Article

Radiation-Induced Grafting with One-Step Process of

Waste Polyurethane onto High-Density Polyethylene
Jong-Seok Park *, Youn-Mook Lim and Young-Chang Nho
Received: 4 September 2015; Accepted: 22 December 2015; Published: 29 December 2015
Academic Editor: Der-Jang Liaw

Radiation Research Division for Industry and Environment, Korea Atomic Energy Research Institute,
1266 Sinjeong-dong, Jeongeup-si, Jeollabuk-do 580-185, Korea; ymlim71@kaeri.re.kr (Y.-M.L.);
jaspa@naver.com (Y.-C.N.)
* Correspondence: jspark75@kaeri.re.kr; Tel.: +82-63-570-3067; Fax: +82-63-570-3079

Abstract: The recycling of waste polyurethane (PU) using radiation-induced grafting was investigated.
The grafting of waste PU onto a high-density polyethylene (HDPE) matrix was carried out using
a radiation technique with maleic anhydride (MAH). HDPE pellets and PU powders were immersed
in a MAH-acetone solution. Finally, the prepared mixtures were irradiated with an electron beam
accelerator. The grafted composites were characterized by Fourier transformed infrared spectroscopy
(FT-IR), surface morphology, and mechanical properties. To make a good composite, the improvement
in compatibility between HDPE and PU is an important factor. Radiation-induced grafting increased
interfacial adhesion between the PU domain and the HDPE matrix. When the absorbed dose was
75 kGy, the surface morphology of the irradiated PU/HDPE composite was nearly a smooth and
single phase, and the elongation at break increased by approximately three times compared with that
of non-irradiated PU/HDPE composite.

Keywords: waste; polyurethane; radiation grafting; recycling; polyethylene

1. Introduction
Polyurethane (PU) has been used in a variety of applications due to its good mechanical, thermal,
and chemical properties. However, the use of PU has led to the environmental issues because the
greater part of the industrial waste PU are being disposed in landfill sites. Thus, research has focused
on alternative options for the disposal of PU [1,2], e.g., the recycling or modification of PU waste into
useful materials [3].
Polymer blending technology is a promising approach for the ecological and economical
remediation of waste plastics [4]. Waste PU can be recycled and used as filler for commodity polymers
to improve thermal and mechanical properties [5]. A high compatibility between the commodity
polymers and waste PU is an important factor to consider in the formation of a good composite.
However, PU is hydrophilic, whereas most commodity polymers are hydrophobic [4,6].
Graft polymerization is an excellent way to improve the miscibility between PU and commodity
polymers [7]. Furthermore, radiation-induced grafting techniques provide several advantages over
classical chemical grafting, including uniform grafting compositions, room temperature processing,
and initiator and catalyst-free processing [3,8,9]. Radiation-induced grafting can be proceeded between
monomer and polymer during the irradiation. The first step is the irradiation to generate polymer
radicals and second step is the graft polymerization of monomer on to the polymer through radical
polymerization (Scheme 1) [10].
Recently, maleic anhydride (MAH) has become an attractive monomer to improve
the hydrophilicity of polyolefin [11]. Polymers grafted with maleic anhydride (MAH) have been
used as compatibilizers to improve the interfacial interaction between immiscible polymers [6,12].

Materials 2016, 9, 13; doi:10.3390/ma9010013 www.mdpi.com/journal/materials

Materials 2016, 9, 13 2 of 8
Materials 2016, 9, 13

Irradiation

·
HDPE free radical

O O

N-C-O N
O O OH
O O C
HO
O
MAH O O
O
PU

Scheme 1.
Scheme Radiation-induced grafting
1. Radiation‐induced grafting polymerization.
polymerization.

