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Melting behavior and isothermal crystallization kinetics of PP/mLLDPE blends

Article in Journal of Polymer Research · October 2008

DOI: 10.1007/s10965-008-9186-2

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J Polym Res (2008) 15:413–420
DOI 10.1007/s10965-008-9186-2
Melting behavior and isothermal crystallization kinetics
of PP/mLLDPE blends
Jianglei Qin & Shaoqiang Guo & Zhiting Li
Received: 15 October 2007 / Accepted: 3 March 2008 / Published online: 25 April 2008
# Springer Science + Business Media B.V. 2008
Abstract The melting/crystallization behavior and isother-
mal crystallization kinetics of polypropylene (PP)/metal-
locene-catalyzed linear low density polyethylene
(mLLDPE) blends were studied with differential scanning
calorimetry (DSC). The results showed that PP and
mLLDPE are partially miscible and interactions mainly
exist between the mLLDPE chains and the PE segments in
PP molecules. The isothermal crystallization kinetics of the
blends was described with the Avrami equation. Values of
the Avrami exponent indicated that crystallization nucle-
ation of the blends is heterogeneous, the growth of
spherulites is almost three-dimensional, and the crystalliza-
tion mechanism of PP is not affected much by mLLDPE.
The Avrami exponents of the blends are higher than that of
pure PP, showing that the mLLDPE helps PP to form
perfect spherulites. The crystallization rates of PP are
decreased by mLLDPE because the crystallization temper-
ature of PP was decreased by addition of mLLDPE and
consequently the supercooling of the PP was correspond-
ingly lower. The crystallization activation energy was
estimated by the Friedman equation, and the result showed
that the activation energy increased by a small degree by
addition of mLLDPE, but changed little with increasing
content of mLLDPE in the blends. The nucleation constant
(Kg) was determined by the Hoffman–Lauritzen theory.
Supported by the Science Foundation of Hebei University (2006Q13).
J. Qin (*) : S. Guo : Z. Li
College of Chemistry and Environmental Science,
Hebei University,
Baoding 071002, China
e-mail: qinjl@mail.hbu.cn
Keywords Polypropylene (PP) . Metallocene-catalyzed
linear low density polyethylene (mLLDPE) .
Melting behavior . Isothermal crystallization kinetics .
Activation energy
Introduction
Polypropylene (PP) is a semicrystalline thermoplastic
polymeric material that has been widely used because of
its attractive combination of good processability, mechan-
ical properties, and chemical resistance. However, its
application in some fields is limited due to its low fracture
toughness at low temperature and high notch sensitivity at
room temperature. To improve the impact property of PP,
physical and chemical methods are practiced. In physical
methods, compounding PP with a dispersed elastomeric
phase is widely practiced [1–6], because the elastomer can
increase the overall toughness of the PP matrix [7];
however, the addition of elastomer often causes negative
effects on some properties of PP, such as stiffness and
hardness [8]. In chemical methods, copolymers of propyl-
ene with low ethylene fraction can improve the impact
property to a large degree and a lot of such polypropylene
has been mass produced. However, even if the impact
strength of polypropylene is high, further modification of
its impact property may still be necessary in certain fields,
as reported in some recent studies [9, 10].
The development of metallocene catalysts has led to
production of numerous new polyolefin materials, both
elastomeric and nonelastomeric. Metallocene-catalyzed
linear low density polyethylene (mLLDPE) is a kind of
nonelastomeric polyolefin material with a narrow molecular
mass distribution. Owing to its good thermal stability, good
mechanical properties, and puncture strength, mLLDPE can
414
endow PP with higher impact strength and other properties
compared with conventional elastomeric modifiers and at
the same time retain good processibility and tensile strength
[10]. In addition, mLLDPE is granular in form and therefore
the processing technology used when blending with PP (e.g.,
extrusion and injection molding) is convenient.
It is well known that the physical properties of
semicrystalline polymeric materials strongly depend on
their crystallinity and microstructure; thus, investigations
of the crystallization behavior are significant both theoret-
ically and practically. In particular, the isothermal crystal-
lization kinetics can afford the Avrami exponent, which
indicates the growing pattern and nucleation mechanism of
the spherulites. Therefore, it is highly desired to investigate
the crystallization kinetics in order to optimize the blend
composition and understand the properties of the products.
However, such detailed investigations on PP/mLLDPE
have not been reported yet.
In this study, the melting behavior and isothermal
crystallization behavior of PP/mLLDPE blends were inves-
tigated; the Avrami analysis was applied to investigate
isothermal crystallization kinetics and nucleation mecha-
nism; the activation energy was calculated with the Friedman
equation; and the nucleation constant (Kg) was determined
by the Hoffman–Lauritzen theory.
Experimental
Materials and sample preparation
The PP [Type k8303, melting flow rate (230 °C/2.16 kg)=
1.9 g/10 min] used in this study was a kind of propylene
impact copolymer, supplied by Yanshan Petrochemical Co.,
China. The mLLDPE [type ECD342, melting flow index
(190 °C/2.16 kg)=1.0 g/10 min] was obtained from Exxon
Petrochemical Co.
Blending process were carried out in a corotational twin-
screw extruder with L/D=28 (TE-34, Coperion Keya,
Nanjing China); the temperature of the barrel was set at
220 °C. The weight ratios of mLLDPE in the blends were
0%, 10%, 20%, 40%, and 100%.
Thermal analysis
A Perkin-Elmer DSC-7 apparatus was used to investigate
the melting/crystallization behavior and isothermal crystal-
