Cellulose

https://doi.org/10.1007/s10570-019-02429-6 (0123456789().,-volV)
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ORIGINAL RESEARCH

Characterization of natural cellulose fiber from corn stalk

waste subjected to different surface treatments
Yucheng Liu . Jun Xie . Na Wu . Yunhai Ma . Carlo Menon .
Jin Tong

Received: 13 December 2018 / Accepted: 11 April 2019

Ó Springer Nature B.V. 2019

Abstract Crop stalk is a valuable source of cellu- characterized. The surface treatments improved the
losic biomass and has attracted increasing attention as chemical and mechanical properties of the corn stem
one kind of renewable resource. Cellulose fibers have fibers. The fibers had rougher surfaces after the surface
potential as a reinforcement material to replace treatments. EDX and FTIR analysis confirmed that the
synthetic fibers used in biopolymer composites. This surface treatments removed a certain amount of
study addresses the modification and characterization hemicelluloses, lignin and pectin from the natural
of corn stem fibers extracted from corn stalk waste. fiber surface. XRD analysis results showed that the
The corn stem fibers were treated with alkali, silane surface treatments had a positive impact on the
and NaOH-silane solutions, and then, the chemical crystallinity index of the natural fibers. The mechan-
properties, surface morphology, mechanical behaviors ical properties and thermal stability of the treated corn
and thermal stability of the corn stem fibers were stem fibers were also found to be improved.

Keywords Corn stalk  Surface treatment  Fiber

Y. Liu  Y. Ma (&)  J. Tong
Key Laboratory of Bionic Engineering (Ministry of extraction  Cellulose fiber  Natural fiber  XRD
Education PR China), Jilin University, Nanling Campus,
Changchun 130022, People’s Republic of China
e-mail: myh@jlu.edu.cn

Y. Liu Introduction
Editorial Department of Journal of Bionic Engineering,
Jilin University, Nanling Campus, Changchun 130022, Environmental pollution, global warning, energy
People’s Republic of China crisis and environment-friendly material needs have
J. Xie encouraged researchers to develop biocomposite
Air Combat Service Academy, Air Force Aviation materials for the aviation, automobile and marine
University, Changchun 130021, People’s Republic of industries (Rashid et al. 2016; Liu et al. 2019a, b;
China
Singh et al. 2019). Natural fiber-reinforced composite
N. Wu materials have attractive properties in comparison to
Collage of Automotive Engineering, Shandong Jiaotong synthetic ones, such as light weight, abundance,
University, Jinan 250023, People’s Republic of China biodegradability, nontoxicity, and low cost (Väisänen
et al. 2017; Barari et al. 2016a, b). In recent years,
C. Menon
School of Engineering Science, Simon Fraser University, natural fibers have attracted increasing attention as an
Burnaby V5A 1S6, BC, Canada eco-friendly and inexpensive substitute for synthetic

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fibers in the reinforcement of composite materials have reported that alkali and silane treatments are two
(Barari et al. 2016a, b; Sepe et al. 2018). Natural fibers of the most effective and most popular methods. These
have many advantages and attractive features, such as two surface treatments could improve the interfacial
abundance, light weight, biodegradability, renewabil- compatibility of the natural fiber and matrix, and
ity, low cost and high specific stiffness (Liu and change the microstructure of the natural fiber. San-
Tisserat 2018; Indran et al. 2018; Sanjay et al. 2018). gappa et al. (2014) evaluated the influence of NaOH
Natural fibers used to reinforce composite materials solution treatment on the physical, chemical, and
mainly include plant, animal and mineral fibers (Mittal surface properties of Indian hemp fibers. The
et al. 2016). In recent years, plant fibers, such as stalk, microstructural parameters of hemp fiber decreased
base, leaf, seed, wood and grass, have become an with increasing treatment time. The surface of the
important part of reinforcing materials and they are the natural fiber became rough and the fiber was suit-
most significant source of cellulosic fibers (Ramesh able for reinforcement. Sang et al. (2017) investigated
et al. 2017). Stalk fibers are mainly sourced from the surface modification of basalt fiber treated with a
straws of different kinds of crops, including corn, silane agent (KH-550). This work revealed that silane
barley, bagasse, wheat, sorghum, and rice (Ramesh treatment could increase the tensile strength and
et al. 2017). modulus of basalt fiber, and improve the interface
Corn is an important worldwide agricultural crop, bonding strength between the poly(butylene succi-
especially in northeast and northern China, such as in nate) matrix and the fiber in biocomposites. Moreover,
Jilin province. It is predicted that there are approxi- the silane treatment of the natural fiber provided an
mately 0.25 billion tons of corn stalks in China each effective way to prepare high-performance and
year (Ma et al. 2018). However, less than half of the biodegradable composite materials.
corn stalks are utilized, and most are thrown away or Although a large number of studies have been
burned by local farmers, which is a waste of renewable devoted to the application of corn stalk wastes and
biomass or biomass-derived resources and pollutes the chemical surface treatment of natural fibers, the
water and air, such as haze (Wang et al. 2011). The effects of different surface treatments on the chemical
pollution caused by corn stalks has become a global properties, surface morphology, mechanical behaviors
issue that needs to be addressed. In fact, numerous and thermal stability of corn stem fibers have seldom
research studies in recent years have investigated the been reported. In fact, different chemical treatment
benefits of using annual corn stalk wastes in fiber methods have a different impact on the natural fiber
reinforced biocomposite materials, low-cost housing, properties. Hence, an attempt is made in this paper to
paper-making and packaging (Ma et al. 2018; Li et al. improve the chemical, morphological and mechanical
2016). Research on the use of corn stalk waste could properties and thermal stability of the raw corn stem
solve energy issues and environmental problems, and fibers by various surface treatments. The present study
boost the agricultural economy (Bi et al. 2009). demonstrated the influence of an alkali treatment, a
It is well documented that a weakness of natural silane treatment and a combined NaOH-silane treat-
fiber is their poor compatibility with composite matrix ment on the chemical properties, surface morphology,
due to their hydrophilic lignocellulosic molecules and mechanical behaviors and thermal stability of such
low thermal stability (Zhou et al. 2016). Surface chemically treated corn stem fibers, and determined an
modification is a necessary step to prepare the effective treatment method to improve the natural fiber
reinforcing fibers used in biocomposite materials, properties. The surface morphology of raw and treated
and it is becoming a major area of research due to their corn stem fibers was observed using scanning electron
large potential in industrial applications. In fact, alkali microscopy (SEM) and energy dispersive X-ray
treatment or mercerization, silane treatment, use of spectroscopy (EDX). The surfaces of untreated and
maleated coupling agents, acetylation treatment, radi- treated corn stem fibers were evaluated using X-ray
ation and discharge treatments, benzoylation treat- diffraction (XRD) and Fourier transform infrared
ment and peroxide treatment have been widely (FTIR) spectroscopy to investigate the structural and
reported so far (Venkata Krishna and Kanny 2016; chemical changes in the fibers, respectively. The
Kumar et al. 2014; Liu et al. 2019a, b). Several studies mechanical properties and thermal stability of the corn
(Yu et al. 2010; Asim et al. 2016; Orue et al. 2016) stem fiber were evaluated using a universal testing

