Recent Advances in Polyurethane Based Nanocomposites: A Review

Rajeswaran Vaithylingam1, M. N. M. Ansari1,, Robert A. Shanks2

1
Centre of Advance Materials, Department of Mechanical Engineering, College of
Engineering, Universiti Tenaga Nasional, Kajang, Selangor, Malaysia
2
School of Science, Engineering and Health RMIT University, Australia

Corresponding Authors M. N. M. Ansari . Email: ansari@uniten.edu.my

Abstract

This review addresses recent advances in polyurethane (PU) based nanocomposites. It

focuses on the enhancement of the mechanical, electrical, thermal, acoustic, chemical,

shape memory and viscoelastic properties of the existing PU using nanoparticles or fiber

materials and it is also directed to analyze the potential of incorporating these hybrid

polymer composites applications. Research on hybrid polymer composites has increased

in recent years due to the inherence properties of mixing two or more constituents to

reinforce the base material properties. From the discussion in this paper, we can see that

PU based nanocomposite can be modified to suit various applications.

KEYWORDS: polyurethane (PU), hybrid polymer composite, nanocomposite,

mechanical properties, applications.

1. INTRODUCTION

The usage of conventional monolithic materials (e.g. metal, ceramic, polymer, etc.) in

different applications is widely practiced since the beginning of human civilization till

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 today. The use of specific materials leads to specific constraints under certain working

conditions [1]. Metal for instance; metals are strong but it can be very heavy and

susceptible to corrosion. As an effort to address this problem, composite materials were

developed [1]. Composites are among the most rapidly growing classes of materials,

which present a great potential in optimization of material performance by combining the

advantages of several different constituent materials [2].

Composites can be defined as a material consisting a reinforcement embedded in or

bonded to a matrix at a macroscopic level with a distinct interfaces or boundaries

between them. The functionality of the matrix is to hold the reinforcement in a desired

geometry and the reinforcements help to improve the properties of the composite based

on the purpose of its application [1]. In particular, polymer matrix composites have drawn

much attention due to its wide application in petroleum chemical industry, aeronautics,

automotive parts and architecture field [2]. The polymer usually acts as the continuous

phase (the matrix) while the nanofiber is the discontinuous phase, improving both the

strength and toughness of the composite [3].

It is commonly acknowledged that the two factors governing the preparation of a high-

performance nanofiber/polymer composite is [4]:

I. Dispersion of nanofiber in the polymer matrix

II. Interfacial interactions between nanofibers and the matrix

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The nanofiber tends to aggregate due to strong van der Waals forces between them,

hindering their homogeneous dispersion in a polymer matrix. Besides, a lack of strong

interfacial interactions between the nanofiber and matrix can greatly compromise the

reinforcement effect of the nanofiber [4]. There are various methods of promoting the

dispersion between the nanofiber and matrix which entirely depends on the compatibility

based on the type of nanofiber and matrix used [5].

2. POLYURETHANE COMPOSITE

Polyurethane (PU) is a diverse group of polymer with many applications and is often

described as bridging the gap between rubber and plastic[6], [7]. PU was discovered by

Otto Bayer and his co-workers around 1930s in Leverkusen, Germany. PU are also

known as urethanes as it contains organic units joined by carbamate (urethane) linkage.

PU is a versatile polymer known for its unique chemistry with excellent mechanical and

optical properties at low temperature; it also can be a good solvent resistant that covers

almost 29% of the material market. This makes PU an excellent choice of matrix for a

hybrid polymer composite [6].

PU composites (PUC) has applaudable properties like low density, excellent flexibility,

shape memory, high abrasion resistance, corrosion resistance, high elongation at break,

damping ability, weathering durability, high elasticity, anti-aging, good processability,

high impact strength, excellent gloss, transparency, controllable hardness, high

biocompatibility and biostability, excellent blood compatibility, and good low

temperature flexibility[6], [7], [8], [9], [10], [11], [12]. PUC has many applications such as fibre,

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coating, adhesives, foams, resins, elastomers, and smart actuators [5],[13]. PUC has

segmented block copolymers that inherent excellent physical properties owing to

microphase separation yielding alternating hard and soft segments [7]. A hard segment

(HS) consists of diisocyanate and chain extender (giving the urethane groups). A soft

segment (SS) from the polyether or polyester polyol [4].

Adjusting these molecular structures of PUC may allow it to suit according to the

application requirements. There are some major drawbacks associated with PUC in terms

of high temperature applications. PUC has some infirmites, i.e. insufficient tensile

strength and thermal stability in high temperature working environment with low anti-

corrosive properties [4]. PUC are highly flammable in these conditions and have poor

adhesion to metal surfaces [8], [9]. The poor heat resistance and low tensile strength of

PUC are the known barrier for their applications [10]. PUC also exhibits poor thermal

and electrical conductivity [11]. The PUC limitations has led to the birth of nanocomposite

to compensate the disadvantages of PUC by addition of other constituents [12].

