Materials Today Communications 30 (2022) 103078

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Materials Today Communications

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Positive temperature coefficient (PTC) materials based on amorphous poly

(methyl methacrylate) with ultrahigh PTC intensity, tunable switching
temperature and good reproducibility
Xiaoling Luo a, *, Dirk W. Schubert a, b
a
Institute of Polymer Materials, Friedrich-Alexander-University Erlangen-Nuremberg, Martensstr. 7, Erlangen 91058, Germany
b
KeyLab Advanced Fiber Technology, Bavarian Polymer Institute, Dr. Mack, Strasse 77, Fürth 90762, Germany

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

Keywords: Positive temperature coefficient (PTC) materials based on amorphous polymers usually suffer from low intensity
Positive temperature coefficient owing to their relatively small volume thermal expansion. Herein, graphene nanoplatelets (GNPs) and carbon
Amorphous polymer fibers (CF) with large aspect ratios were introduced into amorphous poly(methyl methacrylate) (PMMA) via
Graphene nanoplatelets
melting mixing followed by hot pressing to improve the PTC characteristics of the conductive composites. The
Carbon fibers
binary PMMA/GNPs composites showed good reproducibility while the PMMA/CF composites were superior in
PTC intensity and their switching temperature (positive to negative temperature coefficient) could be tuned by
varying the CF concentrations. When the both binary composites were connected in series, their strengths could
be fostered and their weaknesses could be circumvented. The ternary composite exhibited a superior PTC in­
tensity of 7.17, outperforming most of the reported PTC materials. These composites have great potential for
applications as temperature sensors and current limiting devices.

1. Introduction
Conductive polymer composites (CPCs) consisting of insulating
polymer matrix and conductive fillers have received attention in elec­
tronics applications such as conductors, electromagnetic interference
shielding, sensors and anti-static materials [1–5]. Sensors are employed
to detect or monitor environmental conditions such as strain, pressure,
temperature and liquid, since the output electrical signal can change in
the presence of an external stimulus [6–9]. The response of CPCs to
temperature is called pyroresistive effect, which can be divided into two
categories, positive temperature coefficient (PTC) effect and negative
temperature coefficient (NTC) effect. PTC is defined as an increase in
electrical resistivity with increasing temperature within a narrow tem­
perature range [10,11]. It is generally believed that the break-up of the
conductive networks during heating is caused by the thermal expansion
of the polymer and the change in the distance between the conductive
fillers. From the protection point of view, the increase in resistivity with
temperature rising limits both the current and temperature for CPCs
exhibiting PTC effect, therefore it has a wide field of applications in
self-regulating heaters, current limiting tools, temperature sensors and
overheat protectors [12–17].
The sharp increase in the resistivity of such PTC materials usually
occurs during the phase transition of the polymer matrix (the melting
temperature Tm or glass transition temperature Tg), reaching a PTC peak
during this process. On the contrary, when the composite is cooled, the
resistivity decreases due to the reconstruction of the conductive net­
works with the filler distance shortening [13,17]. If CPCs are further
heated after the PTC peak, the conventional NTC effect can be observed
in correspondence of re-aggregation of the conductive particles in the
molten polymer matrix, limiting the use of temperature sensors in
over-temperature and over current protection [18]. To address this
issue, many methods have been proposed and developed to eliminate
the NTC effect such as polymer blending and chemical crosslinking
[19–21]. The absence of an NTC effect has also been found by Zhang
et al. [22,23] when the binding force between high-density polyethylene
matrix and carbon fibers increased due to the very special structure of CF
surface.
In addition to the elimination of NTC phenomenon, an ideal PTC
material should possess these characteristics as well: a great PTC in­
tensity (defined as the logarithm of the ratio of the maximum resistivity
to the resistivity at room temperature, IPTC = log (ρmax/ρ0)), tunable
PTC/NTC switching temperature, and good repeatability for a large

* Corresponding author.
E-mail address: xiaoling.luo@fau.de (X. Luo).

