Composites: Part A 37 (2006) 22132220

www.elsevier.com/locate/compositesa

Improvement of plant based natural bers for toughening

green compositesEect of load application
during mercerization of ramie bers
a,* a,*
Koichi Goda , M.S. Sreekala , Alexandre Gomes b, Takeshi Kaji b, Junji Ohgi a

a
Department of Mechanical Engineering, Yamaguchi University, Tokiwadai, Ube 755-8611, Japan
b
Graduate School of Science and Technology, Yamaguchi University, Tokiwadai, Ube 755-8611, Japan

Received 14 November 2005; received in revised form 16 December 2005; accepted 20 December 2005

Abstract

Eect of mercerization to tensile properties of a ramie ber was explored. Load application technique during mercerization has been
employed in order to improve mechanical properties of the ber. A chemical treatment apparatus with tensile loading portion for apply-
ing monolaments was newly developed. The ramie ber was alkali-treated by 15% NaOH solution with applied loads of 0.049 and
0.098 N. The results showed that tensile strength of the treated ramie ber was improved, 418% higher than that of the untreated ramie
ber, while Youngs modulus of the treated bers decreased. It should be noted that fracture strains of the treated ramie ber drastically
increased to 0.0450.072, that is, twice to three times higher than those of the untreated ramie ber. It was considered that such property
improvements upon mercerization were correlated with change of morphological and chemical structures in microbrils of the ber.
Finally, the plastic deformation behavior and fracture mechanism of the mercerized bers under tensile loading process was explained
using a schematic model.
2005 Elsevier Ltd. All rights reserved.

Keywords: A. Fibres; B. Mechanical properties; E. Surface treatments; Biomaterials

1. Introduction posal problems especially in agricultural elds, environ-

Natural bers play an important role in developing high
performing fully biodegradable green composites [1,2],
which will be a key material to solve the current ecological
and environmental problems. Mohanty et al. reported the
structural aspects and properties of various natural bers
and dierent biodegradable polymers, which are used for
the development of green composites [3]. Major interna-
tional research work on cellulosic bers and their compos-
ites has been reviewed by Eichhorn et al. [4]. It has been
reported that cellulose microbrils and cellulose nanocrys-
tals can be used as a reinforcing phase in polymeric matrix.
Introduction of green composites will reduce the waste dis-
*
Corresponding authors.
E-mail addresses: goda@yamaguchi-u.ac.jp (K. Goda), sreekalams@
yahoo.co.in (M.S. Sreekala).
mental pollution etc. and can nd various applications in
engineering, electronic and automotive elds. Lightweight,
decreased wearing of machines, low abrasiveness, absence
of health hazardness during processing, application and
upon disposal etc. are the added advantages of the green
composites.
Due to many environmental problems, the discarding
method for glass ber reinforced plastics (GFRP) and their
recycling has seriously been realized in the world [5]. As is
widely known, GFRP has excellent thermal and mechani-
cal properties, but these properties make dicult to carry
out suitable disposal processing. For example, incineration
of discarding GFRP generates a lot of black smoke and
bad smells and often gives damage to incinerator by fusion
of glass bers. Reclamation processing generates also a
large environmental load, since GFRP is not decomposed
easily. For the last decade, therefore, natural ber

