Fracture Toughness and Impact Strength of AnhydrideCured Biobased Epoxy

Hiroaki Miyagawa, Manjusri Misra, Lawrence T. Drzal

Composite Materials and Structures Center, 2100 Engineering Building, Michigan State University,
East Lansing, Michigan 48824-1226
Amar K. Mohanty
The School of Packaging, 130 Packaging Building, Michigan State University,
East Lansing, Michigan 48824-1223

Biobased neat epoxy materials containing functionalized vegetable oils (FVO), such as epoxidized linseed
oil (ELO) and epoxidized soybean oil (ESO), were processed with an anhydride curing agent. A percentage
of diglycidyl ether of bisphenol F (DGEBF) was replaced by ELO or ESO. The selection of the DGEBF,
FVO, and an anhydride-curing agent resulted in an
excellent combination to produce a new biobased epoxy material having a high elastic modulus and high
glass transition temperature. Izod impact strength and
fracture toughness were signicantly improved dependent on FVO content, which produced a phaseseparated morphology. POLYM. ENG. SCI., 45:487 495,
2005. 2005 Society of Plastics Engineers

INTRODUCTION
The importance of environmentally friendly natural
products for industrial applications has become radically
clear in recent years with increasing emphasis on environmental issues, waste disposal, and depletion of non-renewable resources. There is a growing trend toward developing
and commercializing renewable resource based polymers,
which have the advantage of eco-friendliness. Renewable
resource based polymers can replace/substitute for fossilfuel based polymers on a cost-performance basis.
Petroleum-derived epoxy resins are known for their
easy processability, compositional versatility, superior
tensile strength, high stiffness, excellent electrical
strength, and exceptional solvent resistance. Further-

Correspondence to: L. Drzal; e-mail: drzal@egr.msu.edu

Contract grant sponsors: National Science Foundation Partnership for
Advancing Technologies in Housing (NSF-PATH), Michigan State Universitys Research Excellence Fund.
DOI 10.1002/pen.20290
Published online
in Wiley InterScience (www.interscience.wiley.
com).
2005 Society of Plastics Engineers

POLYMER ENGINEERING AND SCIENCE2005

more, cured epoxy resins have good resistance to heat

and chemical attack. The chief drawbacks of epoxy resins
are their high cost. Therefore, modifying epoxy resins has
been of intense research interest. A tougher, exible
crosslinked material can be obtained by incorporating a
exible epoxy resin, curing agent, or reactive additives
into the network during curing. In other words, the toughness of epoxy resin can be improved through a blend with
some functionalized vegetable oils (FVOs). Indeed, the
biobased modiers have been around for quite some time
and have been utilized to modify other thermoset polymers [19]. There have been a number of studies regarding the improvement of the fracture properties of rubbertoughened and petroleum-based epoxy materials [10
13]. It was demonstrated that the presence of a second
phase of rubber particles in the epoxy matrix enhanced
plastic/shear deformation, which dissipated fracture energy, and consequently, the impact strength and toughness were signicantly greater with the addition of the
rubber phase.
United States agriculture produces more than 16 billion
pounds of soybean oil annually, only 500 million pounds of
which is used in industrial application. Linseed oil is also
available abundantly across the world. FVOs such as epoxidized soybean oil (ESO) and epoxidized linseed oil
(ELO) are now commercially available in large volume for
applications such as coatings and plasticizer additives. Valueadded applications of FVOs will provide benets to the
agricultural industry.
In this paper, biobased neat epoxy materials containing different FVOs were prepared by using an anhydride
curing agent, and the fracture and impact properties of
these new biobased epoxies are measured and discussed.
Fracture and impact failure surface morphologies are
observed by scanning electron microscopy, and the experimentally measured properties are correlated with different surface morphologies.

man Advanced Materials Americas Inc., Brewster, NY;

equivalent weight 159) and 1-methylimidazole accelerator (DY 070, Huntsman Advanced Materials Americas
Inc.). The amount of curing agent was theoretically calculated to maintain proper stoichiometry.

Dynamic Mechanical Analysis

Dynamic mechanical properties were conducted with a
TA Instruments DMA 2980 operating in the three-point
bending mode at an oscillation frequency of 1.0 Hz. The
amplitude and static force of the DMA measurements were
75 m and 1N, respectively. DMA specimens were in the
form of rectangular bars of nominal 2.0 mm 15 mm 50
mm. Data were collected from ambient to 190 C at a
scanning rate of 2 C/min. The glass transition temperature,
Tg, was assigned as the temperature where loss factor was a
maximum. A minimum of three specimens of each composition were tested.

