Polymer Testing 85 (2020) 106352

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Polymer Testing
journal homepage: http://www.elsevier.com/locate/polytest

The fabrication of affinity improved nanocomposites with plasma treated

polypropylene (PP) and alkaline cellulose nanofiber (CNF) suspension
Bich Nam Jung a, b, Hyun Wook Jung b, DongHo Kang a, Gi Hong Kim a, Miji Lee a, c,
Sung Wook Hwang d, Jin Kie Shim a, *
a
Korea Packaging Center, Korea Institute of Industrial Technology, Bucheon, 14449, South Korea
b
Department of Chemical and Biological Engineering, Korea University, Seoul, 02841, South Korea
c
Department of Biotechnology, Korea University, Seoul, 02841, South Korea
d
Department of Chemical Engineering, Keimyung University, Daegu, 42601, South Korea

A R T I C L E I N F O A B S T R A C T

Keywords: Polypropylene (PP) nanocomposites containing cellulose nanomaterials have been studied for the last decade,
Polypropylene but are still challenging due to the lack of affinity between PP and cellulose nanofiber (CNF), and the uneven
Cellulose nanofiber dispersion of CNF in the PP matrix. In order to achieve the uniform dispersion of CNF in the PP matrix and
Plasma
improve affinity between PP and CNF, plasma-treated PP/aCNF nanocomposites were prepared by adding an
Suspension
Melt mixing
alkaline CNF (aCNF) suspension to the nitrogen (N2) and oxygen (O2) plasma-treated PP. Based on the results of
various analyses, the N2 plasma-treated PP (npPP)/aCNF nanocomposite showed the best performance in tensile
and oxygen barrier properties. The npPP/aCNF nanocomposite increased 32.8 and 26.3% in yield stress and
Young’s modulus, respectively, compared with neat PP, also in O2 permeability, it showed a value of 94.31 cc-
mm/m2-day-atm and showed a statistically significant decrease in contrast to neat PP. The npPP/aCNF nano­
composite has a great feasibility to be applied in various barrier packaging applications.

1. Introduction treatment process is performed under dry conditions through a gas

The development of PP-based nanocomposites has been profoundly
studied over the last decade due their excellent characteristic
enhancement as compared to the homo-polymer. Similarly, in the field
of consumer packaging such as food and pharmaceutical packaging,
research has been being steadily carried out to increase mechanical and
gas barrier properties through the production of PP-based nano­
composites to protect products and improve shelf life [1–3].
PP is a polymer used in many industries due to its various advantages
and properties such as low lost, low density, easy recyclability, and
versatility in terms of properties. However, despite these many merits,
the hydrophobic nature is limited to the fabrication of nanocomposites
using nanofillers such as clay and cellulose, which are hydrophilic.
There is one way to introduce functional groups onto the surface via
plasma treatment to improve compatibility with hydrophilic materials.
The plasma treatment is a useful method because it can fix different
chemical groups on the surface, and can be modified without changing
the characteristics of the materials [4]. In addition, the plasma
without solvent, which can resolve the disadvantages of conventional
wet chemical methods [5,6].
Bleached wood pulps and various non-wood fibers such as cotton
linters, are used as resources for producing cellulose nanofiber (CNF),
and CNF is in the spotlight as reinforcement to enhance the physical
properties such as mechanical and gas barrier properties of the polymer
matrix [7]. According to Yano et al. [8], when volume fraction of CNF
was increased towards 90 vol%, tensile modulus and strength of ~14
GPa and ~350 MPa, respectively, were obtained for the resulting
nanocomposites. However, even with a small amounts of nanocellulose,
a large strengthening effect has been demonstrated and clarified by
Favier at al [9]. Because of the strong bonding between the CNFs, it is
difficult to uniformly disperse them in the polymer matrix, but the ad­
vantages of CNF, with its low density and high specific surface area,
make it possible to form a network within polymer matrix even at low
amounts. In addition, one of the characteristics of CNF is its excellent gas
barrier properties, resulting from the creation of tortuous paths, making
a permeant molecule take more time to permeate the composites

* Corresponding author.
E-mail address: jkshim@kitech.re.kr (J.K. Shim).

