polymers

Article
Effects of Orientation and Dispersion on Electrical Conductivity
and Mechanical Properties of Carbon Nanotube/Polypropylene
Composite
Dashan Mi 1, * , Zhongguo Zhao 2 and Haiqing Bai 1, *

1 School of Mechanical Engineering, Shaanxi University of Technology, Hanzhong 723001, China

2 School of Materials Science and Engineering, Shaanxi University of Technology, Hanzhong 723001, China;
[email protected]
* Correspondence: [email protected] (D.M.); [email protected] (H.B.)

Abstract: The orientation and dispersion of nanoparticles can greatly influence the conductivity and
mechanical properties of nanocomposites. In this study, the Polypropylene/ Carbon Nanotubes
(PP/CNTs) nanocomposites were produced using three different molding methods, i.e., compression
molding (CM), conventional injection molding (IM), and interval injection molding (IntM). Various
CNTs content and shear conditions give CNTs different dispersion and orientation states. Then, three
electrical percolation thresholds (4 wt.% CM, 6 wt.% IM, and 9 wt.% IntM) were obtained by various
CNTs dispersion and orientations. Agglomerate dispersion (Adis), agglomerate orientation (Aori),
and molecular orientation (Mori) are used to quantify the CNTs dispersion and orientation degree.
IntM uses high shear to break the agglomerates and promote the Aori, Mori, and Adis. Large Aori
and Mori can create a path along the flow direction, which lead to an electrical anisotropy of nearly
six orders of magnitude in the flow and transverse direction. On the other hand, when CM and IM
samples already build the conductive network, IntM can triple the Adis and destroy the network.
Moreover, mechanical properties are also been discussed, such as the increase in tensile strength with
Aori and Mori but showing independence with Adis. This paper proves that the high dispersion of
CNTs agglomerate goes against forming a conductivity network. At the same time, the increased
Citation: Mi, D.; Zhao, Z.; Bai, H.
orientation of CNTs causes the electric current to flow only in the orientation direction. It helps to
Effects of Orientation and Dispersion
prepare PP/CNTs nanocomposites on demand by understanding the influence of CNTs dispersion
on Electrical Conductivity and
Mechanical Properties of Carbon
and orientation on mechanical and electrical properties.
Nanotube/Polypropylene Composite.
Polymers 2023, 15, 2370. https:// Keywords: shish-kebab structure; polypropylene; carbon nanotubes; mechanical properties;
doi.org/10.3390/polym15102370 electrical conductivity

Academic Editors: Gabriel Pinto,

Victoria Alcázar Montero and Marina
Patricia Arrieta Dillon
1. Introduction
Received: 4 May 2023 Many theoretical and experimental studies have been done on the effects nanofillers
Revised: 15 May 2023
on the mechanical and electrical properties of nanocomposites in the last decade [1–3].
Accepted: 17 May 2023
Applications using carbon nanotubes (CNTs) as nanofillers have increased [4–7], such
Published: 19 May 2023
as burning anti-dripping performance, electromagnetic shielding, and sensing element.
Polymer blend-based multicomponent nanocomposites with superior mechanical and
thermal properties due to the modification of phase morphology have been reported [8].
Copyright: © 2023 by the authors.
Although CNTs have good mechanical properties, only a small fraction of their conductivity
Licensee MDPI, Basel, Switzerland. and strength can translate into the matrix in which CNTs are embedded and twisted [9].
This article is an open access article CNTs dispersion and orientation can affect the final performance of nanocomposites, but
distributed under the terms and many related theoretical and experimental results are still controversial.
conditions of the Creative Commons For example, some researchers show that well-dispersed CNTs are efficiently inter-
Attribution (CC BY) license (https:// connected and thus decrease the electrical percolation threshold [10–12]. Tanabi et al. [13]
creativecommons.org/licenses/by/ disperse the CNTs via magnetization and calculate the dispersion state using microscopy
4.0/). images. Results showed that the electric conductivity could be increased significantly with

Polymers 2023, 15, 2370. https://doi.org/10.3390/polym15102370 https://www.mdpi.com/journal/polymers

Polymers 2023, 15, 2370 2 of 15

the post-dispersing of CNTs. Burmistrov et al. [14] used two methods to disperse CNTs and
carbon blacks. The twin-roller mixer can give a more uniform dispersion than the Haake
Rheomix Polylab, resulting in a higher electrical conductivity.
Whereas other studies have shown the opposite effect, according to Mold et al. [15],
small-size CNTs agglomerates make it easier to form conductive pathways and enhance the
conductivity of PP/CNTs composites. Mei et al. [16] also suggested that shearing conditions
in micro injection moldings can disperse and align the CNTs along the flow direction, which
is unfavorable for constructing conductive pathways. Ferreira et al. [17] used agglomerate
area ratios (AR ) to calculate CNTs and found that the improved dispersion results in higher
electrical resistivity. It is of great practical significance to clarify the effect of dispersion on
conductivity in the contradictory experimental conclusions. For example, Tang [18] believed
that a moderate CNTs dispersion can help to obtain excellent CNT-based composite sensors
for structural health monitoring and flexible electronics.
In addition, aligned carbon nanotubes have been widely considered ideal nanofillers
for manufacturing anisotropic polymer nanocomposites due to their unique nanostruc-
ture, high conductivity, and strength in the alignment direction. The presence of aligned
CNTs can enhance the orientation of crystalline and polymeric chains along a particular
axis, leading to anisotropic thermal phonon transport, electron conduction, and reinforce-
ment properties [19]. On the other hand, compared with unoriented CNTs, the oriented
nanofibers may get complex results in forming a conductive path. Zhou prepared PP/CNTs
nanocomposites using microinjection molding and found that increased injection velocity
can align CNTs, then increasing the probability of CNT-CNT contact, facilitating the en-
hancement of electrical conductivity in the flow direction [20]. In contrast, Monti et al. [21]
tested the AC dielectric of injected PP/CNTs nanocomposites in the 101 –106 HZ frequency
range and proved that the lower shear stress leads to a rearrangement of the CNTs clusters,
which is more efficient in electrical conduction.
The relationship between the CNTs distribution and properties plays an essential role
in improving the conductivity of components, improving the mechanical strength, and
preparing piezoresistive sensing applications. Although there are many studies on the
orientation or dispersion of nanofillers, as far as we know, few of them have discussed
the combined influence of orientation and dispersion. For this reason, this paper aims
to uncover the impact of CNTs dispersion and orientation on mechanical and electrical
conductivities. In the present work, PP was used as the matrix to prepare PP/CNTs
nanocomposites, which has potential applications in the computer chip, electromagnetic
shielding, and the dissipation of electrostatic discharge [3]. Compression molding (CM),
conventional injection molding (IM), and interval injection molding (IntM) were used
to provide different melt shear rates to change CNTs distribution. Then, the dispersion
and orientation of CNTs were quantified and used to study the relationship with perfor-
mance, which can help to prepare PP/CNTs nanocomposites on demanded mechanical
and electrical properties.

