Polymer-Plastics Technology and Materials

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Thermoplastic polyurethane composites

reinforced with renewable and sustainable fillers –
a review

Mohammed Khalifa , S. Anandhan , Günter Wuzella , Herfried Lammer &

Arunjunai Raj Mahendran

To cite this article: Mohammed Khalifa , S. Anandhan , Günter Wuzella , Herfried Lammer
& Arunjunai Raj Mahendran (2020) Thermoplastic polyurethane composites reinforced with
renewable and sustainable fillers – a review, Polymer-Plastics Technology and Materials, 59:16,
1751-1769, DOI: 10.1080/25740881.2020.1768544

To link to this article: https://doi.org/10.1080/25740881.2020.1768544

Published online: 04 Jun 2020.

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POLYMER-PLASTICS TECHNOLOGY AND MATERIALS
2020, VOL. 59, NO. 16, 1751–1769
https://doi.org/10.1080/25740881.2020.1768544

Thermoplastic polyurethane composites reinforced with renewable and

sustainable fillers – a review
a b
Mohammed Khalifa , S. Anandhan , Günter Wuzellaa, Herfried Lammera, and Arunjunai Raj Mahendran a

a
Kompetenzzentrum Holz GmbH, Wood K plus, Altenberger strasse 69, A-4040, Linz, Austria; bDepartment of Metallurgical and Materials
Engineering, National Institute of Technology, India

ABSTRACT ARTICLE HISTORY

Thermoplastic polyurethane (TPU) reinforced with natural or renewable fillers gained significant Received 12 February 2020
attention in the scientific community and industries. The properties of TPU can be tailored using Revised Vxx xxx xxxx
different reinforcements or blends to enhance its performance and elevate the potential applica­ Accepted 10 May 2020
tions of the composite. Besides, composites offer eco-friendliness, recyclability, and biocompat­ KEYWORDS
ibility thus overcoming the environmental concerns. However, the manufacturing in mass quantity Thermoplastic polyurethane;
and upholding the quality of these composites has remained one of the principal challenges. renewable fillers; natural
Herein, we critically highlighted an overview of the current comprehension of the various eco- fiber reinforcement;
friendly and renewable fillers/fibers reinforced in TPU composites for tuning the mechanical and mechanical properties;
thermal properties of TPU. Some of the important research articles that discuss the influence of composites
interactions, morphology, and modification/treatment of fillers are contained within to understand
the behavior and consequence of reinforcements on the physical properties of TPU composites.

1. Introduction aromatic, or aliphatic); based on application (medical,

automobile, construction, engineering, etc.); based on loca­
Thermoplastic polyurethane (TPU) is a distinctive class of
tion (North America, Asia Pacific, Europe, Middle East,
polymers often called as segmented block co-polymer and
etc.). The major producers of TPU are Applications Plastics
habitually used as an alternative for rubber because of soft,
industrial spa, BASF, Huntsman corporation, Bayer mate­
flexible, and recyclable characteristics with good mechan­
rial science, COIM group, headway PU Co. Ltd, Hexpol,
ical and physical integrity.[1] Among all the polymers, TPU
Lubrizol, etc.[3–5] TPU explored extensively owing to its
is dominating in the global market and expected a growth
biocompatibility, toughness, flexibility, abrasion resistance,
of ~3.5% (CAGR) by 2024. Asia Pacific region contributes
and chemical resistance characteristics.[6,7]
~60% of the total volume production of TPU because of
In the terms of chemical structure, TPU is
high demand in the field of automobile, medical, and aero­
a multiphase block copolymer formed by appropriately
space industries.[2] Table S1 shows the major applications
combining polyol, chain extender, and diisocyanate.
of TPU. TPU is classified based on grade (flame retardant,
TPU backbone chain comprises soft and rigid segments
antistatic, reinforced, flexibility, physical characteristics,
(Figure 1). The soft segment built with polyols provides
etc.); based on type (polyether, polyester, polycaprolactone,

