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Composites: Part A 37 (2006) 22132220

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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-


mental pollution etc. and can nd various applications in
Natural bers play an important role in developing high engineering, electronic and automotive elds. Lightweight,
performing fully biodegradable green composites [1,2], decreased wearing of machines, low abrasiveness, absence
which will be a key material to solve the current ecological of health hazardness during processing, application and
and environmental problems. Mohanty et al. reported the upon disposal etc. are the added advantages of the green
structural aspects and properties of various natural bers composites.
and dierent biodegradable polymers, which are used for Due to many environmental problems, the discarding
the development of green composites [3]. Major interna- method for glass ber reinforced plastics (GFRP) and their
tional research work on cellulosic bers and their compos- recycling has seriously been realized in the world [5]. As is
ites has been reviewed by Eichhorn et al. [4]. It has been widely known, GFRP has excellent thermal and mechani-
reported that cellulose microbrils and cellulose nanocrys- cal properties, but these properties make dicult to carry
tals can be used as a reinforcing phase in polymeric matrix. out suitable disposal processing. For example, incineration
Introduction of green composites will reduce the waste dis- of discarding GFRP generates a lot of black smoke and
bad smells and often gives damage to incinerator by fusion
*
Corresponding authors.
of glass bers. Reclamation processing generates also a
E-mail addresses: goda@yamaguchi-u.ac.jp (K. Goda), sreekalams@ large environmental load, since GFRP is not decomposed
yahoo.co.in (M.S. Sreekala). 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 cerization to the ramie bers improves drastically their duc-
bers such as ramie [6], hemp [7], jute [8], sisal [9], bamboo tility, as well as maintains the strength level. Dierence
[10], banana [11], oil palm [12] bers and so on are used as between tensile behaviors of the untreated and treated
reinforcements in place of glass bers. Flax, kenaf, hemp ramie bers were additionally investigated by cyclic tensile
and wood our are reported to be highly suitable for the test. Finally, a schematic model has been developed in
preparation of load bearing and impact absorbing compo- order to explain the behavior of the treated ramie ber
nents of vehicles [13,14]. Peijs et al. [15] reported that ax under tension.
ber reinforced thermoplastics were of interest in low-cost
engineering applications and can compete with the com- 2. Experimental procedure
mercial glass mat reinforced thermoplastics. The major
problem identied with natural bers during incorporation The ramie bers used in this study was supplied from
in hydrophobic polymers is their poor compatibility. To Enkou Co. Ltd., Japan. Single monolaments of ramie
alleviate this problem various berpolymer interface mod- were easily extracted from the as-supplied ramie bundle.
ications have been proposed which results in improve- The physical and chemical characteristics of ramie bers
ment of performance of the resulting composite. are given in Table 1 which were reported earlier by scien-
Regarding improvement of the compatibility, chemical tists [3]. It is shown that there is little lignin in the bers,
treatment to the bers has often been carried out, in which dierently from other natural bers.