https://doi.org/10.1016/j.mtcomm.2021.103078
Received 1 September 2021; Received in revised form 24 November 2021; Accepted 11 December 2021
Available online 14 December 2021
2352-4928/© 2021 Elsevier Ltd. All rights reserved.
X. Luo and D.W. Schubert
number of heating/cooling cycles [14,24,25]. It has been revealed that
the above characteristics of pyroresistive CPCs depend on both the na­
ture of the matrix polymer (Tg, Tm and crystallinity) and fillers (shape,
size, concentration and distribution) [21,26–31].
Intensive studies have focused on CPCs based on semi-crystalline
polymer matrix since these composites experience more volume ther­
mal expansion, as a consequence, they usually show better PTC in­
tensities compared to the amorphous polymer composites. Conductive
semi-crystalline polymer composites have realized excellent IPTC up to
10, almost spanning from good conductor to insulator [32,33]. How­
ever, such high intensities for PTC materials comprising amorphous
polymers have rarely been reported [34,35]. Luo et al. [29] compared
the PTC behaviors of four polymer/carbon black systems with different
crystallinity of the polymer matrix. The PTC intensities of polymethyl
methacrylate/carbon black (PMMA/CB), low-density polyethylene/­
ethylene vinyl acetate/carbon black (LDPE/EVA/CB), LDPE/CB,
high-density polyethylene/carbon black (HDPE/CB) were 0.5, 3.3, 4.2,
5.0, respectively, increasing with the crystallinity of the polymer matrix.
Similarly, Shen et al. [36] observed an IPTC of about 2 of amorphous
polystyrene/carbon black (PS/CB) composite, while that of
semi-crystalline HDPE/CB was higher than 5. It could be seen that in
such binary amorphous polymer composite, the thermal expansion of
the matrix was inadequate to break the networks of conductive particles.
However, a decent PTC behavior of filled amorphous polymer blends
could be observed when a good dispersion and selective location were
realized. For example, an intensity of about 6 was obtained in the study
of Lai et al. [37] by constructing semi-interpenetrating networks in
amorphous polystyrene/chlorosulfonated polyethylene/multiwalled
carbon nanotubes (PS/CSPE/MWCNT).
Switching temperature depends heavily on the phase transition
temperature of the polymer matrix, therefore it can be tuned by selecting
various polymer matrices or polymer blends [29,34,38]. Other ap­
proaches such as varying the filler loadings have also been reported [32,
39,40]. The reproducibility is a challenge because of the irreversible
self-aggregation of fillers and the random reconstruction of the
conductive network during the repeated temperature cycles. Modifica­
tion of fillers, hybrid fillers, cross-linking of the polymer matrix and
polymer blends are effective strategies for solving this problem[41]. Up
to now, satisfactory reproducibility in amorphous polymer composites
has not been reported yet, let alone tunable switching temperature.
Compared to semi-crystalline polymers, amorphous polymers are easy
to thermoform, they soften over a range of temperatures, they bond well
using as adhesives, and they tend to have better dimensional stability
and impact resistance. However, these advantages have not been fully
taken for their PTC materials due to the above mentioned drawbacks.
The present research aimed to fabricate conductive amorphous
polymer composites with superior PTC behaviors and to determine the
effect of filler shape and content. Polymethyl methacrylate (PMMA) was
selected as the polymer matrix, carbon fibers (CF) and graphene nano­
platelets (GNPs) both with large aspect ratios (AR) were used as
conductive fillers. The PTC performances of binary PMMA/CF, PMMA/
GNPs composites as well as their ternary composites were investigated, a
weak NTC effect, high PTC intensity, tunable PTC/NTC switching tem­
perature and stable PTC repeatability were achieved.
2. Experimental details
2.1. Materials
The matrix material PMMA Plexiglas 7 N was supplied by Evonik
