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Investigating mechanical, thermal, and flammability properties of

thermoplastic polyurethane/carbon nanotube composites

Article  in  Journal of Thermoplastic Composite Materials · November 2017

DOI: 10.1177/0892705717743292

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Original Article
Journal of Thermoplastic Composite
Materials
Investigating mechanical, 1–15
ª The Author(s) 2017
thermal, and flammability Reprints and permissions:
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properties of thermoplastic DOI: 10.1177/0892705717743292

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polyurethane/carbon
nanotube composites
Yasin Kanbur1 and Umit Tayfun2

Abstract
Thermoplastic polyurethane (TPU) composites containing carbon nanotube (CNT) with
the loading ratios from 0.5wt% to 2 wt% were prepared using melt-compounding pro-
cess. Surfaces of the CNT particles were treated with sulfuric acid/nitric acid to purify
CNT and to achieve compatible surface characteristics between TPU matrix and CNT.
Mechanical, thermal, flame retardant, melt flow, and morphological properties of TPU/
CNT composites were investigated. Addition of CNT to TPU matrix causes in a pro-
minent increase in tensile strength, percentage of elongation at break, and tensile
modulus values of TPU. The mechanical properties are improved for lower modified
CNT loadings. CNT inclusions also improve the thermal stability of pristine TPU.
Addition of CNT into TPU matrix causes increase in melting and decomposition tem-
peratures of TPU and decrease in glass transition temperature. The flammability para-
meters of TPU also shift to higher values after CNT loadings to matrix. Modified CNT
additions at higher concentrations exhibit better fire performance. Additions of modified
CNT and pristine CNT show different trends in the case of melt flow rate values.
Modified CNTs disperse more homogeneously relative to pristine ones into TPU matrix
which is due to improvement in interfacial interactions between CNT and TPU.

Keywords
Thermoplastic polyurethane, carbon nanotubes, extrusion, flame retardancy,
nanocomposites

1
Department of Metallurgical and Materials Engineering, Karabuk University, Karabuk, Turkey
2
Inovasens Ltd, Izmir Technopolis, Izmir, Turkey

Corresponding author:
Yasin Kanbur, Department of Metallurgical and Materials Engineering, Karabuk University, 78050 Karabuk,
Turkey.
Email: yasinkanbur@karabuk.edu.tr
2 Journal of Thermoplastic Composite Materials XX(X)

Introduction
Carbon nanotube (CNT) and its derivatives are one of the most important carbon-based
materials in last 50 years due to its aspect ratio1 plus mechanical and electrical prop-
erties.2 CNTs have different usages in polymeric composites including biosensors,3,4
solar cells,5 fuel cells,6 photovoltaics,7 electrochemical capacitors,8 conductive materi-
als,9 electromagnetic interference shielding,10,11 and for the purposes of improvement of
flame retardancy12,13 and mechanical properties.14
CNT has tendency to form agglomerate in polymer matrix due to strong van der
Waals interactions and this property limits its applications. Different methods are
applied to exceed this agglomeration problem including solution mixing,15,16 in situ
polymerization,17,18 melt mixing,19–21 addition of appropriate compatibiliser,22,23 and
surface modification24,25 of CNT with appropriate surface groups to achieve better
interfacial adhesion with polymer matrix. Melt mixing is one of the most useful methods
especially for industrial applications. Shear stress arises from the screw rotations that
provide better dispersion of particle in polymer matrix.
Surface modification is also common and effective method to improve the dispersion
of nanoparticles in polymer matrix. This technique is based on the formation of similar
surface functional groups on particle surface which are compatible with the polymer
structure. In the case of surface treatments with acids, shortening of the CNT lengths
occurs,26,27 and this results with an advantage to get better dispersion in polymer matrix
due to ability of shorter chain to form aggregate is lower than the pure form. On the other
hand, shortening of CNT causes some reductions in mechanical properties because of the
decrease in aspect ratio of nanotubes but dispersion homogeneity and enhancement of
interfacial interactions between CNT and polymer matrix influence more dominantly the
final properties of composites. The decrease in the nanotube length depends on the time
and temperature of the acid treatment.28
Thermoplastic polyurethane (TPU) consists of hard and soft segments. Hard segment
consists of highly polarized group which is hardened by cross-linking29 and soft segment
is a polyester phase. Hard segments disperse as microdomains in the structure and phases
are held together by the hydrogen bonds.30 Easy processability and fully recyclability of
TPU make it a good candidate for broad industrial application area including footwear;
automotive; sporting goods; medical devices; tubes; hoses; wires; cables; and medical
devices in the form of sheets, films, or profiles.31
In this study, mechanical, thermal, and flame resistance properties of CNT-loaded
TPU composites were investigated. Several publications about CNT-reinforced TPU
composites produced exist32–37 in which flame retardancies of these composites have not
reported yet. Espadas-Escalante et al. have studied the thermal conductivity and
flammability of polyurethane foam composites containing CNT in a similar study.38
Mechanical and electrical properties of CNT-reinforced TPU composites were studied in
our earlier publication.39 As a difference from that publication, CNT is treated with nitric
acid (HNO3)/sulfuric acid (H2SO4) for the purpose of purification and to obtain better
interfacial interactions with TPU matrix, and fire performance and thermal stability of
TPU/CNT composites are investigated in this present work. Composites of CNTs and
Kanbur and Tayfun 3

