Industrial Crops & Products 146 (2020) 112185

Contents lists available at ScienceDirect

Industrial Crops & Products

journal homepage: www.elsevier.com/locate/indcrop

Biochar filled high-density polyethylene composites with excellent T

properties: Towards maximizing the utilization of agricultural wastes
Qingfa Zhanga,b, Donghong Zhanga, Hang Xua, Wenyu Lua, Xiajin Rena, Hongzhen Caia,*,
Hanwu Leib,*, Erguang Huob, Yunfeng Zhaob, Moriko Qianb, Xiaona Lina,b, Elmar M. Villotab,
Wendy Mateob
a
School of Agricultural Engineering and Food Science, Shandong Research Center of Engineering & Technology for Clean Energy, Shandong University of Technology, Zibo,
255000, China
b
Department of Biological Systems Engineering, Washington State University, Richland, WA 99354, USA

A R T I C LE I N FO A B S T R A C T

Keywords: Biochar derived from agricultural wastes was used to reinforce high-density polyethylene (HDPE) to obtain
Agricultural wastes composites abbreviated as B10, B20, B30, B40, B50, B60, and B70. Investigating the mechanical, thermal, water
Maximization absorption and flame retardant properties of the composites is one of the objectives while maximizing the
Biochar utilization of agricultural wastes is the ultimate goal of this work. It was found that flexural properties, tensile
Composites
properties, storage modulus, elasticity, creep resistance and anti-stress relaxation ability of HDPE were improved
Properties evaluation
by the inclusion of biochar, and excellent mechanical properties were obtained in 50 % even 60 % biochar added
composites because of good dispersion and unique structure shown in the interface. The composites achieved
good flexural strength of 34.95 MPa in B50, flexural modulus of 1.79 GPa in B40, tensile strength of 29.05 MPa
in B40, and tensile modulus of 2.03 GPa. Additionally, the thermal and flame retardant properties (limited
oxygen index of 25.06 % in B70) increased for the biochar added composites as the biochar loading increased
due to the high thermal stability of biochar, although biochar had a negative effect on water-resistance of the
composites. The results revealed that the ultimate goal was achieved in terms of producing composites with
excellent mechanical, thermal, water absorption and flame retardant properties while maximizing the utilization
of agricultural wastes as a rational balance.

1. Introduction
The demand for fossil fuels increases dramatically along with
worldwide population growth, economic progress, and technological
advancement. One great challenge is the pollution caused by the fossil
fuel with its depletion becoming another problem that cannot be ig-
nored (Das et al., 2015). On the other hand, the urgent demand for food
due to population growth has contributed to the agglomeration of a
large number of agricultural wastes. In traditional agricultural pro-
duction, incineration and discarding are the main ways in disposing of
agricultural wastes (Demirbas, 2011). Nevertheless, these two ways
pollute the air and water and aggravate the greenhouse effect showing a
huge threat to agricultural product security and environmental safety
(Lim et al., 2016). Hence, the effective disposal of agricultural wastes is
an urgent need. In fact, agricultural wastes have great potential for
resource utilization due to their rich organic matters including cellu-
lose, hemicellulose, lignin, etc. Far more important is that agricultural
wastes are renewable comparing with fossil fuels. In a nutshell, in-
cineration and discarding of agricultural wastes are the waste of re-
sources. On the other hand, polyolefine plastics like polyethylene (PE),
polypropylene (PP), polyvinyl chloride (PVC), etc. have become an ir-
replaceable raw material for industrial production and daily life due to
their excellent characteristics with technological advancement (Chow
et al., 2018). Be that as it may, polyolefine plastics show non-degrad-
ability which is responsible for serious environmental pollution. Like-
wise, the main disposals of waste plastics, such as incineration and
landfilling, have created more serious problems of polluting the air and
water seriously (Fa et al., 2019). The recycling of waste plastics has
become another great problem affecting environmental safety. Given all
that, the effective and practical disposal of agricultural and plastic
wastes is a real challenge especially with the current pressure of efforts
on environmental protection.
In the view of efficiently utilizing plastics and agricultural wastes,
biocomposites made great progress worldwide, especially in North

⁎
Corresponding authors.
E-mail addresses: chzh666666@126.com (H. Cai), hlei@wsu.edu (H. Lei).