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machine and TGA analysis, respectively. The were dried in a heat-treatment tank at 90 °C for 24 h.
obtained morphology, chemical and structural infor- The temperature of silane treatment was chosen
mation, as well as mechanical properties and thermal considering references in the literature (Sepe et al.
stability of the corn stem fibers, can help guide the 2018; Zhou et al. 2014). In the combined NaOH-silane
surface treatment of natural fibers and the extraction of treatment, part of the corn stem fibers were treated
cellulose fibers applied in biopolymer composite with NaOH solution as described in the NaOH-
applications. treatment step, and then they were treated with a
silane solution as described in the silane-treatment
step.
Experimental materials and methods
Morphology characterization
Materials
The lateral and transversal surfaces of untreated and
Corn stalk has received extra attention due to its treated corn stem fibers were evaluated by SEM
abundance and easy availability (Cai et al. 2016a, b). (SU3500, Hitachi, Japan) at an operating voltage of
The corn stem has a compact layer of cell walls and a 15 kV. All specimen surfaces were sputter coated with
higher cellulose content in comparison to other parts gold by using a SBC-12 sputter coater to improve the
of corn stalk, which can improve its mechanical conductivity of the natural fibers prior to SEM
strength (Luo et al. 2017). In this study, corn stalks observation.
were harvested on a farm in Jilin province, China.
After air drying, the stems of the corn stalk were EDX measurements
cleaned and dried, and the skins of the corn stems were
obtained using a skin separator. Then, the corn stem Energy dispersive X-ray spectroscopy (EDX) is a
fiber samples were prepared for the experiments. The commonly used method to determine the quantity of
silane coupling agent KH-550, c-Aminopropyltri- elements (such as carbon, oxygen, and nitrogen) on a
ethoxysilane (APS, molecular mass of natural fiber surface. The elemental distributions on
221.37 gmol-1), used in this work was purchased the raw and alkali-, silane- and NaOH-silane-treated
from Jinan Jinhui Chemical Industry Co., Ltd. of corn stem fibers were determined by EDX (Oxford
China. In addition, all other chemical agents, such as INCAx-sight, Oxford Instruments, UK), which was
NaOH and alcohol, were of analytical grade. installed on the SEM. The data is expressed in atomic
and weight percentages.
Fiber surface treatments
FTIR measurements
Corn stem fibers were treated with three types of
chemical treatment methods, namely, an alkali treat- The untreated and treated corn stem fibers were
ment, a silane treatment and a combined NaOH-silane evaluated using a FTIR spectroscopy (6800-50/
treatment. For the alkali treatment, corn stem fibers NEXUS, ThermoNicolet, USA) to analyze the com-
were soaked in 5 wt% sodium hydroxide solution for ponent changes of the natural fibers. FTIR spectra
30 min at room temperature and then rinsed with were recorded using an infrared spectrometer in the
distilled water until the pH was equal to 7. After range of 675–4000 cm-1 with a resolution of 2 cm-1
washing, the corn stem fibers were kept in a heat- at room temperature and in the dry environment. The
treatment tank for 24 h at 90 °C. In the silane corn stem fiber samples were dried using a special
treatment, corn stem fibers were treated using a drying box.
solution containing 5 wt% of silane coupling agent
in a mixture of ethanol and water (80 vol%/20 vol% XRD measurements
solution of ethanol/water) for 60 min under normal
atmospheric pressure at room temperature, and then XRD patterns were obtained at an ambient tempera-
the fibers were rinsed with distilled water until the pH ture of 22 °C from radiation recorded by a 18 KW D/
was equal to 7. Subsequently, the corn stem fibers Max-2500PC diffractometer (Rigaku, Japan). The