signicant change of mechanical properties of the bers has To change the mechanical properties of ramie bers, a
been induced [16]. Thus, research on the compatibility chemical treatment apparatus with tensile load applying
between natural bers and polymer by chemical treatment device was newly developed, in which the treatment of
should be carried out along with the problem of change in the bers were carried out for monolaments as shown in
mechanical properties of natural bers. Fig. 1. This apparatus consists of support portions of four
The present study focuses on the mechanical properties glass plates to maintain alkali solution, and bars for sus-
of the versatile natural ber, ramie. Ramie (Boehmeria taining the weights. First, monolament specimens for
nivea), a bast ber belonging to the family Urticaceae or alkali-treatment were prepared, as shown in Fig. 2, and
Nettle commonly referred to as china grass, white ramie, four specimens were put onto the glass plates. Then one
green ramie and rhea is one of the most valuable natural end of the specimens is clipped and other end attached to
bers. The main natural distribution of ramie lies in sub- the applied loads through the bar, as shown in Fig. 1. Next,
tropical China, Japan, Southeast Asia and in Brazil. Ramie the monolaments were dipped into 15% sodium hydroxide
is characterized by its high length, great strength, much solution by syringing. The treatment time was two hours,
greater than that of cotton and silk. In terms of specic and the weights applied were 0.049 and 0.098 N. It is
strength ramie bers can compete with synthetic bers. expected from the treatment that during the load applica-
The specic strength value of ramie is almost the same as tion, the microbrils will be more closely arranged to the
that of E-glass bers and shows higher elongation [17]. ber axis. After the treatment, one set of the monola-
They can be easily woven and are good candidate for tex- ments were dried without any washing, and another set
tile composites. They are widely used in fabric industry due were washed into the water containing small quantity of
to their softness, bleachability and better dyeability. acetic acid and then dried. The former condition is herein-
The purpose of this study is thus to clarify the eect of after denoted as condition (I), and the latter condition is
chemical treatment on the mechanical properties of ramie denoted as condition (II).
bers. In general, alkali-treatment onto the natural bers, The treated monolaments were xed onto a paper with
called mercerization, is expected to be a much eective a rectangular hole of 10 mm length, as shown in Fig. 3. The
treatment in terms of improving its hydrophilicity by diameters were measured using an optical microscope
breaking the extensive hydrogen bond network in the ber (Nikon Eclipse ME 600, Japan). Tensile test of the speci-
structure and creating many free reactive hydroxyl groups. mens was carried out using a tensile testing machine, fol-
On the other hand, tensile load application to the ramie lowing Japan Industrial Standards (JIS R 7601, Testing
bers during mercerization was expected in this study to methods for carbon bers). The crosshead speed of the ten-
give improved structural and mechanical properties to the sile test was 0.8 mm/min. The applied load was measured
bers, since proper orientation of microbrils along the using a micro-load cell attached to the machine, and the
ber axis may be realized due to the inuence of tension. displacement was measured using laser displacement sys-
The result showed that tensile load application during mer- tem (Anritsu Co. Ltd.). Twenty specimens of each set were