lization kinetics of the blends. All the operations were
carried out under a nitrogen environment. The temperature
and melting enthalpy were calibrated with standard indium.
Sample weight was about 9 mg.
For melting and crystallization behavior, samples were
heated from room temperature to 200 °C at a rate of 10 °C/
J. Qin et al.
min. In order to erase the thermal history, the temperature
was held at 200 °C for 1 min, and then cooled to 50 °C at a
rate of 10 °C/min. For studies of isothermal crystallization
behavior, samples were heated from room temperature to
200 °C and maintained for 1 min, then cooled to the required
crystallization temperature (122–130 °C) at a cooling rate of
150 °C/min and held for 30 min to record the heat flow. The
half-time of isothermal crystallization (t1/2) is defined as the
time taken for 50% crystallization.
Results and discussion
Melting and crystallization behavior of PP/mLLDPE blends
Figure 1 shows the melting heat flow of pure polymers and
their blends. Both the pure PP and pure mLLDPE show two
peaks in the melting process. These are because the PP is a
copolymer of propylene with a low ethylene fraction
formed in a sequential reactor, and the mLLDPE is the
copolymer of ethylene and other kinds of α-olefins. The
two heat flow peaks of PP occur separately at 114.0 °C
and 165.5 °C; the 114.0 °C peak should be the melting
point of PE segments in the PP matrix, but it cannot be
distinguished in the blend system because of disturbance
from the mLLDPE melting peak. The two heat flow
peaks of mLLDPE occur separately at 109.3 °C and
117.5 °C; the 109.3 °C peak should be the melting
temperature of the branches in the spherulites because of
its low stability. The melting temperature of the main PP
(Tm2) heat flow peak decreases with increasing mLLDPE
content (Table 1); however, the melting temperature of the
main mLLDPE (Tm1) heat flow peak also decreases with
Fig. 1 DSC melting heat flow of PP/mLLDPE blends at a heating rate
of 10 °C/min
Melting behavior and isothermal crystallization kinetics of PP/mLLDPE blends
Table 1 Melting temperature (Tm) and crystallization temperature (Tc)
of PP/mLLDPE blends with different mLLDPE content
Sample mLLPE (%) Tm1 (°C) Tm2 (°C) Tc1 (°C)
0 114.0 165.5 93.5
10 114.3 164.8 99.8
20 115.5 164.5 101.5
40 116.3 163.5 103.0
100 109.3 117.5 103.0
The heating and cooling rates are 10 °C/min
increasing PP content. This observation indicates that there
is some interaction between PP and mLLDPE chains,
which is attributed to the partial miscibility between
molecules of PP and mLLDPE. The decrease in the main
heat flow peak of mLLDPE indicated that the main
interactions occur between the mLLDPE chains and the
PE segments in PP copolymer molecules. The melting
temperature (Tm2) of PP in the blends is between 163.5 and
165.5 °C. This indicates that PP, both in the pure state and
in the blends, exhibits only α-crystalline form because the
melting temperature of the α-crystalline form is in the range
of about 160–176 °C [11, 12].
Studies of the crystallization behavior of pure PP, pure
mLLDPE, and their crystallizable blends were also
performed from the molten state by DSC at a cooling rate
of 10 °C/min. Figure 2 shows the crystallization exotherms
for some PP/mLLDPE blends compared with pure PP and
pure mLLDPE, respectively. All DSC traces show two
crystallization peaks including those of pure polymers,
indicating that these systems of blends have two crystalliz-
able components. The two exotherm peaks of mLLDPE
occur separately at 103 °C and 67 °C. The two exotherm
peaks of PP occur at 115.8 °C and 93.5 °C, hence
confirming that the PP is a copolymer of propylene and
ethylene. Crystallization of PP (Tm2) occurs much earlier
than that of mLLDPE upon cooling. The effect of mLLDPE
on PP is similar to that of melting: the crystallization
temperature of the PP matrix decreases with increasing
mLLDPE content, and the crystallization temperature of
mLLDPE decreases with increasing PP content. The
interactions mainly exist between the mLLDPE and PE
segment in pure PP molecules.
Isothermal crystallization kinetics
The isothermal crystallization behavior of samples at
different temperatures was studied with DSC. Figure 3
shows the heat flow of samples that have been isothermally
crystallized at different temperatures. The chosen crystalli-
zation temperatures were determined through a series of
experiments conducted at various crystallization temper-
415
atures. From Fig. 3 we can see that the pure PP and PP/
mLLDPE can crystallize at the same temperatures, and the
Tc2 (°C) shape of the exotherm peaks are similar; however, the time
taken for crystallization to begin (t0) and peak time (tp) are
115.8 different with increasing mLLDPE content: t0 and tp
116.0
increase with increasing mLLDPE content in the blends
114.0
114.0 (Table 2). For a particular sample, exothermal peaks shift to
– longer times and t0 and tp increased with increasing
crystallization temperature, which shows that the higher
the supercooling, the higher the crystallization rate is, and
the crystallization is enhanced as temperature decreases.
The Avrami equation [13, 14] has been widely used to
describe isothermal crystallization kinetics [15–17] and
modified to describe nonisothermal crystallization kinetics
of polymers [16–22]:
1
Xt ¼ expð
kt n Þ ð1Þ
where Xt is the relative crystallinity, k is the growth rate
constant, and n is the Avrami exponent. Here, the value of
the Avrami exponent (n) depends on the nucleation
mechanism and growth dimension, e.g., n=4 indicates the
nucleation mechanism is homogenous and n=3 indicates
the nucleation mechanism is heterogeneous. The parameter
k is a function of the nucleation and the growth rate. In
isothermal crystallization kinetics, the crystallization time
(t) should be expressed as:
t ¼ tc
t0 ð2Þ
where t0 is the time taken for crystallization of the blend
system to begin.
Fig. 2 DSC cooling heat flow curves of PP/mLLDPE blends at a
cooling rate of 10 °C/min
416 J. Qin et al.