Our previous
previouswork
work[13]
[13] presented
presented on polyethylene-graft-maleic
on the the polyethylene‐graft‐maleic anhydride
anhydride (PE‐g‐MA)
(PE-g-MA) grafted
grafted
PU/HDPE PU/HDPE composite
composite via meltviaprocessing
melt processing in a blender
in a blender after radiation‐induced
after radiation-induced grafting
grafting of PUofwith
PU
with PE‐g‐MA. This process was performed with two‐step process. The
PE-g-MA. This process was performed with two-step process. The PE-g-MA easily reacted PE‐g‐MA easily reacted with
the PU according to increasing radiation doses and was located at the interface between the PU and
the HDPE
HDPEduring
duringthe
themelt
meltprocessing
processing in in
thethe
blender, which
blender, improved
which improved the the
interfacial interactions
interfacial and
interactions
the
and mechanical properties
the mechanical of the
properties resultant
of the resultantcomposites.
composites. However,
However, the
theelongation
elongationatatbreak
break for
for PU
contents >>22 phr
phr drastically
drastically decreased
decreased [13].
[13].
The main objective
objectiveof
ofthis
thisstudy
studyisistotodevelop
developanan effective
effective recycling
recycling method
method of industrial
of industrial waste
waste PU
PU by radiation‐induced
by radiation-induced grafting.
grafting. In In this
this study,
study, the
the radiationgrafting
radiation graftingofofwaste
wastePUPUonto
onto an
an HDPE
HDPE matrix
was carried out with MAH. HDPE pellets were immersed in MAH-acetone MAH‐acetone solution, and waste PU
powders were added. The The prepared mixtures were graft-irradiated with
prepared mixtures were graft‐irradiated withan anelectron
electronbeam
beamaccelerator.
accelerator.
The grafted
grafted composites
composites were
were characterized
characterizedby byFourier
Fouriertransformed
transformedinfrared
infrared spectroscopy
spectroscopy (FT‐IR),
(FT-IR),
surface morphology, and mechanical properties.
surface morphology, and mechanical properties.

2. Experimental
Experimental

2.1. Materials
2.1. Materials
Methylene diphenyl
Methylene diphenyldiisocyanate
diisocyanate(MDI)‐based
(MDI)-based polyurethane
polyurethane (PU)
(PU) foam,
foam, yellowish
yellowish in color,
in color, was
was collected from the waste disposals of a railway system from Envista, Inc. (Chungju,
collected from the waste disposals of a railway system from Envista, Inc. (Chungju, Korea). The Korea).
rigid
Thefoams
PU rigid PU
werefoams were
reduced to reduced to powder
powder with a knifewith a knife
cutter. cutter. Commercial-grade
Commercial‐grade high-density
high‐density polyethylene
polyethylene (HDPE; 5305E) was used throughout this study and was supplied by
(HDPE; 5305E) was used throughout this study and was supplied by Lotte Chemical Corporation Lotte Chemical
Corporation
(Yeosu, (Yeosu,
Korea). MaleicKorea). Maleic
anhydride anhydride
(MAH) (MAH) was
was purchased frompurchased from Sigma
Sigma Aldrich Aldrich
(St. Louis, MO, (St. Louis,
USA). All
MO, USA). All other chemicals used were of reagent grade and were applied as purchased without
other chemicals used were of reagent grade and were applied as purchased without further purification.
further purification.
2.2. Radiation‐Induced Grafting
2.2. Radiation-Induced Grafting
HDPE pellets were exposed to a gamma 60 60Co source at a total dose of 50 kGy at 10 kGy/h for
HDPE pellets were exposed to a gamma Co source at a total dose of 50 kGy at 10 kGy/h for
oxidization. The surface modification of HDPE was carried out by grafting MAH using a radiation
oxidization. The surface modification of HDPE was carried out by grafting MAH using a radiation
technique. MAH powder (10 wt %) was dissolved completely in an acetone solution at room
technique. MAH powder (10 wt %) was dissolved completely in an acetone solution at room
temperature. Then, irradiated HDPE pellets and waste PU powder (0–10 phr) were immersed in the
temperature. Then, irradiated HDPE pellets and waste PU powder (0–10 phr) were immersed in
MAH‐acetone solution at an HDPE:MAH‐acetone solution ratio of 5:2. The unit “phr” is the abbreviation
the MAH-acetone solution at an HDPE:MAH-acetone solution ratio of 5:2. The unit “phr” is the
of parts per hundred resin, and the base resin used here is HDPE. They were stirred using a
abbreviation of parts per hundred resin, and the base resin used here is HDPE. They were stirred
mechanical stirrer for 1 h. The prepared mixtures were irradiated with an electron beam accelerator
using a mechanical stirrer for 1 h. The prepared mixtures were irradiated with an electron beam
(10 MeV/1 mA, Jeongup site of KAERI, Jeonbuk, Korea). The total absorbed dose ranged from 25 to
accelerator (10 MeV/1 mA, Jeongup site of KAERI, Jeonbuk, Korea). The total absorbed dose ranged
75 kGy. Thereafter, to remove the remaining solvent and moisture, the irradiated mixtures were
from 25 to 75 kGy. Thereafter, to remove the remaining solvent and moisture, the irradiated mixtures
washed three times with deionized water (DIW) and dried in a vacuum oven at 50 °C for˝ 24 h.
were washed three times with deionized water (DIW) and dried in a vacuum oven at 50 C for 24 h.
2.3. Preparation HDPE/PU Composite
The irradiated HDPE/PU mixtures were melt‐blended in a lab‐scale blender (Brabender D‐47055,
Brabender, Duisburg, Germany) with a screw speed of 50 rpm, at 160 °C for 15 min. After blending,
2
Materials 2016, 9, 13 3 of 8