TPU were prepared using a twin screw extruder. Tensile and shore hardness tests, melt flow
index (MFI) test, differential scanning calorimetry (DSC), thermogravimetric analysis
(TGA) analysis and UL-94, limiting oxygen index (LOI) test, and mass loss calorimeter
measurements were performed to evaluate mechanical characteristics, processability,
thermal properties, and flame retardancy of composites. Scanning electron microscopy
(SEM) was used to investigate the dispersion of CNT particles in TPU matrix.

Experimental
Materials
Polyester-based TPU (Texalan® 485A) was purchased from Pasific (Covina, California,
USA) with density of 1.20 g cm 3 and 85 (Shore A) hardness. This grade of TPU
composes of 45% flexible segment and 55% of rigid segment. CNT used in this study
was supplied from Nanocyl SA (Belgium) under the trade name of NC 7000. This CNT
grade has length, diameter, and carbon purity of 1.5 mm, 9.5 nm, and 90%, respectively,
cited by producer. HNO3 (65%) and H2SO4 (98%) were obtained from Merck, USA.

Surface modifications of CNT

CNT was annealed at 450 C for 4 h before the surface modification treatment. The non-
modified CNT is coded as CNT. Chemical functionalization of CNT was done using the
surface modification route given in the literature40; 1.6 g of CNT was refluxed for 6 h at
120 C with (3:1, v/v) concentrated H2SO4 and concentrated HNO3, respectively. Fol-
lowing the surface modification step, the solution was diluted with distilled water and
filtrated. Then the filtrated solid product was washed with distilled water several times
and dried under vacuum for 5 h. Surface-modified CNT was coded as m-CNT. Detailed
characterizations of the surface-treated CNT were reported in our previous study.41

Preparation of TPU/CNT composites

A DSM Xplore (15 ml) twin screw extruder was used for the preparation of TPU/CNT
composites with a mixing speed of 100 r min 1 and processing temperature of 210 C for
8 min. Prior to preparation of composites, TPU granules were dried at 100 C for 2 h.
TPU/CNT and TPU/m-CNT composites were prepared with four different CNT loading
ratios as 0.5 wt%, 1.0 wt%, 1.5 wt%, and 2.0 wt%. Tensile test samples of the composites
were prepared by Daca Instruments’ microinjection molding at a barrel temperature of
215 C and mold temperature of 40 C.

