Cellulose (2012) 19:1449–1480

DOI 10.1007/s10570-012-9741-1

REVIEW PAPER

Bamboo fiber and its reinforced composites:

structure and properties
Dagang Liu • Jianwei Song • Debbie P. Anderson •

Peter R. Chang • Yan Hua

Received: 4 May 2012 / Accepted: 26 June 2012 / Published online: 25 July 2012
Ó Springer Science+Business Media B.V. 2012

Abstract Natural plant fibers have unequivocally fabrication in order to achieve desirable functionalities
contributed economic prosperity and sustainability in and performance. Because of the hydrophilic nature of
our daily lives. Particularly, bamboo fibers have been BF, different methods may be adopted to improve
used for industrial applications as diverse as textiles, interfacial surface adhesion. A better understanding of
paper, and construction. Recent renewed interest in the fiber structure and characteristics that influence
bamboo fiber (BF) is primarily targeted for the composite performance could lead to the development
replacement or reduction in use of glass fiber from of additives, coatings, binders, or sizing suitable for
non-renewable resources. In this review, various natural fiber and a variety of polymeric matrices.
mechanical, chemical, and biological approaches for
the preparation and separation of macro-, micro-, and Keywords Bamboo fiber  Structure 
nano-sized fibers from raw bamboo are summarized. Reinforcement  Thermoset and thermoplastic
The differences in the mechanical, thermal, and other composites  Biocomposites  Interface adhesion
properties of fibers from different materials are linked
to their size, aspect ratio, surface charge and groups,
and their function in nature. Biocomposites made of BF Introduction
are considered to be green, environmentally responsi-
ble eco-products. Different processing parameters Due to concerns over the environment, the depletion of
such as fiber extraction, surface modification, and fossil fuels, and climate change, there has been an ever-
synthesis of the composites affect the characteristics of increasing interest in the replacement of synthetic fibers
composites. Fiber length, orientation, concentration, in polymeric composites by natural plant fibers such as
dispersion, aspect ratio, selection of matrix, and jute, coir, flax, hemp, bamboo, and sisal. Natural plant
chemistry of the matrix must all be considered during fibers are used due to their low density, good thermal
insulation and mechanical properties, low price, dura-
bility, sustainability, and biodegradability. As replace-
D. Liu (&)  J. Song  Y. Hua
ments for conventional synthetic fibers like aramid
Department of Chemistry, Nanjing University
of Information Science and Technology, and glass fibers, natural plant fibers offer economical,
Nanjing 210044, China functional, and environmental advantages, and are
e-mail: [email protected] gaining popularity particularly in automotive, aircraft,
and structural construction applications.
D. P. Anderson  P. R. Chang
Agriculture and Agri-Food Canada, Biobased Platforms, Among the natural fiber plants, bamboo is by far the
Saskatoon, SK S7N0X2, Canada most important one due to its rapid growth rate and

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universality. Bamboo is a group of perennial ever- elements (including vessels, sieve tubes, and compan-
greens in the true grass family Poaceae, subfamily ion cells). An ultra hierarchical structure of BF over
Bambusoideae, tribe Bambuseae. More than 1,450 different length scales has been proposed and is shown
bamboo species from 70 genera are found in diverse in Fig. 1 (Parameswaran and Liese 1976, 1980). Tiny
climates—from cold mountains to hot tropical regions spindle-like short fibers, tapered at both ends, are
(Gratani et al. 2008; Grosser and Liese 1971). China is intercalated longitudinally with each other along the
known as the ‘‘Kingdom of Bamboo’’ due to the fact culm. Lamellation of BF consists of alternating broad
that there are more than 400 species of bamboo and narrow layers with differing fibrillar orientation,
growing under her sovereignty. China has the world’s which is different from polylamellate structure in
leading bamboo industry in its number of varieties, lumber (Wai et al. 1985). An important feature in
amount of bamboo reserves, as well as production the ultrastructure of the wall is the variability in the
output. In 2010, bamboo plantations in China were orientation of the cellulose fibrils with respect to the
5.38 million hectares with an annual increase of longitudinal cell axis within different cell wall layers.
100,000 hectares (Jiang 2010). Bamboo fiber (BF) has The narrow layers possess a large microfibril angle
long been widely used for construction purposes as indicating the cellulose fibrils are oriented almost
well as for the pulp and paper in industry. Despite the perpendicular to the main cell axis, whereas the broad
above-mentioned desirable attributes and many recent layers show a rather low microfibril angle which
technology developments in products and processes means that the cellulose fibrils are oriented basically
there are several outstanding problems which severely parallel to the cell axis. The degree of lignification
hinder the wider utility of BF, including: varies remarkably across the fiber wall, with higher
lignin content in the narrow layers. Lignin fills the
1. Literature concerning the physical and chemical
spaces in the cell wall between the cellulose, hemi-
properties of BF at the fundamental/molecular
cellulose and pectin components, and holds the
level is scarce and insufficient;
cellulose microfibrils together. Besides the common
2. The current extraction method of BF is not
matrix components of secondary walls (mainly cellu-
suitable for commercial production, and it can’t
loses and lignin), crosslinking glycans play a major
meet the requirements for a textile fiber or non-
role in maintaining the structural integrity of the wall
woven fabric;
through their tight association with cellulose microfi-
3. The resultant composites encounter inconsistent
brils. Phenolic acids (e.g. ferulic and p-coumaric
functionalities/properties primarily due to poor
acids) are also widely distributed within the cell wall
interface interaction and other influencing factors
forming covalent linkages with lignin and polysac-
to a lesser extent.
charide components (Higuchi 1987; Ishii and Hiroi
This article overviews the structure and properties 1990). Overall, on the macro scale BF consists of a
of BF with particular emphasis on how the interface hollow tube with micron-scale fiber bundles organized
between the matrix and BF affects the performance of into functionally graded structures. Between the nano
the resultant composite. Subsequently, we put forward and micron scales individual fibers are organized into
some strategies on physical, chemical and/or biolog- fiber bundles in a lignin matrix. These specific features
ical modification of BF in order to make advancements further contribute to the complexity of design of the
toward further research and industrial applications or natural BF wall.
commercialization.
Extraction and processing of bamboo fiber

Structure of multi-scaled bamboo fiber BF can be processed into different raw materials for
industrial applications by using different processing
Composition and morphology of the bamboo cell methods (Fig. 2). The node portions and a very thin
wall layer of exodermis (bark) are always removed from the
bamboo and the remaining hollow cylindrical portion
BF is distributed in the internodes of vascular bundles of culm is used for extracting the fiber or processing.
as fiber caps or sheaths surrounding the conducting Bamboo strips (Fig. 2a) with long cellulose fiber and

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Fig. 1 a Model of the polylamellate wall structure of a bamboo c The spindle-like short tiny fibers, tapered at both ends, are
fiber. The fiber cell wall exhibits a polylamellate structure with intercalated longitudinally each other along the culm. d Nano-
alternating broad and narrow lamellae. The narrow layers scale cellulose grains with orientation and other distributed
consist of unidirectional microfibril layers, alternatively in components (reprinted from Parameswaran and Liese 1976 with
transverse and longitudinal lamellae, with orientation 2–20°/ permission from Springer, and Parameswaran and Liese 1980
85–90°; the broad layers are the matrix. b The middle lamella with permission from Cellulosechemtechnol)
is the outer-most layer, followed by the primary wall.

lignin components have been directly molded into new and important industrial material for bamboo
sheets with curing thermosetting resin (Fig. 2j), or fabrics and bamboo textiles. Bamboo fiber is normally
further ground into flour (Fig. 2b) for extrusion or extracted using the following methods.
mixing with thermoplastic resin (Fig. 2j). Another
method used is defibrillation of BF with or without Chemical methods
removal of the lignin and other polysaccharides to
obtain raw BF (Fig. 2e) or pure cellulosic fiber Alkali or acid hydrolysis is used in chemical process-
(Fig. 2c, f). Delignified natural BF can be classified ing to delignify and to remove the amorphous regions
into microfibrils (Fig. 2c, f, h), nanofibrils (Fig. 2g), or of raw cellulose fiber. It is worth noting that the alkali
nanocrystals (Fig. 2d). Microfibrils are defined as solution influences not only the cellulosic components
fibers of cellulose with a diameter of 0.1–1 lm and a inside the plant fiber, but also the noncellulosic
corresponding minimum length of 5–50 lm. Nanofi- components (hemicellulose, lignin, and pectin). Bam-
brils are of nanometer scale (1–100 nm) in at least one boo strips were soaked in 4 % NaOH for 72 h to
dimension. While the small fibrils isolated from natural extract the fiber (Kumar et al. 2010). This method
fibers normally have a wide range of diameters, most removed 38–42 % of the polysaccharides plus lignin
are below 100 nm (although some are greater than from the bamboo chips. The obtained pulp was cooled,
0.1 lm). When bamboo cellulose is dissolved and then filtered, and washed, and then further treated with
wet- or melt-spun into fiber, a regenerated BF is glacial acetic acid. Sodium chlorite was used occa-
formed. Also known as bamboo yarn (Fig. 2i), it is a sionally to bleach BF so it was white in color.

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Fig. 2 Development of
bamboo fiber. Bamboo
strips (a) or flour (b) with
long or short cellulose fiber
and lignin components have
been directly molded into
sheets with curing
thermosetting resin (j),
defibrillation of BF with or
without removal of the
lignin and other
polysaccharides is a way to
obtain raw BF (e) or pure
cellulosic fiber (c, f).
Delignified natural BF can
be classified into
microfibrils (c, f, h),
nanofibrils (g), or
nanocrystals (d) according
to fibrous size. When
bamboo cellulose is
dissolved and then wet- or
melt-spun into fiber, a
regenerated BF is formed (i)

