Thermal characterization of the HDPE/LDPE blend (10/90) irradiated using c-rays

C.C. Puig
a
, C. Albano
b,c,
*
, E. Laredo
d
, E. Quero
a
, A. Karam
b
a
Universidad Simn Bolvar, Departamento de Ciencia de los Materiales, Grupo de Polmeros USB, Apdo. 89000, Caracas 1080-A, Venezuela
b
Instituto Venezolano de Investigaciones Cientcas (IVIC), Centro de Qumica, Laboratorio de Polmeros, Apdo. 21827, Caracas 1020-A, Venezuela
c
Universidad Central de Venezuela, Facultad de Ingeniera, Escuela de Ingeniera Qumica, Laboratorio de Polmeros, Caracas, Venezuela
d
Universidad Simn Bolvar, Departamento de Fsica, Grupo de Fsica de Materiales Amorfos y Cristalinos, Apdo. 89000, Caracas 1080-A, Venezuela
a r t i c l e i n f o
Article history:
Received 5 November 2009
Received in revised form 31 December 2009
Available online 18 January 2010
Keywords:
Thermal characterization
Gamma irradiation effect
HDPE/LDPE
Slow cooled HDPE/LDPE 10/90 blend
Fast cooled HDPE/LDPE 10/90 blend
a b s t r a c t
Gamma irradiation effect over the properties of slow cooled and fast cooled HDPE/LDPE 10/90 blend was
studied. The blend and the neat polyethylenes were irradiated at room temperature in the presence of air
using the following doses (4.8 kGy/h): 0, 50, 150, 400 and 1000 kGy. Differential scanning calorimetry
(DSC) experiments were carried out using the following heating rates: 5, 10 and 20 C/min. DSC results
for the slow and fast cooled blend showed traces with three melting peaks and with increasing irradiation
dose two melting peaks were obtained, i.e. the high melting peak shifts toward lower temperatures to
merge with the intermediate melting peak into one endotherm. No changes in crystal structure by X-
ray diffraction were found as a result of samples irradiation. Radiation crosslinking prevents crystal rear-
rangements during heating in the DSC. Gel content and melt ow index (MFI) measurements showed that
radiation induced a high degree of crosslinking for all samples; gel content values were above 50% and a
drop of more than 90% in the MFI was found. Irradiation of slow cooled samples resulted in larger values
of gel content and lower MFI values than for fast cooled samples, mainly because of the higher degree of
crosslinking for the former.
2010 Elsevier B.V. All rights reserved.
1. Introduction
Polyethylene is one of the most demanded plastics materials
around the world and its applications can vary from food packag-
ing to medical industry. It is one of the materials with the most
variety of properties, depending on its macromolecular structure.
This polymer is usually irradiated so it can resist high tempera-
tures (near boiling point of water) without losing its properties,
which is useful for some applications, particularly for medical
use [1,2].
Blends of linear and branched polyethylenes of different densi-
ties and origin are usually prepared to compensate properties re-
lated to mechanical performance and processing; nevertheless,
these blends do not tend to form a single phase in the solid state,
in spite of having the same chemical structure. Results obtained
by DSC and transmission electron microscopy studies allowed Bar-
ham and coworkers [3] to show phase separation in quenched
HDPE/LDPE blends. Agamalian et al. [4] reported miscibility at
160 C from ultra small angle neutron scattering of HDPE/LDPE
blends, indicating that phase segregation takes place on cooling.
Dynamic rheometry tests performed by Hameed and Hussein [5]
showed that miscibility of these blends in the melt depends on
the structure of LDPE, decreasing with an increase in branching
content. In addition, the crystalline morphology of the LDPE/HDPE
blends depends on the composition; Puig [6,7] showed by DSC
experiments that when low percentages of HDPE are added (up
to 10% w/w) the most linear LDPE segments tend to incorporate
into the HDPE crystals, lowering their melting point. Garca-Rejon
and Alvarez [8] showed by examining mechanical properties that
blends of LDPE/HDPE display a linear addition law for HDPE and
LDPE, with a linear increase of the elastic modulus and yielding
