Radiation Physics and Chemistry 125 (2016) 145150

Contents lists available at ScienceDirect

Radiation Physics and Chemistry

journal homepage: www.elsevier.com/locate/radphyschem

Inuence of -ray modied MWCNTs on the structural and thermal

properties of high-density polyethylene
Bilal Ghafoor a, Malik Sajjad Mehmood b,c,n, Umair Shahid a, Mansoor A. Baluch c,
Tariq Yasin b
a

Materials Science and Engineering Department, Institute of Space Technology, 44000 Islamabad, Pakistan
Advance Polymer Laboratory, Pakistan Institute of Engineering and Applied Sciences, 45650 Islamabad, Pakistan
c
University of Engineering and Technology, 47050 Taxila, Pakistan
b

H I G H L I G H T S

Nano composites of HDPE with 100-kGy irradiated MWCNTs are made.

The effect of incorporation of -ray modied MWCNTs in HDPE is studied.

Structural and thermal stability of HDPE/-MWCNTs nano composites is studied.

art ic l e i nf o
Article history:
Received 29 January 2016
Received in revised form
1 April 2016
Accepted 7 April 2016
Available online 8 April 2016
Keywords:
-Irradiation
-Ray modied MWCNTs
HDPE
FTIR
DSC/TGA
Nanocomposites

a b s t r a c t
This study aims to investigate the inuence of adding 100 kGy -irradiated multi wall carbon nano tubes
(MWCNTs) on the structural and thermal properties of high-density polyethylene (HDPE). The effects of
further -irradiation in the presence of -MWCNTs on aforementioned properties have also been investigated. FTIR spectroscopic measurements of HDPE and HDPE/-MWCNTs composites reveal that
modication of MWCNTs with r 100 kGy of -dose reduces its efciency as free radical quencher. This
behavior is found to increase further with the increase in the concentration of -MWCNTs. Wide angle
X-ray diffraction (WAXD) data shows a decrease in percent crystallinity and shifting of crystalline peaks
toward lower values of 2 angles. This behavior is mainly attributed to the oxidation induced due to
residual free radicals. Thermal analysis reveals that addition of -MWCNTs decreases the thermal stability as far as onset thermal degradation temperature, percent crystallinity, and melting temperature of
UHMWPE/-MWCNTs. In addition to this, gel content measurements show that insoluble percentage of
UHMWPE is higher with the incorporation -MWCNTs and further irradiation. The gel contents are found
to improve up to 29% and 60%, respectively with the incorporation of -MWCNTs and further irradiation.
& 2016 Elsevier Ltd. All rights reserved.

1. Introduction
Various chemical and physical properties have made high
density polyethylene (HDPE) a material of choice for many industrial applications such as packaging, wire and cable insulation,
etc. These properties include high mechanical strength, high
crystallinity, light weight and minimum costs for nal product.
However, the thermal and mechanical properties (more specically impact strength) of HDPE are of major concern for its use and
n
Corresponding author at: University of Engineering and Technology, 47050
Taxila, Pakistan.
E-mail addresses: msajjad.82@gmail.com,
malik.mehmood@uettaxila.edu.pk (M.S. Mehmood).

http://dx.doi.org/10.1016/j.radphyschem.2016.04.004
0969-806X/& 2016 Elsevier Ltd. All rights reserved.

service life in many industrial applications (Chowdhury et al.,

2012; Shaq et al., 2013). In this respect, composites of this polymer have been formulated by using various techniques including
self-reinforcement, reinforcement with carbon bers, with llers
of micron size, and with llers of nano size to enhance properties
more specically mechanical properties (Barus et al., 2010;
Dintcheva et al., 2009; Grigoriadou et al., 2011; Roumeli et al.,
2014; Subramaniam et al., 2012). The use of nano scale llers is
preferable because of their larger surface area as compared to
micron size llers. Other notable advantages of using nano llers
for polymer reinforcement are improving or adjusting the optical,
thermal and ame retardant properties (Barus et al., 2010; Grigoriadou et al., 2011; Gutirrez and Palza, 2015).
Composites based on carbon nano tubes (CNTs) have gained