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The treated pulp was called bleached bamboo fiber. Bamboo fibers are reported to have been obtained
The problem with this method was that fiber bundles from bamboo pipe through various mechanical meth-
with diameters of 100 ± 10.4 lm also formed during ods, such as crushing, heat steaming, and shearing,
extraction; therefore, the parameters were chosen to after swelling the bamboo stems (Ogawa et al. 2004,
optimize separation of BFs by using a minimum 2008). The crushing method has lower efficiency
amount of NaOH (Deshpande et al. 2000). because a screening step is needed after crushing in
An HNO3–KClO3 method has also been used to order to obtain uniform size. Fiber sizes obtained by
extract fiber from bamboo samples. Prior to the shearing after swelling vary greatly and show a bulk
addition of KClO3, dry raw bamboo strands were fiber mass. Heat may decrease BF’s natural strength in
immersed in a diluted nitric acid solution (Liu et al. the heat-steaming method. Steam explosion, which
2010a, b). After treating for 24 h at 50 °C, the involves an instant discharge of materials under high-
obtained BF suspension was cooled then dialyzed pressure steam in a sealed container, is a better method
against distilled water to remove low molecular of thermochemical/hydrothermal treatment of materi-
weight compounds. The slurry was then freeze-dried als. Bamboo chips were subjected to a steam explosion
to obtain dry BF. Single fibers were in the range of digester at 2.0 MPa and 210 °C for 5 min, and the
0.01–1 mm, which is shorter than those of multicel- steam-exploded pulp was collected and purified by
lular plant fibers such as flax, and the width was about extraction from dioxane-water (9:1, v/v) (Shao et al.
10–50 lm (as shown in Fig. 2c). After treatment with 2009). The delignified BF obtained showed a smooth
sulfuric acid the BF was degraded into nanocrystals, surface and uniform size.
as shown in Fig. 2d. The diameter of these smaller
spherical crystallites was about 50–100 nm; they were Combined chemical and mechanical methods
aggregated but had a uniform distribution.
He et al. (2007) suggested a complicated method A combination of chemical and mechanical processes is
of obtaining BF. Crude fiber bundles of bamboo, used in the pulp and paper industries for pulping, and is
obtained by drawing bamboo chips roasted at 150 °C applicable for the extraction of BF. Two conventional
for 30 min, were first immersed in water at 60 °C for mechanical methods, compression molding technique
24 h, and then air dried prior to removing impurities (CMT) and roller mill technique (RMT), were explored
further by repeated rollings. Subsequently, the fiber prior to alkali treatment (Deshpande et al. 2000). In the
bundles were heated with 0.5 % NaOH (w/v), 2 % CMT, a bed of bamboo strips was placed between two
sodium sulfite, 2 % sodium silicate and 2 % sodium flat platens and subjected to a constant load for a
polyphosphate solutions for about 60 min at 100 °C. predetermined time. Compression time and the starting
The liquor-to bamboo ratio was 20:1. After being bed thickness are important parameters that must be
washed with hot water, fibers were treated with 0.04 % optimized to obtain good quality fibers. In the RMT, the
xylanase and 0.5 % DTPA (diethylene triamine pent- bamboo strips were forced between two rollers, one of
acetic acid) at 70 °C for 60 min at a pH of 6.5. The which was fixed and the other rotated. The diameter of
fibers obtained were then heated for about 60 min at the rollers, strip thickness, and the speed of the rotating
100 °C, except using 0.7 % NaOH. In the bleaching cylinder were chosen to yield flattened strips of
step, the BF was placed in a polyethylene bag with bamboo. These alkaline and mechanical-treated strips
4 % H2O2, 0.2 % NaOH and 0.5 % sodium silicate for could be easily separated into individual fibers. Rao and
50 min. The liquor ratio was 20 and the pH was Rao (2007) manually decorticated fibrous bamboo
maintained at 10.5. After treatment with 0.5 % strips by repeatedly beating, combing, and scraping
sulfuric acid solution for 10 min and then being until individual fibers separated. The dry fiber was
emulsified for 5 days, refined BF was obtained. extracted by means of a chemical degumming process,
with a final chemical extraction process yield of 33 %
Mechanical methods on a weight basis.
Bamboo yarn is a regenerated BF, which is obtained
Mechanical methods generally include treatment from bamboo pulp resourced from the bamboo stem
using a high pressure refiner, a super grinder, a and leaves. Regenerated BF was first manufactured in
microfluidizer, and/or a high-pressure homogenizer. 2002 by Hebei Jigao Chemical Fiber Co. Ltd. in China.

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A wet-spinning approach quite similar to that of monoclinic cellulose Ib unit cells, in ratios that vary
viscose rayon fiber is used for fabricating bamboo depending on the origin of cellulosic resources. Their
yarns, which includes a process of hydrolysis-alkali- distinction lies simply in the different arrangements
zation and multi-phase bleaching. The processing steps within the crystal lattice, and in the way one parallel
involve steeping, pressing, shredding, ageing, sulfuri- chain is stacked on the others. In 13C-CP/MAS NMR
zation, xanthation, dissolution, spinning, filtering and spectra BF exhibited five main peaks at 105.6, 89.2
degassing. Finally, the viscose bamboo cellulose is (83.9), 74.5 (72.9) ppm assigned to the C1, C4, and C5
forced through spinneret nozzles into a coagulation (C3, C2), respectively, as well as the C6 peak line at
solution of diluted sulfuric acid and reconvert it into 64.6 ppm, which were all attributed to cellulose I (Liu
cellulose BF yarns (Xu et al. 2007). et al. 2010a, b). After fitting the C1 and C4 resonance
regions using four Lorentzian lines, He et al. inves-
Structure of bamboo fiber tigated the Ia and Ib structures of BF by 13C-CP/MAS
NMR. Lorentzian fittings of C1 (left) and C4 regions
Chemical structure (right) resulting from the 13C-CP/MAS NMR spectra
of bamboo fiber are shown in Fig. 3 (He et al. 2007).
Pure bamboo fiber, like other plant fiber, is composed The inner two signals at 105.2 and 104.8 ppm are
of cellulose. Cellulose is the most common organic attributed to cellulose Ia, while an upfield wing
polymer, representing about 1.5 9 1012 tons of the associated with an inconspicuous shoulder of the C4
total annual biomass production (Klemm et al. 2002), signal from BF confirmed the existence of the Ia phase.
and is considered to be an almost inexhaustible source The calculated Ia/Ib ratio in BF was only 0.18, which
of raw material for the increasing demand for envi- suggests that bamboo fibers have a high Ib content and
ronmentally friendly and biocompatible products. low Ia content in contrast to ramie, flax, and cotton
Cellulose is derived from D-glucose units, which fibers. However, the research did not find obvious
condense through b(1 ? 4)-glycosidic bonds. This evidence of cellulose Ia (shoulder peak of C1 or C4) in
linkage motif contrasts with that of the a(1 ? 4)- the NMR results. This is consistent with the specula-
glycosidic bonds present in starch, glycogen, and other tion that higher plants contain no cellulose Ia at all,
carbohydrates. Unlike starch with its coiling or only a distorted form of cellulose Ib located immedi-
branching side chains, cellulose is a straight chain ately below the surface of the crystalline units (Hesse-
polymer with an extended and rather stiff rod-like Ertelt et al. 2008). The crystalline structure of BF as
conformation. Hydrogen bonds form among the investigated by X-ray diffraction showed the typical
multiple hydroxyl groups on the glucose units of the reflection planes of cellulose I peaks 002, 101, and 040
same chain or neighboring chains, holding the chains of the 2h angles at about 22.7°, 16.1°, and 34.5°,
firmly together side-by-side and forming microfibrils respectively. This was different from the alkaline
with high tensile strength. Each of the glucose-based treated bamboo, which had a decreased intensity of the
rings has three hydroxyl groups which lie on the 2, 3, 002 plane and an increased intensity of the 101 and
and 6 carbon atoms, respectively. The hydroxyl on the 021 planes, representing the introduction of cellulose
C6 has an esterification rate that is about 10 times faster II. The crystallite size of BF was determined to be
than the other two hydroxyl groups, and the etherifi- 7.1 nm by XRD, larger than that of cotton (6.1 nm),
cation rate of the C2 hydroxyl is about twice as fast as flax (5.7 nm), and ramie (6.6 nm) (He et al. 2007).
the C3 position. The acidity of the three hydroxyl The above mentioned BF or nanocrystals did not
groups is also different with the C2 having the most transform into another cellulose crystalline structure
acidic hydroxyl and the hydroxyl on the C6 the least after chemical treatment; however, treatment with up
acidic. These hydroxyl functional groups contribute to 15 % alkali solution induced conversion of cellu-
strong polarity and high water absorption to the fiber. lose I to cellulose II (Liu and Hu 2008). Sodium
hydroxide treatment results in a higher amount of
Crystalline structure swelling and leads to the formation of a new Na–
cellulose-I lattice with relatively large distances
It is commonly assumed that higher plants synthesize between the cellulose molecules; and these spaces
both one-chain triclinic cellulose Ia and two-chain are filled with water molecules. The OH-groups of the

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Fig. 3 Lorentzian fitting of C1 (left) and C4 regions (right) from the 13C-CP/MAS NMR spectra of bamboo fibers (reprinted from He
et al. 2007 with permission from Iran Polymer and Petrochemical Institute)

Fig. 4 X-ray diffraction patterns of bamboo fibers treated with when bamboo fiber were treated by NaOH for 20 min at 20 °C
various concentrations of NaOH (left), amount of cellulose II (right) (reprinted from Liu and Hu 2008 with permission from
and crystallinity index of bamboo fibers vs. NaOH concentration Springer)

cellulose are converted into ONa-groups, expanding cellulose II in the BF after treatment are presented in
the dimensions of the molecules. Subsequent neutral- Fig. 4 (right). The crystallinity index increased
izing with H2SO4 removes the linked Na-ions and slightly, by about 2.5 %, when the NaOH concentra-
converts the cellulose to a new crystalline structure, tion increased from 4 to 10 %. However, with the
i.e., cellulose-II, which is thermodynamically more concentration greater than 11 %, the crystallinity
stable than cellulose-I (Das and Chakraborty 2006a). index started to fall sharply and reached its minimum
As shown in Fig. 4 (left), BF treated with 4–11 % value (57.8 %) at 16 % NaOH. After that, the
NaOH solutions display diffraction patterns of cellu- crystallinity index increased slightly until the NaOH
lose I. However, when the NaOH concentration was concentration was 18 %, and then remained constant.
increased to 12 %, two additional diffraction peaks The variation in the amount of cellulose II showed an
appeared at 12.2° and 20.1°, which were assigned to inverse transition, like that of the crystallinity index.
cellulose II. The BF treated with 16–24 % NaOH The calculated results show that the transformation of
solutions show diffraction patterns typical of cellulose cellulose I to cellulose II starts at a concentration of
II. The calculated crystallinity index and the amount of 12 % NaOH, and that the greatest efficiency in

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polymorphic transition of cellulose is obtained under the mechanical properties of different fiber species are
mercerization conditions (16 % alkali and 10 min of linked to their function in nature, which is translated
mercerization at 20 °C with no tension applied to the into their physical, chemical and morphological
fibers). It is well known that cellulosic fibers undergo properties. For example, tensile strength is mainly
three distinct processes during mercerization: fiber provided by the cellulose content, and the microfibril-
swelling, disruption of the crystalline areas, and lar angle is proportional to the strain-to-failure due to
formation of a new crystalline lattice after rinsing irreversible deformation of the cell wall. The modulus
away the mercerizing solution. Alkali could influence of elasticity is proportional to the cellulose content and
the degree of swelling, and hence a complete lattice inversely proportional to the microfibrillar angle. The
transformation from cellulose-I to cellulose-II. Studies almost axially oriented bamboo cellulose fibrils in the
have shown that at lower concentrations, the hydrox- fiber walls maximize the longitudinal elastic modulus
ide ions may be fully hydrated and they may not be of the fibers and their lignification increases the
able to penetrate and disrupt the cellulose lattice due transverse rigidity (Wang et al. 2011). Composition
to size restriction. Only the amorphous regions and and mechanical properties of a few natural and
crystal surfaces can react with alkali and be removed; artificial fibers are given in Table 1.
thus, the interfibrillar regions are likely to be less Among the various lignocellulosic fibers, bamboo
dense and less rigid, and thereby make the fibrils more has a high percentage of lignin (32 %) and its
capable of rearranging by themselves. Consequently, microfibrillar angle is relatively small (2°–10°). These
the crystallinity index of fiber increases at a lower factors lead to the extremely high tensile strength,
NaOH concentration; however, as the NaOH concen- flexural strength, and rigidity of the fiber’s polylamel-
tration increases, the amount of free water available late wall structure. Reported mechanical properties of
for hydrating the hydroxide ions is diminished. In this BF vary because of the different testing methods used
case, the dehydrated hydroxide ions get smaller and and the samples tested. For example, Amada et al.
can more easily penetrate the lattice (Hesse-Ertelt (1997) estimated the tensile strength and modulus of
et al. 2008). With a continuous increase in the NaOH the original BF to be 600 MPa and 46 GPa, respec-
concentration, the crystalline structure of cellulose tively, but when lignin was removed from pristine
swells and relaxes. At the most swollen point, the bamboo fiber by alkali pretreatment, the strength and
hydrated hydroxide ions penetrate the inside of modulus were greatly improved. The mechanical
the crystal, and undergo a thorough reaction with the properties of various bamboo structural entities were
cellulose. measured using specialized techniques and equipment
All in all, most regenerated cellulose fiber loses its (such as a tensile tester, micro-tensile tester, nanoind-
original crystalline structure of cellulose I and con- enter and atomic force microscope) with appropriate
verts to cellulose II. The conversion from cellulose I to sensitivities to obtain precise and repeatable results,
cellulose II is irreversible, suggesting that cellulose I is and with consideration for the size scale and the
metastable and cellulose II is stable. Till now, no corresponding load bearing capacity. For example,
researchers reported the transition of bamboo cellu- dried BF or fiber bundles were measured on a tensile
lose I to cellulose III or IV with various chemical tester at gauge lengths of 10, 20 and 30 mm; whereas
treatments. Therefore, it is important to adopt the single bamboo fibers were tested using a micro-tensile
proper conditions for the chemical extraction of BF tester and the testing length was 1 mm. Mechanical
or regenerated cellulose fiber. properties of nanofibrils were measured using atomic
force microscopy (AFM) by dropping a nanofibril
Properties of bamboo fiber suspension onto a glass slide and then air drying to
obtain an AFM sample. For the measurement, the
Mechanical properties AFM tip was positioned over the points of interest and
then approached the sample surface. The force on
It is well known that bamboo has superior mechanical the specimen was generated from the deflection of
properties primarily due to fiber being its main the cantilever. The elastic modulus of BF can be
constituent and to the unidirectional arrangement of measured directly from the bamboo matrix by a
fiber in the tissue (Wai et al. 1985). The differences in nanoindenter.