stress by increasing the HDPE fraction; Fu et al. [9] found a de-
crease on the elongation at break with an increase of HDPE fraction
due to its higher crystallinity and thus lesser molecular mobility.
Radiation can be applied to a great number of plastics. In this
eld, polyethylenes present various advantages because they
show: an improved impact resistance, a higher thermal stability,
a good chemical compatibility towards aggressive chemicals and
higher barrier properties towards liquid and organic vapors
migrating through the packaging wall [10].
Irradiation of polyethylenes induces crosslinking reactions,
which causes an increase in gel content [1113] and a drastic drop
in melt ow index [14]. Surez et al. [15] reported changes in
mechanical properties of HDPE/LDPE blends, a drop of 50% in the
0168-583X/$ - see front matter 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.nimb.2010.01.008
* Corresponding author. Address: Instituto Venezolano de Investigaciones Cient-
cas (IVIC), Centro de Qumica, Laboratorio de Polmeros, Apdo. 21827, Caracas
1020-A, Venezuela. Tel.: +58 2125041636; fax: +58 2125041371.
E-mail addresses: cpuig@usb.ve (C.C. Puig), calbano@ivic.ve, carmen.albano@
ucv.ve (C. Albano).
Nuclear Instruments and Methods in Physics Research B 268 (2010) 14661473
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elongation at break for a radiation dose of 500 kGy, a decrease in
elastic modulus (for radiation dose up to 2000 kGy) and failure
point; in addition, the authors observed by scanning electron
microscopy of fracture surfaces a ductilefragile transition at
500 kGy. The present work will investigate the effect of gamma
radiation doses, in the range of 501000 kGy, on the melting
behavior of a low content HDPE blend (10% w/w), that was crystal-
lized using two different cooling treatments from the melt.
2. Experimental
2.1. Materials
Two polyethylenes supplied by Polinter, injection grades, were
used to prepare binary blends, a high density polyethylene (HDPE
2908A, q: 0.9595 g/cm
3
, MFI: 7.3 dg/min, Mw: 64904 g/mol, poly-
dispersity: 3.9) and a low density polyethylene (LDPE MD-2002, q:
0.9233 g/cm
3
, MFI: 20 dg/min, Mw: 68997 g/mol, polydispersity:
14.3).
2.2. Preparation of the blends
Polyethylene blends were prepared by extrusion (ATLAS
miniextruder, model LME) at a temperature of 200 C, with a screw
rotating speed of 60 rpm, in the following compositions (HDPE/
LDPE): 0/100, 10/90, 100/0. The extruded blends were then com-
pression molded into sheets at 190 C about 0.70.8 mm thick,
employing two cooling treatments. A fast thermal treatment con-
sisted of immersing the sheets in a mixture of water and ice imme-
diately after the molding cycle. The slow thermal treatment
consisted of holding the sheets between the plates while using a
controlled cooling procedure from the melt to room temperature.
2.3. Irradiation of the blends
A Co
60
isotope was used to irradiate the samples, in a reactor at
room temperature and in the presence of air, at a dose rate of
4.8 kGy/h (1.33 Gy/s). The doses applied to the samples were: 0,
50, 150, 400, and 1000 kGy.
2.4. Differential scanning calorimetry (DSC)
Calorimetry experiments on heating at 10 C/min from 0 C to
160 C of slow and fast cooled HDPE, LDPE and the blend were car-
ried out using a Mettler-Toledo DSC822e. Disc shape samples with
a weight between 10 and 12 mg were used for DSC experiments.
Indium and tin elements were used for calibration. The melting
behavior of both irradiated and nonirradiated samples was investi-
gated in a pure nitrogen atmosphere. The blend was also heated at
5 and 20 C/min. Transition temperatures and enthalpies associ-
ated to the endothermic melting peak were obtained from the
heating thermograms. The degree of crystallinity (X
c
) was deter-
mined by DSC.
X
c
%
DHm
exp
DHm
theo
100
The term DHm
exp
is the heat of fusion of the sample and the
termDHm
theo
is the heat of fusion for a 100% crystalline PE sample,
289.3 J/g [16].
2.5. X-ray diffraction
Wide angle X-ray scattering experiments were carried out in an
automatic X