CONTACT Arunjunai Raj Mahendran a.mahendran@wood-kplus.at Kompetenzzentrum Holz GmbH, Wood K plus, Altenberger strasse 69, A-4040, Linz,
Austria
Supplemental data for this article can be accessed on publisher website.
© 2020 Taylor & Francis
1752 M. KHALIFA ET AL.
Figure 1. Schematic illustration of chemical structure of TPU.
flexibility, while rigid segment built with isocyanate and
chain extender contributes toward mechanical and phy­
sical properties.[8,9] The elastic or plastic characteristics
of TPU rely entirely on the physical crosslinks that are
resulting from the thermodynamical discordance
between the polar (diisocyanate and chain extenders)
and nonpolar segments (polyols).[10] TPU provides
a wide-ranging of physical property combinations
depending on the synthesis process and chemical classes
making it an enormously feasible material for various
applications. The hard segment can be either aliphatic or
aromatic variety. Aromatic TPU is generally based on
isocyanates such as Methylene diphenyl diisocyanate
(MDI), while aliphatic TPUs are based on isocyanates
such as 4, 4ʹ-Methylene dicyclohexyl diisocyanate (H12
MDI). On the other hand, a soft segment of TPU can be
either polyester or polyether depending on the desired
physical properties and applications.[11] On the other
hand, TPU can be processed by various methods such
as extrusion,[12] injection molding,[13] solution cast,[14]
compression molding,[15] electrospinning,[16] melt-
spin,[17] vacuum forming,[18] etc.
Utilization of bio-based raw materials for the synthesis
of TPU is an appealing solution for many industries and
environmental concerns. A wide variety of bio-based or
renewable raw materials such as sugars, polysaccharides,
vegetable oils, etc. have so far been utilized for the synthesis
of TPU. The prime objective of using renewable raw mate­
rials is to offer the biodegradable/biocompatible character­
istics. However, despite the claims, there is no assurance
that TPU can be fully degradable. In addition, preparation
of TPU from bio-based materials does not confirm its
biodegradability because of alteration in the functional
groups, crosslink density, and incompatibility with the
nonrenewable co-monomers. Besides, adaptation of
renewable-based materials for TPU synthesis could possi­
bly be a difficult task to replicate the properties of TPU
synthesized from petroleum-based raw materials.[9, 19–21]
TPU has some limitations such as poor thermal sta­
bility, low mechanical strength, and poor aging charac­
teristics, etc., and hence it is often used in the form of
blends or composites. Use of blends or composites helps
in improving the desirable characteristics and proper­
ties. For example, the interior body component of auto­
mobile required to have explicit properties such as good
strength, grease resistance, surface uniformity, and sta­
bility at varying temperatures. Hence, TPU is reinforced
with carbon fibers or blended with polypropylene.[7]
Fillers or fibers with nanoscale dimensions have been
the subject of research interest because of its unique
characteristics and prospective in various applications.
Fillers such as carbon nanotubes,[22] graphene,[23]
clay,[24] carbon fibers,[25] glass fibers,[26] carbon black,[27]
wood flour,[28] mica,[29] natural fibers[30] etc., have been
explored to improve the properties of the TPU matrix.
Conductive nanofillers actively used with TPU to enhance
the electrical and sensing characteristics of TPU.[31] In
addition, a wide variety of renewable fillers available in
different shape and size which can be utilized to tune the
properties of TPU. Factors such as cost, chemical compo­
sitions, surface chemistry, hardness, aspect ratio, mor­
phology, coefficient of thermal expansion, electrical
properties, optical properties, etc., are some of the impor­
tant aspects for the selection of the filler material.
Recently, research has geared up to the development
of renewable and eco-friendly composites for environ­
mental sustainability. Use of renewable and eco-friendly
fillers has several benefits over nonrenewable fillers,
particularly as an explication to the environmental and
recycling issues. There are a wide variety of reinforcing

Figure 2. (a) FTIR spectra of TPU/CNC nanocomposites (b) Stress-strain curves of TPU/CNC [where PU: TPU] (Reproduced with
permission © 2019, American Chemical Society,[40]).
materials such as clay, silica, wood flour, cotton, mica,
cellulose, waste paper, and fibers extracted from kenaf,
flax, hemp, banana plants, etc., are available abundantly.
Earlier, the purpose of incorporating these fillers into
polymers was simply to reduce the overall cost of the
product, as polymers were expensive. Currently, fillers/
fibers are used to achieve the spectrum of materials with
desired properties and to overcome the environmental
concerns.[32,33] There is continuous scope in improving
the properties and characteristics of TPU composites
with renewable and eco-friendly reinforcement. There
are review articles that focused on the synthesis of TPU
and composites reinforced with conducting material,
carbon nanotubes, and inorganic fillers.[7,9, 34–36]
To the best of our knowledge, no review articles are
available which are dedicated to TPU composites rein­
forced with renewable and eco-friendly fillers. In brief, use
of renewable and eco-friendly fillers particularly in TPU
matrix is a topic of interest to improve the mechanical
strength, thermal stability, and flame retardant character­
istics of TPU. This article provides the summary of recent
advances in TPU composites incorporated with renew­
able and ecofriendly and its influence on mechanical,
thermal, and flammable properties. Also, effect of synth­
esis or processing of TPU composites on its properties has
been discussed in detail. Besides, the morphological, crys­
tallinity, and interactions have been highlighted.
1.1. Cellulose-based TPU composites
Cellulose is among plentiful and widely explored filler
for polymer nanocomposites featuring low density, crys­
tallinity, high surface area, good mechanical properties,
and biodegradability. Cellulose nanocrystals (CNC) also
known as cellulose nano-whiskers or nanocrystalline
POLYMER-PLASTICS TECHNOLOGY AND MATERIALS 1753
cellulose is available in various forms such as nanorods,
fibers, particles, and spheres.[37,38]
The behavior of CNC and its interaction with TPU
defines the properties of nanocomposites. Factors such
as volume fraction, interfacial affinity, crystallization,
aspect ratio, and the processing method influence the
properties of TPU/CNC composites. On the other hand,
dispersion and adhesion of CNC with the TPU matrix is
one of the major concerns because of the hydrophobic
nature of TPU, which could be a defining factor in stress
transfer of CNC.[4,39]
Figure 2a shows the FTIR spectra of TPU/CNC nano­
composite at different CNC loadings. Band arising at
~3300 cm−1 correspond to the N-H stretching of TPU,
while there was no band detected at 3500 cm−1 suggesting
the hydrogen bonding interaction between TPU and CNC.
In addition, the intensity ratio of hydrogen-bonded carbo­
nyl band (~1709 cm−1) to the free carbonyl group band
(~1733 cm−1) deteriorated with the increase in CNC load­
ing. As a result, nanocomposites showed remarkable
improvement in the tensile strength (>200%) compared
with the pristine TPU film (Figure 2b).[40]
Overall, reinforcement efficiency of CNCs in TPU
matrix is also influenced by the dispersibility, aspect ratio,
fraction of hydroxyl groups present at the surface, wettabil­
ity characteristics, moisture content, and surface area of
CNC. In order to improve the reinforcement efficiency,
the CNC surface is modified or functionalized. Surface
treated CNC through the grafting of polyurethane dimers
was used to improve the interactions with TPU. CNCs
grafted with dimers obstruct the hydrogen bonding with-
in the structure of CNC, as a result higher amount of
hydroxyl groups are readily available for the interaction
with the TPU matrix. As a result, glass transition tempera­
ture (Tg) of TPU hard segment increased, while the Tg of
1754 M. KHALIFA ET AL.
Figure 3. DSC curves of TPU nanocomposites at different load­
ings of CNC (where P55D: TPU film; CNC-1: 1 wt% of Cellulose
nanocrystals) (Reproduced with permission © 2019, Wiley and
sons. Inc,[41]).
soft segment remained unaffected suggesting that the CNCs
interacted with the hard segment of the chain.
Furthermore, it resulted in smaller rigid regions that
improved the elongation and toughness of the
nanocomposites.
Figure 3 shows the DSC curves of TPU/CNC nano­
composite films at different loadings of CNC. For pris­
tine TPU film, three different melting points at ~100°C,
175°C, and 220°C were observed, which ascribed to the
para-crystalline rigid segments that are formed by the
reaction of di-isocyanate and a chain extender. The
melting point at 220°C related to the long-chain and
high crystalline hard segments, while the lower melting
points correspond to the short chains and partial dis­
ordered hard segments. Upon the addition of CNC, peak
at 220°C diminished, which may be due to the hindrance
of the CNC on the TPU chains during the crystalliza­
tion. The presence of CNC in TPU resulted in a lower
Figure 5. FESEM images of (a) Bio-based TPU and (b) TPU with modified CNC (Reproduced with permissions ©2019 Elsevier,[43]).
Figure 4. Effect of CNC content on relative crystallinity of hard
and soft segments of TPU (Reproduced with permissions © 2019
Elsevier[42]).
amount of amorphous soft segments participated in the
phase transformation that improved the thermal
stability.[41]
Saralegi et.al.[42] fabricated castor oil-based TPU/
CNC nanocomposites by in-situ synthesis method. The
influence of CNC content on the relative crystallinity of
the hard and soft segments was investigated using ther­
mal transitions obtained from DSC (Figure 4). Upon
increasing the CNC loading, the relative crystallinity of
the hard segment increased indicating the nucleating
activity of CNC with the hard segments of TPU. In
addition, a slight decrement in the soft segment crystal­
linity was observed, which could be attributed to the
hindrance offered by a higher degree of crystallization
of hard segment and CNC. In another study, modifica­
tion of CNCs with acid hydrolysis process improved the
dispersion in bio-based TPU matrix that resulted in the
elevation of thermal and mechanical properties
(Figure 5).[43]
Electrospun TPU nanofibers is one of the acknowl­
edged material for wound healing and scaffolds.