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B. Ghafoor et al. / Radiation Physics and Chemistry 125 (2016) 145150

much attention because of their improved chemical stability, and

mechanical, optical, thermal, and electrical properties. The outstanding results of incorporating CNTs in polymer matrices have
lead researchers to focus on CNT-reinforced polyethylene (PE),
including composites of HDPE (Chaudhari et al., 2011; Dubey et al.,
2012; Kingston et al., 2014; Park et al., 2008; Wang et al., 2009).
Lee et al. incorporated MWCNTs in HDPE/carbon black blend and
reported an improvement in the positive thermal coefcient of
HDPE/carbon black/MWCNTs blend (Lee et al., 2006). In other relevant studies, Kumar and other researchers have placed huge
emphasis on the effects of MWCNTs incorporation on thermal and
mechanical properties of HDPE/MWCNTs composites. They have
found that thermal degradation of these composites started at
lower temperature as compared to unformulated HDPE; however,
improved mechanical properties have been reported by the incorporation of CNTs (Kumar et al., 2013; Martnez-Morlanes et al.,
2012; Rama Sreekanth et al., 2012).
MWCNTs have proved to be potential ller for HDPE. In order to
completely explore and utilize the potential of MWCNTs, compatibility among the polymer and MWCNTs has to be improved
during the physical and chemical techniques and/or methods.
MWCNTs modications involving chemical methods endow them
with various surface functionalities which consequently, are responsible to enhance the compatibility among CNTs and polymer
matrix. Use of toxic chemicals and tiresome time consuming
procedures with chemical modications of CNTs have lead researchers to adopt alternate technique or method that should be
relatively environment-friendly, simple and cost-effective. Ionizing
radiation such as gamma rays and electron beams has been used
for the modication of MWCNTs. Jung et al. has dispersed
MWCNTs in hydrogen peroxide and irradiated the resulting dispersion using an electron beam to obtain CNTs of shorter length
(Jung et al., 2008). Sabonab and other researchers evaluated the
effect of -rays on the surface area of MWCNTs and reported larger
surface area and pore volume along with carbonyl functional
groups for 100 kGy irradiated MWCNTs (Murakami et al., 2015;
Sabonab et al., 2011). Martnez-Morlanes et al. (2011) reported
the improved interaction between MWCNTs and polyethylene on
irradiation which is responsible for enhancing the mechanical
properties of composites. Ionizing radiation has also been used to
modify physico-chemical and structural properties of HDPE. For
comprehensive details of radiation induced structural and chemical modications of HDPE, its composites and the composites of
other members of the polyethylene (PE) family, see: Mehmood
et al. (2014), Mehmood et al. (2013b), Richaud (2015).
In this study, the effects of various -doses on the structural,
morphological and thermal properties of pure HDPE and HDPE/MWCNTs were investigated. Wide angle X-ray diffraction (WAXD),
thermal gravimetric analysis (TGA), differential scanning calorimetric (DSC), BrunauerEmmettTeller (BET), Gel contents analysis, and Fourier transform infrared (FTIR) spectroscopic measurements were performed to have more conclusive results of HDPE
nano-composites with modied/ less defective MWCNTs.

2. Experimental procedure
2.1. Materials
HDPE in powder form (F00952; density 0.952 g/cm3;
MFI 0.05 g/10 min) was purchased from ExxonMobil chemical
(Riyadh, Saudi Arabia). The antioxidants, Irganox-1010 (AO-1) and
Irgafos-168 (AO-2) were purchased from Ciba Specialty Chemicals
(Basel, Switzerland). MWCNTs were gifted by Korea Advanced
Institute of Science and Technology. All other chemicals such as
stearic acid, acetone etc. were used as such without any further