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Table 1 Chemical composition and mechanical properties of 2011; Fakirov and Bhattacharyya 2007; Mishra et al. 2004;
natural and artificial fibers (Bledzki et al. 1996; Satyanarayana Mwaikambo and Ansell 2006)
et al. 1990; Bismarck et al. 2005; Ilvessalo-Pläffli 1995; Pilla
Fibers Density Microfibril Cellulose Lignin Tensile strength Elongation Young’s
(Kg/m3) angle (%) (%) (MPa) at break (%) modulus (GPa)

E-glass 2.5 – – – 2,000–3,500 2.4 70

Aramid 1.4 – – – 3000–3150 3.3–3.7 63–67
Carbon 1.7 – – – 4000 1.4–1.8 230–240
Bagasse 1.3 10–22 55.2 25.3 290 3–7 17
Bamboo 0.6–0.8 2–10 60.8 32.2 140–800 1.3 11–30
Banana 1.4 11 65 5 500 5.9 12
Coir 1.1–1.5 30–49 32–43 40–45 131–220 15–40 4–6
Cotton 1.5–1.6 33–34 85–90 5.7 287–800 1.2–1.5 13–27
Curaua 1.4 – 73.6 7.5 500–1150 3.7–4.3 11.8
Flax 1.5 5–10 64–71 2 345–1100 2.7–3.2 27.6
Hardwood 0.6–0.9 44–50 20–30 90–110 11–13 –
Hemp 1.5 6.2 90 8 310–750 1.6 30–70
Henequen 1.2 14 60 8 430–570 3.7–5.9 10–16
Jute 1.5 8.1 63 11.7 393–1000 1.16–2.5 13–54
Kenaf – – 72 9 930 1.6 53
Oil palm 0.7–1.6 46 65 29 248 25 3.2
Pineapple 0.8–1.6 8–15 81 12.7 1.44 14.5 34.5–82.5
Ramie 1.5 7–12 68–76 0.7 560 15 24.5
Sisal 1.5 20–25 70 12 468–640 5–14 9–22
Softwood 0.3–0.7 – 44–50 20–30 60–90 8–14 –

Table 2 Mechanical
Sample Equipment Strength (MPa) Strain (%) Modulus (GPa)
testing results of bamboo
fibrils Fiber bundle Tensile tester 387 16.7 2.7
Single fiber Micro-tensile tester 916 12.6 13.6
Regenerated fiber Tensile tester 290 71.2 1.8
Single fiber Nanoindenter N/A N/A 13
Bamboo nanofibril AFM N/A N/A 40

As shown in Table 2, the strength of bamboo between BF and the matrix. The AFM testing results
fiber bundles was 387 MPa with an average elastic showed that a nanofibril has a higher modulus than a
modulus of 2.7 GPa. The strength of single bamboo single bamboo fiber due to the size effect. When the
fibers was three times as much. This divergence can size of the fiber is reduced to nanoscale, it becomes
be attributed to the non-uniform diameter of BF or possible for the fibril to avoid the presence of
to the presence of weak points in the fibers. The defects, and the strength will be more likely to reach
average elastic modulus of a single fiber was around the theoretical strength of covalent bonds (Wan and
13 GPa, similar to the nanoindentation result, and Ko 2009). Mechanical properties of bamboo entities
much higher than that of the fiber bundles. The show a strong size effect. Regenerated BF has an
reason for the difference between the mechanical obviously lower strength and modulus than original
properties of fiber bundles and single fibers is that fiber but a higher strain, probably because of the
the strength of the BF is stronger than the bonding conversion of the crystalline structure.

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Dynamic viscoelastic properties treatment of the bamboo strips, the crystallinity

increased and molecular movement of fiber was more
The dynamic storage modulus (E0 ) very closely and more restricted and, as a result, caused Tg to
resembles the flexural modulus of composite materi- increase. The damping parameter (tan d) value was the
als, and is the most important property for assessing maximum for the untreated samples.
the load-bearing capability of a composite material.
Das and Chakraborty investigated the dynamic visco- Thermal properties
elastic properties of bamboo strips and alkali-treated
bamboo strips using dynamic mechanical thermal Differential scanning calorimetry (DSC) analysis
analysis (DMTA) (Das and Chakraborty 2006b). The of BF has also been reported (Sun et al. 2006). The
results showed that the room temperature E0 value of pristine fiber shows a large exotherm in its DSC curve
untreated bamboo strips (about 5 GPa) increased by at about 343.7 °C, which was attributed to a-cellulose.
400 % in the case of the alkali-treated sample to about After treatment with 15 % alkali the exothermic peak
24 GPa. It was also evident that the E0 values for all shifted to 346.2 °C. A second peak that appeared at
treated samples were higher than that of the untreated about 380 °C in samples treated with alkali concen-
sample. The modulus decreased as temperature trations greater than 15 % was probably due to
increased because with increasing alkali treatment, cellulose-II.
more and more lignin and hemicellulose material is The thermal degradation of bamboo fibers is found
removed from the BF. The opening of intermolecular to be a two-stage process in the temperature range of
and intramolecular hydrogen bonding results in an 25–400 °C and 400–700 °C (Varada et al. 2005).
increased number of free hydroxyl groups, which A comparison of the thermal degradation of natural
again involves the regeneration of hydrogen bonding. BF and regenerated BF was performed and is shown
This leads to closer packing of cellulose chains, which in Fig. 5. There are two stages present in the TGA
increases the stiffness of the fibers, and is reflected in curves—the 0–160 °C region which was attributed to
the initial storage modulus values of all the samples. evaporation of water, and the region between 160 and
The primary loss modulus (E00 ) shows a loss modulus 1,000 °C which was assigned to the decomposition of
peak at 111.8 °C which was thought of as the Tg value polysaccharide. Natural BF has a maximum degrada-
of lignin. In the alkali treated samples, that particular tion at about 365.1 °C, whereas the regenerated fiber
peak shifted to higher temperatures (133.6, 143.5, reaches a maximum degradation at 339.9 °C. The
137.5, and 132.1 °C) because with increasing alkali maximum thermal loss during the second stage was

Fig. 5 Natural bamboo fiber (a) and regenerated bamboo fiber maximum degradation at 339.9 °C. The maximum thermal loss
(b). Two stages present in the TGA curves, the region from 0 to during the second stage was 80.57 and 75.74 % for natural BF
160 °C is attributed to evaporation of water; and the region and regenerated BF, respectively; therefore, natural BF shows a
between 160 and 1,000 °C is assigned to the decomposition much better thermal stability than that of regenerated BF
of polysaccharide. Natural BF has a maximum degradation (reprinted from Sun et al. 2006 with permission from Tianjin
at about 365.1 °C, whereas the regenerated fiber reaches a Polytechnic University)

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Cellulose (2012) 19:1449–1480 1459

Table 3 Various physical

Cotton Bamboo Lyocell Viscose Rayon Modal Soybean
parameters of the yarns
Dry tenacity, cN/tex 20–43 22–25 37–45 18–26 24–36 38–40
Wet tenacity, cN/tex 27–56 13–17 30–39 9–15 12–24 25–30
Elongation at break, % 6–10 14–24 12–16 15–25 13–25 18–21
Moisture absorption, % 7–8 13 11–12 10–16 12–13 8–9

80.57 and 75.74 % for natural BF and regenerated BF, structural forms, and most importantly their adverse
respectively; therefore, the thermal stability of natural environmental impact. On the other hand, the substi-
BF is much better than that of regenerated BF tution of conventional synthetic fibers with natural
(Yao and Zhang 2011). Attention should be paid to fibers in structural applications has become one of the
the initial thermal degradation occurring around main concerns in studying the potential use of natural
250 °C as a critical temperature for thermal processing fibers in polymer reinforcement. A substantial increase
of bamboo composites. in agricultural by-products and waste of different types
has attracted researchers to develop and characterize
Properties of regenerated BF new and low-cost materials from renewable local
resources. In light of this, researchers have focused
Typical characteristics of bamboo yarn are shown their attention on natural fiber composites composed
compared to those of other regenerated cellulose fibers of natural or synthetic resins reinforced with natural
in Table 3. Spun bamboo yarn has good wear resis- plant fibers. Various natural fibers (flax, bamboo, sisal,
tance, a bright luster, good absorbance, air permeabil- hemp, ramie, jute, and wood) present many advantages
ity, and a velour feeling. In addition, it has unique compared to synthetic fibers that make them attractive
functions as it is antibacterial, bacteriostatic, and anti- as reinforcements in composite materials. They come
ultraviolet (Kalia and Avérous 2011). from abundant and renewable resources at low cost,
The moisture adsorption and desorption of BF is the thus ensuring a continuous fiber supply and a signif-
best of all natural fibers because of the primary icant saving in material costs for the plastics industry.
structure and pores of its cross section, which serve as Cellulose fibers, despite their low strength, can lead to
channels when moisture is adsorbed and desorbed. composites with high specific properties because of
Compared with other fibers, BF has a unique bacterial their low densities. Unlike brittle fibers, such as glass
resistance that results from natural antibiotics, like and carbon fiber, natural plant fibers are flexible and
chlorophyll and sodium copper chlorophyllin. Bam- will not fracture when processed over sharp curvatures;
boo fabric can inhibit 71 % of a bacteria population in thus enabling the fibers to maintain the aspect ratio
24 h. In addition, the sodium copper chlorophyllin in desired for good performance. Their non-abrasive
BF is a good absorbent of ultraviolet rays; conse- nature permits a high volume fraction for filling during
quently, the UV adsorption of bamboo fabric is 20 processing, and results in good mechanical properties
times higher than that of cotton fiber. without the machine wear problems associated with
synthetic fibers, especially glass and ceramic (Kalia
and Avérous 2011). Natural plant fibers are also non-
Bamboo fiber filled plastic composites toxic, easy to handle, and present no health problems;
unlike glass fibers that can cause skin irritations and
Polymeric materials reinforced with synthetic fibers, respiratory diseases when the fibrous dust is inhaled.
such as glass, carbon, and aramid, provide the advan- They offer a high ability for surface modification,
tages of a high stiffness or strength to weight ratio as are economical, require low amounts of energy for
compared to conventional construction materials, i.e., processing, and are biodegradable. In terms of socio-
wood, concrete, and steel. Despite these advantages, economic issues, the use of natural plant fibers as the
the widespread use of synthetic fiber reinforced source of raw materials is beneficial because it
polymer composites have some problems, such as generates an economic development opportunity for
their high initial costs, their use in non-efficient non-food farm products in rural areas.

