COMPOSITES

SCIENCE AND
TECHNOLOGY
Composites Science and Technology 66 (2006) 2686–2699
www.elsevier.com/locate/compscitech

Interfacial evaluation of modified Jute and Hemp

fibers/polypropylene (PP)-maleic anhydride polypropylene
copolymers (PP-MAPP) composites using micromechanical
technique and nondestructive acoustic emission
a,*
Joung-Man Park , Son Tran Quang a, Byung-Sun Hwang b, K. Lawrence DeVries c

a
School of Materials Science and Engineering/Polymer Science and Engineering, Engineering Research Institute,
Gyeongsang National University, Jinju 660-701, Republic of Korea
b
Composite Materials Group, Korea Institute of Machinery and Materials, Changwon 641-831, Republic of Korea
c
Department of Mechanical Engineering, The University of Utah, Salt Lake City, Utah 84112, USA

Received 6 November 2005; received in revised form 28 February 2006; accepted 17 March 2006
Available online 5 May 2006

Abstract

Interfacial evaluation of the untreated and treated Jute and Hemp fibers reinforced different matrix polypropylene-maleic anhydride
polypropylene copolymer (PP-MAPP) composites was investigated by micromechanical technique combined with acoustic emission (AE)
and dynamic contact angle measurement. For the statistical tensile strength of Jute and Hemp fibers, bimodal Weibull distribution was
fitted better than the unimodal distribution. The acid–base parameter on the interfacial shear strength (IFSS) of the natural fiber com-
posites was characterized by calculating the work adhesion, Wa. The effect of alkaline, silane coupling agent on natural fibers was
obtained with changing MAPP content in PP-MAPP matrices. Alkaline treated fibers made the surface energy to be higher due to
the removal of the weak boundary layers and thus increasing surface area, whereas the surface energy of silane treated Jute and Hemp
fibers decreased due to blocked high energy sites. MAPP in the PP-MAPP matrix caused the surface energy to increase due to introduced
acid–base sites. Microfailure modes of two natural fiber composites were observed clearly differently due to different tensile strength of
natural fibers and the consistent results were also shown by nondestructive AE analysis indirectly.
 2006 Elsevier Ltd. All rights reserved.

Keywords: Natural fiber; Interfacial evaluation; Interfacial shears strength (IFSS); Dynamic contact angle; Surface energy; Acoustic emission (AE)

1. Introduction without affecting the environmental damage, and together

Over the past two decades, natural plant fibers have
been receiving considerable attention as the substitute for
synthetic fiber reinforcement such as glass in plastics
[1,2]. The advantages of plant fibers are low cost, low den-
sity, acceptable specific strength, good thermal insulation
properties, reduced tool wear, reduced dermal and respira-
tory irritation, renewable resource and recycling possible
*
Corresponding author. Tel.: +82 55 751 5300; fax: +82 55 752 0075.
E-mail address: jmpark@gnu.ac.kr (J.-M. Park).
with biodegradable ability [3–7].
However, in origin the plant fibers exhibit a high hydro-
philic property as they are composed of lingo-cellulose,
which contains strongly polarized hydroxyl groups [8,9].
Therefore, these fibers are inherently incompatible with
hydrophobic polymer matrix materials and especially for
poor interfacial adhesion between the hydrophilic natural
fibers and conventional resin matrices. The matrix materi-
als are popularly used in biodegradable composites includ-
ing thermoplastics such as a polypropylene and a
polyethylene as well as even thermosets such as an epoxy,