purication.
2.2. Melt blending and irradiation
Composites of HDPE were prepared by using method of melt
blending in a Thermo Haake Poly-Lab Rheomix 600 (Thermo
Electron Corp, Karlsruhe, Germany). HDPE powder was melted at
170 C at constant rotor speed of 60 rpm, and during melting of
HDPE, stearic acid (1 phr), Irganox-1010 (0.2 phr) and Irgafos-168
(0.1 phr) were added. After next couple of minutes, 0.5% and 1.0%
of gamma irradiated MWCNTs (-MWCNTs) were added in HDPE
containing stearic acid and AO-1 and AO-2. To obtain homogeneous dispersion of -MWCNTs, admixing of composition was
continued for additional 10 min at the same temperature and rotor
speed. The molten compositions containing 0.5% and 1.0% of
MWCNTs were then brought to room temperature and compressed into sheets of 1 mm thickness. The compression process
was carried out using hot press available at Pakistan Institute of
Engineering and Applied Sciences (PIEAS), Islamabad, Pakistan for
1015 min at 180 C under the pressure of 200 bar, followed by
cooling in air down to room temperature (25 C) under the same
pressure. These nano-composites were assigned identication
codes as C, H, and F throughout the text of this manuscript representing the samples containing 0.0%, 0.5%, and 1.0% of MWCNTs, respectively.
MWCNTs were irradiated using gamma rays in open air at an
absorbed dose of 100 kGy to obtained -MWCNTs prior to incorporation in HDPE. Sheets of HDPE and its composites were also
irradiated in open air with -rays at an absorbed dose ranging
from 25 kGy to 150 kGy with at increments of 25 kGy. The subscript with identication codes (i.e. C, H, and F) were used to represent the amount of absorbed dose within the text of manuscript. Irradiation services were provided by Pakistan Radiation
Services (PARAS), Lahore, Pakistan while using 60Co gamma irradiator (Model JS-7900, IR-148, and ATCOP) operating at a constant
dose rate of 1.2 kGy/h and ambient temperature.
2.3. Characterization
To determine the effective surface area of the -MWCNTs, a
high performance volumetric physisorption apparatus at 77 K i.e.
BET was used prior to incorporation of these -MWCNTs in HDPE.
Chemical compositions of un-irradiated HDPE/-MWCNTs composites and irradiated HDPE/-MWCNTs were determined by
Fourier Transform Infrared spectroscopy. The spectra of samples
were collected using Nicolet 6700 FTIR spectrophotometer (Thermo Electron Corp, Waltham, Massachusetts, USA) in attenuated
total reectance mode. Spectra were collected at a constant
spectral resolution of 6 cm  1 in the range of 4000500 cm  1 by
averaging of 216 scans. Thermal decomposition behaviors of the
composites have been assessed by using Mettler-Toledo TGA/
SDTA851 thermo-gravimetric analyzer (Schwerzen-bach, Switzerland). The analyses were performed by heating the samples (approximately having 7 mg weight each and 3 samples of each
group) from ambient temperature to 550 C under continuous
purge of nitrogen (40 mL/min) at a rate of 20 C/min. Calorimetric
analyses were carried out by using Q100 DSC from TA Instruments
(New Castle, DE, USA) at a heating and cooling rates of 10 C/min
in Aluminum pan containing approximately 5 mg sample for each
test. These scans were performed under nitrogen environment and
registered between 20 and 200 C. The melting and re-crystallization temperatures were measured from maximum temperatures of the endothermic and exothermic peaks, respectively.
To have in depth analyses of the effects of -MWCNTs incorporation on the crystal structure, average crystallite size, and
percentage crystallinity, wide angle X-ray diffraction (WAXD)

B. Ghafoor et al. / Radiation Physics and Chemistry 125 (2016) 145150

pattern of all the composites were recorded using X-ray diffractometer (Model X TRA48 Thermo ARL) operating at 45 kV and
40 mA. For all samples, radial scans were recorded in reection
scanning mode from 5 to 60 at a scanning rate of 11/min at room
temperature. In order to investigate the degree of crosslinking of
HDPE and HDPE/-MWCNTs, gel contents measurements were
performed by using Soxhlet extractor and xylene. The percentage
values of gel content were calculated by using the relation:

Gel Contents (%) = Wa/W0 100

where Wo and Wa are the weights of sample before and after
extraction. It is important to mention here that all tests were
performed while following the standard protocols dened by
American Society for Testing and Materials (ASTM, D276511,
2006; ASTM, D341815, 2015; ASTM, E113103, 2003; ASTM,
E142614, 2014; ASTM, F210213, 2013).