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1460 Cellulose (2012) 19:1449–1480

BF is a natural plant fiber with many of the storage moduli of epoxy were about 16.4 and 36.1 %
advantages described above. As a result, composites for the composites with 10 % coupling agent treated
made from BF have become a main interest for fibers and untreated powders, respectively.
researchers. During the last few years, work has been Bamboo fibrous mats were graft copolymerized
done to replace conventional synthetic fiber with BF with 1, 3, and 5 % solutions of methacrylamide
composites, and is overviewed as follows. (MAA). Treatment of bamboo with 1 % MAA gave
optimum results with the epoxy resin by improving the
Bamboo fiber filled thermosetting composites mechanical properties. TGA results revealed that the
degradation temperature of the composite improved
Basically, large sized BF, like bamboo strips, are after grafting. Three percent MMA treatment of
manually aligned, fixed and set in a mold prior to bamboo gave optimum results with the polyester
pouring in a fluidic thermoset. The composites are resin. Grafting increased the thermal stability of
post-cured under a specified load to prepare thermoset bamboo composite, and both the mechanical and
composites. The matrices used most often are epoxy, water resistance properties were improved at a lower
phenolic resin, and unsaturated polyester. graft yield (Kushwaha and Kumar 2010).

Bamboo fiber filled epoxy resin Bamboo fiber filled phenolic resin

Epoxy is widely used in industrial applications, such as Two types of phenolic resins, acid medium (novolac-
adhesives, coatings, electronics and aerospace struc- type) and alkaline medium (resol-type), are found in a
tures. Jain et al. soaked dried BFs in an epoxy resin/ myriad of industrial products. Phenolic resin is a
hardener mixture and kept them unidirectionally adja- versatile matrix that can be reinforced by various fibers
cent to each other in a mold (Jain and Kumar 1992). when impregnating one or more layers of a base fiber
A composite plate of uniformly distributed BF in a resin material into the resin-saturated base material, and then
matrix was obtained after curing the resin. To improve laminating the composite under heat and pressure.
the properties of the epoxy resin, untreated and alkali Many workers have reported the successful fabrication
treated BF were fabricated to reinforce a bamboo epoxy of phenolic-based natural fiber. Das and Chakraborty
resin. The dielectric behavior and electric modulus investigated the effect of mercerization on the mechan-
spectra of composites containing two fiber orientations, ical and thermal properties, fine structure, and mor-
parallel and perpendicular to the electric field, were phology of BF (Das and Chakraborty 2006a, b, 2008).
characterized using a standard impedance analyzer. As Das also studied the mercerization of BF reinforced
compared to other natural fibers, BF shows high volume novolac resin composites, and the effect of merceriza-
resistivity, good mechanical properties (because of its tion on the mechanical and impact properties of
comparatively low cellulose content), and a small bamboo strip-novolac resin composites (Das et al.
microfibrillar angle. In view of its dielectric properties 2006; Das and Chakraborty 2007). Maximum
these composites could be used as dielectric materials improvement in properties was achieved with alkali
(Kumar et al. 2011). treated BF when the alkali concentration was in the
Shih chemically modified water bamboo husk range of 15–20 %. An FTIR study indicated aryl alkyl
fibers with coupling agents, and then added them to ether formation with -OH groups of cellulose and
epoxy resin to form reinforced composites (Shih methylol groups of novolac resin. Beyond 20 % there
2007). The morphological analysis revealed that the was degradation in all strength properties because of
fibers modified by coupling agents exhibited better failure in the mechanical properties of the reinforce-
compatibility with the polymer matrices than the ments. A correlation was found to exist between the
untreated fibers. It was also found that the glass mechanical properties and the developed morphology.
transition temperature of the epoxy increased to about Resol resin composites reinforced with alkali-treated
8–18 °C higher than that of the pristine sample. In bamboo strips were fabricated using a hand-lay-up
addition, the mechanical properties were enhanced technique. The influence of the caustic concentration on
due to the addition of both coupling agent treated the mechanical properties of bamboo-strip-reinforced
fibers and untreated powders. The increases in the resol composites with a constant 50 % load of the

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Cellulose (2012) 19:1449–1480 1461

reinforcement was evaluated. The treatment of BF in bamboo/epoxy and bamboo/polyester composites. An

solutions of sodium hydroxide with increasing con- improvement in properties, such as mechanical
centration resulted in more and more rigid composites; strength, was observed when PEAP was used as an
as a result, the strength and modulus values exhibited interfacial agent. The performance of surface treated
improvements. Another set of composites with vari- bamboo composites, in terms of water resistance, was
able load levels of 20 % alkali treated fiber (40, 50, and significantly better than that of untreated bamboo
60 %) was fabricated, and a 60 % fiber load showed the composites.
best mechanical properties (Das and Chakraborty
2009b). Bamboo fiber filled thermoplastic composites

Bamboo fiber filled unsaturated polyester resin Generally, plastic constitutes from 30 to 70 % of the
entire product mass of a composite. And the leading
Essentially, composites were formed after thermoset- thermoplastics used are conventional petroleum based
ting polyester resin was incorporated into BF of products, i.e., polyethylene (PE), polyvinyl chloride
diameters ranging between 300 and 380 lm and (PVC), polypropylene (PP) and nylon. Unlike long
lengths of about 4, 7 and 10 mm. Fracture behavior fiber/thermosetting composites, which are termed
of the composites was investigated with results orthotropic, short fiber composites are assumed to be
showing that the highest tensile strength, with an isotropic in nature, due to their randomly oriented
improvement of 25 % compared to neat polyester, was dispersion in the matrix. Bamboo fiber powder has
achieved when BF of 10 mm in length was incorpo- been used to melt mix or co-extrude into hybrid
rated at a level of 40 % by volume basis. Fracture thermoplastic composites.
toughness of all types of composites was higher
compared to neat polyester (Wong et al. 2010). Bamboo fiber filled polyolefin
Bamboo fibers obtained from CMT and RMT prior
to alkali pretreatment were used to make unidirec- Bamboo fiber was incorporated into a PP matrix as an
tional composites of polyester with a room tempera- effective reinforcement filler (Li 2005). Using the
ture curing system. High values of tensile strength optimum design method of principal component
were observed in all the composites (Deshpande et al. analysis, it was found that a loading level of 27.71 %
2000). To improve the adhesion between resin and BF resulted in excellent tensile strength, impact, and
fiber, BF was mercerized with 20 % alkali solution. flexural strength. Alkali-treated BF showed a more
Ultimate tensile strength, flexural strength, and flex- favorable reinforcing effect than untreated BF in PP
ural modulus were investigated and found to be composites. Impact strength of alkali-treated BF
strongly affected by alkali treatment, and their max- improved by 25.82 % in comparison with pure PP
imum improvement was achieved with 20 % caustic (Yang 2004). Other approaches, i.e., surface modifi-
treated strip reinforcements. When the fiber loading cation of BF or the use of compatibilizer, have also
level was varied, superior mechanical properties were been explored to improve the properties of BF/PP
achieved with 60 % filler (Das and Chakraborty composites. Maleic anhydride grafted polypropylene
2009a). Jowar, sisal, and BF were extracted under (MAPP) was used as compatibilizer to improve fiber-
similar laboratory conditions and the effects of matrix adhesion (Chattopadhyay et al. 2011a). Short
different types of fiber on the tensile and flexural BF reinforced polypropylene composites were com-
strength were investigated (Ratna Prasad and Mohana pression molded with various levels of chemically
Rao 2011). The bamboo reinforced polyester resin modified BF incorporated. The composites prepared
exhibited a good modulus and had the highest tensile with 5 % MAPP and the optimum 50 % fiber volume,
strength among the three composites. had a 37 % increase in impact strength, 81 % increase
in the flexural strength, 150 % increase in the flexural
Bamboo fiber filled binary thermosetting resin modulus, 105 % increase in the tensile strength, and
191 % increase in the tensile modulus. Thus, a volume
Saxena and Gowri (2003) investigated the effect of fraction of 50 % BF with a fiber length of 1–6 mm
polyesteramide polyol (PEAP) on the properties of and a diameter of 90–125 lm coupled with MAPP

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1462 Cellulose (2012) 19:1449–1480

compatibilizer was the recommended composition, rotor speed of 40 rpm for 8–10 min. After mixing, the
where the mechanical properties were at the maximum mixture of BF, glass fiber, and PP (with and without
and the thermal stability was also high. It was MAPP) was transferred to and homogeneously dis-
suggested that MAPP crystallized not on the surface tributed in a stainless steel mold. It was then pressed at
of PP, but on the bamboo surface (Chen et al. 1998). 190 °C and 3.2 MPa for 30 min. The resultant mate-
It is therefore speculated that the intimate bonding rial was a randomly oriented short fiber composite.
between bamboo and the maleated PP matrix may be The effects of fiber content, bamboo to glass fiber
due partially to the crystallization effect and partially ratio, fiber length, and MAPP content on mechanical
to the hydrogen bonding effect. As a result the BF has properties of BFRP and bamboo-glass fiber reinforced
dual functions, namely, it acts to reinforce the plastics (BGRP) were studied (Thwe and Liao 2002).
composite and also as a nucleator for MAPP. Three It was demonstrated that the environmental resistance
reactive toughening agents, glycidyl methacrylate of BF reinforced composite could be improved with
grafted poly(ethylene-1-octene) (MPOE), maleic the inclusion of glass fiber. This was attributed to the
anhydride grafted poly(ethyleneoctene) (POE-g- slower degradation of glass fiber under the detrimental
MAH), and poly(ethylene-butylacrylate-glycidyl meth- action of water. In general, it was shown that
acrylate) (PTW), were reacted with the hydroxyl hybridization with a synthetic fiber is a viable
groups on the surface of BF. The anhydride and epoxy approach for enhancing mechanical properties and
groups of POE-g-MAH, MPOE, and PTW had syner- durability of natural fiber composites. BF and PP fibers
gistic effects with MAPP, in which a large number of were employed as co-reinforcements in a polypropyl-
the fiber’s surface hydroxyl groups were effectively ene matrix. When the weight ratio of the raw BF and
reduced, and the interfacial bond strength improved. polypropylene fiber was 50/50, the tensile strengths of
The POE sections of POE-g-MAH and MPOE may the composites in longitudinal and transverse direc-
have a cavitation effect that improves the flexibility. tions were 96.6 and 82.3 MPa, and the bending
The butylacrylate segments in PTW provide good low strengths were 400.7 and 367.3 MPa, respectively
temperature properties, and may increase the impact (Wang and Wang 2006).
strength via space deformation of the flexible butylac- BF was also an effective filler for PE (Kumar et al.
rylate chains. To acquire composites with better impact 2010). HDPE/bamboo composites with different
strength, the concentration of the toughening agents nanoclay and maleated polyethylene (MAPE) contents
should be controlled between 6 and 8 %, or they will were fabricated by melt compounding (Han and
have a negative effect on other mechanical properties Cheng 2010; Han et al. 2008). The X-ray diffraction
(Cai et al. 2011). In this research, POE-g-MAH was (XRD) data showed that the clay was exfoliated
preferred for production of composites with better only when 1 % clay was added to pure HDPE. For
properties, especially a better impact strength, the HDPE/BF composites, tensile strength, bending
because the anhydride in MAH may have a better modulus, and strength were improved with the use of
synergistic effect, and also because POE has superior MAPE; however, the use of the clay in the system led
flexibility. to reduced mechanical properties. HDPE/bamboo
Binary fillers such as glass fiber/BF and PP fiber/BF flour composites modified with maleated ethylene/
have also been used to reinforce PP (Nayak et al. propylene elastomers (EPR-g-MA) and MAPE were
2009). Bamboo/glass fiber reinforced PP hybrid also investigated (Liu et al. 2008). The concentration
composites (BGRP) were prepared using an interme- of each modifier varied between 0 and 8.3 wt % based
shing counter rotating twin screw extruder followed by on the total composite weight. It was found that
injection molding. MAPP has been used as a coupling suitable interfacial adhesion and ease of interlayer
agent to improve the interfacial interaction between cavitations between HDPE and BF helped to initiate
the fibers and matrix. The influence of short bamboo/ massive matrix yielding in the composites, thereby
glass fiber on the thermal, dynamic mechanical, and achieving satisfactory impact strength.
rheological properties of polypropylene hybrid com- Bamboo fiber filled binary polymer composites
posites was studied (Thwe and Liao 2000). The hybrid based on a PP/polylactic acid (PLA) matrix were
composites were prepared by first melt mixing the designed by incorporating MAPP into composites
constituents using a torque rheometer at 190 °C and a (Zhang et al. 2010). This new design brought about