0266-3538/$ - see front matter  2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.compscitech.2006.03.014
 J.-M. Park et al. / Composites Science and Technology 66 (2006) 2686–2699
unsaturated polyester, and cardanol based matrix, which is
synthesized between epoxy and cardanol oil to improve the
toughness properties [10,11]. Since the final mechanical
behavior of composite materials depends to a great extent
on the interfacial adhesion between the reinforcing natural
fiber and the surrounding matrix, it is necessary to evaluate
the improvement of the interfacial adhesion extensively
through various surface treatment methods [12,13].
Wetting is a perquisite to get a good interfacial adhe-
sion. However, interfacial adhesion also depends on the
number of functional groups which contribute to acid–base
interaction in interfacial contacting area between the fiber
and the matrix material. The acid–base interaction of the
fiber surface is a significant factor in controlling the degree
of adhesion with a given matrix material. It is possible to
find out the optimal combination of the fiber/matrix resin
if the acid–base interaction of matrix resin is also deter-
mined. It is possible to evaluate the acid–base components
using dynamic contact angle measurement; it follows the
concept proposed by Fowkes which considers that the
short range hydrogen bonding is very important in adhe-
sion [14,15].
Several techniques ranging from grafting of short-chain
molecules and polymers onto the fiber surface to using
silane coupling agents and maleic anhydride-polypropylene
copolymer (MAPP) as well as alkali solution have been
reported for improving the fiber-matrix compatibility
[6,8,16]. Grafting improves the wetting of the fiber with
the matrix by hydrophobizing the fiber surface and
enhances a better interfacial bonding by the diffusion of
the chain segments of grafted molecules into the matrix.
On the other hand, the coupling agents and MAPP can
promote better interfacial bonding through producing
covalent bonds between the fiber and the matrix. In addi-
tion, alkali treatment removes the weak boundary layers
and increases the surface area and gives better fiber disper-
sion [17].
The clarification of microfailure mechanism is a very
important step in investigating the fracture behavior of a
composite structure. Acoustic emission (AE) is well known
as one of the important nondestructive testing methods. It
can monitor the types of fracture sources and their progress
by analyzing AE parameters such as AE energy, AE ampli-
tude, and their frequency emitted from the fiber fracture,
matrix cracking, fibrillation, and debonding. In general,
the AE energy released by the fiber fracture should be lar-
ger than that of the matrix cracking and debonding [18–
21].
In this work, the correlation of the interfacial and
mechanical properties of Jute and Hemp fiber reinforced
polypropylene-maleic anhydride polypropylene copolymer
(PP-MAPP) composites was investigated using microme-
chanical microdroplet test with aid of nondestructive AE.
Nondestructive AE was also used to evaluate microfailure
mechanisms by measuring elastic wave occurring from
fibril strands failure sources and correlated to microme-
chanical test and optical observation.
2687
2. Experimental
2.1. Materials
Hemp and Jute fibers (Carol Leigh’s Hillcreek Fiber Stu-
dio Co.) were used as reinforcing fibers for green composites.
Polypropylene (PP, Polymirae Inc., Korea) was used as ther-
moplastic matrix material and 1%, 3%, 5% modified maleic
anhydride-polypropylene (MAPP-PP, Eastman Chemical
Ltd.) were also used for comparison. Sodium hydroxide
(NaOH) of reagent grade was used for surface treatment of
natural fibers. Silane coupling agent, vinylbenzyl(trimeth-
oxysilyl)propylethane-diaminehydrochloride (Z-6032, Dow
Corning Corp.), was used. Four probe liquids used for con-
tact angle measurement are double purified water, formam-
ide (Dae Jung Chemicals, Korea), diiodomethane (Tokyo
Kasei Kogyo Co., Ltd., Japan), and ethylene glycol (Oriental
Chemical Industries, Korea).
2.2. Methodologies
2.2.1. Measurement of single fiber tensile strength
Jute and Hemp fibers with various surface treated con-
ditions were fixed on a paper frame using Kapton tape at
a gauge length of 20 mm, respectively. Average natural
fiber diameter was measured by optical microscope
attached with calibrated eye’s lens. Three different diame-
ters were averaged due to non-uniform diameter pattern
of natural fiber. Tensile strength of the natural fibers was
obtained using about 60 specimens for statistically mean-
ingful value and analyzed using both uni- and bimodal
Weibull distributions. Fiber failure process of the unimodal
cumulative Weibull distribution function based on one type
defect is
  b 
t
F ðtÞ ¼ 1  exp  ð1Þ
a
where a and b are the shape and scale parameters, respec-
tively. Cumulative bimodal Weibull distribution function
based on the presence of two kinds of defect is described
as follows:
( "   # "   #)
b b
t 1 t 2
F ðtÞ ¼ 1  p exp  þ q exp  ð2Þ
a1 a2
pþq¼1
where p and q are the portions of low and high strength
population, and b1, a1, b2, and a2 are the shape and scale
parameters for the low and high strength portions, respec-
tively [22,23].
2.2.2. Alkali, silane, and thermal treatments
Natural fibers were soaked into purified water bath con-
taining sodium hydroxide solution of 0.5 wt% where the
temperature was maintained throughout at 25 ± 2 C for
2 h. The treated fibers were rinsed in purified water for sev-
eral times until pH of the solution was equal to 7 and then
2688 J.-M. Park et al. / Composites Science and Technology 66 (2006) 2686–2699

left to dry at room temperature before being put into an where F is total force, m is mass of plate, g is acceleration
oven for 4 h at 80 C. The untreated fibers were then dried of gravity, Fb is buoyancy force, P is perimeter of fiber, cLV
in an oven for 4 h at 80 C in the same process as the trea- is surface tension of liquid, and the subtraction of F  mg
ted case. On the other hand, the natural fibers were treated is equal to the measured force. Because the buoyancy force
with silane coupling agent by dipping them into silane solu- value is zero at the immersing interface, Eq. (1) can be ar-
tion of 0.5 wt% for 1 min at room temperature and then ranged as,
were put into the oven for 4 h at 50 C before testing Mg
[24,25]. In addition, the thermal treatment condition of cos h ¼ ð5Þ
pDcLV
the natural fibers was at 140 C for 2 h in the oven before
testing. Here M is a measured force. The acid–base component (or
hydrogen bonding) includes electron acceptor c+ and elec-
2.2.3. Single fiber composites (SFC) preparation and IFSS tron donor c components, which are defined as follows:
measurement þ  2 1
cAB
S ¼ 2ðcS cS Þ ð6Þ
The single fiber composite (SFC) test was done to inves-
tigate the microfailure modes and to obtain AE outcome The calculation of these above components follows the
for Jute and Hemp fibers. SFC specimen was made by modified young-Dupre equation of the work of adhesion
the single fiber embedded inside two previously built sheets which is given as
of PP matrix material by compressing at the melting point h i
LW 12  þ 12 þ  12
of polypropylene (PP) with some light load, and then cool- cL ð1 þ cos hÞ ¼ 2ðcLW
S cS Þ þ 2 ðcS cL Þ þ ðcS cL Þ ð7Þ
ing quickly to make the specimens to be transparent. The
specimens for AE parameters were tested in tension by The value of cLW
S of the solid is evaluated from the contact
man-made mini-UTM (PICO Industrial Inc., Korea) with angle of an apolar liquid which is nonpolar liquid without
a 1 KN load cell and a crossed speed of 0.5 mm/min. Sub- donor and acceptor components, such as diiodomethane
sequent microfailure mechanism of the single fiber and its on the solid in which the above equation [8,14] can reduce
interface between the fiber and the matrix were observed to
and determined via the combination of a polarized-light 1

