Polym. Bull.

(2013) 70:81–96
DOI 10.1007/s00289-012-0781-3

ORIGINAL PAPER

Thermodegradative study of HDPE–HA

nanocomposites: IKP and E2 function

V. Hermán • C. Albano • A. Karam • G. González •

M. Covis

Received: 13 November 2011 / Revised: 9 April 2012 / Accepted: 28 May 2012 /

Published online: 7 June 2012
Ó Springer-Verlag 2012

Abstract IKP and E2 function methods were used to study thermal stability of
HDPE–HA nanocomposites synthesized by in situ ethylene polymerization at dif-
ferent volumes of solvent and temperatures. Thermal analysis was carried out at five
different heating rates, b = 3, 5, 7, 10, and 13 °C/min, under N2 atmosphere.
Kinetics parameters calculated by IKP method presented a slight increase on acti-
vation energy when HA was incorporated in HDPE. A similar tendency was
observed in the results obtained from the E2 function method, where the activation
energy of the nanocomposites increased 100 kJ/mol with respect to unfilled polymer
(420–460 kJ/mol). These results implied higher stability of HDPE due to HA
incorporation. HDPE and HDPE–HA degradation mechanisms are represented by a
set of functions, those with the highest probability were: nucleation and nucleus
growth (S3) 23 %, reaction order (S5) 16 %, reaction in the interface (S6. S7, S8)
11–14 %, and potential law (S14, S17) 3 %.

Keywords Nanocomposites  Thermal stability  Degradation mechanisms 

IKP method  E2 function method

V. Hermán (&)  A. Karam

Centro de Quı́mica, Laboratorio de Polı́meros, Instituto Venezolano de Investigaciones Cientı́ficas
(IVIC), Carretera Panamericana Km11, Caracas 1020, Venezuela
e-mail: vherman@ivic.gob.ve

C. Albano  M. Covis
Universidad Central de Venezuela, Facultad de Ingenierı́a, Escuela de Ingenierı́a Quı́mica,
Caracas 1020, Venezuela
e-mail: carmen.albano@ucv.ve

G. González
Laboratorio de Materiales, Centro de Ingenierı́a de Materiales y Nanotecnologı́a. Instituto
Venezolano de Investigaciones Cientı́ficas (IVIC), Carretera Panamericana Km11,
Caracas 1020, Venezuela

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Introduction

In recent years hydroxyapatite (HA) nanoparticles have been used as reinforce filler
for different polymeric materials [1–5]. In this type of materials high density
polyethylene–hydroxyapatite composites (HDPE–HA) have been used widely in
biomedicine since 1980s and have been available commercially as HAPEXTM from
1990, mainly due to the bioinert characteristics of HDPE and to the bioactive
properties of HA [6–9]. These composites have an interfacial interaction between
the filler and the polymeric matrix, which is translated to an improvement in
mechanical properties of the polyolefin [10, 11]. The study of the thermal properties
of these materials and possible mechanisms of degradation are very important in
order to understand their behavior under thermal heating [12].
To study the thermal stability, the composites are set under a progressive heating,
and the data obtained is evaluated using mathematical models to calculate the
kinetic parameters (Ea, A, and f(a)), involved in the degradation process [13]. All the
mathematical models that have been used are based on the Arrhenius law, and
the analysis can be made using this principal equation [14]:
da da
b ¼ kf ðaÞ ð1Þ
dt dT

where a is the degree of conversion and k ¼ AeðEa=RT Þ according to the Arrhenius

Law.
The Coast–Redfern is an integral method applied to study thermogravimetric
data in which the reaction order is assumed to be equal or different to 1, justified by
most of the decomposition reactions in solid state, following the next equations:
For n = 1
!  
1  ð1  aÞ1n AR 2 RT E
log ¼ log 1   ð2Þ
T 2 ð1  nÞ BE E 2:3 RT

For n = 1
   
 logð1  aÞ AR 2 RT E
log ¼ log 1  ð3Þ
T2 BE E 2:3 RT
On the other hand, the invariant kinetics parameters (IKP) method is a versatile
approach that allows us to calculate the kinetics parameters independent of the
heating rate, and to determine the possible degradation mechanism. This method is
based on the studied of the compensation effect, suggested by Lesnikovich and
Levchik [15–17], were the kinetic parameters are evaluated using a single experi-
mental curve: a = a(T) with different analytical forms, which are correlated through
the compensation effect:
ln A ¼ a þ b Ea ð4Þ
where a* and b* are constant compensation effect parameters. Compensation effect
is observed on each of these functions fj(a), when log (Aj) is plot versus Ej, a straight
line is obtained for each heating rate, define as [18, 19]:

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log Ajv ¼ bv þ Iv Ejv ð5Þ

where Ajv is the apparent calculated pre-exponential factor with fj(a) for bv, and Ejv
is the apparent calculated activation energy [20].
Values of bv and Iv are calculated from the intercept and the slope of the straight
lines obtained from Eq. (3). Lesnikovich and Levchik [15–17] and Levchik et al.
[20] discussed the significance of these values and demonstrated the following
relationships:
bv ¼ logðkv Þ ð6Þ
1
Iv ¼ ð7Þ
2:3RTv
where kv is the rate constant of the system at the temperature Tv; these two
parameters are characteristic of the experimental conditions.
The log kv curves are then plotted against 1/Tv, following the next equation:
Einv
logðkv Þ ¼ logðAinv Þ  ð8Þ
2:3RTv
Thus, the values of the invariant activation energies and pre-exponential factors
can be calculated from the slopes and intercepts of the curves.
On the other hand, the probabilities associated with the eighteen apparent
activation energies (Ejv) and pre-exponential factors (Ajv) are calculated using the
Coast–Redfern method [21], and then computing modeled. Kinetic functions fj(a)
may then be discriminated using the log (Ainv) and Einv values, where n is the ith
term of the experimental values of (da/dT)iv, the residual sum of squares for each
fj(a) and for each heating rate bv may be computed as [19, 22]:
Xi¼n   2

ðn  1ÞS2jv ¼  da  Ainv eðEinv=RTinv Þ fj ðainv Þ ð9Þ
 dT bv 
i¼1

The most probable function is then chosen by the average minimum value of Sj
defined by the relationship:
1X
v¼p
SJ ¼ Sjv ð10Þ
p v¼1

where p is the number of heating rates used. The probability associated with each
fj(a), value can be calculated by defining the ratio:
S2
Fj ¼ 2J ð11Þ
Smin
P 2
where S2 ¼ 1p v¼p 2
v¼1 Sjv and Smin is the average minimum of residual dispersion. This
ratio obeys the F distribution:
v
1
CðvÞ Fj2
qðFj Þ ¼ 2 v  v ð12Þ
C =2 ð1 þ Fj Þ

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where n is equal to the number of degrees of freedom for every dispersion and C is
the gamma function (function that extends the concept of factorial to complex
numbers).
The probabilities of the jth function are computed on the assumption that the
experimental data with L kinetic functions is described by a complete and
independent system of events:
X
j¼L
Pj ¼ 1 ð13Þ
j¼1

In this way, Pj can be obtained, using the function fj(a):

qðFiÞ
Pj ¼ j¼L ð14Þ
P
qðFiÞ
j¼1

Another model used is E2 function [23], an integral method that consists of a

mathematical model based on the equation of Arrhenius, that allows to calculate the
activation energy once the reaction order (n) is known, using Coats–Redfern method
[21]. In addition, three conversions (a1 = 0.05, a2 = 0.50, and a3 = 0.95) with
their decomposition temperatures are used. The equations in this mathematical
model differ according to the reaction order (n) as follows:
n=1
ð1  a1 Þ1n  ð1  a2 Þ1n T2 E2 ðE=RT2 Þ  T1 E2 ðE=RT1 Þ
1n 1n
¼ ð15Þ
ð1  a2 Þ  ð1  a3 Þ T3 E2 ðE=RT3 Þ  T2 E2 ðE=RT2 Þ
n=1
 
1a1
ln 1a2 T2 E2 ðE=RT2 Þ  T1 E2 ðE=RT1 Þ
 ¼ ð16Þ
ln 1a2 T3 E2 ðE=RT3 Þ  T2 E2 ðE=RT2 Þ
1a3

The principal advantage of E2 function model is that only one heating rate is
required, also it is reliable and easy to apply. However, more computational efforts
are required and n-value has to be found using other methods such as Coast–
Redfern.
The mathematical models previously explained were used to study the thermal
stability and possible decomposition mechanisms of HDPE–HA composite, due to
its potential applications in biomedicine.

Experimental

Materials

Calcium hydroxide and di-ammonium hydrogen phosphate were supplied by Fisher

Chemicals. For the polymerization the following reactants were used: ethylene with

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a 5.0 grade of purity (Boc Gases), toluene (Riedel de Haën, p.a.), Cp2ZrCl2 (Sigma
Aldrich), and methylaluminoxane (MAO) with 12.77 % of aluminum (Akzo
Chemicals).