ƒFig. 3 DSC isothermal crystallization curves for PP/mLLDPE blends

with different mLLDPE mass ratio (a 0%, b 20%, c 40%) at various
crystallization temperatures

The relative crystallinity (Xt), as a function of crystalli-

zation time (t), is defined as:
Rt
ðdH=dt Þdt
0
Xt ¼ R1 ð3Þ
ðdH=dt Þdt
0

where dH/dt is the heat flow rate, and t=0 and t=∞ are the
times at which crystallization starts and ends, respectively.
Figure 4 shows the relative crystallinity versus t for PP/
(20%) mLLDPE blends at various temperatures. All curves
in Fig. 4 show a sigmoidal shape, indicating a fast primary
process during the initial stages and slower secondary
process during the later stages. The plot of Xt versus t shifts
to the right with increasing crystallization temperature,
showing the decrease of crystallization rate, indicating that
crystallization rate is enhanced as temperature decreases.
That is because of the strong temperature dependence of the
nucleation and the growth parameters [23]. After the
maximum in the heat flow curves has passed, a small
fraction of crystallinity develops by slower, secondary
kinetics processes.
Assuming the relative degree of crystallinity increases
with increasing crystallization time, the Avrami equation
can be rewritten in a double logarithm form:
lg½
lnð1
Xt Þ ¼ lgðk Þ þ n lgðt Þ ð4Þ