However, they most often display random arrangement
and warp, that limits its applicability. The other difficul­
ties such as non-uniform diameters, interweaving, and
clinging of fibers would minimize the materialization of
3D structure that could be catastrophic to the scaffolds.
It is most important for TPU nanofibers to resemble the
properties of muscles or substituting part. In addition,
adequate mechanical and thermal properties are of high
priority as it enables effective handling and positioning
of the scaffolds. Extensive research is also carried out on
TPU nanofibers for the vascular grafts wherein it should
withstand dynamic environment due to pulsating pres­
sure, cyclic stretching and contraction, and shear stress.
Incompatible properties may perhaps cause the turbu­
lent blood flow, which escalate the chances of intimal
hyperplasia and damage the blood vessel.[44–47]
Chen et.al.[48] developed electrospun TPU/cellulose
blend scaffold for cardiac tissue engineering. The tensile
strength and elastic modulus of the blends were sensitive
to the morphology, orientation, and weight fraction of
cellulose. The tensile strength increased at a lower frac­
tion of cellulose, while tensile strength and elongation at
break decreased at higher loading.
Electrospun TPU/silk fibroin nanocomposites
remained unaffected even after 400 cycles of tensile
test, which is necessary for the vascular grafts as it
undergoes dynamic mechanical behavior.[49] Unnithan
et.al.[50] reported that the non-woven made of electro­
spun TPU/cellulose acetate (CA) blend incorporated
with zein drug can be potentially used for wound dres­
sing. However, tensile strength and elongation at break
decreased significantly for the nanocomposites, which
could be attributed to the stiffening effect (Figure 6).
Thin-film substrates made of TPU/nano-cellulose
nanocomposite are potential material for flexible and
wearable electronic devices. Pursula et.al.[51] investi­
gated the effect of cellulose content on the mechanical
properties of TPU/cellulose nanocomposite thin film
substrate prepared by film cast method. Nano-cellulose
improved the tensile strength and modulus, but the
extensibility reduced significantly. The optimum loading
was in the range of 10–20%, wherein the substrate
showed better properties that are suitable for flexible
and printed electronic application.
1.2. Clay-based TPU composites
Among various TPU-based nanocomposites, clay/TPU
nanocomposites considered as the most fascinating and
widely explored in industries and academia. Toyota
group fabricated nylon-6/clay composite material with
high mechanical properties paved a way for the use of
POLYMER-PLASTICS TECHNOLOGY AND MATERIALS 1755
Figure 6. Stress-strain curves of (a) TPU nanofiber mat (b) TPU/
CA/zein drug mat (c) CA nanofiber mat (Reproduced with per­
missions © 2019 Elsevier,[50]).
clay as the filler material. The most striking feature of clay
is eco-friendliness, non-toxicity, low-cost, and can be mod­
ified effortlessly. Various properties such as mechanical,
thermal, flammability, flexibility, biocompatibility, shape
memory characteristics of TPU can be tuned by incorpor­
ating clay.
Upon the addition of clay to TPU matrix, the degrada­
tion characteristics of TPU changes significantly.
Generally, thermal degradation of pristine TPU takes
place in two stages: the breakdown of urethane linkages
into isocyanate and alcohol followed by the breakdown of
ester bonds of the soft segment domains. Clay has two
effects on the degradation of TPU, i.e. physical barrier and
chemical effect. The barrier effect of clay delay the scissor­
ing of the polymer chains and thereby improving the
thermal stability. On the other hand, acidic sites available
on the surface of functionalized or modified clay surfaces
could possibly quicken the degradation process of poly­
mer. Also, the interfacial bonding and morphology also
affect the degradation behavior of the TPU.[52–55]
Cai et.al.[56] evaluated the thermal properties of TPU/
montmorillonite clay (MMT) nanocomposites prepared by
reactive extrusion process. Di-2-ethyl-hexyl terephthalate
(DOTP) was added to improve the dispersivity of MMT in
TPU matrix. However, the presence of DOTP prompted
the nanocomposite to degrade quickly because of the pre­
sence of ether molecules. As a result, the onset temperature
decreased. On the other hand, nanocomposite showed
higher thermal resistance above 400°C and the residue
content increased with the increase in MMT loading.
Tabuani et.al. reported that the incorporation MMT
intercalated with methyl tallow bis(2-hydroxyethyl)
quaternary ammonium chloride decreased onset
1756 M. KHALIFA ET AL.
Figure 7. DTG curves of TPU, TPU/MMT composites and TPU/
MMT/melamine cyanide nanocomposite (Reproduced with per­
missions © 2019 Elsevier,[59]).
temperature (first stage) due to the acceleration in the
thermal degradation process because of the presence of
free radicals in clay. In the second stage, the degradation
process delayed because of the obstacle effect of clay to
Figure 8. TEM micrograph of (a) TPU/5% clay (b) HRTEM micrograph of TPU/3% clay (with permissions[61]).
Figure 9. AFM images of (a) TPU (b) TPU/3% clay (Reproduced with permissions[61]).
the thermal energy.[57–60] Upon the addition of mela­
mine cyanide to TPU/MMT nanocomposite,
a significant change in the thermal degradation was
observed. Thermal degradation occurred in multiple
steps (~400°C and 440°C) along with shoulder peaks
around 300–350°C (Figure 7).
Anandhan et.al reported two different behavior of clay
dispersion in TPU matrix i.e. intercalated and delaminated
nanocomposites. In intercalated nanocomposites, TPU
chains were intercalated between the clay layers and
formed a well-arranged multilayered structure. Secondly,
delaminated nanocomposites, wherein, clay exfoliated, and
uniformly dispersed in the TPU matrix (Figure 8a-b). TPU
showed the phase-separated morphology was confirmed
through AFM images (Figure 9a). The length of hard
segments was in the range of 4–5 nm and appeared in
bright due to their higher hardness compared with soft
domains, which had a darker appearance. Figure 9b shows
the cross-section profile, which showed the clay layers and
the phase-separated morphology of TPU. The disruption
of morphology may be attributed to the interaction of
functional groups of clay with hard segments of TPU that