147

signicant structural modications are also evident. These modications includes the signicant increase in the absorption bands
at 3444 cm  1 (related to the stretching vibrations of the isolated
surface of OH in the carboxyl group), at 1635 cm  1and 1715 cm  1
(related to the stretching of MWCNTs backbone and C O groups),
at around 2933 cm  1 (related to C-H stretching mode of H-C O),
as shown in Fig. 1. Moreover, the relative decrease of absorption
bands at 2933 cm  1 and 1715 cm  1 in comparison to the peak at
1635 cm  1 further conrms the decrease in the defective structures and improvement in the quality of MWCNTs upon irradiating
them with 100 kGy dose in open air. Comprehensive details on
these structural modications in MWCNTs upon irradiation has
been covered in the literature (Jung et al., 2008; Kingston et al.,
2014; Martnez-Morlanes et al., 2012; Murakami et al., 2015; Sabonab et al., 2011).
3.2. Inuence of -rays on the properties of HDPE/-MWCNTs nanocomposites

3. Results and discussion

3.1. Inuence of -rays on the properties of MWCNTs
In order to have better dispersion and compatibility of
MWCNTs in HDPE for composite preparation, MWCNTs were irradiated in powder form with -rays with a dose of 100 kGy because it was reported by Sabonab et al. (2011) that quality of
MWCNTs can be improved by irradiating them with a dose value of
100 kGy. To evaluate the inuence of -irradiation on the surface
and structural properties, BET and FTIR analysis of raw and irradiated MWCNTs (in open air) was performed. The surface analysis while using BET analysis shows that the surface area of unirradiated MWCNTs and -MWCNTs are 16.57 m2/g and 247.99 m2/
g, respectively. The signicant increase in the surface area of
MWCNTs upon irradiation can be explained by the fact that irradiation results in smaller pore sizes and larger pore volumes on
the surface of MWCNTs. This increase in micro porosity of
MWCNTs is mainly responsible for larger specic surface area of MWCNTs as compared to un-irradiated MWCNTs. In addition to
increase in the specic surface area of MWCNTs upon irradiation,

3.2.1. Structural analysis

3.2.1.1. FTIR spectroscopy. In order to evaluate the inuence of MWCNTs incorporation and high energy irradiations on the
structural properties of HDPE, FTIR spectroscopy has been performed. The scans as described in Section 2.3 were registered and
shown in Fig. 2 for samples containing 1.0% of -MWCNTs to
highlight the signicant structural changes. FTIR spectra of HDPE
and its composites are shown in Fig. 1. Un-irradiated composite
(F0) spectrum exhibited absorption bands corresponding to C-H
asymmetric and symmetric stretching, and bending vibrations. In
addition, bands can also be observed at 1596 cm  1, 1262 cm  1
and in the range of 11001000 cm  1. The bands at 1596 cm  1,
1262, and in the range of 11001000 cm  1 were attributed to the
COO-, C-O stretching and C-C stretching absorption, respectively.
The irradiated composites also exhibited above mentioned absorption bands. However, particular area of interest was the tieline of CH2/CH3 peaks (extended from 1650 to 1750 cm  1, and
13301390 cm  1) which corresponds to oxidation index (OI) of
these nanocomposites. The values of OI represent the degradation
of polyethylene due to oxidation quantitatively on relative scale

Fig. 1. FTIR spectra of HDPE/-MWCNTs un-irradiated and irradiated composites with values of oxidation index (OI).

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B. Ghafoor et al. / Radiation Physics and Chemistry 125 (2016) 145150

Table 1
TGA data of pristine, HDPE/MWCNTs, and HDPE/-MWCNTs.
Sample

TOnset (C) T10 (C) T30 (C) T50 (C) T70 (C)

HDPE, 0% -MWCNTs,0 kGy

HDPE, 0% -MWCNTs,50 kGy
HDPE, 0% MWCNTs,150 kGy
HDPE, 0.5% MWCNTs,0 kGy
HDPE, 0.5% MWCNTs,50 kGy
HDPE, 0.5% MWCNTs,150 kGy
HDPE, 1.0% MWCNTs,0 kGy
HDPE, 1.0% MWCNTs,50 kGy
HDPE, 1.0% MWCNTs,150 kGy

428.0
425.0
420.5

445.0
447.7
443.2

467
468.1
465.9

476.0
478.4
477.2

482.6
484.0
481.8

402.0

436.9

463.0

476.0

482.6

413.6

439.8

465.9

476.1

481.8

406.5

434.4

462.5

473.4

479.6

416.0

441.0

465.9

475.0

481.8

398.8

438.8

467.0

476.1

482.9

388.6

428.4

459.0

472.7

479.5

TOnset temperature at 5% mass loss; T10 temperature at 10% mass loss;

T30 temperature at 30% mass loss; T50 temperature at 50% mass loss;
T70 temperature at 70% mass loss.