Characterization methods
Tensile tests of the composites were performed using a Lloyd LR 30 K, UK universal
tensile testing machine with load cell of 5 kN at a crosshead speed of 5 cm min 1
according to the ASTM D-638 standard. Tension tests were applied on dog-bone-shaped
samples (7.4  2.1  80 mm3). Tensile strength, percentage elongation at break, and
4 Journal of Thermoplastic Composite Materials XX(X)

tensile modulus values were recorded as an average of five samples with standard
deviation. Thermal properties of composites were investigated by TGA analysis (STA
7300 TGA; Hitachi, Japan) between the temperature range of 30–600 C under a nitrogen
atmosphere at a heating rate of 10 C min 1 and DSC (DSC 4000; PerkinElmer, USA)
analysis from 50 C to 250 C under a nitrogen atmosphere at a heating rate of 10 C
min 1. MFI tests were done using Coesfeld Material Test (Germany), Meltfixer LT. The
test was carried out at 215 C under specified load of 5 kg and MFI values are reported as
average of 10 tests. For flammability tests, vertical burning tests (UL 94) were conducted
on the test bars with the dimensions of 130  13  3.2 mm3 according to ASTM D3801
standard. LOI values were also measured using LOI analyzer instrument (Fire Testing
Technology, UK) on specimens of size 130  6.5  3.2 mm3, according to the standard
oxygen index test ASTM D2863. The mass loss calorimeter test was investigated using
mass loss cone of Fire Testing Technology with thermopile attachment according to
procedures in ISO 13927. Square test samples (100  100  3 mm3) were irradiated at a
heat flux of 35 kW m 2, corresponding to a mild fire scenario. SEM photographs were
taken at magnifications in the range of 50,000 to 200,000 for cyro-fractured surface
of composites using FEI Quanta (USA) 400F field emission SEM.

Results and discussion

Tensile test
Tensile test data of TPU and its composites are represented in Figure 1 and Table 1.
Table 1 shows that tensile strength, elongation at break, and elastic modulus values are
improved remarkably by the addition of CNT as compared with neat TPU. Additionally,
m-CNT containing composites give slightly higher results in the case of tensile strength
with respect to unmodified CNT-loaded TPU composites because of better interfacial
interactions between TPU and CNT surfaces after treatment. The highest strength,
elongation at break, and elastic modulus values are obtained for the composites which
contain 0.5 wt% CNT and m-CNT. Further additions of m-CNT cause decrease in
percent elongation of composites which may be attributed to restriction of chain
motions.42 Composites containing modified CNT exhibit slightly lower elastic modulus
as compared to pristine CNT-filled ones.

Shore hardness test

Shore hardness is a specific parameter for elastomers and their composites. Shore A
hardness test results of TPU and TPU/CNT composites are given in Table 2. The results
show that the hardness of TPU decreases slightly with the addition of the lowest loading
level for both cases of CNT and m-CNT. Hardness of the composites containing pristine
CNT decreases with the increase of filling ratio of CNT since the dispersion of pristine
CNT is poor in polymer matrix and their tendency to form agglomerates.31 As a result,
unmodified CNT exhibits sharp reduction for shore hardness of TPU. In contrary,
m-CNT shows increasing trend with increase of its content due to better dispersion of m-
CNT in matrix.
Kanbur and Tayfun 5

Figure 1. Tensile test results of TPU and composites.

TPU: thermoplastic polyurethane.

Table 1. Tensile test data of TPU and composites.

Samples Tensile strength (MPa) Elongation at break (%) Elastic modulus (MPa)

TPU 24.8 + 1.7 331.8 + 4.3 33.4 + 3.0

TPU/0.5% CNT 30.5 + 1.8 510.0 + 5.1 74.8 + 3.3
TPU/1% CNT 29.3 + 1.6 510.3 + 5.5 83.2 + 3.8
TPU/1.5% CNT 28.4 + 2.1 482.6 + 6.4 70.7 + 3.5
TPU/2% CNT 27.2 + 1.9 531.0 + 5.2 74.8 + 3.1
TPU/0.5% m-CNT 34.6 + 1.7 474.4 + 6.6 65.0 + 3.2
TPU/1% m-CNT 30.8 + 1.0 448.2 + 7.1 63.6 + 3.0
TPU/1.5% m-CNT 29.5 + 1.1 430.5 + 6.8 67.5 + 3.4
TPU/2% m-CNT 28.2 + 0.8 417.9 + 6.3 68.9 + 3.3

TPU: thermoplastic polyurethane; CNT: carbon nanotube; m-CNT: modified CNT.

