polymers

Article
Fabrication and Characterization of Aluminum
Nanoparticle-Reinforced Composites
Seongbeom Jeong 1 , Young Seok Song 1,2 and Eunju Lim 1,3, *
1 Department of Convergence Systems Engineering, Dankook University, Youngin 448-701, Korea;
sungbum0414@naver.com (S.J.); ysong@dankook.ac.kr (Y.S.S.)
2 Department of Fiber System Engineering, Dankook University, Youngin 448-701, Korea
3 Department of Science Education, Dankook University, Youngin 448-701, Korea
* Correspondence: elim@dankook.ac.kr




Received: 28 September 2020; Accepted: 18 November 2020; Published: 24 November 2020


Abstract: With the expanding use of polymers in modern our lives, there is an increasing need
to manufacture advanced engineering polymeric parts in a systematic and inexpensive way.
Herein, we developed an organic inorganic hybrid composite material with excellent mechanical
properties by enhancing the dispersion and moldability of fillers. For this, we prepared and analyzed
the physical properties of acrylonitrile butadiene styrene (ABS)/aluminum nanoparticle composites.
Al nanoparticles of various sizes (20 nm and 40 nm) and concentrations (3, 6, 9, and 12 wt.%) were
employed. The mechanical properties of the prepared composites were measured using a universal
testing machine. Rheological and thermal analyses for the composites were carried out with use
of a rheometer and a differential thermal calorimeter (DSC). We also conducted optical, chemical,
electrical, and morphological property studies of the samples in order to help design and produce
high-performance engineering products.

Keywords: acrylonitrile butadiene styrene; Al nanoparticle; composites

1. Introduction
A growing demand for high-performance and fine precision plastics has initiated the incorporation
of composite materials in polymer processing technology [1–3]. In addition, it is critical to develop
new engineering composites as hybrid organic inorganic materials rather than as single material.
Currently, many engineering polymeric materials, such as polycarbonate (PC), nylon, polyester,
urethane, and acrylonitrile butadiene styrene copolymer (ABS), are employed in a wide range of
applications [4–6]. Moreover, the processing technologies for composite materials are being developed
to produce structured products with excellent mechanical properties and geometrical precision.
The physical properties of a product depend on the particle size, distribution, shape, molecular weight,
melting point, and viscosity of the polymer used [7–11]. In the case of reinforcing materials used in
composites, special properties such as high fluidity, thermal conductivity, and interfacial bonding
strength, are required [12,13]. Efforts are ongoing for enhancing not only the functional properties of
composites but also their aesthetic sensibility.
In this study, we fabricated metal nanoparticle-embedded composites via extrusion and injection
molding. Aluminum nanoparticles of various sizes were incorporated into the composites and the
effect of their loading was evaluated [14,15]. The development of conventional metal-like aesthetic
materials was implemented by using micro-sized metal particles, since the glossiness is affected by the
ratio of the content of micro-nanoparticles. The rheological properties of the metal composites, such as
viscosity, storage modulus, and loss elastic modulus, were analyzed. We evaluated the metal-like
properties of ABS/Al nanocomposites after injection molding. In order to improve the gloss and

Polymers 2020, 12, 2772; doi:10.3390/polym12122772 www.mdpi.com/journal/polymers

Polymers 2020, 12, 2772 2 of 10

surface properties, the composite was irradiated with an ion beam, and the electrical properties of the
composite were analyzed. We analyzed the glossiness, color, surface roughness, mechanical strength,
etc., of the composites.