https://doi.org/10.1016/j.indcrop.2020.112185
Received 30 October 2019; Received in revised form 28 December 2019; Accepted 29 January 2020
0926-6690/ © 2020 Elsevier B.V. All rights reserved.
Q. Zhang, et al.
America over the past decades. Normally, some biocomposites are
prepared with plastic wastes like PE, PP, PVC, etc. and agricultural
wastes like corn stalk, rice husk, peanut shell, etc. by extrusion, hot
pressing and injection molding (Arrigo et al., 2019; Ferreira et al.,
2019; Zhang et al., 2019b). The biocomposites have been used in
construction, transportation, industry, and decoration due to their
corrosion resistance, easy processing, and acid and alkali resistance.
Importantly, the biocomposites can be recycled and reused discharging
no pollution in the production process (Wang et al., 2019). Never-
theless, because of the incompatibility between agricultural waste fi-
bers and plastics, the interfacial adhesion of these biocomposites is
typically weak causing the poor mechanical properties subsequently
(Turku et al., 2017). To overcome this issue, interfacial compatibilizers
such as maleic anhydride are added to the biocomposites and the me-
chanical properties are efficiently improved. Bajwa et al. studied the
effect of maleic anhydride grafting polyethylene (MAPE) on the prop-
erties of high-density polyethylene (HDPE)/wood fiber composites, and
better mechanical properties were obtained with the addition of MAPE
(Bajwa et al., 2019). Nevertheless, the addition of costly interfacial
compatibilizers increased the production cost of biocomposites in-
dicating a new problem. The balance of properties and the economic
efficiency of biocomposites has become a new challenge. Therefore, lots
of studies have been done to solve this problem. Among them, the
utilization of biochar for biocomposites attracted extensive attention
due to its porous structure and large surface area in recent years (Das
et al., 2015; Nan et al., 2016).
All the agricultural wastes could be converted to biochar by a
thermochemical process known as carbonization or pyrolysis with
abundance feedstock sources, which lower the production cost of bio-
char. Moreover, biochar reinforced biocomposites achieve the balance
between properties and cost (Behazin et al., 2017; Das et al., 2019). On
the one hand, a physical/mechanical interlocking structure (Das et al.,
2017) formed by porous biochar in plastics effectively transfers stress
and improves the mechanical properties of biocomposites. Bajwa et al.
and Das et al. found that the coupling agent was not effective in biochar
added composites indicating unnecessary of using interfacial compati-
bilizers which reduced the cost (Bajwa et al., 2019; Das et al., 2016b).
Subsequently, lots of efforts have been done in biochar biocomposites in
terms of the unique advantages of biochar. The study of Giorcelli et al.
showed that biochar was a cheap and environmental friendly filler to
improve polymer mechanical properties (Giorcelli et al., 2019). Ho
et al. used bamboo biochar to reinforce polylactic acid (PLA), and an
excellent improvement in the properties of PLA was obtained (Ho et al.,
2015). Das et al. thought that the utilization of biochar to prepare
biocomposites was a sustainable and resilient approach to manage
agricultural wastes (Das et al., 2015). The development of biochar
biocomposites attracted more and more scholars to participate in the
study, and the number of available documents has been more than 50 in
the last five years. The biochar sources (Poulose et al., 2018; Santhiago
et al., 2018; Zhang et al., 2018) are not limited to agricultural wastes
involving forestry wastes, grasses, manure, even bones, etc. Recently,
Mohanty et al. published a paper in Science demonstrating that biochar
was a new sustainable and functional filler material in biocomposites
(Mohanty et al., 2018). Besides, the effects of biochar loading, biochar
feedstock sources and types of polymers on biocomposites are also
studied. Though researchers have a universal agreement that biochar
loading has the greatest influence on biochar biocomposites, the bio-
char loading of most investigations is low. The maximum biochar
loadings were 35 % (Das et al., 2016a), 10 % (Ho et al., 2015), 20 %
(Mashouf Roudsari et al., 2017) shown by available documents re-
spectively. In view of production cost of polymers, it is necessary to
increase the biochar loading in biocomposites. High biochar loadings
help maximize the utilization of agricultural wastes on the premise of
ensuring environmental safety and reducing costs. To date, the effect of
high biochar loadings on biochar biocomposites is rarely investigated.
Hence, the focus of this work is to optimize biocomposites by regulating
2
Industrial Crops & Products 146 (2020) 112185
biochar loadings. A balance of biocomposites properties and economic
efficiency is expected to achieve in terms of maximizing the use of
agricultural wastes while minimizing the production cost.
2. Materials and methods
2.1. The constituents
Rice husk was used as feedstock to produce biochar at 600 °C using a
miniature box furnace (KSL-1100X-S). To get a higher yield, the pyr-
olysis temperature was increased from 25 °C (ambient temperature) to
600 °C at a low heating rate (5 °C/min) under 20 mL/min nitrogen at-
mosphere and held for 2 h to obtain the biochar sample. The biochar
sample was sieved over 150 μm screen to keep biochar particle size
below150 μm. The main parameters of the biochar sample and ashes
were shown in Table S1. HDPE (9001) pellets with a melt index of
0.05 g/10 min and a density of 0.950 g/cm3 were purchased from USI
Corporation. The biochar and HDPE were dried at 105 °C and 50 °C for
24 h prior to compounding with each other.
2.2. Composites processing
Dried biochar particles and HDPE pellets were put into a high-speed
mixer for 10 min to get the uniform blends. Subsequently, a micro twin-
screw extruder (WLG10 G) was used to melt and mix the composites
blends, and then a micro-injection molding machine (WZS10D) was
used to get cuboid shaped and dog bone shaped composite samples. The
extruding zone and blending zone of the extruder were run at 30 rpm
and 180 °C, the four temperature zones of injection moulding were all
set to 180 °C and the mold was kept at 50 °C. To maximize the utili-
zation of agricultural wastes, increasing the loading of biochar as much
as possible is necessary for this study. It was found that 70 wt% loading
of biochar was the maximum load that can be afforded in the compo-
sites in view of molding and deformation as shown in Fig. 1. Based on
this, the biochar/HDPE mixtures contained biochar ranging from 10 to
70 wt% with an interval of 10 wt% each, and the composite samples
under different biochar loadings were named as B10, B20, B30, B40,
B50, B60, and B70 respectively.
2.3. Composites characterization
Chemical characterization of HDPE and different biocomposites was
conducted using Fourier transform infrared spectroscopy (FTIR) and X-
Ray diffraction (XRD). FTIR of the samples was performed in a Fourier
transform infrared spectroscopy (Nicolet 5700, Thermo Fisher Nicolet,
USA) with a scanning range from 4000 cm−1 to 400 cm−1. XRD of the
samples was performed in a polycrystalline X-ray diffractometer
Fig. 1. Composites samples under different biochar loadings.
Q. Zhang, et al. Industrial Crops & Products 146 (2020) 112185