Synthesis and characterization of HA

A wet chemical precipitation method was used to synthesize HA [24], with

equimolar solution of calcium hydroxide and di-ammonium hydrogen phosphate.
The resulting suspension was washed with de-ionized water and centrifuged several
times until pH neutral was achieved. Afterwards, HA was dried at 80 °C for 48 h,
and then pulverized.
Fourier transformed infrared spectroscopy (FTIR, Nicolet iS10) was used to
determine characteristic functional groups of HA, using KBr tablets and 64 scans
[24]. X-ray diffraction was used to determine the crystalline characteristics of HA
(XRD, Siemens D5005 with a Cu source) [25]. Transmission electron microscopy
was used to study morphology and dispersion of HA nanoparticles into the
polymeric matrix, samples were prepared employing a suspension technique. TEM,
Jeol JEM 1220 100 keV was used. In addition, the thermal behavior of the HA was
studied by thermogravimetric analysis using a heating rate of 10 °C/min from 25 to
700 °C, under N2 atmosphere (TGA, Mettler Toledo TGA/STA851e) [26, 27].

Synthesis of HDPE–HA composite

HDPE–HA nanostructure composites were synthesized by in situ ethylene poly-

merization. Toluene was used as solvent, previously dried, and Cp2ZrCl2/MAO as
the catalytic system. In situ ethylene polymerization was carried out at different
volumes of solvent (100–300 ml) and temperatures (10–75 °C), with a constant
percentage of HA (15 % % 0.8720 ± 0.0001 g). HA was suspend in 25 ml of
toluene and transferred to Büchi reactor using Schlenck techniques [28]. Co-catalyst
was dissolved in 10 ml of toluene, and also added to the Büchi reactor. After 10 min
of agitation a solution of pre-catalysts was transferred into the reactor. Polymer-
ization was carried out at constant ethylene pressure (1 bar) for 30 min [29]. The
reaction was quenched by addition of 10 % HCl solution in ethanol. The polymer
obtained was washed three times with ethanol, and dried in vacuum at 60 °C for
12 h.

Thermal studied of HDPE–HA composite

Thermal analysis was carried out in a Metler Toledo TGA/STA851e. All samples
were analyzed under the following conditions: *9.0–10.0 mg of HDPE–HA
nanostructure composites were heated until 700 °C under N2 atmosphere, at five
different heating rates, b = 3, 5, 7, 10, and 13 °C/min. The data obtained was
evaluated using IKP and E2 function methods.

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Fig. 1 FTIR of HA synthesized

nanocrystals

Fig. 2 DRX of HA synthesized

nanocrystals

Results and discussion

HA synthesis was extremely effective, resulting in a high yield (99 %). Charac-
terization by FTIR showed the characteristic HA functional groups (Fig. 1).
Vibration of the hydroxyl group was observed around 3,700 cm-1, while the bands
at 1429, 1089–1035, 962, 603, and 565 cm-1 correspond to the vibration modes
of the phosphate group (PO4-3) [24, 30, 31]. X-ray diffraction presented all
characteristic reflections of HA, with broad peaks, as a result of its nanometric
crystal size (Fig. 2) [24]. HA nanoparticles have needle morphology with an
average length of (55 ± 9) nm and average diameter equal to (10 ± 1) nm [25, 32],
as can be observed in Fig. 3. HA present high thermal stability, only 5 % of mass
was lost at 80 °C (Fig. 4), this mass is associated to the loss of water molecules
adsorbed on the nanoparticle surface [24].
HDPE–HA nanocomposites were obtained by ethylene in situ polymerization,
synthesized at different toluene volume and temperatures (Table 1). Each of these
compounds were analyzed by TGA at five different heating rates, b = 3, 5, 7, 10,
and 13 °C/min. IKP and E2 function methods were used to study their thermal
stability and to determine the kinetic parameters.