Röhm GmbH, Germany, with Mw of 99 kg.mol− 1 and polydispersity
index of 1.52. The filler material chopped carbon fibers were obtained
from Tenax®—JHT C493 6 mm (Toho Tenax Europe GmbH, Wuppertal,
Germany), having a diameter of 7 µm, an initial length of 6 mm, a
density of 1.79 g.cm− 3 and a specific resistance of 1.7 × 10− 3 Ω.cm− 1.
GNPs (ProGraphite GmbH, Germany) are about 10 layers thick, d50 as
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Materials Today Communications 30 (2022) 103078
an index is 50 µm and conductivity is 800–1100 S∙cm− 1.
2.2. Sample preparations
All materials were dried at 80 ◦ C in a vacuum oven for at least 24 h
before processing. Then the melt mixing was conducted to both PMMA/
GNPs and PMMA/CF in an internal kneader PolyDrive (Haake, type
557–8310) at a temperature of 200 ◦ C and a rotation speed of 60/min for
10 min. The volume fractions of GNPs varied from 3.3 vol% to 8.0 vol%,
while those of CF varied from 16 vol% to 49 vol%. The filler concen­
tration was selected according to the percolation threshold (Φc) of each
composite, which was found to be 3.26 ± 0.48 vol% for PMMA/GNPs
composite and 11.5 ± 3 vol% of PMMA/CF composite (Fig. S1), which
has also been reported in our previous work [42,43]. After granulation,
the pellets were hot pressed under vacuum at a temperature of 200 ◦ C
and a pressure of 200 bar for 5 min. The obtained films had a thickness of
about 100 µm. More details regarding the preparation of composites and
the calculation of volume content can be found in our previous work
[42,43].
2.3. Characterization
Investigation of the morphology of the fillers was conducted with an
optical microscope (OM) (Leitz, Orthoplan P), composites were dis­
solved in acetone prior to the observation. Scanning electron microscopy
(SEM) (Carl Zeiss Microscopy, Germany) was conducted to investigate
the morphologies of composite films, operating at an accelerating
voltage of 3 kV. The composite films were previously fractured at room
temperature and the cross-sections were coated with a gold layer using
Sputter Coater S150B from Edwards. Differential scanning calorimetry
(DSC) was carried out on a Q200 DSC instrument (TA Instruments, USA)
to determine the Tg of PMMA. The heating rate was 5 ◦ C/min, and the
second heating cycle was recorded. The inflection midpoint of the heat
flow shift was determined as the Tg. The resistance dependence of
temperature was measured using a Keithley 6487 Pico ammeter (Tek­
tronix, Beaverton, OR, USA) at a constant voltage (1 V) while each
sample was heated at a rate of 5 ◦ C/min in a temperature control device
(IKA Werke GmbH＆Co.KG, Germany) then allowed to cool by normal
cooling rate without applying cooling devices. The electrical resistivity ρ
was then calculated as:
ρ = (R × S)/d (1)
where R is the electrical resistance of the sample, d is the length of the
sample between two electrodes, S is the area of the sample perpendicular
to the electrical field.
3. Results and discussion
3.1. Morphologies of composites
The morphologies of the binary PMMA/GNPs and PMMA/CF com­
posites are shown in Fig. 1. From the OM images Fig. 1a, b, the shape and
size of fillers could be observed. Both GNPs and CF had a broad distri­
bution in filler size, the aspect ratio (AR) was calculated to be over 500
for GNPs and 9.2 ± 1.3 for CF [42–44]. The SEM images Fig. 1c, d show
a rather rough fracture surface for both composites, a great deal of filler
pull-out revealed a poor interfacial bonding between matrix and fillers.
Some stacks of GNPs formed due to the strong π–π bonding between
graphene layers [45]. Therefore, CF showed better dispersion than GNPs
although with a much higher concentration.
3.2. PTC behaviors of binary PMMA/GNPs composites
The resistivity–temperature behaviors of the PMMA/GNPs compos­
ites are shown in Fig. 2a. It can be seen that during the heating run, the
X. Luo and D.W. Schubert Materials Today Communications 30 (2022) 103078