1359-835X/$ - see front matter 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.compositesa.2005.12.014
2214 K. Goda et al. / Composites: Part A 37 (2006) 22132220
composites have been developed, in which several natural
bers such as ramie [6], hemp [7], jute [8], sisal [9], bamboo
[10], banana [11], oil palm [12] bers and so on are used as
reinforcements in place of glass bers. Flax, kenaf, hemp
and wood our are reported to be highly suitable for the
preparation of load bearing and impact absorbing compo-
nents of vehicles [13,14]. Peijs et al. [15] reported that ax
ber reinforced thermoplastics were of interest in low-cost
engineering applications and can compete with the com-
mercial glass mat reinforced thermoplastics. The major
problem identied with natural bers during incorporation
in hydrophobic polymers is their poor compatibility. To
alleviate this problem various berpolymer interface mod-
ications have been proposed which results in improve-
ment of performance of the resulting composite.
Regarding improvement of the compatibility, chemical
treatment to the bers has often been carried out, in which
signicant change of mechanical properties of the bers has
been induced [16]. Thus, research on the compatibility
between natural bers and polymer by chemical treatment
should be carried out along with the problem of change in
mechanical properties of natural bers.
The present study focuses on the mechanical properties
of the versatile natural ber, ramie. Ramie (Boehmeria
nivea), a bast ber belonging to the family Urticaceae or
Nettle commonly referred to as china grass, white ramie,
green ramie and rhea is one of the most valuable natural
bers. The main natural distribution of ramie lies in sub-
tropical China, Japan, Southeast Asia and in Brazil. Ramie
is characterized by its high length, great strength, much
greater than that of cotton and silk. In terms of specic
strength ramie bers can compete with synthetic bers.
The specic strength value of ramie is almost the same as
that of E-glass bers and shows higher elongation [17].
They can be easily woven and are good candidate for tex-
tile composites. They are widely used in fabric industry due
to their softness, bleachability and better dyeability.
The purpose of this study is thus to clarify the eect of
chemical treatment on the mechanical properties of ramie
bers. In general, alkali-treatment onto the natural bers,
called mercerization, is expected to be a much eective
treatment in terms of improving its hydrophilicity by
breaking the extensive hydrogen bond network in the ber
structure and creating many free reactive hydroxyl groups.
On the other hand, tensile load application to the ramie
bers during mercerization was expected in this study to
give improved structural and mechanical properties to the
bers, since proper orientation of microbrils along the
ber axis may be realized due to the inuence of tension.
The result showed that tensile load application during mer-
Table 1
Physical and chemical properties of ramie bers [3]
Cellulose Lignin Hemicellulose Pectin
(wt%) (wt%) (wt%) (wt%)
68.676.2 0.60.7 13.116.7 1.9
cerization to the ramie bers improves drastically their duc-
tility, as well as maintains the strength level. Dierence
between tensile behaviors of the untreated and treated
ramie bers were additionally investigated by cyclic tensile
test. Finally, a schematic model has been developed in
order to explain the behavior of the treated ramie ber
under tension.
2. Experimental procedure
The ramie bers used in this study was supplied from
Enkou Co. Ltd., Japan. Single monolaments of ramie
were easily extracted from the as-supplied ramie bundle.
The physical and chemical characteristics of ramie bers
are given in Table 1 which were reported earlier by scien-
tists [3]. It is shown that there is little lignin in the bers,
dierently from other natural bers.
To change the mechanical properties of ramie bers, a
chemical treatment apparatus with tensile load applying
device was newly developed, in which the treatment of
the bers were carried out for monolaments as shown in
Fig. 1. This apparatus consists of support portions of four
glass plates to maintain alkali solution, and bars for sus-
taining the weights. First, monolament specimens for
alkali-treatment were prepared, as shown in Fig. 2, and
four specimens were put onto the glass plates. Then one
end of the specimens is clipped and other end attached to
the applied loads through the bar, as shown in Fig. 1. Next,
the monolaments were dipped into 15% sodium hydroxide
solution by syringing. The treatment time was two hours,
and the weights applied were 0.049 and 0.098 N. It is
expected from the treatment that during the load applica-
tion, the microbrils will be more closely arranged to the
ber axis. After the treatment, one set of the monola-
ments were dried without any washing, and another set
were washed into the water containing small quantity of
acetic acid and then dried. The former condition is herein-
after denoted as condition (I), and the latter condition is
denoted as condition (II).
The treated monolaments were xed onto a paper with
a rectangular hole of 10 mm length, as shown in Fig. 3. The
diameters were measured using an optical microscope
(Nikon Eclipse ME 600, Japan). Tensile test of the speci-
mens was carried out using a tensile testing machine, fol-
lowing Japan Industrial Standards (JIS R 7601, Testing
methods for carbon bers). The crosshead speed of the ten-
sile test was 0.8 mm/min. The applied load was measured
using a micro-load cell attached to the machine, and the
displacement was measured using laser displacement sys-
tem (Anritsu Co. Ltd.). Twenty specimens of each set were
Wax Microbrillar Moisture Density
(wt%) angle () content (wt%) (mg/m3)
0.3 7.5 8.0 1.50
 K. Goda et al. / Composites: Part A 37 (2006) 22132220 2215

