Thermochimica Acta 545 (2012) 148156

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Thermochimica Acta
journal homepage: www.elsevier.com/locate/tca

Non-isothermal crystallization kinetics of peroxide-crosslinked polyethylene:

Effect of solid state mechanochemical milling
Hejun Wu, Mei Liang , Canhui Lu
State Key Laboratory of Polymer Materials Engineering, Polymer Research Institute of Sichuan University, Chengdu 610065, China

a r t i c l e

i n f o

Article history:
Received 21 April 2012
Received in revised form 13 June 2012
Accepted 10 July 2012
Available online 16 July 2012
Keywords:
Non-isothermal crystallization kinetics
Crosslinked polyethylene
Decrosslinking
Mechanochemical milling

a b s t r a c t
The inuence of solid state mechanochemical milling process on the non-isothermal crystallization of
peroxide-crosslinked-low-density polyethylene (peroxide-XLPE) was investigated via differential scanning calorimetry (DSC) at different cooling rates. Peroxide-XLPE was partially decrosslinked during
mechanochemical milling process. The Avrami method modied by Jeziorny, the Ozawa method and
the Mo method were applied to describe the non-isothermal crystallization process of peroxide-XLPE,
decrosslinked XLPE (de-XLPE) and pure LDPE successfully. The results revealed that the decrosslinking effect could accelerate the crystallization process of XLPE due to the higher chain mobility after
mechanochemical milling, which was conrmed by the values of half crystallization time (t1/2 ), crystallization rate exponent Zc , parameter K(T) and F(T).
2012 Published by Elsevier B.V.

1. Introduction
Crosslinked polyethylene (XLPE) has been widely used as
an insulation material in power cables because of its excellent
mechanical properties and dielectric properties [13]. However,
the three-dimensional network structure formed after crosslinking not only improves its desirable properties [4], but also changes
polyethylene from a thermoplastic to a thermoset [5]. Therefore, it
is very difcult to recycle XLPE due to its low uidity and poor moldability caused by crosslinking. Currently, as the country updates
its electrical infrastructure, waste XLPE from scrap power transmission and distribution cables is becoming a signicant disposal
concern. There are some ways to recycle the waste XLPE, including
conversion into fuel by thermal and catalytic cracking [6,7], and
the use as a powdery ller by blending with thermoplastics in an
extruder to make a thermoplastic recycled polymer [8]. Thermal
and catalytic cracking might be accompanied by a large amount of
energy consumption since it is usually carried out at high temperatures [9], and the poor mechanical properties caused by random
decomposition of the polymer chain during extrusion may also
limit the applications of powdered XLPE as a ller [10].
Considering the prevention of environmental pollution and
resource conservation, the development of more effective recycling technologies of XLPE is desired. Some researchers have
proposed the application of supercritical uids such as water
[11], methanol [12], and alcohol [13] as a recycling method to

Corresponding author. Tel.: +86 28 85460607; fax: +86 28 85402465.

E-mail addresses: liangmeiww@163.com (M. Liang), canhuilu@263.net (C. Lu).
0040-6031/$ see front matter 2012 Published by Elsevier B.V.
http://dx.doi.org/10.1016/j.tca.2012.07.008

achieve selective decrosslinking at crosslinking points of XLPE

which is difcult in conventional processes. For example, Lee et
al. [12] studied a decrosslinking reaction of XLPE in supercritical methanol using a batch reactor and developed a rst-order
kinetics on the basis of experimental results in which the reaction rate was linearly proportional to the gel concentration and
related exponentially to the temperature model. However, problems still persist because the critical temperature and pressure
of these supercritical uids are high [14], relating to the high
cost of equipment and difculty for continuous processing. Thus,
it remains a technological challenge to develop a more effective method for recycling XLPE without any additional materials
and chemicals at ambient temperature. Recently, an eco-friendly
mechanochemical technology called solid state mechanochemical
milling using a pan-mill equipment to recycle crosslinked polymers has been developed in our laboratory [1519]. This method
has been proved to have many advantages over other conventional
recycling methods, such as the fact that it can be conducted at ambient temperature, is chemical free, has low energy consumption, and
is more favorable for the environment. The pan-mill equipment was
designed in the authors laboratory for solid-state mechanochemical reactions of polymers [20], showing multifunction, such as
pulverizing, dispersion, mixing, and activation [2125]. In our previous work [18], it has been demonstrated that the solid state
mechanochemical milling process can be utilized as an effective method to recycle waste XLPE by partial decrosslinking. The
selective decrosslinking was successfully achieved at crosslinking
elements by mechanochemical milling, and consequently led to the
higher chain mobility of XLPE which might affect its crystallization
process.

