CHAPTER 2

LITERATURE REVIEW

2.1 Polyurethane and Thermoplastic Polyurethane (TPU).

Polyurethanes, first discovered by Otto Bayer in 1937, encompass the series of

polymers whose molecular backbone contains a significant number of urethane linkages,
regardless of the content of the rest of the macromolecule. The urethane linkage is formed via
the reaction between an isocyanate group and a hydroxyl group (Martin et al., 2012). Previous
work focused on polyester-based polyols; however, the enhanced hydrolytic stability and
immense versatility afforded by polyether-based polyols saw them become a preferred
precursor in polyurethane synthesis. Recently, the vast selection of polyols, isocyanates, and
chain extenders allows polyurethanes to be varied from soft thermoplastic elastomers to
adhesives, coatings, flexible foams, and rigid thermosets.

Figure 2.1: TPU resin

 TPUs are linear, block copolymers of alternating hard and soft segments. The soft
segments are composed of long-chain diols (most typically polyester, poly-ether, or
polycaprolactone-based) while the hard segments (HSs) commonly consist of alternating di-
isocyanates and short-chain extender sequences (Martin et al., 2012).

Some common applications for TPUs include automotive interiors, footwear, flexible hose
and tubing, cellphone buttons, closures, seals and o-rings, adhesives, cable jacketing, sport
and leisure items, textiles and textile coatings, implantable medical device components,
mining and mineral processing equipment, laminates for impact glazing and wastewater
treatment equipment (Martin et al., 2012).

Figure 2.2: Applications of TPU

Figure 2.3 illustrates the typical chemical structure and the resulting morphology of a TPU
made up of linear primary chains composed of alternating hard and soft segments connected
end-to-end through strong, covalent urethane linkages..
 Figure 2.3: a) typical chemical structure b) the resulting morphology of a TPU

In TPU copolymers, hard segments which comprise alternating di-isocyanate and

short diol chain extender residues are responsible for imparting the stiffness and toughness to
the material, while soft segments (polyols) impart the resilience, extensibility and flexibility
(Guelcher et al., 2005).

2.2 Performance Enhancement by Reinforcement Nano-fillers.

Enhancement of TPU properties can be achieved by either varying the hard-soft segment
composition ratio or by the reinforcement with nanoscale fillers. Many studies have recently
been carried out to improve the physico-mechanical and rheological properties of fibre-
reinforced polymer composites with the addition of nano-fillers into various polymers.
Interest in developing lignocellulosic fibre-reinforced composites has also grown enormously
(Ching et al., 2016). Generally, the addition of nano-fillers to a polymer modifies the
rheological properties of the resulting composites because they embed themselves between
the polymer chains. Various types of nanoparticles, such as clays , carbon nanotubes ,
graphene, and nanocellulose have been used to obtain nanocomposites with different
polymers (Dantas de Oliveira & Augusto Gonçalves Beatrice, 2019).

The evaluation of the nano-filler dispersion in the polymer matrix is very important, since
the mechanical and thermal properties are strongly related to the morphologies obtained.
From Figure 2.4, exfoliated nanocomposites have maximum reinforcement due to the large
surface area of contact between the matrix and nanoparticles.

Figure 2.4: Possible structures of polymer nanocomposites using layered nano-clays:

(a) microcomposite, (b) intercalated nanocomposite and (c) exfoliated nanocomposite

CNCs are ideal candidates as nanomaterials for nanotechnology because of their nano-fibrillar
structure, abundance, biodegradability, renewability and multi-functionality and can replace
high-cost, non-biodegradable synthetic fibres, for example, carbon nanotubes (Moon et al.,
2011). The CNCs induce polymer chain anchors/cross-links to different CNCs as well as the
same CNCs, providing stability to the network structures (Yang et al, 2013a). In addition, by
incorporating nano-fillers it has been found that it is possible to further extend the typical
property profiles of polyurethanes. Due to their high surface area for interactions, stress
transfer and very high individual mechanical properties, nanoscale fillers have been recently
explored for polymer reinforcement (Mohd Amin et al., 2016). To conclude, by incorporating
nano-fillers into TPU, it is possible to reduce the cost of production, increase the tensile
strength and the stiffness of a material depending on processing methods.

