Fullerenes, Nanotubes and Carbon Nanostructures

ISSN: 1536-383X (Print) 1536-4046 (Online) Journal homepage: http://www.tandfonline.com/loi/lfnn20

Effect of Graphene Nanoplatelet Addition on

Properties of Thermo-responsive Shape memory
Polyurethane-based Nanocomposite

Ayesha Kausar & Amin Ur Rahman

To cite this article: Ayesha Kausar & Amin Ur Rahman (2016): Effect of Graphene
Nanoplatelet Addition on Properties of Thermo-responsive Shape memory Polyurethane-
based Nanocomposite, Fullerenes, Nanotubes and Carbon Nanostructures, DOI:
10.1080/1536383X.2016.1144592

To link to this article: http://dx.doi.org/10.1080/1536383X.2016.1144592

Accepted author version posted online: 06

Feb 2016.

Submit your article to this journal

Article views: 4

View related articles

View Crossmark data

Full Terms & Conditions of access and use can be found at

http://www.tandfonline.com/action/journalInformation?journalCode=lfnn20

Download by: [University of California, San Diego] Date: 13 February 2016, At: 21:34
 ACCEPTED MANUSCRIPT

Effect of Graphene Nanoplatelet Addition on Properties of Thermo-responsive Shape memory Polyurethane-based

Nanocomposite

Ayesha Kausar a,* and Amin Ur Rahman b

a
Nanosciences Division, National Centre For Physics, Quaid-i-Azam University Campus, 44000, Islamabad,

Pakistan.
b
Department of Physics, The University of Lahore, Punjab, Pakistan.
Fullerenes, Nanotubes and Carbon Nanostructures

*Corresponding author. Tel.: 0092-51-2077-300; Fax: 0092-51-2077-395 E-mail: asheesgreat@yahoo.com

Abstract

Graphene nanoplatelets (GNP) was added as reinforcement to novel blend of polyurethane (PU) and

poly(ethylene-co-ethyl acrylate-co-maleic anhydride) (PEEAMA) with an intended application for heat

induced shape recovery. Objective of the study was to explore the effect of GNP addition on morphology,

mechanical properties, and heat induced shape recovery. Physical inter-linking of GNP platelets to blend

components directed unique self-assembled pattern. Neat blend revealed gyroid morphology while

addition of functional GNP initiated well-defined double gyroid pattern on folds of primary gyroid

structure. At a concentration of 5 wt.% GNP, the nanocomposite film showed highest improvement in

tensile strength (54%) and Youngs modulus (57%) as compared to blend. The nanocomposite samples

showed shape recovery phenomenon at T m (60 C). In 5 wt.% GNP loaded nanocomposite, the original

shape of samples was nearly 96% recovered within 7 s.

Keywords: Graphene nanoplatelet; polyurethane; gyroid; tensile strength; shape memory.

1
ACCEPTED MANUSCRIPT
 ACCEPTED MANUSCRIPT

1. Introduction

The production of new graphene-based derivatives through top-down approaches has opened doors for

several concealed applications of graphene. Graphene nanoplatelet (GNP) is a recently developed

material. GNP is short bulk of single graphite layer called graphene. GNP has intermediate geometry with

6 nm thickness corresponding to 18 graphitic sheets. It has lateral size of 25m and specific surface area

of 120-150 m2/g. It is low cost material which often increases the tensile modulus of final composite
Fullerenes, Nanotubes and Carbon Nanostructures

material [1-3]. These are particles having several excellent properties of single layer graphene. Several

studies have been carried out regarding the bulk properties of GNP such as electron microscopy and

Raman spectroscopy [4]. GNP may have different geometric properties as a function of size and atomic

number. Due to unique properties, alteration in specific surface area and aspect ratio of GNP may

significantly occur. Owing to excellent mechanical, electrical and thermal properties, graphene has

recently attracted major interest as reinforcing phase in composite materials. One potential route to exploit

the remarkable properties of graphene nanoplatelet for applications would be to incorporate in polymer

materials. However large surface area may increase van der Waals forces and - interaction between the

short platelets [5]. Therefore thin nanoplatelet has tendency to self-roll in matrix. Fabricating such

composites requires consistent dispersion of GNP in matrices. Processability and homogeneous dispersion

of graphene nenopalatelet in polymer matrix depends upon its degree of exfoliation. For exfoliation of

graphene nanoplatelet, composites have been processed using solution-phase mixing. Exfoliated GNP

sheets in aqueous or organic mediums may form well-dispersed colloids. Reduction or functionalization of