DSC analysis
Figure 2 displays the DSC heating curves of TPU and relevant composites. The glass
transition temperatures (Tgs) and melting temperatures (Tms) of samples are given
in Table 3. Tm of TPU shifts to higher temperatures with the addition of CNTs. Tm
value of unmodified CNT-loaded composites increases slightly with increasing CNT
6 Journal of Thermoplastic Composite Materials XX(X)

Table 2. Shore A hardness values of TPU and composites.

CNT content (%) TPU/CNT TPU/m-CNT

0 84.8 + 0.2 84.8 + 0.2

0.5 83.6 + 0.2 84.5 + 0.2
1.0 82.3 + 0.1 85.1 + 0.1
1.5 79.7 + 0.3 85.9 + 0.2
2.0 77.1 + 0.3 86.3 + 0.1

TPU: thermoplastic polyurethane; CNT: carbon nanotube; m-CNT: modified CNT.

Figure 2. DSC heating curves of TPU and composites.

DSC: differential scanning calorimetry; TPU: thermoplastic polyurethane.

composition; however, m-CNT-loaded composites exhibit almost identical Tm values for

all loading ratios. According to Table 3, CNT additions result in the reduction for Tg of
pristine TPU. This result proves that incorporation of CNT into polymer matrix causes an
increase in free volume stem from its nucleating effect.43

Thermogravimetric analysis
TGA curves of TPU and TPU/CNT composites are given in Figure 3. Thermal decom-
position of TPU occurs through double step at around 330 C and 400 C with two
shoulders which can be seen at 280 C and 460 C. The reason for this two-stage degra-
dation is different decomposition behaviors of urethane bonds in hard segment and polyol
groups in soft segment of TPU.44–46 The initial thermal stability of TPU is extended up
significantly with the highest loading ratio of CNT, whereas TGA curve of TPU shifts to
higher temperatures with inclusion of m-CNT at lower loading levels. TGA curves of
Kanbur and Tayfun 7

Table 3. Glass transition and melting temperatures of TPU and composites.

Samples Tg ( C) Tm ( C)

TPU 27.2 194.8

TPU/0.5% CNT 35.4 219.1
TPU/1% CNT 35.3 220.8
TPU/1.5% CNT 34.9 221.1
TPU/2% CNT 34.0 221.6
TPU/0.5% m-CNT 32.7 221.2
TPU/1% m-CNT 32.5 221.5
TPU/1.5% m-CNT 32.1 218.6
TPU/2% m-CNT 32.4 220.3

TPU: thermoplastic polyurethane; CNT: carbon nanotube; m-CNT: modified CNT; Tg: glass transition
temperature; Tm: melting temperature.

Figure 3. TGA curves of TPU and composites.

TGA: thermogravimetric analysis; TPU: thermoplastic polyurethane.

pristine CNT and m-CNT containing curves indicate that unmodified CNT favors the
thermally stable composites as compared with the same compositions of modified CNT.
The highest shift among TGA curves is observed for TPU/2% CNT at the end of the initial
decomposition step which is related to hard domains of TPU. This result also indicates that
CNT particles improve the microphase separation by their interaction with more com-
patible hard domains of TPU.47 Tm value of TPU increases with increase in concentration
of CNT similarly with DSC results.
8 Journal of Thermoplastic Composite Materials XX(X)

Table 4. Flammability test results of TPU and composites.

Samples UL-94 LOI

TPU BC 19.5
TPU/0.5% CNT V2 20.4
TPU/1% CNT V2 20.6
TPU/1.5% CNT V2 20.3
TPU/2% CNT V2 20.1
TPU/0.5% m-CNT V2 20.7
TPU/1% m-CNT V2 21.3
TPU/1.5% m-CNT V2 21.0
TPU/2% m-CNT V2 20.8

TPU: thermoplastic polyurethane; CNT: carbon nanotube; m-CNT: modified CNT; LOI: limiting oxygen index;
BC: burns to clamp.