https://doi.org/10.1016/j.polymertesting.2020.106352
Received 27 October 2019; Received in revised form 31 December 2019; Accepted 14 January 2020
Available online 25 January 2020
0142-9418/© 2020 Published by Elsevier Ltd.
B.N. Jung et al.
containing impermeable cellulose [10,11].
Polymer/CNF nanocomposites are manufactured and applied
through various methods such as solvent casting [12–14], impregnation
[15,16] and melt processing [17–19]. The most common and important
approach among them is the melt processing technique, which is very
suitable because it is related to industrial applications and eliminates
possible polymer–solvent interactions in addition to cost reduction.
However, because of the agglomeration of nanomaterials, there is a
troublesome task to directly put the dried nanomaterials into the melt
process equipment. Strong internal bonds in cellulose are not sufficient
to disperse the shear stress generated in the extruder. Oksman and
co-workers demonstrated this agglomeration by homogeneous disper­
sion in the polymer matrix through liquid-assisted feeding of nano­
materials [20–22]. This method inhibits the aggregation of CNF, as the
solvent is evaporated momentarily when CNF dispersed in the solvent is
put into the extruder. In addition, to maximize this method, CNF should
be included in the form of individual fibers in the CNF suspension. Many
researchers suggested that CNF introduces carboxyl groups through 2, 2,
6, 6-tetramethylpiperidine-1-oxyl radical (TEMPO) oxidation treatment
in order to be dispersed in water as individual fibers [23–26]. The
carboxyl groups on the tempo-oxidized CNF (TOCNF) can be dispersed
more and more in the form of individual fibers in water by electrostatic
repulsion depending on the pH concentration.
In this study, pH concentration (8–12) was controlled to maximize
the dispersion of CNF in NaOH solution, and PP/CNF nanocomposites
were prepared by melt mixing the alkaline suspension into the mixer
through a liquid-assisted feeding method. In addition, the plasma
treatment of the PP improved the affinity between the PP and the
TOCNF and increased the dispersibility of TOCNF in the PP matrix. The
reinforced nanocomposites were ultimately prepared with TOCNF con­
tent of 1 wt%. The mechanical and rheological properties of nano­
composites have been characterized. In the morphological analysis
using scanning electron microscopy (SEM) and three-dimensional (3D)
X-ray CT microscopyconfirmed that TOCNF is well dispersed in the PP
matrix. Balanced properties of nanocomposites have been achieved,
along with improved tensile stress and oxygen barrier, suggesting that
prompt industrial application could be possible for food packaging
industry.
2. Experimental section
2.1. Materials
PP (SEETEC T3410 grade, melt flow index: 7 g/10 min, 230 � C, 2.16
kg ASTM D1238) was obtained from LG Chem (Korea). The PP was cryo-
milled to produce the micro size particles. Freeze dried TOCNF was
purchased from Cellulose Lab (Canada). For TOCNF, its width is in the
range of 20–60 nm, and it has a length of several micrometers. Sodium
hydroxide (NaOH) (�98.0%) was used as received from Sigma Aldrich
(USA). PP and TOCNF were vacuum-dried at 80 � C for 12 h to remove
residual moisture before use.
2.2. Preparation of plasma-treated PP and alkaline CNF suspensions
Micro-sized PP was surface-modified by plasma treatment. The
modification of micro-sized PP was carried out under controlled con­
ditions with 10-min exposure time, gases of nitrogen (N2) or oxygen
(O2), and 50 W of plasma power using a radio frequency plasma
generator (diener FEMTO Version E of 13.56 MHz). Under these con­
ditions, an N2 plasma-treated PP (npPP) and an O2 plasma-treated PP
(opPP) were prepared. A CNF suspension was prepared by adding 25 ml
of distilled water to 0.4 g of freeze-dried TOCNF, and an alkaline sus­
pension (aCNF) was prepared by adding 25 ml of aqueous pH-adjusted