(Bruker AXS D8 Advance, Germany) using CuKα radiation with 2θ

varying between 5° and 60° at 5 °/min. Microstructure characterization
of fractured surfaces of different biocomposites was conducted in a
scanning electron microscope (SEM) (FEI Sirion 200, USA) with a
scanning voltage of 3.0 kV.
Thermal characterization of HDPE and different biocomposites was
conducted using Differential scanning calorimetry (DSC) and thermo-
gravimetric analysis (TGA). DSC of the samples was performed in a
differential scanning calorimeter analyzer (DSC-Q100, TA Instrument,
USA), and all the samples were heated to 180 °C and then cooled to
100 °C and then heated to 180 °C, all at 5 °C/min. TGA of the samples
was performed in a synchronous thermal analyzer (STA 449,
NETZSCH), and all the samples were heated from 30 to 600 °C under
the 20 mL/min nitrogen atmosphere with a heating rate of 10 °C/min.
Mechanical characterization of HDPE and different biocomposites
was conducted by dynamic mechanical analysis (DMA) and static me-
chanical analysis (SMA). DMA including viscoelastic behavior, creep Fig. 2. XRD spectra of HDPE and composites samples.
compliance and relaxation modulus was performed using a DMA Q 800
(TA instrument, USA). The samples were heated from −50 to 150 °C to
obtain the viscoelastic behavior in a single cantilever mode with the Table 1
Crystallization and melting behavior of HDPE and composites samples.
heating rate of 5 °C/min, and the 30 min creep compliance and re-
laxation modulus of the samples were obtained using the Creep TTS and Samples Tc (°C) Tm (°C) Xc (%)
Stress Relaxation TTS models of DMA under 30 °C. SMA including
HDPE 119.78 130.80 74.36
flexural and tensile properties was performed using an electronic uni- B10 119.83 130.96 60.15
versal testing machine (WDW1020, Changchun Kexin Co., Ltd., China). B20 119.88 130.65 58.41
Five specimens of each composite sample were tested. The average B30 120.04 130.54 59.12
values were reported with their standard errors, and the results were B40 120.09 130.51 52.74
B50 120.22 130.48 50.61
analyzed with SPSS using a one-way analysis of variance (ANOVA). The
B60 120.24 130.61 51.08
statistical analysis showed that the composites with varied loadings of B70 120.53 130.24 47.44
biochar had a significant difference in flexural and tensile properties
(p < 0.05).
HDPE and different biocomposites were completely immersed in biochar did not change the crystal planes of HDPE. A big intensity drop
water at ambient temperature for durations of up to 4 weeks, and the was observed in B10, which was due to that biochar addition even at
samples were removed and wiped to dry to measure the weights using a low loading (10 %) reduced the crystallinity degree (Xc) of HDPE as
precision weigh balance. Statistical analysis showed that the composites shown in Table 1. Additionally, the intensity of these two peaks in
with varied biochar loadings had a significant difference in water ab- composites was reduced as the loading of biochar increased. Since the
sorption (p < 0.05). The water uptake of samples was calculated by: biochar is amorphous in nature (Das et al., 2015), the increment of
amorphous biochar and reduction of Xc with the increase of biochar
Water Absorption (%) = (W1 − W0) / W0 × 100 %
loadings should be responsible for the reduction of major peaks in
where W1 and W0 are the weights of before and after soaking respec- composites (Zhang et al., 2019a).
tively.
The flame retardancy of HDPE and different biocomposites was
3.2. FTIR
characterized by a limited oxygen index using an oxygen index tester
(ZR-01, China), and the flow rate of oxygen and oxygen-nitrogen mix-
Fig. 3 illustrates the FTIR spectra of HDPE and composite samples.
ture were 3 L/min and 20 L/min, respectively. Statistical analysis
As can be observed from Fig. 3 that three typical peaks at 2920, 2850
showed that the composites with varied biochar loadings had a sig-
and 1470 cm−1 were shown in the FTIR spectra of HDPE and these
nificant difference in the limited oxygen index (p < 0.05). The limited
oxygen index of samples was calculated by:

Limited Oxygen Index (%) = [O2] / ([O2] + [N2]) × 100 %

where [O2] and [N2] are the flow rate of oxygen and nitrogen, re-
spectively

3. Results and discussion

3.1. XRD

Fig. 2 provides the results obtained from the XRD analysis of HDPE
and composite samples. From the figure, we can see two typical char-
acteristic peaks at 2θ of 21.6° and 24° which corresponded to (110) and
(200) crystal planes. Many documents confirmed that these two typical
crystal planes belonged to neat PE (Arnandha et al., 2017). It should be
noted that the position of the two typical characteristic peaks was not
changed with the addition of loading varied biochars indicating that the
two major peaks were both contributed by HDPE and the addition of Fig. 3. FTIR spectra of HDPE and composites samples.

3
Q. Zhang, et al. Industrial Crops & Products 146 (2020) 112185

three peaks can be assigned to the C–H stretching vibration of aliphatic

structures (Hahn et al., 2019). Highly biochar added composites,
especially B10, showed weaker peaks at 2920, 2850 and 1470 cm−1,
which was attributed to the lack of HDPE in composites. Interestingly,
peaks involving asymmetrical OeH stretching vibration and CeO
stretching vibration around 3400 cm−1 and 1080 cm−1 were weakly
detected in composites samples (Song et al., 2019). In addition, both
two peaks in the composites were contributed by the biochar. The
asymmetrical OeH stretching vibration was from phenolic hydroxyl
and alcohol hydroxyl in rice husk, and CeO stretching vibration was
caused by carbohydrates. The weakening of these two functional groups
indicates that the carbonization at 600 °C reduced the polarity of rice
husk and resulted in a low hydrophilicity. The similar results were also
obtained in Fig. S2. The contact angle analysis showed that biochar
added composites presented lower hydrophilicity compared to rice
husk/HDPE composites, which indicates that biochar added composites
had better mechanical properties than rice husk/HDPE composites. The
document demonstrated that the coupling agent showed little effect in Fig. 5. DSC spectra of HDPE and composites samples.
biochar/HDPE composites, which confirmed the analysis of this study
(Bajwa et al., 2019). Moreover, changes in the peak intensities, shifts due to the overloaded biochar. The effects of biochar loadings on the
and appearances or disappearances were not observed among the microstructure were consistent with those of mechanical properties. As
samples, which was evident that no chemical reaction occurred be- stated earlier, the physical/mechanical interlocking structure caused by
tween HDPE and the biochar. porous biochar was also displayed clearly. It is evident that the pene-
tration of the HDPE matrix in biochar pores and cavitation caused by
the HDPE matrix pullout shown in the images transferred the stress
3.3. SEM effectively. Based on these, good dispersion and unique interface
structure contributed to better mechanical properties of biochar added
SEM images of HDPE, biochar and the fractured surfaces of biochar composites (Zeng et al., 2018). The agglomeration and cracks shown in
added composites are shown in Fig. 4. It is expected that the typical the B70 image also gave an explanation for the high water absorption
smooth structure of HDPE and the porous structure of biochar were and poor mechanical properties of B70.
observed clearly by the SEM images. As can be observed in the SEM
image of B10, the biochar particles were dispersed in the HDPE matrix,
but the dispersion was not uniform. This can be attributed to an im- 3.4. DSC
balance of the ratio between biochar and HDPE. For further char-
acterization, the dispersion gradually improved as the increase of bio- The results obtained from the DSC analysis of HDPE and composite
char loadings, whereas B70 showed poor dispersion and agglomeration samples are illustrated in Fig. 5. In order to clearly reveal the effects of

Fig. 4. SEM images of HDPE, biochar and composites samples.

