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 7

Crystallization and Thermal Properties

of Biofiber-Polypropylene Composites
M. Soleimani1, L. Tabil1, S. Panigrahi1 and I. Oguocha2
1Department of Chemical and Biological Engineering, University of Saskatchewan
2Department of Mechanical Engineering, University of Saskatchewan
Saskatoon,
Canada

1. Introduction
The crystallization of small molecules proceeds by nucleation and growth mechanisms. In
polymers, the basic morphology of the crystals is spherulite lamellar crystal bundles which
results from the growth of a nucleus center followed by branching to form radial structural
equivalence. According to reported observations (Reiter & Strobl 2007), the long-chain
fractions in spherulites enriched in early-formed thick crystals are called dominant lamellae
and the short-chain fractions enriched in later-formed thin crystals are called subsidiary
lamellae.
Polypropylene (PP) is an attractive thermoplastic polymer with exceptional properties such
as high isotacticity, high cost-performance ratio, low processing temperature, excellent
chemical and moisture resistance, low density and good ductility (Somnuk et al. 2007 ;
Zhang et al. 2002). However, it has some inferior mechanical properties such as low impact
resistance and low stiffness, both of which can be improved upon by using additives such as
tougheners and the application of nucleating agents (Zhang et al. 2002).
The application of nucleating agents results in the shortening of injection molding cycle
and, consequently, in the reduction of manufacturing costs. Also, optical and mechanical
properties of polymers can be improved by the generation of small spherulites. As a
common industrial practice, polymers are often mixed with other materials to improve
properties such as strength and biodegradability or to save the starting materials (Mucha
& Krolikowski 2003).
As a coupling agent used for in situ or reactive compatibilization, maleic anhydride-grafted
polypropylene (MAPP) has the same molecular structure as polypropylene while the maleic
anhydride group is attached to the backbone. In a study by Seo et al. (2000), it was reported
that the mechanism of crystallization in isotactic polypropylene (iPP) could be different
from that of MAPP due to their different nucleation mechanisms originating from the
differences in their characteristics and the number of heterogeneous nuclei. Also, the
diffusional activation energy and crystallization half-time were found to be smaller for
MAPP than for iPP under isothermal conditions. The rate of crystallization was decreased

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132 Thermoplastic – Composite Materials

by increasing temperature under isothermal conditions for both materials, however, it was
much more noticeable for iPP. The application of MAPP in iPP affected its crystallization
during the cooling process because of the increase in the number of effective nuclei.
In this paper, non-isothermal crystallization melt behaviour and thermal properties of PP
composite materials with different formulations were studied with respect to the effects of
chemical modification, the use of compatibilizer, and fiber loading. For this purpose,
different theories and models were used to analyze the data obtained in this investigation.

2. Materials and methods

2.1 Materials
A compression-grade PP (PRO-FAX) with density of 0.904 g cm-3, melt flow index of 0.65 g/10
min at 230°C, and low melt flow index (MFI = 0.65 g/10 min at 230°C) was obtained from
Ashland Specialty Chemical Company (Vancouver, BC, Canada), while maleic anhydride-
grafted polypropylene (MAPP) (MFI = 115 g/10 min at 190°C; maleic acid content of
approximately 0.6%) was obtained from Aldrich Chemical Company (Toronto, ON, Canada).
Flax fiber which was already retted with a density of 1.52 g cm-3 was obtained from Biofiber
Ltd., Canora, SK, Canada. For mercerization, the fiber was first washed with a 2%
commercially available detergent solution (Ultra liquid Tide containing cationic and non-ionic
biodegradable detergents) and then washed with distilled water to eliminate extractives,
especially waxy materials. After drying at 60°C for 24 h, it was pretreated with a 5% sodium
hydroxide (NaOH) solution for 3 h and thoroughly washed with distilled water and dried
again in an oven (Despatch Oven Co., Minneapolis, MN, USA). Fiber analysis for
measurement of the components was performed based on the measurement of neutral
detergent fiber (NDF), acid detergent fiber (ADF) and acid detergent lignin (ADL) using a fiber
analyzer (ANKOM Technology, Fairport, NY, USA) to determine cellulose, hemicellulose,
lignin and ash percentages.