Flammability properties
The flammability properties of TPU/CNT composites are investigated by UL-94 rating
and LOI tests and results are given in Table 4. Pristine TPU gives LOI value of 19.5%
and it burns to clamp (BC) during the UL-94 test. Table 4 shows that addition of CNT
enhances LOI of TPU slightly. Modified CNT-filled composites give a bit higher LOI
values. The highest enhancement is obtained for TPU/1.0% m-CNT composite which
has LOI value of 21.3%. Further additions of CNT and m-CNT cause reductions. UL-94
rating of neat TPU increases from BC to V2 for both cases of CNT and m-CNT addi-
tions. This result shows that CNT has no obvious effect for the flammability properties of
TPU because only small changes occur in LOI values and V0 rating is not achieved
during the UL-94 test.

Mass calorimeter study

Fire performances of the composites were investigated using mass loss calorimeter
method. The fire behavior of composites is compared using peak heat release rate
(pHRR), average HRR (aHRR), peak mass loss rate, time to ignition (TTI), time to
flameout, and fire performance index (FPI). The HRR curves of composites are repre-
sented in Figure 4 and the relevant cone calorimeter data are listed in Table 5. The
reductions in HRR curves normally indicate improved fire performance.
According to Figure 4, TPU burns very fast after ignition, and one sharp HRR peak
appears with pHRR and aHRR of 454.6 and 245.8 kWm 2, respectively. HRR curve of
TPU becomes more plateau-like with the extended burning time after m-CNT loadings.
All of the composites show remarkable reductions in HRR curve of TPU. The pHRR
and aHRR values are dropping down nearly 75 and 111 kW m 2 with the inclusion of
2.0% m-CNT, respectively. These data display the sharpest reduction of HRR among
all of the composites.
Kanbur and Tayfun 9

Figure 4. HRR curves of TPU and composites.

HRR: heat release rate; TPU: thermoplastic polyurethane.

Reduction in TTI of TPU is obtained after CNT additions, which means that
CNT inclusions cause the earlier ignition with respect to TPU. The black color of
CNT is the main reason for this observation which leads to increase in absorption
of radiant heat within the top layer of the material.48,49 Similar trend was observed
as other carbonaceous materials such as expandable graphite and carbon fiber
were used as a flame retardant additive for TPU in our previous studies.50,51
The earlier initiation of thermal degradation of TPU occurs because of the higher
heat absorption.
10 Journal of Thermoplastic Composite Materials XX(X)

Table 5. Mass loss calorimeter data of TPU and composites.

pHRR aHRR pMLR TTI TTF Residue FPI

Samples (kW m 2) (kW m 2) (g s 1) (s) (s) (%) (TTI/pHRR)

TPU 454.6 245.8 0.38 69 481 8.6 0.152

TPU/0.5% CNT 411.6 135.5 1.6 35 783 8.8 0.085
TPU/1% CNT 391.3 136.6 1.6 44 794 8.7 0.112
TPU/1.5% CNT 448.0 160.7 1.5 56 737 8.8 0.125
TPU/2% CNT 419.3 161.5 1.5 61 751 8.9 0.145
TPU/0.5% m-CNT 395.2 132.4 2.0 52 1249 8.3 0.132
TPU/1% m-CNT 414.0 150.3 1.6 42 1115 9.2 0.102
TPU/1.5% m-CNT 436.8 131.7 1.6 53 1183 8.8 0.121
TPU/2% m-CNT 379.7 134.8 1.9 78 1245 8.5 0.205

TPU: thermoplastic polyurethane; CNT: carbon nanotube; m-CNT: modified CNT; pHRR: peak heat release
rate; aHRR: average HRR; pMLR: peak mass loss rate; TTI: time to ignition; TTF: time to flameout; FPI: fire
performance index.

TPU and its composites yield almost identical residue content at the end of the mass
loss calorimeter test. Modified CNT additions cause an increase in total burning time
compared to pristine CNT. It is also seen from Table 5 that incorporation of CNT into
TPU gives decreasing trend for FPI except for TPU/2% m-CNT composite in which the
higher FPI is achieved than in TPU which indicates the improvement of fire perfor-
mance. It is found that addition of pristine CNT and increase in CNT contents cause
enhanced fire performance of TPU as an overall investigation from the mass loss
calorimeter study. As a different from other nanomaterials used in polymer composites,
CNT particles tend to act in condensed phase during combustion, thus decrease of
flammability properties is observed since their well-known tapping of free radical
characteristics.52–55