Fig. 1. OM images of (a) GNPs and (b) CF. SEM images of (c) PMMA/GNPs (3.8 vol%) and (d) PMMA/CF (29 vol%) composite.

Fig. 2. (a) Resistivity–temperature behaviors and (b) TCR-temperature curves of PMMA/GNPs composites with various GNPs loadings.

resistivity of composites increased when the temperature increased from
room temperature to the PTC peak temperature at 105–115 ◦ C, and an
NTC behavior occurred above this switching temperature. As expected,
it is near the Tg of the PMMA (109.5 ◦ C), which can be found in Fig. S2.
During the cooling cycles, the resistivity did not follow the same path as
the heating cycles. It dropped but not monotonically as the temperature
decreased, without passing over the PTC peak again. A slight increase
was observed from 110 ◦ C to 85 ◦ C, indicating a hysteresis of the evo­
lution of conductive networks. From 140 ◦ C to 110 ◦ C, probably the re-
aggregation of the conductive GNPs continued since the polymer seg­
ments or chains still had sufficient mobility even though the specimen
was cooled down. From 110 ◦ C to 85 ◦ C, the mobility reduced and the
movement of GNPs particles was confined, that is why the resistivity
increased. From 85 ◦ C to room temperature, the decrease in resistivity
was dominated by the contraction of the polymer matrix. It can be seen
that the resistivity was close to the initial one before heating when it was
cooled to room temperature, the repeatability will be further presented
in Fig. 3. In Fig. 2b, The term temperature coefficient of resistivity (TCR)
is used to indicate the improvement or reduction in electrical resistivity
caused by a temperature increment in the composite [30,46], which can
be calculated from Eq. (2).
(ρ − ρ0 )
TCR (%) = × 100 (2)
ρ0 × (T − T0 )
where ρ0 and ρ are the resistivity at the room temperature T0 and the
ambient temperature T, respectively. It can be observed from Fig. 2b
that the TCR of these composites decreased with GNPs concentration
increasing, composite with 3.3 vol% GNPs exhibited the highest TCR of
6.74%/◦ C at 105 ◦ C. This is due to the small number of conductive
networks and long inter particle gap, which made it more prone to the