2. Experimental Section
2.1. Materials and Sample Preparation
Isotactic polypropylene (iPP, trade name T30S) was purchased from Sinopec Maoming
Petrochemical Co., Ltd., Maoming, China. CNTs were purchased from Suzhou Tanfeng
Graphene Technology Co., Ltd., Suzhou, China. CNTs were multi-walled with an average
diameter of 50 nm, an average length of 20 µm, and a middle surface area of 300 m2 /g,
according to the supplier, with a carbon purity of 90%.
Figure 1 shows a series of polymer composites with filler contents of 0, 1, 2, 4, 6, and 9
wt.% which were blended using a micro-conical double-screw extruder (SJZS-10A, Wuhan
ruiming Co., Ltd., Wuhan, China) at a barrel temperature of 200 ◦ C. Then, three molding
methods were used to provide different shear stress, such as compression molding (CM),
injection molding (IM), and interval injection molding (IntM). All samples were labeled
according to CNTs content and molding method. For example, 2IntM means that the
Polymers 2023, 15, x FOR PEER REVIEW 3 of 15

Polymers 2023, 15, 2370 3 of 15

(CM), injection molding (IM), and interval injection molding (IntM). All samples were la-
beled according to CNTs content and molding method. For example, 2IntM means that
the CNTs content was 2 wt.% and was molded using IntM. The central processing condi-
CNTs
tions werecontent was
denoted as2shown
wt.% and was 1.
in Table molded usingnoting
It is worth IntM.that
Themelt
central processing
viscosity conditions
will rise with
were denoted as shown in Table 1. It is worth noting that melt viscosity
increased CNTs content and even changes from a viscous fluid to an elastic solid with will rise with
high
increased CNTs content and even changes from a viscous fluid to an elastic
CNTs content [16]. In this research, some samples were molded at a higher melt tempera- solid with
high
ture CNTs content
to improve [16].However,
liquidity. In this research, somecontent
if the CNTs samples were
was molded
9 wt.%, evenat with
a higher melt
higher
temperature to improve liquidity. However, if the CNTs content was 9 wt.%,
temperatures, the melt viscosity was still too high to form a secondary flow, so we cannot even with
gethigher temperatures, the melt viscosity was still too high to form a secondary flow, so we
the IntM sample with 9 wt.% of CNTs.
cannot get the IntM sample with 9 wt.% of CNTs.

Figure 1. Schematic of molding methods and CNTs orientation. (a) Compression molding (CM), (b)
Figure 1. Schematic of molding methods and CNTs orientation. (a) Compression molding (CM), (b)
conventional
conventional injection
injection molding
molding (IM),
(IM), (c) (c) intermittent
intermittent injection
injection molding
molding (IntM).
(IntM).

Table
Table 1. Molding
1. Molding parameters
parameters of three
of three molding
molding methods.
methods.

1CM-6CM
1CM-6CM 1IM-5IM
1IM-5IM 6IM
6IM 1IntM-4IntM
1IntM-4IntM 5IntM
5IntM
Melting temperature
Melting temperature (°C)(℃) 200 200 200 200 210
210 200200 210210
CNTs
CNTs content (wt.%)
content (wt.%) 1–6 1–6 1–5 1–5 66 1–41–4 5 5
First
FirstInjection pressure
Injection pressure (bar)
(bar) * * 5.5 5.5 5.5
5.5 22 2 2
Second
SecondInjection pressure
Injection pressure (bar)
(bar) * * 5.55.5 5.55.5
* Note: Injection
* Note: Injectionpressure is the
pressure is theset
setpressure
pressure of the
of the equipment,
equipment, notmelt
not the thepressure.
melt pressure.

CM: CM:Provides
Provides a low
a lowshear
shearcondition
condition(Figure
(Figure 1a). Plates
1a). Plateswere
were compression
compression molded
molded
with 1.2 mm thickness at 200 °C.
◦ Subsequently, the plate was cut
with 1.2 mm thickness at 200 C. Subsequently, the plate was cut into a dumbbell into a dumbbell shape.
shape.
IM:IM:Provides
Provides a moderate
a moderate shear condition
shear condition (Figure
(Figure 1b). Melt
1b). Meltfilled thethe
filled mold chamber
mold chamber
under
under constant
constant pressure.
pressure.Dumbbell-type
Dumbbell-type samples
samples withwith2 mm
2 mmwere wereprepared
prepared using a micro
using a micro
conventional injection molding (SJZS-10A, Wuhan Ruiming
conventional injection molding (SJZS-10A, Wuhan Ruiming Co., Ltd., Wuhan, China)Co., Ltd., Wuhan, China)with
with a mold
a mold temperature
temperature of◦ 50
of 50 °C.barrel
C. A A barrel temperature
temperature of 200of◦ C
200was°Csuitable
was suitable forsamples,
for most most
samples,
except except
the 9IM, the 9IM, needed
which which needed 210complete
210 ◦ C for °C for complete
filling duefilling
to thedue to the
high melthigh melt
viscosity.
viscosity.IntM: Provides a high shear condition (Figure 1c). The melt filled the mold in two
IntM:A Provides
flows. a high shear
gradient pressure condition
setting achieved (Figure
this: The 1c).initial
The melt filledpressure
injection the moldwasintoo
twolow
flows. A the
to fill gradient
cavity.pressure
After 1 ssetting
of thisachieved this:
short shot, theThe initial
filling wasinjection
completed pressure was too
by a higher low
injection
to fill the cavity. After 1 s of this short shot, the filling was completed
pressure. It is worth mentioning that most commercial injection equipment can implement by a higher injection
pressure. It is worth
this pressure mentioning
setting to magnify thatthe
most commercial
shear stress. Ininjection equipment
this manuscript, cansamples
IntM implement were
thisalso
pressure setting to magnify the shear stress. In this manuscript,
prepared using the micro conventional injection molding (similar to IM). Except IntM samples werefor
6IntM, prepared under 210 ◦ C barrel temperature, other samples were molded at 200 ◦ C.
Polymers 2023, 15, 2370 4 of 15

2.2. Sample Testing

2.2.1. Measurement of Mechanical Properties
The tensile test was conducted at room temperature (26 ◦ C) on an electro-universal
testing machine (GOTECH-20KN, GOTECH Testing Machines Co., Ltd., Dongguan, China)
with a 50 mm/min cross-head speed. All tests were conducted along the injection direction,
and more than five sample properties were calculated.

2.2.2. Measurement of Electrical Conductivity

Electrical conductivity was performed using the Keithley 6487 source meter (Tektronix
Inc., Shanghai, China). Both ends of the specimens were coated with conductive silver
paint. The electrical conductivity (σ) was then calculated according to the following:

σ = L/RA (1)

L is the distance between the electrodes, R is the measured resistance, and A is the cross-
sectional area. For IM and IntM samples, the σ was measured along the flow and transverse
directions. The values of σ were calculated as the average of four samples.

2.2.3. X-ray Measurements

The synchrotron 2D-WAXD experiment was carried out on a HomeLab (Rigaku,
Japan) to calculate the molecular chain orientation (Mori ) of a sample. The dimension of the
rectangle-shaped beam was 100 × 100 µm2 , the light wavelength was 0.154 nm, and the
X-rays were imaged after penetrating the sample.
The crystallinity (Xc ) was calculated according to the following [22]:

Ac
Xc = × 100% (2)
Ac + A a

where Ac and Aa are the fitting intensity of the crystallization and amorphous peaks. The
orientation of lamellar crystals in the injection-molded parts was calculated using the
Hermans orientation function. In this method, the crystal orientation was characterized by
the average orientation of the normal to the crystal plane concerning an external reference
frame. Accordingly, the flow direction was taken as the reference direction. For a set of
hkl planes, the average orientation, which can be expressed as cos2 ϕ hkl , was calculated

mathematically using the following equation [23]:

R π/2

2

0 I( ϕ)cos2 ϕsinϕdϕ
cos ϕ = R π/2 (3)
hkl I( ϕ)sinϕdϕ
0

with ϕ being the azimuthal angle and I(ϕ) being the scattered intensity along the angle ϕ.
Herman’s orientation function, f, was defined as

3 cos2 ϕ hkl − 1


f= (4)
2
with f having a value of −0.5 with the normal of the reflection plane being perpendicular to
the reference direction (ϕ = 90◦ ), a value of 1 with the normal of the refection plane parallel
being the reference direction (ϕ = 0◦ ), and a value of 0 with the orientation being random.
 Polymers 2023, 15, x FOR PEER REVIEW 5 of 15
Polymers 2023, 15, 2370 5 of 15

2.2.4. Optical Microscopy (OM)

2.2.4. Optical Microscopy (OM)
Thin slices cut using microtome were used for optical microscopy observations. The
Thin slices cut using microtome were used for optical microscopy observations. The
observation zones were along the flow direction (FD) or transverse direction (TD) as
observation zones were along the flow direction (FD) or transverse direction (TD) as
shown in Figure 2d. The slice thickness was fixed at 5 µm, and ImageJ was used to process
shown in Figure 2d. The slice thickness was fixed at 5 µm, and ImageJ was used to
the images
process after removing
the images the non-clear
after removing parts from
the non-clear these
parts fromimages. More than
these images. nine
More micros-
than nine
copy photos for each sample were used to calculate the Adis (CNTs agglomerate disper-
microscopy photos for each sample were used to calculate the Adis (CNTs agglomerate
sion) and Aand
dispersion) ori (CNTs agglomerate orientation). Moreover, using OM to count too-small
Aori (CNTs agglomerate orientation). Moreover, using OM to count too-
agglomerates
small agglomeratescan easily lead tolead
can easily errors, so onlysoagglomerates
to errors, with anwith
only agglomerates areaan
greater than 10
area greater
µm 10
than
2 were
µmmeasured.
2 were measured.