Izod Impact Strength

The Izod impact strength was measured for neat epoxy
and clay/epoxy nanocomposites at room temperature. Izod
impact specimens with the same dimension as prescribed in
ASTM D 256 standard were tested with a 453 g pendulum.
The dimensions of the notched Izod impact specimens were
63.5 mm (length) 12.7 mm (width) 10 mm (thickness),
with a notch depth of 1.5 mm having a 0.25 mm radius. All
specimens were cast in silicone molds having the same
dimensions. The specimen was held as a vertical cantilever
beam and was impacted on the notched face by a single
swing of the pendulum. Therefore, the crack propagated
from the tip of the notch. A minimum of 5 specimens for
each composition were tested.
FIG. 1. DMA proles of DGEBF and biobased neat epoxies containing
ELO or ESO. (a) Storage modulus. (b) Loss factor.

EXPERIMENTAL

Materials
Diglycidyl ether of bisphenol F (DGEBF, Resolution
Performance Products, Houston, TX, epoxide equivalent
weight 172) was used as the main component.
3050 wt% of DGEBF was substituted with the same
weight of 2 different FVOs, ELO (Vikoex 7190, Atona,
Booming Prairie, MN; epoxide equivalent weight 176) or
ESO (Vikoex 7170, Atona; epoxide equivalent weight
228). The mixture of DGEBF epoxy and FVO was
processed with an anhydride curing agent, methyltetrahydrophthalic anhydride (MTHPA, Aradur HY 917, Hunts488

POLYMER ENGINEERING AND SCIENCE2005

Fracture Testing
Compact tension (CT) specimens were prepared for fracture testing. The crack length a, the width W, and the
thickness B of the CT specimens were determined as 10
mm, 20 mm, and 5 mm, respectively, based on the ASTM
D 5045 standard, as in the previous studies. The notch was
at rst made by a band saw, and then the sharp initial crack
tip was produced by a guillotine crack initiator and a fresh
razor blade. The crack length was measured by optical
microscopy after fracture testing. The experiments were
performed with a crosshead velocity of 15 mm/min to load
the CT specimens. The fracture toughness was measured
with at least 3 specimens for each different material. The
critical energy release rate was calculated from the fracture
toughness in plane-strain state by using the storage modulus
measured by DMA and assuming the Poissons ratio of 0.34
for all neat epoxies.

FIG. 2. Storage modulus at 30 C and glass transition temperature of

anhydride-cured biobased neat epoxies measured by DMA.

Scanning Electron Microscopy

The fracture surfaces of different biobased epoxy nanocomposites were observed with scanning electron microscopy (SEM). A JEOL 6300 SEM with eld emission lament or a JEOL 6400 SEM with LaB6 lament in
accelerating voltage of 10 kV was used to collect SEM
images for all samples. A gold coating, which is a few
nanometers thick, was made on the fracture surfaces to aid
in feature resolution.
RESULTS AND DISCUSSION

FIG. 3. Storage modulus at (Tg30) C and crosslink density of anhydride-cured biobased neat epoxies measured by DMA.

decrease of the storage modulus after processing the anhydride-cured biobased neat epoxies was approximately the
same. Therefore, it can be concluded that ELO provides
higher storage modulus when compared with the same
amount of ESO. The storage modulus measured by DMA
was found to be an unbiased estimator of the elastic modulus that was measured by mechanical testing. It had already
been conrmed that the storage modulus was almost the
same as the tensile modulus for anhydride-cured epoxy,
because of the lack of plastic behavior in the stress-strain

Dynamic Mechanical Analysis

Figure 1 shows the temperature dependency curve of
storage modulus and loss factor of anhydride-cured epoxy
containing 3050 wt% ELO or 30 wt% ESO. In Fig. 1a, the
storage modulus below the glass transition temperature decreased after the addition of ELO or ESO. In Fig. 1b, only
one peak appeared in the temperature range between 30 C
and 150 C for each epoxy material. The symmetric peak of
the loss factor, tan , in Fig. 1b indicates complete cure of
the anhydride-cured epoxy matrix.
Figure 2 shows the storage modulus at 30 C, which is
measured by DMA, of the DGEBF and the biobased neat
epoxies cured with the anhydride curing agent, MTHPA. In
Fig. 2, for example, ELO 50 and ESO 30 indicate that the 50
wt% DGEBF was replaced by ELO, or 30 wt% DGEBF was
replaced by ESO, respectively. After 3050 wt% DGEBF
was replaced by the same amount of ELO or ESO, the
storage modulus of the processed anhydride-cured biobased
neat epoxies showed an up to 20% decrease. When 50 wt%
ELO or 30 wt% ESO was used to replace DGEBF, the

FIG. 4.