2.3 Cellulose
Cellulose is considered to be one of the most abundant natural polymers on earth, and it is
a linear polysaccharide which exists mainly in plants and also synthesised algae, tunicates and
certain types of bacteria (Börjesson & Westman, 2015). The structure of cellulose may differ
as it influenced by the source of the cellulose. Nature cellulose typically consists of highly
ordered crystalline regions and the amorphous regions. Cellulose polymer consists of a linear
homo-polysaccharide composed of D-glucopyranose units, which are linked together by β-
1,4-glycosidic bonds (Cintil, et al. 2014). Each monomer has three hydroxyl groups and they
play an important role in forming ordered crystalline structure by hydrogen bonds (Börjesson
& Westman, 2015) The specific structures of cellulose polymer are presented in Figure 4.

Figure 2.5.: molecular structure of cellulose

As Figure 2.5 shown, the cellulose molecule consists of the reducing end groups, non-
reducing end groups and cellobios units. The reducing end group possesses a free hemiacetal
or aldehyde at C1 position, and non-reducing end groups always contain a free hydroxyl
group at C4 position. Each internal glucose unit links the neighbour unit at C1 and C4
positions. Furthermore, the D- glucopyranose unit has three hydroxyl groups at C6, C2 and
C3 positions, where the hydroxyl groups at C6 position is the most reactive, leading to the
high functionality for the polymers (Roy, et al. 2010). These hydroxyl groups determine the
crystalline structure and the physical properties of cellulose, since they can form different
intermolecular hydrogen bonds or intramolecular hydrogen bonds, which could build a strong
sheet structure in the linear polymer and provide strong stiffness for polymer chains
(Wulandari et al., 2016). Figure 2.6 presents the schematic of crystalline cellulose and
amorphous cellulose.
 Figure 2.6: Schematic of amorphous cellulose and crystalline cellulose (Bhattacharya,
et al. 2008; Sharma et al., 2019).

Cellulose and its derivatives in different forms have been used for energy source,
paper, building material, clothing, foodstuffs, pharmaceuticals, films, coatings, and
membranes for many years (Klemm et al. 2005, 2011). The crystalline region is the important
factor for the crystallinity of cellulose. The degree of crystallinity varies from 60-80%
depending on various sources of cellulose. The amorphous regions, also named disordered
regions, are located between the micro-fibrils. The amorphous regions in cellulose have
relatively lower density than crystalline regions, since the cellulose chains are oriented
randomly with irregular arrangement (Usov et al., 2015). The higher amorphous fraction
results in the higher accessibility to accept the attack by the other molecules such as acid. In
general, CNC could be produced after chemical treatments that have the capable of removing
most of amorphous regions and leaving the crystalline regions intact in the cellulose
materials. The most common treatment is acid hydrolysis.
2.3.1 Introduction to Cellulose Nanocrystals (CNC)
Basically, there are three families of nano-sized cellulosic particles, referred to
cellulose nanocrystals (CNC), nanofibrillated or microfibrillated cellulose (NFC or MFC),
and bacterial nanocellulose (BNC) (Siqueira et al., 2010). Figure 2.7 shows the size and
dimension of the three main classes of nanocellulose.

Figure 2.7: Three main classes of nanocellulose

CNFs are “spaghetti-like” nanofibrils are generally produced by the mechanical

treatment of plant fibers at nanoscale (Siró & Plackett, 2010). Typically, the width of
cellulose nanofibers ranges from 3nm to 50nm, the length ranges from 0.5μm to 5μm.
CNC are the main subject to research in this study. CNC consist of rod-like cellulose
crystals with width in the range of 5–70 nm and lengths between 100 nm to several
micrometers (Klemm et al., 2010). CNCs are commonly produced by hydrochloric or
sulfuric acid hydrolysis from cellulose materials (Nickerson & Habrle, 1947). Long fibers
retain amorphous regions which weaken their mechanical properties, whereas CNC
remove this structural defect by subsequent processing steps by ultrasonic treatment
(Klemm et al., 2011, Moon et al., 2011). In addition, CNCs are reported to be excellent
materials because cellulose possesses fascinating characteristics such as sustainability,
biocompatibility, biodegradability, nontoxicity, and easy surface modification due to the
abundance of primary hydroxyl groups at the surface (Juntao, 2016).
2.3.2 Isolation of Cellulose Nanocrystals (CNC) via Mechanical Methods.