2.2 Fabrication of composites

Pretreated and untreated flax fibers were each milled in a grinder (Retsch GmbH 5657
HAAN, West Germany) through a 2-mm opening to be used in composite formulations as
shown in Table 1. PP and MAPP were dried in the oven at 60°C for 15 h and at 120°C for 15
h, respectively, before use. Materials based on the formulation and after initial mixing were
extruded in a single-screw extruder (Akron Inc., Batavia, OH, USA) at temperatures up to
190°C with a screw speed of 45 rpm and the extrudates were pelletized to be used for
compression molding in a hot press (J.B. Miller Machinery & Supply Co., Toronto, ON,
Canada) under a pressure of 3.5 MPa at 190°C for 7 min to prepare plates with a thickness of
about 3.2 mm. Differential scanning calorimetry (DSC) measurements were carried out from
small pieces cut from moulded composites.

2.3 Thermal conductivity and density measurements

A thermal conductivity analyzer (FOX 200, Saugus, MA, USA) was used to determine the
steady-state effective thermal conductivity of the molded polymer and composites at 25°C

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Crystallization and Thermal Properties of Biofiber-Polypropylene Composites 133

in accordance with ASTM C518. 2002. Each run took 0.5 h, but the first 5 min was used to
bring the samples to the steady-state condition. The density of the test materials was
measured by using a gas (nitrogen)-operated pycnometer (Quantachrome Corp., Boynton
Beach, FL, USA) to measure the volume of the samples and their mass was determined
using a Galaxy 160D weighing scale (OHAUS Scale Corporation, Florham Park, NJ, USA).

2.4 Differential scanning calorimetry

DSC (TA Instruments, New Castle, DE, USA) measurements were performed in a TA
Instrument model 2000 DSC equipped with a cooling system to assess crystallization
properties of the materials. Samples were heated from 40°C to 200°C at a heating rate of
10°C/min and held for 5 min to erase the thermal history of the polymer. Then, the samples
were cooled down at the desired rate (5, 10, 15 and 20°C/min) to analyze and investigate the
crystallization kinetics. The degree of crystallinity (Xc) in biocomposites corrected for
biofibers was determined by integration of the generated DSC exotherms. The crystallinity
of PP or the matrix in the composites was calculated using equation (1).

H c
Xc %   100 (1)
H c0

Where ∆Hºc is the heat of crystallinity of 100% crystalline PP assumed to be 146.5 J/g
(Lonkar, et al. 2009) and ∆Hc is taken as the enthalpy of crystallization corrected for biofiber
in the composites assuming that the contribution of this fraction is ignored.

Fiber PP/MAPP/Fiber Formulation (%)

- PP 100/0/0
C1 85/0/15
C2 80/5/15
Untreated fiber
C3 70/0/30
C4 65/5/30
C5 85/0/15
C6 80/5/15
Alkaline treated fiber
C7 70/0/30
C8 65/5/30
Table 1. Components of the composites based on polypropylene and flax fiber.

3. Results and discussion

Chemical analysis of the (retted) flax fiber before pretreatment showed that the mass
fractions of cellulose, hemicellulose and lignin were 80.9%, 7.9% and 1.4%, respectively.
These changed to 85%, 6.2% and 1.2%, respectively, after mercerization.

3.1 Thermal conductivity

The thermal conductivity values determined at 25C for the slab-shaped test materials are
given in Table 2. It can be seen that thermal conductivity decreased in all composites

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134 Thermoplastic – Composite Materials

compared to the unreinforced plain PP which means that flax fiber can increase the thermal
insulation property of polymers. The reduction in thermal conductivity is due to the
inherent low thermal conductivity of cellulosic materials in comparison to the unreinforced
plain polymer. A close observation shows that the thermal conductivity of the composites
C6 and C8 (those containing treated fiber, plain PP and MAPP) was slightly higher than
similar composites reinforced with untreated fiber (i.e., C2 and C4). This is probably due to
the ability of MAPP to improve cross links between the fiber and matrix as reported by Kim
et al. (2006).