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X. Luo and D.W. Schubert
Fig. 3. Resistivity–temperature curves of PMMA/GNPs composites comprising (a) 3.3 vol%; (b) 4.6 vol%; (c) 8.0 vol% GNPs. (d) PTC and NTC intensity for three
temperature cycles.
destruction of conductive pathways during the differential thermal
expansion [17].
GNPs were introduced due to their large lateral size, since it is
believed that larger particles normally form a smaller number of
conductive pathways. As a result, the entanglement between the parti­
cles and polymer chains increases, the resistivity of the composite is
more sensitive [11,47,48]. This was confirmed by comparing with car­
bon black (CB) and carbon nanotubes (CNTs) loaded PMMA composites
as shown in Fig. S3. Both composites showed a slow but progressive
decrease in resistivity with the rise in temperature, e.g. NTC effect, no
PTC behavior was observed around the Tg of PMMA. Although CB and
CNTs were widely used to produce PTC materials based on polymers,
very high PTC intensity has been achieved as well, these polymers were
mostly semi-crystalline [37,49–51]. It seems that these fillers could form
more robust conductive networks in the amorphous PMMA than GNPs
via conventional melting processing. This structure could not experience
enough destruction during the expansion of the PMMA.
To evaluate the reproducibility, three heating-cooling runs were
carried out under the same condition. The change rate of the resistivity
is calculated according to the two ρ0 values in the different heating runs.
As shown in Figs. 3a-c, 3.3 vol% GNPs-loaded composites showed the
highest change rate up to 30.4% among the three cycles, and this value
became smaller when the concentration of GNPs increased to 4.6 and
8.0 vol%. The evolution of TCR can be seen in Figs. S4a-c, which had a
similar trend to resistivity. This indicates that more conductive fillers
were beneficial to maintain the conductive networks when alternatively
heated and cooled. Interestingly, the resistivity did not rise or reduce
monotonically with the heating-cooling cycle number increasing, which
is likely due to the poor interfacial bonding between the PMMA matrix
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Materials Today Communications 30 (2022) 103078
and GNPs. Therefore the movement of GNPs could be freer and the
reconstruction of the conductive network was random during the tem­
perature cycles. A similar phenomenon has been found in the study of a
silicon rubber composite filled with carbon fibers [52]. However, most
of the resistance or resistivity in literature either monotonically
increased [53–55] or decreased [14,25,56] as the temperature cycle
increased. Overall, compared to the literature, this reproducibility is
acceptable and promising without any strategies being applied [25,56].
The PTC intensity and NTC intensity (the logarithm of the ratio of the
maximum resistivity to the resistivity at 140 ◦ C, INTC = log (ρmax/ρ140))
for the three temperature cycles are shown in Fig. 3d. The highest in­
tensity 0.71 occurred in 3.3 vol% GNPs-filled PMMA composite. For all
the three concentrations, although it fluctuated during the three cycles,
it followed the sequence of 3.3 vol% GNPs ˃ 4.6 vol% GNPs ˃ 8.0 vol%
GNPs. As to the NTC intensity, it was lower than the PTC intensity and
also decreased with the GNPs concentration increasing.
3.3. PTC behaviors of binary PMMA/CF composites
The resistivity of the PMMA/CF composites as a function of tem­
perature is shown in Fig. 4a. Unlike the PMMA/GNPs composites,
PMMA/CF samples exhibited significant changes in resistivity for
several orders of magnitude. The resistivity of these composites was less
than 100 Ω∙cm before heating, while a surge occurred from a certain
temperature (onset temperature) and reached a PTC peak up to 107
Ω∙cm. The onset temperature was 80 ◦ C for 16 vol% CF-filled PMMA
and it shifted to 90 ◦ C when the content of CF increased to 29 vol%, and
both composites had a close PTC peak at around 100 ◦ C. As the con­
centration of CF further increased to 49 vol%, the resistivity rose
X. Luo and D.W. Schubert Materials Today Communications 30 (2022) 103078

Fig. 4. (a) Resistivity–temperature behaviors and (b) TCR-temperature curves of PMMA/CF composites with various CF loadings (inset: NTC region showing TCR
below 0).

gradually and reached around 104 Ω∙cm of a PTC peak at 130 ◦ C. After
the PTC peak, an NTC behavior can also be observed until 140 ◦ C.
However, the resistivity only decreased by less than two orders of
magnitude, which was still much higher than the initial one. During the
cooling process, unlike the PMMA/GNPs composite, the resistivity of
PMMA/CF fell off as cooled down without rising again near Tg. Another
difference with the PMMA/GNPs was found that the PMMA/CF
composite showed a weak NTC effect at the heating run, which started
from room temperature to about 75 ◦ C. This can be clearly seen in
Fig. 4b, the TCR in this temperature range was below 0 and the mini­
mum was − 1.2%/◦ C. This phenomenon has also been found in other
researches [40,57]. It is possibly due to the NTC characteristic of the CF
itself. To verify this, pure CF was heated and cooled under the same
condition as the composites. The result is presented in Fig. S5. The CF

Fig. 5. Resistivity–temperature of the PMMA/CF composites comprising (a) 16 vol%; (b) 29 vol%; (c) 49 vol% CF. (d) PTC and NTC intensity for three tempera­
ture cycles.

