Thermal, morphological, and electrical characterization of

microwave processed natural ber composites

Nikki Sgriccia
*
, M.C. Hawley
Chemical Engineering and Materials Science, Michigan State University, 2527 Engineering Building, East Lansing, MI 48823, United States
Received 20 April 2006; received in revised form 12 July 2006; accepted 20 July 2006
Available online 27 September 2006
Abstract
Experiments to investigate the eectiveness of microwave curing of natural ber reinforced composites have been performed. Hemp,
ax, kenaf, henequen and glass (15 wt.%) reinforced epoxy composed of diglycidyl ether of bisphenol-A (DGEBA) and diaminodiphenyl
sulfone (DDS) composites were studied. Dierential scanning calorimetry (DSC), thermogravimetric analysis (TGA), environmental
scanning electron microscopy (ESEM), and swept frequency diagnostic method were used to investigate material properties. Samples
were processed using both microwave and thermal curing. Glass and ax composites reached a higher nal extent of cure with microwave
curing than with thermal curing. Glass, ax, and hemp cured faster in the microwave than their convection oven counterparts. Natural
bers and their composites degraded at lower temperatures than glass and glass ber composites. ESEM micrographs, used to investigate
ber morphology, indicated a lack of bonding at the interfaces between the bers, natural and glass, and matrix.
2006 Elsevier Ltd. All rights reserved.
Keywords: A. Polymer-matrix composites; B. Electrical properties; B. Thermal properties; D. Dierential scanning calorimetry; Microwave
1. Introduction
There is a growing need to develop biobased products.
Biobased products can form the basis for sustainable and
environmentally friendly materials that can compete in
markets currently dominated by petroleum based products.
Advantages of these products are readily available raw
materials and low cost. Although there is considerable
interest in the eld of natural ber composites in structural
applications, there has been little research on microwave
curing of these composites. Microwaves have been studied
as an alternative processing method for composites due to
their benecial eects on processing time, as well as
mechanical and thermal properties. Applications of this
technology have been limited by the diculty of achieving
even and controlled heating, especially for relatively large
samples. In contrast to convection ovens, microwave heat-
ing is volumetric and not restricted to the surface. As a
result, thermoset polymer materials can be processed more
quickly in a microwave cavity. Lignocellulosic natural
bers such as sisal, coir, jute, ramie, pineapple leaf (PALF),
and kenaf have the potential to be used as a replacement
for glass or other traditional reinforcement materials in
composites. These bers have many properties which make
them an attractive alternative to traditional materials. They
have high specic properties such as stiness [1], impact
resistance [2], exibility [3], and modulus [4]. In addition,
they are available in large amounts [5], and are renewable
and biodegradable. Other desirable properties include low
cost, low density, less equipment abrasion [3,6], less skin
and respiratory irritation [7], vibration damping [1,2], and
enhanced energy recovery [7,8]. Mehta et al. [11] compared
glass and hemp ber composites and determined that both
types of composites had specic tensile strength and tensile
modulus in the same range.
The hydrophilicity of natural bers results in high mois-
ture absorption and weak adhesion to hydrophobic matri-
0266-3538/$ - see front matter 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.compscitech.2006.07.031
*
Corresponding author. Tel.: +1 517 432 5488; fax: +1 517 432 1105.
E-mail address: sgricci1@egr.msu.edu (N. Sgriccia).
www.elsevier.com/locate/compscitech
Composites Science and Technology 67 (2007) 19861991
COMPOSITES
SCIENCE AND
TECHNOLOGY
ces. Additionally, most natural bers have low degradation
temperatures (200 C), which make them incompatible
with thermosets that have high curing temperatures. There
are several other challenges presented by natural bers
such as large variability of mechanical properties [2,4],
lower ultimate strength [6], lower elongation [6], problems
with nozzle ow in injection molding machines [6], bubbles
in the product [6], and poor resistance to weathering [9].
Natural bers can be grouped into three categories; bast,
seed and leaf. In this study, three types of bast bers
(kenaf, ax and industrial hemp) and one kind of leaf ber
(henequen) were used.