H. Wu et al. / Thermochimica Acta 545 (2012) 148156

It is well-known that crystallization behaviors play an important role in the physical, chemical, and mechanical properties of
polymers. Moreover, from the practical view the non-isothermal
crystallization is more useful than the isothermal crystallization because most processing techniques actually occur under
non-isothermal conditions [26]. Therefore, it is of great signicance to understand the effect of milling process on the
thermal behavior and the crystallization kinetics of XLPE, due
to the fact that the resulting physical properties are strongly
dependent on the morphology formed and the extent of crystallization occurring during processing [27]. There are extensive
papers on studying the non-isothermal crystallization kinetics of
polyethylenes [2836], but few publications have been found concerning to the studies of non-isothermal crystallization kinetics of
crosslinked polyethylenes [37,38], especially peroxide-crosslinked
polyethylene (peroxide-XLPE), not to mention the case with the
decrosslinked peroxide-XLPE (de-XLPE). Because of this, more work
should be done to study the non-isothermal crystallization kinetics
of peroxide-XLPE, as well as the inuences of the mechanochemical
milling process on its non-isothermal crystallization behavior.
In this article, to investigate the effect of the decrosslinking on
the non-isothermal crystallization kinetics of XLPE, low-density
polyethylene (LDPE) was crosslinked by dicumyl peroxide (DCP)
without further additives, and then subjected to solid state
mechanochemical milling using a pan-mill equipment to obtain
decrosslinked XLPE (de-XLPE). Several theoretical models were
applied to describe the process of non-isothermal crystallization based on the differential scanning calorimeter (DSC) data.
Simultaneously, pure LDPE was analyzed in the same process for
comparison.
2. Experimental

149

Fig. 1. Effect of mechanochemical milling on the gel content of XLPE.

parameters during milling: the velocity and force. The repetition

operation continued for 20 cycles to produce decrosslinked XLPE.
2.3. Characterization
2.3.1. Determination of gel content
The gel content of crosslinked and decrosslinked samples was
determined gravimetrically, according to ASTM D 2765, using a 24h soxhlet extraction cycle, with p-xylene as the solvent at 140 C.
Approximately 0.3 g weighed samples were cut into small pieces
and placed in a pre-weighted stainless steel, ne wire mesh. After
the extraction cycle, the samples were washed with acetone and
vacuum-dried to a constant weight. The gel fraction was calculated
as the percentage ratio of the nal weight of the polymer to its
initial weight.

2.1. Materials
Low density polyethylene (LDPE 1254NT) was obtained from the
Dow Chemical Company, with a melt index of 8 g/10 min and a density of 0.918 g/cm3 . The crosslinking agent employed was dicumyl
peroxide (DCP, >99% purity), provided by SinopecShanghaiGaoQiao
Petrochemical Corporation.
2.2. Preparation of samples
LDPE was mixed with 1.5 wt % DCP on a two roll mill at 110 C
for 58 min. At this state the DCP was mixed with LDPE without
going through chemical reactions because the mixing temperature was not sufcient to activate the peroxide initiation reactions.
Afterwards, the samples were compressed molded at 170 C for
15 min under 15 MPa, and then cooled to ambient temperature at
the same pressure, obtaining the peroxide-crosslinked polyethylene (peroxide-XLPE) sheets of 2 mm thickness.
A pan-mill type mechanochemical reactor was used to perform
the decrosslinking of XLPEs at ambient temperature, as described in
the previous article [18]. The sheets of XLPE were chipped into granules (510 mm in diameter) with a rotary blade chipping machine.
After that, the chips of XLPE were fed in hopper set at the middle
of the moving pan at a rotating speed of 30 rpm from the inlet and
driven by shear force, moving along a spiral route toward the edge
of the pan until they came out from the outlet. The discharged powder was collected for the next cycle of milling. The average retention
time of the powder during milling was 2540 s per cycle, and the
heat generated during milling was removed by water circulation.
The chain-transmission system and a screw-pressure system were
set to regulate the rotation speed of the moving pan and imposed
load, respectively, which could strictly control two major dynamic