microscope and AE signals. cL ð1 þ cos hÞ ¼ 2ðcLW LW 2

The IFSS of Jute and Hemp fibers/PP composites was
measured by microdroplet test. The natural fibers were
fixed with regularly separated distance in a steel frame.
Microdroplets of PP were formed on each natural fiber
using a tip pin. The microdroplet specimen was fixed by
the microvice using a specially designed micrometer. The
IFSS was calculated from the measured pullout force, F,
using the following equation:
F cL ð1 þ cos hÞ ¼ 2ðcdS cL dÞ2 þ 2ðcpS cpL Þ2
s¼
pDf L
where Df and L are fiber diameter and fiber embedded
length in the matrix, respectively [26]. Although interface
end theory can re-evaluate IFSS due to stress non-singular-
ity at the interface end by Mai group in detail [27], compar-
ative IFSS was obtained using conventional Eq. (3) for
different surface treatment conditions in this work.
2.2.4. Measurement of wettability and surface energies
Dynamic contact angle of Jute and Hemp fibers was
measured using Wilhelmy plate technique [21,23] (Sigma
70, KSV Co., Finland). Four dipping liquids, double puri-
fied water, formamide, ethylene glycol, and diiodomethane,
were used. Dynamic contact angle, interfacial energies,
donor and acceptor components, and polar and dispersive
free energy terms of the fibers with various treated condi-
tions were measured. The basic equation for Wilhelmy
plate method is
F ¼ mg þ P cLV cos h  F b
S cS Þ ð8Þ
þ 
where cL, cLW
L , cL and cL are known for the testing liquids
and cos h can be measured using Eq. (2).
A commonly used approach to considering solid surface
energies is to express it as a sum of dispersive and polar
components which can influence on the work of adhesion
and interfacial adhesion between the fiber surface and the
matrix material. To measure polar and dispersive surface
free energies, Owens–Wendt equation was expressed as
1 1
ð9Þ
ð3Þ
where cL, cdL ,
and cpL
are known for the test liquids and cpS
d
and cS can be calculated from the measured contact angles.
Eventually, the dispersive and acid–base components of
both the fiber and matrix can be determined. It is possible
to calculate the work of adhesion, Wad, between the fiber
and matrix at the interface using the following equation:
h i
LW 12  þ 12 þ  12
W ad ¼ 2 ðcLW
F c M Þ þ ðc c
F M Þ þ ðc c
F M Þ ð10Þ
2.2.5. Acoustic emission (AE) measurement
To determine the microfailure mechanism inside the
composite material structure is one of the most important
factors in investigating the fracture behavior of a compos-
ite structure. Since AE method is well known as one of the
important nondestructive testing methods, it was coupled
with the micromechanical test as worked previously
[18,20,21]. Testing specimen was gripped on the UTM
and AE PZT sensor was attached in the center of the sam-
ð4Þ ple using vacuum grease couplant. AE signals were
 J.-M. Park et al. / Composites Science and Technology 66 (2006) 2686–2699 2689

obtained using a miniature sensor (Wide band, WD model
by Physical Acoustics Co.) with peak sensitivity of 55 Ref.
V/(m/s) [62.5 Ref. V/mbar] and resonant frequency at
125 [650] kHz. Sensor output was amplified by 40 dB at
preamplifier and passed through a band-pass filter with a
range of 100–1000 kHz and the threshold level was set as
35 dB. The wide band PZT sensor was fixed in the center
of the SFC specimen. Elastic waves occurring from micro-
failure were recorded and transferred to voltage signals by
PZT sensor, and then AE parameters. The fast Fourier

Microfibril

Cellulose crystalline region

Fig. 1. Schematic structure of the natural fibers.

Fig. 2. Photographs of diameter direction and cross-section of (a) Jute fiber; and (b) Hemp fiber.

Table 1
Mechanical properties of Jute and Hemp fibers with various treated conditions
Fiber Treated Diameter (lm) Strength (MPa) Modulus (GPa) Elongation (%) COVb (%) ac bd a1 b1 a1 b2
types conditions
Hemp Untreated 10.86 (1.6) 2140 (504)a 143.2 (26.7) 1.8 (0.7) 23.5 2342 4.6 l886 6.8 2652 6.7
NaOH 11.0 (2.8) 2230 (563) 131.9 (44.9) 2.3 (0.6) 31.8 2484 3.4 1893 4.8 3192 7.1
Silane 10.40 (1.7) 2251 (627) 195 (57.4) 1.9 (0.4) 26.9 2363 4.1 1994 9.8 2514 6.1
Temperaturee 10.5 (2.0) 1802 (562) 133.0 (30.5) 1.7 (0.4) 29.1 1853 3.0 1853 3.0 2144 13.0
Jute Untreated 26.0 (4.5) 1316 (457)a 91.9 (27.8) 1.5 (0.4) 34.7 1477 3.0 883 5.8 1690 5.9
NaOH 27.5 (5.4) 1453 (346) 107.6 (55.9) 1.6 (0.4) 33.6 1454 3.2 1020 14.6 1535 3.1
Silane 27 (6.0) 1461 (395) 113.6 (29.3) 1.4 (0.2) 28.0 1563 3.5 846 4.1 1571 4.3
Temperature 28.0 (6.8) 983 (429) 84.3 (28.7) 1.2 (0.3) 42.4 1155 2.7 1116 19.1 1655 3.3
a
Standard deviation (SD).
b
Coefficient of variation (COV) for fiber tensile strength. (%) = SD/mean · 100.
c
Scale parameter for fiber strength.
d
Shape parameter for fiber strength.
e
Thermal treatment at 140 C for 2 h.
2690 J.-M. Park et al. / Composites Science and Technology 66 (2006) 2686–2699