With the exception of the E-glass dielectric constant [10],
the dielectric properties of natural bers are not available
in literature. The dielectric constant, e
0
, is a measure of
energy absorption. The dielectric loss factor, e
00
, is a mea-
sure of a materials ability to convert stored energy into
heat. Generally a high dielectric loss factor, e
00
is needed
to heat materials eciently with microwaves. The dielectric
properties of the bers were determined so their eect on
the microwave processing of natural and glass ber com-
posites could be evaluated.
These experiments will ultimately be used to determine
the suitability of natural bers as composite reinforcement
materials. To this end, cure time and extent of cure, ther-
mal degradation, ber and composite morphologies, and
electrical properties were studied. The study of composite
curing was conducted using microwave and convection
oven cured processing.
2. Experiments
2.1. Fiber preparation
The natural bers (kenaf, ax, industrial hemp supplied
by Flax Craft and henequen supplied by Dr. Pedro Herrera
Franco from Mexico) were soaked in hot distilled water for
1 h, dried for 48 h in air at room temperature, and dried in
the oven at 100 C for 3 h. The epoxy compatible chopped
glass bers were supplied by Johns Manville (JM) Com-
pany and were used as such.
2.2. Composite preparation
Diglycidyl ether of bisphenol-A (DGEBA), supplied by
Adtech Corp., cured with diaminodiphenyl sulfone (DDS),
supplied by TCI, was used to produce the epoxy. The
DGEBA was mixed with the DDS in the ratio of 2.79:1.
Next 15 wt.% of bers were mixed into the epoxy. The mix-
ture was degassed in a 100 C vacuum oven for 20 min.
2.3. Microwave processing
Samples were processed in a Lambda Technologies
Vari-wave Model 1000. Several grams of composite were
placed in a silicone rubber mold and capped with a Teon
lid. An infrared temperature probe was inserted into the
sample through the hole in the center of the Teon lid. A
heating mode was determined by frequency sweeping. A
heating mode occurs when the reected power is zero and
the temperature rises quickly. Other modes, where the
reected power is zero, may be non-heating due to the
shape of the EM eld in the cavity. The samples were then
heated to 145 C in 3 min. Samples were held at the cur-
ing temperature for 20, 40, 60, 80, 100 and 120 min to
develop an extent of cure versus time curve.
2.4. Oven processing
The thermally cured samples are prepared from the
same batch of material as the microwave cured samples.
Several grams of composite were placed in a silicone rubber
mold. The six samples are placed in the oven, without Tef-
lon lids after the oven has reached 145 C. Samples were
held at the curing temperature for 20, 40, 60, 80, 100 and
120 min to develop an extent of cure versus time curve.
2.5. Measurements
2.5.1. Dierential scanning calorimetry (DSC)
The dierential scanning calorimetry was carried out in
a TA Instruments DSC 2920. The sample was ramped to
350 C at 5 C/min then cooled with nitrogen to 40 C.
This experiment was performed to determine the extent
of cure versus cure time curves for the dierent composites.
2.5.2. Thermogravimetric analysis (TGA)
The thermogravimetric analysis was carried out in a TA
Instruments Hi-Res TGA 2950 that was tted to a nitrogen
purge gas. The sample was heated from ambient tempera-
ture to 600 C at 25 C/min. Degradation temperatures of
natural and glass bers and their composites were deter-
mined using this technique.
2.5.3. Environmental scanning electron microscopy (ESEM)
The samples were observed in Philips ElectroScan 2020
ESEM. The sample chamber pressure was reduced to
586.6 Pa. ESEM is used to examine the morphology of
the bers and the composites.
2.5.4. Swept microwave diagnostic system (EM cavity)
Tests to determine the dielectric properties of natural
and glass bers using perturbation method were conducted
in a single-port microwave cavity. The perturbation
method uses changes in the cavity Q factor and resonant
frequency to calculate the dielectric constant and loss fac-
tor of a material. The swept-frequency method is used to
determine the cavity length, empty and loaded cavity reso-
nant frequencies, and half-power bandwidth necessary to
calculate the dielectric properties. Fibers were prepared
as described in Section 2.1. The bers were then placed in
a small Teon holder and compressed. The bers were
placed in an oven at 100 C for until tested in the micro-
wave cavity to ensure that the bers were as dry as possible.