2.3.2. Differential scanning calorimetry (DSC) measurement

The non-isothermal crystallization was carried out by a differential scanning calorimeter (DSC-204, Netzsch, Germany). Samples
weighing about 5 mg were cut off for characterization. Nitrogen
purge gas with a ux of 40 ml/min was used to prevent thermal
degradation of samples during scanning. All samples were rst
quickly heated at 40 C/min up to 180 C and held isothermally for
5 min to eliminate the thermal history of the polymers, and then
they were cooled to room temperature at four different cooling
rates: 2.5, 5, 10, and 20 C/min, respectively.
3. Results and discussion
3.1. Effect of mechanochemical milling on the gel content of XLPE
To elucidate the effect of mechanochemical milling on the nonisothermal crystallization kinetics of XLPE, LDPE was crosslinked by
1.5 wt% DCP, and then subjected to 20 cycles of mechanochemical
milling using a pan-mill equipment to obtain decrosslinked XLPE.
The effect of mechanochemical milling on the gel content of XLPE
is shown in Fig. 1. It was evident that the gel content decreased
remarkably after mechanochemical milling, from its initial 62.3 to
14.6% after 20 cycles of milling. This indicated that the crosslinked
structure of XLPE was broken during the mechanochemical milling
process, which made the soluble fractions of the samples increase.
As the results of our previous article [18], it was conrmed by the
SEC test that the molecular weights of the sol fraction of XLPE before
and after decrosslinking were close, which further demonstrated
that the XLPE was fairly selectively decomposed at the crosslink
points rather than at random sites [1012]. As illustrated in Fig. 2,
the crosslinking points of XLPE additionally made the chains

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H. Wu et al. / Thermochimica Acta 545 (2012) 148156

Fig. 2. Scheme for the decrosslinking process of XLPE.

prestressed to move physically close enough to become crosslinked

and also restricted the movement of the molecular chains. Therefore, when the molecular network and the entire structure was
in motion during mechanochemical milling, the crosslinked structure of XLPE would most likely have had a higher opportunity for
chain scissions and been broken preferably, because it had the highest stress and moment under the action of the adequately strong
squeezing and shearing forces exerted by the pan-mill equipment.
3.2. Non-isothermal crystallization behavior
The non-isothermal crystallization of XLPE, de-XLPE, LDPE from
the melt at four cooling rates of 2.5, 5, 10, and 20 C/min was
studied using DSC. Fig. 3 shows the nonisothermal crystallization
exotherms of all samples at a cooling rate of 2.5 C/min. It can be
seen from Fig. 3 that both pure LDPE and de-XLPE has a single
peak, whereas XLPE seems to have double peaks. The appearance of
bimodal peaks for XLPE at low cooling rate is caused by the formation of network after crosslinking, which may work as a physical
barrier for the crystal growth and consequently yield peak with
lower crystallization temperature. Similar results are reported by
Jiao et al. for silane-crosslinked LLDPE [37] and Hutzler et al. for