Pert Pro diffractometer equipped with a fast data

acquisition X

celerator both from PANalytical. The X-ray source

was operated at 45 kV and 40 mA and the Cu radiation was Ni-l-
tered in order to select the Ka radiation, k = 1.5418 . The angular
range swept in each run went from 10 to 30 in 2h, at a speed of
0.0020/s and 10 s counting time.
2.6. Gel content determination
Gel content of irradiated samples (ca. 1 g) was determined by
Soxhlet reux experiments after 72 h of extraction, using xylene
as a solvent and cellulose extraction lters. After drying, the sam-
ple was weighed, and the gel content (GC) was calculated as a rel-
ative difference between the initial and nal masses of the
samples.
GC
W
f
W
d
W
i
W
d

100
The term W
i
is the initial total weight of the extraction lter
plus the sample, the term W
f
is the nal total weight of the extrac-
tion lter plus the sample and the term W
d
is the weight of the
extraction lter.
2.7. Determination of the melt ow index (MFI)
The melt ow index of the irradiated blends was measured in a
plastomer (Ray Ran) at a temperature of 190 C, using a 2.16 kg
weightpiston pair, after a 6 min pre-heating treatment. Volumet-
ric measurements were made in a 20 mm range for nonirradiated
blends and in a 5 mm range length for irradiated samples, due to
a drastic drop on the uidity of those blends.
3. Results and discussion
In a recent study, by Colin and coworkers, the authors proposed
a kinetic model to predict the lifetime and thickness of oxidized
layer of unstabilised and unlled polyethylene exposed to gamma
irradiation at room temperature in air [17]. Using the results re-
ported by the authors, for the experimental conditions (1.33 Gy/
s) and samples (0.70.8 mm) used in the present work, a thickness
of oxidized layer of about 177 lm is estimated. Degradation is het-
erogeneous, a surface layer composed of oxidized material (mainly
as a result of chain scission reactions) and a bulk composed of
crosslinked material. The experimental techniques used in this
work examined the whole sample. For commercial HDPE, Placek
and Bartonicek [18] showed that due to the complexity of the radi-
ation chemistry of this material (containing HDPE base, antioxi-
dants, llers and other additives) and its high inhomogeneity, it
is difcult to estimate which process inuences the dose rate effect
at most, however, for dose rates above 0.1 kGy/h limited oxidation
diffusion was suggested to play a more important role.
The effect of branching content in the melting behavior of poly-
ethylene has been extensively reported in the literature [19,20]. By
introducing branches along the chain, linear methylene sequences
are drastically disrupted and crystals that are formed subsequently
are of lower thermal stability. The melting temperature peaks of
slow and fast cooled HDPE are about 20 C higher than for LDPE
(Fig. 1).
Slow cooling treatments from the melt favors polyethylene
crystal growth and an increase in crystals thermal stability is ex-
pected on subsequent heating [21,22], as shown for neat HDPE in
Fig. 1. Nevertheless, neat LDPE failed to show similar behavior
and melting temperature peak for the fast cooled sample is higher
than for the slow cooled sample, 1.1 C. Peeters et al. [23] ex-
plained that polyethylenes go through recrystallization processes
during heating in the DSC, and these processes are more pro-
nounced on rapid cooled samples and as the branching content is
C.C. Puig et al. / Nuclear Instruments and Methods in Physics Research B 268 (2010) 14661473 1467
larger; long and short linear methylene sequences crystallize to-
gether, the obtained crystals are thermodynamically less stable
in comparison to slow cooled formed crystals. In this manner, a
higher melting temperature for the fast cooled LDPE is found on
subsequent heating.
Slow and fast cooled blend showed multiple melting peaks in
Fig. 1. Three melting peaks are clearly observed in the slow cooled
blend. Separate crystallization of the blend components on cooling
explains the presence of multiple endotherms on subsequent heat-
ing. Shifts in melting peak temperatures when compared with the
values for neat polyethylenes may be the result of changes in crys-
tals composition. The high endothermic temperature peak at
127 C (6 C lower than for the neat HDPE) corresponds to the
melting of rich HDPE crystals. The formation of crystals that con-
tains LDPE as well as HDPE segments is revealed by the presence
of an intermediate melting peak. The low endothermic peak at
110 C, at a slightly lower temperature than for the neat LDPE,
suggests that the most linear methylene sequences are included
in the crystals that melt at higher temperatures.
Fig. 2 shows how the degree of crystallinity (X
c
), obtained by
DSC, of the neat polyethylenes and the blend changes with radia-
tion dose. Neat HDPE failed to show signicant changes. There is
an increase in X
c
with radiation dose for neat LDPE by both cooling
treatments (the largest increase occurs in the 0150 kGy range). It
is expected that since LDPE and the blend have a large amorphous
proportion in the solid state, the samples are more affected by
gamma radiation compared to HDPE, which has a much lower
amorphous content. Yeom et al. [24] reported an increase in the
degree of crystallinity of an irradiated ultra high molecular weight
polyethylene, due to oxidation induced chain scission when in the
presence of oxygen, which gives place to shorter, crystallizable
chain segments that will go through a crystallization process. Radi-
ation induced crosslinking usually takes place inside the irradiated
samples, where the oxygen diffusion from air is lower. In low crys-
talline LDPE, oxidation at ambient temperature might occur both
on the sample surface and bulk. Therefore, some chain scission in
the amorphous phase because of radiation is expected, followed
by crystallization of the newly formed segments at a rather large
supercooling at room temperature, increasing the degree of
crystallinity.
The radiation induced degradation mechanisms that modify the
polymer chain structure in the presence of oxygen, which also af-
fect the degree of crystallinity are: crosslinking, chain scission (also
in the absence of oxygen) and the oxygen diffusion dependent oxi-
dation, the former being more limited by a higher degree of crys-
tallinity [2527]. The plateau reached for doses above 150 kGy in
Fig. 2 may be caused by the restriction of molecular movement
due to extensive crosslinking that limits the degree of recrystalliza-
tion [12].
Figs. 3 and 4 show DSC heating thermograms of neat LDPE and
HDPE for each radiation dose studied, respectively. Both polyethyl-
enes showed a single melting peak, independently of the cooling
treatment used. The prole of the melting endotherm of the LDPE
crystals failed to show signicant changes, however, the endo-
therm of HDPE crystals was slightly affected by gamma irradiation.
According to Vaughan et al. [28], when radiation dose is high en-
ough (above 5000 kGy) important changes on crystalline structure
are introduced, a second peak appears because the unit cell of the
crystals is modied from orthorhombic to hexagonal form, with a
lower melting point than of the orthorhombic form. The results ob-
tained from X-ray diffraction experiments at room temperature
conrm that at these low radiation doses no crystal transformation
from orthorhombic to hexagonal unit cell in the irradiated homo-
polymers was observed (see Fig. 5 for the fast cooled HDPE). There-
fore, the appearance of a shoulder to the left of the HDPE melting
endotherm for the irradiated samples might indicate the presence
of a small population of crystals of lower thermal stability that is
formed after oxidation and chain scission processes as explained
earlier.
Table 1 shows the melting peak temperatures of the neat poly-
ethylenes for both cooling treatments, recorded at 10 C/min, as a
function of radiation dose; we observed no signicant differences
between nonirradiated samples processed according to two cool-
ing methods. It is observed that the melting temperature peak of
the slowly cooled neat LDPE failed to show relevant changes. Dif-
ferences in melting temperatures is generally caused by changes
on macromolecules, due to radiation induced free radical type
reactions like chain scission, crosslinking and branching [13,15]
and by changes in crystalline structure due to the introduction of
defects. In addition, the decrease in melting point might be due
0 20 40 60 80 100 120 140 160
127.5
115.1
110.1
113.3
134.7
127.3
120.4
109.6
112.1
133.6
10/90
100/0
0/100 H
e
a
t