Figure2.
Figure 2. OM
OM picture
picture of
of 2IM,
2IM, (a)
(a) overall
overall image
image of
of 2IM
2IM in
in FD,
FD, (b)
(b) enlarged
enlarged detail
detail of
of shear
shear layer
layer in
in FD,
FD,
(c) enlarged detail of core layer in FD, (d) schematical of samples, (e) enlarged detail of shear layer
(c) enlarged detail of core layer in FD, (d) schematical of samples, (e) enlarged detail of shear layer in
in TD, (f) enlarged detail of core layer in TD.
TD, (f) enlarged detail of core layer in TD.

2.2.5. Scanning
2.2.5. Scanning Electron
Electron Microscope
Microscope(SEM)
(SEM)
A Ascanning
scanningelectron
electronmicroscope
microscope (ZEISS
(ZEISS Gemini
Gemini 300, ZEISS
300, ZEISS Microscopy
Microscopy LLC, Ober-
LLC, Oberkochen,
kochen, Germany)
Germany) was usedwas forused for fracture
fracture surface surface observations.
observations. The fracture
The fracture surfacesurface was
was gold
sputtered after being
gold sputtered yield stretched.
after being yield stretched.

3.
3. Results
Results and
and Discussion
Discussion
3.1. Sample Structure
3.1. Sample Structure
3.1.1. CNTs Orientation
3.1.1. CNTs Orientation
As shown in Figure 2d, IM and IntM samples were molded into dumbbell-type
shapes,Asand
shown
the OM in Figure
images2d, of 2IMIM and
wereIntM samples
obtained fromwere
both molded
FD and TD. into Oriented
dumbbell-type
CNTs
shapes, and the OM images of 2IM were obtained from both FD and
agglomerates can be observed in FD, as shown in Figure 2a, a typical three-layer structure TD. Oriented CNTs
is
agglomerates can be observed in FD, as shown in Figure 2a, a typical
formed. As the name implies, the frozen layer is in contact with the cold mold wall, where three-layer structure
is formed.
polymer As can
melts the name implies,
be “frozen” the frozen
instantly layer istoinform
and unable contact with CNTs
oriented the cold mold wall,
agglomerates.
wherelayers,
Shear polymer melts can
as shown be “frozen”
in Figure instantly
2a,b, are where and unable
a large numberto form
of CNTsoriented CNTs ag-
agglomerates
glomerates. Shear layers, as shown in Figure 2a,b, are where a large
were oriented along the flow direction, while in the core layer, the CNTs agglomerates number of CNTs ag-
returned to a spherical form. In contrast, no oriented structure can be found in TD, ag-
glomerates were oriented along the flow direction, while in the core layer, the CNTs as
glomerates
shown returned
in Figure 2e,f.toIta means
spherical all form.
CNT In contrast, noin
agglomerates oriented
2IM were structure canalong
oriented be found
FD
in TD,
and as shown in Figure
perpendicular to TD. 2e,f. It means
So, this all CNT
research usedagglomerates
images captured in 2IMfrom
wereFDoriented along
to calculate
FD and perpendicular
agglomerate orientationto(A TD. So, this research used images captured from FD to calculate
ori ), while figures from TD were used to calculate agglomerate
agglomerate
dispersion (Aorientation
dis ), in order (A ori),
to whilethe
avoid figures from of
influence TDorientation.
were used to Thecalculate
specificagglomerate
calculation
dispersion (A ), in order
method will be introduced later.
dis to avoid the influence of orientation. The specific calculation
method will be introduced later.
Polymers 2023, 15, x FOR PEER REVIEW 6 of 15
Polymers 2023, 15, 2370 6 of 15

OM images of 2CM, 2IM, and 2IntM in FD are shown in Figure 3. Shear can change
the morphologies
OM images of of2CM,
CNTs2IM,
agglomerates;
and 2IntMfor in example, no oriented
FD are shown structure
in Figure 3. Shear can
canbechange
found
in
the2CM, while bothofIM
morphologies andagglomerates;
CNTs IntM can alignfor CNTs agglomerates.
example, Thestructure
no oriented shear layer
canthickness
be found
of 2IntMwhile
in 2CM, was much
both IM greater thancan
and IntM that of 2IM
align CNTsasagglomerates.
shown in Figure 3b,c. layer
The shear As the enlarged
thickness of
images
2IntM was(Figure
much3e,f) show
greater some
than thatoriented
of 2IM as CNTs
shown agglomerates were
in Figure 3b,c. Aslonger than 100
the enlarged µm
images
along
(Figurethe flow
3e,f) direction.
show They were
some oriented expected
CNTs to form awere
agglomerates conductive
longer path
than in100the
µm flow direc-
along the
tion
flowwith increased
direction. TheyCNTs
werecontent,
expected and their effects
to form on mechanical
a conductive properties
path in the will bewith
flow direction dis-
cussed later.
increased CNTs content, and their effects on mechanical properties will be discussed later.

Figure 3.
Figure OM images
3. OM images in
in FD,
FD, (a,d)
(a,d) 2CM,
2CM, (b,e)
(b,e) 2IM,
2IM, (c,f)
(c,f) 2IntM.
2IntM.