2.3. Preparation HDPE/PU Composite

The irradiated HDPE/PU mixtures were melt-blended in a lab-scale blender (Brabender D-47055,
Brabender, Duisburg, Germany) with a screw speed of 50 rpm, at 160 ˝ C for 15 min. After blending,
the mixtures were prepared using square shaped sheets by hot-press molding at 180 ˝ C for 10 min.
The size of the specimens was 100 mm ˆ 100 mm, the thickness was 2 mm.

2.4. Characterization of PU/HDPE Composite

The chemical structure of HDPE/PU composites with radiation-induced grafting was confirmed
by Fourier transformed infrared spectroscopy (FT-IR; Bruker Tensor 37, Bruker, MA, USA). FT-IR
spectra were recorded in the range 2000 to 600 cm´1 at a resolution of 4 cm´1 in attenuated total
reflectance (ATR) mode.
The tensile strength and elongation at break was measured with universal testing machine (Model
4210, Instron Engineering Co., Canton, MA, USA) according to the ASTM Standard D 638 [14]. The size
of the specimens was 5 mm ˆ 20 mm, the thickness was 2 mm, and the head speed was 50 mm/min.
The dynamic mechanical properties were investigated with a dynamic mechanical analyzer (DMA;
DMA Q800, TA Instruments, New Castle, DE, USA), which was varied from 25 to 130 ˝ C at 1 Hz at
a heating rate of 5 ˝ C/min.
To observe the high-resolution images, the samples were covered with a layer of osmium (Os)
for 60 s by sputter coating. The surface morphology of the HDPE/PU were investigated with a field
emission scanning electron microscope (FE-SEM S-4700, Hitachi, Tokyo, Japan) at a resolution of 60 Å
at 5 kV, with a magnification of 5.0 K and a working distance of 10–12 mm.
The thermal properties of the HDPE/PU composites were analyzed using a differential scanning
calorimetry (DSC) (TA Q100, TA Instrument). The thermograms were recorded from room temperature
to 180 ˝ C at a rate of 10 ˝ C/min under N2 gas. The degree of crystallinity (Xc) of HDPE composite can
be calculated by the following equation:

∆Hm
Xcp%q “ o ˆ 100 (1)
∆Hm

where ∆Hm o = 290 J/g is the fusion enthalpy for a totally crystalline HDPE and ∆ is the fusion
m
enthalpy calculated from the area of the endothermic melting peak.

3. Results and Discussion

The immiscible properties of PU and HDPE presents a significant challenge in incorporating
PU onto an HDPE matrix. PU is hydrophilic, whereas HDPE is hydrophobic. Any blends of these
two polymers are generally immiscible. Thus, the interfacial compatibility between PU and an HDPE
matrix must be resolved to obtain good mechanical properties [6].
In our previous work, the radiation-induced grafting was carried out with two-step process.
The waste PU and PE-g-MA were dissolved in a DMF solution and irradiated to graft using an electron
beam accelerator. The PE-g-MA-grafted PU and HDPE were blended using a lab-scale blender.
The PU could be easily introduced to the HDPE during the melt processing in the blender after
the radiation-induced grafting of PU with PE-g-MA. PE-g-MA was easily reacted with PU according to
the increasing radiation dose. However, the elongation at break for a PU content >2 phr was drastically
decreased [13].
In this study, the surface modification of HDPE and PU was simultaneously progressed with
one-step process by grafting MAH using a radiation technique. The HDPE pellets and waste PU
powders were immersed in a MAH-acetone solution. The prepared mixtures were irradiated to graft
using an electron beam accelerator. Finally, the irradiated HDPE/PU mixtures were melt-blended in
a lab-scale blender.
Materials 2016, 9, 13 4 of 8