(pH 8–12) solution through NaOH to 0.4 g of freezed-dried TOCNF.
Then, they were homogenized with a homogenizer (model: T10 basic
ULTA- TURRAX®, IKA, Germany). A dispersing element for mixing,
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Polymer Testing 85 (2020) 106352
Table 1
The description of PP/CNF nanocomposites used in this study.
Sample Code PPs CNF suspensions
Control Micro-sized PP CNF suspension
PP/aCNF Micro-sized PP Alkaline CNF suspension
npPP/aCNF Nitrogen plasma-treated PP Alkaline CNF suspension
opPP/aCNF Oxygen plasma-treated PP Alkaline CNF suspension
which is not for crushing, was used, and homogenization was carried out
at 6000 rpm for 0.5 h. The optimal pH concentration of the alkaline CNF
suspension was later determined by the zeta potential and viscosity
results.
2.3. Preparation of PP/CNF nanocomposites
Four kinds of PP/CNF nanocomposites were prepared with 1 wt%
TOCNF composition by a small-scale internal mixer (Model: W50 Plas­
tograph®, Lab-Station, Brabender Gmb & Co KG, Germany) equipped
with a counter-rotating twin-screw with a barrel capacity of 50 ml. All of
PP/CNF nanocomposites were produced under a barrel temperature of
200 � C with an 80-rpm rotation speed and 6-min mixing time. Micro-
sized PP and plasma-treated PPs were first melted for 1 min in the
mixer, and then CNF suspensions were added and mixed for an addi­
tional 5 min. In the meantime, distilled water contained in the CNF
suspensions evaporated during processing. Nanocomposites used in this
study are described in Table 1.
The bulk-shaped composite samples were ground and dried at 105 � C
for 12 h to sufficiently remove remaining moisture, and then composite
granules were compression-molded to a film for measuring oxygen
barrier properties, and they were also molded for measuring the
morphological, rheological, and mechanical properties.
Compression molding was performed using a hot press system
(Model: QM900A, Quality & Measurement System, Korea), and the
molding process was carried out at 200 � C through a 4-min pre-heating,
1-min pressing, and 4-min cooling time. The composite granules were
also injection-molded at 200 � C, using a micro injection molding ma­
chine (Model: Xplore Micro 10 cc Injection Molding Machine, Xplore
Instruments, Netherlands), into test specimens with a disk shape of 25.4-
mm diameter and 1-mm thickness and dumbbell shape of 50-mm length,
4-mm width, and 2-mm thickness. Schematic illustration of PP/CNF
nanocomposite is described in Fig. 1.
2.4. Characterization
X-ray photoelectron spectroscopy (XPS, Model: K-alpha, Thermo
scientific, UK) was used to measure the elemental composition of neat
PP, npPP, and opPP. Thus, the effect of plasma treatment on the mo­
lecular weight of PP was evaluated via high-temperature gel permeation
chromatography (GPC, Model: HLC-8321 GPC/HT, Tosoh, Germany).
Zeta potential measurement was carried out with a zeta potential
analyzer (Model: Zetasizer Nano ZS, Malvern, UK). After homogeniza­
tion, the CNF suspensions were injected through the syringe into
measuring cells. The macroscopic viscosity of alkaline suspensions with
CNFs in dispersed phase was measured in a rheometer (Model: Physica
MCR302, Anton Paar GmbH, Austria) using a cup and bob system in a
shear rate range of 0.01–100 s 1.
The morphology of PP/CNF nanocomposites were observed with a
field emission scanning electron microscope (Model: SU8020, Hitachi,
Japan). Injection molded samples were cryo-fractured using liquid ni­
trogen to prevent deformation during fracture. All of the samples were
coated with Pt/Pd alloy using an ion sputter (Model: E 1045, Hitachi,
Japan). 3D X-ray CT measurements were carried out using a SKYSCAN
1172 (Bruker-Micro CT, Belgium). The area of the specimens used for
the evaluation was 400 � 600 � 400 μm, with a 700-nm resolution.
The degree of crystallinity (Xc) of neat PP and PP/CNF
B.N. Jung et al.
Fig. 1. Schematic illustration of PP/CNF nanocomposite preparation.