The length-diameter
The length-diameter ratio ratio of
of CNTs
CNTs agglomerate
agglomerate was was calculated
calculated from
from OM OM images
images for for
different CNT content and processing methods. If CNTs agglomerate
different CNT content and processing methods. If CNTs agglomerate is abstracted into a is abstracted into
a cylinder,
cylinder, thethegreater
greateritsitsorientation,
orientation,thethelarger
largerthethelength-diameter
length-diameterratio ratiowill
will be.
be. So,
So, asas
shown in Figure 4a, the length-diameter ratio of CNTs agglomerate
shown in Figure 4a, the length-diameter ratio of CNTs agglomerate was calculated and was calculated and
named as
named as AAori
ori. .With
Withthethehelp
helpof ofImage
ImageJ,J,more
morethanthan sixsix OM
OM pictures
pictures were
were used
used for
for each
each
sample to calculate Aori .
sample to calculate Aori.
Aori = Llong /Lshort (5)
A ori = Llong/Lshort
where Llong is the length of the CNTs agglomerate in the longest direction, and Lshort is
(5)
the length
where Llong of
is the
the CNTs
lengthagglomerate
of the CNTs in the shortest
agglomerate inpath. Largerdirection,
the longest Aori valueandsuggests
Lshort ishigh
the
agglomerate CNTs orientation.
length of the CNTs agglomerate in the shortest path. Larger Aori value suggests high ag-
Because
glomerate CNTsbothorientation.
oriented and non-oriented CNT agglomerates existed in each sample, the
Aori variance
Because both orientedAs
is significant. anddisplayed in Figure
non-oriented CNT4b, the Aori of IntM
agglomerates samples
existed wassample,
in each always
the Aori variance is significant. As displayed in Figure 4b, the Aori of IntM sampleslayer.
larger than that of IM and CM because the secondary flow formed a wider shear was
In addition,
always largerCM-A than ori did
that ofnotIM equal
and CM 1 but remained
because about 2, because,
the secondary beforeacompression
flow formed wider shear
molding,
layer. the CNTs
In addition, agglomerate
CM-A had been stretched in the extrusion colling process. This
ori did not equal 1 but remained about 2, because, before compres-
stretched oriented structure can be retained ◦ C. It is worth noticing that these oriented
at 200stretched
sion molding, the CNTs agglomerate had been in the extrusion colling process.
structures
This haveoriented
stretched been cutstructure
short andcan rearranged
be retained in CM,
at 200 so°C.
they It will not show
is worth anisotropy
noticing that these on
the macro level. In general, although very low shear existed in
oriented structures have been cut short and rearranged in CM, so they will not show ani- the compression molding
process,on
sotropy randomly
the macro orientated agglomerates
level. In general, although remained.
very lowItshearis worth noting
existed that
in the when CNT
compression
content is higher than 6 wt.%, some CNTs agglomerates will connect and form a continuous
molding process, randomly orientated agglomerates remained. It is worth noting that
phase (Figure 4d), which can hinder statistics on the shape of individual agglomerates, and
when CNT content is higher than 6 wt.%, some CNTs agglomerates will connect and form
Aori loses its value. In this way, if CNTs content was higher than 4 wt.%, Aori could not be
a continuous phase (Figure 4d), which can hinder statistics on the shape of individual
used to describe the orientation.
agglomerates, and Aori loses its value. In this way, if CNTs content was higher than 4 wt.%,
Aori could not be used to describe the orientation.
 Polymers2023,
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2023, 15,2370
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Figure 4. (a) Calculation method of Agglomerate orientation degree (Aori), (b) Aori of CM, IM, and
Figure4.4.(a)
Figure (a)Calculation
Calculationmethod
methodofofAgglomerate
Agglomerateorientation
orientationdegree
degree(A
(Aori),),(b)
(b)AAori of
of CM,
CM,IM,
IM,and
and
IntM change with CNT content, (c) OM image of 1IntM, (d) OM image ofori 6IntM. ori
IntM change with CNT content, (c) OM image of 1IntM, (d) OM image of
IntM change with CNT content, (c) OM image of 1IntM, (d) OM image of 6IntM. 6IntM.

Compared with Aori, every sample’s molecular chain orientation (Mori) can be ex-
Compared
Comparedwith withAori , every
Aori , everysample’s
sample’smolecular
molecularchain orientation
chain (Mori )(M
orientation can
ori)be explored
can be ex-
plored through the transmission mode of WAXD. Because CNTs flowed with PP during
through the transmission mode of WAXD. Because CNTs flowed
plored through the transmission mode of WAXD. Because CNTs flowed with PP during with PP during the
the molding process, Mori can reflect the CNTs orientation, especially for these dispersed
molding process,
the molding Mori can
process, Morireflect the CNTs
can reflect orientation,
the CNTs especially
orientation, for these
especially fordispersed CNTs.
these dispersed
CNTs. WAXD images are shown in Figure 5. For CM and IntM samples, such as 2CM,
WAXD images images
CNTs. WAXD are shownare in Figure
shown in 5. For CM
Figure 5. ForandCMIntM
andsamples, such assuch
IntM samples, 2CM, as 6CM,
2CM,
6CM, 0IntM, 2IntM, and 6IntM, the orientation almost did not change with CNTs content,
0IntM, 2IntM,2IntM,
6CM, 0IntM, and 6IntM, the orientation
and 6IntM, almost
the orientation did not
almost didchange
not changewithwith
CNTs CNTscontent,
content,so
so only parts of them were selected for WAXD testing. The diffraction ring of CM always
only parts
so only of them
parts were
of them wereselected forfor
selected WAXD
WAXD testing.
testing.The
Thediffraction
diffractionringringofofCM CMalways
always
presented a complete circle, representing its random orientation structure. In contrast, the
presented
presentedaacomplete
completecircle,
circle,representing
representingits itsrandom
randomorientation
orientationstructure.
structure.In Incontrast,
contrast,the the
IntM sample presented a prominent arc bright spot inside the ring, indicating that it exists
IntM
IntM sample
sample presented
presented aa prominent
prominent arc
arcbright
bright spot
spot inside
inside the
the ring,
ring, indicating
indicating that
thatititexists
exists
in both high orientation and random structure. Correspondingly, IM samples showed
in
inboth
both high
highorientation
orientationand random structure. Correspondingly, IM samples showed some
some IntM-like diffraction and random
rings, but thestructure.
orientation Correspondingly,
rises with increased IM samples showed
CNTs content,
IntM-like
some will diffraction
IntM-like rings, but
diffraction the orientation rises with increased CNTs content, which
which be discussed later.rings, but the orientation rises with increased CNTs content,
will be discussed
which later. later.
will be discussed

Figure
Figure 5.
5. 2D-WAXD
2D-WAXDpatterns
patternsof
ofsamples
sampleswith
withdifferent
differentmolding
moldingmethods
methodsand
andCNTs
CNTscontent.
content.
Figure 5. 2D-WAXD patterns of samples with different molding methods and CNTs content.
The (040) α plane was calculated to estimate Mori. Figure 6a shows the azimuth angle
of theThe
CM,(040)
IM, and IntMwas
α plane samples with to
calculated 2 or 6 wt.% M
estimate CNTs. CM samples
ori. Figure 6a showshad
theaazimuth
very gentle
angle
curve,
of the while the and
CM, IM, peaks, denoted
IntM with
samples arrows,
with 2 or 6indicated
wt.% CNTs.highCM
orientation
samples degrees formed
had a very gentle
using
curve,IM and the
while IntM. In Figure
peaks, denoted6b,with
the M ori can be
arrows, separated
indicated into
high HIGH, MEDIUM,
orientation and
degrees formed
using IM and IntM. In Figure 6b, the Mori can be separated into HIGH, MEDIUM, and
 Polymers 2023, 15, 2370 8 of 15

ymers 2023, 15, x FOR PEER REVIEW The (040) α plane was calculated to estimate Mori . Figure 6a shows the
8 ofazimuth
15 angle
of the CM, IM, and IntM samples with 2 or 6 wt.% CNTs. CM samples had a very gentle
curve, while the peaks, denoted with arrows, indicated high orientation degrees formed
using IM and IntM. In Figure 6b, the Mori can be separated into HIGH, MEDIUM, and
LOW areas. The dividing standards are shown in Table 2. When the CNTs content was
LOW areas. The dividing standards are shown in Table 2. When the CNTs content was
lower than 6 wt.%, Mori showed a similar trend to Aori as shown in Figure 3: CM, IM and
lower than 6 wt.%, Mori showed a similar trend to Aori as shown in Figure 3: CM, IM and
IntM increased
IntMinincreased
turn. in turn.

Figure 6. (a) Figure

Azimuthal profiles
6. (a) taken profiles
Azimuthal at the (040) α reflection
taken at the (040)as α
a function
reflectionofas
azimuthal angle,
a function (b)
of azimuthal angle,
Degree of molecular orientation
(b) Degree of molecular ) of CM, IM,(M
(Moriorientation and
ori ) IntM calculated
of CM, from Azimuthal
IM, and IntM profiles.
calculated from Azimuthal profiles.