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tests were performed at 40 kV and 20 mA (5̊–40̊, 2̊/ Results and discussion

min). The corn stem fiber samples are dry. The
crystallinity index (CrI) was evaluated by the follow- SEM analysis
ing equation based on the Segal empirical method
(Segal et al. 1959): The effect of different surface treatments on transver-
I200  Iam sal and lateral surfaces was investigated using SEM.
CrI¼  100%; ð1Þ Figure 1a–1d show SEM micrographs of transversal
I200
surfaces of untreated and treated corn stem fibers. It
where I200 is the maximum intensity of the (200) can be observed in Fig. 1a that a vascular bundle and
lattice diffraction peak at a 2h angle between 22° and complete parenchyma cell were presented on the
23°, and Iam is the minimum intensity of an amorphous transversal surface of the fiber, and there was a large
area at a 2h angle between 18° and 19° (Öztürk et al. visible lumen in the center of the vascular bundle and
2010; Borchani et al. 2015; Seki et al. 2018). parenchyma cell. Figure 1b–d show that the size of the
lumen decreased, and the shape of lumen was
Mechanical property measurements irregular. The lumen of the corn stem fibers was
invisible, and a large swelling of parenchyma cell
Mechanical properties, including tensile strength, walls could be observed in Fig. 1b and d. Meanwhile,
Young’s modulus and elongation at break of the corn the thickness of the cell wall of the fibers treated with
stem fibers, were measured at room temperature using alkali solution and silane solution increased, which is
an MTS Criterion40 universal testing machine (MTS slightly larger than that of untreated fiber. However,
Systems Corporation, USA) with a cross head speed of the lumen completely collapsed in the process of
1 mm/min and a fiber gauge length of 40 mm at NaOH-silane treatment, as shown in Fig. 1c. A similar
35 ± 3% relative humidity (RH). Twenty-five corn result was reported by John and Anandjiwala (2008),
stem fibers were measured in each sample, and the test who concluded that the natural crystalline structure of
results were recorded as the average. The cross- the cellulose was relaxed, which led to swelling of
sectional dimensions of the natural fiber samples were natural fibers during chemical treatment.
calculated accurately according to the failure surfaces Figure 2a–d show SEM micrographs of lateral
of the fiber after each test. The tensile strength was surfaces of the corn stem fibers. As shown in Fig. 2a,
evaluated by the following equation: the surface of the natural fiber was smooth, unbroken
r ¼ Fb =S0 ; ð2Þ and uniform. Generally, wax, pectin, lignin, hemicel-
luloses and cellulose are presented on a fiber surface
where r is the tensile strength, Fb is the max force at (Nadlene et al. 2016); Except for cellulose, the other
fiber break, S0 is the area of fracture, and the values of compositions could be removed by chemical treat-
Fb can be obtained from the experimental data. ment, which improved the mechanical properties and
Young’s modulus was obtained from the slope of the the poor compatibility of the natural fiber (Ramamoor-
stress–strain curves, and the elongation at break was thy et al. 2015). In comparison with the untreated corn
also obtained from the experimental data. stem fiber, the treated fibers had rough surfaces and
appeared jagged in Fig. 2b and c. A possible expla-
TGA measurements nation is that chemical treatments of the fibers lead to
removal of hemicellulose, lignin and ash. Meanwhile,
The thermal stability of the raw and silane-treated corn natural fibers with a rough surface would be the most
stem fibers was measured by thermogravimetric desired (Ramamoorthy et al. 2015). According to the
analysis (TGA) (SDT Q600, TA Instruments, USA) literature (Alvarez et al. 2003), alkali treatment of sisal
to evaluate the thermal degradation of the natural fibers leads to rough fiber surfaces, and it also
fibers. Approximately 10 mg of the natural fiber improves the mechanical properties of the natural
powder samples was analyzed, and the spectrum was fiber and the interface bonding strength between the
recorded under an argon atmosphere from 40 to fiber and composite matrix. Mohd Edeerozey et al.
650 °C at a heating rate of 10 °C/min and a flow rate (2004) also evaluated the surface morphology of kenaf
of 30 mL/min. fibers treated with various NaOH concentrations. The

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Fig. 1 SEM images of transversal surfaces of corn stem fibers. a Untreated fiber; b alkali-treated fiber; c NaOH-silane-treated fiber;
d silane-treated fiber

Fig. 2 SEM images of lateral surfaces of corn stem fibers. a Untreated fiber; b alkali-treated fiber; c NaOH-silane-treated fiber;
d silane-treated fiber

experimental results concluded that the treated fibers fibers. This difference is vital for the following
had outstanding mechanical properties in comparison reasons: (1) the ethanol/water mixture in the solution
to the untreated fibers. The surface morphology of the could remove part of pectin and hemicelluloses
silane-treated corn stem fiber in Fig. 2c and d (Rachini et al. 2009) and (2) a siloxane layer formed
presented a slightly regular and unadulterated surface on the surface of the fiber as the condensation of the
free of residues in comparison to that of the other silane groups [see Fig. 3 Liu et al. (2019a, b)]. The

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Fig. 3 Mechanism of interaction between the APS (KH-550) and cellulosic fibers

presence of APS could change the chemical compo- analysis (Hassaini et al. 2017). A corn stem fiber is
sition of the surface of the corn stem fiber and, in turn, mainly composed of cellulose, lignin, hemicelluloses
the surface morphology of the natural fibers. and waxes, and the chemical composition of the corn
stem has been reported by Luo et al. (2017). The basic
EDX analysis chemical elements in the corn stem fibers are carbon
and oxygen. Inorganic elements, such as Al, Mg, Cl, K
The data from the quantitative elemental corn stem and Ca, can also be presented on the fiber surface, but
fiber analysis before and after chemical modification in trace amounts (see Table 1). Table 1 shows that a
in terms of weight and atomic weight are presented in certain amount of Na was presented in the outer layer
Table 1. EDX analysis is one of the most popular of the natural fiber after NaOH treatment. This could
techniques for quantitative and qualitative elemental be attributed to the type of bond formation and