nanocomposites was analyzed by differential scanning calorimetry
(Model: DSC 250, TA instruments, USA). The samples were placed in a
packed aluminum pan and then heated and cooled from 20 to 200 � C,
using 10 � C/min heating and cooling rate. In addition, the sample was
measured in 2 cycles and the results of second cycle were used to
eliminate the influence on the thermal history.
Oscillatory shear measurement and stress relaxation in the linear
viscoelastic region were carried out on a rheometer using parallel-plate
geometry (25-mm diameter, 1-mm gap) at 200 � C. Frequency sweeps
were performed after 3 min temperature equilibration with decreasing
frequency from 100 to 0.1 rad/s and strain at 1%. All samples were
measured under air atmosphere.
The mechanical properties such as tensile strength and elongation at
break were measured with a universal testing machine (Model: INS­
TRON 3367, INSTRON, USA) equipped with a 30 kN cell force in
accordance with ASTM D638, measuring force over displacement for
each sample at 100 mm/min. The gauge length was fixed at 19 mm.
Oxygen permeability measurements of PP and PP/CNF nano­
composite films were performed by oxygen transmission rate analyzer
(Model: 702, MOCON, USA), complying with ASTM 3985; aluminum
masks (5 cm2) were used to prepare the samples, and the permeation test
was performed at 23 � C and 0% relative humidity at 100% oxygen at­
mosphere. Water vapor permeability of PP and PP/CNF nanocomposite
films was measured by water vapor transmission rate analysis (Model:
W700, MOCON, USA), complying with ASTM F372; aluminum masks (5
cm2) were used to prepare the samples, and the permeation test was
performed under at 37.8 � C and 100% relative humidity. The oxygen
and water vapor transmission rates were measured over 24–48 h until it
reached a steady state. Oxygen and water vapor permeability (P) was
obtained from the steady state permeate flux Jo according to
Jo l
P¼ (1)
p
where p is the oxygen and water vapor pressure and l is the film
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Polymer Testing 85 (2020) 106352
thickness [27].
Multiple comparisons of each experimental value set were analyzed
by means of one-way ANOVA and Tukey’s honestly significant differ­
ences test (α ¼ 0.05) from IBM SPSS Statistics version 23 (IBM SPSS).
3. Results and discussion
3.1. Chemical properties of plasma-treated PPs
Fig. 2 shows XPS spectra of neat PP, and plasma-treated PPs with N2
and O2 (npPP, opPP). The opPP contained three peaks at 287.4
(O–C¼O), 286.5 (C–O–C), and 284.6 (C–C) eV in C1s spectrum, and one
peak at 533 eV in the O1s spectrum (Fig. 2. (c)). However, the C1s
spectrum of npPP contained new peaks at 286.4 (C¼N), and 285.8 eV
(C–N) in the C1 spectrum. Also, additional peaks in the N1s spectrum
were observed at ~400 (C–NH2) eV. From the point of atomic concen­
tration, opPP was about 2.2 at% higher than npPP, and O2 plasma was
found to be more effective in functionalizing neat PP than N2 plasma. In
contrast, the N2 content of npPP increased from 0 to 2.8 at%, and the
npPP has the advantage of generating amide bonds with TOCNF due to
the addition of amine groups.
As a result of the high-temperature GPC measurement, the npPP
(448,582 g/mol) and opPP (458,392 g/mol) decreased in molecular
weight (Mw) values compared to neat PP (463,270 g/mol). Degradation
of the polymer surface during plasma treatment occurs mainly when
rapidly interacting with radicals or ions, and chain scission take place
due to plasma exposure power and time [28].
3.2. Dispersion properties of alkaline CNF suspensions
Fig. 3 shows the zeta potential and viscosity values for characterizing
the dispersion of CNF with pH concentration in aCNF suspension. The
electrostatic repulsive effect acting between the carboxylate anions on
the surface of CNF results in the formation of fully individualized TOCNF
B.N. Jung et al. Polymer Testing 85 (2020) 106352