Table 2. Criteria
Tablefor2.the level of
Criteria fororientation.
the level of orientation.
CM CM
IM IM
IM IM
IntM IntM
(0~9 wt.%CNT) (0~9
(0~4 wt.%CNT)(0~4(6~9
wt.%CNT) wt.%CNT)
wt.%CNT) (0~6 wt.%CNT)
(6~9 wt.%CNT) (0~6 wt.%CNT)
Mori 0~0.5
Mori 0.8~0.88
0~0.5 0.91~0.92
0.8~0.88 0.91~0.92 0.91~0.92
0.91~0.92
level-FD LOW MEDIUM (FD) HIGH (FD) HIGH (FD)
level-FD LOW MEDIUM (FD) HIGH (FD) HIGH (FD)
level-TD LOW MEDIUM (TD) HIGH (TD) HIGH (TD)
level-TD LOW MEDIUM (TD) HIGH (TD) HIGH (TD)

For CM samples, the Mori was lower than 0.5, and all were located in the LOW area.
In comparison, all Forthe
CMIntMsamples,
samples the Mori was lower
ori were higherthan than0.5,
0.9and
andall were located
located in the LOW area.
in the HIGH
In comparison,
area. However, all thethe
for IM samples, IntM samples M
orientation ori werewith
changed higher thancontent.
CNTs 0.9 andWhen locatedthein the HIGH
CNT content area.
wasHowever,
low, its M forori IM
wassamples,
located the orientation
between CM and changed
IntM,with
whichCNTs
wascontent.
situatedWhen
in the CNT
the MEDIUM content wasHowever,
region. low, its MM orioriwas located
jumped to between
the HIGH CM andafter
part IntM,thewhich
CNT was situated in the
content
MEDIUM region. However,
reached 6 wt.%. Increased Mori attributes to M jumped to the HIGH part after
ori added rigid particles such as CNTs, improve the CNT content reached
6 wt.%.
both the storage andIncreased
the lossMmodulus,
ori attributes andtocan added
helprigid particles
increase such as
the shear areaCNTs, improve
[21,24]. In both the
storage
addition, CNTs not and
onlythe loss modulus,
improved the meltand can help
viscosity butincrease
also acted theasshear area [21,24].
a nucleation site toIn addition,
CNTs not
freeze the oriented only improved
molecular chains and the form
melt viscosity but also acted
a hybrid shish-kebab as a nucleation
structure, which can site to freeze
super improve the mechanical performance [25–27]. That is to say, with increased CNTs can super
the oriented molecular chains and form a hybrid shish-kebab structure, which
content, IMimprove
can obtain theamechanical
high shear stressperformance
similar [25–27].
to IntM and Thatmake
is to say,
Mori with
greaterincreased CNTs content,
than 0.91.
IM can obtain a high shear stress similar to IntM
It is worth mentioning that the 9IM-Mori p slightly because the molding temperature and make M ori greater was 0.91. It is
than
worth mentioning that the
10℃ higher than others. The higher melt temperature 9IM-M ori p slightlymade it easier for the oriented mo- was 10°C
because the molding temperature
higher
lecular chains than others.
to recover, and in The higher
higher meltcontent,
CNTs temperature made it easier
the entangled CNTsfor the oriented
network also molecular
hindered the orientation. Even though the 9IM-Mori was lower than 6IM-Mori, the 9IM-Malso
chains to recover, and in higher CNTs content, the entangled CNTs network ori
hindered
the orientation. Even
was still located in the high area. though the 9IM-M ori was lower than 6IM-M ori , the 9IM-M ori was still
located in the high area.
3.1.2. CNTs Dispersion
In order to quantity dispersion degree, we introduce the parameter of CNTs aggerate
dispersion (Adis). The number of CNTs aggregates per unit area is used to represent the
dispersion. OM Images obtained from TD were used to calculate Adis. Adis is equal to the
number of agglomerates within 1 mm2, and the Adis can be obtained using Equation (6):

A
A = 10 × A (6)

where Anumber represents the number of agglomerates, Aarea is the OM images area in µm2.
When an aggregate has been completely aggregated into one mass, that is, the dispersion
Polymers 2023, 15, 2370 9 of 15

3.1.2. CNTs Dispersion

In order to quantity dispersion degree, we introduce the parameter of CNTs aggerate
dispersion (Adis ). The number of CNTs aggregates per unit area is used to represent the
dispersion. OM Images obtained from TD were used to calculate Adis . Adis is equal to the
number of agglomerates within 1 mm2 , and the Adis can be obtained using Equation (6):
.
Polymers 2023, 15, x FOR PEER REVIEW Adis = 106 × Anumber 9 of(6)
15
Aarea

where Anumber represents the number of agglomerates, Aarea is the OM images area in µm2 .
is the an
When worst, Adis is equal
aggregate to 1.completely
has been As the aggregate disperses
aggregated into oneinto particles,
mass, Athe
that is, dis will gradually
dispersion is
the worst,The
increase. Adisresults
is equal ofto 1. As
Adis are the aggregate
shown disperses
in Figure 7. When intothe
particles, Adis will
CNTs content gradually
was 1 wt.%,
increase.
the Adis of The results
1IntM wasof significantly
Adis are shown in Figure
higher than 7.that
When the CNTs
of 1CM content
and 1IM, was 1 wt.%,
indicating that the
the
A dis offormed
shear 1IntM was significantly
by secondary flowhigher than that
can further of 1CMthe
promote anddispersion
1IM, indicating
of CNTs. thatThe
the large-
shear
formed
size CNTs by agglomerates
secondary flow cancan further promote
be ruptured the dispersion
by the high shear force,ofdoubling
CNTs. The large-size
the number of
CNTs agglomerates
agglomerates per unitcanarea.
be ruptured by the high
Other researchers have shear
also force, doubling
reported the number
that CNTs achievedofa
agglomerates
relatively better perdistribution
unit area. Other
when researchers
processed underhave also reported
high-shear that CNTs
conditions achieved
[16,28]. When a
relatively better distribution when processed under high-shear conditions
CNTs content increased to 2 wt.%, such as 2IntM, about 6000 CNTs agglomerates existing [16,28]. When
CNTs
in 1 mm content
2, whileincreased
for CM to 2 wt.%,the
samples, such as 2IntM,
number wasabout 6000small,
relatively CNTssuchagglomerates
as for 2CM existing
which
in 2
1 mm , 4000whileCNTs
for CM samples, theItnumber
achieved agglomerates. means was
that relatively
the diametersmall,
of such as foragglomerates
the CNT 2CM which
achieved
in CM was 4000 CNTs
larger thanagglomerates.
IM and IntM, It or
means
somethat the diameter
adjacent of the CNT agglomerates
CNTs agglomerates have been in-
in CM was larger
terconnected than IM and
and integrated. TheIntM,
Adis oforeach
some adjacent
sample will CNTs agglomerates
reach the maximum value have been
if the
interconnected and integrated.
CNTs content increases to 4 wt.%. The A dis of each sample will reach the maximum value if
the CNTs content increases to 4 wt.%.

Figure 7. Agglomerate
Figure7. Agglomerate dispersion
dispersiondegree
degree(A dis) as a function of CNTs content.
(Adis

IfIf the
the CNTs
CNTscontent
contentisisincreased
increasedtoto66wt.%,
wt.%,the
theAAdis of 6IM and 6CM drops to nearly
dis of 6IM and 6CM drops to nearly
1200,
1200, indicating that the CNTs agglomerates cannot maintain aa high
indicating that the CNTs agglomerates cannot maintain high dispersion
dispersion atat high
high
CNTs content but combine to form larger agglomerates. Even if the secondary
CNTs content but combine to form larger agglomerates. Even if the secondary shearing of shearing
of IntM
IntM cancan promote
promote thethe distribution
distribution of CNTs,
of CNTs, the Athe A 6IntM
dis of dis
of 6IntM
dropsdrops to around
to around 3000.
3000. When
When the CNTs content reached 9 wt.%,
the CNTs content reached 9 wt.%, the Adis of 9CMthe A dis of 9CM reduced to 20, and most
reduced to 20, and most CNTs were CNTs
were joined together. Meanwhile, although the Adis of 9IM was slightly higher by shearing,
joined together. Meanwhile, although the Adis of 9IM was slightly higher by shearing, the
2 also decreased to 400. The decreased A
the number of agglomerates in 1mm dis and the
number of agglomerates in 1mm2 also decreased to 400. The decreased Adis and the for-
mation of a continuous CNTs phase was expected to improve the conductivity, tensile
strength, and modulus, which will be discussed in the next section.