Figure 1 shows the mechanical properties, including tensile strength and elongation at break
of the PU/HDPE composites at various content of PU. In this experiment, the radiation dose was
25 kGy. No changes in the tensile strength were observed in the PU/HDPE composites with increasing
concentrations of PU. However, the elongation at break of the PU/HDPE composites increased with
increasing contents up to 3 phr. When the content of PU was 3 phr, the elongation at break reached
Materials 2016, 9, 13
a maximum average value of 380%. The elongation at break increased by approximately four times
compared with
Materials 2016,that
9, 13 of our previous work. The maximum elongation at break of the PU/HDPE
maximum average value of 380%. The elongation at break increased by approximately four times
composites
compared in with
our previous
that of ourwork was 280%, when the contentelongation
of PU wasat1break phr. This results indicates
maximum average value ofprevious
380%. The work. The maximum
elongation at break increased by approximately of the fourPU/HDPE
times
a significant
composites
compared
improvement
in with
our previous
that of our
in the
work compatibility
was 280%,
previous work.when
between
The the
PU and
contentelongation
maximum
HDPE compared
of PU wasat1 break
phr. Thisof the
to our
results
PU/HDPE
previous
indicates
work [13]. This
a significant
composites result
improvementis probably
in our previous inwork that one-step
the compatibility
was 280%, when process
between promoted
PU of
the content andPUHDPEgrafting through
compared
was 1 phr. to our
This results the previous of
reactions
indicates
the peroxy
work groups
a significant
[13]. of theisoxidized
improvement
This result in theHDPE
probably that with the
compatibility
one‐step carbon
between
process PUdouble
and HDPE
promoted bonds of MAH,
compared
grafting through to our
theand through
previous
reactions of the
carbonyl work
the peroxy [13].
groups This
of
groups MAHresult
of the isoxidized
with probably
the aminothat one‐step
HDPE groups
with the process
of carbon promoted
PU during doublethegrafting through
radiation
bonds of the
processing
MAH, and reactions of the
[4,11].
through
the peroxy
carbonyl
Figure 2groups
shows groups
ofthe
MAH of the oxidized
with
mechanical the aminoHDPEgroups
propertieswith ofthe carbon
ofthe
PUPU/HDPEdouble
during thebonds of MAH,
radiation
composites and
processing
at through
various [4,11]. the
absorption
carbonyl
Figure groups
2 shows ofthe
MAH with the amino
mechanical groupsofofthe
properties PU PU/HDPE
during the radiation
composites processing
at various[4,11].absorption
doses. During this experiment, the content of the PU dose was 3 phr. The tensile strength was tested for
Figure 2 shows the mechanical properties of the PU/HDPE composites at various absorption
eachdoses.
sample During
doses.at
thisfive
least
During
experiment,
times, and
this experiment,
thethe
content
average
the content
of the PU at
value
of the
dose
PU dose
was
thewas 3 phr. The tensile
maximum
3 phr. Thepoint
tensilewas
strength
recorded.
strength
wasThe
was tested
tested
tensile
for each
strengthfor sample
slightly at least
increased five times, and the average value at the maximum point was recorded. The
each sample at leastasfive
thetimes,
radiation
and thedose increased.
average value atAsthe shown
maximum in Figure
point was 2, recorded.
the tensile Thestrength
tensile strength slightly increased as the radiation dose increased. As shown in Figure 2, the tensile
at a 75 kGy
tensileirradiation
strength slightly doseincreased
was 24 as MPa. However,
the radiation dosethe elongation
increased. As shownat break
in Figure drastically
2, the tensile increased
strength at aat75
strength a 75kGy kGy irradiation
irradiationdosedose was 24
wasthe MPa.
24 absorbed However,the
MPa. However, theelongation
elongation at break drastically
when the absorbed dose increased. When dose was 75 kGy, atthe break drastically
elongation at break
increased when
increased whenthetheabsorbed
absorbed dose
doseincreased.
increased.When
When the absorbeddose
the absorbed dosewaswas7575 kGy,
kGy, thethe elongation
elongation at at
of the PU/HDPE
break of the
composite
PU/HDPE
was 460% 460%
composite
and increased by approximately three-fold over that of of the
break of the PU/HDPE compositewas was 460%and and increased
increased by byapproximately
approximately three‐fold
three‐fold over over
thatthat
of
non-irradiated
the the PU/HDPE
non‐irradiated PU/HDPEcomposite. This result indicates a significant improvement in the interfacial
non‐irradiated PU/HDPEcomposite.composite. ThisThis result indicates aasignificant
result indicates significantimprovement
improvement in the
in the
stateinterfacial
between
interfacialthestate
state HDPE
between and
between the
thetheHDPEPU after
HDPE and thePU
andthe
the radiation-induced
PU after graftinggrafting
the radiation‐induced
after the radiation‐induced of PU.of PU.
grafting of PU.