2.1 Mechanical And Thermal Properties

In recent years, the development of composites frequently involves the dispersion of

inorganic nanoscale materials in a polymer matrix to improve the mechanical, physical

and thermal properties at very low fiber content [14]. Mechanical properties are physical

properties that are exhibited by a material upon application of forces, often associated

with strength, ductility, hardness, impact resistance, and fracture toughness. Mechanical

characterization of a composite can be done via tensile test, impact test, flexural test, and

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dynamic mechanical analysis (DMA). Thermal properties are the ability of the material to

conduct or insulate heat, often associated with service temperature, thermal stability and

glass transition temperature [1]. Thermal characterization of a composite can be done via

thermogravimetry analysis (TGA), DMA, differential scanning calorimetry (DSC),

thermo-mechanical analysis (TMA), and differential thermal analysis (DTA) [1].Since the

first report of polymer nanocomposite using CNT as a fiber, CNT enhanced polymer

nanocomposites has become a remarkable breakthrough in material science both in

academic and industrial field [15]. Reinforcing ability of carbonaceous fiber is mainly

related to improving the mechanical properties, thermal properties and electrical

conductivity for polymer composite applications [11], [16]. The addition of CNT for

reinforcement increases the hardness, compressive strength, tensile strength, modulus,

stiffness, toughness, flexural strength, thermal conductivity and thermal stability of the

PU composite [9], [5], [13], [2], [15].

Subhani et al. has discussed usage of CNT and introduced ND into composites. Tensile

testing of the composites containing 0.2 %w/w MWCNT and 0.2 %w/w ND showed an

increase in tensile (70 %) and flexural (104 %) strengths along with the tensile (84 %)

and flexural (56 %) moduli in comparison to neat epoxy. The increase in tensile

properties of the composites is related to uniform dispersion of nanofillers and their

strong interfacial adhesion with the epoxy matrix as shown in Figure 1 [13].

CNT have recently emerged as a promising fiber for a thermally conductive polymer

composite as it is able to provide sufficient thermal conductivity at low loading and also

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reduces the flammability [9], [16]. However, the moduli and stiffness were lowered when

the content of CNT exceeds the 2 %w/w due to agglomeration [5]. Agglomeration

appears due to the strong Van der Waal forces causing the CNT to bundle with each other

and thus limiting the dispersion in polymer matrix [15]. There are many different process

developed to disperse CNT in polymers [13]. In general, there are two methods used to

fabricate polymer/CNT composite. Firstly, in-situ polymerization at their surface

(covalent attachment) [5]. This includes ultrasonification, calendaring, ball milling, shear

mixing and extrusion, together with physical and chemical functionalization techniques

to increase the interfacial interactions between reinforced CNT and polymer matrix [13].

Secondly, direct incorporation of functionalized CNT into polymer matrix (non-covalent

attachment) [5]. The non-covalent approach mainly involves surfactants,

biomacromolecules, or polymer wrapping [15]. Investigation by Xiong et al., states that

the covalent attachment is considered to be more advantageous than the non-covalent

attachment [5]. However, the investigation of Mu et al. states otherwise. The CNT surface

functionalization approach has some obvious drawbacks such as tedious chemical

reactions and involvements of highly corrosive or toxic chemicals. This may cause

structural defects and fragmentation of the nanotubes which drastically decrease the

mechanical durability and electronic properties of CNT [15].

Therefore, the non-covalent approach was developed because these methods would not

compromise the physical properties of CNT but improve the solubility and processability.

Although, the non-covalent method is effective in isolation and debonding of CNT, there

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remains problems that limit their wide application. Example, wrapping polymer method

requires complicated chemical reactions that involves high cost [15]. In an effort to locate

a promising method to enhance the interfacial interaction between CNT and polymer,

some researchers came across polydopamine (PDA) coated CNT [2]. This may hold the

key for an excellent dispersion of CNT in polymer matrix.

Dopamine, a substance produced by the brains of many organisms including humans has

attracted much attention owing to strong chemical bonding forces with substrates [2].

PDA is produce via oxidation of dopamine. Motivated by mussel adhesive proteins,

dopamine was found to form PDA layer on various type of materials such as polymer,

ceramic and metals through self-polymerization dopamine in aqueous solution. The

PDA-CNT is prepared using 2 mg/ml dopamine added to CNT/DMF suspension and

stirred magnetically for 6 hours. Then, the PDA-CNT/PU composite is prepared using in-

situ polymerization method [15]. The adhesion between the fiber and matrix of the

composite can be measured using the friction and wear test [2]. The PDA-CNT

preparation by self-oxidative polymerization of dopamine in dimethylformamide (DMF)

solution is illustrated in Figure 2 [15].

The addition of PDA-CNT into the polymer composite improved the wear resistance,

tensile strength, impact strength, thermal stability and has a low friction coefficient due to

good interfacial interaction between the PDA-CNT and PU [2], [15]. Further increasing the

PDA-CNT to 0.5%w/w, unexpected aggregation of PDA-CNT occurs that results in

decreased tensile properties [15]. In order to improve the thermal conductivity of CNT, it

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can be hybridized using aluminum hydroxide (Al(OH)3) via thermal decomposition of an

aluminum precursor. The hybridized polar is able to modify the compatibility of the CNT

and PU matrix by alleviating the modulus mismatch at the interface. The hybrid Al

(OH)3-CNT/PU composite showed poor tensile strength and elongation at break due to

the early agglomeration [16].

Any nanocarbon structure can also be hybridized with ceramics like silica to improve the

thermal conductivity due to the enhanced phonon transfer at the fiber/polymer interface

region [16]. Nanodiamonds (ND) are diamonds that exist at nano scale (about 4-5 nano-

meters). Addition of ND in a PU matrix improves the hardness, modulus of elasticity,

scratch resistance, tensile strength, the storage modulus, thermal conductivity and glass

transition temperature. However, a large quantity of ND composition is required, about

25 % in volume for a significant change. Similar to CNT, ND is required to be

chemically functionalized before mixing and prepared using in situ polymerization

(covalent attachment) for best results [13].

The isolation of single layer of graphene from graphite with unique physico-chemical

properties have attracted considerable interest in both academia and industry [12], [17].