transformation (FFT) was analyzed using built-in other aspects. There are celluloses, hemicelluloses, pectic
software. materials and lignins. The pectins occur in most mature
plant cell walls with the exception of woody tissues,
3. Results and discussion wherein extensive secondary wall thickening replaces
almost all of the pectin with lignin [28].
3.1. Analysis of tensile strength distributions of natural fibers The other components are universal to all plant fibers,
which contain some materials such as water, wax, and
Fig. 1 shows the typical morphology and structure of extractive. Cellulose is the reinforcing material within the
natural microfibril containing four main types of polymers
in varying amounts according to species, varieties, and
3
Jute fiber
Hemp fiber
1.0

1
0.8

ln(-ln(1-P))
Cumulative Probability

-1
0.6

0.4 -3

Untreated fiber
0.2
Fiber
Fiberunder
undertemperature
temperature
-5
Bimodal equation
0 1000 2000 3000 4000
Uni
Uni equation
equation

0.0 Stress (MPa)

0 1000 2000 3000 Fig. 4. Strength distribution of Jute and Hemp fibers at gauge length of
(a) Stress (MPa) 20 mm by two-parameter Weibull distribution equation.

1.0 300
Jute fiber

Hemp fiber

0.8 200
Cumulative Probability

Modulus (GPa)

0.6 150

0.4 100

0.2 Untreated fiber 50

Fiber under temperature
Bimodal equation
Uni equation

0 0
0 1000 2000 3000 4000 0 10 20 30 40 50
(b) Stress (MPa) Diameter (μm)

Fig. 3. Uni- and bimodal Weibull distributions of (a) Jute fiber and Fig. 5. The scattering of modulus with different diameters of Jute and
(b) Hemp fiber. Hemp fibers.
 J.-M. Park et al. / Composites Science and Technology 66 (2006) 2686–2699 2691

120 120
MAPP (0 %) MAPP (1 %)
Hemp fiber Hemp fiber
100 Jute fiber 100 Jute fiber

80 80
Force (gr)

Force (gr)
60 60

40 40

20 20
Critical embedded area Critical embedded area

0 0
0 50 100 150 200 250 0 50 100 150 200 250
(a) Embedded Area (x10 μm ) 3 2
(b) Embedded Area (x10 µm ) 3 2

120 120
MAPP (3 %) MAPP (5 %)
Hemp fiber Hemp fiber
100 Jute fiber 100 Jute fiber

80 80
Force (gr)
Force (gr)

60 60

40 40

20 20
Critical embedded area
Critical embedded area

0 0
0 50 100 150 200 250 0 50 100 150 200 250
(c) Embedded Area (x103 µm2) (d) Embedded Area (x103 μm2)
Fig. 6. Plot of force versus embedded area for (a) MAPP (0%); (b) MAPP (1%); (c) MAPP (3%); and (d) MAPP (5%).

7
5.5

6
IFSS (MPa)

5.0
IFSS (MPa)

4 4.5
Jute fiber
Hemp fiber
Jute fiber
Hemp fiber

0
0 1 2 3 4 5 0.0
MAPP (%) Untreated Silane Alkaline
Types
Fig. 7. IFSS of Jute and Hemp fibers/ MAPP-PP with various contents of
MAPP. Fig. 8. IFSS of Jute and Hemp fibers/PP with various treated conditions.
2692 J.-M. Park et al. / Composites Science and Technology 66 (2006) 2686–2699