It has found that the ramie ber exhibits relatively high

M without load application exhibited the largest diameter.
Fig. 1. Shape and dimension of chemical treatment apparatus with load
applying system.
Fig. 2. Specimen for alkali-treatment.
Fig. 3. Specimen for tensile-test.
tested and the tensile strength of each specimen was calcu-
lated by assuming that the cross-sectional area of each
specimen is a circle. To clarify plastic deformation behavior
of the treated bers more exactly, a cyclic tensile test was
additionally carried out for the untreated and treated
specimens.
strength properties as compared with other natural bers.
On the other hand, the ber fracture strain is not so large,
and comparable to that of synthetic bers such as glass and
carbon.
Treated ramie bers were also tensile-tested for each
condition and the values are shown in averages in Table
3. Since condition (I) has no washing process, the ber
diameter increased largely due to their expansion by exces-
sive reaction. Especially, the bers treated by condition (I)
Such an increase in ber diameter may lead to decrease
in tensile strength to approximately 3080% of that of
the untreated bers. The bers treated by condition (I)
without load application also showed the lowest strength.
Since in condition (I), traces of sodium hydroxide still
remains on the ber after unloading, it is considered that
further reaction damaged excessively the structure of cellu-
lose. On the other hand, the diameter of the bers treated
by condition (II) is not changed so much. Due to washing
process, no reaction in the bers occurs after treatment. As
a matter of fact, we additionally investigated the dimen-
sional changes to the same bers before and after merceri-
zation with loading application of 0.098 N using condition
(II). The result of measurements of 143 ramie bers showed
that average diameters before and after the treatment were
0.027 and 0.028 mm, respectively, and coecients of varia-
tion in diameter were 0.391 and 0.353, respectively. Thus,
little change in diameter occurs by the treatment using con-
dition (II). It is proved from Table 3 that condition (II)
increases tensile strength of the ramie bers except for
0 N loading condition. Especially, 0.049 N loading condi-
tion gives the highest strength, i.e., 661 MPa. This may
be related with change of orientation angle of microbrils
in the ber. Thus, load application during mercerization
using condition (II) can increase the tensile strength, 4
18% higher than that of untreated ber. It should be noted
that considerable enhancement in fracture strain is realized
by the present treatments. Fracture strains of the treated
ber drastically increased to 0.0450.072 in average, that
is, twice to three times higher than fracture strain of the
untreated ramie ber. According to the result of Table 3,

3. Experimental results Table 3

Tensile properties of load applying alkali-treated ramie ber
3.1. Tensile properties Applied Fiber Fracture Tensile Fracture
load diameter load strength strain
The results of the tensile properties of untreated ramie (N) (mm) (N) (MPa) (%)
bers are shown in Table 2. The values are all averages. Condition (I)
0 0.049 0.252 151 0.045
0.049 0.046 0.434 306 0.061
Table 2 0.098 0.044 0.562 441 0.065
Mechanical properties of untreated ramie bers
Condition (II)
Fiber diameter Fracture Tensile Fracture
0 0.031 0.380 550 0.069
(mm) load (N) strength (MPa) strain (%)
0.049 0.028 0.408 661 0.072
0.034 0.467 560 0.025 0.098 0.026 0.373 606 0.072
2216 K. Goda et al. / Composites: Part A 37 (2006) 22132220

1800 1000
1600 0N
Tensile strength (MPa)

1400
0.049N
1200 0.098N 800
untreated
1000
0g
800 10g

600 600

Stress (MPa)
400
200

0 400
0 100 200 300 400 500
Applied stress (MPa)

Fig. 4. Eect of load application during mercerization using condition (II)

200
on tensile strength of ramie bers.

the fracture strains are increased even in the condition 0

without load application. That is to say, improvement of 0 2 4 6 8 10

fracture strain is considered to be due to the eect of Strain (%)

mercerization. Fig. 5. Typical stressstrain diagrams of ramie bers treated by condition