Graphene, a one atom thickness hexagonal lattice of sp2 carbon atoms, exhibit a two-

dimensional sheet like structure. Graphene was proven experimentally to be the strongest

material developed so far [4]. Due to an inert nature of graphene, an appropriate

modification is essential for the incorporation of graphene into polymer matrices [17]. In

particular, the covalent attachment of polymers onto graphene helps to prevent

8
aggregation of graphene [18]. This leads to exfoliation or oxidation of graphite oxide to

produce graphene oxide (GO) as an alternative to graphene [4], [12].

GO has the advantages in production yield and cost that makes it an attractive candidate

as a nanofiber used in polymer composites [4].The addition of GO into a polymer matrix

enhances the tensile strength, flexibility, thermal stability, stiffness and toughness [4], [12],
[18] [17]
, . Based on an investigation by Pokharel et al., addition of only 1%w/w of GO into

PU by in-situ polymerization, showed an improvement of 40.5 % in tensile strength and

19 % in elasticity compared to pristine PU [17]. Carbon fibers (CF) combine exceptional

mechanical properties with conductive properties, making it an ideal reinforcement in

advanced composite materials [10]. CF is composed mainly of carbon atoms, fibers of 5-

10 micrometers in diameter bonded in crystals that aligned to the long axis of the fiber [3].

Increased interest in carbon fiber reinforced polymer (CFRP) composite materials

amongst researchers and academician due to their unique attributes; light weight and high

strength. The incompatibility between the inorganic CF and PU matrix, lead to a poor

fiber-matrix interfacial adhesion resulting in decreased mechanical properties of the

composite [10]. Thus, researchers devote to modify the surface of CF to improve the

interfacial adhesion between the fiber and matrix [3]. There are numerous methods

concerning the surface modification of CFs, such as gaseous oxidation, liquid oxidation,

electromechanical oxidation, plasmaoxidation, surface grafting, polymer sizing, and multi

scale reinforcements, have been developed to improve the interfacial adhesion through

9
forming chemical bonding and/or enhancing the mechanical interlocking between CF and

matrix [10], [3].

The addition of CF into the polymer matrix increases the tensile modulus, tensile

strength, elongation at break, roughness, storage modulus, shear strength, hardness,

stiffness, low weight, chemical resistance, high temperature tolerance and thermal

expansion [10], [3]. Further, based on the investigation by Zhang et al., the CF modified

with 4, 4-diphenylmethane diisocyanate (MDI) molecules has better interfacial adhesion

with PU matrix and increased overall tensile and tribological properties [3]. Fullerene is a

member of the carbon nanostructure family which has a zero-dimensional structure. The

research efforts based on fullerene chemistry with combination of macromolecular

chemistry led to the development of easily processable fullerene containing polymeric

composite materials [11].

The addition of surface modified fullerene into polymer composite improves the tensile

strength, percentage of elongation, Youngs modulus, melting point, and the glass

transition temperature due to specific volume enlargement. Based on the investigation of

Tayfun et al., surface oxidation and silanization of fullerene exhibit better mechanical

and thermal properties due to the improved interactions between the nanofiber and matrix
[11]
. Iron oxide (Fe2O3) is one of the most important inorganic compound used as fibers in

polymer matrix. Fe2O3 is also known as ferric oxide or simply rust. Similar to other

nanoparticles, Fe2O3 require surface modification due to the hydrophilic nature of the

nanoparticles [8].

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Silane coupling agents are well known materials used to modify the nanoparticles due to

their unique bifunctional structure. Surface modification using coupling agents can

modify the surface chemistry of the particles from hydrophilic to hydrophobic [19]. The

grafting silane coupling agents like 3-aminopropyltrimethoxysilane (APTMS) are

commonly used to modify the Fe2O3 to show better results in mechanical and thermal

properties of the polymer composite. Addition of the modified Fe2O3 improves the

energy at break, toughness, tensile strength, glass transition temperature, cross linking

density, and surface roughness [8]. Chromium (III) oxide (Cr2O3) is an inorganic

compound commonly used as pigment in nature [19].

Similar to Fe2O3, the Cr2O3 requires surface modification to improve the adhesion with

the polymer matrix by converting the hydrophilic nature of the nanoparticle surface to

hydrophobic. The addition of Cr2O3 modified with APTMS into polymer matrix increases

the tensile strength, toughness, and energy at break. However, the addition of modified

Cr2O3 decreases the glass transition temperature and cross linking density of the polymer

composite [19]. Titanium dioxide (TiO2) in the crystal form of rutile, is one of the most

important inorganic material for nanocomposites with increasing interest from both

academic and industrial field. Similar to other nanoparticles, TiO2 tend to strongly

agglomerate due to the extremely large surface area/particle size ratio [20].

Hence, reducing the resultant tensile properties of the nanocomposite material. Different

coupling agents such as amino propyl trimethoxy silane (APS) for surface modification is

strongly recommended to achieve proper dispersion of nanoparticle in polymer matrix

11
and to yield a better compatibility between the nanoparticle and host polymeric materials.

The addition of TiO2 into PU matrix improves the tensile strength, elastic modulus,

hardness, energy to break, storage modulus, and glass transition temperature of the

composite [20]. Zinc oxide (ZnO) has attracted great attention as a fine inorganic semi

conductive material for various types of industrial applications [21].

Different results concerning the influence of ZnO fibers on the mechanical properties PU

composites can be found in the literature. On the basis of different approaches, it was

confirmed that tensile properties are strongly correlated to the PU phase separation. The

phase separation of PU may be disrupted by the reactions between ZnO hydroxyl groups

and the polymer upon the addition of ZnO fiber. This results in unusual mechanical and

thermal properties due to the disruption of phase separation. Hence, the addition of ZnO

nanoparticle actually decreases the tensile strength, Young modulus, elongation at break,

hardness, and thermal stability of the composite [21]. The inorganic/organic composite

composed of copper (Cu) fiber and PU have high potentials for applications in low

infrared emissivity coatings [22].