Izod impact strength of anhydride-cured biobased neat epoxies.

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489

FIG. 5. SEM micrographs of different impact

failure surfaces of anhydride-cured neat epoxies.
(a) DGEBF at high magnication. Scale bar 2
m. (b) Biobased epoxy containing 50 wt%
ELO at high magnication. Scale bar 2 m.
(c) Biobased epoxy containing 30 wt% ESO at
low magnication. Scale bar 20 m. (d) Biobased epoxy containing 30 wt% ESO at high
magnication. Scale bar 1 m.

diagram [14]. Therefore, the storage modulus measured by

DMA is used to calculate the critical energy release rate
from the fracture toughness in the plane-strain state.
Figure 2 also shows the glass transition temperature,
which is assigned as the peak position of loss factor curve
measured by DMA, of the DGEBF and the biobased neat
epoxies cured with MTHPA. In Fig. 2, the storage modulus
of the processed biobased neat epoxies showed an approximately 79 C decrease, after 3050 wt % DGEBF were
replaced by the same amount of ELO or ESO. In general, a
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higher glass transition temperature is obtained when the

main component has a lower epoxide equivalent weight and
higher epoxy functionality, because this results in a higher
crosslink density [15]. Indeed, ELO has a lower epoxide
equivalent weight and higher epoxy functionality (that is
theoretically 7) than ESO, whose epoxy functionality is
theoretically 6. Therefore, comparing ELO and ESO, it
can be concluded that it is easier to maintain the high glass
transition temperature of the biobased neat epoxy when
ELO is used as a partial replacement for DGEBF.

FIG. 5.

The crosslink density of anhydride-cured biobased

neat epoxies was evaluated by DMA. Figure 3 shows the
storage modulus at (Tg30) C and the crosslink density.
Interestingly, the storage modulus at (Tg30) C did not
change with the substitution with 3050 wt% ELO, in
spite of the slight reduction with 30 wt% ESO. By using
the glass transition temperature shown in Fig. 3, the
crosslink density can be calculated from the following
equation:

(Continued)

E 3 eRT
where, E, ve, R, and T are the storage modulus at (Tg30)
C, crosslink density, gas constant (8.314 J/(K mol)), and
temperature in K, respectively. Although the crosslink density for anhydride-cured ELO was constant with 3050
wt% of ELO, the slight decrease in the crosslink density was
observed with 30 wt% ESO.
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491

Izod Impact Strength

Figure 4 shows the Izod impact strength of the anhydride-cured DGEBF and biobased neat epoxies. The anhydride-cured rigid epoxy sample has a high crosslink density;
therefore, the value of the Izod impact strength was relatively low. Comparing the DGEBF with the biobased neat
epoxies containing 3050 wt% ELO, the Izod impact
strength was almost the same. As discussed in Fig. 2, a
glassy epoxy material, having high glass transition temperature, was obtained after replacing 3050 wt% of DGEBF
with ELO, although the glass transition temperature slightly
decreased. On the other hand, the Izod impact strength was
improved more than 25% when 30 wt% of DGEBF was
replaced by ESO.
It was already discussed in Fig. 2 that the storage modulus and the glass transition temperature were almost the
same for both ELO and ESO neat epoxies. To investigate
the difference of the Izod impact strength of the anhydridecured biobased epoxies, it is necessary to observe the morphology of the impact failure surfaces by SEM. Figure 5
shows SEM micrographs of the impact failure surfaces of
the anhydride-cured DGEBF and biobased epoxy materials.
In Fig. 5a, the failure surface of the anhydride-cured
DGEBF was completely at and featureless. This suggests
that the behavior of the anhydride-cured DGEBF was linear
elastic, and the crack propagated in a planar manner under
the impact loading, although several small pieces of resin
were found on the failure surface. In Fig. 5b, the failure
surface of the anhydride-cured biobased neat epoxy containing 50 wt% ELO was similar to that of the DGEBF,
although the failure surface was slightly rougher than that of
Fig. 5a. Therefore, the behavior of the anhydride-cured
biobased epoxy containing 3050 wt% ELO was also linear elastic, and thus the crack propagated in a planar manner
under the impact loading.
In contrast, the failure surface of the anhydride-cured
biobased neat epoxy containing 30 wt% ESO was much
rougher, and a larger number of the small resin pieces were
found on the failure surface in Fig. 5c. Figure 5d is a higher
magnication SEM micrograph of the same failure surface
of the anhydride-cured biobased neat epoxy containing 30
wt% ESO. The regions, indicated with arrows in Fig. 5d, are
ESO-rich rubber phases. The presence of a second phase is
clearly evident in Fig. 5d. It is known that the rubbertoughened epoxy shows much larger improvement on the
Izod impact strength, although the solid particlereinforced
epoxy often showed lower Izod impact strength than the
neat epoxy. It is likely that the main epoxy matrix is more
rigid than the separated ESO phase, since 100% ESO has
much lower storage modulus at room temperature than
DGEBF neat epoxy. Indeed, the loss factor curve for the
anhydride-cured biobased neat epoxy containing 30 wt%
ESO showed only one peak between 30 and 170 C in spite
of the phase separation, as discussed in Fig. 1b. This suggests that the glass transition temperature of the rubber ESO
phase is below 30 C. The anhydride-cured biobased neat
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FIG. 6. Typical examples of load-COD diagram of anhydride-cured