2. Materials and Methods

2.1. Materials Preparation

The organic material purchased to produce the organic/inorganic nanocomplex was acrylonitrile
butadiene styrene (ABS) from LG Chem., Seoul, Korea. The used inorganic materials were aluminum
nanoparticles, which have two particle sizes of 20 nm and 40 nm from CN vision. An extruder
(Thermo Fisher Scientific’s Process 11 Parallel Twin-Screw Extruder, Waltham, MA, USA) was used to
integrate Al nanoparticles into the ABS polymer. Prior to the extrusion, the material was stored in a
dryer for 24 h. The 20 nm and 40 nm Al nanoparticles were dispersed in ABS at a weight ratio of 0, 3,
6, 9, and 12. The temperature and rotation speed applied to the extruder were 235 ◦ C and 250 rpm,
respectively. Resin preparation (Thermo Fisher Scientific’s Minijet Pro Piston Injection Molding System)
was carried out for 5 s at 400 bar under conditions of cylinder 400 ◦ C and mold 120 ◦ C. Nitrogen
and chromium ion beams were applied to increase the surface gloss of the ABS/Al nanocomposites.
Ion beam irradiation was performed in the Korea Multipurpose Accelerator Complex (KOMAC,
Seoul, Korea). The energy of the ion was 100 KeV, and the dose was 1013 , 1014 , and 1015 ions/cm2 .

2.2. Methods
The rheological properties of the Al/ABS composites were measured using a rheometer (MCR302,
Anton Parr, Graz, Austria) [16–19]. For rheological measurements, disk-shaped parts fabricated
via injection molding were employed. The shear viscosity was measured in the shear rate range
0.01–1000 s−1 . The oscillatory shear test was conducted in the frequency range 0.1–100 rad s−1 .
The storage modulus (G0 ) and loss modulus (G”) were analyzed [20]. Tensile tests were performed
using a universal testing machine (UTM, Instron, Norwood, MA, USA). Young’s modulus, yield
strength, and elongation at break were measured. To confirm the microstructure morphology of the
nanocomposite, a scanning electron microscope (SEM, S-4700, Hitach, Tokyo, Japan) was used to
observe the dispersion of nanoparticles in the sample. The thermal properties of the samples were
measured using differential scanning calorimetry (DSC, Q2000 system, TA instrument, New Castle,
DE, USA) [21–26]. Stopping and range of ions in matter (SRIM) simulation was performed to estimate
the thickness of the ion beam penetration into the composite, and ion beam injection was performed
at different flow rates/energies using two ion species (N and Cr) at room temperature. The beam
flux was maintained at a fixed value. In order to evaluate the electrical features, Ag electrodes were
fabricated at 1 cm intervals parallel to the sample. A voltage up to 5 V was applied to the sample
at 0.1 V intervals. Current–voltage (I–V) observations were made using a semiconductor parameter
analyzer (HP 4155A) [27,28].

3. Results and Discussion

Figure 1 shows the SEM images of the Al nanoparticles of sizes 20 nm and 40 nm. The spherical
nanoparticles were dispersed in the ABS plastic with the use of an extruder. Figure 2a,b present the
SEM images of the fractured surface. The nanoparticles were found to be evenly dispersed. In addition,
as expected, more particles were observed as the particle loading increased. Figure 3 shows the DSC
results of the composites. The effects of the particle content and the size of the nanoparticles on
the glass transition temperature (Tg ) were analyzed. The transition temperatures of the 20 nm and
40 nm particle-embedded composites were found to increase with increasing the particle content from
0 to 12 wt.%. The change in the glass transition temperature is shown to be relatively large for the
40 nm particle-reinforced composite. In the case of the 40 nm particle-reinforced composite, the effect
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264 of particle addition was dramatic, but there was no significant difference between the samples with
265 weight percentages of 3 to 12 %. This may be due to the decrease in the molecular mobility of ABS.

266

267 (a) (b)

268

269 40 nm
Polymers 2020, 12, x FOR PEER REVIEW 9 of 17

270
293
271 294
(a) (a)-1 Pure ABS20 nm (a)-2
40nm
3 wt% Al NPs (20 nm) (a)-3 6 wt% Al NPs100nm
(2040nm
nm)
272 Polymers 2020, 12, x FOR PEER REVIEW 9 of 17
295
273 293 Figure
Figure 1. SEM images 1. S.
of Al: (a)Jeong
20 nmetand
al. (b) 40 nm nanoparticles.