However, the poor tensile properties of PU/Cu composite are the major causes limiting its

application. Thus, bronze (Cu-Sn based alloys) and epoxy-polyurethane (EPU) is

employed to substitute Cu and PU respectively. Owing to the strong adhesion to a variety

of treated or untreated metal surfaces, epoxy based adhesives are extensively used in

many industries, in order to bond different material substrates. Based on the investigation

by Yan et al., the addition of bronze content below 40 %w/w improved the cohesive

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strength and impact resistance of the EPU composite [22]. Molybdenum disulfide (MoS2)

is another promising class of layered material with attractive properties in the field of

polymer composites [23].

MoS2 exist in three crystalline form; trigonal, hexagonal and rhombohedral. There lies an

obstacle to implement MoS2 fiber as reinforcement for polymer composites. The MoS2

layers hold themselves together via intrinsic van der Waals interactions to form the MoS2

stacks that results in reduced efficiency for reinforcement. Fortunately, the MoS2 can be

intercalated with lithium ions (Li+) to produce LixMoS2 compound that can be easily

exfoliated chemically to prepare the MoS2/polymer composite. Addition of MoS2 into

polymer composite improves the thermal stability, tensile strength and Young modulus

[23]. Natural fiber composites are having strong influence in the field of composite

material due to the cost effective production, lighter in weight, lower abrasion of

equipment and renewability [24].

Kenaf plant has a single, straight, and unbranched stem that is traditionally used in

cordage, canvas and sacking manufacturing. Natural fibre-polymer incompatibility is a

known factor limiting the usage of such PU/KF composite. The incompatibility is caused

by the hydrophilic nature of the fiber with and the hydrophobic nature of the polymer.

The presence of hemi cellulose, lignin and other impurities also cause the incompatibility.

Based on the investigation of El-Shekeil et al., KF pretreated with polymeric methylene

diphenyl diisocyanate (pMDI) chemical treatment improves the PU/KF adhesion produce

high tensile strength, tensile modulus, and compressive strength composite [24]. The

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anionic clay, namely layered double hydroxides (LDH, hydrocalcites) are subject of

increasing interest in recent composite studies [14].

Typical example is the naturally occurring magnesium-aluminum hydroxcarbonate (Mg6

Al2 (OH)16 [CO3].4H2O), named hydrotalcite (HT) due to its talc-like appearance with

high water content. The layered structure and possibility of making them hydrophobic by

intercalation of organic anions has inspired many researchers to investigate HT as a

nanofiber in polymeric matrices. The incorporation of few percent HT additive can give

an improvement in hardness, impact strength, fire retardancy, elasticity and scratch

resistance of the PU/HT composite [22].In recent years, polymer/layered silicate

nanocomposites (PLSN) have drawn more attention due to their unique mechanical and

thermal properties compared to virgin polymer or conventional micro-composites [25].

In addition, the enhancement of the barrier properties of polymers and increased

biodegradability due to addition of organic clay has been reported. Organic-inorganic

nanocomposites, comprised of organically modified clay dispersed in selected polymer

matrices have attracted considerable attention to the research field. Organically modified

clay is added into PU matrix to produce clay polyurethane nanocomposite (CPN) via

ultrasonification method. Based on the investigation by El-Fattah et al., very low addition

of CPN (about less than 5 %w/w) is reported to have high hardness, impact strength,

thermal stability and flame retardancy compared to pristine PU [25]. Nano-silica are found

commonly in nature as quartz or sand, it can exist as several minerals or can be produced

synthetically [7].

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These nanofibers are expected to contribute to the strength of the matrix due to the

composite strengthening effect of the particles. Silane coupling agents (SCA) are

commonly utilized to link the native hydroxyl groups available on the surface of the

nano-silica particles with PU matrix. The addition of nano-silica improves the composite

mechanical and thermal properties such as hardness, tensile strength, elastic modulus,

yield strength, toughness, and thermal stability [7]. Polymer concrete has mainly been

around for industrial flooring casting, retouching of damaged concrete structures or

underground pipes, and for civil applications that require high strength, fast cure and

durability. There is a growing interest in polymer concrete due to the remarkable qualities

compared to conventional construction material [26].

Based on the study by Hussain et al., a new material PU cement (PUC) was produced

upon curing the mixture of PU and cement for 24 hours. PUC has applaudable

mechanical properties such as high compressive strength, tensile strength, bending

strength, elastic modulus and light weight [26]. Dope dying is an economic method used

for manufacturing fibers such as acrylic, nylon/polyamide and polyester. It has the

advantage to upgrade the polymer properties with the addition of dye using a chemical

catalyst such as -cyclodextrin. The -cyclodextrin is used as a bridge to link the PU and

the dye as it has a truncated cone structure which can form inclusions with disperse dyes

and hydrogen bond with PU as shown in Figure 3 [27].

Based on the investigation by Wan et al., the PU mixed with Disperse Orange 31 dye

using -cyclodextrin catalyst via dope dying process produce a resultant composite with

15
improved thermal stability, tensile strength, storage modulus and low degradation due to

the hydrogen bond [27]. Castor oil is a type of vegetable oil that can be directly utilized as

polyol in PU synthesis. This is because 90 % composition of castor oil is ricinoleic acid

with one hydroxyl group on every 12thcarbon and a double bond between the 9th and 10th

carbon. The thermoplastic castor oil based segmented PU polymer reinforced with

cellulose nanocrystals (CNC) is becoming a topic of high interest in the medical field due

to its non-toxicity and good mechanical properties [28].