Figure 10. DSC curves of ether-based-TPU nanocomposites
where PM: pristine montmorillonite; C30B & C25A: organo mod­
ified clay (Reproduced with permissions, © 2019 Elsevier[62]).
hindered the formation of hard domains. The ultrafine
dispersion of clay in the TPU matrix synergistically
enhanced the thermal stability of the nanocomposites.[61]
Dan et.al.[62] studied the effect of cloisite Na+ on the
physical properties of injection mold ether-based TPU
nanocomposite. From the DSC curves of TPU
Figure 11. SEM micrographs of (a) Pristine TPU (b) TPU/1% clay (c) TPU/3% clay (d) TPU/10% clay (Reproduced with permissions, 2019
©Elsevier,[63]).
POLYMER-PLASTICS TECHNOLOGY AND MATERIALS 1757
nanocomposites for the first heating cylce, endothermic
peak was observed at ~80°C, which is attributed to the
commotion of short-range order persuaded by anneal­
ing process at room temperature and another peak at
~160°C ascribed to the disordered hard segment regions
(Figure 10). Therefore, the area under the peak at ~160°
C generally considered as the expression of degree of
hard segment regions in the TPU chain.
Pizzato et.al.[63] studied the effect of clay loading on
the tensile properties of TPU nanocomposite films
synthesized by extrusion and compression molding pro­
cess. The morphology of extruded pristine TPU
appeared in the form of small spherulites, while TPU
loaded with HNT did not show spherulite structure,
which ascribed to the uniform dispersion and intercala­
tion of clay within the TPU matrix (Figure 11). As
a result, the tensile stress and elongation at break
increased by 28% and 35%, respectively, for 3% HNT
loaded TPU nanocomposite.
Meng et.al. evaluated the tensile, rheological proper­
ties by varying the mixing time (1 –10 min) of cloisite
30B clay with TPU in brabender machine at a constant
rotating speed (100 rpm). The processing method and
time for mixing the clay in TPU matrix affect the
1758 M. KHALIFA ET AL.

Figure 12. Effect of mixing time on the TPU/clay nanocomposites (a). Young’s modulus (b). Stress-strain curves (Reproduced with
permissions ©2019 Elsevier,[64]).