3.2. Effects of Orientation and Dispersion

3.2.1. Orientation Effect on Yield Properties
Polymers 2023, 15, 2370 10 of 15

formation of a continuous CNTs phase was expected to improve the conductivity, tensile
strength, and modulus, which will be discussed in the next section.

3.2. Effects of Orientation and Dispersion

3.2.1. Orientation Effect on Yield Properties
Figure 8 shows the relationship between tensile properties and the CNTs content of the
Polymers 2023, 15, x FOR PEER REVIEW
samples obtained by different molding methods. These colors are used to divide the three 10 of 15
Mori types, which are high, middle, and low. The dividing standards are already shown
in Table 2, and the selectivity yield curves are given in support information in Figure S1.
Regardless
and HIGH of ranges,
the content of CNTs,InCM,
respectively. and IntM
contrast, IM-M samples were located in the LOW and
ori can leap from Medium to High ranges
HIGH
when CNTs content reaches 6 wt.%. Due orito the formationMedium
ranges, respectively. In contrast, IM-M can leap from to High
of oriented ranges in
structures
when CNTs content
PP/CNTs reaches 6 wt.%.
nanocomposites underDue
hightoshear
the formation
conditions, of such
oriented structures inhybrid
as shish-kebab, PP/CNTsshish-
nanocomposites under high shear conditions, such as shish-kebab, hybrid shish-kebab,
kebab, and oriented CNTs, the tensile strength and toughness of the material can be im- and
oriented
proved. CNTs,
Under thethe
tensile
samestrength and toughness
CNT content, of strength
the tensile the material can
of the be improved.
IntM sample was Under
always
thehigher
same CNT content, the tensile strength of the IntM sample was always
than that of IM and CM due to the higher Mori (Figure 8a). The tensile strength higher than of
that
theofIntM
IM and
andCM CMdue to thedid
samples higher
not M ori (Figure
change 8a). The but
significantly, tensile
the strength of the IntM
tensile strength of IMand
sam-
CM samples did not change significantly, but the tensile strength of IM samples greatly
ples greatly increased when Mori jumped to HIGH ranges when the CNTs content reached
increased when Mori jumped to HIGH ranges when the CNTs content reached 6 wt.%. This
6 wt.%. This is also due to the massive formation of orientation structure at high Mori. As
is also due to the massive formation of orientation structure at high Mori . As shown in
shown in Figure 8b, with the increased CNTs content, the tensile modulus of all samples
Figure 8b, with the increased CNTs content, the tensile modulus of all samples showed an
showed an increasing trend. It has been proved that CNTs can improve the strength and
increasing trend. It has been proved that CNTs can improve the strength and stiffness of
stiffness of PP at the expense of toughness, because CNTs can induce α-nuclei in PP and
PP at the expense of toughness, because CNTs can induce α-nuclei in PP and increase the
increase the crystallinity leading to superior stiffness [29–31]. On the other hand, shear
crystallinity leading to superior stiffness [29–31]. On the other hand, shear can promote the
can promote the formation of oriented crystals, further improving the modulus. For ex-
formation of oriented crystals, further improving the modulus. For example, the modulus
ample, the modulus of 6IntM was higher than that of 6IM and 6CM. In general, within the
of 6IntM was higher than that of 6IM and 6CM. In general, within the higher CNTs content,
higher CNTs content, higher Mori always brought a higher strength and modulus [32]. As
higher Mori always brought a higher strength and modulus [32]. As a result, the tensile
a result, the tensile strength of 4IntM was 13% higher than that of 0CM, while the tensile
strength of 4IntM was 13% higher than that of 0CM, while the tensile modulus of 5IntM
wasmodulus of 5IntM
35% higher was of
than that 35% higher than that of 0CM.
0CM.

Figure 8. (a) Yield strength, (b) yield modulus along FD as a function of CNTs content.
Figure 8. (a) Yield strength, (b) yield modulus along FD as a function of CNTs content.
Figure 9a shows the Low Mori -CNTs agglomerates in the tensile fraction surface,
Figure 9a shows the Low Mori-CNTs agglomerates in the tensile fraction surface,
which is smooth and shows many CNTs agglomerates. In the fracture mode, as shown in
which is smooth and shows many CNTs agglomerates. In the fracture mode, as shown in
Figure 9a, the CNTs agglomeration acts as stress concentration points, which is unfavorable
forFigure
enhancing9a, the CNTs agglomeration
mechanical acts as stress concentration
properties. Agglomeration can induce thepoints, which is
generation ofunfavora-
cracks,
andbletheforcracks
enhancing mechanical
are easy to spreadproperties.
along the Agglomeration
interface of the can induce the
un-oriented generation of
agglomerates
cracks,damaging
without and the cracks
CNTs.areSo,
easy to spread
Low alongagglomerates
Mori -CNTs the interface ofare
thehard
un-oriented
to exertagglomer-
a high
ates without damaging CNTs. So, Low M ori-CNTs agglomerates are hard to exert a high
mechanical strength [33]. However, cracks cannot bypass the CNTs agglomerates for high
mechanical
Mori products strength [33].them.
but destroy However,
Thiscracks
is duecannot
to the bypass the CNTs
CNTs bridge agglomerates
effect which has for high
been
M ori products but destroy them. This is due to the CNTs bridge effect which has been high-
highlighted for toughening mechanisms, since CNTs can induce crack propagation and
lighted
crack for toughening
deviation to increasemechanisms, since CNTs
fracture toughness can
[34]. In theinduce crack propagation
destruction process, someand crack
CNTs
deviation to increase fracture toughness [34]. In the destruction process,
were pulled out of the matrix, and good wettability allowed the PP matrix to be coated some CNTs were
pulled out of the matrix, and good wettability allowed the PP matrix to be coated on CNTs,
thus forming many fibers on the fracture surface, as shown in Figure 9b. This process can
prevent the rapid propagation of cracks and improve the tensile strength of the parts.
Polymers 2023, 15, 2370 11 of 15

Polymers 2023, 15, x FOR PEER REVIEW 11 of 15

on CNTs, thus forming many fibers on the fracture surface, as shown in Figure 9b. This
Polymers 2023, 15, x FOR PEER REVIEW 11 of 15
process can prevent the rapid propagation of cracks and improve the tensile strength of
the parts.