25 25 400
400

20
20
300
(%)

300
Tensile strength (MPa)

break(%)
Tensile strength (MPa)

15
break

15
at at

200
Elongation

200
Elongation

10
10

100
5 100
5

0 0
HDPE PU 0.5 phr PU 1 phr PU 2 Phr PU 3 Phr PU 5 phr PU 10 phr HDPE PU 0.5 phr PU 1 phr PU 2 Phr PU 3 Phr PU 5 phr PU 10 phr
0 0
HDPE PU 0.5 phr PU 1 phr PU 2 Phr PU 3 Phr PU 5 phr PU 10 phr HDPE PU 0.5 phr PU 1 phr PU 2 Phr PU 3 Phr PU 5 phr PU 10 phr
(a) (b)
(a) (b)
Figure 1. (a) Tensile strength and (b) elongation at break of polyurethane/high‐density polyethylene
Figure 1. (a) Tensile strength; and (b) elongation at break of polyurethane/high-density polyethylene
(PU/HDPE)
Figure composite
1. (a) Tensile at various
strength content
and (b) of PU; radiation
elongation at breakdose is 25 kGy.
of polyurethane/high‐density polyethylene
(PU/HDPE) composite at various content of PU; radiation dose is 25 kGy.
(PU/HDPE) composite at various content of PU; radiation500dose is 25 kGy.
25

25 500
20 400
break (%)
Tensile strength (MPa)

20 400
15 300
(%)
Tensile strength (MPa)

at break at
Elongation

15 300
200
10
Elongation

10 5 200
100

0 0
100
5
0 25 50 75 0 25 50 75

Radiation dose (kGy) Radiation dose (kGy)

0 0
0 25 (a) 50 75 0 (b)
25 50 75

Radiation dose (kGy) Radiation dose (kGy)

Figure 2. (a) Tensile strength and (b) elongation at break of PU (3 phr)/HDPE composite at various
absorption doses. (a) (b)
Figure 2. (a) Tensile strength and (b) elongation at break of PU (3 phr)/HDPE composite at various
(a)chemical
The
Figure 2. Tensile strength;
changes and (b) elongation
of PU/HDPE at break
composites of PU
after (3 phr)/HDPE grafting
radiation‐induced composite
at at various
various
absorption doses.
absorbeddoses.
absorption doses were investigated by FT‐IR spectroscopy. Figure 3 shows the FT‐IR spectra of the
neat HDPE and irradiated PU/HDPE composite at various absorption doses from 2000 to 600 cm−1.
The chemical changes of PU/HDPE composites after radiation‐induced grafting at various
As shown in the non‐irradiated PU/HDPE composite spectra, the typical carbonyl group of maleic
absorbed doses
anhydride were
was investigated
observed by−1. FT‐IR
at 1740 cm spectroscopy.
However, the intensityFigure 3 shows
of this peak the FT‐IRsignificantly
was decreased spectra of the
neat HDPE and irradiated PU/HDPE composite at various absorption doses from 2000 to 600 cm−1.
4
As shown in the non‐irradiated PU/HDPE composite spectra, the typical carbonyl group of maleic
anhydride was observed at 1740 cm−1. However, the intensity of this peak was decreased significantly
4
Materials 2016, 9, 13 5 of 8