Table 2 Isothermal crystallization parameters of PP/mLLDPE blends

at different crystallization temperatures

Sample T (°C) n log k t0 (min) t1/2 (min) tp (min)

mLLDPE (%)

0 122 2.33 −0.090 0.4 0.93 0.85

124 2.44 −0.625 0.4 1.54 1.45
126 2.28 −1.10 0.6 2.61 2.50
128 2.18 −1.60 0.9 4.71 4.80
130 2.15 −2.10 1.05 8.15 8.10
122 2.35 −0.139 0.55 1.03 0.95
124 2.54 −0.782 0.7 1.77 1.70
20 126 2.82 −1.49 0.9 2.99 2.70
128 2.95 −2.17 1.0 4.81 4.75
130 3.05 −2.85 1.2 7.65 7.65
122 2.54 −0.481 0.55 1.35 1.35
124 2.61 −1.02 0.7 2.15 2.10
40 126 2.79 −1.70 0.7 3.60 3.50
128 2.89 −2.34 0.8 5.75 5.70
130 2.99 −3.01 1.0 9.02 8.95
Melting behavior and isothermal crystallization kinetics of PP/mLLDPE blends
Fig. 4 Plot of relative crystallinity (Xt) versus crystallization time (t)
for PP/(20%) mLLDPE blends at various crystallization temperatures
where the Avrami exponent (n) is a constant that depends
on the nucleation and growth mechanism of the crystals; k
is the crystallization rate constant involving both nucleation
and growth rate parameters under isothermal conditions.
Usually, the values of n should be an integer between 1 and
4 for different crystallization mechanisms. Since other
complex factors, such as the competition with a diffusion-
controlled growth and/or to the irregular boundary of the
spherulites, are probably involved during the process, the
Avrami exponent (n) is not a straight forward integer [24].
By plotting lg[−ln(1−Xt)] versus lgt, we can obtain n and
lgk from the slope and intercept, respectively; the lg[−ln
(1−Xt)] versus lgt plots of PP/(20%) mLLDPE are shown in
Fig. 5. Each plot exhibits good linear behavior, indicating
that the Avrami equation properly describes the isothermal
crystallization behavior of these samples with Xt ranges
from 10 to 90%. Similar shapes and trends appear in pure
PP and PP/(40%) mLLDPE blends.
All lines in Fig. 5 are almost parallel, shifting to less
time with decreasing crystallization temperature. This
implies that the nucleation mechanism and crystal growth
geometries are similar, although the crystallization temper-
atures are different. The Avrami exponents are estimated
from the plot of lg[−ln(1−Xt)] versus lgt, and the values are
listed in Table 2. Regardless of the temperatures, the
Avrami exponents (n) for the pure PP are in the range of
ca. 2.15–2.44, comparable with literature data obtained
under isothermal conditions [25, 26], indicating that the
heterogeneous nucleation and growth of spherulites are
between two-dimensional and three-dimensional. The
Avrami exponents for the PP/mLLDPE blends are in the
range of ca. 2.35–3.05, and larger than that of pure PP. These
results show that mLLDPE helps PP to form more perfect
spherulites, but exhibits no obvious nucleation effect. The
417
following mechanism describes in more detail how mLLDPE
influences crystallization behavior of PP: At crystallization
temperatures, because of the high supercooling, the mobility
of PP chains is not high enough to transit from amorphous
state to growing crystal, and the spherulites are not perfect;
however, at that temperature, the mLLDPE molecules are
unable to crystallize, and the mobility of mLLDPE chains is
still high; at the same time, the partial miscibility and
interaction of PP and mLLDPE lead to a small part of the PP
chains dissolving into the molten mLLDPE (the mobility of
dissolved PP is much higher than in pure PP), and the PP
chains can then transit to growing crystal and form compact
spherulites through the molten mLLDPE. Because the
mLLDPE cannot form solid nuclei at crystallization temper-
atures, the nucleation mechanism of PP is not obviously
affected.
However, the crystallization rate is dependent upon the
blend composition and crystallization temperature. On the
one hand, for pure PP, the crystallization rate constant (k)
increases with decreasing crystallization temperature,
whereas the half-time of crystallization (t1/2) decreases with
decreasing crystallization temperature (see Table 2). Similar
trends in k and t1/2 are observed for the PP/(20%)mLLDPE
and PP/(40%) mLLDPE blends. On the other hand, k and
t1/2 are also influenced by the addition of mLLDPE, i.e., at
the same crystallization temperature, the k slightly
decreases with increasing mLLDPE content, and the t1/2 is
adversely affected. Thus, the crystallization rate is deceler-
ated by introduction of mLLDPE into PP, which is due to
the partial miscibility of PP and mLLDPE decreasing the
crystallization temperature of PP. So at the same crystalli-
zation temperature, the supercooling is then decreased by
addition of mLLDPE, and the crystallization rates are
enhanced by supercooling. At the same crystallization
temperatures, the mLLDPE improves the mobility of PP
Fig. 5 Avrami plot of PP/(20%) mLLDPE blends for isothermal
crystallization at various crystallization temperatures
418 J. Qin et al.