F
l
o
w
,

W
/
g
Temperature, C
Slow Cooling
Fast Cooling
100/0
10/90
0/100
2

W
/
g
e
n
d
o
Fig. 1. DSC heating thermograms of the pure polymers and the HDPE/LDPE 10/90
without radiation.
0 200 400 600 800 1000
45
50
55
60
65
70
75
80
HDPE/LDPE
Slow Cooling
0/100
10/90
100/0
Fast Cooling
0/100
10/90
100/0
x
c

(
%
)
Radiation Dose (kGy)
Fig. 2. Degree of crystallinity of the HDPE/LDPE blends as a function of radiation
dose. Filled series correspond to slowly cooled blends, and hollow series to rapidly
cooled blends.
1468 C.C. Puig et al. / Nuclear Instruments and Methods in Physics Research B 268 (2010) 14661473
to restriction on crystal rearrangement that usually takes place
near the melting point, for heating rates typically used for DSC
scans as introduced before [29]. Crystal rearrangements during
heating at high temperatures generally include lamellar thickening
(a) (b)
0 20 40 60 80 100 120 140 160
50 kGy
400 kGy
150 kGy
1000 kGy
0 kGy
0
.
5

W
/
g
e
n
d
o
H
e
a
t

F
l
o
w
,

W
/
g
Temperature, C
0 20 40 60 80 100 120 140 160
50 kGy
400 kGy
150 kGy
1000 kGy
0 kGy
0
.
5