Most commonly, the hydrolysis of cellulose using sulphuric acid is adopted, as it

results in CNC with high crystallinity, appreciable production yield and attractive
dimensionality. The CNC isolated from this process generally exhibit low thermal
stability due to the dehydration, degradation and charring facilitated by the sulphate
groups left on the CNC. In this research, MCC has been chosen as the cellulose resources
for producing CNCs. The isolation of CNC from cellulose fibers by low cost,
environmental method is a great challenge. Mechanical methods have sparked interest
among academicians to produce nanocellulose based products. These methods including
homogenization under high pressure, microfluidization, nano-grinding, ultrasonication
and freezing smashing (W. Yang et al., 2015). Recently, it is reported that CNC can be
isolated with enhanced thermal stability and high production yield, from commercially
available microcrystalline cellulose (MCC) via mechanical methods such as ultra-
sonication and nano-grinding techniques without the use of any strong acids like sulphuric
acid (Mohd Amin et al., 2015). Ultrasound treatment (sonication) is commonly used to
disperse CNC particles in suspensions, which in general causes a decrease in their
viscosity.

2.3.3 Isolation of CNCs via Ultrasonicaton

Ultrasonication is a common laboratory mechanical technique used sound energy to

physical and chemical systems. The effect of ultrasonication in degrading polysaccharide
linkages has been well described (Faria et al, 2010). This method operates on a well-
known high speed shear mechanism. Upon ultrasonication, high speed liquid jets are
created. These liquid jets pressurize the liquid between the particles at high speed (1000
km/hr) to separate the fibrillate them and to promote additional particle collisions, so as
result in very small particles (Mohd Amin et al., 2015). The diameters of the obtained
fibrils are widely distributed from 20nm to several microns, indicating that ultrasonication
method gives aggregated fibrils with a broad width distribution. With the aim of
developing convenient, environmentally method for CNCs preparation, the thesis
investigated the isolation and characterization of CNC prepared from MCC using
ultrasonication without any chemical treatments. The rheology properties of obtained
CNCs was investigated by adding it to TPU matrix (Du et al., 2017).

2.3.4 Isolation of CNCs via Nano-grinding.

Another technique to isolate fibers into nano-sized fibrils is grinding. The fibrillation
mechanism in the grinder utilizes shear forces to degrade the cell wall structure and
individualize the nanoscale fibrils (Plackett et al, 2010). When centrifugal force is
generated in the grinder, beads are forced to rotate around the grinder. The reverse
rotation of disc also applies centrifugal force in the opposite direction leading to the
transition of balls to the opposite walls of grinder providing an impact effect to micronize
the materials in between the beads (Baheti et al, 2012). The relative rotation of the two
discs produced the force crush, shearing, friction grinding and tearing to divide the fibers
as well as decrease their size to obtain nanocellulose. Wang et al investigated the effect of
energy consumption and fibrillation time on crystallinity. They found that after 11 hours
grinding, the energy input increased from 5 to 30 Wh/kg with noticeable decrease of
crystallinity index. Hassan et al, produced nanofibers by passing bleached pulp made from
rice straw and bagasse through a high-shear grinder and an HPC, using 30 and 10 passes.
The result shows the other treatment using homogenizer obtained smaller size of
nanofibers and same pattern.
2.4 Cellulose reinforced polymer nanocomposites.

The polymer industry is continually researching to find new materials that offer
increased performance at lower costs (Martin et al., 2012). One of the methods to improve the
properties of TPU is by using reinforcing filler (Garces et al., 2020) . The incorporation of
nanoscale fillers, even at low fractions (<5 wt. %), into TPU matrices has given rise to some
remarkable improvements in the mechanical properties, thus sparking an interest in their
further development with respect to cost and processing (Mohd Amin et al., 2016).
Previously, a range of nanoparticles has been used in TPU-based composites, with varying
levels of success. The bulk of this work has involved the use of carbon nanotube or layered
silicate-based nanofillers (Martin et al., 2012). (Ching et al., 2016). CNCs combined with
polymeric materials such as poly (ethylene oxide) (PEO) and polylactic acid (PLA) have
proven applicability as reinforcing agents due to enhanced dynamic and mechanical properties
of the nanocomposites (Xu et al., 2013). It is investigated that CNC has high elastic modulus
and Young’s modulus, which are two important physical parameters for bio-composites
materials (Hon-Meng, et al. 2015). Recently, several researchers have reported some
remarkable reinforcement of TPU through the incorporation of CNC.