properties of TPU nanocomposites. The tensile modulus

of the nanocomposites improved gradually upon
increasing the mixing time (Figure 12a). On the other
hand, tensile strength increased and elongation at break
decreased when clay and TPU mixed for 1 min, while it
increased marginally when the mixing time increased to
3 min because of exfoliation and better dispersion of clay
in the TPU matrix. Further increasing of mixing time
showed a detrimental effect on the tensile strength and
extensibility of nanocomposites (Figure 12b). It is
obvious that increasing the mixing time leads to the
degradation of the TPU and the presence of clay accel­
erates the degradation process. For that reason, long
mixing time and lower molecular weight are not favor­
able to the tensile properties of TPU/clay
nanocomposites.[64]
The compatibility between clay and TPU plays
a decisive factor that affects the physical properties of
the nanocomposites, therefore functionalized/modified Figure 13. Interaction mechanism of TPU chains with clay
clay has been used widely for improving the same. (Reproduced with permissions ©2019 John Wiley and Sons.
Organically modified clay offers high content of hydro­ Inc[65]).
xyl groups and hence, it enriches the hydrophilicity that
eases the TPU chain to pierce into the clay interlayers.
Further, the interaction between the clay and the TPU expansion into the composite, which results in the vola­
chain segments provides the necessary tethering effect tilization of flammable degradation products and distri­
(Figure 13). The dispersion of the clay in the TPU matrix butes the oxygen molecules in the composite. The
affect the phase separation and physical properties of the formation of bubbles from the decomposed products
nanocomposite.[65,66] pushes the clay onto the surface of the composite
Clay significantly reduces the peak heat release rate (Figure 14). Hence, surface quality and dispersion of
(PHRR) by creating the insulating barrier layer of clay the clay in the TPU matrix define the flame retardant
and contains char. During the combustion of the com­ efficiency. In addition to the barrier effect, chemical
posite, a barrier forms onto a surface of the composite. reactions are also involved that limits the heat and
With an increase in the temperature, the viscosity of the mass transfer.[67,68] Koo et.al.[69] explored the thermo-
silicate layers reduces thereby facilitating the formation physical and flammability characteristics of injection
of clay layer on the surface. On the other hand, the molded TPU/nanoclay composite. The heat release rate
development of protonic catalytic sites on the clay sur­ of the TPU/clay nanocomposite reduced drastically
face enables the organization of the char residue layer. (71%) compared to pristine TPU along with increased
The protective layer acts as a barrier to the thermal ignition time. In addition, the carbon monoxide (CO)
 POLYMER-PLASTICS TECHNOLOGY AND MATERIALS 1759

Figure 14. Flame retardant mechanism of clay particles.

concentration was much lower upon the addition of The effect of wood flour on the morphological, ther­
clay. mal, and mechanical properties of polyurethane foam
In another study, heat release rate reduced by 44% in was carried out by Hosur et.al.[71] For the pristine TPU
TPU/clay composite compared with pristine TPU. foam, morphology displayed uniform spherical cell
However, the time of ignition of flammable gases structure, while upon the addition of wood flour, the
reduced for the nanocomposite, attributing to the cells appeared to be elliptical and smaller indicating the
Hofmann degradation of the quaternary ammonium increment in cell density of the composites. The reduc­
compound in clay. TPU/clay foams showed substantially tion of cell size is attributed to the nucleation activity of
lower heat release capacity (27%) compared to that of wood flour due to which the polymer chain movement is
pristine TPU foams. restricted. As a result, the composite foams become
stiffer and the storage modulus and flexural strength
increased.
1.3. Wood flour/TPU composites Three-dimensional (3D) printing technology was
used to fabricate the TPU/wood flour composites. The
Wood flour is another most widely explored filler for
extensibility of the composites decreased with the
polyurethane composites. Wood flour is generally
increase in the wood flour loading, while the tensile
extracted from the scrap wood from the wood proces­
strength decreased initially, but increased at higher
sing industries and composed of lignin, hemicellulose,
and cellulose. Wood flour extracted from pine, oak,
and maple trees are most commonly used in polymer
composites for tuning the mechanical and thermal
properties. Inclusion of wood flour into the polymer
matrix stiffens the polymer but improves the tensile
and flexural strength. However, wettability of wood
flour and compatibility with polymer are poor, which
is unfavorable for improving the properties of the
composites. Hence, surface treatment or coupling
agents fused with the wood flour particles for improv­
ing the compatibility with the polymer. Furthermore,
processing of wood flour is cheaper and easily pro­
cessed along with biodegradable characteristics.
Though it is not used in polymers for imparting the
biodegradability, but it can be used in biocompatible/
biodegradable polymer matrices to improve the Figure 15. Effect of wood flour content on the tensile properties
mechanical properties without compromising the bio­ of TPU composite (Reproduced with permissions ©2019
degradable characteristics.[70] Elsevier[28]).
1760 M. KHALIFA ET AL.
loading (Figure 15).[28] To improve the tensile strength,
wood flour was treated with different modifiers such as
maleic anhydride grafted ethylene propylene diene
monomer rubber (EPDM-g-MAH), maleic anhydride
grafted ethylene-octene copolymer, polyethylene glycol
6000, chitosan, and MDI.[28]
In another study, the effect of EPDM-g-MAH loading
on the properties of 3D-printed TPU/wood flour compo­
sites was investigated. At 4 wt% EPDM-g-MAH loading,
the composite showed highest tensile strength (~16 MPa)
and extensibility (~591%), while it declined with further
addition of the latter. From the thermal analysis, Tg of
modified composite was higher than that of unmodified
composite. Also, the thermal degradation temperature
increased up to 4 wt% loading of EPDM-g-MAH.[72]
1.4. Natural fiber reinforced TPU composites
From the past two decades, natural fibers have been the
center of focus and attracted the research community
and industries owing to their explicit advantageous
compared to the artificial fibers. Natural fibers potential
benefits such as eco-friendliness, low cost, lightweight,
high specific strength to weight ratio along with their
sustainable and biodegradable characteristics. The pro­
blem of the natural fibers is its poor interactions with the
polymer matrix along with high moisture absorption
and poor durability. The difference in the surface ener­
gies of the fiber-matrix and the hydrophobic character­
istics displays poor interfacial bonding, which could be
detrimental to the composite properties and impedes its
practical utilization. To overcome the deficiencies, sev­
eral approaches have been recognized, such as coupling
agents, surface treatments, , to supplement the incom­
patibility issues.[73]
El-Shekeil et.al.[74] studied the effect of kenaf fiber on
the mechanical properties of TPU. Composites were
prepared at 180–200°C; processing time: 11–15 min;
processing speed: 30–50 rpm. The maximum tensile
strength was obtained for the composite processed at
190°C (~19 MPa), whereas it decreased with further
increase in the processing temperature, which is
ascribed to the initiation of degradation of kenaf fibers.
Furthermore, the tensile strength was sensitive to the
processing speed. At 50 rpm, the tensile strength
decreased significantly, as it leads to fiber breakage.
Datta and Kopczynska[75] examined the mechanical
properties of TPU/kenaf fiber composite prepared by
melt-mixing and pressing method. The kenaf fibers
were modified with different surface treatments (acety­
lation, blocked isocyanate, maleic anhydride, and
permanganate treatment). Among all the modifications,
permanganate treated fibers offered good mechanical
properties.
El-shekeil et al.[76] studied the effect of kenaf fiber
content on the mechanical and thermal properties of
compression-molded TPU composites. The tensile
strength of the composite was lowest for 20% fiber
loading, while it increased significantly for 30% loading
and decreased thereafter. Furthermore, the flexural
properties increased, while the impact strength of the
composite decreased with the increase in fiber loading.
TPU matrix reinforced with sodium hydroxide trea­
ted kenaf fibers showed decrement in the tensile strength
compared to the untreated kenaf fiber/TPU composite,
while it increased slightly for pMDI-treated fibers. The
combination of sodium hydroxide and pMDI treatment
significantly increased the tensile strength and tensile
modulus of the composite by 33% and 42%, respectively.
Sodium hydroxide treatment provides rough surface,
but softened the interfibrillar matrix and removes cer­
tain amount of impurities. Also, the hydrogen bonding
interaction between TPU groups and hydroxyl groups
on the surface of kenaf fibers improves the tensile
properties.[77] Figure 16 shows the SEM micrographs
of kenaf fibers with different chemical treatments. The
surface treatment makes the surface of the kenaf fibers
rough, irregular, and porous that allow the better inter­
facial bonding between the fibers and matrix.[75,77]
However, the surface treatment on the fibers is often
non-homogenous that result in poor adhesion of the
fibers with the matrix, which leads to a detrimental effect
on the mechanical properties.
TPU/kenaf fiber composites were buried in soil for
20, 40, 60, and 80 days and their mechanical properties
were investigated. The tensile properties of soil-buried
composites deteriorated with time, while the flexural
properties remained unaffected.[78] In fact, natural fibers
are susceptible to the growth of microorganisms and
produce cellular enzymes and thus it deteriorates the
strength of the fibers.[79]
Haghighatnia et al.[80] investigated the mechanical
properties of hemp fiber reinforced TPU composite.
Prior to the impregnation, hemp fibers were treated
with sodium hydroxide solution. Tensile strength of
the composite was sensitive to the fiber length and the
optimum fiber length was 15 mm, while the tensile
modulus was highest for composite with 6 mm fiber
length. The fiber length influences the friction between
fiber-fiber and fiber-matrix that could significantly affect
the mechanical properties of the composites. Hence,
estimation of critical length of the fiber is important to