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Cellulose (2012) 19:1449–1480 1463

beneficial changes in morphology and rheology, Carboxylic polyether formed chemical and hydrogen
related to the improved dispersion of PLA and bonds with the fiber and the polyamide resin at the
increased BF–matrix interactions. The SEM results interface of the composite (which played a role in
showed that the particle size of the dispersed PLA and coupling) improving the connection intensity at the
BF phase was significantly reduced with the addition interface and the strength of the composite.
of small amounts of MAPP. The best rheological,
morphological and thermal properties for all compos-
ites were obtained when the ratio of PP/PLA/BF/ Bamboo fiber filled rubber or elastomeric
MAH-g-PP was 48.75/13/35/3.25. composites
Silane modified BF and calcium carbonate were
compounded with recycled PP/PE resin (Kim et al. Natural fiber reinforced rubber composites are of
2012). Silane treatment of the bamboo filler noticeably tremendous importance both in end-use applications
increased the mechanical properties. Modulus values and in research and development. These composites
of the calcium carbonate-bamboo-polymer compos- exhibit the combined behavior of the soft, elastic
ites were 3–4 times higher than those of calcium rubber matrix and the stiff, strong fibrous reinforce-
carbonate-polymer composites. ment. Generally, natural fiber reinforced rubber com-
posites have become popular in industrial fields
Bamboo fiber filled polyvinylchloride (PVC) because of the processing advantages and the increase
in strength, stiffness, modulus and damping. The
Hot-press molding was used to incorporate BF particles design of a short fiber reinforced rubber composite
into PVC composite panels (Wang et al. 2008). The depends on several factors such as the aspect ratio of
impact of moisture content, granular size of the bamboo the fiber, control of fiber orientation and dispersion,
particles, and the proportions of the components on the and the existence of a strong interface between fiber
stability and mechanical properties of bamboo-plastic and rubber. Ismail et al. (2002a) mixed bamboo short
composites was investigated. The composites were fibers with natural rubber on a conventional laboratory
made using virgin PVC with bamboo granules as filler. two roll mill. The sheeted rubber compound was
The tensile and flexural properties of the composites conditioned in a closed container before cure assess-
were optimal when the granule size of bamboo was 40 ment using a rheometer. The curing characteristics and
mesh. BF particles modified by sodium silicate were mechanical properties of BF reinforced natural rubber
also used as reinforcement for PVC (Wang et al. 2010). composites were examined as a function of fiber
Results showed that the tensile strength and modulus of loading and bonding agent. In order to improve the
elasticity of the composites increased when the con- interface bonding a silane coupling agent, Si69
centration of the sodium silicate solution was less than (bis(triethoxysilyl propyl)tetra sulfide), was added to
5 %, and were at their maximum values of 15.72 and composite (Ismail et al. 2002b). The presence of the
2,956.80 MPa, respectively, at 5 %. The modulus of coupling agent improved adhesion between the fiber
rupture obtained its maximum value of 27.73 MPa at and rubber matrix and consequently enhanced the
2 % concentration. It was concluded that sodium mechanical properties of the composites.
silicate is a feasible and competitive agent for creating Chang et al. created an approach to prepare
moso bamboo particle reinforced PVC composites. cellulose nanofiber using the combined method of
Poly(styrene-co-maleic anhydride)-block-poly(sty- hot-compressed water (HCW) treatment and disk
rene-co-acrylonitrile) was also employed as a coupling milling (Chang et al. 2012). The HCW treatment
agent for PVC/bamboo flour composites. Improved was effective in loosening the cell wall structure and
morphological and mechanical behaviors were enhancing fibrillation by disk milling. Tensile prop-
observed in this research (Kim et al. 2008). erties of the nanofiber reinforced polyurethane com-
posite were drastically improved by the increased
Bamboo fiber filled polyamide nanofiber content. With 30 % fiber content, values of
tensile strength and Young’s modulus reached 32 and
Polyamide resin composite was prepared from mal- 1,453 MPa, respectively, showing increases of more
eated BF and polyamide (nylon 6) (Li et al. 2005). than two-fold compared with those of the unfilled pure

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1464 Cellulose (2012) 19:1449–1480

PU. Elongation at break rapidly decreased with the sufficient to withstand the imposed high stretching
addition of 10 % fiber and then leveled off. This may forces, resulting in a decrease in tensile strength.
be attributed to an increase in the discontinuity of the
polymer matrix with the increase in the dispersed Bamboo fiber/protein biocomposites
phase. These results indicate that disk-milled BF can
be an excellent reinforcement material for PU-based Micro/nano-sized bamboo fibrils were incorporated into
nanocomposites. soy protein for fabrication of environmentally friendly
biocomposites (Huang and Netravali 2009). The frac-
ture stress and Young’s modulus of the composites
Bamboo fiber filled biocomposites based on modified soy protein concentrate (SPC) and
bamboo fibrils, with weight ratio of 100:30, increased
Biopolymers from biomass, such as protein, starch, from 20.2 to 59.3 MPa and from 596 to 1,816 MPa,
polylactic acid (PLA), polycaprolactone (PCL), poly- respectively. The fracture stress and Young’s modulus
hydroxyalkanoates (PHA), poly(butylene succinate) of the SPC increased significantly with no loss in the
(PBS), and other bio-oil based resins, are being fracture strain. When the composite was crosslinked by
envisaged as prospective alternates to their counter- silane, fracture toughness showed an obvious increasing
parts in olefin plastics. Biocomposites consist of only tendency; however, incorporation of up to 12 wt % of
biopolymer and natural fiber and are regarded as eco- silane crosslinker did not show a significant increase in
friendly and fully biodegradable because all compo- the Young’s modulus and fracture stress. It was thought
nents eventually break down to water and carbon that the fully biodegradable and green SPC/bamboo
dioxide after service (John and Thomas 2008). Lately, fibrils resin composites have excellent properties with
BF has attracted attention as an alternative to wood great potential to replace traditional petroleum-based
fiber for the production of natural fiber reinforced materials in many applications.
biocomposites.
Bamboo fiber/PHA biocomposites
Bamboo fiber/polysaccharide biocomposites
Polyhydroxyalkanoates are a family of biopolymers
BF/corn starch biocomposites were fabricated using a synthesized by many bacteria as intracellular carbon
thermal-press for comparison with kenaf fiber/starch and energy storage granules. Since PHAs are mainly
composites. The relationship between the fibers’ produced from renewable resources by fermentation,
Young’s modulus and flexural modulus in composites PHAs are compatible with the growing worldwide
was investigated. The flexural modulus in composites interest in environmentally friendly materials and
was predicted by the Cox model, which incorporated sustainable development (Chen 2009). The main
the effect of unidirectional fiber compression. The homopolymers or copolymers of the PHA family are
flexural modulus of both fiber filled starch composites poly(3-hydroxybutyrate) (PHB), poly(3-hydroxy-
increased when the fiber content was increased butyrate-co-3-hydroxyvalerate) (PHBV), poly
(Shibata et al. 2008). In our previous work we (3-hydroxybutyrate-co-hydroxyhexanoate), and poly
successfully prepared nanosized BF, or nanocrystals, (3-hydroxybutyrate-co-hydroxyoctanoate). PHA,
which was mixed with starch and glycerol and then PHB and PHBV are among the biobased polymers
cast into biocomposite films (Liu et al. 2010a, b). most studied as alternatives to the current mainstream
When the nanocrystal content increased from 0 to 8 %, petrochemical plastics. Their chemical structures are
tensile strength and Young’s modulus both increased shown in Fig. 6. Reinforcing and toughening PHA and
sharply from 2.5 to 12.8 MPa, and from 20.4 to PHBVs by blending them with natural fiber has also
210.3 MPa, respectively. The elongation at break been attempted (Coats et al. 2008). It was also found
increased with a decrease in bamboo nanocrystal that natural fibers increased the modulus, glass transi-
content. While increasing bamboo cellulosic nano- tion temperature (Tg), and heat distortion temperature
crystal content led to increases in both tensile of PHB or PHBV samples (Wong et al. 2002; Bhardwaj
strength and Young’s modulus, when the BCC content et al. 2006). Bamboo microfibril was used to fill
was higher than 10 %, interface adhesion was not PHB based biocomposites, and it was found that the

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Cellulose (2012) 19:1449–1480 1465

Fig. 6 Structures of several

polymers from the PHA
family. a P(3HA),
b P(3HB), c P(3HV),
d P(3HB-co-3HV),
and e P(4HB-co-5HV)

optimum loading level for maximized mechanical insufficient interfacial adhesion between the fiber
properties was 20 wt % (Krishnaprasad et al. 2009). and the matrix. The pullout process in impact testing
The microfibrils initiated the formation of transcrys- dissipated a significant amount of energy and hence
talline layers and resulted in the overall increase of substantially improved the impact toughness of the
mechanical properties. In other research, PHBV, boron composites. With the improved interfacial adhesion
nitride, and pMDI were mixed manually by tumbling in provided by the coupling agent, polymeric diph-
a sealed plastic bag before they were fed into a mixer enylmethane diisocyanate (pMDI), the strength and
(Jiang et al. 2010). The fiber was fed into the mixer as modulus of the composites were further increased;
soon as the polymer was melted. The mixing temper- however, the toughness was decreased due to inhibi-
ature was controlled by three heating plates which were tion of the fiber pullout. An acoustic emission test
all set at 170 °C. The roller speed was maintained at revealed a significantly different process of structural
50 rpm and the total mixing time was 5 min for all change for the composites with/without pMDI during
samples. After mixing, the blend was ground into the tension test. Bamboo pulp fiber (BPF)/PHBV
pellets using a granulator (Nelmor) with a screen size composites were prepared by melt compounding and
of 1/4 in. Tensile, impact and dynamic mechanical injection molding (Jiang et al. 2008). The crystalliza-
properties of the composites were studied. In contrast tion ability, tensile strength and modulus, flexural
to many other short natural fiber reinforced biocom- strength and modulus, and impact strength were found
posites which demonstrate decreased strain-at-break, to be substantially increased by the addition of BPF.
impact toughness and tensile strength, the PHBV/ Tensile and flexural elongations were moderately
bamboo pulp fiber composites displayed increased increased at low fiber contents (\20 %).
tensile strength and impact toughness, and maintained/ Comparative analysis of two different kinds of
increased strain-at-break. Microscopic study of the lignocellulosic fiber (wood and bamboo) at 30 and 40
fracture surfaces revealed extensive fiber pullout in wt % fiber loading were carried out with respect to their
both tensile and impact tests. The fiber pullout suggests mechanical, thermomechanical, thermal, FTIR and

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1466 Cellulose (2012) 19:1449–1480

morphological aspects (Singh 2009). Both fibers Poly(poly(ethylene glycol) methyl ether methacry-
embedded in a PHBV matrix gave similar tensile and late)- (PPEGMA)-grafted BF (BF@PPEGMA) was
flexural modulus, even though they had different aspect successfully synthesized via esterification and atom
ratios. Statistically, there was no appreciable difference transfer radical polymerization (ATRP) (Bao et al.
between the mechanical properties of the biocompos- 2011). The PBS matrix-based composites including BF
ites obtained from the two different types of lignocel- and BF@PPEGMA were prepared using a twin-screw
lulosic fibers. Notch impact strength of PHBV extruder. Results indicated that PPEGMA was suc-
decreased with fiber addition and the reduction was cessfully grafted onto the BF surfaces, making the BF
greater in the case of BF composites. The effect of fiber surfaces rough and less thermally stable. The
type on the thermal stability of composites was not BF@PPEGMA showed stronger interactions with the
observed, but incorporation of wood fiber gave a higher PBS matrix than with pristine BF, leading to improve-
heat deflection temperature versus the BF. The differ- ments in the tensile modulus, tensile strength, and
ence between the HDT of bamboo and wood fiber elongation at break of the composites. The PBS/
composites can be attributed to a more uniform BF@PPEGMA composites absorbed less water than
distribution of the lower density and smaller sized BF PBS/BF composites due to the lower concentration of
than of the wood fiber. This increased the volume hydroxyl groups after surface modification.
fraction of BF with respect to the matrix in the
composite (Singh et al. 2008). Bamboo fiber/PCL biocomposites