296
294
274 (a) (a)-1 Pure ABS (a)-2 3 wt% Al NPs (20 nm) (a)-3 6 wt% Al NPs (20 nm)

275 297
295
(a)-4 9 wt% Al NPs (20 nm) (a)-5 12 wt% Al NPs (20 nm)
276 298
296

277
299
297
278 (a)-4 9 wt% Al NPs (20 nm) (a)-5 12 wt% Al NPs (20 nm)
300
298
279

280 301
299

281
302
300
282 303
301 (b) (b)-1 Pure ABS (b)-2 3 wt% Al NPs (40 nm) (b)-3 6 wt% Al NPs (40 nm)
283 304
284 302
305
303
285 (b) (b)-1 Pure ABS (b)-2 3 wt% Al NPs (40 nm) (b)-3 6 wt% Al NPs (40 nm)

286 306
304

(b)-4 9 wt% Al NPs (40 nm) (b)-5 12 wt% Al NPs (40 nm)
287 307
305

288
308
306
289
(b)-4 9 wt% Al NPs (40 nm) (b)-5 12 wt% Al NPs (40 nm)
309
307
290
310 Figure 2. S. Jeong et al.
291 Figure 2. SEM image of cross-section of composite material of ABS and Al: (a) 20 nm and (b) 40 nm
308
nanoparticles from 0 to 12 wt.%.
311
292
309
312
310 Figure 2. S. Jeong et al.

313
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Figure 3. DSC of ABS/Al (a) 20 nm and (b) 40 nm nanoparticle composites.

Figure 3. DSC of ABS/Al (a) 20 nm and (b) 40 nm nanoparticle composites.
Figure 3. DSC of ABS/Al (a) 20 nm and (b) 40 nm nanoparticle composites.
Rheology is a powerful tool for characterizing the internal structure of complex materials [16–
Rheology is a powerful tool for characterizing the internal structure of complex materials [16–19].
19]. For instance, the viscoelastic characteristics can provide a variety of information regarding the
Rheology
For instance, is the
a powerful toolcharacteristics
viscoelastic for characterizing the internal
can provide structure
a variety of complex
of information materials
regarding the[16–
internal
internal structure of the test material such as particle dispersion, size, shape, and surface properties
19]. structure
For instance, thetest
of the viscoelastic
materialcharacteristics
such as particle candispersion,
provide a variety of information
size, shape, and surface regarding
properties the [29].
[29]. Figure 4a,b present the viscosity of the nanocomposites filled with 20 nm and 40 nm aluminum
internal
Figurestructure of the test
4a,b present the material
viscositysuch as nanocomposites
of the particle dispersion, size,with
filled shape, and and
20 nm surface
40 nmproperties
aluminum
nanoparticles, respectively. The graph shows the so-called zero shear-rate viscosity and shear-
[29].nanoparticles,
Figure 4a,b present the viscosity
respectively. The graphof the nanocomposites
shows the so-calledfilled with 20 nm
zero shear-rate and 40 and
viscosity nm aluminum
shear-thinning
thinning behavior. This means that the composite materials can be modeled with the help of the
nanoparticles,
behavior. This respectively.
means that The
thegraph shows
composite the so-called
materials can be zero
modeledshear-rate
with the viscosity
help of and shear-
the Cross-WLF
Cross-WLF model: η = η_∞ + (η_0 [−η]_∞)/(1 + (Cγ)^(1 − n)), where η_∞ is the infinite shear-rate
thinning
model: η = η_∞This
behavior. + (η_0
means that the
[−η]_∞)/(1 + (Cγ)ˆ(1
composite materials
− n)), where η_∞ canisbethe modeled with the help
infinite shear-rate of the
viscosity, η_0 is
viscosity, η_0 is the zero shear rate viscosity, C is a time constant, and n is the power law index. The
Cross-WLF
the zero model:
shear rateη =viscosity,
η_∞ + (η_0C is [−η]_∞)/(1 + (Cγ)^(1
a time constant, and n− isn)),
thewhere
powerη_∞ law is the infinite
index. The model shear-rate
is a widely
model is a widely used rheological model for injection molding. As the filler loading increased, the
viscosity, η_0 is the zero
used rheological shear
model forrate viscosity,
injection C is a As
molding. timetheconstant, and nincreased,
filler loading is the power thelaw index.viscosity
resulting The
resulting viscosity also increased. Interestingly, the nanocomposites filled with the 20 nm
modelalsois increased.
a widely used rheological
Interestingly, themodel for injection
nanocomposites molding.
filled with theAs 20thenm
filler loading increased,
nanoparticles showedthe higher
nanoparticles showed higher viscosity than those with the 40 nm ones. This is due to the fact that one
resulting
viscosityviscosity
than thosealsowith
increased.
the 40 nmInterestingly, the tonanocomposites
ones. This is due the fact that one had filleda higher
with effective
the 20 volume
nm
had a higher effective volume of filler than the other. When a shear stress was applied to the samples,
nanoparticles
of filler thanshowed higher
the other. viscosity
When a shear than those
stress waswith the 40tonm
applied theones. This the
samples, is due
flowto resistance
the fact that one
decreased.
the flow resistance decreased. This is because the ABS molecules and Al nanoparticles were oriented
had This
a higher effective
is because thevolume of filler than
ABS molecules and Althenanoparticles
other. When werea shear stress was
oriented in theapplied to the
direction samples,
of the shear flow.
in the direction of the shear flow.
the flow resistance decreased. This is because the ABS molecules and Al nanoparticles were oriented
in the direction of the shear flow.