Fig. 4 shows relation between applied stress during mer- (I).
cerization using condition (II) and tensile strength. The
applied stresses were obtained by dividing the two applied
loads, 0.049 and 0.098 N, by cross-sectional area of each 1000
untreated
0g
ber. A larger applied stress in the same load condition
10g
means a smaller diameter. It is proved from Fig. 4 that 900
the ber strength increases by giving applied stresses of
800
50200 MPa. There may be an optimal applied stress
around 100 MPa, but this value is not exact because of 700
large variation in strength. Further experiment should be
done in order to nd the optimal applied stress as a future 600
Stress (MPa)

subject. In any case, it was proved that the ramie bers

500
clearly increase not only in fracture strain by mercerization,
but also increase in strength by load application during 400
mercerization.
300

3.2. Static and cyclic stressstrain behaviors 200

Figs. 5 and 6 indicate typical stressstrain diagrams of 100

ramie bers untreated and treated by conditions (I) and
(II), respectively. As seen in the gures, the untreated ber
behaves with almost linearity. On the other hand, slopes of
the stressstrain relation of the treated bers are obviously
lowered, and their behaviors are no longer linear. And as
mentioned earlier, mercerization generates a dramatic
increase in fracture strain of this ber. Furthermore, it
should be noted that the stressstrain relations under
unloading and loading conditions are almost in agreement.
Table 4 shows Youngs moduli of untreated and treated
ramie bers, which were obtained from initial slopes of
the stressstrain diagrams. Youngs modulus was largely
decreased by mercerization, especially by the severe treat-
ment, i.e., condition (I). According to the result of Table
4, Youngs modulus of this ber is not aected by dier-
ence of the load conditions, but aected by chemical condi-
tion. In any case, it is expected that such an improvement
of fracture strain may increase mechanical properties such
0
0 2 4 6 8 10
Strain (%)
Fig. 6. Typical stressstrain diagrams of ramie bers treated by condition
(II).
as fracture toughness, impact strength etc. of the ber com-
posite if the treated bers are used as the reinforcement.
The cyclic tensile tests of untreated and treated ramie
bers were carried out in order to explore the plastic defor-
mation function more exactly. Condition (II) was
employed for the treated ber. The results are shown in
Figs. 7 and 8. It is observed that untreated ramie ber
undergoes less plastic deformation while the treated ber
exhibits larger plastic deformation accompanied with strain
hardening. In other words, plastic deformation function of
ramie bers was veried from the stressstrain behavior of
 K. Goda et al. / Composites: Part A 37 (2006) 22132220 2217

Table 4 4. Discussion
Youngs moduli of load applied alkali-treated ramie bers
Applied load (N) Youngs modulus (GPa) The ber surface topography for the untreated and trea-
Untreated ted ramie bers was studied using a scanning electron
0 24.5 microscope. The microscope observation showed that,
while the treated ber using condition (I) was changed into
Condition (I)
0 8.5
an extremely rough surface, the surface of the treated ber
0.049 6.1 using condition (II) was almost the same as that of the
0.098 6.7 untreated ber. This fact may be the reason why the ber
strength was lowered by condition (I), but not the reason
Condition (II) why the fracture strain is largely improved. In this chapter,
0 14.5
0.049 15.0
thus, we propose a schematic model regarding changes in
0.098 17.0 fracture strain and tensile strength by mercerization with
tensile load application.

1000
4.1. Plastic deformation behavior of mercerized ramie bers

Natural bers can be considered as a bundle of micro-

800
brils bound together by amorphous lignin, waxy materials
and other impurities. The arrangement of microbrils is a
600 determining factor of the luster and strength of the ber.
Stress (MPa)

Microbrils are made up of long cellulose chains and hemi-

400 cellulose [18]. Fig. 9 shows schematic presentation of
untreated ramie ber monolament showing the structure
200
of microbril bundle. The microbrils are extensively
hydrogen bonded with more crystalline form of cellulose.
The detailed chemical structure of the untreated microbril
0
0 2 4 6 8 is also shown in the right-hand of the gure [19]. It contains
Strain (%) long crystalline portions composed of only cellulose as well
Fig. 7. Typical stressstrain diagram of untreated ramie single ber in as small regions of amorphous region composed of several
cyclic tensile test. pentose and hexose sugars.
Upon application of tensile stress, the microbrils in the
untreated ber tend to slip one another. However the Bio-
1000 cement present in between the microbrils tend to retain
the microbrils in the original position. This results in
800 the reversible behavior of microbrils which is responsible
for the less plastic deformation in untreated ber. When
the applied stress on the ber increases, a small scale of
Stress (MPa)