4
Q. Zhang, et al.
biochar loadings on the thermal properties of composite samples, the
DSC curves of different samples showed in Fig. 5. Looking at the DSC
curves of HDPE, two main peaks were observed. The first peak around
119.78 °C and the second peak around 130.80 °C are attributed to
exothermic crystallization and endothermic melting of HDPE respec-
tively (Pandey et al., 2017). What is interesting is that the DSC curves of
biochar added composite samples showed significant differences. All
the crystallization temperatures of the composite samples appeared to
be higher than that of HDPE. The higher the biochar loading, the higher
the crystallization temperature. Biochar acted as the crystal growth
point as a nucleating agent for crystallization of the HDPE with the
early onset of exothermic crystallization occurred (Das et al., 2016c),
although the addition of biochar reduced the Xc of HDPE shown in
Table 1 and Fig. 2. However, all the melting temperatures of the
composites were slightly lower compared to neat HDPE indicating a
decreasing lamella thickness and smaller crystals (Li et al., 2016).
Moreover, the increase of energy required for melting in biochar added
composites was observed (Das et al., 2018). The increase of biochar
loadings resulted in the increase of the required energy, suggesting that
the addition of biochar improved the thermal stability of HDPE.
3.5. TGA
The TG and DTG curves of HDPE and biochar added composites are
demonstrated in Fig. 6. Fig. 6(a) shows the mass loss curves and
Fig. 6(b) shows the derivatives of the mass loss curves. It can be ob-
served from Fig. 6 that the degradation of HDPE started at about 450 °C
and tended to be stable after 500 °C, the most intense degradation oc-
curred at about 480 °C, and this result belongs to the typical thermal
Fig. 6. TGA of HDPE and composites samples: (a) TG (b) DTG.
5
Industrial Crops & Products 146 (2020) 112185
decomposition process of HDPE (Lin et al., 2019). Comparing with
HDPE, all these three temperatures for all biochar added composites
showed a delay. And this delay was more significant in higher loadings
of biochar added composites especially for B70. On the other hand, the
residue produced after the degradation of all samples also showed a
different trend. As shown in Fig. 6(a), there was little residue produced
from HDPE after the temperature cycle indicating an almost complete
degradation. It should be noted that the biochar loading was positively
correlated with the amount of residue produced, and the comparison
was as follows: B70 > B60 > B50 > B40 > B30 > B20 > B10 >
HDPE. B70 retained the maximum amount of residue (∼60 %). The
proximate analysis from Fig. S1 showed a high ash content (∼43.45 %)
in the biochar sample and a high SiO2 content (∼89.5 wt%) in the ash.
The enrichment of stable SiO2 in biochar should be responsible for the
amount of residue produced (De Bhowmick et al., 2018). Moreover, the
increase of the stable biochar was the main reason for the increase of
the amount of residue produced (Das et al., 2016a). In conclusion,
biochar can enhance the thermal property of HDPE in terms of the delay
of decomposition temperatures. Biochar shows great potential and
benefits in the preparation of high thermal stability materials.
3.6. Viscoelastic behavior
Fig. 7 presents the viscoelastic behavior including a variation of
storage modulus and loss factor with temperatures of HDPE and biochar
added composites. According to Fig. 7(a), increasing temperatures from
−50 to 150 °C resulted in decreased storage modulus of all samples.
Since the increase of the temperature aggravated the thermal move-
ment of HDPE molecules, the deformation of composites resulted in
Fig. 7. Viscoelastic behavior of HDPE and composites samples: (a) storage
modulus (b) loss factor.
Q. Zhang, et al.
Fig. 8. Variation of (a) creep behavior and (b) stress relaxation in 30 min for
HDPE and composites samples.
poor dimensional stability (Pillai and Renneckar, 2016). In addition, it
is obvious that all the biochar added composites showed higher storage
modulus than that of HDPE suggesting that the stiffness of HDPE was
improved with the addition of biochars. As stated earlier, rigid biochar
particles resulted in an increase of stiffness. The large difference be-
tween the static mechanical properties and dynamic mechanical prop-
erties was that B70 showed higher storage modulus among the samples.
Subsequently, a variation of loss factor with temperatures of all samples
was shown in Fig. 7(b). It should be noted that all the biochar added
composites showed lower loss factor values than that of neat HDPE,
which was attributed to good interfacial interactions between biochar
and HDPE. The decrease of the composites caused by biochar in loss
factor also indicated an improvement of HDPE elasticity.
3.7. Creep behavior and stress relaxation
Creep behavior and stress relaxation reflect the dimensional stabi-
lity of a composite, and also can be used to characterize the mechanical
properties of a composite. As shown in Fig. 8, the creep behavior and
stress relaxation of neat HDPE and biochar added composites were
characterized using creep compliance and stress relaxation modulus in
this study. Both creep behavior and stress relaxation of all samples
showed three main stages suggesting the properties of typical thermo-
plastic polymers. Interestingly, all the biochar added composites
showed lower creep compliance than that of HDPE, and the creep
compliance continuously decreased with an increase of the biochar
amount in the HDPE composites. It can be stated that the addition of
biochar improved the creep resistance of HDPE. This can be attributed
to the improvement of dimensional stability, and the addition of rigid
6
Industrial Crops & Products 146 (2020) 112185
Fig. 9. Flexural properties of HDPE and composites samples: (a) flexural
strength (b) flexural modulus.
biochar improved the stiffness and increased the ability to resist the
deformation of the composites (Davis et al., 2019). Likewise, the stress
relaxation modulus continuously increased with an increase of the
biochar amount in the HDPE composites, and this suggested that the
addition of biochar improved the anti-stress relaxation ability of HDPE.
Having better rigidity and a special porous structure should be re-
sponsible for the enhancement of creep resistance and anti-stress re-
laxation ability. Hence, biochar exhibited critical benefits in the me-
chanical properties of composites.
3.8. Flexural properties
Fig. 9 compares the flexural properties including flexural strength
and flexural modulus of HDPE and biochar added composites. It can be
observed that there was a significant difference in HDPE with the ad-
dition of biochar in terms of flexural properties. Improvement of both
flexural strength and flexural modulus was achieved on the whole. The
flexural strength and modulus of HDPE were 14.14 MPa and 0.88 GPa,
respectively whereas those of B10 were 16.37 MPa and 0.91 GPa, re-
spectively. And this increment of flexural properties was reached due to
the unique characteristics of biochar. Having a high surface area
(297.36 m2/g) and a special porous structure should be responsible for
the improvement of flexural properties. Das et al. (Das et al., 2016a)
reported that at high temperatures, HPDE, which was in a fluid state,
could fill the pores of the biochar under the extrusion of the screw, and
a physical/mechanical interlocking was resulted after cooling. Since
this physical/mechanical interlocking can transfer stress efficiently, it
was the main contribution for the better flexural properties. It can also
Q. Zhang, et al. Industrial Crops & Products 146 (2020) 112185