Figure 9. Yield schematic and SEM images of fracture surface after yield. (a) Low Mori CNTs agglom-
erates,
Figure(b)
Figure 9. High
9. Yield ori CNTs agglomerates.
Mschematic
Yieldschematic and
and SEM
SEM images
images of fracture
of fracture surface
surface after after
yield.yield. (a)MLow
(a) Low M agglom-
ori CNTsori
CNTs
agglomerates, (b) High M CNTs agglomerates.
erates, (b) High Mori CNTsoriagglomerates.
3.2.2. Orientation Effect on Electrical Conductivity
3.2.2. Orientation Effect on Electrical Conductivity
3.2.2.The
Orientation
electrical Effect on Electrical
conductivity (σ) ofConductivity
various samples were measured in FD and TD di-
The electrical conductivity (σ) of various samples were measured in FD and TD
rections. As shown in Figure 10a, samples
The electrical conductivity (σ) of various with different
samples were Mori values
measuredshowedin FD different
and TD per-
di-
directions. As shown in Figure 10a, samples with different Mori values showed different
colation thresholds. That is, the sample conductivity underwent multiple
rections. As shown in Figure 10a, samples with different Mori values showed different per- orders of mag-
percolation thresholds. That is, the sample conductivity underwent multiple orders of
nitude
colationtransitions
thresholds.at aThat
certain CNTs content. For CM samples with low Moriorders
, the percola-
magnitude transitions at is, the sample
a certain CNTs conductivity
content. For underwent
CM samples multiple
with low Mof mag-
ori , the
tion threshold
nitude was 4atwt.%,
transitions a while
certain for IM
CNTs and IntM
content. For samples
CM withwith
samples highlowMori,Mthe
ori, percolation
the percola-
percolation threshold was 4 wt.%, while for IM and IntM samples with high Mori , the
threshold was 6was
tion threshold wt.% in FD and 9for
4 wt.%, wt.% in TD, respectively. Thishigh
phenomenon was also
percolation threshold was 6 while
wt.% in FD IMand
and 9IntM
wt.%samples with
in TD, respectively. MThis
ori, the percolation
phenomenon
found by
threshold other
was by researchers,
6 wt.% such as Ameli et al. [35] who studied injection molded
was also found otherinresearchers,
FD and 9 wt.% in Ameli
such as TD, respectively.
et al. [35] who This phenomenon
studied injectionwas molded also
PP/CNTs
found by nanocomposite
other researchers,foams,suchandastheir results
Ameli et al.showed
[35] low
who conductivity
studied injectionwhich was
molded
PP/CNTs nanocomposite foams, and their results showed low conductivity which was
attributed
PP/CNTs to the one-dimensional
nanocomposite foams, andoriented
theirCNTs
resultsin showed
the flow direction. This is which
consistent
attributed to the one-dimensional oriented CNTs in the flowlow conductivity
direction. This is consistent was
with our previous
attributed to the research conclusions
one-dimensional on CNTs
oriented PP/PA/CNTs
in the blends.
flow When This
direction. CNTsis choose
consistent to
with our previous research conclusions on PP/PA/CNTs blends. When CNTs choose to
disperse
with ourin
disperse in the PA
previous phase,
research
the PA phase, although the
conclusions
although elongated PA
on PP/PA/CNTs
the elongated phase
PA phase holds
blends. advantages
holdsWhen in
CNTs choose
advantages terms
in terms of
to
its
of tensile
disperse properties,
in
its tensile the its conductivity
PA phase,
properties, itsalthough
conductivitynetwork
the is defective
elongated
network [36].
PAdefective
is phase In general,
holds
[36]. orientated
advantages
In general, in con-
terms
orientated of
ductive phases,
its tensile
conductive such
properties,
phases, as
suchitselongated
conductivity
as elongated CNTs
CNTsagglomerates
network is defective
agglomerates ororPA/CNTs
[36].
PA/CNTs phases,
In general,
phases, are
arerelatively
orientated con-
relatively
hard to
ductive form a
phases, conductive
such as
hard to form a conductive path. path.
elongated CNTs agglomerates or PA/CNTs phases, are relatively
hard to form a conductive path.

Figure 10. (a) Direct current conductivity of various samples as a function of CNTs content,
Figure 10. (a) Direct current conductivity of various samples as a function of CNTs content, (b)
(b) anisotropy
anisotropy intensity
intensity σFD
σFD/σ TD.
/σTD .
Figure 10. (a) Direct current conductivity of various samples as a function of CNTs content, (b)
In
In addition,
anisotropy aa higher
intensity
addition, σFD/σTD.orientation
higher orientation brings
brings anisotropy
anisotropy while,
while, atat the
the same
same time,
time, reducing
reducing
conductivity.
conductivity. Figure
In addition, 10b
a higher
Figure shows the samples
orientation
10b shows the samples anisotropyintensity
brings anisotropy
anisotropy intensity
while, derived
at derived
the using
sameusing σFD/σ/σTD. .
time,σreducing
FD TD
σσconductivity.
FD and σTD areFigure
the conductivity
10b shows the samples anisotropy intensity derived using σFDand
in FD and TD directions, separately. For 6IM, 6IntM, /σTD.
FD and σTD are the conductivity in FD and TD directions, separately. For 6IM, 6IntM, and
9IM
9IM samples,
σFD and
samples, the
σTD are conductivity
the
the conductivity
conductivity in
ininFDFDwas
FD andabout
was four
four or
or five
TD directions,
about orders
orders of
separately.
five magnitude
ofFor higher
6IM, 6IntM,
magnitude and
higher
than
9IM that in TD.
samples, These
the samples
conductivity can
in be
FD called
was anisotropic
about four orpolymer
five composites,
orders of
than that in TD. These samples can be called anisotropic polymer composites, which have which
magnitude have
higher
recently
than thatattracted muchsamples
in TD. These attentioncan forbetheir essential
called applications
anisotropic polymer[37]. In general,
composites, a lower
which have
orientation
recently attracted much attention for their essential applications [37]. In general,while
helps to improve conductivity and reduce the percolation threshold, a lowera
higher orientation leads to anisotropy.
orientation helps to improve conductivity and reduce the percolation threshold, while a
higher orientation leads to anisotropy.
Polymers 2023, 15, 2370 12 of 15

recently
Polymers 2023, 15, x FOR PEER REVIEW attracted much attention for their essential applications [37]. In general, 12
a lower
of 15
orientation helps to improve conductivity and reduce the percolation threshold, while a
higher orientation leads to anisotropy.
3.2.3.
3.2.3. Combined
CombinedInfluence
InfluencebybyOrientation
Orientation and
and Dispersion
Dispersion
To
To clarify the combined
clarify the combinedinfluence
influenceofoforientation
orientationandand dispersion,
dispersion, thethe area
area of circles
of circles has
has been used to express the electrical conductivity, as shown in Figure 11a.
been used to express the electrical conductivity, as shown in Figure 11a. Mori is divided M ori is divided
into
into three
three levels (LOW, MEDIUM,
levels (LOW, MEDIUM,and andHIGH),
HIGH),differentiated
differentiatedusingusingcolor.
color. When
When thethe Moriis
Mori
isLOW,
LOW, higher conductivity can be obtained even if A is high; however, for
higher conductivity can be obtained even if Adis is high; however, for other samples,
dis other sam-
ples, the lower
the lower the Athe Adis value
dis value is,higher
is, the the higher conductivity
conductivity will be.willThe
be. lower
The lower Adis helps
Adis helps ori-
oriented
ented
CNTsCNTsform aform a conductive
conductive network,
network, whilewhile un-oriented
un-oriented CNTsCNTs can form
can form a conductivity
a conductivity path
path regardless
regardless of.Adis.
of Adis

Figure11.
Figure Agglomeratedispersion
11.Agglomerate dispersion degree
degree (Adis
dis))versus
versusMolecular
Molecular orientation
orientation (Mori
ori).).(a)
(a)the
theelectrical
electrical
conductivity and (b) the yield strength of the samples is expressed
conductivity and (b) the yield strength of the samples is expressed using the area of circles.