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Fig. 3 TEM of HA synthesized

nanocrystals

Fig. 4 TGA of HA synthesized

nanocrystals

Table 1 HDPE–HA
composites codification
Reaction conditions 2,000 rpm,
1 bar, 30 min, [Al]/[Zr] = 500
Sample Polymerization conditions
HDPE 100 ml of solvent, 25 °C
HDPE–HA_100 ml 100 ml of solvent, 25 °C, 15 % of HA
HDPE–HA_200 ml 200 ml of solvent, 25 °C, 15 % of HA
HDPE–HA_300 ml 300 ml of solvent, 25 °C, 15 % of HA
HDPE–HA_10 °C 100 ml of solvent, 10 °C, 15 % of HA
HDPE–HA_75 °C 100 ml of solvent, 75 °C, 15 % of HA

The thermograms obtained (Fig. 5) showed that the decomposition process of

HDPE–HA composites goes on a single step between 430 and 509 °C. As can be
seen on Table 2 when the heating rate increased it is observed that the initial (Tid),
final (Tfd) decomposition temperatures, and the peak temperatures (Tp) were shifted
to higher values, this could be attributed to a reduced heat transfer requiring greater
energy for the degradative processes to occur resulting in an increase in the
temperatures (Fig. 6) [23, 33].

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Fig. 5 TGA of: a HDPE, b HDPE–HA_100 ml, c HDPE–HA_200 ml, d HDPE–HA_300 ml, e HDPE–
HA_10 °C, and f HDPE–HA_75 °C

Even though a significance change in the Tid, Tfd, and Tp was not observed when
the filler was incorporated into the polymer, the slope of the thermograms changed,
as can been seen on Fig. 7, thermograms of HDPE–HA composites present a higher
slope compared to HDPE. This could indicate an increase in the stability of the
materials, although it is not reflected in the decomposition temperatures.
The IKP method allowed to determine the invariant kinetic parameters, such as
activation energy and Arrhenius pre-exponential factor that are independent of the
temperature at which the experiment was carried out (Table 3). Figure 8 showed the

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Table 2 HDPE–HA composite

Sample Heating Tid (°C) Tfd (°C) Tp (°C)
decompositions temperatures
velocity (°C)

HDPE 3 436 483 465

5 437 491 470
7 437 496 474
10 447 503 480
13 460 506 486
HDPE–HA_100 ml 3 436 482 464
5 443 490 470
7 454 496 479
10 458 503 484
13 453 505 483
HDPE–HA_200 ml 3 441 481 466
5 445 488 471
7 455 496 480
10 458 502 483
13 462 508 487
HDPE–HA_300 ml 3 436 482 465
5 448 489 473
7 455 496 475
10 459 502 483
13 461 507 486
HDPE–HA_10 °C 3 439 480 464
5 447 487 472
7 451 494 477
10 458 502 483
13 461 509 488
HDPE–HA_75 °C 3 440 481 466
5 447 489 472
Tid initial decomposition
temperature, Tfd final 7 452 494 477
decomposition temperature, 10 454 500 481
Tp maximum decomposition 13 461 507 488
temperature

compensation effect for HDPE, (log (Ajv) vs Ej), similar results were obtained for
each HDPE–HA composites [18, 19].
These results demonstrate a slight increase in the invariant kinetic parameters
when the filler was added into the polymeric matrix. This suggests that HA confers
thermal stability to polyethylene, and this can be attributed to a good dispersion of
the filler, that delays the thermodegradatives processes, in good agreement with the
observed change in slope of the thermograms (Fig. 7) [22].
By adding HA into the polymer matrix the chemical reaction kinetics slowed
down, similar results were obtained by Chrissafisa et al. [33, 34], who studied the
effect of different inorganic nanoparticles on the thermal stability of polymers, and

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Fig. 6 First derivate of: a HDPE, b HDPE–HA_100 ml, c HDPE–HA_200 ml, d HDPE–HA_300 ml,
e HDPE–HA_10 °C, and f HDPE–HA_75 °C

attributed the thermal stability improvement to different reasons, such as, shielding
effect, the gas impermeability of inorganic nanoparticles, which inhibit the
formation and escape of volatile by products during degradation, reducing the
chain mobility and consequently delaying degradation in polymer–ceramics
composites. The kinetic analysis demonstrates that the process of degradation
requires higher activation energy for the composite than for the polymer. The
highest energy barrier indicates that the presence of HA decreases molecular
mobility and consequently, increasing chemical and physical stability. During

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Fig. 7 Thermogram zooms (in the range 420–500 °C) of HDPE–HA composites at different heating
rates: a 3 °C/min and b 10 °C/min

Table 3 Invariant kinetic

Sample Eainv (kJ/mol) Ainv (l/min)
parameters obtained by IKP
method
HDPE 303 3.149E ? 20
HDPE–HA_100 ml 320 5.561E ? 21
HDPE–HA_200 ml 325 1.281E ? 19
HDPE–HA_300 ml 323 7.335E ? 21
HDPE–HA_10 °C 327 3.260E ? 18
HDPE–HA_75 °C 318 3.855E ? 21