W
/
g
e
n
d
o
H
e
a
t

F
l
o
w
,

W
/
g
Temperature, C
Fig. 3. DSC heating thermograms of pure LDPE exposed to several radiation doses. (a) Slowly cooled LDPE and (b) rapidly cooled LDPE.
(a) (b)
0 20 40 60 80 100 120 140 160
50 kGy
400 kGy
150 kGy
1000 kGy
0 kGy
2

W
/
g
e
n
d
o
H
e
a
t

F
l
o
w
,

W
/
g
Temperature, C
0 20 40 60 80 100 120 140 160
50 kGy
400 kGy
150 kGy
1000 kGy
0 kGy
2

W
/
g
e
n
d
o
H
e
a
t

F
l
o
w
,

W
/
g
Temperature, C
Fig. 4. DSC heating thermograms of pure HDPE exposed to several radiation doses. (a) Slowly cooled HDPE and (b) rapidly cooled HDPE.
Fig. 5. WAXS spectrum of HDPE: (a) neat, rapid cooling and (b) neat, irradiated
(1000 kGy), rapid cooling.
Table 1
Melting peak temperatures of the pure polymers for the different radiation doses
applied, and both cooling rates.
Dose (kGy) Slow cooling Fast cooling
T
LDPE
(C) T
HDPE
(C) T
LDPE
(C) T
HDPE
(C)
0 112.1 134.7 113.3 133.6
50 110.5 136.0 110.3 131.9
150 111.0 136.4 111.6 131.5
400 110.9 136.7 109.3 130.2
1000 110.4 134.9 108.0 130.1
C.C. Puig et al. / Nuclear Instruments and Methods in Physics Research B 268 (2010) 14661473 1469
and recrystallization processes resulting in higher melting temper-
ature peaks. When irradiation takes place, the amorphous region
stiffens as a result of chemical crosslinking and hinders lamellar
thickening or crystal rearrangement processes during DSC heating
runs. It may also be expected that some changes in crystalline
structure occurs that lowers the thermal stability of the crystals;
especially in the fast cooled formed lamellae. Both factors would
explain the observed behavior in Table 1 whereby the depression
in melting temperature peak is larger for the fast cooled LDPE sam-
ples. Similar behavior is found for fast cooled HDPE. The slowly
cooled HDPE, samples with the largest degree of crystallinity,
showed a slight increase in melting peak temperature with radia-
tion dose (0400 kGy). Crosslinking may shift the melting temper-
ature peak to higher values.
Previous studies have shown that radiation affects mainly the
amorphous zone in polyethylenes [27], because the formed radi-
cals in this region diffuse favoring crosslinking. This reaction can-
not take place within the rigid crystalline regions since the free
radicals remain trapped. This is supported by paramagnetic reso-
nance results reported by Albano et al. [12], showing that the den-
sity of free radicals decrease more rapidly in polyethylene of a low
crystallinity (LDPE) compared to a highly crystalline one (HDPE);
this is caused by the fact that the diffusion of radicals is more dif-
cult within the crystalline zones. When cooling is fast, the degree
of crystallinity is lower as explained previously, and LDPE tends to
suffer more rearrangements and recrystallization during subse-
quent DSC heating scans [23]; in addition, the degree of crosslink-
ing is higher due to the larger amorphous content, which produces
a more rigid zone and the rearrangements during the DSC heating
scan are more limited, hindering crystal rearrangements. This re-
sults in a decrease of the melting peak temperature for the rapidly
cooled samples, when compared to the slowly cooled ones.
Fig. 6 shows heating thermograms of the blend for both cooling
treatments and for the various irradiation doses used. With
increasing radiation dose the melting behavior changes from three
melting peaks to two melting peaks. The appearance of two endo-
therms instead of three with increasing radiation dose might be
explained by two reasons. The rst involves crystal destruction
by radiation; nevertheless, this possibility may be thought not to
occur to a large extent since crystallinity fails to change profoundly
(Fig. 2). Additionally, WAXS spectrum of the most highly irradiated
slow cooled blend is similar to that of the nonirradiated slow
cooled LDPE and fast cooled blend (Fig. 7). The second reason
might be the displacement to lower temperatures of the high melt-
ing temperature peak as radiation dose increased. These results
suggest peak position of the high melting endotherm in an irradi-
ated blend is the result of crystal rearrangement processes during
heating that are suppressed after crosslinking by gamma
irradiation.
Table 2 shows melting peak temperatures of the blend for the
different radiation doses and the two cooling treatments used.
There is a decrease in melting peak temperature of both rich HDPE
and LDPE crystals (T
3
and T
1
; respectively) with radiation dose. On
the other hand, the intermediate endothermic peak (T
2
) remained
practically constant. For fast cooled sample the level of depression
in melting temperature with radiation dose is larger. Fast cooling
treatment from the melt does not favor perfect crystalline packing
and the presence of defects, upon gamma irradiation at such doses,
lower the thermal stability of crystals. For the slowcooled blend the
intermediate melting peak (T
2
) is about 5 C higher than for the fast
cooled blend. The population of crystals that melts at the interme-
diate melting peak incorporates HDPE and LDPE segments and they
are thought to be less prone to rearrange due to their complex
structure. As pointed out by Briskman, melting behavior of irradi-
ated polyethylene depends on the initial degree of crystallinity,
(a) (b)
0 20 40 60 80 100 120 140 160
50 kGy
400 kGy
150 kGy
1000 kGy
0 kGy
0
.
5