The chemical changes of PU/HDPE composites after radiation-induced grafting at various

absorbed doses were investigated by FT-IR spectroscopy. Figure 3 shows the FT-IR spectra of the
neat HDPE and irradiated PU/HDPE composite at various absorption doses from 2000 to 600 cm´1 .
As shown in the non-irradiated PU/HDPE composite spectra, the typical carbonyl group of
maleic anhydride was observed at 1740 cm´1 . However, the intensity of this peak was decreased
significantly as the absorption dose increased. The IR absorption peaks of PU correspond to carbonyl
Materials 2016, 9, 13
vibrations at 1650 cm´1 (C=O stretching). Bending vibrations at 1590 cm´1 (N–H bending) were
clearly as
observed
the absorption[15]. dose
In addition,
increased.the The PU signal in peaks
IR absorption the irradiated PU/HDPE
of PU correspond composites
to carbonyl vibrationsrevealed
at 1650
characteristic cm
Materials at131250 cm´1Bending
−1 (C=O stretching).
bands
2016, 9, vibrations at 1590
(C–N stretching), 1120cmcm ´1 (C=O
−1 (N–H bending) were clearly
stretching andobserved
O–CH2 [15].stretching),
and 1050In cm
addition,
´1 (C–O the PU signal in the
stretching) [16].irradiated PU/HDPE
These results composites revealed
demonstrated characteristic
the successful bands atinduced
radiation
1250as cm
the−1absorption dose increased.
(C–N stretching), 1120 Thecm−1IR(C=O
absorption peaks of
stretching andPUO–CH
correspond to carbonyl
2 stretching), andvibrations
1050 cm−1
grafting of PU onto an HDPE matrix.
(C–Oat 1650 cm−1 (C=O
stretching) stretching).
[16]. Bendingdemonstrated
These results vibrations at 1590
thecm −1 (N–H bending) were clearly observed [15].
successful radiation induced grafting of PU
Further
ontoInan evidence
addition, theof
HDPE matrix. PUthe successful
signal radiation-induced
in the irradiated PU/HDPE composites grafting were confirmed
revealed characteristic by SEM.
bands at
Figure 4
1250 shows
cm the surface morphologies of the PU/HDPE composites
−1 (C–N stretching), 1120 cm−1 (C=O stretching and O–CH2 stretching), and 1050 cm−1
Further evidence of the successful radiation‐induced grafting were confirmed by SEM. at various absorption
(C–O
doses. The Figure stretching)
large domains
4 shows the[16]. These
ofsurface results demonstrated
PU at morphologies
0 and 25 kGy the
of were successful radiation
irregularly
the PU/HDPE induced
distributed
composites grafting
in the
at various of PU
HDPE matrix
absorption
onto an HDPE matrix.
doses.
due to weak The large domains
interfacial bonding.of PUHowever,
at 0 and 25 kGy wereirradiation
higher irregularly distributed
doses in 50
(i.e., the and
HDPE 75matrix
kGy) due
promoted
Further evidence of the successful radiation‐induced grafting were confirmed by SEM.
to weak
interfacial adhesion interfacial bonding. However, higher irradiation doses (i.e., 50 and 75 kGy) promoted
Figure 4 between
shows the the surfacePUmorphologies
domain and of the HDPE matrix.
the PU/HDPE composites When the absorbed
at various absorption dose was
interfacial adhesion between the PU domain and the HDPE matrix. When the absorbed dose was 75 kGy,
75 kGy, thedoses.
surface morphologies
The large domains of PU were nearly
at 0 and 25 kGysmooth and consisted
were irregularly distributedof in
a single
the HDPEphase.
matrix due
the surface morphologies were nearly smooth and consisted of a single phase.
to weak interfacial bonding. However, higher irradiation doses (i.e., 50 and 75 kGy) promoted
interfacial adhesion between the PU domain and the HDPE matrix. When the absorbed dose was 75 kGy,
the surface morphologies were nearly smooth and consisted of a single phase.

1,740 1,250 1,050

1,120
Absorbance

1,590
1,740 1,250 1,050
1,650
1,120
Absorbance

1,590
1,650

neat HDPE
PU 3 phr, 0 kGy
PU 3 phr, 25 kGy
PU 3
neat phr, 50 kGy
HDPE
PU33phr,
PU phr,0 75
kGykGy
PU 3 phr, 25 kGy
PU 3 phr, 50 kGy
2000 1750 1500 1250 PU1000
3 phr, 75 kGy 750
-1
Wavenumber (cm )
2000 1750 1500 1250 1000 750
-1
Figure 3. Fourier transformed infrared Wavenumber
spectroscopy (cm ) spectra
(FT‐IR) of neat HDPE and irradiated
Figure 3. Fourier transformed infrared spectroscopy (FT-IR) spectra of neat HDPE and irradiated PU
PU Figure
(3 phr)/HDPE composite at various absorption doses.
3. Fourier transformed infrared spectroscopy (FT‐IR) spectra of neat HDPE and irradiated
(3 phr)/HDPE composite at various absorption doses.
PU (3 phr)/HDPE composite at various absorption doses.