Figure 4.
Figure 4. Viscosity
Viscosity of
of ABS/Al:
ABS/Al: (a)
(a) 20
20 nm
nm and
and (b)
(b) 40
40 nm
nm nanoparticle
nanoparticle composites.
composites.

Figure 4. Viscosity of ABS/Al: (a) 20 nm and (b) 40 nm nanoparticle composites.

The
The small-amplitude
small-amplitude oscillatory
oscillatory shear
shear test
test (SAOS)
(SAOS) was was used
used for
for nondestructive
nondestructive analysis
analysis of
of
viscoelastic materials [30].
viscoelastic materials [30].Figure
Figure 5a,b
5a,b show
show thethe storage
storage modulus
modulus of theofcomposites
the composites filled20
filled with with
nm
The small-amplitude oscillatory shear test (SAOS) was used for nondestructive analysis of
20
andnm40and
nm40Alnm Al nanoparticles.
nanoparticles. The storage
The storage modulusmodulus increased
increased withwith increasing
increasing filler
filler loading.
loading. In
viscoelastic materials [30]. Figure 5a,b show the storage modulus of the composites filled with 20 nm
In particular,
particular, thethe composites
composites with
with 20 20
nmnm particles
particles showed
showed higher
higher modulus
modulus values
values than
than those
those with
with 40
and 40 nm Al nanoparticles. The storage modulus increased with increasing filler loading. In
40
nmnm particles,
particles, which
which indicated
indicated thethe so-called
so-called sizesize effect,
effect, that
that is, is, larger
larger particle
particle matrix
matrix interaction.
interaction. In
particular, the composites with 20 nm particles showed higher modulus values than those with 40
In addition,
addition, thethe compositesreinforced
composites reinforcedwith
with2020nmnmparticles
particlesexhibited
exhibited more
more solid-like behavior in the the
nm particles, which indicated the so-called size effect, that is, larger particle matrix interaction. In
addition, the composites reinforced with 20 nm particles exhibited more solid-like behavior in the
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low-frequency
low-frequencyregion
regionthan
thanthose
thosewith
with4040nm
nmparticles. The
particles. loss
The modulus
loss showed
modulus a similar
showed behavior
a similar to
behavior
the storage modulus as presented in Figure 5c,d.
to the storage modulus as presented in Figure 5c,d.