The PU/CNC composite has improved ductility, tensile strength, tensile modulus,

elongation at break, storage modulus, and thermal stability [28]. Adjustment to the

molecular structure also could improve the mechanical properties of PU. Most of the

commercially available PU contains aromatic diphenylmethane diisocyanate (MDI) that

produce mutagenic and carcinogenic substances on degradation. Replacing MDI with

1,4-butanediisocyanate (BDI) is the optimal choice for its chemical reactivity, but BDI is

expensive. 1,6-hexanediisocyanate (HDI) is much cheaper but has medium chemical

reactivity and exhibit poor mechanical properties. Based on the investigation by Qu et al.,

pre-polymer chain extended with an isocyanate-terminated urethane triblock resulted in

PU with high tensile strength and elongation at break [29].

2.2 Electrical Properties

Electrical properties of a material is determined by the ability of the material to be

conducting or insulating electricity based on the parameters such as resistivity,

conductivity, dielectric strength, temperature coefficient of resistance, and

16
thermoelectricity [1]. The conductive fibers known to improve electrical conductivity in

polymer composites are such as carbon, silver, gold, copper, and nickel of various shapes

and sizes [30]. In the composite field, maximum electrical conductivity of 10 S/m at a

loading of 7.4%w/w of MWCNT and 0.3 %w/w as the percolation threshold for

MWCNT/polyimide (MWCNT/PI) composite was achieved using in-situ polymerization

method based on a study by Jiang et al. This concluded the ability of CNT to improve the

EC of a polymer composite [31].

Under the investigation of Souri et al., the EC value of 0.33 S/m was achieved at 7%w/w

loading of MWCNT and 5%w/was the percolation threshold for MWCNT/PU composite

using three roll milling machine technique. It was established through this study, this

technique is quick, simple and compatible with standard industrial techniques to produce

high percolation threshold composite compared to in-situ polymerization, solution

compound and combination of different techniques [32], [31]. The addition of CNT can

achieve high dielectric strength at a very low loading fraction (< 5 %w/w).CNT can also

alter the electrical resistance of the composite under applied load/strain, a phenomenon

known as piezoresistivity that can be measured using a two-probe method. Based on the

investigation by Souri et al., the composite with 5 %w/w loading of MWCNT showed

92.92 %, highest achieved piezoresistivity [31].

Further loading of CNT into the composite potentially decreases the EC, piezoresistivity

and dielectric strength due to the entanglement and agglomeration [32], [31]. Based on the

investigation by Ji et al., the agglomeration degree of the one-dimensional CNT can be

17
reduced using two-dimensional GO as a novel dispersant to promote the adhesion

between the CNT and PU matrix. The discovery of single layer graphite also known as

graphene have brought a great improvement in electrical properties of polymer

composites [33]. In order to obtain high yield graphene, the top-down methods such as the

combination of oxidation, exfoliation and reduction of graphite is often practiced GO is

produced from exfoliation and oxidation of graphite. GO consist of large number of

versatile oxygen functional groups on its edge and basal planes leading to a stable

dispersion in aqueous solution [34].

Nevertheless, the disruption of the sp2 carbon structure by the oxygen functional groups

results in poor electrical conductivity GO. Chemical reduction is an effective method to

obtain RGO which is able to be dispersed in aqueous or solvent media and fix the

disruption of sp2 carbon structure [34]. However, GO tends to aggregate and re-stack due

to their large van der Waals forces and - interactions [33], [32]. Compatibilization of

graphene via non-covalent and/or covalent interactions is an effective way to enhance

surface adhesion with polymer matrix and prevent aggregation. The existence of

functional groups such as hydroxyl, carbonyl and carboxyl promotes the covalent

interaction. Hydroxyl groups can be reacted with silicone coupling agents to enhance the

graphene adhesion to the polymer matrix [33].

Under the investigation of She et al., incorporating modified expanded graphene (EG)

showed the electrical conductivity of 10-1 S/m at 8 %w/w loading and 5.7 %w/w as the

percolation threshold for EG/PU composite using in-situ polymerization method [31].

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Recently, sulfonated graphite oxide (SGO) is found to be more effective in facilitating the

oxygen reduction reaction of GO. Hydroiodic acid (HI) can be used a strong reducing

agent as it is an environmentally friendly inorganic acid. The strength and conductivity of

GO filled polymers is increased after reduction with HI due to the reaction with the

epoxy groups in GO. Thus, the reduced SGO (RSGO) has great potential to improve the

electrical and thermal conductivity of polymer composite [35]. Similar to CNT,

introducing graphene to the polymer matrices significantly improves the EC,

piezoresistivity and dielectric strength of the composite [33], [32], [31].

In recent years, silver nanoparticles (AgNP) have drawn a great attention as it is widely

used as conductive fibers for electrically conductive composites. Ag are known for its

high aspect ratio which is beneficial to form electrically conductive networks at a

relatively low percolation threshold in polymer composite. However, Ag has a tendency

to agglomerate due to their fine size and large specific surface area, which could reduce

conductive path. Ag is also prone to sedimentation as the density of Ag (10.53 g/cm3) is

higher than the polymer density (around 1.0 g/cm3). Therefore is it required to address the

Ag sedimentation and agglomeration issue before proceeding with the preparation of

Ag/polymer composite with high EC. The usage of Nano-silica (SiO2) as a dispersant

may not be an option in this case as SiO2 is more of an electrical insulator. As step to

improve the performance of Ag/PU composite, GO or LDH can be used as a novel

dispersant to improve the EC of the composite [30].