W
/
g
e
n
d
o
H
e
a
t

F
l
o
w
,

W
/
g
Temperature, C
0 20 40 60 80 100 120 140 160
50 kGy
400 kGy
150 kGy
1000 kGy
0 kGy
0
.
5

W
/
g
e
n
d
o
H
e
a
t

F
l
o
w
,

W
/
g
Temperature, C
Fig. 6. DSC heating thermograms of the HDPE/LDPE 10/90 blend exposed to several radiation doses. (a) Slowly cooled and (b) rapidly cooled.
Fig. 7. WAXS spectrum of: (a) LDPE neat, slow cooling; (b) HDPE/LDPE, 10/90, rapid
cooling and (c) HDPE/LDPE, 10/90, irradiated (1000 kGy), slow cooling.
1470 C.C. Puig et al. / Nuclear Instruments and Methods in Physics Research B 268 (2010) 14661473
irradiation temperature and previous thermal treatment (lamellar
thickness) [30].
Fig. 8 shows the thermograms of the blend irradiated at various
doses and examined by DSC using three different heating rates: 5,
10 and 20 C/min. With increasing heating rate the two higher
melting peaks tend to merge with one another, this is specially ob-
served for the slow cooled blend after low radiation dose. In order
to corroborate the existence of a crystal population responsible of
the intermediate melting peak in the blend, the height ratio of the
melting endotherms of the nonirradiated blend as a function of
heating rate was calculated. Fig. 9 shows the height ratio of the
intermediate melting peak (Y
2
) to the lower temperature peak
Table 2
Melting peak temperatures of the HDPE/LDPE 10/90 blend for the different radiation
doses applied, and both cooling rates.
Dose (kGy) Slow cooling Fast cooling
T
1
(C) T
2
(C) T
3
(C) T
1
(C) T
2
(C) T
3
(C)
0 109.6 120.4 127.3 110.1 115.1 127.5
50 109.8 121.9 126.7 109.1 115.4 126.1
150 108.8 120.1 125.3 108.4 116.2 125.2
400 108.3 121.5 108.3 115.0 118.4
1000 108.3 119.3 114.8
0 20 40 60 80 100 120 140 160
5 C/min
5 C/min
20 C/min
10 C/min
10 C/min
20 C/min
5 C/min
10C/min
20 C/min
5 C/min
20 C/min
10 C/min
5 C/min
10 C/min
20 C/min
50 kGy
400 kGy
150 kGy
1000 kGy
0 kGy
1

W
/
g
e
n
d
o
H
e
a
t

F
l
o
w
,

W
/
g
Temperature, C
0 20 40 60 80 100 120 140 160
5 C/min
5 C/min
5 C/min
10 C/min
10 C/min
10 C/min
20 C/min
20 C/min
20 C/min
5 C/min
10 C/min
20 C/min
5 C/min
10 C/min
20 C/min
50 kGy
400 kGy
150 kGy
1000 kGy
0 kGy
1

W
/
g
e
n
d
o
H
e
a
t

F
l
o
w
,

W
/
g
Temperature, C
(a)
(b)
Fig. 8. DSC heating thermograms of the HDPE/LDPE 10/90 blend at different heating rates and exposed to several gamma radiation doses and submitted to different cooling
rates prior to irradiation: slow cooling (a) and fast cooling (b).
5 10 15 20
0.75
0.80
0.85
0.90
0.95
1.00
Slow Cooling
Fast Cooling
H
e
i
g
h
t