Table 1 Weight and Elements Untreated (%) NaOH (%) NaOH-silane (%) Silane (%)
atomic percentage of
untreated and treated corn Weight Atomic Weight Atomic Weight Atomic Weight Atomic
stem fibers using EDX
C 55.95 63.06 35.87 44.17 48.47 56.48 44.03 52.35
O 43.11 36.47 53.11 49.10 47.01 41.12 52.08 45.34
Si 0.88 0.44 0.37 0.19 2.19 1.09 2.43 1.24
Na – – 9.01 5.80 1.82 1.11 – –
Al 0.06 0.03 – – – – – –
Mg – – 0.49 0.30 0.12 0.07 0.20 0.12
Cl – – 0.27 0.11 – – 0.48 0.24
K – – 0.44 0.17 – – 0.46 0.19
Ca – – 0.44 0.16 0.39 0.14 0.36 0.13

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changes that take place on the surface of the corn stem cellulose, hemicellulose, pectin and lignin are visible,
fiber during the NaOH treatment. The reaction of as mentioned in a previous publication (Sepe et al.
NaOH and the corn stem fiber is as follows: 2018).
After alkali treatment, the peak at approximately
Fiber  OH þ NaOH ! Fiber  O Naþ þ H2 O:
1723 cm-1 can be ascribed to the C=O bonds stretch-
ð3Þ ing from the hemicelluloses and pectin in the raw corn
The corn stem fiber treated with a silane solution led to stem fibers, which was no longer visible in the treated
incorporation of silicon. The results obtained are a corn stem fiber (Sepe et al. 2018). Meanwhile, a weak
good indication of Si in the silane-corn stem fiber peak, at approximately 1513 cm-1, could be ascribed
structure, which could be explained by the fact that the to C=C group stretching vibration in the carbonyl of
silanization of cellulosic constituents of the corn stem hemicellulose (Maache et al. 2017), and its absorbance
fiber led to the formation of silanol functional groups was lower than that of the untreated fiber. A weak peak
(see Fig. 3). Table 1 also reveals a decrease in the and lower absorbance in treated fibers were due to
percentage of carbon content and an increase in partial removal of lignin from the natural fiber surface.
oxygen content after chemical treatments because the Moreover, the peak observed at approximately
surface treatments may have removed part of the 1243 cm-1 (C–O bond stretching) was no longer
pectin and hemicelluloses from the surface of the observed in the corn stem fibers treated with alkali
treated fibers (Senthamaraikannan & Kathiresan, solution and NaOH-silane solution. This indicated that
2018). This result is consistent with the FTIR analysis parts of lignin and hemicellulose in the treated fibers
results in ‘‘FTIR analysis’’ section. were removed (Shanmugasundaram et al. 2018).
It is well known that there should be Si–O–Si and
FTIR analysis Si–C stretching vibrations in the spectral curve of the
silane-treated corn stem fibers (viridis and blue curves
Figure 4 shows the FTIR spectra of the corn stem in Fig. 4). This agrees with the EDX analysis result,
fibers treated with different chemical solutions com- which confirmed the existence of silicon on the fiber
pared with that of the untreated fiber. The character- surface after the silane treatments. However, the peak
istic peaks at approximately 3349 cm-1, 2917 cm-1, is not visible, as the concentration of the silane
1723 cm-1, 1513 cm-1, 1243 cm-1, and 898 cm-1 solution is relatively low and the signals are over-
correspond to the O–H, C–H, C=O, C=C, C–O, C1–H lapped by organic component signals of the corn stem
bonds, respectively. fibers (Sepe et al. 2018). Moreover, the peak at
In the FTIR spectrum of the untreated corn stem approximately 1243 cm-1 was lower than that of the
fiber (black curve in Fig. 4), the characteristic peaks of untreated fiber, which indicated that part of the
hemicellulose was removed during the silane treat-
ment due to the effect of the ethanol/water mixture
(Rachini et al. 2009).

XRD analysis

The X-ray diffraction patterns of untreated and treated

corn stem fibers are shown in Fig. 5. As shown in
Fig. 5, the X-ray diffraction pattern of the corn stem
fiber presented major peaks at 2h angles of approxi-
mately 15.54°, 16.28°, 22.12° and 34.54°, correspond-
ing to lattice planes of peak 1 ((1–10)), peak 2 ((110)),
peak 3 ((200)) and peak 4 ((004)) for cellulose I
crystallites (French 2014; Dong et al. 2014; Jayara-
mudu et al. 2010). Peaks 1–3 are the characteristic
peaks of cellulose I (French and Santiago 2013; Li
Fig. 4 FT-IR spectra of untreated and treated corn stem fibers et al. 2014; Borchani et al. 2015). Peaks 1 and 2 are

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to the degradation of amorphous components in

natural fibers and the rearrangement of cellulose
molecules. The increase of CrI in the treated fibers
could contribute towards its enhanced mechanical
properties (Rong et al. 2001) and was also ideal for
preparing biocomposite applications (Cai et al.
2016a, b).

