International Journal of Polymer Analysis and

Characterization

ISSN: 1023-666X (Print) 1563-5341 (Online) Journal homepage: http://www.tandfonline.com/loi/gpac20

Preparation and characterization of biodegradable

sugarcane bagasse nano reinforcement for
polymer composites using ball milling operation

M. Kathiresan & P. Sivaraj

To cite this article: M. Kathiresan & P. Sivaraj (2016) Preparation and characterization of
biodegradable sugarcane bagasse nano reinforcement for polymer composites using ball
milling operation, International Journal of Polymer Analysis and Characterization, 21:5,
428-435, DOI: 10.1080/1023666X.2016.1168061

To link to this article: http://dx.doi.org/10.1080/1023666X.2016.1168061

Accepted author version posted online: 22

Mar 2016.
Published online: 22 Mar 2016.

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 INTERNATIONAL JOURNAL OF POLYMER ANALYSIS AND CHARACTERIZATION
2016, VOL. 21, NO. 5, 428–435
http://dx.doi.org/10.1080/1023666X.2016.1168061

Preparation and characterization of biodegradable sugarcane

bagasse nano reinforcement for polymer composites using ball
milling operation
M. Kathiresana and P. Sivarajb
a
Department of Mechanical Engineering, Thiagarajar College of Engineering, Madurai, Tamil Nadu, India; bDepartment
of Mechanical Engineering, Theni Kammavar Sangam College of Technology, Koduvilarpatti, Theni, Tamil Nadu, India

ABSTRACT ARTICLE HISTORY

The present work includes the processing and characterization of nano- Submitted 26 February 2016
based natural reinforcement for polymer composite materials. Sugarcane Accepted 16 March 2016
bagasse has been collected and the fibers were extracted using manual KEYWORDS
striping process. Undesirable materials present in the extracted fibers were Bagasse; ball milling;
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removed by 1% NaOH-based chemical treatment. The macrofibers were characterization; nano; TGA
reduced to nano scale by using high-energy ball milling process.
Nanoparticles from bagasse fibers were characterized by X-ray diffraction
(XRD), Fourier transform infrared (FTIR) spectroscopy, scanning electron
microscopy (SEM), and thermogravimetric analysis (TGA). The degree of
crystallinity of nano bagasse is 55.2% and it was reported by using XRD. A
FTIR spectrum confirms the presence of cellulose functional groups in nano
bagasse. The nano bagasse dimensions and morphology were investigated
using SEM. The average length and diameter of the nano bagasse is 51.2 and
46.1 nm, respectively. Thermal stability of the nano bagasse was revealed by
TGA analysis. The chemical composition of cellulose, lignin, and hemi-
cellulose contents was also investigated.

Introduction
In the recent decades, nano-structured natural-fiber materials have attracted the attention of many
researchers for reinforcement in the field of composite materials due to their eco-friendly nature
and unique characteristics such as high surface area-to-volume ratio, high Young's modulus, high
tensile strength, and low coefficient of thermal expansion. Nanoparticles are roughly having
1–100 nm dimensions and their unique phenomena enable novel applications.[1] The nano-sized
natural fibers can be isolated by new top-down mechanical processing technique by using
high-energy ball milling.[2–4]
Sugarcane is a renewable and natural agricultural resource. It provides sugar and bagasse as a
major byproduct. As much as 200 million tons of bagasse are obtained every year. Sugarcane bagasse
is composed of outer rind and inner pith. The pith is a soft-core part in bagasse, whereas rind is outer
hard part. Rind mainly consists of a fiber that includes cellulose, hemicelluloses, and lignin with low
molecular weight.[5,6] Natural fibers are mainly used in the preparation of biocomposites in
automotive industry, aerospace industry, building industry, furniture industry, biomedical industry,
and so on.[7–13]
The present research was focused on preparation of nano-based sugarcane bagasse by using high-
energy ball milling process, and the crystallinity, chemical composition, morphology, dimensions, and

CONTACT M. Kathiresan umkathir@yahoo.com Department of Mechanical Engineering, Thiagarajar College of Engineering,

Madurai 625015, Tamil Nadu, India.
Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/gpac.
© 2016 Taylor & Francis
 INTERNATIONAL JOURNAL OF POLYMER ANALYSIS AND CHARACTERIZATION 429

thermal stability of nano bagasse were studied to evaluate their suitability as reinforcement for
polymer composites.[14–19]

Materials and methods

Materials
The crushed sugarcane bagasse was obtained from Theni district (Tamil Nadu, India). The chemicals
used in this research, such as sodium hydroxide, sodium chloride, glacial acetic acid, sulfuric acid, acet-
one, and ethyl alcohol, were obtained from Modern Scientific Company, Madurai (Tamil Nadu, India).