Table 2 rials to be poor due to inherent properties of weak bound-

Surface energy components of probe liquids ary layer.
Solvent cTL cw
L cAB c+ c cd cp Fig. 2 shows photographs of morphology in diameter
Formamide 58 39 19 2.28 39.6 32 26 direction and cross-section of (a) Jute and (b) Hemp fibers.
Ethylene-glycol 48 29 19 1.92 57.4 29 19 For the natural fibers, the cross-sectional shape is generally
Water 72.8 21.8 51.0 65.0 10.0 21.8 51.0 not circular and the diameter is not uniformed along their
Diiodomethane 50.8 50.8 48.5 2.3
length with large scattering level. The mechanical properties
of both Jute and Hemp fibers at gauge length of 20 mm are
Table 3 listed in Table 1. Under high temperature, the tensile
Contact angles for Jute and Hemp fibers with MAPP-PP matrix as
strength of the natural fibers decreased significantly because
determined by Wilhelmy plate technique
the chemical structures of the fibers were thermally damaged
Materials Conditions Contact angle (h)
seriously. On the other hand, the tensile strength of the nat-
Formamide Ethylene Diiodo- Water ural fiber increased slightly after treating either with alkaline
glycol methane
solution or silane coupling agent. It may be because crystal
Jute fiber Untreated 68.18 62.80 63.90 78.46 cellular composition increased using alkaline solution due
Silane 76.11 63.70 64.10 79.74
to the removal of hemi-celluloses, waxs, lignin, and pectin,
NaOH 63.34 49.50 52.70 71.10
which can respond low tensile strength. The flaws on the fiber
Hemp fiber Untreated 59.67 51.68 54.69 67.05 surface were removed using silane coupling agents, which
Silane 61.12 51.68 55.73 68.90
NaOH 59.30 47.93 50.94 65.10
can make the tensile strength of the natural fibers to increase.
Fig. 3 shows the cumulative strength distribution of the
MAPP (%) 0 81.10 71.46 74.10 85.60
untreated and treated (a) Jute and (b) Hemp fibers at the
1 76.70 71.03 73.74 84.78
3 76.70 68.72 73.50 84.31 gauge length of 20 mm, respectively. The experimental
5 74.39 65.79 66.67 83.68 strength data were estimated from F(N) = i/(N + 1), where
N is the total number of samples tested and i is the number
cell wall. Plant cell walls can be envisaged as spirally in ascendingly ordered strength data. It was easily noted
wound composites with microfibrils within the matrix of that for both Jute and Hemp fibers, bimodal distribution
hemicellulose and lignin. There is extensive hydrogen curves were fitted better for the measured data than unimo-
bonding between cellulose chains producing a strong crys- dal distribution curves. The distribution of the tensile
talline structure. The microfibril is reported to be of either strength shifted significantly to the left hand side under
ovoid patterns or almost square in cross-section, and high temperature due to their damaged chemical structure.
aspect ratio of the individual microfibril is therefore high. It is indicated that approximately similar portion of two
The cellulose can respond to high stress, whereas hemicel- different types of defects can exist in both natural fibers,
luloses can respond only to low stress due to amorphous such as external and internal.
structure and inhomogeneous property [29]. In addition, Fig. 4 shows experimental fiber strength distribution
wax and lignin appear to have low tensile strength and produced by SFT test. It is known that two-parameter
make adhesion between the fiber surface and matrix mate- Weibull distribution approximates the experimental data

CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3

Peroxide +
H H H δ+ H H δ+ H
H

Polypropylene PP Radicals
(PP)
O O O
CH3
O

Maleated polypropylene
O

Maleic anhydride H (MAPP)

(MA)
O

O
Natural fibers

Natural fibers

O
O

OH C C
C C C
+ H
O

OH O O C
O

O
H

Fig. 9. Chemical reaction mechanism of the natural fiber and MAPP matrix.
 J.-M. Park et al. / Composites Science and Technology 66 (2006) 2686–2699 2693

better than uni-parameter Weibull distribution. Deviations
from conventional unimodal Weibull distribution are
mostly due to either the weakest fibers or can be related
to the minor or fatal damage to the fibers during the spec-
imen preparation process.
In Fig. 5, Young’s modulus exhibited a scattering with
various diameters for both Jute and Hemp fibers. Scatter-
ing in modulus of the natural fibers may be influenced by
inhomogeneous distribution of their chemical structure
and inherent properties of composite materials. Hemp fiber
shows wider range scattering of modulus distribution than
Jute fiber case.
3.2. Interfacial shear strength (IFSS)
Fig. 6 shows the plots of the debonding force versus the
embedded area for both Jute and Hemp fibers/PP and PP-
MAPP with various treated conditions. Critical embedded
area means the intimately contacting area between natural
fiber and PP matrix systems. The critical embedded area
was used instead of the conventional critical embedded
length due to the different diameter for both fibers.
The critical embedded area was obtained by the intersec-
tion of two linear regression lines: one is the fiber pullout
linear regression line, while another is the fiber fracture

Table 4
Acid–base surface energy components of Jute fibers using three liquid solvents
Fiber types Solvents Untreated Silane treated NaOH treated
cLW
S c c+ cTS cLW
S c c+ cTS cLW
S c c+ cTS
Jute Water/formamide 26.4 4.72 0.71 29.5 26.2 4.70 0.33 28.7 32.8 6.76 0.37 35.9
Water/ethylene glycol 26.4 4.96 0.56 28.9 26.2 3.28 0.29 28.2 32.8 6.10 0.70 36.9
Ethylene glycol/formamide 26.4 4.85 0.65 30.0 26.2 3.96 0.47 29.0 32.8 7.84 0.41 36.3

Average 26.4 4.84 0.64 29.5 26.2 3.98 0.36 28.6 32.8 6.90 0.65 36.4

Hemp Water/formamide 31.6 7.54 0.49 35.5 31.0 7.04 0.45 34.6 33.7 8.10 0.30 36.8
Water/ethylene glycol 31.6 7.33 0.64 35.9 31.0 7.00 0.48 34.7 33.7 7.80 0.43 37.4
Ethylene glycol/formamide 31.6 5.42 0.30 34.2 31.0 5.50 0.56 34.5 33.7 7.65 0.50 37.6

Average 31.6 6.76 0.48 35.2 31.0 6.51 0.50 34.6 33.7 7.85 0.41 37.3

Table 5
Acid–base surface energy components of MAPP-PP matrices using three liquid solvents
MAPP (0%) MAPP (1%) MAPP (3%) MAPP (5%)
cLW
S c c+ cTS cLW
S c c+ cTS cLW
S c c+ cTS cLW
S c c+ cTS
Water/formamide 20.1 3.80 0.05 21.0 20.1 4.10 0.58 23.2 21.0 4.28 0.38 23.6 24.8 4.10 1.21 29.3
Water/ethylene glycol 20.1 3.14 0.47 22.5 20.1 4.50 0.24 22.2 21.0 4.16 0.47 23.8 24.8 4.50 1.10 29.3
Ethylene glycol/formamide 20.1 3.36 0.25 21.9 20.1 4.15 0.45 22.8 21.0 4.05 0.81 24.6 24.8 9.24 0.76 30.1
Average 20.1 3.43 0.26 21.9 20.1 4.25 0.42 22.7 21.0 4.16 0.55 24.0 24.8 5.95 1.03 29.6