Fig. 8 The straight line log (Aj)

vs. Ej for the thermal
degradation of HDPE, at all used
heating rates (corroborating
compensation effect)

degradation, an increase in the activation energy also means an increase in stability

due to the retarding effect.
On the other hand, the distributions of probabilities associated with the 18
degradation functions proposed in the literature are presented in Fig. 9. Degradation
of HDPE and HDPE–HA composites are a complex phenomenon and are
represented by a set of functions: ‘‘nucleation and nucleus growth kinetic model’’

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Fig. 9 Probabilities evaluated by IKP

Fig. 10 Possible routes of radical formation involved in HDPE degradation

with approximately 23 % of probability (S3) and ‘‘reaction order’’ with a 16 % of

probability (S5). Also, mechanisms with lower probabilities occurred, like reaction
at the interface 11–14 % (S6, S7, and S8), and potential law, with very low
probability, around 3 % (S14 and S17). The probability of the latter mechanism
decreases when HA is incorporated into the polymeric matrix; this might indicate
that HA avoided fast reactions between molecules with low molecular weight.
From these results it can be inferred that thermal degradation of HDPE and
HDPE–HA composites initiate on the polymer melt. Therefore, at this stage the
reactions that might be involved are ‘‘nucleation and nucleus growth kinetic’’
mechanism (S1, S2, S3, and S4), forming free radicals by two possible routes
(Fig. 10) [35], these isolated radicals begin to form very close radical groups (called
clusters). When part of this polymer is carbonized forming a solid, the mechanisms
of degradation might be changed, due to the diffusion of low molecular weight

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Fig. 11 Activation energy

obtained by E2 function

chains into the interface, allowing the degradation processes to continue. However,
as can be observed in Fig. 9, diffusion processes do not occurred. Also, degradation
mechanisms of ‘‘reaction at the interface’’ are present, corresponding to S6, S7, and
S8; this is attributed to crosslinking reactions between the melt polymer, degraded
material, and decomposition gases. Finally, the molecules of low molecular weight
formed in the first stage of decomposition lead to the formation of a new phase that
corresponds mainly to a reaction order mechanism (S5) and to potential law (S14,
S17), similar results were obtained by Albano et al. [36]. These results indicated that
incorporation of HA into the polymeric matrix do not modified significantly the
degradation mechanisms of HDPE.
The kinetic parameters calculated by the E2 function method (Fig. 11), presented
a similar tendency to the results obtained by IKP. The activation energy exhibits an
increase when HA is incorporated into the polyethylene matrix, this energy is
between 420 and 460 kJ/mol, which confirms that HA produces an increase in the
stability of the polymer. It is worth to mention that the differences between Ea
calculated by both methods are based on the approximations of the mathematical
models employed by each method.
The Ea obtained by the two mathematical methods is high compared to reports in
the literature for polyethylene of low molecular weight (Mw = 23.000) [35].
However, the Mw of our polymer is Mw = 425.000 (measured by viscosimetry
method). This result suggests a direct relationship between molecular weight and
activation energy, when Mw increases a decrease in the chain mobility is obtained,
so a greater energy is required to degrade the polymer.
A good dispersion of HA was observed by TEM, with the characteristic needle
morphology and nanometric size. The images obtained indicate that the best HA
dispersion was achieved when polymerization was carried out at 10 °C and 200 ml
(Fig. 12), whereas under the other conditions employed formation of agglomerates
was observed. However, these agglomerates have small sizes that did not produce
significant change in the kinetic parameters, calculated by the IKP and E2 function
methods.

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Fig. 12 TEM of: a HDPE–HA_10 °C and b HDPE–HA_200 ml

Conclusions

IKP and E2 function methods allowed determining the kinetic parameters of the
HDPE–HA composites obtained by in situ ethylene polymerization.
The activation energy, Ea, calculated using IKP and E2 function presented the
same tendency; both results indicated an increase in the activation energy of HDPE
when HA was included. This increase in the activation energy indicates an increase
in the thermal stability of the polymer. Also, not significant differences were
observed when the synthesis was carried out at different conditions.
HDPE and HDPE–HA degradation mechanisms are represented by a set of
functions, those with higher probability are: nucleation and nucleus growth (S3)
23 %, reaction order (S5) 16 %, reaction at the interface (S6, S7, S8) 11–14 %, and
potential law (S14, S17) 3 %.

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