R
a
t
i
o

Y
2
/
Y
1
DSC Heating Rate, C/min
Fig. 9. Height ratio (Y
2
/Y
1
) of melting peaks vs. DSC heating rate of the nonirra-
diated HDPE/LDPE 10/90 blend, for the two cooling rates used.
C.C. Puig et al. / Nuclear Instruments and Methods in Physics Research B 268 (2010) 14661473 1471
(Y
1
), for both cooling treatments. The height ratio (Y
2
/Y
1
) obtained
for the slowly cooled blend turned out to be independent of the
heating rate during DSC scans. For the rapidly cooled blend, a slight
variation of the height ratio with DSC scans heating rate is found at
5 C/min. These results constitute further evidence to support the
existence of lamellae formed by HDPE and some LDPE segments
that had cocrystallized and that melts at 115 C for the fast
cooled blend and at 120 C for the slow cooled blend.
Table 3 shows gel content values for slow and fast cooled sam-
ples irradiated at 400 and 1000 kGy. The gel content is dened by
the percentage of insoluble polymer in a good solvent, after extrac-
tion by reuxing this solvent for a determined length of time, un-
der some specic conditions and it is taken as a measurement of
the degree of crosslinking of any polymeric material [31]. The free
radicals that are formed by c-rays irradiation impart energy to the
covalent bonds of the chains through a series of reactions as seen in
Fig. 10. Reaction (1) implies the formation of a nonterminal poly-
meric radical, and reaction (2) the formation of a covalent bond be-
tween two of these radicals.
For the different radiation doses and cooling treatments used,
the gel content is higher for neat HDPE than for neat LDPE. Similar
results were reported by Albano et al. [12] and Edin [32]. According
to Chapiro [25], crystallinity and branching density of polyethylene
affect considerably the changes induced by irradiation. Albano
et al. [12] explained that the variation in gel content between both
polyethylenes depends on the diffusion rate of oxygen from the
surface to the bulk of the sample. Oxygen diffusion into the inner
sections of a highly crystalline sample such as HDPE is limited
and active radicals inside crosslink in a higher proportion and oxi-
dation reactions are more difcult to occur, being limited to the
surface of the samples [24]. Consequently, the gel content of neat
HDPE, having a higher degree of crystallinity, should be higher
than that of neat LDPE. In LDPE oxygen diffusion is improved and
chain oxidation starts competing with crosslinking reactions, since
the oxygen present in air also reacts with free radicals formed by
the presence of gamma radiation (as described in the reaction
(1), Fig. 10), as it is shown in reaction (3), forming a peroxy radical.
These peroxy radicals can react with themselves forming crosslinks
according to reactions (6), (7), and the obtained products are differ-
ent of those obtained from reaction (2). This bonding could also be
contributing to the increase on the gel content, in both the blend
and the neat polymers.
Neat LDPE and the blend that were fast cooled from the melt
showed a decrease in gel content when the radiation doses in-
creased from 400 to 1000 kGy. Surez et al. proposed that a de-
crease in gel content may be attributed to chain scission
reactions at high radiation doses that are more probable to occur
than crosslinking reactions [15,33]. On the other hand, the acceler-
ated chain scission by the presence of oxygen is also favored by
higher diffusion of oxygen within the sample due to the relatively
low degree of crystallinity of the high LDPE content blend [12].
Additionally, chain scission may be increased by the cleavage of
peroxy-like linkages formed as stated in reactions (4) and (5)
(Fig. 10), these being found in higher proportion within LDPE
chains than in HDPE chains, because of faster oxygen diffusion
rates. Regarding to the blend, due to its low HDPE content, it is rea-
sonable to expect that its behavior is similar to that found for neat
LDPE.
Reactions (6), (7) and (8) show possible degradation mecha-
nisms of both peroxy and alkoxy radicals, which were proposed
by Chapiro [25] and Yu et al. [34]. It is possible that these reactions
contribute to chain cleavage, which is the predominating reaction
type at the highest radiation doses used for neat LDPE and the
blend. In fact, Albano et al. [12] carried out Fourier-transform infra-
red studies of gamma irradiated HDPE and LDPE using radiation
dose in the range of 0930 kGy and observed an increase in inten-
sity of carbonyl band in the 16001800 cm