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X. Luo and D.W. Schubert
showed decreasing resistivity in the whole temperature range owing to
the increase in the energy and mobility of the electrons [58]. That is to
say, the thermally assisted tunneling transport at the CF junctions was in
competition with the thermal expansion of the matrix, and the former
controlled the temperature coefficient of resistivity of the PMMA/CF
well below 75 ◦ C. It can be noted that pure GNPs also showed an NTC
effect like the CF, however, only the PTC effect was seen in that tem­
perature range when the GNPs were included into the PMMA. The dif­
ference in PTC/NTC behavior between the two composites is considered
to be related to the filler concentration and their interfacial bonding
with the matrix. On the one hand, the concentration of the GNPs was
lower than the CF, thus, the number of conductive pathways was less. On
the other hand, the GNPs had worse interfacial bonding with the PMMA
so they were more easily moved. Hence the PMMA/GNPs was more
vulnerable to the polymer volume expansion at low and moderate
temperatures. However, the contradictory situation happened at high
temperature, where the resistivity of PMMA/CF composite increased
rapidly between 75 ◦ C to 130 ◦ C and a much higher PTC intensity was
obtained. The reason behind this phenomenon needs further research.
The repeatability of the PMMA/CF materials was shown in Fig. 5. As
shown in Fig. 5a-c, the switching temperature almost remained the same
during the three runs, however ρ0 shows a significant change up to
117.4%. This could be attributed to the complete destruction of
conductive networks at the switching temperature, at which the com­
posite became an insulator. Thus it was difficult to reform during the
cooling cycles. Moreover, the slight NTC behavior below 75 ◦ C also
appeared in the subsequent two heating runs (Fig. S6). The PTC and NTC
intensity of the three cycles was shown in Fig. 5d. Compared to the PTC
intensity of the PMMA/CF composite, the NTC intensity was pretty low.
The composite containing 29 vol% CF had the greatest IPTC of 6.98 and
the lowest INTC of 0.78. The optimal IPTC resulted from the very high ρmax
and relatively low ρ0, and the lowest INTC might be ascribed to the
appropriate distance between fibers, which was large enough for suffi­
cient mobility of both polymer chains and fillers, and also small enough
for easy reconnection of fibers above the switching temperature [34,59].
3.4. PTC behaviors of ternary composites
As discussed above, the binary PMMA/CF materials showed ultra­
high PTC intensity and the PTC/NTC switching temperature can be
tailored by changing the filler concentration, while its reproducibility
needed to be improved, and the NTC effect below 75 ◦ C needed to be
eliminated. On the contrary, although the PTC intensity of the PMMA/
GNPs samples was lower and the switching temperature did not show
much change at different GNPs volume fractions, the reproducibility
Fig. 6. Schematic sketch of the three types of ternary composites. Series PMMA/GNPs-PMMA/CF, parallel PMMA/GNPs-PMMA/CF and mixed PMMA/GNPs/CF are
equivalent to series circuit, parallel circuit and series-parallel circuit, respectively.
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Materials Today Communications 30 (2022) 103078
was satisfactory and no NTC effect appeared below 75 ◦ C. Therefore
ternary composites comprising PMMA, GNPs and CF were prepared in
order to take the best of both binary composites. Three kinds of ternary
composites, series, parallel and mixed composite were compared, which
is schematically illustrated in Fig. 6. Since the resistance measuring di­
rection was the in-plane direction, series means the PMMA/GNPs and
PMMA/CF composite films were fabricated and then joined together in
the in-plane direction, while the parallel composite film was the stack of
both binary composites in the through-plane direction. The mixed
composite was produced by compounding three materials, PMMA,
GNPs, CF via melt mixing, the two fillers could distribute homoge­
neously in the matrix. These three composites can be equivalent to a
series circuit, parallel circuit and series-parallel circuit, respectively.
For the series ternary composites, GNPs were first fixed at 3.8 vol%
and the content of CF was varied, the resistivity-temperature curves are
shown in Fig. 7a. These PTC materials showed a similar PTC intensity
and switching temperature to the binary PMMA/CF composites as
shown in Fig. 4a, fortunately, the NTC behavior below 75 ◦ C was
eliminated at the same time (Fig. S7a). Since the ρ0 of the PMMA/3.8 vol
% GNPs sample was greater than all the CF-filled PMMA composites
(Fig. S1), the resistivity of the series circuit was more dependent on the
PMMA/GNPs, thus this series composite exhibited PTC effect like the
binary PMMA/GNPs films. As the temperature continued to increase, the
resistivity of the PMMA/CF part began to rise rapidly and surpassed that
of the PMMA/GNPs part in the series circuit, therefore the resistivity
more depended on the PMMA/CF resistor, that is why superior PTC
intensity and tunable switching temperature could also be obtained. In
the case of varied GNPs concentrations, the loading of CF was fixed at
16 vol% in the PMMA/CF composite part. Due to the PTC characteristic
of the PMMA/CF, these composites also achieved very high PTC in­
tensity, verifying the advantage of series ternary composite again.
However, because the resistivity of PMMA/CF was lower than the
PMMA/8.0 vol% GNPs composite, the NTC effect below 75 ◦ C still
occurred as shown in Fig. S7b. This phenomenon further confirms a
precondition for eliminating the NTC behavior in a series circuit was
that the resistivity of the PMMA/GNPs composite was higher than the
PMMA/CF.
Among these series materials, the PMMA/3.8 vol% GNPs/16 vol%
CF composite showed the best PTC performance in terms of the PTC
intensity, thus the repeatability of this composite, as well as the parallel
and mixed composite at the same filler concentration and the mixing
ratio was measured. As shown in Fig. 8a, the series specimen showed
satisfactory reproducibility, the resistivity–temperature curves of the
three heating runs coincided well with each other and this consistency
was better than the corresponding binary PMMA/CF composites
X. Luo and D.W. Schubert Materials Today Communications 30 (2022) 103078