molecules and reduces the supercooling; hence, the crystalli-

zation rate decreases but the spherulites become more perfect
with addition of mLLDPE into the PP/mLLDPE blends.
Half-time of crystallization (t1/2) is a very important
parameter, which is defined as the time at which the extent
of crystallinity (taken from the onset of the crystallization)
has reached 50% completion. The t1/2 values can always be
calculated directly from the relative crystallinity versus time
plot (see results in Table 2). From Table 2 we can see that
the tp values are near but a little lower than t1/2, which is
because of the secondary crystallization of PP, and the Xt
values are lower than 0.5 when the crystallization rate
reaches its highest value.
The t1/2 values can be determined from the measured
kinetics parameters, as follows [27]: Fig. 6 Friedman plot of dXt /dt versus 1/Tc for PP/(20%) mLLDPE

 blends at different Xt values
ln 2 1=n
t1=2 ¼ ð5Þ
k chains entered the PP crystals. This is another proof
showing miscibility of PP and mLLDPE. The crystallinity
The t1/2 values obtained from crystallinity versus time
plot and calculated from Eq. (5) are listed in Table 3 for of PP and PP/mLLDPE blends increased and then de-
comparison, and the values are very similar, showing the creased with increasing temperature, and this result indi-
cates that the mobility of PP chains increases with
good consistency of the two methods.
For all the samples, sample crystallinity (XPP) is defined increasing temperature, and the crystallinity corresponding-
as: ly increased. But when the temperature is too high, the
supercooling of PP chains is obviously lower than that at
$Hc low temperature, and it is not enough of a driving force for
Xpp ¼ ð6Þ
187:7  PP% PP molecules to transit from amorphous state to the
where 187.7 (J/g) is the 100% crystallization enthalpy of PP growing crystal, and the crystallinity therefore decreases.
[28], ΔHc is the crystallization enthalpy of PP in the pure At the same time, the addition of mLLDPE lengthened the
PP or the PP/mLLDPE blends. The Xpp values are also distances between PP chains and the crystallizing nuclei,
listed in Table 3. The Xpp values of PP/mLLDPE were and thereby decreased the overall crystallization rate.
higher than that of pure PP, meaning that the mLLDPE
Crystallization activation energy

Table 3 Comparison of t1/2 and the crystallinity of the blends at In order to obtain reliable values of the effective activation
different crystallization temperatures energy of the melt cooling process, Friedman [29] and
Vyazovkin [30, 31] developed methods to deal with the
Sample Experimental Calculated XPP
isothermal crystallization and isoconversed to deal with the
mLLDPE (%) (min) from k (min) (%)
nonisothermal crystallization kinetics. These two methods
0 0.93 0.934 36.55 afforded similar results. The Friedman equation is shown
1.54 1.55 39.48 below:
2.61 2.59 41.61

Ea
4.71 4.58 42.36 dXt =dt ¼ k0 exp
ð7Þ
8.15 7.99 40.22 RTc
1.03 0.980 41.16
1.77 1.76 42.89 The Friedman plots of ln(dXt /dt) versus 1/Tc for PP/
20 2.99 2.96 43.15 (20%) mLLDPE blends at different Xt values are shown in
4.81 4.80 44.29 Fig. 6 and the slope of ln(dXt /dt) versus 1/Tc determines Ea/
7.65 7.62 44.15 R. Figure 7 shows the dependence of the effective
1.35 1.34 44.58 activation energy (Ea) on the extent of crystallization Xt.
2.15 2.14 44.75 For each sample, the activation energy increases gradually
40 3.60 3.57 46.35
with increasing crystallinity. The activation energies of PP
5.75 5.68 45.82
9.02 8.98 43.78
increase from −385.4 to −324.4 kJ/mol with Xt increasing
from 10 to 90%. At the same time, the activation energies
Melting behavior and isothermal crystallization kinetics of PP/mLLDPE blends 419