Density Thermal conductivity

Fiber Material
(g cm-3) (W/m°C)
- PP 0.901 0.152
C1 0.956 0.133
C2 0.957 0.133
Untreated fiber
C3 1.006 0.126
C4 1.013 0.126
C5 0.964 0.135
C6 0.963 0.137
Alkaline treated fiber
C7 1.021 0.130
C8 1.022 0.133
Table 2. Density and thermal conductivity of PP (polypropylene) and composites(C1 to C8
as indicated by Table 1).

3.2 Crystallization behavior

Figure 1 shows the DSC exotherms obtained for samples cooled from the melt at different
cooling rates (5 to 20ºC/min). The crystallization temperature (Tc) and crystallinity (Xc%) of
the test materials are presented in Table 3.
The effect of cooling rate on the shape and relative position of the peak temperature (i.e.,
crystallization temperature, Tc) of the exotherms can be readily discerned from Figure 1 and
Table 3. All the curves shifted to lower temperatures as heating rate increased. It can be
observed that the higher the cooling rate, the lower the crystallization temperature and
degree of crystallinity. The data indicate that the average shift in crystallization temperature
for composites is approximately 6C as the cooling rate increased from 5 to 20C/min. For
pure PP, it is about 4ºC. The crystallinity of both pure PP and composites decreased with the
cooling rate apparently because the low cooling rates provide higher fluidity and diffusivity
for the polymer matrix molecules, thereby improving secondary crystallization and
inducing more crystallinity at high temperatures than at high cooling rates. Furthermore,
the results also indicate that the addition of fiber increased crystallinity of the test materials.
This is attributed to the nucleation effect of the fibers which provide nucleation sites and
facilitate crystallization of the polymer as well as transcrystallinity (Somnuk et al. 2007). It
can also be discerned from Table 3 that the contribution of biofiber in the composites not
only increased crystallinity of the material, but also increased crystallization temperature at
the same cooling rate (Table 3).

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Crystallization and Thermal Properties of Biofiber-Polypropylene Composites 135

PP
50

45

40

35 5 ºC/min
10 ºC/min
30
Heat Flow

15 ºC/min
25
20 ºC/min
20

15

10

0
95 100 105 110 115 120 125 130 135
Tem perature (ºC)
C6
40

35
5 ºC/min
30 10 ºC/min
15 ºC/min
25 20 ºC/min
Heat flow

20

15

10

0
95 100 105 110 115 120 125 130 135
Tem perature (ºC)
C8
35

30 5 ºC/min
10 ºC/min
25 15 ºC/min
20 ºC/min
Heat flow

20

15

10

0
95 100 105 110 115 120 125 130 135
Tem perature (ºC)

Fig. 1. Non-isothermal crystallization thermograms of PP (polypropylene), C6

(PP/MAPP/Fiber: 80/5/15) and C8 (PP/MAPP/Fiber: 65/5/30) at different cooling rates.

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136 Thermoplastic – Composite Materials

Formulation 5 ºC/min 10 ºC/min 15 ºC/min 20 ºC/min

Tc Xc(%) Tc Xc(%) Tc Xc(%) Tc Xc(%)
(ºC) (ºC) (ºC) (ºC)
PP 115.3 59.5 113.4 59.1 112.2 59.6 111.1 58.2
C1 123.4 63.1 120.1 62.9 118.3 62.1 116.9 61.2
C2 125.1 62.3 122.3 62.5 120.5 61.0 119.3 61.0
C3 124.8 66.4 121.7 65.9 120.0 65.2 118.7 65.1
C4 126.1 63.2 123.1 62.0 121.4 61.0 120.1 60.0
C5 122.6 62.1 119.2 61.9 117.3 60.5 115.9 60.2
C6 125.3 61.4 122.0 60.3 120.4 60.1 119.1 60.0
C7 124.5 65.2 121.0 64.2 119.3 64.0 118.1 63.1
C8 126.3 62.8 123.3 61.8 121.5 60.9 120.3 60.5
PP: polypropylene; C1 to C8: composites; Tc: crystallization temperature; Xc: crystallinity.
Table 3. Crystallization temperature and crystallinity of PP and biocomposites at different
cooling rates (5, 10, 15 and 20 ºC/min).