600
400
200
0 bers is attributed to the various changes in the physical
0 2 4 6
Strain (%)
Fig. 8. Typical stressstrain diagram of ramie single ber treated using
condition (II) in cyclic tensile test.
the bers during cyclic tensile loading. In Figs. 5 and 6, it
seems that the untreated ber behaves like a linear body,
but in fact this ber showed a small-scale plastic strain.
On the other hand, it should be noted that the treated ber
behaves in the rising at reloading similarly to the initial
behavior. In addition it is found that the treated ber indi-
cates viscoelastic behavior at unloading process.
irreversible slippage may occur within the microbril.
However, presence of hemicellulose between microbrils
acts as a bonding agent and restricts the slippage to an
extent. Hence the untreated ber behaves like an elastic
body up to fracture, though it is not a strict elasticity.
The change in the deformation behavior of the treated
8
and chemical structure of the bers occurring during mer-
cerization. Cellulose molecular chains in a microbril lose
their crystalline structure locally by mercerization. For
example, it is pointed out that conversion of crystalline cel-
lulose I to amorphous cellulose II can occur during mercer-
ization [20]. And the alignment of the microbrils is
destroyed and the overall crystallinity reduced due to the
breakage of the three dimensional network of cellulose by
the extensive cleavage of hydrogen bonding, as shown in
Fig. 10. The decreased crystallinity and the disorder of
the microbrils alignment decrease the stiness of the ber.
In addition, many changes happen to the amorphous
2218 K. Goda et al. / Composites: Part A 37 (2006) 22132220

Fig. 9. Detailed chemical structure of a microbril.

Fig. 10. Detailed structural changes of microbrils during mercerization.

region by dissolution of its major components in alkali
solution. Mercerization results in bleaching of the ber
which removes the impurities, waxy materials and lignin.
Mercerization also removes hemicellulose from the ber
resulting in an easy deformation of the cellular networks.
The extensive hydrogen bonding network will also be bro-
ken and the ordered structural arrangement of cellulose
may loose. The hydroxyl groups of cellulose become more
active as they are free from hydrogen bonding after the
mercerization. The deformation of individual microbrils
becomes easier due to the absence of interlocking hydrogen
bonding. Through the above-mentioned changes, the
microcrystalline microbrils may be more prone to irre-
versible slippage and even breakage resulting in the plastic
deformation of the ber upon tensile load. When the stress
acts upon the slipped out microbril, a large scale of irre-
versible slippage may occur. Thus, higher elongation at
break is observed for the mercerized ber because of the
decreased crystallinity in cellulose and the loosely bound
structure of the microbrils within the ber.
4.2. Tensile fracture mechanism of mercerized ramie ber
with load application explained by schematic model
The hemicellulose and amorphous lignin even
though present in small amount in ramie bers undergoes
 K. Goda et al. / Composites: Part A 37 (2006) 22132220 2219

disintegration in presence of strong alkali and will be and lack of waviness occur to the ber upon mercerization.
removed from the ber. The waxy materials and impurities Removal of such binding materials will bring plastic defor-
were also removed due to the bleaching action of alkali as mation of microbrils on the application of tensile stress,
is estimated in the model. Weight reduction, color change as mentioned in Section 4.1. Fig. 11(a) shows the changes