Table 6
Work of adhesion Wa, fiber surface energies (total, cSV; polar, cpSV ; dispersive, cdSV , components) and interfacial energy, cLS, of Jute fibers
Fiber types Conditions Wa (dyne cm1) cSV (dyne cm1) cpSV (dyne cm1) cdSV (dyne cm1) cLS (dyne cm1)
FM EG DO Water FM EG DO Water
Jute Untreated 69.6 67.7 69.1 78.4 29.5 8.8 20.7 17.9 9.8 11.2 23.9
Silane 73.1 69.3 73.0 85.8 28.6 9.0 19.6 13.5 7.3 6.4 15.6
NaOH 84.0 79.2 81.6 97.7 36.4 12.3 24.1 10.4 5.2 5.6 11.5
Hemp Untreated 87.3 77.8 80.2 101.2 35.2 15.2 20.0 5.9 5.4 5.8 6.8
Silane 86.0 77.8 79.4 99.0 34.6 14.1 20.5 6.6 4.8 6.0 8.4
NaOH 87.6 80.2 82.8 103.4 37.3 15.4 21.9 7.7 5.1 5.3 6.7

Table 7
Work of adhesion Wa, fiber surface energies (total, cSV; polar, cpSV ; dispersive, cdSV , components) and interfacial energy, cLS, of MAPP-PP matrices
MAPP-PP Wa (dyne cm1) cSV(dyne cm1) cpSV (dyne cm1) cdSV (dyne cm1) cLS (dyne cm1)
FM EG DO Water FM EG DO Water
MAPP(0%) 67.0 63.3 64.7 78.4 21.9 4.58 17.32 12.9 6.6 8.0 16.4
MAPP(1%) 71.7 63.6 68.5 79.4 22.7 7.56 15.14 9.0 7.1 5.0 16.1
MAPP(3%) 70.9 65.4 68.6 80.0 24.0 7.78 16.22 11.1 6.6 6.2 16.8
MAPP(5%) 73.6 67.7 70.9 82.3 29.6 8.13 21.47 14.0 9.9 9.5 20.1
2694 J.-M. Park et al. / Composites Science and Technology 66 (2006) 2686–2699

linear regression line. It was noticed that the IFSS of given 8

natural fiber/matrix system could increase when the critical
embedded area decreased. From the experimental plots, the
critical embedded area decreased with an increase in
MAPP content in PP-MAPP matrix material or after treat-
6
ing the natural fibers with alkaline solution and silane

IFSS (MPa)
coupling agent.
Figs. 7 and 8 show the IFSS of both Jute and Hemp
fibers/PP-MAPP composites with different treated condi- MAPP (0 %)

tions being calculated for each sample by Eq. (3) and then 4 MAPP (1 %)

determined by simply averaging. The IFSS of the natural MAPP (3 %)

fibers/MAPP-PP significantly increases with increasing MAPP (5 %)

Jute fiber
the content of MAPP introduced into the mixture of the
Hemp fiber
materials as well as after treating with alkaline solution
and silane coupling agent. It may be because the chemi- 0
52 56 60 64 68
cal-bridge could be created in interfacial area between the
Wad (mJ/m2)
fiber surface and the matrix for MAPP and silane coupling
agent. However, the IFSS improvement under alkaline Fig. 11. The relationship between the IFSS and work of adhesion for both
solution is because the weak boundary layers were removed Jute and Hemp fibers/MAPP-PP matrices.
and increased the surface area [16,30].

1.5
Untreated

Silane
NaOH
66 7
MAPP (0 %)
1.0
MAPP (1 %)

MAPP (3 %)
Force (mg)

62 MAPP (5 %)

0.5 6
Wad (mJ/m2)

IFSS (MPa)
58

0.0
5
54

-0.5
-1 0 1 2 3 4
(a) Immersion Depth (mm) 50 4
4 5 6 7 8 9
0.6 (a) Polar Surface Free Energy (mJ/m2)
Untreated

Silane 74 7.0
NaOH
MAPP (0 %)

MAPP (1 %)
0.4 MAPP (3 %)
6.5
70
MAPP (5 %)
Force (mg)

6.0
Wad (mJ/m2)

IFSS (MPa)

66
0.2
5.5

62
5.0
0.0
58
4.5

-0.2 54 4.0
-1 0 1 2 3 4 4 5 6 7 8 9
2
(b) Immersion Depth (mm) (b) Polar Surface Free Energy (mJ/m )

Fig. 10. Dynamic contact angle of the natural fibers in diiodomethane Fig. 12. Plots of work of adhesion and the IFSS with polar surface free
solvent for (a) Jute fiber; and (b) Hemp fiber. energy of the matrix materials for (a) Jute fiber; and (b) Hemp fiber.
 J.-M. Park et al. / Composites Science and Technology 66 (2006) 2686–2699 2695

70 7
IFSS
Wad

67
6
Wad (mJ/m2)

IFSS (MPa)
64

61

4
58

55 3
1 2 3 4 5 6
(a) γAB

70 7
IFSS
Wad

67
6
Wa d ( m J / m 2 )

IFSS (MPa)