biobased neat epoxies. DGEBF: a 8.03 mm, W 21.4 mm, B 6.55
mm; ELO 50: a 7.73 mm, W 21.3 mm, B 5.84 mm; ESO 30: a
5.24 mm, W 21.5 mm, B 6.06 mm.

epoxy containing 30 wt% ESO was not transparent, although the anhydride-cured DGEBF and biobased neat epoxies containing 3050 wt% ELO were transparent. In
other words, the lack of the transparency was the result of
the phase separation. As discussed in Fig. 2, ELO has higher
epoxy functionality than ESO. In addition, ELO has lower
molecular weight. Consequently, ELO has higher polarity
than ESO and hence ELO has better solubility and compatibility with polar DGEBF [1], while ESO has a larger
possibility to create phase separation than ELO.
The size of the ESO rubber phase was measured to be d
250650 nm in Fig. 5d. The void-like feature of the ESO
rubber phases was created by distortional pullout of the
rubbery particles under the impact loading. A much greater
energy is dissipated to pull out rubber phases because of
excellent adhesion in the epoxy/rubber interfaces. Therefore, the anhydride-cured ESO neat epoxy having the phase
separation showed more than 25% higher Izod impact
strength. The change in the crosslink density can also affect
the Izod impact strength. In other words, it was found in
Figs. 2 and 3 that the glass transition temperature and the
crosslink density slightly decreased, and this can result in
increased Izod impact strength. However, the contribution
of both the decreased glass transition temperature and
crosslink density is small, since the range of these decreases
was quite small. The DGEBF and ELO neat epoxies that did
not have any phase separation exhibited a lower impact
strength.
Fracture Testing
Figure 6 shows examples of load-crack opening displacement (COD) curves of the DGEBF and the biobased
neat epoxies. Non-linearity was not observed in the load-

FIG. 7. Fracture toughness and critical energy release rate of anhydridecured biobased neat epoxies.

COD diagrams of both the anhydride-cured DGEBF and

ELO neat epoxies. Therefore, the maximum load was used
to evaluate fracture toughness. For the anhydride-cured
ESO neat epoxy, slight non-linearity was observed in the
load-COD diagram after COD reached approximately 2.0
mm. However, the critical load could not be dened as the
intersection of the load-COD diagram and 5% offset line
because of the linearity in the load-COD diagram. Therefore, the maximum load was used to determine the fracture
toughness of the anhydride-cured ESO neat epoxy. It should
also be noted that the size of the plastic zone for all neat
epoxies is small enough based on the linear fracture mechanics, since the load-COD diagram is linear in Fig. 6.
Figure 7 shows the fracture toughness of the anhydridecured DGEBF and biobased neat epoxies. As seen in Fig. 7,
the anhydride-cured ELO neat epoxy showed almost the
same value as the fracture toughness of the anhydride-cured
DGEBF epoxy. In contrast, the anhydride-cured ESO neat
epoxy showed extremely high fracture toughness, when
compared with the DGEBF and ELO neat epoxies. This was
a result of the presence of a second rubbery phase. This is
further explained with SEM micrographs.
The fracture properties can also be discussed with the
critical energy release rate shown in Fig. 7. The anhydridecured neat ELO epoxy has slightly smaller storage modulus
than the DGEBF, as discussed in Fig. 2. Therefore, the
critical energy release rate of the ELO neat epoxy was
slightly higher than that of the DGEBF. In the four different
anhydride-cured epoxies, the ESO neat epoxy has the largest critical energy release rate, and was more than 10 times
as large as that of the DGEBF, after 30 wt% of DGEBF was
replaced by ESO. This large improvement was also seen as
a much larger integrated area of the load-COD diagram of