Fig. 11. Schematic representation of structural changes of a ramie ber (a) upon mercerization, (b) upon application of tensile stress and (c) upon
continued application of tensile stress.
2220 K. Goda et al. / Composites: Part A 37 (2006) 22132220
occurring to the ramie ber monolament with and with-
out load application. The load application during merceri-
zation will lead to a decrease in the microbrillar angle, as
shown in the Fig. 11(a). Fig. 11(b) explains the changes
occurring to the microbrils when tensile stress is applied
to the mercerized bers. Upon the application of tensile
stress the microbrils with load application during mercer-
ization become more oriented along the axis of tension, as
compared to the microbrils without load application.
Further application of tensile stress results in the easy
deformation and the partial breakage of many bonds in
the amorphous region. This decreases further, the crystal-
linity of the system. In this case the microbrils with load
application during mercerization can maintain higher stress
because of the less microbrillar angle. Finally the break-
age of the microbrils by large deformations of cellulose
chains in the crystallites and amorphous parts occur, as
shown in Fig. 11(c), and this leads to the catastrophic fail-
ure of the ber monolament. Thus, appropriately mercer-
ized ramie bers with load application, as seen in the
condition (II), may generate an increase in strength, as
compared to those bers without load application.
5. Conclusions
Eect of tensile load application during mercerization
on the structure property relationship of ramie bers was
investigated. A chemical treatment apparatus with load
applying portion was newly developed, in which the treat-
ment of natural bers can be carried out for monola-
ments. The results showed that mercerized bers in 15%
NaOH solution with load application obviously increased
in fracture strain, twice to three times higher than that of
untreated ber. Especially, the mercerized ber with load
application improves tensile strength as well as fracture
strain, as compared to that ber without load application.
Cyclic test showed that the treated ber behaves with pre-
dominantly larger plastic deformation at tensile loading
process, as compared with the untreated ber. Such
changes in mechanical properties were discussed from the
viewpoint of structural changes in a ramie ber. That is
to say, it was considered that change in fracture strain is
related with decrease in the microcrystalline in the micro-
brils and removal of binding materials around the micro-
brils during mercerization. And increase in tensile strength
is related with change in the microbrillar angle by the load
application during mercerization. Since plant-based natu-
ral bers are essentially composed of microbrils of cellu-
lose, similar results are expected in all such bers.
References
[1] Netravali AN, Chabba S. Mater Today 2003:22.
[2] Mohanty AK, Wibowo A, Misra M, Drzal LT. Comp Part A
2004;35:363.
[3] Mohanty AK, Misra M, Hinrichsen G. Macromol Mater Eng
2000;276/277:1.
[4] Eichhorn SJ, Baillie CA, Zafeiropoulos N, Mwaikambo LY, Ansell
MP, Dufresne A, et al. J Mater Sci 2001;36:2107.
[5] Hill S. New Scientist 1997;1(February):36.
[6] Goda K, Asai T, Yamane T. J Soc Mat Sci Japan 2003;52(October):
1245 [in Japanese].
[7] Ochi S, Takagi H, Tanaka H. J Soc Mat Sci Japan 2003;52(July):857
[in Japanese];
Ochi S, Takagi H, Tanaka H. J Soc Mat Sci Japan
2003;52(August):916.
[8] Shima K, Mizoguchi H, Okubo K, Fujii T, Tanaka T. J Soc Mat Sci
Japan 2002;51:826 [in Japanese].
[9] Rong MZ, Zhang MQ, Liu Y, Yang GC, Zeng HM. Compos Sci
Technol 2001;61:1437.
[10] Jiang J, Fujii T. Reinforcing Plastics 1999;45:365 [in Japanese].
[11] Joseph S, Sreekala MS, Bharadwaj YK, Sabarwal S, Thomas S.
Radiation ageing eects on banana bre reinforced phenol formal-
dehyde composites by electron beam. Compos Sci Technol [in press].
[12] Sreekala MS. Ph.D. thesis, Mahatma Gandhi University, Kottayam,
Kerala, India, 1999.
[13] Yuan XH, Zhang YX, Zhang XF. J Appl Polym Sci 1999;71:333.
[14] Oksman K, Lindberg H. J Appl Polym Sci 1998;68:1845.
[15] Peijs T, Garkhail S, Heijenrath R, Vanden Oever M, Bos H.
Macromol Symp 1998;127:193.
[16] Sreekala MS, Kumaran MG, Thomas S. J Appl Polym Sci
1997;66:821.
[17] Herrmann AS, Nickel J, Riedel U. Polym Degrad Stab 1998;59:
251.
[18] Nishiyama Y, Okano T. J Wood Sci 1998;44:310.
[19] Takabe K. Highly ordered structure of cellulose. In: Fiber micro-
structure. Dictionary of cellulose. The Cellulose Society of Japan,
Asakura-shoten; 2000. p. 102 [chapter 3 (3.5), in Japanese].
[20] Isogai A et al. Science of cellulose. Asakura-shoten; 2003 [in
Japanese].