biocomposites had com­ [25] An XP, Chen JH, Li YD, Zhu J, Zeng JB. Rational design of sustainable
polyurethanes from castor oil: towards simultaneous reinforcement and
parable or superior properties than their conventional biobased or toughening. Sci China Mater 2018;61(7):993–1000.
petroleum-based counterparts while maintaining high biobased content. [26] Gandini A. Polymers from renewable resources: a challenge for the future of
Investigations on the structure-property relationship from fibers, resins macromolecular materials. Macromolecules 2008;41(24):9491–504.
[27] Llevot A. Sustainable synthetic approaches for the preparation of plant oil-based
to composites could contribute to better understanding of these bio­
thermosets. J Am Oil Chem Soc 2017;94(2):169–86.
based resins in the development of biocomposites. [28] Kumar S, Samal SK, Mohanty S, Nayak SK. Epoxidized soybean oil based epoxy
blend cured with anhydride based crosslinker: thermal and mechanical
Acknowledgment characterization. Ind Eng Chem Res 2017;56(3):687–98.
[29] Huang K, Liu Z, Zhang J, Li S, Li M, Xia J, et al. A self-crosslinking thermosetting
monomer with both epoxy and anhydride groups derived from tung oil fatty acids:
We gratefully thank the funding from the National Natural Science synthesis and properties. Eur Polym J 2015;70:45–54.
Foundation of China (Grant No. 31670568 and 31800486), the China [30] Zhang C, Kessler MR. Bio-based polyurethane foam made from compatible blends
of vegetable-oil-based polyol and petroleum-based polyol. ACS Sustainable Chem
Postdoctoral Science Foundation (Grant No. 2017M622039), and Fujian Eng 2015;3(4):743–9.
Agriculture and Forestry University (Grant No. KXB16007A). [31] Zhang C, Madbouly SA, Kessler MR. Biobased polyurethanes prepared from
different vegetable oils. ACS Appl Mater Interfaces 2015;7(2):1226–33.
[32] Liu C, Shang Q, Jia P, Dai Y, Zhou Y, Liu Z. Tung oil-based unsaturated co-ester
References macromonomer for thermosetting polymers: synergetic synthesis and
copolymerization with styrene. ACS Sustainable Chem Eng 2016;4(6):3437–49.
[1] Yaghoobi H, Fereidoon A. Preparation and characterization of short kenaf fiber- [33] Liu C, Dai Y, Hu Y, Shang Q, Feng G, Zhou J, et al. Highly functional unsaturated
based biocomposites reinforced with multi-walled carbon nanotubes. Composites ester macromonomer derived from soybean oil: synthesis and copolymerization
Part B 2019;162:314–22. with styrene. ACS Sustainable Chem Eng 2016;4(8):4208–16.
[2] Essabir H, Raji M, Laaziz SA, Rodrique D, Bouhfid R, Qaiss A. Thermo-mechanical [34] Narewska J, Lassila L, Fardim P. Preparation and characterization of new
performances of polypropylene biocomposites based on untreated, treated and mouldable cellulose-AESO biocomposites. Cellulose 2014;21(3):1769–80.
compatibilized spent coffee grounds. Composites Part B 2018;149:1–11. [35] Åkesson D, Skrifvars M, Walkenstr€ om P. Preparation of thermoset composites from
[3] Kumar N, Das D. Fibrous biocomposites from nettle (Girardinia diversifolia) and natural fibres and acrylate modified soybean oil resins. J Appl Polym Sci 2009;114
poly (lactic acid) fibers for automotive dashboard panel application. Composites (4):2502–8.
Part B 2017;130:54–63. [36] Adekunle K, Ghoreishi R, Ehsani M, Cho S-W, Skrifvars M. Jute fiber reinforced
[4] Zuccarello B, Scaffaro R. Experimental analysis and micromechanical models of methacrylated soybean oil based thermoset composites prepared by vacuum
high performance renewable agave reinforced biocomposites. Composites Part B injection molding technique. J Biobased Mater Bioenergy 2012;6(2):172–7.
2017;119:141–52. [37] Lee TS, Choi HY, Choi HN, Lee K-Y, Kim S-H, Lee SG, et al. Effect of surface
[5] Sun E, Liao G, Zhang Q, Qu P, Wu G, Huang H. Biodegradable copolymer-based treatment of ramie fiber on the interfacial adhesion of ramie/acetylated epoxidized
composites made from straw fiber for biocomposite flowerpots application. soybean oil (AESO) green composite. J Adhes Sci Technol 2013;27(12):1335–47.
Composites Part B 2019;165:193–8. [38] Ramamoorthy SK, Kundu CK, Adekunle K, Bashir T, Skrifvars M. Properties of
[6] Zhang C, Garrison TF, Madbouly SA, Kessler MR. Recent advances in vegetable oil- green composites with regenerated cellulose fiber and soybean-based thermoset for
based polymers and their composites. Prog Polym Sci 2017;71:91–143. technical applications. J Reinf Plast Compos 2014;33(2):193–201.
[7] Hidalgo P, Navia R, Hunter R, Gonzalez ME, Echeverría A. Development of novel [39] Liu W, Chen T, Xie T, Qiu R. Soybean oil-based thermosets with N-vinyl-2-
bio-based epoxides from microalgae Nannochloropsis gaditana lipids. Composites pyrrolidone as crosslinking agent for hemp fiber composites. Composites Part A
Part B 2019;166:653–62. 2016;82:1–7.
[8] Cicala G, Pergolizzi E, Piscopo F, Carbone D, Recca G. Hybrid composites [40] Liu W, Xie T, Qiu R. Improvement of properties for biobased composites from
manufactured by resin infusion with a fully recyclable bioepoxy resin. Composites modified soybean oil and hemp fibers: dual role of diisocyanate. Composites Part A
Part B 2018;132:69–76. 2016;90:278–85.
[9] Dittenber DB, GangaRao HV. Critical review of recent publications on use of [41] Liu W, Fei M-e, Ban Y, Jia A, Qiu R, Qiu J. Concurrent improvements in
natural composites in infrastructure. Composites Part A 2012;43(8):1419–29. crosslinking degree and interfacial adhesion of hemp fibers reinforced acrylated
epoxidized soybean oil composites. Compos Sci Technol 2018;160:60–8.