64

61

4
58

Fig. 15. Microfailure modes of untreated natural fibers/PP systems under

tension for (a) Jute fiber; and (b) Hemp fiber.
55 3
1 2 3 4 5 6
(b) γAB
3.3. Surface energy analysis and their wettability
Fig. 13. Plots of work of adhesion and the IFSS with acid–base
interaction of the matrix materials for (a) Jute fiber; and (b) Hemp fiber. The surface energy components of some probe liquids to
be used in the fiber and matrix wetting experiments are
given in Table 2. Diiodomethane (DO) was used as the

Fig. 14. Microfailure modes of Jute and Hemp fibers/PP microdroplet before and after testing for (a) Jute/PP; and (b) Hemp/PP.
2696 J.-M. Park et al. / Composites Science and Technology 66 (2006) 2686–2699
probe liquid for Lifshitz–van der Waals interactions,
whereas water, formamide (FM), and ethylene-glycol
(EG) were used as probe liquids for the acid–base interac-
tion [14]. The contact angle, h of the natural fibers and the
matrix materials were calculated from wetting force, M, of
each liquid according to Eq. (5).
The values of the advancing contact angle of both the
fibers and the matrix materials are also given in Table 3.
Although for Jute and Hemp fibers, the contact angles
became lower after treating with alkaline solution com-
pared to the untreated fibers, it became higher after dipping
with silane coupling agent. It may be because the contact-
ing surface area can increase by extracting wax, lignin, and
pectin using alkaline solution, which removes the weak
boundary layer [16]. On the other hand, the treatment of
vinylbenzyl silane coupling agent can cover hydrophilic
fiber surface with high surface energy. For the matrix mate-
rials of PP-MAPP, the contact angles decreased with an
increase in the content of MAPP, as expected. It may be
because hydrophilic maleic anhydride groups with the high
surface energy were produced incrementally when the con-
tent of MAPP increased. Fig. 9 shows the possible chemical
reaction mechanism on such interfacial bond formation
between the fiber surface and the matrix. It is believed that
the peroxide catalyst initiates radical formation on the PP
backbone by hydrogen abstraction and chain scission.
The radicals then react with MA to form MAPP.
Fig. 16. Microfailure modes of neat single Jute fiber under tension for
(a) high strength portion; and (b) low strength portion.
Tables 4 and 5 show the results of surface energy mea-
surements. The cLW S component of the fiber and the matrix
material surface energy was calculated by using diiodome-
thane according to Eq. (8). The donor–acceptor compo-
nents were evaluated by using polar probe liquids and
following Eq. (7). The basic component, c, of the surface
energy of silane treated Jute and Hemp fibers slightly
decreased in comparison with the untreated cases, whereas
the one of alkaline treated Jute and Hemp fibers increased.
The basic character of the natural fibers may be basically
decided by contribution of hydroxyl groups on the fiber
surface. Hydroxyl group sites were covered by silane cou-
pling agents, whereas the basic component of the natural
fibers increased after treating with alkaline solution due
to the removal of weak boundary layer and increasing
the surface area.
Tables 6 and 7 show the wetting parameters of the nat-
ural fibers and the matrix materials with various treated
conditions, such as the work of adhesion, Wa, the fiber sur-
face energy, cSV, and the interfacial energy with these probe
liquids, cLS. The hydrophilic property of the natural fiber
was investigated using dynamic contact angle measurement
by single cyclic test for each fiber. Fig. 10 shows the plots of
dynamic contact angles for (a) Jute and (b) Hemp fibers
with various treated conditions. The advancing contact
angle of both the fibers after treating with silane coupling
agent was slightly lower than that of untreated fiber since
Fig. 17. Microfailure modes of neat single Hemp fiber under tension for
(a) high strength portion; and (b) low strength portion.
 J.-M. Park et al. / Composites Science and Technology 66 (2006) 2686–2699 2697

the fiber surface became more hydrophobic. On the other microdroplet appeared on the matrix crack modes and thus
hand, the advancing contact angle increased after treating pulled out shape due to less strong interfacial adhesion.
with alkaline solution due to more hydrophilic fiber Fig. 15 shows typical microfailure modes in tension of
surface. the combinations of the natural fibers/polypropylene com-
Fig. 11 shows the relationship between interfacial shear posites for (a) Jute and (b) Hemp fibers. The micrographs
strength (IFSS) and the work of adhesion as a function of showed that the fiber failures indicated typically weak
the content of MAPP. The IFSS increases with an increase interfacial bond, whereas the fiber breakage could not
in the work of adhesion for both Jute and Hemp fibers. occur to be extended into the matrix but the debonding
Figs. 12 and 13 show the relationships between the IFSS could extend through the fibril interface. It is also clear that
and work of adhesion as a function of the polar surface free the microfailure with fibril splitting occurred for Jute fiber
energy and the acid–base interaction. The work of adhe- mainly, whereas the microfailure modes for Hemp fiber
sion increases with an increase in both the polar surface showed the final fiber fracture mostly.
free energy and the acid–base interaction. The increase in Figs. 16 and 17 show the different microfailure modes of
the work of adhesion and the IFSS may result from an single Jute and Hemp fibers after single fiber tensile testing
increase in the acidic-basic character of the matrix materi- for both low portion and high portion strength. The photo-
als in the order MAPP (5%) > MAPP (3%) > MAPP graph also shows that the microfailure mode of the high
(1%) > MAPP (0%), respectively. portion can be caused by slipping the elementary fibers
inside the crystal material area where they can respond to
3.4. Microfailure modes of natural fibers the high tensile strength before fracture occurs. It can also
be seen that the microfailure modes of the low portion can
Fig. 14 shows the photographs of the typical microfai- be caused by microfailure process inside the amorphous
lure modes of the Jute and Hemp fibers/polypropylene sys- material area in which they can respond to the low tensile
tems before and after microdroplet pull-out testing. The strength.