tensile strength among the samples was obtained. In addition, the

tensile modulus of HDPE, B10, B20, B30, B40, B50, B60 and B70
samples were 1.33, 1.36, 1.47, 1.69, 1.70, 1.87, 2.03 and 0.98 GPa,
respectively. Also, B60 illustrated the maximum tensile modulus with a
significant increase by 52.63 %, from 1.33 GPa for the neat HDPE to
2.03 GPa. Li et al. (Li et al., 2018) have summarized that better tensile
strength of a composite can be obtained by homogenous dispersion of
filler particles in a polymer matrix, which could give an explanation for
better tensile strength of B40 and B50. Also, the stress transfer me-
chanism caused by interfacial bonding dictates the tensile strength of a
composite (Fu et al., 2008). Thus, the betterment of the tensile strength
in biochar added composites was strongly dependent on the afore-
mentioned special interface bonding. The increase of tensile modulus in
biochar added composites suggests another advantage in mechanics,
and this improvement can be attributed to the rigidity of biochars. The
incorporation of rigid biochars into the HDPE matrix reduced the de-
formability and mobility of HDPE macromolecules (Siebert and Wilker,
2019), which improved the stiffness of biochar added composites.
Moreover, biochar obtained at 600 °C carbonization showed low hy-
drophilicity in this study, and this was confirmed by the contact angle
in Fig. S2. Similar polarities resulting in good affinity could also be
responsible for the improvement of tensile properties of biochar added
composites. Nevertheless, the tensile properties of B70 decreased ob-
viously. As can be known from Fig. 1 that B70 was severely deformed.
Limited HDPE matrix cannot afford excessive biochar particles and the
plasticity of the composites was reduced. Excessive biochar caused the
agglomeration, resulting in the fact that the interfacial bonding strength
of B70 was weakened, stress propagation was obstructed, and the ten-
sile properties of B70 were decreased (Nasser et al., 2019).

3.10. Water absorption

In addition to the above mechanical properties, water absorption is

also an important factor affecting the dimensional stability of a com-
Fig. 10. Tensile properties of HDPE and composites samples: (a) tensile
posite. The results of water absorption for HDPE and biochar added
strength (b) tensile modulus.
composites in 28 days at room temperature are presented in Fig. 11.
According to the figure, it is expected that the water absorption of all
be observed from Fig. 9 that flexural strength and modulus of samples the samples increased with the immersion time indicating the damage
B50 and B40 reached a maximum of 34.95 MPa and 1.79 GPa, respec- of dimensional stability by long-time immersion. Besides, HDPE showed
tively. As stated earlier in Table S1, the high SiO2 content (∼89.5 wt%) lower water absorption below 0.2 %, this can be attributed to the mi-
in the ash of biochar was beneficial to improve the mechanical prop- crocracks produced in the manufacturing process. Upon closer ob-
erties of the composites. Bulota et al. obtained a similar result in PLA/ servation in Fig. 11, it can be observed that the water absorption in-
algae composites (Bulota and Budtova, 2015). On the other hand, this creased for the biochar added composites as the biochar loading
particular good increase can also be attributed to the good dispersion of increased, and there was a positive correlation between water absorp-
biochar in HDPE as shown in Fig. S3. Many documents (Goud et al., tion and biochar loading. This result exhibited the worse water-re-
2019; Oliveira et al., 2018) confirmed that the particle dispersion of sistance of biochar added composites than that of neat HDPE with the
fillers in the matrix was important for the flexural strength of a com-
posite. Also, the flexural properties of B60 and B70 confirmed this
theory exactly. From B40 and B50 to B60 and B70, the flexural prop-
erties of biochar added composites showed a significant reduction. The
most important reason for this decrease was the poor particle dispersion
in the matrix. Less HDPE matrix cannot effectively load more biochar
particles, resulting in serious particle agglomeration (Aliotta et al.,
2019) and a compromise of flexural properties.

3.9. Tensile properties

Fig. 10 compares the tensile properties including tensile strength

and tensile modulus of HDPE and biochar added composite samples.
Determining the tensile properties of a composite dictates its applica-
tions, and an overall improvement can be observed from Fig. 10 with
the addition of biochar. The tensile strength of HDPE, B10, B20, B30,
B40, B50, B60 and B70 samples were 23.54, 23.21, 24.88, 25.20, 29.05,
26.25, 24.90 and 19.02 MPa, respectively. When the B40 biochar
loading reached 40 wt%, the tensile strength increased by 23.41 %, Fig. 11. Variation of water absorption in 28 days for HDPE and composites
from 23.54 MPa for the neat HDPE to 29.05 MPa, and the maximum samples.