GNP surface is also essential to enhance its dispersion in polymers. Moreover, melt route is also used for

2
ACCEPTED MANUSCRIPT
 ACCEPTED MANUSCRIPT

the exfoliation and dispersion of GNP in polymers. GNP has intrinsic energy dissipating mechanisms

(sheet bending and sliding) to improve the toughness of composites [6, 7]. In composites, noteworthy

reduction in surface area of platelets may occur. There are several advantages of GNP such as structural

integrity, low production cost, low thickness, and several properties similar to single layer graphene.

Moreover the presence of functional groups develop stable interface through reaction with organic

molecules.

Polyurethanes (PU) have been frequently used in several engineering applications such as coatings,

medical implants, paints, electrical encapsulation, foams, sealants, and adhesive [8]. Polyurethanes have
Fullerenes, Nanotubes and Carbon Nanostructures

changeable characteristics from rigid thermoplastic to thermoset materials [9]. Chemical composition of

PU depends upon several factors such as nature of chain extender, monomer functionality, and molecular

weight of polyols [10]. Polyurethanes also demonstrate interesting shape-memory properties. The shape-

memorizing property of PU is often attributed to molecular motion of soft segments [11]. The shape-

memory effect can be induced by chemicals, pH change, electric field, and thermal stimulation. Polymer

blending has been a subject of research interest due to unique blend properties. The key objective of

blending is the modification of the mechanical properties at low temperature and improvement in

processability [12]. Mostly polymer blends are intimate mixtures of polymers without any covalent

connection between individual components [13]. Polymer blends are mostly immiscible. The properties of

the resulting blend material can be varied to meet the industrial demands [14]. The control of the blend

phase structure/morphology in processing has been used to tailor the final material properties [15, 16].

Morphology of uncompatibilized polymer blends depends on the viscosity, elasticity, interfacial tension

and composition of blends. The self-assembly in polymer blends usually originates from the structure in

which distinct blocks are thermodynamically incompatible. Accordingly, self-assembly may be initiated

3
ACCEPTED MANUSCRIPT
 ACCEPTED MANUSCRIPT

through strong molecular interaction such as hydrogen bonding. Different microphase-separated diblock

copolymers with various compositions or different overall molecular weight have been blended in order to

study their morphological behavior [17]. The double-gyroid morphology has been recognized for binary

block copolymers where the phases build up two interpenetrating cylinder networks [18]. A core-shell

double gyroid was also observed in blends of triblock copolymers. In this regard polyacrylate blends with

functional characteristics have also been found in literature [19]. The copolymers of polyacrylate possess

high-molecular weight ethylene and acrylate monomeric units in the backbone. In this study, the shape

recovery of polyurethane (PU)/poly(ethylene-co-ethyl acrylate-co-maleic anhydride) (PEEAMA) hybrid

Fullerenes, Nanotubes and Carbon Nanostructures

with functional GNP was investigated by applying thermal heating. The effect of GNP addition on the

structure, morphology, and mechanical properties of nanocomposite was studied.

2. Experimental

2.1. Chemicals

Poly(ethylene-co-ethyl acrylate-co-maleic anhydride) pellets (PEEAMA), poly(ethylene glycol)

bis(amine) (PEGBA, Mw 3,000), 2,4-toluene diisocyanate (TDI, 99%) and tetrahydrofuran (THF, 99.5%)

were procured from Aldrich. Graphene nanoplatelet (powder, surface area 110 m2/g) was also purchased

from Aldrich.