Fig. 2. C1s, O1s, and N1s regions of X-ray photoelectron spectroscopy (XPS) spectra of (a) neat PP, (b) npPP, and (c) opPP.

Fig. 3. (a) Zeta potential and (b) viscosity values of aCNF suspensions of various pH concentrations.

dispersed in water by TEMPO oxidation treatment [29]. In general,
electrostatic attractive and repulsive interactions are increased by high
surface charges. In Fig. 3. (a), as the pH was increases from 8 to 11, the
absolute value of the zeta potential increases from 62.3 to 76.7 mV.
These results can be inferred from the highest surface charge value and
the highest electrostatic repulsion at pH 11. However, the zeta potential
was rather reduced owing to the effect of cellulose degradation at pH 12.
Cellulose has been reported to be degraded due to β-elimination at pH 12
and 13, resulting in peeling off reaction [30].
The results of the viscosity analysis shown in Fig. 3. (b) exhibit the
same trend as in Fig. 3. (a), and it is confirmed that the viscosities of pH
11 and pH 12 were reversed in the range of high shear rate because of
the degradation of cellulose. In the low shear rate range, the viscosity of
the suspensions increased with decreasing pH concentration, and the
dispersibility was increased due to the electrostatic repulsion of TOCNF
individual fibers. In particular, when TOCNF is uniformly dispersed in a
solvent, dispersion is improved due to the blow-up phenomenon caused
by the pressurized liquid evaporated from the polymer melt [31]. Based
on these results, an aCNF suspension with a pH 11 was prepared and
applied to the fabrication of the PPs/aCNF composite group (PP/aCNF,

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B.N. Jung et al. Polymer Testing 85 (2020) 106352

Fig. 4. SEM micrographs of TOCNF, and fractured surfaces images of neat PP and PP/CNF nanocomposites: (a) TOCNF (x 110k), (b) neat PP (x 350), (c) control (x
350), (d) control (x 1.0k), (e) npPP/aCNF (x 2.0k), (f) opPP/aCNF (x 2.0k), (g) schematic representation of TOCNF and plasma-treated PPs interaction.

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B.N. Jung et al. Polymer Testing 85 (2020) 106352

Fig. 5. 3D X-ray tomography images of neat PP and PP/CNF nanocomposites: (a) neat PP, (b) control, (c) PP/aCNF, (d) npPP/aCNF, and (e) opPP/aCNF.

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B.N. Jung et al. Polymer Testing 85 (2020) 106352

Table 2 Table 3
DSC results for the neat PP and PP/CNF nanocomposites. Mechanical properties of the neat PP and PP/CNF nanocomposites.
Sample Crystalline Melting Heat of Crystallinity, Sample Yield Tensile stress at Elongation at Young’s
Code temperature, temperature, fusion, Xc (%) Code stress break point break (%) modulus
Tc (� C) Tm (� C) ΔHm (J/g) (MPa) (MPa) (MPa)

Neat PP 98.80 � 0.53b 134.42 � 0.72a 68.17 � 32.62 � Neat PP 26.15 � 34.03 � 0.09b 946.01 � 242.61 �
1.88a 0.90a 0.33a 15.74c 10.55a
Control 97.32 � 0.19a 134.88 � 0.27a 69.56 � 33.58 � Control 27.49 � 35.06 � 0.17b 895.04 � 241.94 �
0.21a 0.10a 0.14a 17.54c 1.73a
PP/aCNF 99.11 � 0.11b 136.95 � 0.13b 75.87 � 36.63 � PP/aCNF 29.82 � 23.13 � 0.88a 656.48 � 243.93 �
1.49b 0.72b 0.62b 47.67b 1.39a
c b a
npPP/ 100.99 � 0.14 137.18 � 0.27 75.62 � 36.51 � npPP/ 34.73 � 24.53 � 0.76 413.52 � 306.51 �
aCNF 1.39b 0.67b aCNF 0.59d 26.86a 10.79b
b b a b
opPP/ 99.50 � 0.34 137.06 � 0.13 75.96 � 36.67 � opPP/ 31.94 � 23.57 � 0.72 658.39 � 7.87 285.49 �
aCNF 0.51b 0.25b aCNF 0.75c 22.60b

Different superscripts in same column indicate that there are statistically Different superscripts in same column indicate that there are statistically
significantly different at 95% confidence level (α ¼ 0.05). significantly different at 95% confidence level (α ¼ 0.05).