Figure 16. SEM micrographs of kenaf fibers with different surface treatments (a) Untreated fibers (b) Sodium hydroxide (c) Acetylate (d)
Permanganate (e) Maleic anhydride (f) Block Isocyanate (Reproduced with permissions ©2019 Elsevier[75,77]).
predict the mechanical properties of the composite. The
fiber length should be higher than the critical length to
ensure proper stress transfer at the interfaces. The
mechanical properties of the composites increase with
an increase in the fiber length up to 10 times the critical
length. Most often, the short fibers tend to make the
composite brittle compared to long fibers. The brittle
behavior of the composite is due to the fact that the
number of fiber ends increase in short fibers and each
end behave as a defect in the composite structure.
Hence, stress transfer through the fibers is hindered
and form stress concentration at each end of the fiber
and the fibers are pulled out under low strains. This
phenomenon leads to the fracture of the composites.
On the other hand, immoderate increase in the fiber
length is also detrimental to the tensile properties. It is
expected that the long fiber tends to break easily during
the processing and interweaves themselves, which may
lead to the breakage of the fibers under small stresses.
Hence, selection of the optimum length of the fiber is
important for the appropriate orientation, stress trans­
fer, and fiber packing that improve the tensile strength
of the composite.[81–85]
Duan et al.[86] reported that the silane treated sugar
palm fibers reduce the density, water absorption, and
swelling characteristics of TPU/sugar palm fiber compo­
site. In another study, sugar palm fibers were treated with
sodium hydroxide at different temperatures (70°C, 80°C,
and 90°C) significantly improved the tensile properties of
TPU composite.[87]
Compression-molded TPU composite reinforced
with banana fiber woven at different fiber loadings
POLYMER-PLASTICS TECHNOLOGY AND MATERIALS 1761
augmented the tensile strength and modulus, while
extensibility declined, which ascribed to the forma­
tion of discontinuities at the interface.[88] Other nat­
ural fibers extracted from cocoa pod husk, pineapple,
coconut husk, corncob, and coconut shell were also
explored as a reinforcing agent in TPU matrix to
improve the thermal stability and tensile properties
of the composite.[89] Further, the swelling and
absorption characteristics of the TPU composite
vary with different type and content of fiber.[90,91]
1.5. Alumina-based TPU nanocomposites
TPU/Ethylene–propylene–diene monomer (EPDM)/
γ-alumina nanocomposites were prepared by the
extrusion method at different loadings of alumina
(0–4 phr). Alumina act as a reinforcement agent
and possess intrinsic mechanical properties, which
increased the tensile strength of the TPU/EPDM
blend significantly. The alumina loading was seen to
have a noticeable effect on the tensile properties of
the nanocomposite. The tensile strength improved up
to 2 phr alumina concentration thereafter, it
decreased, which could be ascribed to the formation
of agglomerations.[92]
Liu et al. reported the influence of alumina trihydrate
(ATH) on the thermal properties of TPU nanocompo­
sites. ATH triggers the scissoring of TPU chains; as
a result, the decomposition temperature of the nano­
composites was lower than that of pristine TPU.
Further, the char content increased from 3.7% to 30%
for nanocomposites.[93]
1762 M. KHALIFA ET AL.