Figure 4. Scanning
Figure electron
4. Scanning microscope
electron microscope(SEM)
(SEM)micrographs of PU
micrographs of PU(3
(3phr)/HDPE
phr)/HDPEcomposites
compositesat at various
various
Figure 4. Scanning
absorption electron microscope (SEM) micrographs of PU (3 phr)/HDPE composites at various
doses.
absorption doses.
absorption doses.

55
Materials 2016, 9, 13 6 of 8
Materials 2016, 9, 13
Materials 2016, 9, 13

The thermal-mechanical properties of the samples were measured using a DMA, which was
thermal‐mechanical properties
The thermal‐mechanical properties of the samples were measured using a DMA, which was
varied from
from room temperatureto
room temperature 130˝°C
to130 C at
at aa heating
heating rate of 55 ˝°C/min.
rate of C/min. TheThe temperature
temperature dependencies
dependencies
varied from room temperature to 130 °C at a heating rate of 5 °C/min. The temperature dependencies
of the storage modulus of the PU/HDPE compositesat
PU/HDPE composites at various
various absorption
absorptiondoses
dosesareareshown
shown in in Figure
Figure 5.
5.
of the storage modulus of the PU/HDPE composites at various absorption doses are shown in Figure 5.
The storage modulus increased when the absorbed absorbed dosedose increased.
increased. As a results of of the
the radiation-induced
radiation‐induced
The storage modulus increased when the absorbed dose increased. As a results of the radiation‐induced
grafting, the
the irradiated
irradiatedPU/HDPE
PU/HDPEcompositecompositelikely
likelydeveloped
developed a stronger
a stronger interfacial
interfacialbond between
bond betweenthe
grafting, the irradiated PU/HDPE composite likely developed a stronger interfacial bond between
PU
the and the HDPE
PU and the HDPEcompared
compared withwith
non-irradiated
non‐irradiated PU/HDPE
PU/HDPE composites.
composites.
the PU and the HDPE compared with non‐irradiated PU/HDPE composites.
Figure 6 shows the DSC heating thermograms
thermograms of of the
the PU/HDPE composites at
PU/HDPE composites at various
various absorption
absorption
Figure 6 shows the DSC heating ˝ thermograms of the PU/HDPE composites˝at various ˝ absorption
doses under
under aaheating
heatingrate
rateofof1010 C/min.
°C/min.The Themelting
meltingpeak peakatatapproximately
approximately 127 –128 corresponds
127°–128° corresponds to
doses under a heating rate of 10 °C/min. The melting peak at approximately 127°–128° corresponds
the melting
to the meltingtemperature
temperatureof the
of theHDPE.
HDPE. TheThe
melting
meltingtemperature
temperature slightly increased
slightly increased withwith
increasing
increasingthe
to the melting temperature of the HDPE. The melting temperature slightly increased with increasing
radiation doses.
the radiation The melting
doses. temperature
The melting increased
temperature after radiation-induced
increased grafting reaction.
after radiation‐induced grafting However,
reaction.
the radiation doses. The melting temperature increased after radiation‐induced grafting reaction.
the crystallinity
However, decreased with
the crystallinity increasing
decreased withradiation
increasing dose. As shown
radiation in As
dose. Figure
shown5, the
incrystallinity
Figure 5, the at
However, the crystallinity decreased with increasing radiation dose. As shown in Figure 5, the
0crystallinity
kGy was 64.4%, whereas
at 0 kGy at 75 kGy,
was 64.4%, it decreased
whereas to 61.7%.
at 75 kGy, It was probably
it decreased to 61.7%.due to the
It was grafteddue
probably branches,
to the
crystallinity at 0 kGy was 64.4%, whereas at 75 kGy, it decreased to 61.7%. It was probably due to the
which
grafteddisrupted
branches,the regularity
which disruptedof the
thechain structure.
regularity of theThus,
chainthe irregular
structure. structures
Thus, formed
the irregular through
structures
grafted branches, which disrupted the regularity of the chain structure. Thus, the irregular structures
the grafting
formed process
through the reduce
graftingthe crystallinity
process reduceof HDPE
the molecular
crystallinity chainsmolecular
of HDPE [13,17,18].chains [13,17,18].
formed through the grafting process reduce the crystallinity of HDPE molecular chains [13,17,18].
1400
1400
neat HDPE
1200 neat(3HDPE
PU phr) 0 kGy
1200 PU (3
PU (3 phr)
phr) 25
0 kGy
kGy
PU (3
PU (3 phr)
phr) 75
25 kGy
kGy
PU (3 phr) 75 kGy
(MPa)