Preparation of nano bagasse

The schematic diagram of the preparation of nano bagasse by various stages is illustrated in Figure 1.

Extraction of macro-bagasse fiber

The collected sugarcane bagasse samples were juice-free and contained only the inner pith and outer
rind. The pith was removed by using mechanical stripping process to get the hard rind. The rind was
chopped into small pieces of about 10 mm cut across the length so that it was free from nodes.
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Figure 1. Preparation of nano bagasse.

 430 M. KATHIRESAN AND P. SIVARAJ

The chopped pieces were then boiled in water at 100°C for 1 h. Then the samples were dried under
sunlight. The dried samples were boiled with 1% NaOH solution at 80°C for 2 h. The fibers were
separated in this treatment. The fiber samples were washed in running water and then with distilled
water. The separated macro-bagasse fibers were then dried.[3,6]

Reduction of macrofiber to nano bagasse

The reduction of macrofiber to nano bagasse was carried out by using high-energy ball mill (Model:
PM 100, Retsch, Germany). The ball material used in the ball milling process was tungsten carbide.
The dried sample of macro-bagasse fiber is milled in high-energy ball milling at 300 rpm for 5 h to
prepare nano-sized bagasse.

Characterization of nano bagasse

Chemical composition
The chemical contents of the nano bagasse were estimated by using the following methods:[20]
Holocellulose contents: A quantity of 3 g of dried sample was put in a flask and 160 ml of distilled
water, 0.5 ml of glacial CH3COOH, and 1.5 g of NaCl were added to the sample. The flask was heated
up to 75°C by using water bath for an hour and then additional quantity of 0.5 ml of glacial
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CH3COOH and 1.5 g of NaCl were added for two times on an hourly basis. The flask was cooled
down below 10°C in an ice bath. The holocellulose was transferred to the crucible and washed with
acetone, C2H5OH, and water, respectively. Then the collected holocellulose was dried and weighed.
Cellulose contents: A further quantity of 2 g of holocellulose was added with 10 ml of 17.5% H2SO4
solution in a beaker and this mixture was stirred up vigorously with a glass rod. Then H2SO4 solution
was added to the mixture once every 5 min for half an hour at 20°C. Next, 33 ml of distilled water was
added to the mixture for an hour. The residue was filtered and transferred to the crucible and washed
with 100 ml of 8.3% H2SO4, 200 ml of distilled water, 15 ml of 10% CH3COOH, and again with water.
The collected cellulose was dried and weighed.
Hemicellulose contents: Hemicellulose ¼ holocellulose – cellulose.
Lignin contents: A quantity of 2 g of sample was taken and mixed with 15 ml of 72% H2SO4. This
mixture was stirred for 2 h and 30 min at 25°C and then 200 ml of distilled water was further added to
this mixture. Then this mixture was boiled for 2 h and allowed to cool. After 24 h, the lignin was
transferred to the crucible and repeatedly washed with hot water. The collected lignin was dried
and weighed.

Fourier transform infrared spectroscopy

Fourier transform infrared spectra were obtained by Bruker Alpha T, Germany. The samples
were mixed with KBr at the ratio of 1:99. The mixture was compressed to prepare pellets.
Fourier transform infrared (FTIR) spectral analysis was performed within the wave number range
of 400–4,000 cm 1.

X-ray diffraction
The crystallinity of the nano bagasse was examined by Rigaku X-ray diffractometer by using Cu-Ka
radiation, wavelength of 1.5406 Å, and operation at 30 mA, 40 kV. The samples were scanned within
the range of 10–80° of 2h. The crystallinity index (CI) was estimated by using the integrated
intensities of the Bragg peaks in the nano bagasse spectrum.

Scanning electron microscopy

The morphology of the nano bagasse was characterized by scanning electron microscopy (SEM)
model Hitachi S-4800, Japan. The dimensions of the nano bagasse were also estimated by using
SEM image. The samples were coated with gold to record the micrographs.
 INTERNATIONAL JOURNAL OF POLYMER ANALYSIS AND CHARACTERIZATION 431

Thermogravimetric analysis
Thermogravimetric analysis (TGA) was performed by using TGA 4000 Perkin Elmer, USA. The
analysis was carried out with a constant heating rate of 20° min 1 under nitrogen atmosphere with
the flow rate of 20 ml min 1. The temperature range was used from 35 to 900°C.

Results and discussion

The various stages during the preparation of nano bagasse such as mechanical stripped raw bagasse,
chopped samples, macrofiber extraction, and nano sugarcane bagasse are shown in Figure 2.