irradiated LDPE [39]. The onset temperature (To ), which is the temperature at the crossing point of the tangents of the baseline and
the high temperature side of the exotherm, the peak temperature
(Tp ), the crystallization enthalpy (Hc ) and the relative crystallinity
(Xc ), dened by the ratio of Hc to the heat of fusion of the purely
crystalline form of PE, Hf0 (Hf0 = 289.9 J/g [40]) derived from
the DSC curves are listed in Table 1.
It could be found that Tp shifted toward lower temperature and
the exothermic peak became broader with increasing cooling rates
for all samples. As is known, the faster cooling rate means the
shorter time stayed at every temperature for the polymer matrix
to develop crystallization from the melt, and thus the crystallization process is restrained. Meanwhile a wider temperature range
was needed for the samples to accomplish their crystallization as
the cooling rate increased. Furthermore the increase of cooling
rate could also make the crystal structure imperfect and irregular, which then induced the lower Hc and Xc . It should be noticed
that for a given cooling rate, values of these aforementioned parameters listed in Table 1 followed the order: XLPE < de-XLPE < LDPE,
which could be explained by the partial decrosslinking effect during
mechanochemical milling. The crystallization process of LDPE was
hindered after the crosslinking because XLPE formed a net structure. In contrast, mechanochemical milling could primarily result
in partial decrosslinking at the crosslinking points of XLPE, which
destroyed its crosslinked structure to make the macromolecule
chains more exible. So the crystallization became easier, and consequently the crystallization temperature and relative crystallinity
of de-XLPE became higher than those of XLPE.
3.3. Non-isothermal crystallization kinetics
In order to further analyze the non-isothermal crystallization
process, the crystallization kinetics of XLPE, de-XLPE, and LDPE
were compared. The relative crystallinity as a function of crystallization temperature, XT , was calculated as the ratio of the
exothermic peak areas [4143] according to Eq. (1):

T
XT =

To

Fig. 3. DSC thermograms of non-isothermal crystallization for XLPE (a), de-XLPE (b),
and LDPE (c) at the cooling rate of 2.5 C/min.

(dHc /dT )dT

 To

(1)

(dHc /dT )dT

where To and T are the onset and end crystallization temperature, respectively, T is an arbitrary crystallization temperature at

H. Wu et al. / Thermochimica Acta 545 (2012) 148156

151

Table 1
Characteristic data of nonisothermal crystallization exotherms for XLPE, de-XLPE, and LDPE at different cooling rates.
Sample

Cooling rate (K/min)

To ( C)

Tp ( C)

Hc (J/g)

Xc (%)

t1/2 a (min)

XLPE

2.5
5
10
20

112.8
112.0
110.8
109.0

109.1
106.8
103.0
97.1

100.0
97.3
91.7
85.8

34.5
33.6
31.6
29.6

1.60
1.13
0.91
0.61

de-XLPE

2.5
5
10
20

116.2
115.2
114.1
112.3

111.2
109.5
107.8
104.5

135.2
132.7
128.2
112.7

46.6
45.8
44.2
38.9

1.94
1.09
0.70
0.43

LDPE

2.5
5
10
20

118.7
118.0
117.0
114.9

116.6
114.7
112.0
108.2

194.3
192.9
189.5
168.9

67.0
66.5
65.4
58.3

1.04
0.78
0.62
0.41

The half crystallization time, dened as the time from the onset of crystallization to the time at which the relative crystallinity is 50% from Fig. 4.

time t, and dHc is the enthalpy of crystallization released during

an innitesimal temperature interval dT. The horizontal temperature scale can be transformed into the time domain based on the
following equation in which the stands for the cooling rate:



 To T 


t=

(2)

As a representation, the plot of the relative degree of crystallinity

as a function of time, Xt , for all samples at different cooling rates is
illustrated in Fig. 4. It could be seen clearly from Fig. 4 that the higher
the cooling rate, the shorter the time for completing the crystallization process. The half crystallization time (t1/2 ), dened as the time
from the onset of crystallization to the time at which the relative
crystallinity is 50%, can be directly estimated from Fig. 4 and the
results are listed in Table 1. As expected, the value of t1/2 decreased
with increasing cooling rates for all samples, indicating that the
polymer crystallized faster when the cooling rate is increased. At a
given cooling rate, the value of t1/2 for de-XLPE was lower than that
for XLPE except at 2.5 C/min. On the basis of the molecular motion
theory, the crystallization of XLPE is affected by the crosslinking
density of its molecules. The mechanochemical milling process
could destroy the crosslinked structure of XLPE and increase the sol
fraction (decreased the crosslinking density) with different molecular weights of de-XLPE. When the cooling rate was low enough,
for example at 2.5 C/min, it might allow more molecular chains
with different molecular weights of de-XLPE to entrance into crystalline regions, resulting in a higher t1/2. Nevertheless, this different
in t1/2 between de-XLPE and XLPE is almost negligible, and both the
To and Tp of de-XLPE are higher than those of XLPE at the cooling
rate of 2.5 C/min as listed in Table 1. In this case, it can still be
concluded that the decrosslinking effect due to mechanochemical
milling could accelerate the overall crystallization process.
For the analysis of the experimental results of XLPE, de-XLPE,
and LPDE under non-isothermal conditions, the modied Avrami
equation, the Ozawa analysis, and the Mo method were applied
to describe their crystallization process to obtain the parameters
characterizing the kinetics of non-isothermal crystallization.
3.3.1. Avrami method
The Avrami method [44,45] is most widely applied in describing
the isothermal crystallization kinetics of polymers. According to
the Avrami theory the relative crystallinity at a time t, Xt , can be
calculated from the following equation:
Xt = 1 exp(Zt t n )