of PP/(20%) mLLDPE and PP/(40%) mLLDPE increase

from −317.8 to −260.0 kJ/mol and from −306.3 to
−265.1 kJ/mol, respectively. This result shows that the
crystallization rate of PP is more sensitive to temperature
than that of blends, and it is easier for the polymer and the
blends to crystallize at the beginning of crystallization,
while it becomes difficult as the crystallization proceeds.
In order to further investigate the crystal growth kinetics
of PP and the blends isothermally crystallized from the
melt, secondary nucleation Lauritzen–Hoffman theory [32]
is applied to analyze the spherulitic growth rate of the
system. The crystal growth rate (G) at a given crystalliza-
tion temperature (Tc) is expressed by the following
equation:
" #  
U* Kg Fig. 8 Plot of ln(t1/2) +U*/R(Tc−) versus 1/TcΔT f of PP/mLLDPE
G ¼ G0 exp
exp
ð8Þ
RðTc
T1 Þ Tc ð$T Þf blends for isothermal crystallization at different mLLDPE content

where G0 is a pre-exponential factor, U* is the activation

energy for transporting the polymer chain segments to the calculations [32]. Plots of ln(t1/2) +U*/R(Tc−T1 ) versus 1/
crystallization site, R is the gas constant, T1 is a temperature TcΔT f of PP/mLLDPE blends for isothermal crystallization
below which the polymer chain movement ceases, ΔT is the are shown in Fig. 8. The values of Kg and ln[1/(t1/2)0] can
degree of supercooling described as Tc
Tm0 with Tm0 being be obtained from the slopes and the intercepts of lines in
the equilibrium melting point, f is a correction factor Fig. 8; the Kg and ln[1/(t1/2)0] values are listed in Table 4.
accounting for
 the variation
 in the enthalpy of fusion given The Kg of pure PP is higher than that of the PP/mLLDPE
as f ¼ 2Tc Tm0 þ Tc , and Kg is the nucleation constant. blends, showing the higher nucleation rate than of the
For practical convenience, the (1/t1/2) and (1/t1/2)0 are used to blends. The higher value of ln[1/(t1/2)0] also shows lower t1/
substitute for G and G0 in the calculation, following Chan 2 values and a higher crystallization rate. These results are
and Isayev [33]. Equation (9) is then usually rewritten as consistent with the conclusion derived from the Friedman
follows. equation that the activation energy of PP is lower than that

 "
 # of PP/mLLDPE blends.
1 U* 1 Kg
ln þ ¼ ln
ð9Þ
t1=2 R ð Tc
T 1 Þ t1=2 0 Tc ð$T Þf
Conclusions
In this work, the universal values of U* =6,300 J/mol or
1,500 cal/mol, and T1 ¼ Tg
30K are used in all The melting behavior and isothermal crystallization kinetics
of PP/mLLDPE blends, prepared by the conventional melt
blending method, were investigated and the following
conclusions were drawn: (1) The study of melting and
crystallization behavior shows that PP and mLLDPE are
partially miscible. The crystallinity of the blends decreases
with increasing mLLDPE content, indicating that the
mLLDPE enters the PP matrix. (2) The isothermal
crystallization kinetics of the blends was investigated fairly
well by Avrami analysis. The values of the Avrami

Table 4 Parameters ln[1/(t1/2)0] and Kg of PP/mLLDPE blends

calculated from the Lauritzen–Hoffman equation

Sample mLLDPE(%) Kg (K2) ln[1/(t1/2)0]

0 5.55×105 28.87
20 5.14×105 26.97
Fig. 7 Dependence of the effective activation energy (Ea) on the 40 4.94×105 25.88
extent of crystallization (Xt)
420 J. Qin et al.

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12. Ha CS, Kim SC (1988) J Appl Polym Sci 35:2211
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13. Avrami M (1939) J Chem Phys 7:1103
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to form more perfect spherulites. (3) Both the nucleation 15. LU XL, Hay JN (2001) Polymer 42:9423
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18. Ozawa T (1971) Polymer 12:150
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