Bamboo fiber/PBS biocomposites Bamboo fiber is an effective reinforcement filler for

biodegradable polycaprolactone (PCL) composite (Hu-
Poly(butylene succinate) (PBS) is an aliphatic ther- ang et al. 2010). PCL and modified bamboo fiber (MBF)
moplastic polyester with a range of desirable properties that had been modified with a silane coupling agent were
including biodegradability, melt processability, and mixed in a blender. It was found that the melting
both thermal and chemical resistance. It is produced temperature and the onset crystallization temperature of
through a condensation reaction with glycols, such as the MBF/PCL composites shifted higher when modified
1,4-butanediol, and aliphatic dicarboxylic acids, such BF was added to the PCL. The isothermal crystallization
as succinic acid, used as the principal raw materials. kinetics of BF/polycaprolactone (BF/PCL) composites
Aliphatic polyesters can be degraded into the environ- was investigated by differential scanning calorimetry
ment by naturally occurring bacteria and fungi. In (DSC). The crystallization half-time (t1/2) showed that the
recent years, many attempts have focused on making crystallization rates of the MBF/PCL composites were
aliphatic polyester composites from cellulosic materi- faster than that of the pure MBF at given cooling rates,
als with low cost, renewability, biodegradability, and which implied that BF acted as a nucleating agent for the
nontoxicity. Kori et al. dealt with the effect of the PCL matrix. Meanwhile, the addition of BC into the PCL
kneading temperature on the crystallization of a matrix matrix can induce heterogeneous nucleation and increase
polymer and the viscoelasticity of a bamboo-fiber- the crystallization ability of PCL during the crystalliza-
reinforced biodegradable polymer composite (Kori tion processes. As compared to neat PCL, all PCL/BF
et al. 2005). Upon investigation of PBS after melt composites had a higher folding-surface free energy
mixing, spherulite generation was observed with value. This indicated that there were constraints on the
polarized light microscopy and differential scanning mobility of the PCL chains in the interspherulitic regions
calorimetry measurements. An increase in the spher- due to the presence of BF. The nonisothermal crystalli-
ulite dimensions was observed at high kneading zation kinetics of the pure PCL and the BF/PCL
temperatures (150 °C) in both the neat polymer and composites were also studied in another research (Liu
the bamboo-fiber composite. Spherulite growth was et al. 2010a, b).
initiated from the bulk matrix polymer and not from
the surface of the BF. The kneading temperature Bamboo fiber/PLA biocomposites
influenced the melt viscoelasticity above the melting
point of poly(butylene succinate) but did not influence PLA is a product produced after the polymerization of
the viscoelasticity below the melting point. lactic acid of which it was produced after fermentation

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Cellulose (2012) 19:1449–1480 1467

of sugar. PLA is now available commercially; how- and flexural strength than a PLA composite containing
ever, applications for PLA are limited because it is pristine BF; and the tensile strength was twice that of
relatively low heat resistant and brittle. The mechan- the PLA composite containing untreated BF. This
ical properties of PLA at elevated temperatures are not enhancement in the mechanical properties was attrib-
acceptable for use in automobiles or electrical and uted to surface modification and improvement of
medical appliances. One idea for solving these prob- interfacial adhesion between the PLA matrix and BF.
lems is to add natural fibers into PLA. Single-bundle Reinforcing PLA with BF led to composites of
BF composites were produced by suspending the fiber increased stiffness and resulted in lower strain at
in a mold cavity by attaching it to a small piece of break than neat PLA, with slightly decreased tensile
wood in the grip area of the specimen. The melt PLA strengths (González et al. 2011). For comparative
resin was then injected into a pre-heated mold to form purposes, three additional types of bamboo-derived
BF/PLA composite. Due to the relative difference in fibrous reinforcements (short bamboo fiber with
scale between microfibrillated cellulose and bamboo, particle size between 150 and 500 lm, large bamboo
a hierarchy of reinforcement was created where BF fiber with particle size between 500 and 1000 lm,
bundles were the primary load-carrying reinforce- and autohydrolyzed bamboo fiber with particle size
ment, and cellulose created an interphase in the between 150 and 500 lm) were also employed.
polymer matrix around the BF that prevented sudden Reinforcing PLA with auto hydrolyzed bamboo
crack growth (Okubo et al. 2009). liquors containing mainly hemicellulose-derived
Three different types of BF were extracted from products led to composites of increased stiffness and
raw bamboo by either sodium hydroxide treatment or resulted in lower strain at break than neat PLA, with
steam explosion in conjunction with mechanical slightly decreased tensile strengths. Impact strength of
processing, which were designated as ‘short fiber composites increased with increased fiber length,
bundles’, ‘alkali-treated filaments’, and ‘steam- which is in agreement with the results of experiments
exploded filaments’, respectively (Tokoro et al. with kenaf fiber-reinforced PLA (Serizawa et al.
2008). Composite samples were fabricated by injec- 2006).
tion molding using PLA/BF pellets prepared by a Sometimes binary fillers present synergistic
twin-screw extruder. The highest bending strength effects that improve the properties of PLA. For
was obtained when steam-exploded filaments were example, loading 20 wt % BF or 20 wt % talc
added to the PLA matrix. The impact strength of PLA improved the HDT in PLA composite by about
with short fiber bundles did not improve as much as it 10 °C compared with neat PLA after heat treatment
did with both filaments. The addition of BF promoted (Shi et al. 2012). Transcrystallization and isothermal
the crystallinity of PLA in PLA/BF composites. When crystallization were observed during heat treatment
medium length BF bundles were added into PLA, the of PLA composites by loading BF and talc simul-
impact strength increased significantly and the occur- taneously. No similar phenomenon was observed in
rence of long fiber pull-outs also became more other PLA composites, which was thought to be a
frequent. PLA/BF biocomposites treated with an alkali result of the synergism between BF and talc in PLA
solution and a silane coupling agent were prepared by composites. Okubo et al. (2009) developed novel
melt compounding (Kang and Kim 2011). The PLA hybrid biocomposites based upon a biodegradable
composite containing delignified BF showed a narrow PLA matrix reinforced with microfibrillated cellu-
decomposition range of 300–400 °C compared to the lose (MFC) and BF bundlesalthougth cracks
PLA composite containing pristine BF (210–430 °C). occurred arround BF bundles. However, an adequate
The tensile and flexural moduli of the treated PLA/BF level of MFC dispersion in PLA/BF could achieve to
composite increased with increasing BF content. The prevent sudden crack formation. By adding just 1
tensile and flexural moduli of the PLA/BF composite wt % MFC with a high degree of dispersion, an
treated with an alkali solution were higher than that of increase in the fracture energy of nearly 200 % was
the PLA/BF composite containing pristine BF. The obtained. In the hybrid BF/MFC/PLA composites
PLA/BF biocomposites treated with an alkali solution there was also a dramatic change in the fracture
and a silane coupling agent exhibited higher tensile morphology around the BF bundles.

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1468 Cellulose (2012) 19:1449–1480

Table 4 Effect of bamboo

Composition Tensile modulus Tensile strength Impact strength
fraction on the mechanical
(wt% BF) (GPa) (MPa) (KJ/m2)
properties of BF/PP
composites (Mi et al. 1999) BF/PP composites 17 2.8 ± 0.3 17.5 ± 1.4 2.9 ± 0.5
29 2.7 ± 0.4 16.5 ± 1.3 3.0 ± 0.5
39 2.9 ± 0.4 16.9 ± 0.7 3.4 ± 0.4
48 3.4 ± 0.4 15.0 ± 1.0 3.7 ± 0.4
58 2.9 ± 0.2 11.8 ± 1.5 3.8 ± 0.5

Effects of bamboo fiber on the properties the energy dissipated as heat during dynamic testing.
of composites The tan d peak occurs approximately 10–20 °C above
the Tg of PHBV and its fiber composites. The
Mechanical and thermo-mechanical properties increased stiffness of PHBV due to fiber loading
decreases the tan d peak value, thus reflecting the
In most applications, BF is used in the preparation of reduced energy losses in the interfacial regions. Low
reinforced composites because of its high strength and dampening of the composites in the transition region is
stiffness in low density materials. Table 4 shows the attributed to the fineness of the BF, which allows for
influence of BF on the mechanical properties of BF/PP their uniform distribution and their effect on the
composites (Mi et al. 1999). Tensile modulus and crystallinity of the matrix. Wood fibers, with lengths
impact strength increased with the increasing BF of between 1,600 and 1,650 lm and diameters
fraction, which indicated a significant reinforcement between 300 and 400 lm, and BF, with lengths of
by the fibers. However, because of the poor interface 500 lm and diameters between 10 and 100 lm, were
adhesion the tensile strength had a tendency to used to fill PHBV. Results from mechanical tests show
decrease. Most studies demonstrated that the increase that there was no significant difference among the
in sample toughness was at the expense of its strain. tensile properties of bamboo and wood fiber based
When the interface affinity was improved the forma- composites at the same loading level, even though the
tion of crazes/cracks in the PHBV8 (PHBV containing aspect ratios of the two fibers were different. The
8 mol % 3-HV) matrix could be delayed (Jiang et al. flexural strength of both types of biocomposites
2008). The presence of fiber was evidence that the remained somewhat unaltered with the addition of
propagation of cracks could be slowed by fiber up to 40 wt % fiber. The modulus of the wood fiber
bridging; as a result, bamboo pulp fiber maintained, composites was 14 % greater than that of the BF
or even increased, the failure strain of the composites composites. This may be due to the higher order
(Mi et al. 1999). stiffness of maple wood fiber versus BF (Singh et al.
The dynamic mechanical properties of BF/PHBV 2008; Singh 2009).
were investigated (Singh 2009). It was found that the
storage modulus (E0 ) of PHBV increased with fiber Thermal properties
loading up to 40 wt %. The E0 of BF composites at
25 °C improved by 157 and 173 % at 30 and 40 wt % Heat deflection temperature (HDT)
fiber, respectively. Among the dynamic mechanical
properties, dampening is the most sensitive to struc- The HDT of a polymeric material is an important
tural heterogeneity, morphological and transitional index of its heat resistance towards an applied load.
changes of the system, and to fiber-matrix interfacial There are several ways to improve the HDT of
interactions. The loss modulus E00 versus temperature polymers, like forming crosslinks or improving the
curves show that incorporation of fiber into PHBV glass transition of polymers. In addition, an easy way
slightly increased its Tg. This may be due to the to increase the HDT value of a polymer is to increase
restriction imposed by the fibers on the movement of its polymeric crystallinity by loading fillers, such as
the expanding molecular chains in the amorphous natural fibers and inorganic filler (Agarwal et al.
region. Tan d is the ratio of E00 to E0 that accounts for 2006). The HDT of PHBV was enhanced by the