2.2. Instrumentation

Infrared (IR) spectra were recorded using Excalibur Series FTIR Spectrometer, FTSW 300 MX

manufactured by BIO-RAD, in transmission mode (4000-400 cm-1). Field Emission Scanning Electron

Microscopy (FE-SEM) of fractured samples was performed using Scanning Electron Microscope S-4700

4
ACCEPTED MANUSCRIPT
 ACCEPTED MANUSCRIPT

(Japan Hitachi Co. Ltd.). The samples were fractured under liquid nitrogen, and then vacuum-coated with

thin gold layer before analysis. The stress-strain behavior of the samples (501010.03 mm3 ) was

examined using universal testing machine (Instron 4466) and ASTM D638 standard method. The

crosshead speed of 20 mm/min was used during the test. The shape-memory effect of rectangular strips

with dimension 351010.05 mm3 was observed by heating the samples at 60 C, while monitoring the

shape recovery (SR) by using a video camera. The shape recovery was calculated using following Eq. (1).

SR (%) = [90-]/90 100 (1)

Fullerenes, Nanotubes and Carbon Nanostructures

Where in degree symbolizes angle between the tangential line at midpoint of the sample and the line

joining the midpoint and the end of the curved samples.

2.3. Preparation of PU

The polyurethane, PEGBA-TDI synthesized by the addition polymerization. PEGBA was used as

soft segments while TDI was employed as hard segment. The molar ratio of NCO/OH was adjusted as 1

representing 50 wt. % of hard segment content. The preferred amount of PEGBA, TDI, and THF were

charged into a three-necked round bottom flask equipped with a thermometer, reflux condenser, and

heating bath. The mixture was refluxed at 70 C for 6h [20]. The polyurethane solution prepared was cast

into glass Petri dish at room temperature. The dried PU film was obtained with thickness of 1 0.01 mm.

The chemical route for the synthesis of PU is shown in Fig. 1.

2.4. Preparation of PU/PEEAMA blend

5
ACCEPTED MANUSCRIPT
 ACCEPTED MANUSCRIPT

PU and PEEAMA were blended at preset composition ratio in a twin-screw extruder, followed by

cooling and pelletizing. The blends were labeled as PU/PEEAMA 50, PU/PEEAMA 70 and PU/PEEAMA

90 (number is indicating PEEAMA content). The blend pellets were dried in an oven at 70 C for 6 h.

2.5. Functionalization of GNP

Functionalization was carried out by dispersing 1g GNP in 50 mL THF. To this reaction mixture,

Afterwards 50 mL of conc. HNO3 was slowly injected drop wise followed by continuous stirring and

heating at 60 C. The washing of resulting product was carried out with excess amount of distilled water to
Fullerenes, Nanotubes and Carbon Nanostructures

obtain functional filler.

2.6. Preparation of PU/PEEAMA/GNP nanocomposite

Three nanocomposites of PU/PEEAMA 50 and GNP (1, 3 and 5 wt. %) were prepared using twin-

screw extruder, followed by cooling and pelletizing. The blends were labeled as PU/PEEAMA/GNP 1,

PU/PEEAMA/GNP 3, and PU/PEEAMA/GNP 5. The pellets were dried in an oven at 70 C for 6 h (Fig.

2).

3. Results and Discussion

3.1. FTIR analysis

IR spectra of polyurethane and PU/PEEAMA blend (400-4000 cm-1) at room temperature are

presented in Fig. 3A and B. In case of polyurethane, a strong band appeared at 3390 cm-1 due to NH

stretching vibration (Fig. 3A). The NH bending vibration of urethane group was also found at 1599 cm-1.

The asymmetric aliphatic CH stretch was seen at 2965 cm-1, while aromatic CH stretch appeared at

6
ACCEPTED MANUSCRIPT
 ACCEPTED MANUSCRIPT

3033 cm-1. The urethane carbonyl linkage was also identified in the spectrum. Consequently peak at 1736

cm-1 was allocated to the urethane C=O stretch. A broad peak at 1273 cm-1 was attributed to CO stretch.