The use of the compatibilizer seems to have reduced the level of crystallinity in the
composites for the same levels of fiber loading, while it resulted in a marginal increase in the
crystallization temperature. For instance, at the cooling rate of 5ºC/min, the crystallization
temperature increased from 124.5ºC to 126.3ºC, while the crystallinity decreased from 65.2%
to 62.8% for C7 and C8, respectively; and this could be attributed to the application of
MAPP in C8. In the same vein, chemical pretreatment seems to marginally reduce the
degree of crystallinity for all composites irrespective of their fiber content in comparison
with composites reinforced with the untreated fiber with or without the compatibilizer.
Therefore, among all formulations, the highest value of crystallinity was obtained for
composite sample C3 at the cooling rate of 5ºC/min.
Fiber mercerization also slightly caused the reduction of crystallization temperature at the
constant level of fiber loading as well as constant cooling rate only for samples without MAPP,
but it almost did not have any influence on crystallization temperature with the presence of
MAPP. For example, at the cooling rate of 10ºC/min, crystallization temperature changed
from 120.1ºC for C1 to 119.2ºC for C5 and this is only because of the chemical modification.
The values of onset temperature (T0), end temperature of crystallization exotherm (Te), peak
time (tc) and half crystallization time (t0.5) determined for all samples at different cooling
rates are summarized in Table 4. It can be seen that these four parameters decreased with
increasing cooling rate. The application of MAPP in the composites reduced the half-time of
crystallization for composites reinforced with pretreated and untreated biofiber. For
example, t0.5 decreased from 55 to 48 s for C7 and C8 at 5ºC/min, respectively. However, the
magnitude of reduction in half-time due to the compatibilizer was less at high cooling rates.
Also, a comparison of the data in Table 4 indicates that chemical pretreatment of the fiber
increased the magnitude of t0.5 in the biocomposites at the same level of fiber content and
cooling rate. This result is consistent with those reported by Garbarczyk et al. (2000) who
observed that PP crystallized faster when reinforced with untreated natural fiber than with
chemically modified fibers. Furthermore, a close look at the data shows that lowest value of
half crystallization time occurred in pure PP for all cooling rates. Although its crystallinity is
lower at all cooling rates, it is observed that non-isothermal crystallization occurred faster in
PP than in the biocomposites.

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Crystallization and Thermal Properties of Biofiber-Polypropylene Composites 137

Formu- 5 ºC/min 10 ºC/min 15 ºC/min 20 ºC/min

lation T0 Te tc t0.5 T0 Te tc t0.5 T0 Te tc t0.5 T0 Te tc t0.5
(ºC) (ºC) (s) (s) (ºC) (ºC) (s) (s) (ºC) (ºC) (s) (s) (ºC) (ºC) (s) (s)
PP 116.9 103.3 29 26 114.9 101.9 17 16 113.7 98.5 13 13 112.7 97.8 10 10
C1 128.0 111.4 59 55 125.2 104.2 34 31 123.5 103.3 25 23 122.3 102.1 19 18
C2 128.8 112.5 50 46 125.9 106.1 26 25 124.2 106.1 19 18 122.9 104.7 14 14
C3 128.6 112.8 50 49 125.9 107.8 29 28 124.3 105.9 21 20 123.2 103.1 17 16
C4 130.1 109.7 53 48 127.3 110.2 29 26 125.7 107.8 20 19 124.4 104.5 16 15
C5 127.4 110.2 61 57 124.4 104.9 34 32 122.7 104.7 25 23 121.5 102.1 20 19
C6 129.2 111.8 52 48 126.1 108.3 29 27 124.4 106.4 20 19 123.1 103.8 16 15
C7 128.9 111.1 57 55 125.9 109.5 32 31 124.3 105.9 23 22 123.2 103.5 18 17
C8 130.4 112.8 53 48 127.6 123.3 30 28 126.0 109.0 21 19 124.8 105.2 17 16
PP: polypropylene; C1 to C8: composites; T0: onset temperature, Te: end temperature of crystallization, tc:
peak time and t0.5: half crystallization time.
Table 4. Crystallization parameters obtained from DSC exotherms.