MFI test
MFI values of the composites are important to choose the process conditions during their
production steps.56 MFI values of TPU and relevant composites are given in Figure 5. It
can be seen from Figure 5 that MFI of neat TPU shows a reduction trend with the
addition of unmodified CNT into polymer matrix. In contrary to this result, MFI value
of TPU gets much higher with the addition of m-CNT, and these composites give
higher MFI values than that of unmodified ones, as well. MFI value of TPU/unmo-
dified CNT composites decreases with increasing content of CNT as a result of CNT
particles prefer interparticle interactions instead of CNT-matrix adhesion. Agglom-
eration of CNT particles in matrix causes remarkable improvement in melt viscosity, in
contrary reduction in MFI values. MFI value of modified CNT-loaded composites
shows decreasing trend after initial improvement through TPU/1.0% m-CNT com-
posites. As a sum of these results, addition of unmodified CNT at 0.5% concentration
Kanbur and Tayfun 11

Figure 5. MFI values of TPU and composites.

MFI: melt flow index; TPU: thermoplastic polyurethane.

has no significant effect on MFI value of TPU. This means that no obvious problems
will be found such as high shear mixing and feeding difficulties at the processing
stages of its TPU-based composites.

SEM analysis
SEM micrographs of cryo-fractured surfaces of TPU/CNT and TPU/m-CNT composites
for the lowest and highest CNT loading ratio are shown in Figure 6. According to SEM
micrographs, modified CNT particles show better dispersion in TPU matrix than the
pristine CNT particles as a result of surface compatibility of m-CNT particles with TPU
matrix. For higher loading ratio of unmodified CNT, CNT particles form large
agglomeration parts into TPU matrix. Bundle formations gradually disappear for TPU/
m-CNT composites especially for its 0.5% filling ratio. m-CNT containing composites
show homogeneous dispersion even at the highest loading level as compared to
unmodified CNT containing composites. These findings also support the mechanical and
thermal properties results of the composites discussed earlier.

Conclusions
This study deals with the influence of content and surface treatment of CNT on
mechanical, melt flow, thermal, and flammability properties of TPU/CNT composites.
Tensile test results indicate that addition of CNT into TPU leads to a distinct increase in
tensile strength, percentage of elongation at break, and elastic modulus values. Shore
hardness of TPU exhibits a reduction trend with the inclusion of CNT. The higher
mechanical properties are obtained for modified CNT containing composites at their
lowest concentrations. DSC analysis results show that Tm of TPU shifts to higher values;
12 Journal of Thermoplastic Composite Materials XX(X)

Figure 6. SEM micrographs of composites.

SEM: Scanning electron microscopy.

on the other hand, Tg shows decreasing trend with the addition of CNT. TGA analysis
implies that CNT containing TPU composites have better thermal stability than neat
TPU. The UL-94 rating of V2 and LOI value of 21.3% are reached with the addition of
modified CNT into TPU according to flammability tests. Enhancement of fire perfor-
mance is observed with both the pristine and modified CNT inclusions. The highest
decrease in HRR curve is found in modified CNT containing composite at its highest
loading level among all samples. MFI test results exhibit that melt flow behavior of TPU
does not change drastically at lower concentrations of CNT. Modified and unmodified
CNT-filled composites display completely different trends for MFI values in the case of
their compositions. According to morphological studies with SEM micrographs of
composites, formations of large agglomerates are observed for high loading percents of
unmodified CNT. Modified CNT containing composites show more homogeneous
dispersion homogeneity than the unmodified ones. Surface modification and low loading
ratio of CNT in polymer matrix give better mechanical, thermal, melt flow and mor-
phological properties due to better physical interactions between CNT and TPU matrix
with the surface modification.
Kanbur and Tayfun 13

Declaration of conflicting interests

The author(s) declared no potential conflicts of interest with respect to the research,
authorship, and/or publication of this article.

Funding
The author(s) received no financial support for the research, authorship, and/or publi-
cation of this article.

ORCID iD
Yasin Kanbur http://orcid.org/0000-0003-3996-458X.
Umit Tayfun http://orcid.org/0000-0001-5978-5162.

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