the anhydride-cured ESO neat epoxy, when compared with

the DGEBF and ELO neat epoxies. The improvement ratio
of the critical energy release rate with ESO was much larger
than that of the Izod impact strength, because of timetemperature superposition. Under impact conditions, a very
fast loading is applied, resulting in polymer behavior similar
to low-temperature fracture.
Figure 8 shows the SEM micrographs of the fracture
surfaces of the anhydride-cured DGEBF and biobased neat
epoxies. In Fig. 8a and b, the fracture surface was completely at. This suggests that the anhydride-cured DGEBF
and ELO neat epoxies are brittle and the load-COD diagram
was almost completely linear elastic as discussed in Fig. 6.
Hence, the crack propagated in a planar manner, and a
minimal fracture surface area was created by the crack
propagation. Minimal fracture surface area means minimal
consumption of the energy for crack propagation. On the
other hand, in Fig. 8c, the fracture surface of the anhydridecured ESO neat epoxy was extremely rough, as the high
critical energy release rate was observed in Fig. 7. This
feature in Fig. 8c was clearly distinctive, when compared
with the completely at fracture surfaces of the anhydridecured DGEBF and ELO neat epoxies, which did not have
the second phase as shown in Fig. 8a and b. The rougher
surface is identical for dissipating more energy that is due to
shear deformation during the crack propagation. It was
reported that the addition of the rubber particles to epoxy
could cause (i) localized cavitation in the rubber or the
rubber/epoxy interface and (ii) plastic shear yielding [10
12]. The change in the crosslink density can also affect the
critical energy release rate. In other words, it was found in
Figs. 2 and 3 that the glass transition temperature and the
crosslink density slightly decreased, and this can result in
the increased critical energy release rate. However, the
contribution of both the decreased glass transition temperature and crosslink density is too small to obtain 10 times
greater critical energy release rate, since the decreases of
both the glass transition temperature and the crosslink density were quite small. For the epoxy, the critical energy
release rate in Mode II, crack shearing mode, was approximately 10 times larger than that of the same epoxy in Mode
I, crack opening mode [16]. The ESO rubber phase observed by SEM, as shown in Fig. 8c, has the same role as
previously reported for petroleum-based rubber-toughened
epoxy, and the sight non-linearity for the anhydride-cured
ESO neat epoxy in Fig. 6 was caused by the plastic shear
yielding. As a result, the critical energy release rate was
improved almost 10 times after 30 wt% DGEBF was replaced by ESO. Grifth explained that a crack is propagated
when the strain energy reaches the certain value, and as a
result new fracture surface is created [17]. A large fracture
surface requires more strain energy to be released as the
crack propagates. Consequently, the fracture surface area is
larger when the critical energy release rate is larger. Some
energy was dissipated by the plastic deformation in front of
the crack tip, since the plastic zone always exists in front of
the crack tip. However, as discussed in Fig. 6, the size of the
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493

FIG. 8. SEM micrographs of different fracture surfaces of anhydride-cured neat epoxies. (a) DGEBF. Scale bar
50 m. (b) Biobased epoxy containing 50 wt% ELO. Scale bar 20 m. (c) Biobased epoxy containing 30
wt% ESO. Scale bar 20 m.

plastic zone for the biobased neat epoxy containing 30 wt%

ESO is small enough, since the load-COD diagram is almost
linear. As a result, it can be concluded that most of the
energy was dissipated during the crack propagation. The
experimental results shown in Fig. 7 agreed well with the
morphological observations in Fig. 8.
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POLYMER ENGINEERING AND SCIENCE2005

CONCLUSIONS
The DGEBF and biobased epoxies were processed with
an anhydride curing agent. The fracture and impact properties were measured for 4 different anhydride-cured epoxies.
The fracture toughness and the critical energy release rate of
the anhydride-cured epoxy were greatly improved with the

FIG. 8.

addition of ESO. The improvement of both the impact

strength and the fracture toughness was the result of a phase
separation of the ESO into rubbery particles. The existence
of the rubber ESO phases added a signicant amount of
energy to the crack propagation process. The fracture and
failure surface morphology correlated well with the experimental measurements of the critical energy release rate.
ACKNOWLEDGMENTS
The authors are grateful to National Science Foundation
Partnership for Advancing Technologies in Housing (NSFPATH) 2001 Award No. 0122108 and Michigan State Universitys Research Excellence Fund for partial nancial
supports. The authors are also thankful to Atona, Booming
Prairie, MN, and Huntsman Advanced Materials Americas
Inc., Brewster, NY, for supplying samples.

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