(3)

where n is the Avrami crystallization exponent dependent on the

type of nucleation mechanism and growth parameters, t is the
time taken during the crystallization process, Zt is a composite rate

constant involving both nucleation and growth rate parameters. Eq.

(3) can be liberated in its double logarithmic form as:
ln[ ln(1 Xt )] = ln Zt + n ln t

(4)

Plotting ln[ln(1 Xt )] versus ln t for each cooling rate, a straight

line would be obtained and the values of n and Zt can be calculated
from the slopes and intercepts of the lines, respectively.
It should be noted that n and Zt in non-isothermal crystallization do not have the same physical signicance as in the isothermal
crystallization because temperature is lowered constantly during non-isothermal crystallization. Considering the non-isothermal
character of the process investigated, Jeziorny [46] extended the
isothermal Avrami equation to the nonisothermal situation by
proposing that the rate parameter Zt should be corrected by cooling
rate as follows:
ln Zc =

ln Zt

(5)

where Zc is the corrected kinetic rate constant. According to the

previous reports [47], the half crystallization time, can also be calculated from the corrected constant using the equation
t1/2 =

 ln 2 1/n

(6)

Zt

The plots of ln[ln(1 Xt )] versus ln t at different cooling rates are

given in Fig. 5 and the results obtained from the Avrami plots and
Jeziorny method are summarized in Table 2 as well.
On the whole, the good linearity of the curves (correlation coefcient R2 > 0.99) in Fig. 5 demonstrates that the Avrami equation ts
well with the non-isothermal crystallization kinetics of all samples.
For LDPE, the Avrami plots shown in Fig. 5c were also linear over the
Table 2
Non-isothermal crystallization kinetic parameters based on the Avrami and Jeziorny
method.
Sample

(K/min)

Zt

R2

Zc

t1/2 a (min)

XLPE

2.5
5
10
20

2.63
2.48
2.35
2.30

0.18
0.49
1.06
2.22

0.998
0.998
0.997
0.996

0.50
0.87
1.00
1.04

1.67
1.15
0.83
0.60

de-XLPE

2.5
5
10
20

2.40
2.38
2.32
2.26

0.17
0.67
2.09
5.03

0.997
0.997
0.996
0.997

0.49
0.92
1.08
1.08

1.80
1.01
0.62
0.42

LDPE

2.5
5
10
20

2.09
2.12
2.12
1.97

0.70
1.31
1.79
4.52

0.996
0.997
0.996
0.994

0.87
1.06
1.06
1.08

1.00
0.74
0.64
0.39

a
The half crystallization time calculated from the corrected kinetic rate constant
Zc by Eq. (6).

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H. Wu et al. / Thermochimica Acta 545 (2012) 148156

Fig. 4. Relative crystallinity versus time of XLPE (a), de-XLPE (b), and LDPE (c) at
various cooling rates.

whole range implying that it had only one crystallization process,

and this was different from the result of Ref. [48] in which the secondary crystallization of LDPE was observed. This difference may be
due to the initial portion of short ethylene branches in LDPE which
could inhibit its overall crystallization behavior [35,36]. LDPE used
in this study might have fewer short ethylene branches since its
crystallinity as listed in Table 1 was almost more than 65%.
The values of Avrami exponents n for all the samples were
between 2 and 3, suggesting that crystallites are two- or
three- dimensional and nucleation may be between instantaneous

Fig. 5. Plots of ln[ln(1 Xt )] versus ln t for the non-isothermal crystallization of