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Based on the investigation by Hsiao et al., the Ag/GO/PU composite exhibit superior

electrical property (<10/sq) [34]. As the global warming issues are on the rise,

employing piezoelectric generator composites which is able to convert vibration and

mechanical energy source from human activities such as pressure, bending and stretching

motion into electrical energy. This is becoming a topic of high interest in recent

composite studies. Material like zinc oxide (ZnO) and barium titanate (BaTiO3) can be

used as fibers to improve the piezoelectric properties of the polymer composite. Based on

the investigation by Souri et al., the generator composite prepared using ZnO

incorporated in PU matrix showed greatest peak voltage value of 40.45 V upon cyclic

loading [36]. In order to improve the capability of electromechanical response, an increase

in dielectric constant with low Youngs modulus is required to perform in low electric

field [37].

Among the various methods to improve the dielectric permittivity of a polymer

composite, the development of incorporating conductive loading fibers is most

promising. Polyaniline (PANI) is one of the most conductive polymers which has

advantages like high conductivity, ease of polymerization, environmentally stable and

compatible for dispersion in a variety of polymer matrices. The electrostriction of PU can

be modified with the addition of PANI, emeraldine salt (ES), and hydrochloric acid

(HCl). Based on the investigation by Putson et al., the modified PU/PANI-ES-HCL

exhibits enhanced electrostrictive strain response under low electric fields, high dielectric

constant and strong induced strain response [37].

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2.3 Acoustic Properties

Acoustic properties of a material can be determine by its ability to perform as an insulator

or conductor often involving vibration, ultrasound and infrasound [1]. PU foams are

commonly used for its cellular structure which can be used for sound absorption and

insulation. Nano-clay, Titania nanoparticles (TiO2) and MWCNT can be incorporated

into the PU matrix for further improvement in the sound absorption properties. Based on

the investigation by Orfali, the MWCNT/SiO2/PU composite showed remarkable sound

insulation properties compared to pristine PU where the addition of 0.2 %w/w SiO2 and

0.35 %w/w CNT to PU composition improved sound transmission loss up to 80 dB that

of pure PU foam sample. Figure 5 shows the results for the transmission loss based on

different loading types of the composite within the range of 0-160 Hz [38].

The results also indicate that the silica P-type had better sound absorption ratio compared

to nano-silica S-type over all frequency ranges. Surprisingly, the continuous addition of

CNT of up to 2 %w/w had poorer sound insulation than the pristine PU foam due to the

high loading of CNT effectively preventing the interactions between the polyol and

isocyanate [38].

2.4 Chemical Properties

Chemical properties determines the ability to resist or comply in a chemical reaction

based on the parameters like toxicity, corrosion resistant, chemical stability,

flammability, and enthalpy of formation that governs in composite classification [1].

Monolithic materials such as steel are subjected to corrosion in most outdoor

21
applications. Organic based coatings are commonly used to prevent the corrosion

degradation of steel. However, organic coatings often fail due to electrolyte exposure

causing cathodic delamination and physical damage like impact, scratch or wear during

service. This allows direct contact of underlying steel substrates to aggressive

environment and electrochemical reaction taking place at coating/substrate interface. The

increase in hydroxide ions concentration result in alkalization, which weakens the

adhesion of steel substrate and coating. The cathodic delamination is the primary cause of

coating mechanism failure [39].

Transport of water and oxygen molecules through organic coatings plays a critical part in

reducing oxygen while the transport of cations along the interface is the controlling factor

of cathodic delamination [39]. The use of nanoparticles (NP) as additives in coatings has

improved the thermal stability of the polymer, enhance scratch and abrasion resistance,

barrier properties including corrosion resistance of the coatings without disturbing their

other properties. NP most commonly used in coatings are like SiO2, TiO2, ZnO, Al2O3,

MWCNT, and CaCO3. NP can be used based on their inherent properties [40].

Incorporation of MWCNT in polymer matrices improves the wear resistance as tensile

strength and friction reduction of the composite is upgraded. The Scanning Kelvin Probe

(SKP) is used to measure cathodic delamination of PU composite [39].

Based on the investigation by Khun et al., the SKP results concluded the increased

MWCNT content from 0 to 0.5%w/w decreased the cathodic delamination of the PU

composite as much dense MWCNT effectively blocked the oxygen and water molecules

22
pathways through the coating during cathodic delamination process [39]. ZnO is well

known for its multi-functional properties due to its unique physical and chemical

properties. Incorporation of ZnO into the polymer matrix improves the heat, scratch,

abrasion resistance and thermal stability of composite. ZnO can be used as an

antibacterial and antifungal agent when incorporated into the PU matrix. Based on an

investigation by Saeed et al., ZnO with the loading of 2 %w/w showed obvious

inhibitory effect of the growth of both positive and negative bacteria, improved corrosion

and mechanical resistance significantly, and reduce the surface wettability [40].

The low infrared emissivity (near to 0.10) ability of Cu/PU composite is currently getting

great attention from the civil and military applications. However, low emissivity infrared

Cu/PU coating are restricted due to the localized corrosion of Cu caused by sodium

chloride (NaCl) solution and weak interaction between the fiber and matrix. Based on the

investigation by Yan et al., about 0.2g quantity of silane coupling agent (KH550) was

employed for Cu surface modification. The KH550 act as a bridge-link to improve the

interfacial adhesion and corrosion resistance without sacrificing the low infrared

emissivity of the Cu/PU composite [41]. During fire, heat releases and inhaling toxic gases

has led to heavy casualties and property loses in case of fire accidents. Flame retardants

can be employed to reduce the peak heat release rate and the total heat release [42].