7
Q. Zhang, et al.
Fig. 12. Limited oxygen index of HDPE and composites samples.
addition of biochar. The water absorption of a composite is dependent
on some factors such as fine pores, lumens, and the gaps in the interface
(Zabihzadeh, 2010). On the one hand, some interfacial voids between
biochar and HDPE were produced during the composite making pro-
cess, and water was absorbed by these interfacial voids (Guo et al.,
2019). On the other hand, the porous structure of biochar should also
be responsible for the poor water resistance, although biochar showed
low hydrophilicity because of the decrease of hydroxyl groups under
high temperatures. Additionally, there was a significant difference in
water absorption between B70 and other samples, and B70 showed the
worst water resistance. This result can be attributed to the agglom-
eration of biochar in HDPE and many biochar particles agglomerated
together, which increased the contact area with water and resulted in
higher water absorption.
3.11. Flame retardancy
Since the flammability of a composite dictates application in out-
door, limited oxygen index measurements were performed to char-
acterize flame retardancy of HDPE and biochar added composites in
this study. Limited oxygen index refers to the volume ratio of oxygen in
the mixture of oxygen and nitrogen., The greater the limited oxygen
index, the lower the flammability and the better the flame retardant
effect. As shown in Fig. 12, HDPE shows a lower limited oxygen index
of 18.21 % indicating its poor flame retardant, and this result was
consistent with the report of Jiang et al. (Jiang et al., 2018). It should
be noted that the limited oxygen index increased for the biochar added
composites as the biochar loading increased, which indicates that an
increase in the flame retardancy was obtained by adding biochar to
HDPE. As stated earlier, the addition of biochar improved the thermal
properties of HDPE due to its high thermal stability. Thus, it can be
stated that the improvement of flame retardancy in HDPE was obtained
by the addition of biochar, and this can be attributed to that the biochar
with high thermal stability hindered the transport of heat between the
heat source and HPDE (Das et al., 2016a). On the other hand, many
documents have reported that the preparation of biochar was accom-
panied by the production of a large number of metal oxides and in-
organic substances in the process of carbonization (Chen et al., 2019;
Wei et al., 2018). These nonflammable metal oxides and inorganic
substances acting as flame retardants can effectively slow down the
combustion of HDPE and improve the flame retardancy of it. Besides,
the greatest limited oxygen index of 25.06 % was obtained in B70 in-
dicating the potential of biochar in flame retardant of composites.
4. Conclusions
In order to maximize the utilization of agricultural wastes, the effect
of high biochar loadings on biochar added composites was investigated
8
Industrial Crops & Products 146 (2020) 112185
and interesting results were obtained in this study. The addition of
biochar did not change the crystal planes of HDPE and no chemical
reaction occurred between HDPE and the biochar. Biochar caused the
early onset of exothermic crystallization of biochar added composites
by DSC and improvement of thermal properties in biochar added
composites was achieved in terms of the amount of residue produced by
TGA. Moreover, the addition of biochar improved the mechanical
properties of HDPE. Best flexural strength of 34.95 MPa in B50, the
flexural modulus of 1.79 GPa in B40, the tensile strength of 29.05 MPa
in B40, and the tensile modulus of 2.03 GPa were obtained, which in-
dicated that high biochar loading filled composites with good me-
chanical properties were achieved. Besides, good stiffness, elasticity,
creep resistance and anti-stress relaxation ability were also obtained in
high biochar added composites. Although the increase of biochar
loadings decreased the water-resistance of the composites, the compo-
sites with highly filled biochars suggested better flame retardant. The
results presented here indicated that maximizing the utilization of
agricultural wastes to prepare green products with excellent properties
can be achieved by highly loaded biochar composites.
CRediT authorship contribution statement
Qingfa Zhang: Conceptualization, Methodology, Formal analysis,
Investigation, Writing - original draft. Donghong Zhang: Methodology,
Writing - review & editing. Hang Xu: Methodology, Writing - review &
editing. Wenyu Lu: Methodology, Writing - review & editing. Xiajin
Ren: Methodology, Writing - review & editing. Hongzhen Cai:
Conceptualization, Funding acquisition, Writing - review & editing,
Supervision. Hanwu Lei: Conceptualization, Funding acquisition,
Writing - review & editing, Supervision. Erguang Huo: Validation,
Writing - review & editing. Yunfeng Zhao: Validation, Writing - review
& editing. Moriko Qian: Validation, Writing - review & editing. Xiaona
Lin: Validation, Writing - review & editing. Elmar M. Villota: Writing -
review & editing. Wendy Mateo: Writing - review & editing.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgments
The authors appreciate that this work was financially supported by
the Natural Science Foundation of Shandong Province of China (No.
ZR2019MEE036); the Agriculture and Food Research Initiative
Competitive Grant (No. 2016-67021-24533, and 2014-38502-22598)