Fig. 7. Resistivity–temperature curves of series PMMA/GNPs-PMMA/CF composites (a) at 3.8 vol% GNPs and various CF volume fraction; (b) at 16 vol% CF and
various GNPs volume fractions.

Fig. 8. Resistivity–temperature curves of (a) series PMMA/GNPs-PMMA/CF composite; (b) parallel PMMA/GNPs-PMMA/CF composite; (c) mixed PMMA/GNPs/CF
composite. (d) PTC intensity for three temperature cycles.

(Fig. 5a). The variation of ρ0 was 75.8%, which was slightly lower than
86.3% of the PMMA/16 vol% CF material. The PTC and NTC intensity
are shown in Fig. 8d, the series specimen showed the highest IPTC of
7.17, which is higher than 6.57 of 16 vol% CF-loaded binary composite,
and even higher than the best value 6.89 achieved by the PMMA/29 vol
% CF sample (Fig. 5d). In addition, this specimen also had a rather low
INTC of 1.12, and no NTC effect happened below 75 ◦ C (Fig. S8a). In
comparison, the variation of the room temperature resistivity of the
parallel specimen was higher, and it also had lower IPTC and higher INTC
than the series materials. NTC phenomenon appeared below 75 ◦ C
(Fig. S8b), because the equivalent resistance of the parallel resistor is
theoretically always less than the smallest resistor in the parallel
network, and R0 of the PMMA/CF part was lower than that of the
PMMA/GNPs part in the parallel system. As the temperature further

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X. Luo and D.W. Schubert Materials Today Communications 30 (2022) 103078