3.3 Modeling of crystallization

The relative degree of crystallinity (Xt) was calculated from the relationship in equation (2) as:

T
T ( dHc dT )dT
Xt  T
0
(2)
T
0
dH c / dT )dT

where dH denotes the enthalpy of crystallization measured during the time interval dt and
T is the end temperature of crystallization. Figure 2 shows typical plots of relative
crystallinty vs. temperature obtained for representative samples of the tested materials (PP,
C6 and C8). Similar plots were obtained for all samples tested in this study. It can be seen
that the shape of the curves is sigmoidal. It can be observed from these plots that, for the
cooling rates studied, PP crystallized at lower temperatures than the composite materials.
The activation energy for crystallization (∆E) was determined for pure PP and the
biocomposite samples using the Kissinger model (1957) shown in equation (3).

E d(ln( Tc2 ))

 (3)
R d(1 T c )

where R is the universal gas constant (kJ/mol.K) and φ is the cooling rate. The values of
activation energy for PP and its composites were determined from the slope of the linear
plots shown in Figures 3 and 4. It can be seen from Table 4 that the addition of biofiber
markedly reduced the activation energy for crystallization in pure PP. The low activation
energy for crystallization obtained for the composites is consistent with their high
crystallinity reported in Table 3, which could be attributed to the fact that biofibers, being
high energy sites, lowered the activation energy for nucleation as similarly reported by Page
& Gopakumar (2006). A close inspection of the data in Table 4 for the composites shows that
at each level of fiber content, the application of MAPP increased their activation energy. For
instance, it was increased from 287 to 306 kJ/mol for C7 and C8, respectively.

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138 Thermoplastic – Composite Materials

The Avrami model given in equation (4) is used extensively to evaluate the isothermal
kinetics of polymer crystallization:

1 – X t  exp kt n  (4)

where Xt is the relative crystallinity at time t and constant temperature; k is the

crystallization rate constant containing the nucleation and growth rates and is temperature
dependent; and n is the Avrami index or exponent which depends on the type of nucleation
and growth process. Ozawa (1971) extended the Avrami model to non-isothermal processes
by assuming that they are the result of infinitely small changes in the isothermal
crystallization steps and obtained:


1 – X t  exp  x /  m  (5)

where m is the Ozawa exponent which is dependent on the nucleation density and the
spherulitic radial growth rate and x is a function of the overall crystallization rate.
The linearized form of equation (5) is given as:

ln  ln  1  X t    ln x – m ln (6)

Hence, a plot of ln[−ln(1 − Xt)] vs. ln(t) has a slope of m and a y-intercept of ln(x).
By combining the Avrami and Ozawa models, Liu et al. (1997) introduced another
crystallization kinetic model:

ln  lnF  T  – a lnt (7)

where F(T) = [x/k]1/m refers to the crystallization kinetic parameter and a is the ratio of the
exponents in Avrami and Ozawa models : a = n/m
Typical results of kinetic analysis of the DSC data using the Ozawa model are shown in
Figure 5 for PP, C6 and C8, while Table 5 summarizes the results for all formulations.
As shown, the maximum value of x for pure PP is much higher than the values obtained for
composites indicating that PP crystallized faster than the matrix in the composites. Amongst
the composites, it can be observed in Table 5 that the value of x was affected by fiber content
or by compatibilizer for a given fiber content. The parameter m decreased with decreasing
temperature for all test materials. Its value ranged from 0.6 to 5.0 for PP and from 1 to 4.2 for
the composites. The more limited range of m values obtained for the composites indicates
that the crystal growth rate of spherulites was higher in PP than in the composites. This
agrees with the result reported by Somnuk et al. (2007) for PP and natural fiber-based
composites such that the spherulitic growth rate was higher in neat PP than composites.
However, in their study, composites exhibited a higher rate of crystallization compared to
neat PP which is different from the result in this study. The F(T) values obtained from the
Liu et al. (1997) model increased systematically with the relative crystallinity of pure PP and
composites as shown in Table 6. Also, at a given relative crystallinity, the values of F(T) are
lower for PP than for the composites at most levels of Xt which indicates that crystallization
was faster in pure pp compared to the composites. Furthermore, the application of MAPP in
the composites resulted in low values of F(T) or higher crystallization rates.