from the National Institute of Food and Agriculture, United States
Department of Agriculture; the National Key Research and
Development Program of China (No. 2018YFD1101001); the National
Natural Science Fund of China (No. 51806129); the distinguished ex-
pert of Taishan scholars Shandong province project and the higher
education superior discipline team training program of Shandong pro-
vince.
Appendix A. Supplementary data
Supplementary material related to this article can be found, in the
online version, at doi:https://doi.org/10.1016/j.indcrop.2020.112185.
References
Aliotta, L., Cinelli, P., Coltelli, M.B., Lazzeri, A., 2019. Rigid filler toughening in PLA-
Calcium Carbonate composites: effect of particle surface treatment and matrix plas-
ticization. Eur. Polym. J. 113, 78–88.
Arnandha, Y., Satyarno, I., Awaludin, A., Irawati, I.S., Prasetya, Y., Prayitno, D.A.,
Q. Zhang, et al.
Winata, D.C., Satrio, M.H., Amalia, A., 2017. Physical and mechanical properties of
WPC board from sengon sawdust and recycled HDPE plastic. Procedia Eng. 171,
695–704.
Arrigo, R., Jagdale, P., Bartoli, M., Tagliaferro, A., Malucelli, G., 2019. Structure–property
relationships in polyethylene-based composites filled with biochar derived from
waste coffee grounds. Polymers 11, 1336.
Bajwa, D.S., Adhikari, S., Shojaeiarani, J., Bajwa, S.G., Pandey, P., Shanmugam, S.R.,
2019. Characterization of bio-carbon and ligno-cellulosic fiber reinforced bio-com-
posites with compatibilizer. Constr. Build. Mater. 204, 193–202.
Behazin, E., Misra, M., Mohanty, A.K., 2017. Sustainable biocarbon from pyrolyzed
perennial grasses and their effects on impact modified polypropylene biocomposites.
Compos. Part B Eng. 118, 116–124.
Bulota, M., Budtova, T., 2015. PLA/algae composites: morphology and mechanical
properties. Compos. Part A Appl. Sci. Manuf. 73, 109–115.
Chen, C., Yan, X., Xu, Y., Yoza, B.A., Wang, X., Kou, Y., Ye, H., Wang, Q., Li, Q.X., 2019.
Activated petroleum waste sludge biochar for efficient catalytic ozonation of refinery
wastewater. Sci. Total Environ. 651, 2631–2640.
Chow, C.-F., Wong, W.-L., Chan, C.-W., Chan, C.-S., 2018. Converting inert plastic waste
into energetic materials: a study on the light-accelerated decomposition of plastic
waste with the Fenton reaction. Waste Manag. 75, 174–180.
Das, O., Sarmah, A.K., Bhattacharyya, D., 2015. A sustainable and resilient approach
through biochar addition in wood polymer composites. Sci. Total Environ. 512,
326–336.
Das, O., Bhattacharyya, D., Hui, D., Lau, K.-T., 2016a. Mechanical and flammability
characterisations of biochar/polypropylene biocomposites. Compos. Part B Eng. 106,
120–128.
Das, O., Bhattacharyya, D., Sarmah, A.K., 2016b. Sustainable eco–composites obtained
from waste derived biochar: a consideration in performance properties, production
costs, and environmental impact. J. Clean. Prod. 129, 159–168.
Das, O., Sarmah, A.K., Zujovic, Z., Bhattacharyya, D., 2016c. Characterisation of waste
derived biochar added biocomposites: chemical and thermal modifications. Sci. Total
Environ. 550, 133–142.
Das, O., Kim, N.K., Kalamkarov, A.L., Sarmah, A.K., Bhattacharyya, D., 2017. Biochar to
the rescue: balancing the fire performance and mechanical properties of poly-
propylene composites. Polym. Degrad. Stab. 144, 485–496.
Das, O., Kim, N.K., Hedenqvist, M.S., Lin, R.J., Sarmah, A.K., Bhattacharyya, D., 2018. An
attempt to find a suitable biomass for biochar-based polypropylene biocomposites.
Environ. Manage. 62, 403–413.
Das, O., Hedenqvist, M.S., Johansson, E., Olsson, R.T., Loho, T.A., Capezza, A.J., Raman,
R.S., Holder, S., 2019. An all-gluten biocomposite: comparisons with carbon black
and pine char composites. Compos. Part A Appl. Sci. Manuf. 120, 42–48.
Davis, A.M., Hanzly, L.E., DeButts, B.L., Barone, J.R., 2019. Characterization of dimen-
sional stability in flax fiber reinforced polypropylene composites. Polym. Compos. 40,
132–140.
De Bhowmick, G., Sarmah, A.K., Sen, R., 2018. Production and characterization of a value
added biochar mix using seaweed, rice husk and pine sawdust: a parametric study. J.
Clean. Prod. 200, 641–656.
Demirbas, A., 2011. Waste management, waste resource facilities and waste conversion
processes. Energy Convers. Manage. 52, 1280–1287.
Fa, W., Wang, J., Ge, S., Chao, C., 2019. Performance of photo-degradation and thermo-
degradation of polyethylene with photo-catalysts and thermo-oxidant additives.
Polym. Bull. 1–16.
Ferreira, G.F., Pierozzi, M., Fingolo, A.C., da Silva, W.P., Strauss, M., 2019. Tuning su-
garcane bagasse biochar into a potential carbon black substitute for polyethylene
composites. J. Polym. Environ. 27, 1735–1745.
Fu, S.-Y., Feng, X.-Q., Lauke, B., Mai, Y.-W., 2008. Effects of particle size, particle/matrix
interface adhesion and particle loading on mechanical properties of particulate–po-
lymer composites. Compos. Part B Eng. 39, 933–961.
Giorcelli, M., Khan, A., Pugno, N.M., Rosso, C., Tagliaferro, A., 2019. Biochar as a cheap
and environmental friendly filler able to improve polymer mechanical properties.
Biomass Bioenergy 120, 219–223.
Goud, V., Alagirusamy, R., Das, A., Kalyanasundaram, D., 2019. Influence of various
forms of polypropylene matrix (fiber, powder and film states) on the flexural strength
of carbon-polypropylene composites. Compos. Part B Eng. 166, 56–64.
Guo, G., Finkenstadt, V.L., Nimmagadda, Y., 2019. Mechanical properties and water