Chemical composition
The main chemical compositions of nano sugarcane bagasse such as holocellulose, cellulose, hemicel-
lulose, and lignin are listed in Table 1. The chemical constituents were the major factors influencing
the mechanical strength of the reinforcement in polymer-reinforced composites. The results indicated
that nano sugarcane bagasse raw material has a high potential for use as reinforcement for polymer
composites.
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FTIR analysis
The spectrum of nano sugarcane bagasse is shown in Figure 3. IR spectra peaks with its respective
assignments are listed in Table 2.
The FTIR spectra of nano sugarcane bagasse showed dominant peaks around 3,303, 2,881, 1,645,
1,634, 1,455, 1,318, and 1,033 cm 1, which corresponded to the functional group of cellulose, C–H
stretching of cellulose, C ¼ O stretch of the acetyl groups of hemicelluloses, C ¼ O bonds on the
hemicelluloses, CH2 symmetric bending band, C–O stretch of the acetyl group of lignin, and the
functional group of lignin, respectively. Thus, the IR spectrum confirms the presence of chemical
groups of the main constituents present in the nano sugarcane bagasse.

X-ray diffraction analysis

The X-ray spectrum of nano sugarcane bagasse is shown in Figure 4. This spectrum contains two
peaks, which are particularly well-defined for the natural fiber. The spectrum corresponding to the
nano sugarcane bagasse showed diffraction peaks at the following 2h angles: 22.7° and 48.3°. The
diffraction peaks present in the spectrum indicate that the nano sugarcane bagasse is semi-crystalline.
The CI was estimated using the following expression:[7]
CI ¼ ðH22:7 H48:3 Þ=H22:7 ð1Þ

Figure 2. (a) Bagasse after stripping, (b) chopped bagasse, (c) extracted macro-bagasse fiber, and (d) nano bagasse.
 432 M. KATHIRESAN AND P. SIVARAJ

Table 1. Chemical constituents of nano sugarcane bagasse.

Constituents Amount (w/w%)
Holocellulose 80.7
Cellulose 58.1
Hemicellulose 22.7
Lignin 13.9
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Figure 3. Fourier transform infrared spectra of nano sugarcane bagasse.

where H22.7 is the height of the peak at 2 h ¼ 22.7° and H48.3 is the height of the peak at 2 h ¼ 48.3°.
The calculation yields the percentage of crystallinity for the nano sugarcane bagasse, which is 55.2%.
Thus, the nano sugarcane bagasse shows reasonable crystallinity index to facilitate greater
reinforcement of polymer composites.

SEM analysis
The morphology of nano sugarcane bagasse can be observed in the Figure 5. Most of the nano par-
ticles appear to be in close, ellipsoidal shape. The average length and diameter of the nano sugarcane
bagasse are 51.2 and 46.1 nm, respectively. The size and morphological structure of sugarcane bagasse

Table 2. Assignment of Fourier transform infrared peaks.

Wavenumber (cm 1) Origin
3,303 Cellulose
2,881 CH stretch
1,645 C ¼ O stretch of the acetyl groups of hemicelluloses
1,634 C ¼ O bonds on the hemicelluloses
1,455 CH2 symmetric bending band
1,318 C–O stretch of the acetyl group of lignin
1,033 Lignin
 INTERNATIONAL JOURNAL OF POLYMER ANALYSIS AND CHARACTERIZATION 433

Figure 4. X-ray spectrum of nano sugarcane bagasse.

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reveals that it supports strongly the interface between the matrix and the reinforcement for the
polymer nano composites.

Thermogravimetric analysis
The result of the thermal analysis of nano sugarcane bagasse is shown in Figure 6. It was observed that
the initial peak showed the moisture content of the sample. Then the peak extends due to the thermal
stability of the constituents present in the nano sugarcane bagasse. Thereafter, the peak drops down
due to the degradation of constituents such as cellulose, hemicelluloses, and lignin. The result indi-
cates that decomposition occurs between temperatures ranging from 300 to 380°C.

Figure 5. Scanning electron microscopy photograph of nano sugarcane bagasse.

 434 M. KATHIRESAN AND P. SIVARAJ
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Figure 6. Thermogravimetric analysis of nano sugarcane bagasse.

Conclusion
The general observations of this work can be attributed to the compatibility of nano sugarcane
bagasse as reinforcement for nano natural reinforcement composites. The cellulose content of nano
sugarcane bagasse is 58.1%. The X-ray diffraction (XRD) and FTIR analyses showed that nano
sugarcane bagasse is semi-crystalline and the cellulose is present. The SEM photograph confirms that
the samples are in nano-scale dimensions. TGA analysis revealed that the decomposition temperature
range of nano sugarcane bagasse is 300–380°C. The various results such as chemical constitution
estimation, FTIR analysis, XRD analysis, SEM investigation, and TGA analysis revealed that nano
sugarcane bagasse has a huge potential to serve as an excellent natural renewable reinforcement
for manufacturing various polymer composite products.

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