increased to the switching temperature, the resistance of the PMMA/CF

part surged and surpassed that of the PMMA/GNPs, the equivalent
resistance was more dependent on the PMMA/GNPs and thus the PTC
intensity was limited. This theory probably also worked in the following
NTC region, the resistance of the PMMA/GNPs dropped more rapidly so
that the NTC intensity became higher. As to the mixed specimen, it
showed a rather small variation of ρ0 of 46.6% and a much lower IPTC of
3.02. This is likely due to the synergistic effect of hybrid fillers [14,55],
the conductive networks could better maintain the position of particles
during thermal expansion.
Overall, these results confirmed the feasibility of the combination of
the strength of both binary composites, the facile construction of the
series resistor seems to best endow the ternary composite with an
excellent comprehensive PTC performance with respect to the conven­
tional mixing method. By selecting a certain binary system and ternary
system in this work, different characteristics of the PTC material could
be satisfied for different applications. For example, for an over-current
or over-heating protection device, the strong PTC effect is required to
ensure the protection, and the NTC effect needs to be eliminated to avoid
the adverse influence on the application. The PMMA/CF composites
possessed a high PTC intensity and a low NTC intensity, the weak NTC Fig. 9. Comparison of the PTC intensity of composites in this work (stars) with
effect below 75 ◦ C could be eliminated when it was in series with the literature data [61–72].
PMMA/GNPs composite. In addition, tunable switching temperatures
from 100 ◦ C to 130 ◦ C could be achieved by simply using variable CF work. Besides, the undesired NTC effect below 75 ◦ C for PMMA/CF
concentrations in the composites. As to the reproducibility of these PTC composite was eliminated in the ternary system. This work provides a
materials, it was decent without any modification. ρ0 fluctuated within facile route to produce high-performance PTC materials with great po­
117.4%, IPTC and INTC did not change much during the three temperature tential for applications as temperature sensors and current limiting de­
cycles. Further improving the repeatability in more temperature cycles vices based on the amorphous polymer matrix.
could be realized in continuous research.
Typically, the PTC intensity in this work was compared with other CRediT authorship contribution statement
reports intensively as shown in Fig. 9. Mainly depending on the type of
the polymer matrix, the PTC/NTC switching temperature of these ma­ Xiaoling Luo: Conceptualization, Methodology, Validation, Formal
terials ranged from 45 ◦ C to 215 ◦ C. It can also be seen that for the same analysis, Investigation, Writing – original draft. Dirk W. Schubert:
polymer matrix, the difference in switching temperature for different Writing – review & editing, Supervision.
reports was not that significant. For example, most of the HDPE-based
PTC materials had switching temperatures around 140 ◦ C. These were
as low as 120 ◦ C [50] and up to 150 ◦ C [34]. However, for the same Declaration of Competing Interest
polymer, the PTC intensity could vary significantly. For example, the
IPTC of an HDPE/CB composite was just about 1 in one study [60], while The authors declare that they have no known competing financial
it was about 8 for an HDPE/AgS system (silver coated glass spheres) in interests or personal relationships that could have appeared to influence
another research [34]. Overall, the PTC intensities of the ternary the work reported in this paper.
PMMA/GNPs/CF and the binary PMMA/CF in this work are relatively
superior to most of the listed works, including semi-crystalline polymer Acknowledgments
composites. Some strategies for improving the PTC intensity in amor­
phous polymer systems could be borrowed. For instance, for a CB-filled The authors would like to thank Inge Herzer from Institute of Poly­
amorphous ethylene–propylene–diene terpolymer (EPDM) composite mer Materials (Friedrich-Alexander-University Erlangen-Nuremberg)
[35], γ-ray irradiation was applied to crosslink the polymer matrix, the for the DSC measurements.
NTC effect was eliminated and a high PTC effect was obtained at the
same time. For a polycarbonate (PC) filled with AgS with distinct di­ Appendix A. Supporting information
ameters, 50 µm and 100 µm AgS based composites showed a very high
PTC intensity while 2.5 µm AgS based composite showed small IPTC. The Supplementary data associated with this article can be found in the
idea was that the number of conductive filler contact points is limited for online version at doi:10.1016/j.mtcomm.2021.103078.
large-sized fillers, thus the conductive network was more sensitive to the
perturbations.
References

4. Conclusions
In this study, GNPs and CF with large aspect ratios were introduced
into the amorphous PMMA matrix to develop PTC materials. The binary
PMMA/GNPs composites exhibited good reproducibility while the
PMMA/CF composites showed excellent PTC intensities, ultralow NTC
intensities and tunable PTC/NTC switching temperatures from 100 ◦ C to
130 ◦ C by adjusting the filler loadings. Both the binary composites
complemented each other when they were simply connected in series as
ternary composites. In this series PTC material, an ultrahigh PTC in­
tensity of 7.17 was achieved, which is higher than most of the reported
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