Fig. 2. Wide angle X-ray diffraction patterns of composites containing 1.0% of MWCNTs.

(Khan et al. (2015)). The values of oxidation index for samples

containing 1.0% of -MWCNTs is shown in Fig. 1 and it can be seen
that values of OI increases with absorbed dose due to chain scission and oxidation reaction by radiation induced free radicals.
Although, it has been recently reported that MWCNTs acts as radical scavengers (Martnez-Morlanes et al., 2012) but action of
MWCNTs as scavenging agent is less prominent here. The irradiation of MWCNTs before composite formulation might be reason
for this behavior because, it has also been reported that irradiating
MWCNTs with r100 kGy of -dose resulted in improving their
qualities via reducing the defects already present in them and
these defective sites are responsible for quenching the free radicals
(Jung et al., 2008; Sabonab et al., 2011).
3.2.1.2. Wide angle X-ray diffraction (WAXD) analysis. Wide angle
X-ray diffraction (WAXD) study has been conducted to perform
detailed investigation of HDPE and its composites with the addition of -irradiated MWCNTs. Shown in Fig. 2, are the WAXD
patterns of HDPE/-MWCNTs containing 1.0% of -MWCNTs as
nano-additives. The gure clearly indicates that these patterns
exhibit the diffraction peaks at 21.6 and 24.0, which correspond
to the (110) and (200) planes of polyethylene (PE). However, these
peaks are found to be less intense and shifted toward the lower
values of 2 (see Fig. 2) i.e. for the composites irradiated with
50 kGy and 150 kGy of -dose, and the peak at L(110) were shifted
from 21.50 to 21.30 along with a signicant decrease in intensity.
The reduction in intensity shows the decrease in percent
crystallinity of nano-composites with irradiation. This decrease in
crystallinity may be due to the scissioning of polymer chains in the
boundaries of crystalline region, whereas the chain scission is
mainly due to the free radicals induced by the oxidation reactions
of radiation induce free radicals which are also responsible for the
reduction of average crystallite sizes. The shifting of peak positions
towards lower values of 2 is the experimental evidence for this
reduction in average crystallite sizes with irradiation treatment of
these HDPE/-MWCNTs. Other plausible reasons for decrease in
percentage values of crystallinity and average crystallite sizes also
include:
Enhancement of MWCNTs quality by reducing/eliminating the

defects inside MWCNTs by treating them with r100 kGy of dose (Jung et al., 2008; Sabonab et al., 2011).
Higher chain mobility of PE with MWCNTs incorporation which
results in slightly boosted migration of trapped free radicals inside
the crystalline core, causes chain scission at the boundaries of
crystalline core by reacting with diffused oxygen (Mehmood et al.,
2013a).
The results obtained from WAXD study i.e. decrease in the
percentage crystallinity and average crystallite sizes affects the
thermal characteristics of these composites (as explained in Section 3) and also support our claim regarding the higher values of O.
I of these HDPE/-MWCNTs.
3.2.2. Thermal analysis
3.2.2.1. Thermo gravimetric analysis. The thermal stabilities of
HDPE and HDPE/-MWCNTs composites were investigated in inert
atmosphere. The results which include the Tonset, T10, T30, T50, T70,
(temperature at which 10%, 30%, 50%, and 70%, weight has been
lost) are summarized in Table 1. HDPE and HDPE/-MWCNTs
composites show the single step mass loss and almost the similar
degradation prole with an abrupt single step mass loss and nal
volatilization. This single step mass loss is ascribed to the degradation of polyethylene back bone while the 5% mass loss is
selected as a criterion for onset degradation temperature, and is
found to have slightly lower values with the incorporation of
MWCNTs and irradiation. This behavior of composite is attributed
to higher chain mobility due to plasticity induced by MWCNTs
incorporation along with the radiation induced oxidation degradation (Oral and Muratoglu, 2011). However, for 30%, 50%, and
70% weight loss there is no signicant difference (see Table 1).
3.2.2.2. Differential Scanning Calorimetry (DSC). For further investigation of the thermal characteristics of HDPE and HDPE/MWCNTs composites, DSC has been performed and the results of
second heating and cooling run are shown in Fig. 3. The control
sample i.e. HDPE shows its characteristics melting and re-crystallization temperatures which are affected with -irradiation. A
signicant decrease in the heat of fusion (which is calculated as
the area under the endothermic peak) with -irradiation, is found.
Moreover, further decrease in the heat of fusion values has been
visualized by increasing the -dose (see Fig. 4 below). The plausible elucidation for this behavior is the chain scissions close to
crystalline lamella immediately after irradiation due to radiation
induced free radicals. The decrease in heat of fusion with