1.6. Silica-based TPU nanocomposites size significantly influences the tensile properties of TPU
nanocomposites. Decrease in the silicate size effectively
Tensile properties of electrospun TPU nanofibers
enhanced the tensile strength of the nanocomposites.
improved upon the addition of silica nanoparticles.
Smaller silicates efficiently act as nucleating sites,
The silica nanoparticles bring about a significant rein­
which increase the soft segment crystallization. Also,
forcement effect in TPU nanofibers without distressing
the strong interaction between TPU and silicates
the ductility of nanofibers. Also, storage modulus at
strengthens the bonds, which prevents during the strain­
glassy state (−50°C) increased with silica loading, while
ing of the nanocomposites.[98]
Tg was seen to remain unchanged indicating the poor
Also, modification of nano-silica spheres with
interaction between the TPU and silica nanoparticles. In
(3-Aminopropyl)triethoxysilane offers excellent tensile
another study, Tg value increased when the nanocom­
strength and extensibility.[99] Swain et al.[100] examined
posites were prepared by the solution cast process indi­
the impact of moisture absorption on thermal and tensile
cating that the properties and behavior of
properties of TPU nanocomposites embedded with silica
nanocomposites vary depending on the processing
and alumina particles (Figure 17). Water molecules act as
method and source of silica nanoparticles.[94,95]
a plasticizer of the TPU and increase the chain mobility,
Contrary to the earlier discussions, the work reported
which leads to a decrease in Tg. In addition, the thermal
by Sibaja et.al, solution cast TPU/silica nanocomposites
stability decreased drastically with the increase in moist­
showed a decreased trend in Tg, which could be attrib­
ure content in the composites. An analogous develop­
uted to the higher amount of phase separation among
ment was observed in the case of tensile properties of
TPU segments. The amount of phase separation can be
nanocomposites. The decrement in the nanocomposite
reduced by decorating silanol groups on the surface of
properties attributed to the infusion for water molecules
silica nanoparticles that form a strong hydrogen bond­
in the composite and lead to the debounding of the inter­
ing and increase the Tg of the nanocomposites.[96]
face that reduces the stress transfer efficiency.
Beloqui et al.[97] evaluated the influence of surface
area of fumed silica particles on the rheological and
thermal properties of TPU. The storage modulus of the
1.7. Other fillers
TPU is particularly higher when incorporated with silica
and susceptible to its surface area up to 200 m2/g, there­ Hydroxyapatite is a naturally occurring mineral found
after there was no noticeable change observed. For com­ in human and animal bones. It is generally extracted
posites with higher surface area of silica particles from different processes that usually available as calcium
(>130 m2/g), the storage and loss moduli curves phosphate. Hydroxyapatite is known to be a very useful
diverged at low frequencies suggesting that the modulus mineral for chemical, agriculture, and biomedical indus­
is independent of the frequency. This could be ascribed tries. With an advancement in nanotechnology, hydro­
to the interfacial bonding of silica with TPU chains. xyapatite attracted the researchers as the potential
Further, activation energy and Tg increased upon biomaterial due to its resemblance with the human
increasing the surface area of silica. The silicate layer hard tissues.

Figure 17. Tensile strength of silica/TPU and alumina/TPU nanocomposites at different filler loading and moisture content
(Reproduced with permissions ©2013 KIEEME[100]).