Moreover, CNC-reinforced nanocomposites have potential in a greater improvement

of the mechanical properties with an increased addition of CNCs in the matrix. To fully
exploit the reinforcement potential of CNC, high quality dispersion in the polymer matrix is
vital and, for TPU, conventional solvent method have been found to show a high degree of
dispersion (Mohd Amin et al., 2016). To obtain high performance in TPU nanocomposites,
the interactions between CNC and TPU segments must be investigated. Hence, this study will
focus on the comprehensive evaluation of the structure-property relationships of TPU/CNC
nanocomposites.

2.4.1 Processing of cellulose reinforcing polymer nanocomposites.

 Nanocomposites with CNC can be processed via four different methods as illustrated
in Figure 2.8. The first and most common is the ‘solution method’ or ‘solvent casting
method’ in which CNC is first dispersed in a solvent in which the polymer is also soluble
followed by casting and evaporation of solvent (Favier et al, 1995). However, according
to Siemann, 2005 mentioned this method has disadvantages with respect to production
costs and film quality because CNC tends to re-aggregates.

Figure 2.8: General schematic diagram of processing TPU Nanocomposites

In the second method, ‘in-situ polymerisation’, CNC is dispersed well in the

monomers (with or without the use of solvent) and subsequently polymerised to get the
nanocomposites. The presence of cellulose in the pre-polymerisation state of TPU
encourages a chemical bonding with the polymer matrices (Wang et al, 2011). Despite the
enhancement in mechanical properties, it was found that the nanofiller could negatively
impact upon on the crosslink density, thereby reduced the potential benefits from the
reinforcing the nanofillers (Schmidt, 2003). The third method is based on a solvent
exchange sol-gel process, where it is versatile and becomes very crucial for achieving a
higher dispersion and transport properties where CNC plays a vital role. However, solvent
exchange is a relatively slow processing method and it is not an environmentally friendly
method (Ishii et al, 2003).

The fourth method is a conventional ‘melt blending’ method where CNC can be melt
blended with any polymer whose softening or melting temperature is below the
degradation temperature of the CNC used. This method is preferred by the industry as it is
economically viable and environmentally friendly (almost zero usage of solvents). The
 melt compounding method simplifies TPU fabrication compared with other methods,
which are complex and time consuming (Oksman et al, 2006).

2.4.2 TPU Nanocomposites

Table 2.1 summarize the significance and importance of using CNC as reinforced
filler in TPU matrix.

Table 2.1: TPU reinforced with different CNCs amount of loading.

Amount of Key findings References

CNCs

1–5 wt % This study demonstrated that the addition of small (Liu et al., 2015)
amounts of CNCs to TPU minimally affected the
ultimate tensile strength and strain to failure of the
nanocomposites by additions up to 5 wt % CNCs,
whereas the elastic modulus was increased by about
70%.

0-1 wt% The tensile strength of TPU reinforced with CNCs shows (Mohd Amin et
improvement up to 20% al., 2016)

5 wt% In this study, the fabricated CNC/TPU nanocomposites (Yadav et al.,

with up to 5 wt % CNC loadings via the two-step 2020)
polymerization process reported 450– 500% increases
in both elastic modulus and ultimate tensile strength
while a high strain to failure was still maintained.

1wt% In this work, the tensile strength and Young (Z. Yang et al.,
modulus increase from 5.43 MPa to 12.22 MPa and 2010)
1.16MPa to 4.38MPa.
 0-30 Tensile strength and elastic modulus increases from (Gao et al., 2012)
3.9 – 11.5 MPa and 31.9 MPa- 823.9 MPa.
wt%

From Table 2.1, the result in the increased strength and toughness of the composite are
because CNCs were covalently bonded with specific sites of the hard segment within the
TPU, and this resulted in the strengthening of the interfacial bonding between CNCs and
TPU (Liu et al., 2015). Thus, the CNCs could tune the modulus, maintain the elongation,
and at low loadings, increase the thermal degradation temperature and so may ultimately
be most useful as a thermal stability additive for TPUs. In general, the mechanical
properties of CNC/TPU nanocomposites such as elastic modulus and ultimate tensile
strength increased 20–80% without sacrificing the strain to failure at low CNC contents
(0.25–1.5 wt %) (Liu et al., 2015). CNC have high-axial mechanical properties and
reinforcing capability, abundance, low density, renewability and biodegradability which
make them ideal candidates for incorporation (Dufresne, 2013).