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Cellulose (2012) 19:1449–1480 1469

addition of BF, from 114 to 120 and 123 °C at 30 and Coefficient of thermal expansion (CTE)
40 wt %, respectively. The major contributing factor
to the improved HDT from the higher fiber content CTE is a vital property of composites in structural
was that the reinforcing fiber had a better HDT than the applications, and a low CTE value is desirable for
matrix (Singh 2009). achieving dimensional stability. The CTE of crystalline
The HDT of chemically treated fiber composites polymers depends on various parameters such as
with MA-g-PP compatibilizer increased by 23–38 °C processing conditions, thermal history, degree of crys-
(when compared to virgin PP) when the fiber volume tallinity, and crystallite size. Filler aspect ratio, volume
increased from 30 to 50 % (Chattopadhyay et al. fraction, orientation and distribution in the matrix also
2011a, b). play a role in determining the CTE of a composite,
which is affected by mismatches of high CTE matrices
Thermal degradability and low CTE fibers. Fibers are tightly squeezed in the
matrix during mold cooling, and so during heating the
Thermal stability of BF filled composites was evalu- fiber poses a mechanical restraint on the extension of
ated by thermal gravimetric analysis. Singh reported the polymer chain and thus reduces the overall CTE of
that BFs began to thermally degrade at 250 °C, the composite. As the ratio of fiber to matrix volume
reaching the maximum at 380 °C and entirely degrad- increases, the decrease in the CTE of the composite is
ing at around 500 °C (Singh 2009). The PHBV mainly due to the lower CTE of the fiber. However, BF
gradually lost weight as the temperature increased did not show any remarkable effects on reducing CTE
and its maximum thermal degradation occurred at as wood fiber did (Singh and Mohanty 2007).
316 °C. Above 250 °C the degradation process
involved chain scission and hydrolysis which led to Rheological properties
a reduction in molecular weight and the formation of
crotonic acid (Gatenholm and Mathiasson 1994). The Rheological properties of BF/PP composites displayed
presence of moisture further promotes hydrolytic evidence of shear thinning, which is characteristic of
degradation. The thermal degradation of biocompos- non-Newtonian pseudoplastic fluid (Nayak et al.
ites appeared to be cumulative phenomenon of thermal 2009). In general, the pseudoplastic behavior of fiber
degradation of the matrix (PHBV) and fiber alone. reinforced polymer composites can be explained in
Degradation of composites was initiated around two ways: (a) a weak interfacial bond between the
250 °C in the case of both fiber and PHBV and ceased fiber and matrix tends to be created at high frequency;
around 400 °C. The TGA of composites also showed and (b) in molten polymeric systems, when chemical
fiber to be the final constituent to undergo degradation interaction among polymer particles exists, the layers
in composites. The composite degradation maxima may be sheared away and increase the shear rate
occurred at a temperature a little higher than that of resulting in decreased viscosity. In composite systems,
PHBV. The maximum degradation temperature of the the presence of fibers disturbs the normal flow of the
composite shifted to a temperature higher than that of polymer and hinders the mobility of chain segments in
PHBV, indicating it was slightly more thermally stable the flow causing the viscosity of the filled polymer
than PHBV. Thus the presence of BF (a lignocellulosic system to increase (Mohanty and Nayak 2007).
fiber) did not have any effect on degradation of PHBV. Results from frequency-sweep dynamic experiments
Thermal analysis showed the initial decomposition showed that both storage modulus and loss modulus
temperature of PLA composite with delignified BF increased linearly with an increase in angular fre-
increased, but the maximum decomposition tempera- quency. The BF/PP composites exhibited a higher
ture decreased as compared to PLA composite magnitude of modulus revealing a reinforcing effect
containing pristine BF (Singh 2009). The addition of imparted by the fibers (Nayak et al. 2009).
BF could improve thermal properties and heat resis-
tance of annealed PLA/BF composites in comparison Crystalline properties
with annealed PLA, due to the deformation constraint
of PLA around BF, as well as the crystallinity The melting temperature of pure PP was observed to
promoted by annealing the PLA (Tokoro et al. 2008). be around 162 °C. Addition of BF did not significantly

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1470 Cellulose (2012) 19:1449–1480

Table 5 Melting and crystallization properties of PP and BF/ PP, s-MAPP, and m-MAPP indicating that BF acted as
PP composites (Nayak et al. 2009) a b-nucleator. The nucleation density of both s-MAPP
Sample type Tm (°C) Tc (°C) DHm (J/g) %Xc and m-MAPP at the fiber surface was remarkably
higher than that of PP because improved interfacial
PP 162.00 116.54 71.5 29.80 adhesion was achieved with the s-MAPP and
PP ? BF30 % 162.36 117.01 76.20 31.70 m-MAPP matrices. The transcrystalline growth of
s-MAPP and m-MAPP on the BF surface was
affect the melting and crystallization temperatures of observed and is shown in Fig. 7 (middle and right).
the PP matrix; however the Xc values, depicted in Others have reported that an increase in the spherulite
Table 5, revealed that the degree of crystallinity dimensions was observed at high kneading tempera-
increased with the incorporation of BF fibers. This is tures (150 °C) in both the neat polymer and the
an indication of the formation of nucleation sites in the bamboo-fiber composite. At all kneading tempera-
presence of fibers (Nayak et al. 2009). The enthalpy of tures, spherulite growth was initiated from the bulk
crystallization (DHm) was elevated in PP/BF30 %, matrix polymer and not from the surface of the BF or
and was also evidenced in a sample of PHBV8/ treated BF. On the contrary, no significant transcrys-
bamboo pulp fiber where the DHm of PHBV8 tallization was observed for PBS (Kori et al. 2005).
increased significantly increased 20.7–53.3 J/g after The melt crystallization temperature (Tc) of PHBV
the addition of bamboo pulp fiber (Jiang et al. 2008). was observed to be 101 °C. The addition of 30 wt %
It is thought to be a common phenomenon that the wood fiber increased this temperature to 104 °C,
fiber surface provides nucleation sites for semi- whereas the BF decreased it to 99 °C; indicating an
crystalline polymers. In the extreme case of fiber- increase in the rate of crystallization in the presence of
induced crystallization, when the nucleation density wood fiber and a decrease in the case of bamboo fiber.
on the fiber surface is so high that crystal growth along This may be due to slower diffusion of molecular
the fiber axis is inhibited by the neighboring crystals, chains though the well dispersed BF to the nucleus,
the crystalline structure manifests as tightly aligned thus decreasing the crystallinity rate in the BF
spherulites growing outward from the fiber (termed composite. Similarities in the melt crystallization
transcrystallization). Mi et al. (1997) reported that peaks of PHBV and its fibrous composites during
transcrystals of polypropylene were generated on the cooling provided evidence for divergence in their
surface of BF in a composite of polypropylene and BF, crystalline morphologies (Singh et al. 2008).
shown in Fig. 7 (left). It was shown that the addition of
BF to any of the three polymers caused an increase in Dielectric properties and conductivity
the overall crystallization rate. A considerable amount
of b-form crystallinity was produced in the PP, Dielectric properties of natural fiber reinforced poly-
s-MAPP, and m-MAPP by mixing with BF; and all mer composites at different frequencies and temper-
the BF-filled samples contained both the a- and atures depend very strongly on the contribution of
b-forms. There is no b-form observed in the pure interfacial, ionic, and orientation polarization. As

Fig. 7 POM micrographs of bamboo fiber in PP matrix (left), in s-MAPP matrix (middle), and in m-MAPP matrix (right) (9100)
(reprinted from Mi et al. 1997 with permission from Wiley)

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Cellulose (2012) 19:1449–1480 1471

Weathering or aging

Natural fibers have weaker weathering and aging

properties than artificial fibers; however these proper-
ties could be improved with the proper treatment. Das
et al. (2009) investigated the effect of alkali treatment
of bamboo strips on the weathering properties of
unidirectional bamboo strip-novolac resin composites.
All types of composite specimens were subjected to
testing for accelerated weathering, % water absorp-
tion, UV exposure, and exposure to 100 % humidity.
The results showed that the composites made with
treated bamboo strips had better weathering charac-
teristics compared with the untreated ones. Moisture
sorption and strength reduction were reported as being
Fig. 8 Dependence of dielectric constant of BF with parallel or
perpendicular orientation on the temperature at 2 MHz fre- suppressed when maleic anhydride polypropylene
quency (reprinted from Kumar et al. 2011 with permission from (MAPP) was used as a coupling agent in both types
Springer) of composite systems (Thwe and Liao 2003).

shown in Fig. 8, dielectric constant at different Biodegradability

temperatures for 2 MHz frequency exhibited a strong
dependence on the fiber orientation (Kumar et al. Commodity polymers such as PP and PE were
2011). The dielectric constant, conductivity, and developed to provide durability and resistance to
dielectric dissipation factor of parallely oriented various forms of degradation, including photodegra-
bamboo/epoxy composites were higher than that of dation and attack from fungi and microbial agents;
the perpendicularly oriented composites. The conduc- however, the disposal of plastic products that are
tivity activation energy, dielectric dissipation factor, nonbiodegradable has become a major concern for the
and dielectric constant all decreased when the fre- current environment. Biodegradation is brought about
quency increased at all temperatures studied. This was by biological activity, predominantly the enzymatic
attributed to the decrease in orientation polarization of action of microorganisms, and can be measured by
the polar groups present in lignocellulosic fibers. The standard tests over a specified period of time.
dielectric properties were improved after merceriza- Chattopadhyay et al. (2011b) investigated the
tion due to a decrease in the orientation polarization. degree and rate of aerobic biodegradation of various
polypropylene (PP) composites produced using 10, 15,
and 50 % volume fractions of natural fibers such as
Volume resistivity pineapple leaf fiber, banana fiber, and bamboo fiber.
A soil contact incubation apparatus was set up accord-
The volume resistivity of natural fiber composites is a ing to ASTM D5988-96 and is shown in Fig. 9. The
function of shape, size, microfibril angle of cellulose, volume of CO2 released (degree of biodegradation)
crystalline and amorphous components present, chem- from test specimens plateaued after 70–90 days. In
ical composition, presence of impurities, moisture, addition, results showed that 5–15 % degradation had
and the voltage applied. According to the equation: occurred in areas of the fibers that were physically
cellulose content (%) = 73.78–3.09 q, where q is the embedded in the resin matrix, but the covalently
volume resistivity, BF should have the highest volume linked areas between the natural fiber and the MA-g-
resistivity of all other natural fibers (Kumar et al. PP compatibilizer remained. Thus, although natural
2011). BF composites have a high volume resistivity fiber reinforced PP composites are not excellent
because of its comparatively low cellulose content and biodegradable materials, they can address the man-
small microfibrillar angle. agement of waste plastics by reducing the amount of

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1472 Cellulose (2012) 19:1449–1480

Fig. 9 Soil-contact incubation apparatus (left); and the bio- NFPC, degradation phase of NFPC, plateau phase of NFPC).
degradation curves for various natural fiber PP composites (reprinted from Chattopadhyay et al. 2011b with permission
(right, in it 1–6 represent lag phase of cellulose, degradation from Wiley)
phase of cellulose, plateau phase of cellulose, lag phase of

Table 6 Effects of size on

Size (lm) Tensile Tensile Impact
the mechanical properties of
modulus (GPa) strength (MPa) strength (KJ/m2)
BF/PP composites (Thwe
and Liao 2000) BF/PP Composites \500 2.7 ± 0.3 15.3 ± 0.4 2.8 ± 0.4
(50 wt% BF) 500–850 2.2 ± 0.3 12.6 ± 0.4 2.8 ± 0.2
850–1000 2.3 ± 0.1 11.6 ± 0.7 3.3 ± 0.4

polymer used. That in turn will reduce the generation (5) high biodegradability when exposed to the envi-
of nonbiodegradable polymeric wastes. ronment which limits the service life of composites,
particularly in outdoor applications. Enhancement of
the properties of BF filled polymer composites is
Factors influencing the properties of BF fiber filled governed by the properties of the matrix and the
polymer composites reinforcement, the phase state of the matrix after
reinforcement, and the interface developed due to
Despite the advantages mentioned above, the use of interaction between the matrix and reinforcement. The
cellulose fibers in thermoplastics has not been exten- amount, shape (aspect ratio), distribution/dispersion
sive. Possible reasons that contribute to unsatisfactory and alignment/orientation of the fibers within the
final properties of the composite include: (1) limited composite matrix, and the fabrication process also
thermal stability at typical melt processing tempera- play crucial roles in governing the properties of the
tures of about 200 °C limits the type of thermoplastic composites. To gain advantageous properties, the
that can be used with the fibers; (2) poor dispersion following factors should be considered during fabri-
characteristics in the non-polar, olefinic thermoplastic cation of BF or other cellulose fiber filled polymer
melt due to strong hydrogen forces between the fibers; composites.
(3) poor compatibility with many thermoplastic
matrices due to their highly hydrophilic character, Dispersion and orientation
which results in poor mechanical properties of the
composites produced; (4) high moisture absorption of The size and aspect ratio of BF has a great impact on
the fibers that can affect the dimensional stability of the mechanical properties of composites. Short fibers
the composite and the interfacial bond strength; and cost less and are easier to use in processing methods,