Table 1
Physical and chemical properties of ramie bers [3]
Cellulose Lignin Hemicellulose Pectin Wax Microbrillar Moisture Density
(wt%) (wt%) (wt%) (wt%) (wt%) angle () content (wt%) (mg/m3)
68.676.2 0.60.7 13.116.7 1.9 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


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)
M without load application exhibited the largest diameter.
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)
Fig. 1. Shape and dimension of chemical treatment apparatus with load without load application also showed the lowest strength.
applying system. 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
Fig. 2. Specimen for alkali-treatment. 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
Fig. 3. Specimen for tensile-test. 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
tested and the tensile strength of each specimen was calcu- that considerable enhancement in fracture strain is realized
lated by assuming that the cross-sectional area of each by the present treatments. Fracture strains of the treated
specimen is a circle. To clarify plastic deformation behavior ber drastically increased to 0.0450.072 in average, that
of the treated bers more exactly, a cyclic tensile test was is, twice to three times higher than fracture strain of the
additionally carried out for the untreated and treated untreated ramie ber. According to the result of Table 3,
specimens.

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
0
(II), respectively. As seen in the gures, the untreated ber 0 2 4 6 8 10
behaves with almost linearity. On the other hand, slopes of
Strain (%)
the stressstrain relation of the treated bers are obviously
lowered, and their behaviors are no longer linear. And as Fig. 6. Typical stressstrain diagrams of ramie bers treated by condition
mentioned earlier, mercerization generates a dramatic (II).
increase in fracture strain of this ber. Furthermore, it
should be noted that the stressstrain relations under as fracture toughness, impact strength etc. of the ber com-
unloading and loading conditions are almost in agreement. posite if the treated bers are used as the reinforcement.
Table 4 shows Youngs moduli of untreated and treated The cyclic tensile tests of untreated and treated ramie
ramie bers, which were obtained from initial slopes of bers were carried out in order to explore the plastic defor-
the stressstrain diagrams. Youngs modulus was largely mation function more exactly. Condition (II) was
decreased by mercerization, especially by the severe treat- employed for the treated ber. The results are shown in
ment, i.e., condition (I). According to the result of Table Figs. 7 and 8. It is observed that untreated ramie ber
4, Youngs modulus of this ber is not aected by dier- undergoes less plastic deformation while the treated ber
ence of the load conditions, but aected by chemical condi- exhibits larger plastic deformation accompanied with strain
tion. In any case, it is expected that such an improvement hardening. In other words, plastic deformation function of
of fracture strain may increase mechanical properties such 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
irreversible slippage may occur within the microbril.
However, presence of hemicellulose between microbrils
400
acts as a bonding agent and restricts the slippage to an
extent. Hence the untreated ber behaves like an elastic
200 body up to fracture, though it is not a strict elasticity.
The change in the deformation behavior of the treated
0 bers is attributed to the various changes in the physical
0 2 4 6 8
Strain (%)
and chemical structure of the bers occurring during mer-
cerization. Cellulose molecular chains in a microbril lose
Fig. 8. Typical stressstrain diagram of ramie single ber treated using their crystalline structure locally by mercerization. For
condition (II) in cyclic tensile test.
example, it is pointed out that conversion of crystalline cel-
lulose I to amorphous cellulose II can occur during mercer-
the bers during cyclic tensile loading. In Figs. 5 and 6, it ization [20]. And the alignment of the microbrils is
seems that the untreated ber behaves like a linear body, destroyed and the overall crystallinity reduced due to the
but in fact this ber showed a small-scale plastic strain. breakage of the three dimensional network of cellulose by
On the other hand, it should be noted that the treated ber the extensive cleavage of hydrogen bonding, as shown in
behaves in the rising at reloading similarly to the initial Fig. 10. The decreased crystallinity and the disorder of
behavior. In addition it is found that the treated ber indi- the microbrils alignment decrease the stiness of the ber.
cates viscoelastic behavior at unloading process. 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 versible slippage and even breakage resulting in the plastic
solution. Mercerization results in bleaching of the ber deformation of the ber upon tensile load. When the stress
which removes the impurities, waxy materials and lignin. acts upon the slipped out microbril, a large scale of irre-
Mercerization also removes hemicellulose from the ber versible slippage may occur. Thus, higher elongation at
resulting in an easy deformation of the cellular networks. break is observed for the mercerized ber because of the
The extensive hydrogen bonding network will also be bro- decreased crystallinity in cellulose and the loosely bound
ken and the ordered structural arrangement of cellulose structure of the microbrils within the ber.
may loose. The hydroxyl groups of cellulose become more
active as they are free from hydrogen bonding after the 4.2. Tensile fracture mechanism of mercerized ramie ber
mercerization. The deformation of individual microbrils with load application explained by schematic model
becomes easier due to the absence of interlocking hydrogen
bonding. Through the above-mentioned changes, the The hemicellulose and amorphous lignin even
microcrystalline microbrils may be more prone to irre- 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- related with decrease in the microcrystalline in the micro-
out load application. The load application during merceri- brils and removal of binding materials around the micro-
zation will lead to a decrease in the microbrillar angle, as brils during mercerization. And increase in tensile strength
shown in the Fig. 11(a). Fig. 11(b) explains the changes is related with change in the microbrillar angle by the load
occurring to the microbrils when tensile stress is applied application during mercerization. Since plant-based natu-
to the mercerized bers. Upon the application of tensile ral bers are essentially composed of microbrils of cellu-
stress the microbrils with load application during mercer- lose, similar results are expected in all such bers.
ization become more oriented along the axis of tension, as
compared to the microbrils without load application. References
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