Increasing environmental concerns have forced out halogenated compounds as early

flame retardants. Phosphorous, nitrogen, boron silicon, LDH, montmorillonite, and

graphite, can be used to enhance the fire retardancy in thermoplastic PU (TPU). Toxic

23
smoke composed of smoke particles, organic volatiles, carbon dioxide (CO2), carbon

monoxide (CO), and hydrogen cyanide (HCN) are released during combustion of

polymers. For this reason, the multi metal element compounds have attracted

considerable attention due to its excellent properties in catalytic charring and degradation

of toxic gases. Metal hydroxystannate (MSn (OH)6 where M = Zn, Mg, Ca, Co, and Cu),

received extensive attention for its high efficient catalysis in many fields such as

photocatalyst, smoke suppression agent and gas sensors. Based on the investigation by

Wang et al., the combination of zinc hydroxystannate (ZnHS)/ammonium polyphosphate

(APP)/TPU composite featured high efficiency in flame retardancy, suppressed toxic

gases, thermal stability, smoke and heat suppression for a safe polymer composite [42].

2.5 Viscoelastic Properties

Viscoelastic properties of a composite is defined as the ability to exhibit both viscous and

elastic characteristic when undergoing deformation. The material is able to resist shear

flow and strain linearly with time while being stretched and quickly returning to its

original state when stress is applied [1]. New inventions in composite field has led to the

discovery of smart materials such as electroactive polymers (EAP), that is able to change

in size or shape when stimulated by the right external electrical activation mechanism.

EAP are able to convert electrical energy to mechanical energy. EAP are highly attractive

for their large strain capability and resilience. PU based composites are very favorable

when taking viscoelastic properties into consideration as they are flexible, light weight,

biocompatibility, ease of processing, and the ability to be molded into various shapes [43].

24
Metal organic frameworks (MOF) compounds are made up of metallic ion centers

coordinated by organic linkers, forming a repeating continuous three-dimensional porous

framework with large surface areas, increased accessible active sites and low densities.

MOF is dominated by combined secondary chemical interactions such as hydrogen

bonds, van der Waals forces and - stacking. Based on the investigation by Mahdi et al.,

a resilient rubbery MOF nanocomposites produced by incorporating zeolitic imidazolate

framework (ZIF-8) into PU matrix that has the combined malleability, ease of

processability, scalability of polymer, porosity and accessability of hybrid inorganic-

organic materials creates a unique composite that exhibited adaptability and durability

with enhanced porosity, high surface area, and multi-functionality, within one continuous

structure [44]. Result in distinctive and highly recognizable responses from external

stimuli [43], [44].

Based on the investigation by Jomaa et al., incorporation of grafted CNT into PU matrix

using grafting onto technique increased the interfacial adhesion, dielectric strength,

permittivity, and 5%w/was the percolation threshold of the CNT/PU composite. The

electromechanical performance of the composite was also increased by a factor of 2,

hence enabling high viscoelastic behavior [43].

2.6 Shape Memory Properties

Shape memory property of a composite dictates its ability to change from a temporary

programmed shape to an original permanent shape when exposed to external stimuli like

heat, electricity, light, magnetic field, or solution and able to return to its former shape

25
upon removing the external stimulus subjected on the composite [1], [45]. In recent years,

shape memory polymers (SMP) are receiving a great deal of attention from researchers

due to their advantages like light weight, flexible, ease of processing, high shape

recovery, broad range of shape recovery temperature, high capacity for elastic

deformation (up to 200 %), potential biocompatibility, biodegradability and low cost

compared to the shape memory alloys (SMA). However, SMP has major limitation like

small recovery stresses due to low rubbery moduli (0.1 10 MPa), low recovery speed

due to poor thermal conductivities, and inert to electromagnetic stimuli due to the

electrical insulation of most polymeric materials [46], [47].

SMPs are also subjected to poor tensile properties and low chemical resistance restricting

its practical applications. As a measure of addressing these key limitations, nanofibers

like carbon black, short carbon fibers, nickel and polypyrrole due to their ability to

generate heat according to Joules law that eventually facilitate the heat transfer in

triggering the recovery of PU matrix [47]. The formation of interpenetrating polymer

networks (IPN), consist of two polymer networks held together by a permanent covalent

entanglement, is an effective way to combine the respective outstanding properties of

different polymeric materials [48]. The combination of fiber with PU matrix creates a

unique property and enables some attractive performances, leading to derive a

multifunctional smart material system (MSMS) [49].

Introducing polylactide (PLA) into the blend of PU matrix can upgrade the SMPs

biodegradability, biocompatibility, and improve the tensile strength. However, PLA

26
applications are restricted owing to its brittleness. Based on an investigation by Raja et

al., CNT/PU/PLA composite produce using modified CNT via melt mixing process

showed significant improvement in tensile strength, dynamic storage modulus, and glass

transition temperature with excellent thermal and electrical conductivity. Figure 6 shows

the significant improvement in the electro active shape memory behavior of the resultant

composite [46].