Mechanical property analysis

Tensile tests were performed to investigate the

mechanical properties of the corn stem fibers. Three
important properties, including tensile strength,
Young’s modulus and elongation at break, were
Fig. 5 XRD curves of untreated and treated corn stem fibers investigated in the tensile tests. In the present study,
we learned that the mechanical properties were
most likely overlapping and appear as a single broad significantly affected by the chemical and morpho-
peak due to a large full-width at half-maximum logical changes of the corn stem fibers.
(French and Santiago 2013; Ornaghi et al. 2014). Figure 6 shows typical tensile stress–strain curves
XRD results also show that no structural transforma- of the raw and treated corn stem fibers. As shown in
tion from the cellulose I to cellulose II polymorph Fig. 6, the stress value in these curves suddenly
occurred after the surface treatments. dropped, which indicated that both raw and treated
The cellulose CrI calculated from the XRD patterns corn stem fibers are brittle in nature (Maache et al.
of each natural fiber is presented in Table 2. The CrI of 2017).
the corn stem fibers that were untreated and treated The mechanical properties of the corn stem fibers
with alkali solution, NaOH-silane solution and silane are presented in Table 2 and Fig. 7. From the results, it
solution were approximately 58.2%, 65.7%, 64.4% can be observed that the mechanical properties of the
and 69.7%, respectively. Interestingly, the degree of natural fiber changed dramatically with chemical
cellulose crystallinity increased after the chemical treatments. The corn stem fiber treated with silane
treatments, which is described as follows. The chem- solution showed the highest tensile strength,
ical treatments removed a part of noncrystalline 223.33 MPa, followed by the fiber treated with alkali
materials, namely, hemicelluloses or lignin, in the solution, 152.90 MPa. The tensile strength of the fiber
natural fibers (‘‘FTIR analysis’’ section), which could treated with NaOH-silane is 113.87 MPa, and the
allow the cellulose fibers to adopt a more crystalline untreated fiber is 112.95 MPa. Overall, the decrease in
structure (Obi Reddy et al. 2013), and they also caused tensile strength follows the order: silane [ NaOH [
swelling of the parenchyma cell walls (‘‘SEM analy- NaOH-silane [ untreated. The variations in the
sis’’ section). Esteves (2009) concluded that cellulose Young’s modulus of untreated and treated natural
crystallinity could increase after surface treatment due fibers were similar to their tensile strengths. The

Table 2 Crystallinity characteristics and mechanical properties of untreated and treated corn stem fibers
CrI (%) Tensile strength (MPa) Young’s modulus (GPa) Elongation at break (%)

Utreated 58.2 112.95 ± 24.15 3.69 ± 0.96 3.64 ± 0.52

NaOH 65.7 152.90 ± 32.51 5.13 ± 1.18 3.67 ± 1.05
NaOH-silane 64.4 113.87 ± 19.36 4.63 ± 0.81 2.74 ± 0.36
Silane 69.7 223.33 ± 41.22 7.05 ± 1.07 4.02 ± 1.24

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Fig. 6 Tensile stress–strain curves of untreated and treated

corn stem fibers

Young’s modulus of the treated corn stem fibers was

higher than that of the untreated fiber. The Young’s
modulus of the fibers treated with silane and NaOH
solutions increased by 91.06% and 39.02%, respec-
tively, and by 25.47% in the fibers treated with NaOH-
silane solution, with respect to the native fibers.
Compared to the untreated natural fiber, the elongation
at break improved 0.82% and 10.44% after silane and
alkali treatments, respectively; however, it decreased
by 24.73% in the fiber treated with NaOH-silane. The
increases in the tensile strength and Young’s modulus
after chemical treatments can be attributed to the
removal of hemicelluloses, pectin, and lignin from the
corn stem fibers (‘‘FTIR analysis’’ section) and the
improved crystallinity of the natural fibers (‘‘XRD
analysis’’ section). As mentioned in the literature
review (Onuaguluchi and Banthia 2016), the chemical
composition of the natural fibers had a great effect on
their mechanical properties; that is to say, their
mechanical properties depended on the cellulose
content in the natural fiber as well as the fiber surface
treatment methods. Shanmugasundaram et al. (2018)
also observed that appropriate removal of the noncel-
lulose contents could improve the tensile strength and
Young’s modulus of the natural fibers. Moreover, Fig. 7 Mechanical properties of untreated and treated corn
Sang et al. (2017) mentioned that the surface modi- stem fibers. a Tensile strength, b Young’s modulus, c Elongation
at break
fication of the fibers could improve the interfacial
adhesion and the transmission of stress from the
Higher chemical concentration could remove more
matrix to natural fibers to a certain degree. The slight
noncellulosic composition and impurities, but chem-
increases in the tensile strength and Young’s modulus
ical degradation of the fiber and fiber breakdown
and the decrease in the elongation at break occurred
decreased the tenacity and elongation at break (Ra-
when the fiber was treated with NaOH-silane solution.
mamoorthy et al. 2015; Puglia et al. 2013). Fernandez

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Fig. 8 TGA/DTG curves of a raw corn stem fiber and b silane treated corn stem fiber