120 16 120 14
High portion High portion
Low portion Low portion
14 12
100 100
12
10
Amplitude (dB)

Amplitude (dB)

80 80

Stress (MPa)
Stress (MPa)

10
8
60 8 60
6
6
40 40
4
4
20 20 2
2

0 0 0 0
0 5 10 15 20 0 10 20 30
Strain (%) Strain (%)
15000 16 5000 14
High portion High portion
Low portion Low portion
14 12
4000
12
10
Stress (MPa)

10000
Stress (MPa)

AE Energy

10
AE Energy

3000
8
8
6
6 2000
5000
4
4
1000
2 2

0 0 0 0
0 5 10 15 20 0 10 20 30
(a) Strain (%) (b) Strain (%)

Fig. 18. AE amplitude and AE energy of single natural fibers/PP composites for (a) Jute fiber; and (b) Hemp fiber.
2698 J.-M. Park et al. / Composites Science and Technology 66 (2006) 2686–2699

3.5. AE outcomes correlating with their microfailure modes
As mentioned above, microfailure modes of both Jute
and Hem fibers showing the low and high strength portion
were clarified directly via scanning electron microscope
(SEM). It is also very interesting to find out the difference
of AE signals emitted during the fiber fracture between the
low and the high tensile strength portions by AE using a
piezoelectric transducer. The combination of the optical
method with nondestructive AE method can provide useful
information for evaluating the microfailure mechanisms of
the natural fibers in the SFC specimens.
Fig. 18 shows AE amplitude and AE energy of two nat-
ural fibers/polypropylene (PP) composites for (a) Jute and
(b) Hemp fibers, respectively. The experimental results
showed that the amplitude and the energy of AE signals
emitted by fractured process of high strength fibers are sig-
nificantly higher than those of low strength fibers. It may be
because the microfailure process of the high portion could
occur through the crystal areas, whereas one of the low por-
tions occurred through the amorphous areas. Figs. 19 and
20 show AE waveform and their FFT analysis of both Jute
and Hemp fibers/polypropylene (PP) composites for (a)
high and (b) low portions. For the high portion fracture,
AE energy was significantly higher than that of the low por-
tion and its frequency tended to shift to higher level. For
Jute fibers, a number of wave signals with higher AE energy
and AE amplitude occurred than those for Hemp fiber. The
number of AE events by fibrillation could take place for
Jute fiber much more likely than in the case of Hemp fiber
to be consistent with their observed microfailure modes.
4. Conclusion
Interfacial evaluation of Jute and Hemp fibers/various
matrix composites was investigated using micromechanical
technique and nondestructive AE. With increasing the con-
tent of MAPP in the blend of PP, the IFSS increased. It
could be because the number of polar groups introduced
into the matrix increased and thus improved the IFSS
between the fiber surface and the PP matrix. The IFSS also
increased after treating the natural fibers with alkaline solu-
tion and silane coupling agent. The surface energy compo-
nents of the fibers slightly decreased with silane coupling

8 3
Voltage (V)

Voltage (V)

0 0

-8 -3
0 100 200 300 400 0 100 200 300 400
Time (μsec) Time (μsec)
Abitrary

Abitrary

0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Frequency (MHz) Frequency (MHz)
(a) (b)

Fig. 19. AE energy and FFT analysis for single Jute fiber/PP composite for (a) high portion; and (b) low portion.

2 2
Voltage (V)

Voltage (V)

0 0

-2 -2
0 100 200 300 400 0 100 200 300 400
Time (μsec) Time (μsec)
Abitrary

Abitrary

0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Frequency (MHz) Frequency (MHz)
(a) (b)

Fig. 20. AE energy and FFT analysis for single Hemp fiber/PP composite for (a) high portion; and (b) low portion.
 J.-M. Park et al. / Composites Science and Technology 66 (2006) 2686–2699
agent due to the blocked high energy sites, whereas surface
energy increased after treating with alkaline solution. It
may be because under alkaline solution, the weaker bound-
ary layers could be removed and increase the surface area.
On the other hand, the surface energy component increased
with an increase in the MAPP content due to the number of
the high energy sites introduced continuously as the content
of MAPP increased. Tensile strength of Jute and Hemp
fibers was investigated using single fiber tensile test, and sta-
tistically analyzed using both uni- and bimodal Weibull dis-
tributions. Bimodal Weibull distribution was fitted better
than the unimodal distribution. The effects of treated condi-
tions such as thermal treatment, alkaline solution, and
silane treatments on mechanical properties were evaluated
for both natural fibers. The mechanical properties of the
natural fiber significantly decreased under high temperature
treatment and slightly increased after treating with alkaline
solution. Two different microfailure modes of various Jute
and Hemp fibers/polypropylene systems were observed for
microdroplet specimens and dogbone-shaped specimens as
well as single-fiber under tensile loading. Microfailure
mechanisms of the single Jute and Hemp fibers with
MAPP-PP systems were clarified consistently using nonde-
structive acoustic emission technique.
Acknowledgement
This research was supported by MOST-MOCIE of
Korea under contact No. M10436010010-04L3601-01-000.
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