1000
modulus(MPa)

1000

800
Storgaemodulus

800

600
600
Storgae

400
400

200
200

0
0 20 40 60 80 100 120 140
20 40 60 80 100 120 140
Temperature (ooC)
Temperature ( C)

Figure
5.5. Storagemodulus
modulus of PU(3(3 phr)/HDPE composite
compositeat various
variousabsorption doses.
Figure
Figure 5.Storage
Storage modulusofofPU
PU (3phr)/HDPE
phr)/HDPE composite atatvarious absorption
absorption doses.
doses.

75 kGy 127.64 ooC, 61.7%

75 kGy 127.64 C, 61.7%
50 kGy 127.42 ooC, 62.4%
50 kGy 127.42 C, 62.4%
(m/w)
Flow(m/w)

25 kGy 127.32 ooC, 63.4%

25 kGy 127.32 C, 63.4%
0 kGy 127.29 ooC, 64.4%
Flow

0 kGy 127.29 C, 64.4%

Heat

neat HDPE 127.22 ooC, 65.9%

Heat

neat HDPE 127.22 C, 65.9%

40 60 80 100 120 140 160 180 200

40 60 80 100 120 140 160 180 200
Temperature (ooC)
Temperature ( C)

Figure 6. Differential scanning calorimetry (DSC) micrographs of PU (3 phr)/HDPE composites at

Figure 6.
Figure 6. Differential
Differential scanning
scanning calorimetry
calorimetry (DSC)
(DSC) micrographs
micrographs of
of PU
PU (3
(3phr)/HDPE
phr)/HDPE composites
composites at
at
various absorption doses.
various absorption
various absorptiondoses.
doses.
4. Conclusions
4. Conclusions
4. Conclusions
To reduce the environmental impact of industrial waste PU, the alternative recycling and reuse
To reduce the
the environmental
environmental impact
impact of industrial
industrial waste
waste PU,
PU, the
the alternative
alternative recycling
recycling and
and reuse
reuse
of PUToisreduce
very important. In this study, weofexplored the utilization of waste PU as polymer filler via
of
of PU is very important.
PU is very important. In this study, we explored the utilization of waste PU as polymer filler via
radiation‐induced grafting.InThe
thisgrafting
study, of
wewaste
explored the utilization
PU onto of waste
HDPE matrices was PU as polymer
carried out withfiller
one
radiation‐induced
via grafting.
radiation-induced The grafting
grafting. of waste PU onto HDPE matrices was was
carried out with one
process using radiation with TheMAH.grafting
The of waste PU onto
radiation‐induced HDPE matrices
grafting promoted carried out with
the interfacial
process using radiation with MAH. The radiation‐induced grafting promoted the interfacial
adhesion of PU onto HDPE matrices. When the absorbed dose was 75 kGy, the surface morphologies
adhesion of PU onto HDPE matrices. When the absorbed dose was 75 kGy, the surface morphologies
6
6
Materials 2016, 9, 13 7 of 8

one process using radiation with MAH. The radiation-induced grafting promoted the interfacial
adhesion of PU onto HDPE matrices. When the absorbed dose was 75 kGy, the surface morphologies
of the irradiated PU/HDPE composites presented as a smooth and single phase, and the elongation
at break increased by approximately three-fold compared with that of non-irradiated PU/HDPE
composites. Furthermore, the ductility of the HDPE composite was improved due to the successful
radiation-induced grafting of waste PU onto the HDPE matrix. The improved properties suggest
that HDPE/PU composite can be a good candidate for applications in high performance engineering,
membranes for lithium ion batteries, and packaging.

Acknowledgments: This work was supported by National Research Foundation of Korea (NRF) grant funded by
the Ministry of Science, ICT (Information & Communication Technology) and Future Planning, Korea government
(No.2013M2A2A6042482).
Author Contributions: Jong-Seok Park designed and performed the experiment. Young-Chang Nho and
Youn-Mook Lim analyzed the data and discussed the experiment. Jong-Seok Park wrote the manuscript.
The manuscript was reviewed by all authors.
Conflicts of Interest: The authors declare no conflict of interest.

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