et al. (2016) also concluded that a large removal of phase of mass loss occurred in the temperature range
non-cellulosic composition induce the degradation of of 300–450 °C for the raw and silane-treated corn
the natural fiber and then seriously impact the stem fibers. At this stage, a dramatic mass reduction of
transverse tensile behaviors of the natural fiber approximately 70% was observed at 323 °C for the
reinforced composites. Moreover, it is need to develop raw corn stem fiber and 327 °C for the silane-treated
the selective and non-degrading treatments which are corn stem fiber, which could be attributed to the
better able to control the final performances of the bio- thermal decomposition of a-cellulose (Belouadah
composite materials. et al. 2015). After saline solution treatment, the
thermal stability and degradation temperature
TGA analysis increased from 130 to 152 °C and from 323 to
327 °C, respectively. Similar degradation behavior
Through the above analysis, silane-treated corn stem could be found in previously published papers
fiber showed excellent chemical and mechanical (Belouadah et al. 2015; Senthamaraikannan and
properties. In this section, we emphasize on the Kathiresan 2018). From the DTG curves of the raw
comparison and analysis of the thermal stability of and treated natural fibers, it is indicated that both the
the raw and silane-treated corn stem fibers. Thermal thermal stability and degradation temperature of the
stability was investigated by TGA, and the TGA/DTG treated fiber were increased, which could be attributed
curves are presented in Fig. 8. The TGA/DTG curves to the formation of a siloxane layer on the surface of
clearly show that degradation of the raw and silane- the corn stem fiber (Seki et al. 2018). At 650 °C, the
treated corn stem fibers occurs in three different residual mass or char residue also increased from 16 to
phases (Senthamaraikannan and Kathiresan 2018). In 22% after silane treatment. These residuals of cellu-
the first phase, 12.3% and 7.4% mass loss was lose degradation mainly included carbon residues and
presented for the raw and silane-treated corn stem nondegraded fillers (Maache et al. 2017).
fibers, respectively, at temperatures of 40–130 °C.
The changes were attributed to the vaporization of
moisture in the natural fibers (Mayandi et al. 2018; Conclusion
Rajan et al. 2018). In the second phase, thermal
degradation occurred at approximately 180–300 °C The influence of different surface chemical treatments
with a mass-loss of 42.4% for the raw corn stem fiber on the chemical properties, surface morphology,
and 36.3% for the silane-treated corn stem fiber due to mechanical behavior and thermal stability of the corn
the degradation of hemicellulose and the glycosidic stem fibers were investigated, and the obtained results
linkages of cellulose (Indran et al. 2014). The final were discussed and reported in the present paper. SEM

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images showed that the lumen of the corn stem fibers Asim M, Jawaid M, Abdan K, Ishak MR (2016) Effect of alkali
collapsed due to swelling of the cell wall, and the fiber and silane treatments on mechanical and fibre-matrix bond
strength of kenaf and pineapple leaf fibres. J Bionic Eng
lateral surface had a rough surface and appeared 13(3):426–435
jagged due to the removal of noncellulosic contents Barari B, Omrani E, Moghadam AD, Menezes PL, Pillai KM,
after chemical treatments. EDX results are evidence of Rohatgi PK (2016a) Mechanical, physical and tribological
Si in the silane-corn stem fiber structure due to the characterization of nano-cellulose fibers reinforced bio-
epoxy composites: an attempt to fabricate and scale the
formation of silanol functional groups on the fiber ‘Green’ composite. Carbohyd Polym 147:282–293
surface. The results obtained from the FTIR study Barari B, Ellingham TK, Ghamhia II, Pillai KM, El-Hajjar R,
confirm that noncellulosic materials are removed due Turng LS, Sabo R (2016b) Mechanical characterization of
to the influence of chemical treatments. XRD results scalable cellulose nano-fiber based composites made using
liquid composite molding process. Compos B Eng
proved that the crystallinity index of the corn stem 84:277–284
fibers improved by following the chemical treatments. Belouadah Z, Ati A, Rokbi M (2015) Characterization of new
The chemical treatments led to improved mechanical natural cellulosic fiber from Lygeum spartum L. Carbohyd
properties of the corn stem fibers, which could Polym 134:429–437
Bi YY, Wang YJ, Gao CY (2009) Problems of burning straw and
contribute to different chemical structures and molec- its management countermeasures in China. J Anhui Agric
ular rearrangements of the corn stem fibers. Moreover, Sci 37(27):13181–13184
appropriate removal of the noncellulose contents Borchani KE, Carrot C, Jaziri M (2015) Untreated and alkali
could improve the tensile strength and Young’s treated fibers from Alfa stem: effect of alkali treatment on
structural, morphological and thermal features. Cellulose
modulus of the corn stem fibers. The thermal stability 22(3):1577–1589
and degradation temperature of the treated fibers were Cai D, Li P, Luo Z, Qin P, Chen C, Wang Y, Wang Z, Tan TW
also improved after surface treatments. The above (2016a) Effect of dilute alkaline pretreatment on the con-
comparison results confirm that the silane treatment version of different parts of corn stalk to fermentable sug-
ars and its application in acetone-butanol-ethanol
was the optimum way to improve the comprehensive fermentation. Biores Technol 211:117–124
properties of the corn stem fibers. The improvements Cai M, Takagi H, Nakagaito AN, Li Y, Waterhouse GIN
demonstrated in the present paper are critical to (2016b) Effect of alkali treatment on interfacial bonding in
efficiently produce natural cellulosic fibers for fabri- abaca fiber-reinforced composites. Compos A Appl Sci
Manuf 90:589–597
cation of various biopolymer composite applications Dong Z, Hou X, Sun F, Zhang L, Yang Y (2014) Textile grade
that could be applied in the aviation, automobile and long natural cellulose fibers from bark of cotton stalks
marine industries. In the further work, we will further using steam explosion as a pretreatment. Cellulose
investigate the effect of silane solution with various 21(5):3851–3860
Esteves B (2009) Wood modification by heat treatment: a
concentrations on the morphological, chemical, phys- review. BioResources 4(1):370–404
ical and mechanical properties of the corn stem fibers. Fernandez JA, Moigne NL, Caro-Bretelle AS, Hage RE, Duc
AL, Lozachmeur M et al (2016) Role of flax cell wall
Acknowledgments This project was supported by National components on the microstructure and transverse
Natural Science Foundation of China (Grant Nos. 51875242 and mechanical behaviour of flax fabrics reinforced epoxy
51505259), by the China-EU H2020 FabSurfWAR project biocomposites. Ind Crops Prod 85:93–108
(Grant Nos. 2016YFE0112100 and 644971), by Natural Science French AD (2014) Idealized powder diffraction patterns for
Foundation of Jilin Province of China (Grant No. cellulose polymorphs. Cellulose 21(2):885–896
20190302129GX), by China Postdoctoral Science Foundation French AD, Santiago Cintrón M (2013) Cellulose polymorphy,
(Grant No. 2016M601383), by Jilin Province Science and crystallite size, and the Segal crystallinity index. Cellulose
Technology Development Plan Item (Grant Nos. 20(1):583–588
20170101173JC and 20170204015NY), by the 111 project Hassaini L, Kaci M, Touati N, Pillin I, Kervoelen A, Bruzaud S
(Grant No. B16020), by Jilin Province Development and (2017) Valorization of olive husk flour as a filler for bio-
Reform Commission Plan Item (Grant No. 2018C044-3). composites based on poly(3-hydroxybutyrate-co-3-hy-
droxyvalerate): effects of silane treatment. Polym Testing
59:430–440
Indran S, Raj RE, Sreenivasan VS (2014) Characterization of
References new natural cellulosic fiber from Cissus quadrangularis
root. Carbohyd Polym 110(18):423–429
Alvarez VA, Ruscekaite RA, Vazquez A (2003) Mechanical Indran S, Raj RDE, Daniel BSS, Binoj JS (2018) Comprehen-
properties and water absorption behaviour of composites sive characterization of natural Cissus quadrangularis stem
made from a biodegradable matrix and alkaline-treated fiber composites as an alternate for conventional FRP
sisal fibres. J Compos Mater 37:1575–1588 composites. J Bionic Eng 15(5):914–923