Apart from PLA and PU, shape memory effect is observed in polymers such as poly

(vinylidene fluoride) (PVDF), in which shape memory effect is induced by thermal

stimulation via heating above the transition temperature or melting temperature. Based on

another study by Raja et al., investigation on the CNT/PU/PVDF composite showed

similar results as the CNT/PU/PLA composite where significant improvement to the

electro active shape memory behavior was detected [47]. Epoxy resins (EP) are commonly

associated with high modulus and strength which led to the wide application in structural

composites. However, the major limitation of EP is brittleness. The combination of PU

and EP has excellent synergistic effect in tensile properties based on the good

compatibility between them. Based on the investigation by Zhang et al., the KH550

functionalized graphene (FG) incorporated in PU/EP matrix via in-situ polymerization

produce the FG/PU/EP composite [48].

The FG/PU/EP composite showed an improved shape recovery ratio of 94 % and thermo-

electric dual responsive characteristic of 82.7 x 10-6 S/m. A simple method to effectively

improve both electrical and magnetic properties is by incorporating magnetic particles

27
(MNP).The magnetic particles (Fe3O4) have attracted much interest due to their good

biocompatibility, low toxicity, high saturation magnetization and easy preparation.

Therefore, desired electrical and magnetic properties can be obtained using magnetite.

Based on the investigation by Petcharoen et al., the MNP/PU composite showed full

recoverability, good bending performances, high electro- and magneto-phoresis, and

produced very fast response time during the time sweep test under applied electric field
[49]
.

3. APPLICATIONS OF POLYURETHANE COMPOSITES

Optimized mechanical and thermal characteristic of PU based composites can be used for

applications like hydrogen storage, super capacitors, biosensors, electromechanical

actuators/resonators, nano-probes for high resolution imaging, solar cells, aerospace

shuttle parts, aeronautical parts, photovoltaic devices, cardiac assist pumps, blood bags,

coatings, wind turbine blades, body armor, car parts, yacht structures, semiconductor, and

sports equipment (shoes, rackets, golf clubs, etc). These composites also have introduced

a whole new era in the automotive industry by producing high technology gadgets to

improve both the driving luxury and fuel saving [4], [9], [11], [5], [18], [17], [28], [21], [50].

Enhanced electrical characteristic of PU based composites can be used for applications

like micro-pumps, energy harvesters, fast response actuators, robotics, positioners, bio-

inspired robotics, electronic components, energy storage, automotive parts, light emitting

diode, liquid crystal display, electromagnetic interference shielding, radio frequency

28
identification, optoelectronic devices, flexible electronic products, and piezoelectric

generator [32], [36], [30], [34]. The improved acoustic characteristic of PU based composites

can be used for applications for sound insulation such as sound absorbing automotive

parts and sound proof foam cascade walls for studios [38].

High chemical characteristic of PU based composites can be used for applications like

catalytic converters in automotive exhaust system, smoke suppression agent, gas sensor,

photocatalyst, camouflaging attire/equipment in military applications, coatings for pipes,

coatings for steel structures, UV blocking agents, and anti-microbial coating for medical

equipment [40], [39], [42], [41]. Excellent viscoelastic characteristic of PU based composites

can be used for application like drug delivery, food packaging, protective clothing, tires,

heat shields, and actuators [43], [44].

Improved shape memory characteristics of PU based composites can be used for

application like clothing manufacturing, deployable space structures, morphing aircraft,

medical treatment equipment, actuators, semiconductors, biosensors, artificial skin

bioengineering, tissue engineering, implantable pancreas, shape memory foam, robotics,

ophthalmic devices, orthodontic wires, and cardiovascular stents [46], [49]. As previously

discussed in every chapter of each properties, the selection of the fillers/fibers for cost

reduction or reinforcement and strong interfacial adhesion treatment plays an important

role in modifying the PU based composites. Acquiring the combination of the various

required properties is a major challenge to suit the appropriate applications with the

desired effects.

29
 4. CONCLUSIONS

Based on the literature review, it is of importance to identify the right type of nanofiber to

be incorporated with the PU matrix. For instance, to upgrade the mechanical, shape

memory and electrical properties of a PU based composite, carbon based nanofibers like

CNT or graphene can be employed as they inherent these properties in a pristine state.

The method of incorporating the fiber into the matrix is the second most important task,

where the process treatment is necessary to improve the adhesion between the fiber and

matrix. For instance, CNT can be modified using in-situ polymerization or functionalized

via chemical treatment to improve the dispersion in the matrix. The method of

modification also determines the type of attachment that will be produced between the

fiber and matrix, for example, in-situ polymerization promotes covalent bonding and

functionalization promotes non-covalent bonding. Therefore, the method of fiber

modification can be determined by its application. The fiber type and modification

method is very important as these factors govern the cost of production and ease of

manufacturing the composite. A combination of these findings can produce a scientific

breakthrough in the composite world and further upgrade the everyday life of a person by

incorporating these ideas into new innovations. The use of graphene composite to extend

battery life in cellular industry is one example of new innovations.

ACKNOWLEGMENTS

Authors would like to express their gratitude to the Universiti Tenaga Nasional,

Putrajaya, Malaysia and RMIT University, Melbourne, Australia for providing the

resources and facilities to carry out the research.

30
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Figure 1: Model of epoxy matrix hybrid nanocomposite showing crack propagation

through epoxy matrix and the interaction of the crack with MWCNT and ND producing

toughening mechanisms, including crack deflection, MWCNT bridging and MWCNT

pullout [13].

39
Figure 2: Schematic illustration for the preparation of PDACNT [15].

40
Figure 3: The scheme of the dope dying method [27].

41
Figure 4: Average absolute peak voltages for various types of piezoelectric sensors in a

foot stamping test [31].

42
Figure 5: PU, PUnano-silica (P-Type, S-Type), and PUCNT composites (0-160 Hz)

[38].

43
Figure 6: Variation of shape memory recovery ratio of PUPLA nanocomposite as a

function of cycle number [46].

44