Figure5.
Figure 5. Storage
Storage modulus
modulus(G
(G′) and loss
0 ) and loss modulus
modulus (G”)
(G″) curves
curves of
of ABS/Al
ABS/Al 20
20 nm
nm and
and 40
40 nm
nm nanoparticle
nanoparticle
composites. (a,c) are ABS/Al 20 nm, (b,d) are the storage modulus and loss modulus
composites. (a,c) are ABS/Al 20 nm, (b,d) are the storage modulus and loss modulus curves curves of of
thethe
40
nm nanoparticle composite.
40 nm nanoparticle composite.

Theviscoelastic
The viscoelasticcharacteristics
characteristicsarearecorrelated
correlated toto
thethe mechanical
mechanical properties
properties of the
of the samples.
samples. Figure
Figure 6a
6a shows
shows the the Young’s
Young’s moduli
moduli of the
of the composites.The
composites. Theelastic
elasticmodulus
modulusincreased
increasedas asthe
theAl Al particle
particle
concentration increased.
concentration increased. Similar
Similar to the results of the storage storage andand loss
loss moduli,
moduli, the the 20
20 nm
nm particle
particle
embedded composite
embedded composite was was found
found to to show
show higher
higher elastic
elastic modulus
modulus than than the
the 4040 nmnm particle-filled
particle-filled
composite. Figure
composite. Figure 6b6bshows
showsthat
thatthe
theelongation
elongationatatbreakbreak hadhada tendency
a tendency to to
gradually
gradually decrease
decreaseas the
as
concentration
the concentration of aluminum
of aluminum nanoparticles
nanoparticles increased.
increased.In the casecase
In the of the 20 nm
of the particle
20 nm composite,
particle the
composite,
elongation
the elongation at break
at break decreased
decreased linearly.
linearly.The Theelastic
elasticmodulus
modulusand andelongation
elongation at at break showed
showed an an
inverse relationship
inverse relationship withwith each
each other.
other. The
The tensile
tensile strength
strengthresults
resultsareareshown
shownin inFigure
Figure6c. 6c. The
Thetensile
tensile
strength of
strength of the
the20
20nmnmparticle
particlecomposite
composite had had aatendency
tendency to toincrease
increaseas asthe
theconcentration
concentrationof ofparticles
particles
increased,but
increased, butthat
thatofofthe
the
4040
nmnm particle
particle composite
composite showedshowed a different
a different trend.trend.
Figure Figure 6d shows
6d shows the
the yield
strength of the composites. The yield strength indicates the degree of maximum stress that a materiala
yield strength of the composites. The yield strength indicates the degree of maximum stress that
material
can can without
undergo undergocausing
withoutplastic
causing plastic deformation.
deformation. Plastic deformation
Plastic deformation is awhich
is a state in state the
in which the
material
material permanently
deforms deforms permanently dueFor
due to slip. to the
slip.composite
For the composite
filled with filled
40 nmwith 40 nm particles,
particles, the yield the yield
strength
strength decreased
decreased with increasing
with increasing particle loading.
particle loading.
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Figure6.6. (a)
Figure (a) Young’s
Young’s modulus,
modulus, (b)
(b) elongation
elongation at
at break,
break, (c)
(c) tensile
tensile strength,
strength, and
and (d)
(d)yield
yieldstrength
strength
results
resultsof
ofABS/Al
ABS/Alcomposites.
composites.