absorption behavior of injection-molded wood fiber/carbon fiber high-density poly-
ethylene hybrid composites. Adv. Compos. Hybrid Mater. 1–11.
Hahn, A., Gerdts, G., Völker, C., Niebühr, V., 2019. Using FTIRS as pre-screening method
for detection of microplastic in bulk sediment samples. Sci. Total Environ. 689,
341–346.
Ho, M.-p., Lau, K.-t., Wang, H., Hui, D., 2015. Improvement on the properties of polylactic
Industrial Crops & Products 146 (2020) 112185
acid (PLA) using bamboo charcoal particles. Compos. Part B Eng. 81, 14–25.
Jiang, D., Pan, M., Cai, X., Zhao, Y., 2018. Flame retardancy of rice straw-polyethylene
composites affected by in situ polymerization of ammonium polyphosphate/silica.
Compos. Part A Appl. Sci. Manuf. 109, 1–9.
Li, S., Li, X., Chen, C., Wang, H., Deng, Q., Gong, M., Li, D., 2016. Development of
electrically conductive nano bamboo charcoal/ultra-high molecular weight poly-
ethylene composites with a segregated network. Compos. Sci. Technol. 132, 31–37.
Li, S., Huang, A., Chen, Y.-J., Li, D., Turng, L.-S., 2018. Highly filled biochar/ultra-high
molecular weight polyethylene/linear low density polyethylene composites for high-
performance electromagnetic interference shielding. Compos. Part B Eng. 153,
277–284.
Lim, S.L., Lee, L.H., Wu, T.Y., 2016. Sustainability of using composting and vermi-
composting technologies for organic solid waste biotransformation: recent overview,
greenhouse gases emissions and economic analysis. J. Clean. Prod. 111, 262–278.
Lin, X., Kong, L., Cai, H., Zhang, Q., Bi, D., Yi, W., 2019. Effects of alkali and alkaline
earth metals on the co-pyrolysis of cellulose and high density polyethylene using TGA
and Py-GC/MS. Fuel Process. Technol. 191, 71–78.
Mashouf Roudsari, G., Mohanty, A.K., Misra, M., 2017. A statistical approach to develop
biocomposites from epoxy resin, poly (furfuryl alcohol), poly (propylene carbonate),
and biochar. J. Appl. Polym. Sci. 134, 45307.
Mohanty, A.K., Vivekanandhan, S., Pin, J.-M., Misra, M., 2018. Composites from re-
newable and sustainable resources: challenges and innovations. Science 362,
536–542.
Nan, N., DeVallance, D.B., Xie, X., Wang, J., 2016. The effect of bio-carbon addition on
the electrical, mechanical, and thermal properties of polyvinyl alcohol/biochar
composites. J. Compos. Mater. 50, 1161–1168.
Nasser, J., Lin, J., Steinke, K., Sodano, H.A., 2019. Enhanced interfacial strength of
aramid fiber reinforced composites through adsorbed aramid nanofiber coatings.
Compos. Sci. Technol. 174, 125–133.
Oliveira, L.Á., Santos, J.C., Panzera, T.H., Freire, R.T., Vieira, L.M., Scarpa, F., 2018.
Evaluation of hybrid-short-coir-fibre-reinforced composites via full factorial design.
Compos. Struct. 202, 313–323.
Pandey, P., Bajwa, S.G., Bajwa, D.S., Englund, K., 2017. Performance of UV weathered
HDPE composites containing hull fiber from DDGS and corn grain. Ind. Crops Prod.
107, 409–419.
Pillai, K.V., Renneckar, S., 2016. Dynamic mechanical analysis of layer-by-layer cellulose
nanocomposites. Ind. Crops Prod. 93, 267–275.
Poulose, A.M., Elnour, A.Y., Anis, A., Shaikh, H., Al-Zahrani, S., George, J., Al-Wabel,
M.I., Usman, A.R., Ok, Y.S., Tsang, D.C., 2018. Date palm biochar-polymer compo-
sites: an investigation of electrical, mechanical, thermal and rheological character-
istics. Sci. Total Environ. 619, 311–318.
Santhiago, M., Garcia, P.S., Strauss, M., 2018. Bio-based nanostructured carbons toward
sustainable technologies. Curr. Opin. Green Sustain. Chem. 12, 22–26.
Siebert, H.M., Wilker, J.J., 2019. Deriving commercial level adhesive performance from a
bio-based mussel mimetic polymer. ACS Sustain. Chem. Eng. 7, 13315–13323.
Song, B., Chen, M., Zhao, L., Qiu, H., Cao, X., 2019. Physicochemical property and col-
loidal stability of micron-and nano-particle biochar derived from a variety of feed-
stock sources. Sci. Total Environ. 661, 685–695.
Turku, I., Keskisaari, A., Kärki, T., Puurtinen, A., Marttila, P., 2017. Characterization of
wood plastic composites manufactured from recycled plastic blends. Compos. Struct.
161, 469–476.
Wang, X., Peng, S., Chen, H., Yu, X., Zhao, X., 2019. Mechanical properties, rheological
behaviors, and phase morphologies of high-toughness PLA/PBAT blends by in-situ
reactive compatibilization. Compos. Part B Eng., 107028.
Wei, D., Li, B., Huang, H., Luo, L., Zhang, J., Yang, Y., Guo, J., Tang, L., Zeng, G., Zhou, Y.,
2018. Biochar-based functional materials in the purification of agricultural waste-
water: fabrication, application and future research needs. Chemosphere 197,
165–180.
Zabihzadeh, S.M., 2010. Water uptake and flexural properties of natural filler/HDPE
composites. BioResources 5, 316 -232.
Zeng, S., Shen, M., Yang, L., Xue, Y., Lu, F., Chen, S., 2018. Self-assembled montmor-
illonite–carbon nanotube for epoxy composites with superior mechanical and thermal
properties. Compos. Sci. Technol. 162, 131–139.
Zhang, Q., Yi, W., Li, Z., Wang, L., Cai, H., 2018. Mechanical properties of rice husk
biochar reinforced high density polyethylene composites. Polymers 10, 286.
Zhang, Q., Khan, M.U., Lin, X., Cai, H., Lei, H., 2019a. Temperature varied biochar as a
reinforcing filler for high-density polyethylene composites. Compos. Part B Eng. 175,
107151.
Zhang, Q., Li, Y., Cai, H., Lin, X., Yi, W., Zhang, J., 2019b. Properties comparison of high
density polyethylene composites filled with three kinds of shell fibers. Results Phys.
12, 1542–1546.