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Cellulose (2012) 19:1449–1480 1473

such as extrusion, compounding by intensive mixing, above mentioned adhesion phenomenon to exist in an
conventional injection molding, and complex shapes. appreciable amounts. To improve interface interaction
Its disadvantages are that it has lower strength and for development of BF composites with improved
impact, and is hard to orient. In long fiber systems, properties many modifications have been adopted.
higher impact strength will be obtained although
it is harder to make prepreg. As shown in Table 6, Mercerization
increased BF length did not result in increased strength
of BF/PP composites (Thwe and Liao 2000). On the Bamboo strips contain lignin which not only leads to
contrary, the tensile strength of BF filled PP samples ineffective interfacial adhesion, but also has an acrid
showed a more or less decreasing trend; however, the aroma. Alkali pretreatment, namely mercerization,
impact strength increased with longer BF length. This may reduce the smell of BF by removing the lignin and
is easily explained because longer fibers carry a higher other undesirable components. Furthermore, it may
tensile load as a result of increased transfer length. also remove amorphous cellulose from cellulose fiber
bundles and create a rough fiber surface, thus forming
Interface adhesion cellulose micro- or nano- crystals. Mercerization also
activates hydroxyl groups in natural fiber and
Interface adhesion is one of most important issues for improves fiber tensile strength. The result is increased
all composites. Possible adhesion mechanisms that adhesion due to increased fiber surface area and
occur between the matrix and the reinforcement filler mechanical interlocking between the fiber and matrix;
are adsorption, chemisorption, electrostatic interac- and hence improved tensile strength and thermal
tion, and mechanical interlocking. Adsorption hap- stability which lead to improved composite properties.
pens due to intimate intermolecular interactions A PLA composite containing delignified BF showed
between the molecules of the fiber substrate and the a higher tensile and flexural modulus than a PLA
thermoplastic resin, which results from Van der Waals composite containing pristine BF (Kang and Kim
forces or hydrogen bonding. Chemisorption occurs 2011). In addition, mercerization of BF made the
when chemical bonds are created between the sub- composites more thermally stable over a certain
stance and the substrate surface as a result of chemical temperature range during the study. As a result,
reactions. Electrostatic adhesion is attributed to the composites fabricated from treated strips also gained
creation of opposite charges on the interacting more stability; however, when treated with greater
surfaces of fibers and thermoplastics; thus, an interface than 15 % alkali the composite exhibited the opposite
consisting of two layers of opposite charges is formed, properties (Das and Chakraborty 2009a, b).
which accounts for the adhesion of the two. The
mechanical interlocking phenomenon explains the Compatibilizer
adhesion when a matrix penetrates into the pores,
holes, and crevices or other irregularities of the Functionalized polyolefins are often used as compat-
substrate, and mechanically locks to it. A good wetting ibilizers to create a chemical link between the polymer
of the resin on the substrate is essential for all the and fiber; and maleated polypropylene has been the

Table 7 Effect of MAH

s-MAPP/PP MAH in the Tensile Tensile Impact
content on the mechanical
(w/w) composites (wt%) modulus (GPa) strength (MPa) strength (KJ/m2)
properties of BF/PP
composites (50 wt% BF) 0/50 0.0 2.8 ± 0.2 14.4 ± 1.0 3.2 ± 0.5
(Mi et al. 1999)
8/42 0.038 3.2 ± 0.5 19.0 ± 2.1 3.6 ± 0.7
16/34 0.077 4.2 ± 0.5 24.5 ± 2.1 3.5 ± 0.7
24/26 0.11 4.1 ± 0.4 30.1 ± 1.2 3.7 ± 0.7
32/18 0.15 4.4 ± 0.5 30.5 ± 1.3 3.3 ± 0.7
41/9 0.19 4.3 ± 0.6 31.1 ± 1.6 3.8 ± 0.7
50/0 0.24 4.2 ± 0.5 32.4 ± 1.2 3.6 ± 0.5

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1474 Cellulose (2012) 19:1449–1480

most commonly used compatibilizer in BF/PP com- fracture surfaces (Fig. 10a,b) indicating insufficient
posites. Table 7 shows the impact of MAH content on interfacial bonding strength between the fiber and the
the mechanical properties of BF/PP composites (50 matrix. With pMDI, interfacial bonding was strong
wt % BF). As the MAH content increases there is little and all fibers were broken on the fracture surfaces
difference in the tensile modulus or the impact (Fig. 10 c,d). Fiber pullout is detrimental to the
strength, but there is a significant increase in the strength and modulus of composites; thus the impact
tensile strength as the degree of maleation increases strength was reduced but the tensile and flexural
(Mi et al. 1999). Semi-crystalline and amorphous strength increased with the addition of MDI. The
EPR-g-MA, PE-g-MA, and several combinations improved interfacial adhesion enabled higher stress
thereof, were incorporated into HDPE/bamboo flour transfer between the fibers and matrix and reduced the
composites as interfacial modifiers. It was found that chance of fiber debonding. As such, the fibers shared a
incorporation of either PE-g-MA or sEPR-g-MA larger load (up to the maximum strength of the fibers)
enhanced both tensile and flexural strength and impact with the matrix and thereby increased the strength and
toughness of the resulting composites; while aEPR-g- modulus of the composites. Improved interfacial
MA had a negative effect on the strengths despite a adhesion also prevented fiber pullout, which is a
moderate enhancement of impact toughness (with major source of energy dissipation for increased
respect to the uncompatibilized composite). Strength toughness of the composites; therefore, tensile and
of the resultant composites modified by either PE-g- flexural strength improved at the expense of the
MA or sEPR-g-MA increased with the amount of ductility of the composites.
compatibilizer added; however, the effect began to
level-off when the concentration exceeded 2.9 wt %. Coupling
The maximum strength and impact toughness were
achieved in both PE-g-MA and sEPR-g-MA modified Silanes are recognized as efficient coupling agents that
composites. In HDPE/BF composites the introduction are used extensively in composites and adhesive
of each individual modifier caused a drop in modulus formulations. Silane coupling agents have a hydro-
to a different extent. At a fixed BF loading level (40 philic structure with different groups attached to the
wt %) and 8.3 wt % of modifiers, the combination of silicon atoms that can act as a bridge; one end
PE-g-MA with small percentages of EPR-g-MA interacting with the matrix and the other end reacting
improved impact toughness while simultaneously with the hydrophilic fibers. A functional silane, as
maintaining the strength of the composite at an shown in Fig. 11, was employed as a coupling agent to
acceptable level, as compared to that compatibilized enhance the interfacial adhesion between BF and PLA
with either PE-g-MA or sEPR-g-MA alone. An (Kang and Kim 2011). Silane treated BF reinforced
optimum strength/toughness balance of composite PLA composite showed excellent mechanical and
properties can be achieved with a lower percentage of thermal properties compared with the properties of
sEPR-g-MA and a medium BF-loading level. It was PLA composite containing delignified BF. It was
found that suitable interfacial adhesion and ease of thought that effective surface treatment from the silane
interlayer cavitations between HDPE and BF were coupling agent improved adhesion between the PLA
beneficial to initiate massive matrix yielding in the matrix and the BF. The functional group in the silane
composites, thereby achieving satisfactory impact coupling agent confers excellent compatibility
strength (Liu et al. 2008). The addition of maleic between the biodegradable matrix and the natural
anhydride grafted PHBV8 (MAPHBV8) as a compat- fibers. The amine groups of 3-aminopropyl triethox-
ibilizer resulted in increased strength and modulus but ysilane are promising for improving the interfacial
reduced toughness (Jiang et al. 2008). adhesion of PLA/BF composites. Tung et al. had
Isocyanates, like MDI, are commonly used as similar results in that isocyanate silane and amino
compatibilizers in BF reinforced composites (Jiang silane treated BF bundles exhibited improved interfa-
et al. 2010). Figure 10 shows the fracture surface cial shear strength with raw BF/PP composites.
morphology of PHBV8/bamboo pulp fiber composites However, without any treatment steam exploded fiber
with and without pMDI. Without pMDI, significant showed good interfacial adhesion with PP in the
fiber pullout was observed on both tensile and impact composite (Tung et al. 2004).

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Cellulose (2012) 19:1449–1480 1475

Fig. 10 SEM micrographs of tensile (a and c) and impact (c and d) (reprinted from Jiang 2010 with permission from
(b and d) fracture surfaces of the PHBV8/bamboo pulp fiber (80/ American Chemical Society Publication)
20 w/w) composites without pMDI (a and b) and with pMDI

Various other physical and chemical methods have wettability and dyeability of the natural fiber. There
been employed to modify natural fibers and improve are many other methods, such as acetylation, benzo-
the properties of composites. Exposure to plasma can ylation, acrylation, and permanganate treatments that
have different effects on a fiber’s surface including: can be used to improve the interfacial adhesion
cleaning the surface (which promotes adhesion and the between fiber and matrix by modifying the fiber
action of coupling agents); etching or ablation of surface.
materials resulting in a rougher surface; crosslinking
or branching of materials at the surface; modification Moisture absorption
of the surface chemical structure; and introduction of
free radicals. Xu et al. (2006) employed argon plasma Moisture absorption is a major concern for natural
at atmospheric pressure to treat BF and improve the fibers used as reinforcements in structural composites.

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1476 Cellulose (2012) 19:1449–1480

Fig. 11 Schematic
illustration of the silane
treatment of bamboo fiber
(reprinted from Kang and
Kim 2011 with permission
from Springer)

BF is a hydrophilic material that absorbs a significant the interface. The absorbed water starts to establish
amount of moisture under standard humidity condi- intermolecular hydrogen bonding with the fibers and
tions. BF demonstrates moisture sorption hysteresis thereby reduces interfacial adhesion between the fiber
similar to other natural fibers such as flax and hemp and matrix; and water soluble substances start leach-
(Chen et al. 2009). Besides affecting the properties of ing from the fibers. This ultimately leads to debonding
the polymer matrix and the natural fibers themselves, between the fiber and the matrix. Moisture absorption
moisture can seriously damage the fiber–matrix inter- softened the BF, causing an increase in extensibility
face, leading to poor stress transfer efficiencies from and a reduction in the elastic modulus, while the
matrix to reinforcement. The degradation process tensile strength was not significantly affected. The
starts with the swelling of cellulose fibers which influence of moisture sorption on the interfacial shear
develops stress at the interface and causes microcracks strength (IFSS) of bamboo/vinyl ester composite was
to form in the matrix around the swollen fibers. The investigated. The IFSS achieved at normal room
cracks exacerbate water absorption and its attack on conditions (20 °C, 60 % RH) was only half of what

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Cellulose (2012) 19:1449–1480 1477

was achieved under dry conditions. Composites pro- viable option for employment generation and rural
duced at high relative humidity conditions (80 and development. Further systematic and persistent
90 %) had negligible interfacial strength. Exposure of research on BF composite technologies will lead to
the bamboo/vinyl ester composite to water caused greater scope in the use of this plant resource.
significant damage to the interfacial shear strength,
which occurred in the first 9 days causing a 38 % Acknowledgments The authors are grateful to National
Natural Science Foundation of China (No. 51103073) and
reduction in IFSS. Prolonged water immersion of up to
Natural Science Foundation of Jiangsu Province (No.
100 days did not result in further reduction of IFSS; BK2011828) for financial support.
meaning that, exposure to high humidity during
material storage and composite manufacture can be
much more damaging to the interfacial strength of the References
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