XLPE (a), de-XLPE (b), and LDPE (c) at various cooling rates.

and sporadic [49]. These values of n were consistent with corresponding literature data reported for polyethylene in range from 2
to 4 (mostly for isothermal crystallization) [5052]. It could be seen
that for all samples the values of Zc increased and t1/2 decreased
as the cooling rate increased, which meant an increase of crystallization rate. For a given cooling rate, Zc for de-XLPE was higher
than that for XLPE and t1/2 for de-XLPE was lower, signifying that
de-XLPE had a faster crystallization rate than XLPE. This could be
explained by the enhanced mobility of the polymer chains due to

H. Wu et al. / Thermochimica Acta 545 (2012) 148156

Fig. 6. Ozawa plots of ln[ln(1 Xt )] versus ln for the non-isothermal crystallization of XLPE (a), de-XLPE (b), and LDPE (c) at different temperatures.

decrosslinking of XLPE after mechanochemical milling. In addition,

the uniformity of measured and calculated values of t1/2 (listed
in Tables 1 and 2, respectively) also indicated clearly that modied Avrami equation can be used to describe the non-isothermal
crystallization kinetics of XLPE, de-XLPE and LDPE.

153

Fig. 7. Plots of the ln versus ln t for the non-isothermal crystallization of XLPE (a),
de-XLPE (b), and LDPE (c) at different degrees of crystallinity.

3.3.2. Ozawa method

The Ozawa equation has been successfully used for describing the non-isothermal crystallization of many polymers [5357],
including some polyethylene [37]. However, the nonlinearity of the
Ozawa plot for polyethylene was also found in some literatures
[32,58,59]. Thereby, it is necessary to investigate the validity of the
Ozawa model for the samples used in the current paper.

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H. Wu et al. / Thermochimica Acta 545 (2012) 148156

Table 3
Non-isothermal crystallization kinetic parameters based on the Ozawa method.
Temperature ( C)

XLPE

107
108
109
110
111
112

de-XLPE
2

K(T)

K(T)

K(T)

R2

1.75
1.89
2.01
2.13

8.76
6.30
3.82
1.75

1.00
1.00
1.00
0.98

1.38
1.42
1.53
1.70
1.65
1.73

16.78
12.43
9.49
8.08
7.17
2.59

0.99
0.99
0.98
0.95
0.99
0.98

1.60
1.67
1.71
1.80

47.47
40.85
33.12
27.11

0.99
1.00
1.00
1.00

According to the Ozawa theory [60], the non-isothermal crystallization process is the result of an innite number of small
isothermal crystallization steps and the degree of conversion or
relative crystallinity Xt can be calculated as follows:
1 Xt = exp

 K(T ) 
m

ln[ ln(1 Xt )] = ln K(T ) m ln

Table 4
Non-isothermal crystallization kinetic parameters based on the Mo method.
Sample

Xt (%)

F(T)

R2

XLPE

20
40
60
80

2.05
2.16
2.23
2.28

2.66
5.31
9.12
15.64

0.98
0.99
0.99
0.99

de-XLPE

20
40
60
80

1.33
1.38
1.40
1.45

3.13
5.00
7.10
9.87

1.00
1.00
1.00
0.99

LDPE

20
40
60
80

1.93
2.15
2.21
2.20

1.05
2.12
4.10
7.85

0.97
0.97
0.98
0.97

(7)

where is cooling rate, m is Ozawa exponent that depends on

the dimension of crystal growth, and K(T) is the cooling crystallization function, which is related to the overall crystallization rate and
indicates how fast crystallization occurs. The above equation can be
written as
(8)