npPP/aCNF, and opPP/aCNF).
3.3. Morphological properties for PP/CNF nanocomposites
Fig. 4. (a) shows the SEM images of the TOCNF, and the measure­
ment results were observed on the order of tens of nanometers in width
and the length on micro-sized scale. The SEM images of the fractured
surfaces of PP/CNF nanocomposites with different magnifications were
given in Fig. 4. In the case of the control sample, TOCNFs formed ag­
gregates in the PP matrix, with voids between the PP and TOCNF ag­
gregates. When fabricating control sample using only water-based CNF
suspension, it is difficult to achieve sufficient dispersion of TOCNF. In
addition, the shear stress generated in the extruder was found to be
insufficient to physically disconnect strong hydrogen bonds between
TOCNFs. In contrast, in Fig. 4. (e), and Fig. 4. (f), the npPP/aCNF and
opPP/aCNF nanocomposites were dispersed in the form of TOCNF in­
dividual fibers in PP matrix, and unlike the control sample, TOCNF
showed a high affinity between the interfaces of the plasma-treated PP
matrix, which can be inferred as a result of the formation of interactions
as shown in Fig. 4. (g).
X-ray CT tomography measurement was used to characterize the
dispersion efficiency of alkaline CNF suspension through 3D images. In
the image, the fillers appeared white, and because of the resolution, they
did not show particles below 700 nm. A large agglomeration of TOCNFs
is shown in Fig. 5. (b), while Fig. 5. (c) shows a relatively uniform dis­
tribution of TOCNFs. It was confirmed that alkaline CNF suspension
contributed more to the uniform distribution of TOCNF in the nano­
composite rather than in the water-based suspension. Based on these
results, it can be assumed that the TOCNF in the solvent affects its dis­
persibility as a filler in the finally produced composites with the PP. The
uniform distribution of TOCNF in the PP matrix led to the increase in
crystallinity, shown in Table 2. Additionally, in Fig. 5. (d) and Fig. 5. (e),
the npPP/aCNF and opPP/aCNF nanocomposites prepared using alka­
line CNF suspension showed a uniform distribution of TOCNF, which
was more evenly distributed than in the control sample. The hydro­
philicity of PP assisted to the dispersion of CNF through plasma
treatment.
3.4. Crystallization behavior properties for PP/CNF nanocomposites
The Xc values of the neat PP and PP/CNF nanocomposites were
calculated from the following equation:
ΔHm
Xc ¼ � 100; (2)
ΔH100 ð1 ∅Þ
where ΔHm, the heat of fusion at melting point of the sample is analyzed
(J/g) and ΔH100 is a reference value that represents the heat of fusion for
a 100% α-crystalline polymer. For PP, ΔH100 is 209 J/g [32], and Ф is the
weight fraction of fillers.
The DSC results of neat PP and PP/CNF nanocomposites are given in
Table 2. The Tc, Tm, and Xc of PP/aCNF were increase in comparison to
those of neat PP due to nucleating effect of the TOCNF. In particular, the
Xc was increased by 4% compared to neat PP. In addition, In Fig. 6. (a),
these β-crystalline structures were formed in PP/CNF nanocomposites,
except in the control sample. CNF allows heterogeneous nucleation
mechanisms, leading to reduction of free energy barriers and thus
accelerating crystallization [33]. It was shown that the Xc increased only
by physical mixing without chemical interaction between PP matrix and
TOCNF. On the other hand, in the control sample, TOCNF did not act as a
nucleating agent because it was not uniformly dispersed in the PP

Fig. 6. (a) Heating and (b) cooling curves of the neat PP and PP/CNF nanocomposites.