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Crystallization and Thermal Properties of Biofiber-Polypropylene Composites 139

PP
1.2

5 °C/min
0.8
10 °C/min
0.6
Xt

15 °C/min
20 °C/min
0.4

0.2

0
95 100 105 110 115 120 125 130 135
Tem perature (°C)
C6
1.2

1
5 °C/min
0.8 10 °C/min
15 °C/min
0.6
Xt

20 °C/min

0.4

0.2

0
95 100 105 110 115 120 125 130 135
Tem perature (°C)
C8
1.2

1
5 °C/min
0.8 10 °C/min
15 °C/min
0.6
Xt

20 °C/min

0.4

0.2

0
95 100 105 110 115 120 125 130 135
Tem perature (°C)

Fig. 2. Relative crystallinity of PP (polypropylene), C6 (PP/MAPP/Fiber: 80/5/15) and C8

(PP/MAPP/Fiber: 65/5/30) at different cooling rates.

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140 Thermoplastic – Composite Materials

-8.6
-8.8
-9
-9.2 PP
-9.4
Ln(Ø/Tc2)

C1
-9.6 C2
-9.8 C3
-10 C4
-10.2
-10.4
-10.6
0.00248 0.00252 0.00256 0.0026
1/Tc (K-1)

Fig. 3. Kissinger plots of crystallization activation energies of PP (419 kJ/mol) and non-
compatibilized formulations: C1 (292 kJ/mol ), C2 (314 kJ/mol), C3 (297 kJ/mol) and C4
(310 kJ/mol). PP: polypropylene ; C1, C2, C3 and C4: composites formulations.

-8.6
-8.8
-9
-9.2 PP
-9.4
Ln(Ø/Tc2)

C5
-9.6 C6
-9.8 C7
-10 C8
-10.2
-10.4
-10.6
0.00248 0.00252 0.00256 0.0026
1/Tc (K-1)

Fig. 4. Kissinger plots of crystallization activation energies of PP (419 kJ/mol) and

compatibilized formulations: C5 (272 kJ/mol), C6 (297 kJ/mol), C7 (287 kJ/mol) and C8 (306
kJ/mol). PP: polypropylene ; C5, C6, C7 and C8: composites formulations.

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Crystallization and Thermal Properties of Biofiber-Polypropylene Composites 141

PP
3
116 ºC
1 114 ºC
112 ºC
-1
110 ºC
ln(-ln(1-xt))

108 ºC
-3

-5

-7

-9
1 1.5 2 ln(Ø) 2.5 3 3.5
C6
3

126 ºC
1
124 ºC
122 ºC
-1
120 ºC
ln(-ln(1-xt))

118 ºC
-3

-5

-7

-9
1 1.5 2 2.5 3 3.5
ln(Ø)
C8
3

126 ºC
1
124 ºC
122 ºC
-1
120 ºC
ln(-ln(1-xt))

118 ºC
-3

-5

-7

-9
1 1.5 2 2.5 3 3.5
ln(Ø)

Fig. 5. Ozawa plots for non-isothermal melt crystallization of polypropylene (PP) and
composites : C6 (PP/MAPP/Fiber: 80/5/15) and C8 (PP/MAPP/Fiber: 65/5/30).

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142 Thermoplastic – Composite Materials

Material T(ºC) m x R2
PP 108 0.6 14.9 0.92
110 0.7 10.0 0.83
112 1.9 99.5 0.84
114 4.1 1998.2 0.96
116 5.0 1212.0 0.99
C1 118 1.4 40.4 0.97
120 2.0 81.5 0.99
122 2.5 99.5 0.99
124 2.9 73.4 1.00
126 3.4 49.4 1.00
C2 118 0.8 16.4 0.96
120 1.3 33.1 0.94
122 2.2 109.9 0.96
124 2.9 164.0 1.00
126 3.3 99.5 1.00
C3 118 1.0 22.2 0.98
120 1.5 40.4 0.97
122 2.3 99.5 0.98
124 3.0 148.4 1.00
126 3.6 121.5 0.99
C4 118 0.7 14.9 0.92
120 1.0 22.2 0.93
122 1.8 66.7 0.96
124 2.5 148.4 0.99
126 3.1 134.3 1.00
C5 118 1.8 66.7 0.99
120 2.3 109.9 0.99
122 2.8 109.9 1.00
124 3.3 81.5 1.00
126 4.2 109.9 0.99
C6 118 0.8 16.4 0.94
120 1.3 36.6 0.95
122 2.3 121.5 0.98
124 2.9 200.3 1.00
126 3.3 109.9 1.00
C7 118 1.1 27.1 0.97
120 1.7 44.7 0.98
122 2.3 90.0 0.99
124 2.7 81.5 1.00
126 3.0 36.6 1.00
C8 118 0.7 14.9 0.93
120 1.0 22.2 0.94
122 1.7 60.3 0.96
124 2.4 134.3 0.99
126 2.9 109.9 1.00
PP: polypropylene; C1 to C8: composites; m and x: Ozawa constants, and R2: coefficient of
determination.
Table 5. Kinetic parameters obtained for PP and the composites, T: temperature; using the
Ozawa model.