2.5 Application of TPU/CNC Nanocomposites

Few researchers have recognized the potential of TPU nanocomposites as biomaterials

even though recent studies have revealed that TPU nanocomposites have the potential to be
developed for biomedical device components due to the enhancement of thermal, mechanical,
and barrier properties and their capability in tuning cell-material interactions. Furthermore,
nano-fillers can introduce new functionality, such as antimicrobials. TPU nanocomposites can
provide a combination of bio-stability and advantageous mechanical properties. They are,
therefore, promising candidates for use as biomaterials in the fabrication of a wide range of
medical devices (Martin et al., 2012a). According to Patton et al., 2017, Ag-Carbon black
TPU nanocomposite has high potential application in additive manufacturing.
2.6 Rheology Properties

Many studies have recently been carried out to improve the rheological properties of
fibre-reinforced polymer composites with the addition of nanofillers into various polymers
(Ching et al., 2016). In past a few years, a growing number of studies have reappeared in the
field of rheology of CNC due to the increasing needs in formulation and processing
challenges that are not restricted to academia.

Table 2.2: Rheology properties of different polymer nanocomposite.

Polymer-CNC Key findings references

Polylactide 1. Complex viscosity and storage modulus (Bagheriasl et al., 2016)
(PLA)/CNC of PLA/CNC increased with CNC (Kamal & Khoshkava,
content. 2015)
2. When the concentration inceased, the
PLA/CNC shows highly shear thinning.

Polyethylene oxide Viscosity reduced if 1wt% PEO in (Pereda et al., 2014)

(PEO)/CNC different loading of CNCs.

In this thesis the effect of the CNCs on the rheology properties of TPU was
investigated. Rheological measurements, including linear and non-linear viscoelastic tests
were performed on TPU/CNC samples. In this kind of test, the stress is not applied in a one-
dimensional axis in relation to the material, such in traditional tensile tests, but with an
angular variation between two plates (or cones). The rheology properties can provide
parameters related to the mechanical properties of a system and its rheological behaviour. In
the case of suspensions and polymer melts, the obtained data provide information about how
the material flow and deform through the interpretation of parameters such as viscosity, shear
stress and shear rate.

The rheological properties of nanocrystals cellulose are dictated by many parameters.

For example, the overall trend of viscosity could be improved with the increasing mass
fraction. The reason might be due to there is limited amount of water that can be adsorbed by
crystalline when the mass fraction is relatively lower (Ravisankar & Tara Chand, 2013).
While increasing mass fraction of CNCs trends to rise up viscosity significantly. It is shown
that CNCs have the higher viscosity performance at higher temperature, since the stiffness of
fibrils would be enhanced and the fibres would swell simultaneously at the higher temperature
(Lee et al., 2016). In addition, some research has also focused on the effect of pH on
rheological properties. It is believed that there are much more charges on the surface of CNCs
when the pH is increased, leading to more repulsion between fibrils, which could lower the
viscosity (Reid et al., 2017). Furthermore, diluted CNCs suspension has shown shear thinning
behaviour at low shear rates. That is because the rod-shaped nanocrystals cellulose tend to
align at a critical shear rate, but the chirality of CNCs can be broken down if the shear rate is
over the critical point (Shafiei-Sabet et al., 2012).The viscosity of aqueous nanocrystals
cellulose suspension can also be expressed as a function of aspect ratio of CNCs. CNCs with
higher aspect ratios stay aligned for longer times even after shear (Boluk et al., 2011).

For all nanocomposites, even those with CNC concentration as low as 0.5 wt%,
spectacular increases of complex viscosity η* and storage modulus G’ are observed, mainly at
low frequencies, which clearly show the strong effect of CNCs on the rheological properties
of PLA (Bagheriasl et al., 2016). The complex viscosity, η*, of the neat PLA exhibits a long
plateau, with a slight shear- thinning behavior at high frequencies. In addition, the G’ was
dependent on frequency to some extends. For an ideal gel which behaves elastically, the
storage modulus is expected to be independent of frequency and G’ > G’’. As for 15.0 wt %
sample, G’ is higher than G’’, and the frequency independence of storage modulus occurs,
which demonstrates a typical stiff gel behavior (Jia et al., 2014; Urena-Benavides et al.,
2011). It is concluded that the CNC suspensions shift from a viscous fluid to an elastic gel
when the particle concentration increases.