123
 Cellulose

Jayaramudu J, Guduri BR, Rajulu AV (2010) Characterization Ornaghi HL, Poletto M, Zattera AJ, Amico SC (2014) Corre-
of new natural cellulosic fabric Grewia tilifolia. Carbohyd lation of the thermal stability and the decomposition
Polym 79(4):847–851 kinetics of six different vegetal fibers. Cellulose
John MJ, Anandjiwala RD (2008) Recent developments in 21(1):177–188
chemical modification and characterization of natural Orue A, Jauregi A, Unsuain U, Labidi J, Eceiza A, Arbelaiz A
fiber-reinforced composites. Polym Compos 29:187–207 (2016) The effect of alkaline and silane treatments on
Kumar SMS, Duraibabu D, Subramanian K (2014) Studies on mechanical properties and breakage of sisal fibers and poly
mechanical, thermal and dynamic mechanical properties of (lactic acid)/sisal fiber composites. Compos A Appl Sci
untreated (raw) and treated coconut sheath fiber reinforced Manuf 84:186–195
epoxy composites. Mater Des 59:63–69 Öztürk I, Irmak S, Hesenov A, Erbatur O (2010) Hydrolysis of
Li Y, Li G, Zou Y, Zhou Q, Lian X (2014) Preparation and kenaf (Hibiscus cannabinus L.) stems by catalytical ther-
characterization of cellulose nanofibers from partly mal treatment in subcritical water. Biomass Bioenerg
mercerized cotton by mixed acid hydrolysis. Cellulose 34(11):1578–1585
21(1):301–309 Puglia D, Monti M, Santulli C, Sarasini F, De Rosa IM, Kenny
Li P, Cai D, Luo ZF, Qin PY, Chen CJ, Wang Y, Zhang C, Wang JM (2013) Effect of alkali and silane treatments on
Z, Tan T (2016) Effect of acid pretreatment on different mechanical and thermal behavior of Phormium tenax
parts of corn stalk for second generation ethanol produc- fibers. Fibers Polym 14:423–427
tion. Bioresour Technol 206:86–92 Rachini A, Le Troedec M, Peyratout C, Smith A (2009) Com-
Liu Z, Tisserat BH (2018) Coating applications to natural fiber parison of the thermal degradation of natural, alkali-treated
composites to improve their physical, surface and water and silane-treated hemp fibers under air and an inert
absorption characters. Ind Crops Prod 112:196–199 atmosphere. J Appl Polym Sci 112(1):226–234
Liu YC, Xie J, Wu N, Wang LD, Ma YH, Tong J (2019a) Rajan BS, Balaji MAS, Saravanakumar SS (2018) Effect of
Influence of silane treatment on the mechanical, tribolog- chemical treatment and fiber loading on physico-mechan-
ical and morphological properties of corn stalk fiber rein- ical properties of Prosopis juliflora fiber reinforced hybrid
forced polymer composites. Tribol Int 131:398–405 friction composite. Mater Res Express 6(3):035302
Liu YC, Ma YH, Yu JT, Zhuang J, Wu SY, Tong J (2019b) Ramamoorthy SK, Skrifvars M, Rissanen M (2015) Effect of
Development and characterization of alkali treated abaca alkali and silane surface treatments on regenerated cellu-
fiber reinforced friction composites. Compos Interfaces lose fibre type (lyocell) intended for composites. Cellulose
26(1):67–82 22(1):637–654
Luo Z, Li P, Cai D, Chen Q, Qin P, Tan T, Gao H (2017) Ramesh M, Palanikumar K, Reddy KH (2017) Plant fibre based
Comparison of performances of corn fiber plastic com- bio-composites: sustainable and renewable green materi-
posites made from different parts of corn stalk. Ind Crops als. Renew Sustain Energy Rev 79:558–584
Prod 95:521–527 Rashid B, Leman Z, Jawaid M, Ghazali MJ, Ishak MR (2016)
Ma C, Zhang S, Dong RD, Wang M, Jia WD, Lu ZG (2018) Physicochemical and thermal properties of lignocellulosic
Corn stalk fiber-based biomass brick reinforced by com- fiber from sugar palm fibers: effect of treatment. Cellulose
pact organic/inorganic calcification composites. ACS 23(5):2905–2916
Sustain Chem Eng 6:2086–2093 Rong MZ, Zhang MQ, Liu Y, Yang GC, Zeng HM (2001) The
Maache M, Bezazi A, Amroune S, Scarpa F, Dufresne A (2017) effect of fiber treatment on the mechanical properties of
Characterization of a novel natural cellulosic fiber from unidirectional sisal-reinforced epoxy composites. Compos
Juncus effusus L. Carbohyd Polym 171:163–172 Sci Technol 61(10):1437–1447
Mayandi K, Rajini N, Pitchipoo P, Jappes JTW, Rajulu AV (2018) Sang L, Zhao M, Liang Q, Wei Z (2017) Silane-treated basalt
Properties of untreated and chemically treated Cissus quad- fiber-reinforced poly(butylene succinate) biocomposites:
rangularis natural fibers and their composites with polyester interfacial crystallization and tensile properties. Polymers
as the matrix. Polym Compos 39(3):876–886 9(8):351
Mittal V, Saini R, Sinha S (2016) Natural fiber-mediated epoxy Sangappa BL, Rao Asha S, Kumar RM, Somashekar R (2014)
composites—a review. Compos B Eng 99:425–435 Physical, chemical, and surface properties of alkali-treated
Mohd Edeerozey AM, Hazizan MD, Akil Azhar AB, Zainal Indian hemp fibers. Compos Interfaces 21:153–159
Ariffin MI (2004) Chemical modification of kenaf fibers. Sanjay MR, Siengchin S, Parameswaranpillai J, Jawaid M,
Mater Lett 61(10):2023–2025 Pruncu CI, Khan A (2018) A comprehensive review of
Nadlene R, Sapuan SM, Jawaid M, Ishak MR, Yusriah L (2016) techniques for natural fibers as reinforcement in compos-
The effects of chemical treatment on the structural and ites: preparation, processing and characterization. Carbo-
thermal, physical, and mechanical and morphological hyd Polym 207:108–121
properties of roselle fiber-einforced vinyl ester composites. Segal L, Creely JJ, Martin AE, Conrad CM (1959) An empirical
Polym Compos 27(5):519–523 method for estimating the degree of crystallinity of native
Obi Reddy K, Uma Maheswari C, Shukla M, Song JI, Varada cellulose using the X-ray diffractometer. Text Res J
Rajulu A (2013) Tensile and structural characterization of 29(10):786–794
alkali treated Borassus fruit fine fibers. Compos B Eng Seki Y, Kılınç AÇ, Dalmis R, Atagür M, Köktaş S, Göktaş AA,
44(1):433–438 Çelik E, Seydibeyoğlu MÖ, Önay AB (2018) Surface
Onuaguluchi O, Banthia N (2016) Plant-based natural fibre modification of new cellulose fiber extracted from Conium
reinforced cement composites: a review. Cement Concr maculatum plant: a comparative study. Cellulose
Compos 68:96–108 25(6):3267–3280