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Crystallization and Thermal Properties of Biofiber-Polypropylene Composites 143

Material xt(%) F(T) B R2

PP 20 6.7 1.0 0.99
40 7.4 1.0 0.99
60 8.2 1.0 0.99
80 9.0 1.1 0.99
C1 20 7.4 1.2 1.00
40 10.0 1.2 1.00
60 11.0 1.2 1.00
80 13.5 1.2 1.00
C2 20 6.7 1.2 1.00
40 9.0 1.2 1.00
60 10.0 1.2 1.00
80 11.0 1.1 1.00
C3 20 6.1 1.3 0.99
40 8.2 1.3 0.99
60 9.0 1.3 1.00
80 11.0 1.3 1.00
C4 20 6.7 1.1 0.99
40 9.0 1.1 1.00
60 10.0 1.1 1.00
80 11.0 1.1 1.00
C5 20 8.2 1.1 0.95
40 10.0 1.2 0.97
60 11.0 1.2 0.97
80 13.5 1.2 0.98
C6 20 8.2 1.1 1.00
40 10.0 1.1 1.00
60 11.0 1.1 1.00
80 12.2 1.1 1.00
C7 20 7.4 1.3 1.00
40 10.0 1.3 1.00
60 11.0 1.3 1.00
80 13.5 1.3 1.00
C8 20 6.7 1.3 0.99
40 8.2 1.3 1.00
60 10.0 1.3 1.00
80 12.2 1.3 1.00

Table 6. Kinetic parameters obtained for PP (polypropylene) and its composites (C1 to C8)
using the model of Liu et al. (1997).

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144 Thermoplastic – Composite Materials

PP
3.5

3 0.2
0.4
2.5
0.6
2 0.8
ln(Ø)

1.5

0.5

0
-1.5 -1 -0.5 0 0.5 1
ln(t)
C6
3.5
0.2
3
0.4
2.5 0.6
0.8
2
ln(Ø)

1.5

0.5

0
-1.5 -1 -0.5 0 0.5 1
ln(t)
C8
3.5

0.2
3
0.4
2.5 0.6
0.8
2
ln(Ø)

1.5

0.5

0
-1.5 -1 -0.5 0 0.5 1
ln(t)

Fig. 6. Non-isothermal crystallization plots based on Liu et al. (1997) model. PP:
polypropylene; C6 (PP/MAPP/Fiber: 80/5/15) and C8: (PP/MAPP/Fiber: 65/5/30).
composites.

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Crystallization and Thermal Properties of Biofiber-Polypropylene Composites 145

4. Conclusions
From the experimental results, the following conclusions can be drawn:
1. The thermal conductivity and non-isothermal crystallization kinetics of biofiber-
reinforced PP composites were influenced by fiber content and chemical modifications
of the biofiber.
2. The addition of fiber reduced the thermal conductivity of pure PP.
3. The biocomposites exhibited higher crystallinity, crystallization temperature, half-time
but lower crystallization rate than pure PP,.
4. Composites fabricated with chemically-modified fibers exhibited lower degree of
crystallinity than those reinforced with untreated fibers.
5. The addition of MAPP into the composites accelerated the crystallization process but
had a negative impact on the degree of crystallinity.
6. The important process parameter of cooling rate also was strongly effective on the
behaviour of crystallization in that involving higher cooling rate resulted to lower
degree of crystallinity and lower crystallization temperature, but accelerated
crystallization process. Activation energy of crystallization determined using Kissinger
model for composites (around 300 kJ/mol) was much lower than that of PP (419
kJ/mol) in this study which is consistent with the degrees of crystallinity.
7. Analyzing the data using Ozawa and Liu et al. models resulted to a good linearity and
conclusion.