On the
On the other hand, as as shown
shownin inFigure
Figure11b,11b,thethearea
areaofof
circles
circlescan bebe
can used to express
used to expressthe
yield strength. The tensile strength is highly correlated
the yield strength. The tensile strength is highly correlated withori with M and almost unaffected
Mori and almost unaffected by
A
bydis , meaning high tensile strength can only be obtained
Adis, meaning high tensile strength can only be obtained in the high in the high M region. Meanwhile,
ori Mori region. Mean-
the tensile
while, strength
the tensile showsshows
strength no change with the
no change increased
with dispersion
the increased degree.degree.
dispersion
The conductivity
The conductivity of of the
the lower
lower M Mori sampleisisschematically
orisample schematicallyshown shownin inFigure
Figure 12a.
12a. The
The
agglomeratesand
agglomerates anddispersive
dispersiveCNTs CNTsremained
remainedrandomly
randomly arranged.
arranged. TheThe electronics
electronics cancanbe
be transferred along the horizontal and vertical directions, which
transferred along the horizontal and vertical directions, which has a high probability of has a high probability
of forming
forming a conductive
a conductive pathway
pathway in three-dimensions.
in three-dimensions. EvenEven
if theifagglomerates
the agglomerates do notdocon-
not
connect, they can still develop conductive pathways via a physical
nect, they can still develop conductive pathways via a physical connection among indi- connection among indi-
vidual fillers.
vidual fillers. So,
So, the
the low-oriented
low-oriented CM CMsample
sampleobtained
obtainedthe thelowest
lowestpercolation
percolationthreshold
threshold at
4 wt.%. However,
at 4 wt.%. However, when Mwhen M was high, as shown in Figure 12b, with the
oriori was high, as shown in Figure 12b, with the orientated CNTs orientated CNTs
and CNTs agglomerates, electrons
and CNTs agglomerates, electrons lost losttheir
theirability
abilityto topropagate
propagatein inthe
thevertical
verticaldirection.
direction.
The CNTs content must be increased to form a pathway
The CNTs content must be increased to form a pathway in FD. Correspondingly, in in FD. Correspondingly, inFD,
FD,
the percolation threshold of highly oriented IM and IntM samples
the percolation threshold of highly oriented IM and IntM samples rises to 6 wt.%. In high rises to 6 wt.%. In high
orientation, the
orientation, the conductive
conductivepath pathin in TD
TD isis the
the most
most difficult
difficult toto form
form and
and has
has the
the lowest
lowest
conductivity. In addition, shear provided by the injection molding can improve the CNTs
conductivity. In addition, shear provided by the injection molding can improve the CNTs
interface and even generate a hybrid shish-kebab. Hence, a layer of PP matrix surrounding
interface and even generate a hybrid shish-kebab. Hence, a layer of PP matrix surrounding
CNTs impairs the enhancement of σ [38,39]. Ultimately, the conductive path in TD is
CNTs impairs the enhancement of σ [38,39]. Ultimately, the conductive path in TD is
formed until Adis is less than 100, which corresponds to the highest percolation threshold
formed until Adis is less than 100, which corresponds to the highest percolation threshold
of 9 wt.%.
of 9 wt.%.
Mori can constrain the effect of Adis on conductivity. For low-oriented products
(Figure 12c), the Adis does not affect the conductivity because even at high Adis , there is an
opportunity to construct a three-dimensional conductive pathway for randomly distributed
CNTs agglomerates. However, for oriented CNTs agglomerates (Figure 12d), high Adis is
more likely to destroy their conductive pathways in the flow direction, thus increasing the
percolation threshold.
Polymers 2023,15,
Polymers2023, 15,2370
x FOR PEER REVIEW 13 of
of1515

Figure 12.Schematic
Figure12. Schematic ofof the
the conductivity
conductivity for
for (a)
(a) Low
Low M
Mori , (b) High Mori
ori, (b) High Mori, ,(c)
(c)Low
LowAA
disdis
andand M,ori
Mori (d),
(d) High
High Adis
Adis andand
MoriMsamples.
ori samples.

4. Conclusions
Mori can constrain the effect of Adis on conductivity. For low-oriented products (Figure
12c), the IM,
CM, Adisand
doesIntMnot prepared
affect thePP/CNTs
conductivitycomposites,
because which
even atcould
highprovide
Adis, theredifferent shear
is an oppor-
strengths. The dispersion and orientation of CNTs were quantified
tunity to construct a three-dimensional conductive pathway for randomly distributed using A ori (Agglomerate
orientation),
CNTs agglomerates. Mori (Molecular
However,orientation),
for orientedand CNTs Adis (Agglomerate
agglomerates orientation)
(Figure 12d), high at A both
dis is
aggregate
more likely to destroy their conductive pathways in the flow direction, thus increasingthe
and molecular chain scales. The results showed that high shear can increase the
Aori , Mori and Adis .
percolation threshold.
Increasing both orientation and CNTs content can increase the tensile strength and
modulus by 13% and 35%, respectively, but dispersion degree at the micro level has little
4. Conclusions
effect on the tensile strength. The oriented CNTs can form many fibers at the fracture
CM,and
interface IM,inhibit
and IntMcrackprepared
propagation.PP/CNTsThus,composites, which results
a high orientation could provide
in a highdifferent
tensile
shear strengths. The dispersion and orientation of CNTs
strength and modulus. Increasing CNTs content, the Mori of CM and IntM almost were quantified using A ori (Ag-
did not
glomerate orientation), M ori (Molecular orientation), and Adis (Agglomerate orientation) at
change, but Mori of the IM samples realized a transition from medium to high. Meanwhile,
both
the aggregate
tensile strength andand molecular
modulus chain
of IM scales. The results
also jumped withshowed
Mori . On that
thehigh
othershearhand, canAdisin-
crease the A ori, Mori and Adis.
almost does not affect the tensile properties.
Increasing
Both both orientation
high orientation and high and CNTs content
dispersion can increase
are averse the tensileofstrength
to the formation conductive and
modulus by 13% and 35%, respectively, but dispersion degree
pathways. Three percolation thresholds of 4, 6, and 9 wt.% can be obtained under three at the micro level has little
effect on
special the tensileand
orientations strength. The states
dispersion oriented CNTsrespectively.
of CNTs, can form many The fibers at the fracture
conductivity is affected in-
terface and inhibit crack propagation. Thus, a high orientation
by both CNTs orientation and dispersion. The conductivity percolation threshold of low results in a high tensile
Mstrength and modulus. Increasing CNTs content, the Mori of CM and IntM almost did not
ori samples is 4 wt.%, the CNTs are more likely to form a three-dimensional conductive
change, but
pathway, andMAoridis ofdo
thenot
IM affect
samples therealized a transition
conductivity. from the
However, medium to high.threshold
percolation Meanwhile, of
the tensile
high strength
Mori samples in and
FD ismodulus
raised toof6 IMwt.%, also
and jumped
in TD with Mori. Ontothe
is increased otherHigh
9 wt.%. hand,MA oridis
almost does
samples get an notanisotropy
affect the tensile
of nearlyproperties.
six orders of magnitude in FD and TD, which can
already Bothbe high
usedorientation and high
as anisotropically dispersionpolymer
conductive are averse to the formation
composites. High M oforiconductive
samples
pathways. Three percolation thresholds of 4, 6, and 9 wt.%
cannot form a three-dimensional pathway but prioritize creating a pathway in the can be obtained under three
FD, then
special orientations
forming a pathway inand TD dispersion
with further states of CNTs,
increased CNTs respectively. The conductivity
content. Meanwhile, the value is of
af-
Afected by both CNTs
dis is negatively orientation
correlated andconductivity;
with the dispersion. The thatconductivity percolation
is, high conductivity canthreshold
only be
of low Munder
obtained ori samples is 4 wt.%,
low CNTs the CNTs
aggregation are more likely to form a three-dimensional con-
dispersion.
In general,
ductive pathway, bothand
high orientation
Adis do not affectand high dispersion of However,
the conductivity. CNTs agglomerate against the
the percolation for-
thresh-
mation
old of of conductive
high Mori samplesnetwork,
in FD while a hightoorientation
is raised 6 wt.%, and caninimprove the mechanical
TD is increased properties.
to 9 wt.%. High
Mori samples get an anisotropy of nearly six orders of magnitude in FD and TD, which can
already be used as anisotropically conductive polymer composites. High Mori samples
cannot form a three-dimensional pathway but prioritize creating a pathway in the FD,
then forming a pathway in TD with further increased CNTs content. Meanwhile, the value
Polymers 2023, 15, 2370 14 of 15

Supplementary Materials: The following supporting information can be downloaded at: https:
//www.mdpi.com/article/10.3390/polym15102370/s1, Figure S1. Stress-strain curves of PP/CNT
composites.
Author Contributions: Conceptualization, D.M.; methodology, D.M. and Z.Z.; formal analysis, D.M.;
writing—original draft preparation, D.M.; writing—review and editing, D.M. and Z.Z; supervision,
H.B.; project administration, H.B. and D.M.; funding acquisition, D.M. and H.B. All authors have
read and agreed to the published version of the manuscript.
Funding: This research was funded by the Nature Foundation of Shaanxi Province (2023-JC-QN-
0593), Education Commission of Shaanxi Province (22JK0316), Nature Science Foundation of Shaanxi
Province (2023-YBGY-385).
Institutional Review Board Statement: Not applicable.
Data Availability Statement: Some or all data, models, or code generated or used during the study
are available from the corresponding author by request.
Conflicts of Interest: The authors declare no conflict of interest.

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