Studying the process at different cooling rates and plotting

ln[ln(1 Xt )] against ln at a given temperature, a straight line
should be obtained if the Ozawa method is valid, and parameters
of m and K(T) can be determined from the slope and intercept,
respectively.
The Ozawa plots of XLPE, de-XLPE and LDPE are presented in
Fig. 6. In order to obtain a reliable and comparable result from
least-square lines drawn through plots of at least three points, the
temperature range varies from sample to sample, lying in the range
of 107112 C. It was shown obviously in Fig. 6 that the lines of the
Ozawa plots for a certain sample were linear and nearly parallel,
indicating that that the Ozawa model is suitable for describing the
non-isothermal crystallization kinetics of XLPE, de-XLPE and LDPE.
Values of m and K(T) as well as the corresponding correlation coefcient R2 for each sample are summarized in Table 3. For all the
samples, the Ozawa exponent m was found to roughly increase with
increasing temperature, while the Ozawa rate constant K(T) was
found to decrease, suggesting that the higher the temperature was,
the slower the polymers crystallized. For a given temperature, the
value of K(T) for de-XLPE was higher than that for XLPE, suggesting
that de-XLPE had a faster crystallization rate. This result was also
in agreement with the previous observations of the parameters Zc
and t1/2 obtained through the modied Avrami method mentioned
above.
Moreover, based on the corresponding correlation coefcient
R2 , it can be concluded fairly that the Ozawa method is a satisfactory description of the non-isothermal crystallization kinetics of
polyethylene studied in this article, regardless of whether or not it
is crosslinked [61]. The most possible reason for this may be that
primary crystallization these polymers played a predominant role
and the second crystallization could be neglected [32,36,62], which
was in favor of the results of the Avrami analysis.
3.3.3. Mo method
By combining the Ozawa and Avrami equations, a method
modied by Mo [63] has been successfully employed to describe
the non-isothermal crystallization kinetics of various polymers
[6467]. The nal form of modied equation is given as follows:
ln = ln F(T ) ln t

LDPE

(9)

where the parameter F(T) = [K(T)/Zt ]1/m refers to the value of cooling rate chosen at unit crystallization time when the system has
a certain degree of crystallinity, m is the Ozawa exponent, and
refers to the ratio of the Avrami exponent n to the Ozawa exponent
m ( = n/m).
According to Eq. (9), at a given degree of crystallinity the plot
of ln versus ln t for a certain sample would yield a straight line
as shown in Fig. 7, and the value of a and F(T) could be obtained
by the slope and the intercept of the line as listed in Table 4. It
could be seen clearly that the plots showed a good linear relationship between ln and ln t, verifying obviously that Mo method
described appropriately the non-isothermal crystallization kinetics
of all samples.
The values of F(T) and systematically increased with a rise in
the relative degree of crystallinity. F(T) has a denite physical and
practical meaning, for a given degree of crystallinity, the higher the
value of F(T), the higher the cooling rate needed within unit crystallization time, indicating the difculty of polymer crystallization.
By comparing the values of F(T) of different samples, it was found
that the values of de-XLPE were almost lower than those of XLPE,
indicating that the crystallization rate of de-XLPE was faster than
that of XLPE. This was in good accordance with the results obtained
from the Avrami and Ozawa approach.
4. Conclusions
It have been demonstrated that solid state mechanochemical
milling using a pan-mill equipment is a good method to recycle
XLPE by partial decrosslinking. In order to investigate the effect of
milling process on the crystallization kinetics of XLPE, three different kinetic models of the Avrami, the Ozawa and the Mo were
applied to systematically study the non-isothermal crystallization
kinetics of XLPE, de-XLPE and LDPE based on the DSC technique.
All the three models were found to describe the experimental data
very well.
The parameters Zc and t1/2 derived from the modied Avrami
method suggested that de-XLPE had a faster crystallization rate
than XLPE due to the higher chain mobility resulted from partial

H. Wu et al. / Thermochimica Acta 545 (2012) 148156

decrosslinking. K(T) from the Ozawa method revealed a tendency

that accorded well with results of the Avrami method. In addition,
the Ozawa method was found to be a satisfactory description of
the non-isothermal crystallization process of LDPE for its secondary
crystallization was not obvious and could be neglected. From the
Mo method, the value of F(T) of de-XLPE was found to be lower than
that of XLPE, which also indicated that the decrosslinking effect of
mechanochemical milling could accelerate the overall crystallization process.
Acknowledgments
This study is supported by the National Natural Science Foundation of China (50903053 and 51073108) and the Applied Basic
Research Programs of Science and Technology Commission Foundation of Sichuan Province (2010JY0022), and the authors would
like to thank Analytical and Testing Group of Polymer Research
Institute of Sichuan University for providing DSC measurements
facility.
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