N. Sgriccia, M.C. Hawley / Composites Science and Technology 67 (2007) 19861991 1987
3. Results
3.1. Dierential scanning calorimetry
Composites were cured in the single port microwave
cavity and in a convection oven from 20 min to 120 min.
Dierential scanning calorimetry was used to determine
the extent of cure at each cure time. Plots of extent of cure
versus cure time show that there is more scatter present in
the composites that were cured in the microwave than in
convection oven cured ones (see Fig. 1). The lines connect
the average extent of cure for each time. The spread in the
data decreases as the composites reach larger extents of
cure.
Fig. 2 shows the extent of cure versus cure time for glass,
ax, henequen, and kenaf composites cured in the micro-
wave and convection oven. Hemp composite and epoxy
were omitted for clarity. Both microwave and convection
oven cured ber composites follow the same general trend.
Microwave cured hemp, ax, and glass composites cured
faster than their convection oven cured counterparts.
ANOVA and Tukeys tests were performed using MINI-
TAB to determine whether the materials had the same
mean extent of cure given constant cure time and curing
method. Results are shown in the following two gures.
In Figs. 3 and 4, materials labeled a had the greatest
extent of cure per cure time and curing method, b had
the lowest, and ab had an intermediate extent of cure.
Cure times that are not labeled had materials with the same
extent of cure. For microwave and convection oven curing,
ax composites had the greatest extent of cure at 20 min.
After 40 min of microwave curing, there is no dierence
in mean extent of cure among the composites (see Fig. 5).
ANOVA and Tukeys tests were also performed to
determine whether the microwave and convection oven
cured composites yielded the same extent of cure given cure
time and material. Glass and ax composites reached lar-
ger extents of cure in the microwave at 120 min. Hemp
and kenaf composites microwave and convection oven
composites reached the same extent of cure. Henequen
Fig. 1. Individual value plots of extent of cure versus time curves showing
microwave (top) and convection oven (bottom) cured ax composites.
Fig. 2. Curing curves for microwave and convection oven composite
samples.
Fig. 3. Comparison of microwave cured composites.
Fig. 4. Comparison of convection oven cured composites.
1988 N. Sgriccia, M.C. Hawley / Composites Science and Technology 67 (2007) 19861991
composites and epoxy convection oven cured composites
reached a larger extent of cure at 100 min.
3.2. EM cavity tests
A single port cavity was used to determine the dielectric
properties of the natural and glass bers. The dielectric
constants of natural bers range from 2.8 to 3.2. The
dielectric loss factors range from 0.07 to 0.15. The dielectric
properties of bers in Figs. 6 and 7 are 5% trimmed means.
The trimmed mean was used as a measure of location to
minimize the impact of outliers. ANOVA and Tukeys tests
indicated that the dielectric loss factors of the natural and
glass bers are the same.
3.3. Thermogravimetric analysis
TGA was used to determine the degradation tempera-
tures of natural and glass bers and composites. The deg-
radation temperatures for natural ber composites
(microwave and convection oven cured) fall between the
degradation temperatures for the matrix and the bers
(see Tables 1 and 2). The glass ber composites break this
trend at 5% weight lost. Hemp had the highest degradation
temperatures out of the natural bers.
3.4. Environmental scanning and electron microscopy
The ESEM images were taken of the composites used
for DSC analysis (see Fig. 8). Most of the bers that can
be seen are relatively free of the resin material. Notable
exceptions are the kenaf composites, microwave and con-
vection oven, which had many resin coated bers.
4. Discussion
Glass and ax composites reached a larger extent of cure
and cured faster with microwave processing suggesting that
they would make good candidates for future experiments
involving larger composites for tensile and exural testing.
In microwave heating, an alternating electromagnetic eld
is applied to a material. This causes friction as the polar
molecules align themselves with the eld resulting in gener-
ated heat. Materials can be cured more quickly in the
microwave due to this volumetric heating eect.
Fig. 5. Comparison of microwave and convection oven cured glass and
ax composite samples.
*
denotes larger extent of cure reached in the
microwave.