7
B.N. Jung et al.
Fig. 7. (a), (c), (e) Storage modulus (G0 ), and (b), (d), (f) complex viscosity (η*) of the neat PP, npPP, opPP, and PP/CNF nanocomposites.
matrix.
As shown in Fig. 6. (b), the npPP/aCNF and opPP/aCNF nano­
composites have Tc increased by 0.4–1.9 � C compared to the PP/aCNF
nanocomposites. It can be interpreted by an accelerated crystallization
rate due to the improved interfacial adhesion between the plasma-
treated PP and TOCNF. Moreover, in the case of npPP/aCNF nano­
composites, the crystallization peak was the broadest compared to other
samples. This means that the crystal size distribution becomes wider due
to interfacial crystallization by TOCNF. Interfacial crystallization can
actually enhance interfacial adhesion, which helps to improve me­
chanical properties [34]. In Table 3, the increase in Young’s modulus of
the npPP/aCNF nanocomposite was the most significant and supported
the correlation between interfacial crystallization and mechanical
properties.
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Polymer Testing 85 (2020) 106352
3.5. Rheological properties for PP/CNF nanocomposites
Fig. 7 shows storage modulus (G0 ), and complex viscosity (η*) of the
neat PP, plasma-treated PP (npPP, opPP), and PP/CNF nanocomposites
containing TOCNF of 1 wt%. Compared with the neat PP, the control and
PP/aCNF nanocomposites containing TOCNF have higher G’. At the low
frequency region, neat PP shows typical homopolymer-like terminal
behavior, whereas control and PP/aCNF nanocomposites exhibit
behavior that interferes with full relaxation of the PP chains due to the
role of CNF as filler in the terminal behavior. In addition, the PP/aCNF
nanocomposites had higher G’ and η* than the control, which is a result
of the degree of CNF dispersion. This result revealed that the injection of
CNF through the alkaline solvent into the extruder was more effective
than injection through water only.
In Fig. 7. (c)–(f), the G0 and η* of the PP treated with N2 and O2
B.N. Jung et al.
Fig. 8. Stress-strain (S–S) curves up to yield point of the neat PP and PP/CNF
nanocomposites.
plasma are lower than that of neat PP. This is due to the mixing of low-
viscosity shorter-chain-length functional groups produced by plasma
treatment with high-viscous PP. Similarly, Ray and coworkers reported
that the G0 and η* decreased when PP and PP-grafted maleic anhydride
(PP-g-MA) were mixed together [35]. It is also closely related to mo­
lecular weight and can be supported by molecular weight results. Both
the npPP and opPP had reduced molecular weight compared to neat PP,
which caused a decrease in G0 and η*. Similar to the above results, the G’
and η* of the npPP/aCNF and opPP/aCNF nanocomposites containing
TOCNF were increased compared to neat PP and plasma-treated PPs.
This is the result of two factors, the first of which relies on the uniform
dispersion of CNF in the plasma-treated polymer matrix. In Fig. 5, the
npPP/aCNF and opPP/aCNF nanocomposites showed superior CNF
dispersion compared to other PP/CNF composites in 3D X-ray CT to­
mography results. The second factor is the improvement of interfacial
adhesion between plasma-treated polymer matrix and CNF. The
plasma-treated PPs functionalized the functional groups on the surface
of the PPs, and the hydrogen bonding between these and TOCNF,
Fig. 9. Oxygen permeability and water vapor permeability of the neat PP and PP/CNF nanocomposites. (Different superscripts in same column indicate that there are
statistically significantly different at 95% confidence level (α ¼ 0.05).).
9
Polymer Testing 85 (2020) 106352
resulting in enhanced interfacial adhesion. The effect of improving the
interfacial adhesion between the polymer and the filler through the
plasma treatment was confirmed. Youn et al. [4], demonstrated a sig­
nificant improvement of interfacial adhesion over plasma treatment
methods over CNT/epoxy nanocomposites by other chemical treatments
such as amine or acid treatment through rheology analysis.
3.6. Mechanical properties for PP/CNF nanocomposites
Table 3 describes the results of tensile stress, elongation at break, and
Young’s moduli of the neat PP and PP/CNF nanocomposites. In the
control sample, in which CNF was not uniformly dispersed in the PP
matrix, the tensile stress and Young’s modulus were not significantly
increased or decreased compared to neat PP, but the elongation at break
was decreased. It can be seen that the aggregation of TOCNF acts as a
defect in mechanical properties. On the other hand, PP/aCNF nano­
composite showed a different tendency compared to neat PP, showing
rubber-like properties. As TOCNF was uniformly dispersed in the PP
matrix, the yield stress increased by 14% and the elongation at break
decreased by 31%. For cellulose fiber, it is reported to be a very good
strength and modulus enhancer, while at the same time a stiffener,