Water absorption and mechanical properties are con­
sidered essential for the tissue engineering scaffolds. The
hydrophilicity of scaffolds directly reflects the cell adhe­
sion and growth. It is a well-known fact that hydroxya­
patite offers good hydrophilicity, and its usage in TPU
matrix influences in enhancing the water absorption and
wettability characteristics. Also, strong interaction
between the TPU chains and hydroxyapatite significantly
improved the tensile properties of the scaffolds.[101]
Compared to microparticles of hydroxyapatite, nano­
particles offer high compressive strength, thermal stabi­
lity, and storage modulus. In addition, nanoparticles
have a positive impact on the porosity of the TPU
matrix.[102] However, the mechanical properties of
TPU/hydroxyapatite nanocomposites are sensitive to
the weight fraction of hydroxyapatite. The presence of
nanoparticles deteriorated the ductility of the nanocom­
posite due to its rigid and stiff characteristics.[103–105]
Hydroxyapatite was treated with chitosan not only
improved the tensile strength and modulus but also
improved the extensibility of the nanocomposite.[106]
On the other hand, scaffolds based on polymers filled
with collagen are most widely used because of its
Figure 18. Laser microscopy images of TPU and TPU/CaCO3 composites, where TPU-5/10/20 (5, 10 & 20 is CaCO3 loading) (Reproduced
with permissions ©2019 Elsevier,[114]).
POLYMER-PLASTICS TECHNOLOGY AND MATERIALS 1763
compatibility and affinity for the growth of the cells.
However, TPU incorporated with collagen deteriorate
the mechanical properties of the nanofiber.[107,108]
Chicken feather/TPU bio-composites prepared by
solution cast method enhanced the thermal stability
and mechanical properties of the composite. Also, elastic
and storage modulus was found to be sensitive to the
chicken feather loading.[109] In another study, keratin
bio-fiber incorporated with bio-based TPU increased the
tensile strength and elongation at break. In addition,
wettability and porosity of the composite surface
improved, which play a vital role in cell viability.[110]
Keratin extracted from human hair was used as
a reinforcement in TPU nanocomposite synthesized by
melt compounding method for an eco-friendly e-skin for
different sensing applications. The keratin and its bypro­
ducts interact with the TPU polar groups, which form
a strong hydrogen bonding interaction. As a result, the
intramolecular bonding between cysteine-rich keratin
exhibited unique rheological properties of the nanocompo­
sites. At lower keratin loading, the hydrogen bonding
(intermolecular bonding) dominated, while the intramole­
cular bonding dominated at higher keratin loading in the
1764 M. KHALIFA ET AL.
nanocomposite. Since the interaction was strong, the elastic
modulus, melting point, and crystallinity of the nanocom­
posite increased.[109,111] Lin et al.[112] demonstrated the
impact of crab shell acetylation chitin nanocrystals on the
mechanical properties of castor-oil-based TPU nanocom­
posites. The acetylation of nanocrystals helped in trans­
forming the hydrophilic hydroxyl groups to hydrophobic
acetyl group, which enhanced the compatibility between
the chitin and TPU matrix. As a result, chitin nanocrystals
offered reinforcing effect, which significantly improved the
strength, stiffness, and toughness to the TPU matrix.
Calcium carbonate (CaCO3) is another natural mate­
rial and abundantly available, which is frequently used as
a reinforcing material in polymer composites. It is
a replenishing material through shells, skeletons, stalag­
mites, limestone, marbles, etc. TPU/CaCO3 composite
offers a wide range of properties, which makes it suitable
for biomedical and shape memory devices.
The surface topography of TPU altered upon the inclu­
sion of CaCO3, augmented the rheological and mechanical
properties of the composites.[113] In another study, inclu­
sion of CaCO3 altered the spherulite size of TPU. The
presence of spherulite in TPU and TPU/CaCO3 compo­
sites is shown in Figure 18. In-fact the spherulite size
decreased signifying the nucleating effect of CaCO3 and
as a result, the degree of crystallinity of TPU declined.[114]
In another study, CaCO3 modified with oleic acid offered
better reinforcement effect in the TPU matrix and offered
enhanced tensile and thermal properties.[115]
There are several papers that are dedicated to the
TPU composites with renewable and eco-friendly fillers,
summary of those reports is described in Table S2.
2. Conclusions
TPU-based composites reinforced with renewable and
natural fillers are a fascinating group of resource for
exploring in research and industries. The combina­
tion of natural/renewable fillers and bio-based TPUs
is seen to be interesting material because of its bio­
compatible characteristics and economical aspects.
Renewable and natural reinforcements enhance the
mechanical and thermal properties of TPU compo­
sites/nanocomposites. At the same time, the proper­
ties are susceptible to different processing techniques,
and most importantly, it is a challenging task to find
the optimum composition, property balance, para­
meters, and technological aspects. Surface treatments
of fillers offer better thermal stability and improved
tensile properties. The combination of property
enhancement and advancement in the fabrication
techniques, TPU composites offer a significant pro­
spective in various applications such as biomedical,
structural, automobile, and electronic devices.
Funding
This work was funded by the Austrian Ministry for Transport,
Innovation and Technology in frame of the program
“Produktion der Zukunft” under contract No. [861065].
Notes on contributors
Mohammed Khalifa is currently working at
Kompetenzzentrum Holz GmbH, Austria as a Research scien­
tist. He received his Doctorate degree from National institute
of Technology, Surathkal, Karnataka, India. He completed his
under graduate and postgraduate degree in Machine Design
from B.L.D.E.A engineering college, Vijayapur, India. He was
a visiting researcher at Kompetenzzentrum Holz GmbH,
Austria. His research area are polymer nanocomposites, bio-
based TPU nanocomposites, electrospinning, piezoelectric
polymers, battery separators, and structural health monitoring
and gas sensors.
S. Anandhan obtained his PhD in Polymer Science and
Technology from IIT Kharagpur in 2004. He is currently
Professor in the Department of Metallurgical and Materials
Engineering, National Institute of Technology Karnataka. His
research areas are functional nanotextiles from ceramics and
polymers by electrospinning; multiphase material systems;
materials for energy storage and conversion. He has 65 pub­
lications in international journals.
Günter Wuzella received his Ph.D. from University of Natural
Resources and Life Sciences, Austria in thermal characteriza­
tion of thermosetting resins. He obtained his masters in
“Polymer Engineering and Science” at Montanuniversität
Leoben. He is currently working as a head of the “Team
green composites” at Kompetenzzentrum Holz GmbH,
Austria. His research areas are: Natural fiber reinforced com­
posites, cure kinetic studies, thermoanalysis.
Herfried Lammer is currently working as “Area Manager” at
Kompetenzzentrum Holz GmbH, Austria. He obtained his
masters in “Polymer Engineering and Science” at
Montanuniversität Leoben. His research areas are long fiber
reinforced composites, mechanical and thermal characteriza­
tion of polymers. He has won several innovation awards and
worked as R&D Director and General Manager for “Head
Technology” later joined Kompetenzzentrum Holz GmbH.
So far, he has 13 patents and authored in several publications
and book chapters.
Arunjunai Raj Mahendran obtained his Doctorate degree
from Montanuniversität Leoben, Austria in the area of bio-
based resins and composites. He obtained his masters in
“Polymer Engineering and Science” at Montanuniversität
Leoben, Austria. He is currently working as senior researcher
at Kompetenzzentrum Holz GmbH, Austria. His research
areas are bio-based thermoplastics and thermosets, natural
fiber reinforced composites and nanofillers synthesis.

ORCID
Mohammed Khalifa http://orcid.org/0000-0002-6024-3720
S. Anandhan http://orcid.org/0000-0002-4429-7550
Arunjunai Raj Mahendran http://orcid.org/0000-0003-
3898-5370
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