Fig. 6. Dielectric constants of natural and glass bers.
Fig. 7. Dielectric loss factors of natural and glass bers.
Table 1
Degradation temperatures for glass and natural bers (temperatures are
given at 5, 25, 50, and 75% of total weight loss)
Weight loss percent T (C) 5% T (C) 25% T (C) 50% T (C) 75%
Hemp 104.6 329.2 341.1 457.8
Kenaf 64.3 313.4 340.5 370.8
Henequen 61.1 301.4 337.4 391.6
Flax 88.2 322.8 338.6 441.4
Glass
*
586.4
*
Ultimate ber weight loss was 1.6%.
Table 2
Degradation temperatures for glass and natural ber composites
Weight loss percent T (C)
5%
T (C)
25%
T (C)
50%
T (C)
75%
Glass oven 400.3 N/A 401.8 538.6
Glass microwave 400.4 N/A 401.7 481.7
Henequen oven 305.8 374.6 391.0 455.9
Henequen microwave 355.0 389.1 392.2 483.0
Kenaf oven 321.0 370.8 390.3 479.2
Kenaf microwave 336.1 382.1 391.6 479.2
Flax oven 363.8 389.1 392.8 473.6
Flax microwave 351.2 385.3 391.0 471.7
Hemp oven 348.1 383.6 392.0 472.2
Hemp microwave 352.3 390.2 392.8 473.6
Neat epoxy oven 396.6 N/A 397.9 489.8
Neat epoxy microwave 403.3 N/A N/A 484.3
N. Sgriccia, M.C. Hawley / Composites Science and Technology 67 (2007) 19861991 1989
The dielectric constants of the natural and glass
bers are low and will not aect the microwave
processing of the composites. At the start of the cure,
the dielectric loss factor of the epoxy is larger than that
of the natural or glass bers and the microwaves will pri-
marily heat the epoxy. As the epoxy cures, its dielectric
loss factor decreases. The loss factor of the epoxy will
eventually drop below that of the natural and glass bers
at which point the bers will be preferentially heated by
microwaves. Since the natural and glass bers have the
same dielectric loss factor, we would expect to see them
have the same extent of cure for a given cure time. This
holds true for the composites cured for more than
40 min. The variation in the 20 and 40 min composites
may be due to diculties controlling the curing temper-
ature at those times. As the composites cure, the curing
temperature becomes easier to control. This is seen in
Fig. 1.
The low degradation temperatures of natural bers
place restrictions on the cure temperature for microwave
and thermal curing. Also, the natural ber composites
would not be suitable for applications with temperatures
as high as those of glass ber composites.
Most bers are free of resin materials indicating that the
bond between the bers and matrix is weak. Future exper-
iments will investigate the eect of ber treatments to
improve the bonding between the bers and matrix.
5. Conclusions
Dierential scanning calorimetry experiments revealed
that ax and glass composites reached a larger extent of
Fig. 8. ESEM micrographs of microwave cured composites. (A) Kenaf; (B) Hemp; (C) Henequen; (D) Flax; (E) Glass. Scale bar: 100 lm. Magnication:
500.
1990 N. Sgriccia, M.C. Hawley / Composites Science and Technology 67 (2007) 19861991
cure in the microwave than in the convection oven. Hemp
and kenaf composites reached the same extent of cure in
the microwave and convection oven. Natural and glass
ber composites have the same dielectric loss. At the start
of the microwave curing process, microwave primarily heat
the epoxy while at the end bers are primarily heated. Nat-
ural bers have lower degradation temperature than glass
bers which aects processing of the composites and usage
temperatures. The natural and glass bers did not adhere
well to the epoxy.
Hemp, kenaf, and glass will be used in future experi-
ments to determine tensile and exural strength with and
without modiers to improve adhesion. Tests for water
absorption rates will also be conducted.
Acknowledgements
This work was supported by the National Science Foun-
dation (DMI 0200346). Biobers from Flaxcraft Inc.,
Cresskill, NJ, Hempline, Ontario, Canada and Dr. Pedro,
Mexico, as well as glass ber samples from Johns Manville
are gratefully acknowledged.
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