94
W. Liu et al. Composites Part B 171 (2019) 87–95

[42] Campanella A, Zhan M, Watt P, Grous AT, Shen C, Wool RP. Triglyceride-based [52] Stanzione III JF, Sadler JM, La Scala JJ, Wool RP. Lignin model compounds as bio-
thermosetting resins with different reactive diluents and fiber reinforced composite based reactive diluents for liquid molding resins. ChemSusChem 2012;5(7):
applications. Composites Part A 2015;72:192–9. 1291–7.
[43] Zhang H, Yang Y, Shen M, Shang S, Song J, Jiang J, et al. Soybean oil-based [53] Liu W, Xie T, Qiu R. Styrene-free unsaturated polyesters for hemp fibre composites.
thermoset reinforced with rosin-based monomer. Iran Polym J (Engl Ed) 2018;27 Compos Sci Technol 2015;120:66–72.
(6):405–11. [54] Sadler JM, Nguyen A-PT, Toulan FR, Szabo JP, Palmese GR, Scheck C, et al.
[44] Dai J, Liu X, Ma S, Wang J, Shen X, You S, et al. Soybean oil-based UV-curable Isosorbide-methacrylate as a bio-based low viscosity resin for high performance
coatings strengthened by crosslink agent derived from itaconic acid together with thermosetting applications. J Mater Chem 2013;1(40):12579–86.
2-hydroxyethyl methacrylate phosphate. Prog Org Coating 2016;97:210–5. [55] Peng X, Zhong L, Ren J, Sun R. Laccase and alkali treatments of cellulose fibre:
[45] Zhang Y, Thakur VK, Li Y, Garrison TF, Gao Z, Gu J, et al. Soybean-oil-based surface lignin and its influences on fibre surface properties and interfacial
thermosetting resins with methacrylated vanillyl alcohol as bio-based, low- behaviour of sisal fibre/phenolic resin composites. Composites Part A 2010;41(12):
viscosity comonomer. Macromol Mater Eng 2018;303(1). 1700278. 1848–56.
[46] Zhang Y, Li Y, Wang L, Gao Z, Kessler MR. Synthesis and characterization of [56] Benítez-Guerrero M, L� opez-Beceiro J, S�
anchez-Jim�enez PE, Pascual-Cosp J.
methacrylated eugenol as a sustainable reactive diluent for a maleinated acrylated Comparison of thermal behavior of natural and hot-washed sisal fibers based on
epoxidized soybean oil resin. ACS Sustainable Chem Eng 2017;5(10):8876–83. their main components: cellulose, xylan and lignin. TG-FTIR analysis of volatile
[47] Liu W, Xie T, Qiu R. Biobased thermosets prepared from rigid isosorbide and products. Thermochim Acta 2014;581:70–86.
flexible soybean oil derivatives. ACS Sustainable Chem Eng 2017;5(1):774–83. [57] Liu R, Peng Y, Cao J, Chen Y. Comparison on properties of lignocellulosic flour/
[48] Shahzad A. Hemp fiber and its composites-a review. J Compos Mater 2012;46(8): polymer composites by using wood, cellulose, and lignin flours as fillers. Compos
973–86. Sci Technol 2014;103:1–7.
[49] Khalil HA, Bhat IUH, Jawaid M, Zaidon A, Hermawan D, Hadi YS. Bamboo fibre [58] Kushwaha PK, Kumar R. Studies on water absorption of bamboo-epoxy composites:
reinforced biocomposites: a review. Mater Des 2012;42:353–68. effect of silane treatment of mercerized bamboo. J Appl Polym Sci 2010;115(3):
[50] Taylor C, Amiri A, Paramarta A, Ulven C, Webster D. Development and 1846–52.
weatherability of bio-based composites of structural quality using flax fiber and [59] Dai J, Ma S, Wu Y, Han L, Zhang L, Zhu J, et al. Polyesters derived from itaconic
epoxidized sucrose soyate. Mater Des 2017;113:17–26. acid for the properties and bio-based content enhancement of soybean oil-based
[51] Liu W, Chen T, Wen X, Qiu R, Zhang X. Enhanced mechanical properties and water thermosets. Green Chem 2015;17(4):2383–92.
resistance of bamboo fiber-unsaturated polyester composites coupled by [60] Morye SS, Wool RP. Mechanical properties of glass/flax hybrid composites based
isocyanatoethyl methacrylate. Wood Sci Technol 2014;48(6):1241–55. on a novel modified soybean oil matrix material. Polym Compos 2005;26(4):
407–16.

95