B. Ghafoor et al. / Radiation Physics and Chemistry 125 (2016) 145150

149

crosslinking of polymer chains with -irradiation. For nanocomposites, gel content is increased up to 100 kGy dose. As can be
noticed from the gure, the nanocomposites possessed higher gel
content than that of HDPE. This might be due to the higher
crosslinking effect of -MWCNTs. The defects produced during the
radiation treatment with 4100 kGy of MWCNTs have contributed
to crosslinking by the generation of radicals during gamma irradiation of nanocomposites. The nanocomposites irradiated at
150 kGy absorbed dose showed low gel content. This is mainly due
to the defects induced in MWCNTS by irradiating the HDPE/MWCNTs with 4100 kGy (as MWCNTs are already irradiated with
100 kGy of -dose) of -dose serves as radical quenchers which
results in reduction of crosslink density.
Fig. 3. Representative DSC heating curves of HDPE/-MWCNTs composites containing 1.0% of -MWCNTs.

4. Conclusion
HDPE/-MWCNTs nano composites were prepared and these
composites were irradiated with various -doses. The infrared
spectra revealed that modication of MWCNTs with -rays reduces its efcacy as free radical quencher and as a result of which
radiation induced oxidation is increased. The percentage crystallinity, thermal stability, and crystalline lamellae thicknesses of the
composites were observed to decrease with the addition of MWNCTs while the behavior of HDPE/-MWCNTs composites with
irradiation was not that different than the irradiated HDPE. Gel
content measurements revealed that the irradiation of HDPE in the
presence of -MWCNTs increased the crosslink density up to 60%.
A signicant increase in crosslink density is of particular importance for industrial application of the composites.

Acknowledgement

Fig. 4. Percentage values of gel contents of HDPE and its composites as a function
of absorbed dose.

irradiation reveals that percentage crystallinity of HDPE is also

decreased with irradiation. The results of DSC are in agreement
with WAXD data presented in Section 3.2.2. In addition, the recrystallization behavior also follows the same trend as that of
melting as far as radiation of HDPE is concerned.
The melting temperature (Tm) is increased slightly with the
incorporation of -MWCNTs. On the other hand considering the
heat of fusion, initially it decreases up to 50 kGy of -dose and
increases for the composites irradiated with the dose level of
100 kGy. The increase in heat of fusion and percent crystallinity for
100 kGy irradiated composite is due to the fact that exposure of
MWCNTs with further 100 kGy induces the defective sites which
serves as free radical quenchers (Martnez-Morlanes et al., 2012;
Park et al., 2008). Occurrence of crystallization at lower temperature in irradiated nanocomposites compared with the un-irradiated ones is due to the degradation effect. The exposure of PE to
higher doses give rise to the degradation and hence, shorting of
polymer chains. These shorter polymer chains consequently entangle and disentangle easily as compared to the longer chains.
The reduction in melting temperature and crystallinity of nanocomposites was monotonic with increase in -dose.
3.2.3. Gel contents measurements
Gel content of irradiated samples is presented in Fig. 4. The
graph showed improvement in the gel content of HDPE with absorbed dose. The increase in gel content is due to increase in

Dr Malik Sajjad Mehmood acknowledges the nancial support

provided by Directorate of ASR&TD, UET, Taxila, Pakistan under
research project entitled "Non Destructive Radiation Dosimetery
using UV-Visible and FT-IR Spectroscopy" for conducting this
study. The technical and moral support by Mr. Muhammad Shaq
from PIEAS, Islamabad and Anna Sanawaar from UET, Taxila is also
acknowledged here.

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