reducing elongation at break [36].
In Fig. 8, npPP/aCNF and opPP/aCNF nanocomposites showed a
significant increase in yield stress and Young’s modulus compared to the
neat PP. Especially, the npPP/aCNF nanocomposite increased 32.8 and
26.3% compared with neat PP in yield stress and Young’s modulus,
respectively. This is a result of the uniform dispersion of TOCNF in the
plasma-treated PP matrix and the improvement of affinity between
them, which is supported by the rheological properties in Fig. 7. It is
inferred that this is a result of improving the interfacial adhesion be­
tween TOCNF and the npPP due to amide and hydrogen bonding of
functional groups such as –NH2, and –COOH group of npPP and –COOH,
and –OH group of TOCNF.
3.7. Barrier properties for PP/CNF nanocomposites
Fig. 9 shows the oxygen and water vapor permeability of the neat PP
and PP/CNF nanocomposites. It has been widely known that PP had
poor O2 barrier properties and excellent moisture barrier properties. In
B.N. Jung et al.
this study, neat PP showed an O2 permeability value of 129.61 cc-mm/
m2-day-atm and a water vapor (WP) permeability value of 0.52 g-mm/
m2-day-atm. Several factors, such as polymer internal structure, mo­
lecular weight, crystallinity, and molecular chain entanglement, affect
barrier properties [37]. As shown in Fig. 4. (d), the control sample
negatively affected the barrier properties due to the aggregation of
TOCNF and the existence of the voids between PP and TOCNF. Likewise,
the PP/aCNF nanocomposite had no effect on improving O2 and water
vapor barrier and resulted in easy permeation of the permeant molecules
due to lack of interfacial adhesion between the polymer matrix and the
filler.
The npPP/aCNF and opPP/aCNF nanocomposites showed statisti­
cally significant decreases in O2 and water vapor permeability compared
to the neat PP. Similar to this study, studies have been reported in which
cellulose nanomaterials are incorporated into polymer matrices such as
PHBV (Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) and PLA (Poly­
lactic acid) to be made into nanocomposites to improve barrier prop­
erties [38,39]. The increased Xc in the nanocomposites and the
improved affinity between the plasma-treated PP and the TOCNF offered
a synergetic effect on the enhancement of barrier properties. PP-g-MA,
which is used to improve the compatibility between PP and the hydro­
philic filler, increases the affinity between the surfaces of the polymer
with water and rather increases water vapor permeability [40]. How­
ever, it has been reported that functional groups formed on the surface
of the polymer by plasma treatment disappeared due to the their
diffusion into the bulk polymer [41–43]. Therefore, the method of
dispersing the filler through plasma treatment is more effective in
improving water vapor barrier property than using a compatibilizer.
4. Conclusions
In summary, PP/CNF nanocomposites were prepared in which
TOCNF was more uniformly dispersed in the PP matrix via an aCNF
suspension. It was confirmed by XPS analysis that the surface of the PP
was functionalized through plasma treatment, and the modification of
the PP improved affinity with CNF. Based on the results of various an­
alyses, the npPP/aCNF nanocomposite showed the best performance in
tensile and oxygen barrier properties. The npPP/aCNF nanocomposite
increased 32.8 and 26.3% compared with neat PP in yield stress and
Young’s modulus, respectively, and it also showed statistically signifi­
cant decrease in O2 permeability compared to neat PP. Moreover, the
increase in water vapor permeability caused by the functionalization of
the polymer did not occur in the functionalization of polypropylene
through plasma treatment, and may be selected as a good approach for
the production of barrier films. In addition, nanocomposites produced
through the synergy effect of plasma-treated PP and aCNF suspensions
enhance the performance required for various industrial applications.
This approach is suitably applicable to the fabrication of nano­
composites that disperse hydrophilic fillers in hydrophobic polymers.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
CRediT authorship contribution statement
Bich Nam Jung: Conceptualization, Methodology, Validation,
Writing - original draft. Hyun Wook Jung: Writing - review & editing,
Validation. DongHo Kang: Software, Investigation. Gi Hong Kim: Re­
sources, Investigation. Miji Lee: Resources, Investigation. Sung Wook
Hwang: Investigation. Jin Kie Shim: Conceptualization, Methodology,
Project administration.
10
Polymer Testing 85 (2020) 106352
Acknowledgements
This research is financially supported by the Ministry of Agriculture,
Food, and Rural Affairs in South Korea (Project number: 318089-03).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.polymertesting.2020.106352.
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