123
Cellulose

Senthamaraikannan P, Kathiresan M (2018) Characterization of Venkata Krishna K, Kanny K (2016) The effect of treatment on
raw and alkali treated new natural cellulosic fiber from kenaf fiber using green approach and their reinforced
Coccinia grandis L. Carbohydrate Polym 186:332–343 epoxy composites. Compos B Eng 104:111–117
Sepe R, Bollino F, Boccarusso L, Caputo F (2018) Influence of Wang G, Chen C, Li J, Zhou B, Xie M, Hu S, Chen Y (2011)
chemical treatments on mechanical properties of hemp Molecular composition and size distribution of sugars,
fiber reinforced composites. Compos B Eng 133:210–217 sugar-alcohols and carboxylic acids in airborne particles
Shanmugasundaram N, Rajendran I, Ramkumar T (2018) during a severe urban haze event caused by wheat straw
Characterization of untreated and alkali treated new cel- burning. Atmos Environ 45(15):2473–2479
lulosic fiber from an Areca palm leaf stalk as potential Yu T, Ren J, Li S, Yuan H, Li Y (2010) Effect of fiber surface-
reinforcement in polymer composites. Carbohyd Polym treatments on the properties of poly (lactic acid)/ramie
195:566–575 composites. Compos A Appl Sci Manuf 41:499–505
Singh T, Gangil B, Patnaik A, Biswas D, Fekete G (2019) Zhou F, Cheng G, Jiang B (2014) Effect of silane treatment on
Agriculture waste reinforced cornstarch-based biocom- microstructure of sisal fibers. Appl Surf Sci 292:806–812
posites: effect of rice husk/walnut shell on physicome- Zhou Y, Fan M, Chen L (2016) Interface and bonding mecha-
chanical, biodegradable and thermal properties. Mater Res nisms of plant fibre composites: an overview. Compos B
Express 6(4):045702 Eng 101:31–45
Väisänen T, Das O, Tomppo L (2017) A review on new bio-
based constituents for natural fiber-polymer composites.
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