To
Toenhance
enhancethe thesurface
surfaceproperties,
properties,the thecomposites
compositeswere wereirradiated
irradiatedwith withaanitrogen
nitrogengas gasionionbeam
beam
and a chromium metal ion beam [31]. Figure 7 shows the penetration
and a chromium metal ion beam [31]. Figure 7 shows the penetration depth calculated through the depth calculated through
the
SRIMSRIM simulation
simulation [32].
[32]. It was
It was shown
shown ininthe
theSRIM
SRIMsimulation
simulationresults
results that
that the
the nitrogen
nitrogen ion ion beam
beam
penetrated into the surface by about 400 nm (Figure 7(a-1,a-2)), and the
penetrated into the surface by about 400 nm (Figure 7a), and the chromium ion beam penetrated intochromium ion beam penetrated
into the surface
the surface by about
by about 200 nm 200(Figure
nm (Figure 7(b-1,b-2)).
7b). The The inset
inset in Figure 7b-1inshows
Figurethe7(b-1) showsirradiated
FIB image the FIB image from
irradiated from the
the side after side afterirradiation
chromium chromium irradiation on the composite
on the composite material.material. The difference
The difference between between
SRIM
SRIM simulations
simulations and experiments
and experiments indicates
indicates thatall
that not not all beam
beam irradiations
irradiations lead
lead to thetocontribution
the contribution to poreto
pore formation onto the surface. When nitrogen and chromium ion
formation onto the surface. When nitrogen and chromium ion beams were irradiated, small pores beams were irradiated, small pores
were
wereformed
formedon onthe
thesurface
surfacedue dueto toion
ionsize
sizeor
oraabeam
beamthatthathadhadnot
notyetyetpenetrated.
penetrated. TheThe corresponding
corresponding
experiments
experiments were divided into three cases: a nitrogen ion beam, chromium ion beam,and
were divided into three cases: a nitrogen ion beam, chromium ion beam, andnitrogen
nitrogen
and
andchromium.
chromium. Figure Figure 8a,b
8a,b show
showthe theresults
resultsof ofnanoindentation
nanoindentationtests. tests. The
Thesamples
sampleswere wereirradiated
irradiated
with 15 2
with100100eV eVion ionbeam
beamenergy
energyatataadose doseofof101015ions/cm
ions/cm2 in inABS
ABSand andABS/Al
ABS/Al12 12wt.%.
wt.%. TheTheion ionbeam
beam
effect
effect was analyzed. Irradiating a composite surface with an ion beam increased the hardnessof
was analyzed. Irradiating a composite surface with an ion beam increased the hardness ofthe
the
surface
surfacedepending
dependingon onthe
thetype
typeandandmixing
mixingof ofthe
theion
ionbeam.
beam. In In the
the case
case of
of chromium
chromium beam beam irradiation,
irradiation,
the
the mechanical
mechanical strength
strength was was the the highest
highest among
amongthe thesamples.
samples. ThisThis isis because
because whenwhen thethe polymer
polymer
material
material is irradiated with an ion beam, the surface hardness and density change, increasing the
is irradiated with an ion beam, the surface hardness and density change, increasing the
mechanical
mechanicalstrength.
strength.Also,
Also,the thesurface
surfacestructure
structureof ofthe
thepenetration
penetrationlayer layervaries
variesdepending
dependingon onthethetype
type
of
ofirradiation
irradiationion beam.
ion beam. To Todetermine
determine the surface conduction
the surface characteristics
conduction of the samples,
characteristics the current
of the samples, the
voltage
currentrelation
voltage was analyzed
relation after the Al
was analyzed aftermetal
the Alelectrode was positioned
metal electrode in parallelinwith
was positioned the samples.
parallel with the
Figure
samples.9a compares
Figure 9a the current the
compares values fromvalues
current 0 to 5 Vfrom
when 0 three
to 5 Vtypes
when ofthree
ion beams
typeswereof ionapplied
beamstowere the
applied to the samples. In Figure 9b, the current difference at a voltage of 5 V was replotted and