5. References
ASTM C518. 2002. Standard Test Method for Steady-State Heat Flux Measurements and
Thermal Transmission Properties by Means of the Heat Flow Meter Apparatus,
Philadelphia, PA.
ANKOM Technology (2005) ANKOM Technology Method.
http://www.ankom.com/09_procedures/ procedures.shtml .
Garbarczyk, J. & Borysiak, S. (2000). Crystallization of isotactic polypropylene at surfaces of
cellulose natural fibers. 3rd International Wood and Natural Fibre Composites
Symposium Kassel, Germany.
Kim, S.W.; Lee, S.H.; Kang, J.S. & Kang, K.H. (2006). Thermal conductivity of thermoplastics
reinforced with natural fibers. International Journal of Thermophysics vol.27, No.6, pp.
1873-1881, ISSN 1572-9567.
Kissinger, H.T. (1957). Reaction Kinetics in Differential Thermal Analysis. Analytical
Chemistry Vol.29, No.11, pp. 1702-1706, ISSN 0003-2700.
Liu, T.; Mo, Z.; Wang, S. & Zhang, H. (1997). Nonisothermal melt and cold crystallization
kinetics of poly(aryl ether ether ketone ketone). Polymer Engineering & Science
Vo.37, No.3, pp. 568-575, ISSN 1548-2634.
Lonkar, S.P.; Morlat-Therias, S.; Caperaa, N.; Leroux, F,; Gardette, J.L. & Singh, R.P. (2009).
Preparation and nonisothermal crystallization behavior of polypropylene/layered
double hydroxide nanocomposites. Polymer Vol.50, No.6, pp. 1505-1515, ISSN
0032-3861.

www.intechopen.com
146 Thermoplastic – Composite Materials

Mucha, M. & Krolikowski. (2003). Application of DSC to study crystallization kinetics of

polypropylene containing fillers. Journal of Thermal Analysis and Calorimetry Vol.74,
pp. 549-557, ISSN 1572-8943.
Ozawa, T. (1971). Kinetics of non-isothermal crystallization, Polymer 12(3): 150-158.
Page, D.J.Y.S. & T.G. Gopakumar. (2006). Properties and crystallization of maleated
polypropylene/graphite flake nanocomposites. Polymer Journal Vol.38, No.9, pp.
920-929, ISSN 0032-3896.
Reiter, G. & Strobl, G.R. (2007). Progress in understanding of polymer crystallization. Springer-
Verlag Berlin Heidelberg. NY, USA.
Seo, Y.; Kim, J.; Kim, K.U. & Kim, Y.C. (2000). Study of the crystallization behaviors of
polypropylene and maleic anhydride grafted polypropylene. Polymer Vol.41, pp.
2639-2646, ISSN 0032-3861.
Somnuk, U.; Eder, G.; Phinyocheep, P.; Suppakarn, N.; Sutapun, W. & Ruksakulpiwat, Y.
(2007). Quiescent crystallization of natural fibers-polypropylene composites. Journal
of Applied Polymer Science Vol.106, pp. 2997–3006, ISSN 1097-4628.
Zhang, X.; Xie, F.; Pen, Z. & Zhang, Y. & Zhou W. (2002). Effect of nucleating agent on the
structure and properties of polypropylene/poly (ethylene–octene) blends. European
Polymer Journal Vol.38, No.1, pp. 1-6, ISSN 0014-3057.

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 Thermoplastic - Composite Materials
Edited by Prof. Adel El-Sonbati

ISBN 978-953-51-0310-3
Hard cover, 146 pages
Publisher InTech
Published online 16, March, 2012
Published in print edition March, 2012

Composite materials often demand a unique combination of properties, including high thermal and oxidative
stability, toughness, solvent resistance and low dielectric constant. This book, "Thermoplastic - Composite
Materials", is comprised of seven excellent chapters, written for all specialized scientists and engineers dealing
with characterization, thermal, mechanical and technical properties, rheological, morphological and
microstructure properties and processing design of composite materials.

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Polypropylene Composites, Thermoplastic - Composite Materials, Prof. Adel El-Sonbati (Ed.), ISBN: 978-953-
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