1
range. The band was
reported to broaden with irradiation dose as degradation products
include esters, carboxylic acids and aldehydes. In addition, the
authors observed and increase in intensity of the band at
964 cm
1
, attributed to the absorption of transvinylene groups,
and a decrease in intensity of the band located between 880 and
909 cm
1
, attributed to vinylene and terminal vinyl groups, all of
which supports the formation of crosslinking and/or the formation
of long chain branching. Similar results were obtained by Cheng et
al. [35].
Slow and fast cooled neat HDPE showed an increase in gel con-
tent by increasing radiation dose from 400 to 1000 kGy. This indi-
cates that the oxygen diffusion to the bulk of the samples during
radiation was low enough to become less important than the radi-
ation induced crosslinking reactions. The low diffusion rate may be
explained by the high degree of crystallinity obtained in HDPE by
both cooling treatments (70% and 75% for fast and slow cooling,
respectively), limiting the diffusion of oxygen within the sample
[24].
Table 3
Gel content of the pure polymers and the HDPE/LDPE 10/90 blend at a radiation dose
of 400 and 1000 kGy.
Cooling rates HDPE/LDPE % Gel
400 kGy 1000 kGy
Slow cooling 0/100 51.0 58.2
10/90 86.0 66.7
100/0 79.5 95.6
Fast cooling 0/100 69.8 56.6
10/90 70.5 56.4
100/0 80.7 88.6
Fig. 10. Scheme of the gamma radiation induced reactions in polyethylenes [23,34].
1472 C.C. Puig et al. / Nuclear Instruments and Methods in Physics Research B 268 (2010) 14661473
In melt index tests nonirradiated slow and fast cooled blends
erase their previous thermal history during pre-heating for mea-
surements. The slow and fast cooled polyethylene samples showed
a drastic drop in MFI values when compared with irradiated sam-
ples (150 kGy radiation dose) as reported in Table 4. This is in
agreement with previous results reported by Surez et al.
[13,15,33], which showed that crosslinking of polyethylenes and
their blends takes place at low radiation doses. According to results
in Table 4, slow cooled polyethylene samples showed lower MFI
values than fast cooled samples. Slow cooled samples developed
greater crystallinity allowing a higher amount of active radicals
to be trapped in crystalline regions compared to a less crystalline
sample. Albano et al. [12] showed that the loss in density of active
radicals is slower for HDPE than for LDPE. Melting the polymer
crystals, during heating prior to MFI measurements, active radicals
that were trapped within the crystals, higher for the slowly cooled
polymers, react forming additional crosslinking. In neat LDPE, the
difference between the MFI values obtained for both cooling treat-
ments was lower when compared to the difference obtained for the
blend and neat HDPE. Degrees of crystallinity of slow and fast
cooled LDPE were closer than those found for HDPE and the blend.
4. Conclusions
Gamma radiation of HDPE/LDPE 10/90 blend and neat polyeth-
ylenes caused chemical reactions, being crosslinking of the amor-
phous phase one of them, as revealed by the drastic drop in MFI
values. Slow cooled samples consistently showed lower MFI values
than fast cooled samples after irradiation. Free radicals formed in
the crystalline regions are trapped and after crystal melting are
able to recombine. No changes in crystal structure by X-ray diffrac-
tion were found as a result of samples irradiation. The melting of
LDPE crystals failed to show signicant changes, however, the
endotherm of HDPE crystals was slightly affected by gamma irradi-
ation and that was explained by crystallization of segments as a re-
sult of oxidation and chain scission processes that takes place
during irradiation at room temperature. In slow cooled and fast
cooled blend with increasing radiation dose the melting behavior
changes from three melting peaks to two melting peaks. Radiation
crosslinking prevents crystal rearrangements during heating in the
DSC and the high melting peak shifts toward lower temperatures
to merge with the intermediate melting peak into one endotherm.
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Table 4
MFI values of the pure polymers and the HDPE/LDPE 10/90 blend, without radiation
and at a radiation dose of 50 kGy.
% HDPE MFI (g/10 min)
0 kGy 150 kGy
Slowly cooled Rapidly cooled
0 16.0 1.0 0.170 0.010 0.21 0.03
10 14.8 0.8 0.085 0.009 0.16 0.03
100 9.0 0.4 0.070 0.006 0.24 0.02
C.C. Puig et al. / Nuclear Instruments and Methods in Physics Research B 268 (2010) 14661473 1473