analyzed according to the type of ion beam irradiation. The difference in surface resistances in the
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samples. and
presence In Figure 9b, the current
the absence of metal difference at a voltage
nanoparticles was the of 5largest
V wasin replotted
the caseand of analyzed
nitrogen ion according
beam
irradiation, and the value of conductivity of the ion beam type was the highest in the absence
to the type of ion beam irradiation. The difference in surface resistances in the presence and the case of
of metal nanoparticlesion
chromium/nitrogen wasbeam
the largest
mixedin the case of nitrogen
irradiation. The ion ion beam
beamirradiation,
irradiation andcanthe value
change of
conductivity of the ion beam type was the highest in the case of chromium/nitrogen
macromolecular structures, e.g., the formation of new double bond structure or cross-linking ion beam mixed
irradiation.More
structure. The specifically,
ion beam irradiation
when thecan changeion
nitrogen macromolecular
beam is imposed, structures,
the C–N e.g.,and
theC–C
formation
bond canof new
be
double bond
formed, structure
resulting or cross-linking
in an increase structure.
in electrical More specifically,
conductivity [33]. when the nitrogen ion beam is
imposed,
Figurethe10C–N
shows andtheC–C bond
result of can be formed,
the surface resulting
gloss in an increase
of the composite. The in electrical
effects of theconductivity
ion beam types [33].
Figure
and ion beam10 shows
doses the wereresult of the surface
experimentally gloss of Figure
analyzed. the composite.
10a shows Thetheeffects
glossofresults
the ionofbeam the
types and ion beam doses were experimentally analyzed. Figure 10a shows
composite material. In the case of nitrogen ion beam irradiation, the gloss was greatly increased the gloss results ofat the
a
composite material. In the case of nitrogen ion beam irradiation, the gloss
small amount (3 wt.%) of Al nanoparticles. There was no significant difference in gloss when Al metal was greatly increased at
a small amount
nanoparticles (3 9,
at 6, wt.%)
and12 ofwt.%
Al nanoparticles.
were dispersed. There wascase
In the no significant
of chromium difference
ion beam inirradiation,
gloss whenthe Al
metal nanoparticles at 6, 9, and12 wt.% were dispersed. In the case of chromium
glossiness tended to decrease as the content of Al nanoparticles increased from 3 to 12 wt.%. In the ion beam irradiation,
the glossiness tended ion
nitrogen/chromium to decrease
beam as the contentthe
irradiation, of Algloss
nanoparticles
gradually increased
increased fromas3 tothe12 wt.%.
contentIn the
of
nitrogen/chromium
nanoparticles ion beam
increased fromirradiation,
0 to 12 wt.%. the gloss gradually
The most increased
effective as the for
condition content
glossofisnanoparticles
the case of
increasedion
nitrogen from
beam 0 toirradiation
12 wt.%. at The most effective
a particle contentcondition
of 3 wt.%.for Whengloss
theiscomposite
the case ofmaterial
nitrogencontaining
ion beam
irradiation
Al at a particle
nanoparticles content of
was irradiated with3 wt.%. Whenion
a nitrogen thebeam,
composite material
not only containing
structural changesAl of
nanoparticles
C–C, C–H,
was irradiated with a nitrogen ion beam, not only structural changes of C–C,
and C–O bonds but also changes in the surface’s structure occurred. This led to changes in glossiness C–H, and C–O bonds but
also changes in the surface’s structure occurred. This led to changes in glossiness
[33,34]. Figure 10b shows the change in gloss caused by the change in nitrogen ion beam dose. The [33,34]. Figure 10b
showsincreased
gloss the change asinthe gloss
dosecaused by theIncreased
increased. change in ion nitrogen
beamion beam
doses dose. The
affected the gloss
surfaceincreased
densityasandthe
dose increased. Increased
cross-linking structure. ion beam doses affected the surface density and cross-linking structure.

Figure 7. (a-1,a-2) Nitrogen and (b-1,b-2) chromium ion beams irradiation by SRIM simulation result.
Figure 7. (a-1,a-2) Nitrogen and (b-1,b-2) chromium ion beams irradiation by SRIM simulation result.
The inset figure in (b-1) shows the FIB image investigated from the side after irradiating chromium
The inset figure in (b-1) shows the FIB image investigated from the side after irradiating chromium on
on
thethe composite
composite material.
material.
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Polymers 2020, 12, x FOR PEER REVIEW 8 of 10

Polymers 2020, 12, x FOR PEER REVIEW 16 of 17

402
Figure 8.
Figure 8. (a) Nanoindentation results of nitrogen and chromium
chromium ionion beams
beams irradiation
irradiation composite
composite
samples and (b)(b) difference
difference value
value of
of nanoindentation
nanoindentation results.
results. (b) The inserted figure is aa simplified
simplified
403 structural image
structural image ofof the
the nanoindenter.
nanoindenter.
Figure 8. (a) Nanoindentation results of nitrogen and chromium ion beams irradiation composite
samples and (b) difference value of nanoindentation results. (b) The inserted figure is a simplified
structural image of the nanoindenter.

404 Figure 9. (a) Investigation of surface electrical properties through I–V measurement after nitrogen ion
beam and chromium ion beam irradiation. (b) The difference in current when a voltage of 5 V was
405 Figure
Figure 9. (a) Investigation of surface electrical 9. S. Jeong
properties et al. I–V measurement after nitrogen ion
through
applied is shown. (a) Inset image shows I-V measuring element.
beam and
Figure 9. (a)chromium ion of
Investigation beam irradiation.
surface electrical(b) The difference
properties throughinI–V
current when a voltage
measurement of 5 V was
after nitrogen ion
applied
beam andis chromium
shown. (a) ion
Inset image
beam shows I-V(b)
irradiation. measuring element.
The difference in current when a voltage of 5 V was
406
applied is shown. (a) Inset image shows I-V measuring element.

407

408

409

410 Figure 10. (a) Change of glossiness after irradiation with (a) nitrogen ion beam according to difference
in irradiation amount and (b) nitrogen, chromium, nitrogen, and chromium ion beam irradiation
under 1.8 × 1016 ions cm−2.
411 Figure
Figure10.10.(a)(a)Change
Changeofofglossiness
glossinessafter
afterirradiation
irradiationwith
with(a)
(a)nitrogen
nitrogenion
ionbeam
beamaccording
accordingtotodifference
difference
in
in irradiation
irradiation
4. Conclusions amount
amount and
and (b)
(b) nitrogen,
nitrogen, chromium,
chromium, nitrogen,
nitrogen, and and chromium
chromium ion ion
beam beam irradiation
irradiation under
1.8 × 10
under 1.816×ions
1016 cm −2 .cm−2.
ions
412 In this study, we fabricated organic inorganic composites by incorporating Al nanoparticles in
an ABS polymer. The composites were extruded and injection-molded for experimental analyses. The
4. Conclusions
In this study, we fabricated organic inorganic composites by incorporating Al nanoparticles in
413 an ABS polymer. The composites were extruded and injection-molded for experimental analyses. The
Polymers 2020, 12, 2772 9 of 10

4. Conclusions
In this study, we fabricated organic inorganic composites by incorporating Al nanoparticles in
an ABS polymer. The composites were extruded and injection-molded for experimental analyses.
The mechanical, thermal, optical, chemical, and electrical properties of the composites were evaluated.
The effects of nanoparticle size, concentration, and type of ion beam were analyzed. It was found that
the composites prepared with 40 nm particles showed significantly enhanced thermal and mechanical
properties. Also, the electrical properties of the polymer material could be improved by adjusting the
nanoparticle content and ion beam irradiation. This study is expected to help to provide a way to
design and manufacture metal nanoparticle embedded polymeric composites for high performance
engineering products.

Author Contributions: S.J. performed the experiments, analyzed the results. Y.S.S. discussed the result and
analyzed the theory. E.L. conceived the concept, supervised the research, analyzed the result and wrote the
manuscript. All authors have read and agreed to the published version of the manuscript.
Funding: This research was partially supported by the Basic Research Program (No. 2018R1D1A1A09084192 and
No. NRF-2018R1A5A1024127) of the National Research Foundation (NRF) funded by the Ministry of Education,
Science and Technology, Korea. The authors also acknowledge the support from the Soft Chemical Materials
Research Center for Organic Inorganic Multi-Dimensional Structures, which is funded by the Gyeonggi Regional
Research Center Program (GRRC dankook 2016-B03).
Conflicts of Interest: The authors declare no conflict of interest.

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