The peaks observed in the spectrum indicated the formation of polyurethane. The structure and physical

interaction in compatible blend was confirmed from the spectrum in Fig. 3B. In PU/PEEAMA blend, peak

positions were shifted to lower intensity due to hydrogen bonding between the components. The bonded

NH band was shifted from 3420 cm-1 to 3361 cm-1. There was also a shift in the absorption band of NH

bending vibration. Therefore NH bending of urethane group appeared at 1589 cm-1. Here again aliphatic

and aromatic CH stretching vibration appeared at 2933 and 3010 cm-1. Lowering in urethane carbonyl
Fullerenes, Nanotubes and Carbon Nanostructures

peak towards 1695 cm-1 depicted interactions between PEEAMA and rigid PU segments. The broad CO

stretching vibration occurred at 1246 cm-1.

3.2. Morphology investigation

Scanning electron micropraphs of blends and nanocomposite are given in Fig. 4. In case of

PU/PEEAMA 50 blend, a self-assembled gyroid like morphology was observed due to physical

interlinking and compatibility between the blend components (Fig. 4A). However dispersed phase

morphology was observed in the case of PU/PEEAMA 70 (Fig. 4B) and PU/PEEAMA 90 ((Fig. 4C)

nanocomposites. The particles of polyurethane were seemed to be dispersed among the PEEAMA

granules. From morphology study it was observed that the polyurethane was better compatible with

PEEAMA at 1:1 ratio. However beyond this composition the ratio of two phases was disturbed. The

morphology of PU/PEEAMA/GNP nanocomposite was somewhat different than the PU/PEEAMA 70 and

PU/PEEAMA 90 blends. The nanocomposite revealed gyroid like morphology resembling the micrograph

of PU/PEEAMA 50 blend. The morphology was unique in texture and attained double gyroid pattern.

7
ACCEPTED MANUSCRIPT
 ACCEPTED MANUSCRIPT

With the addition of GNP, the gyroid morphology of PU/PEEAMA 50 became well-defined (Fig. 4D-F).

It seemed that the GNP platelets initiated well-defined double gyroid pattern on the folds of primary

gyroid structure. This unique self-assembled pattern was obviously due to physical inter-linking of GNP

platelets to the blend components. The functional nanoplatelet actually initiated fine self-assembled

structure [21, 22]. However with the increase in nanofiller content (5 wt.%), the morphology assumed a

broad gyroid pattern (Fig. 4F).

3.3. Mechanical property study

Fullerenes, Nanotubes and Carbon Nanostructures

Mechanical properties of specimens are given in Table 1. The data shows increasing tend in tensile

strength while decreasing trend in elongation at break for blends and nanocomposite. The neat

polyurethane showed tensile strength of 20.1 MPa, which increased to 35.8 MPa in PU/PEEAMA 50

blend. The strain of the neat polyurethane was 40.4 % which decreased to 35.1% in PU/PEEAMA 50. In

nanocomposite system, increase in functional GNP from 1 to 5 wt.% increased the tensile strength from

39.4 to 43.7 MPa (Fig. 5). On the other hand increasing nanofiller content decreased the elongation at

break considerably. Generally higher the content of nanoparticle in the polymer matrix, more brittle is the

nanocomposite. PU/PEEAMA/GNP 1 depicted 29.2 % strain, which was decreased to 12.3% in

PU/PEEAMA/GNP 5 nanocomposite. It seemed that the presence of functional nanoplatelet restricted the

macromolecular chain motion, so decreased the backbone flexibility. The Youngs modulus of

PU/PEEAMA/GNP 1-5 nanocomposite was also increased from 30.5 to 36.9 GPa with filler addition (Fig.

5). Consequently, Youngs modulus of PU/PEEAMA/GNP 5 was 57% higher than neat polyurethane

(15.5 GPa). The results recommended that the functional graphene nanoplatelet had greater influence on

the mechanical properties of PU/PEEAMA blends [23].

8
ACCEPTED MANUSCRIPT
 ACCEPTED MANUSCRIPT

3.4. Heat induced shape memory study

Heat induced shape memory properties of PU/PEEAMA/GNP 1-5 nanocomposite are shown in Table

2. The PU/PEEAMA 50, PU/PEEAMA 70, and PU/PEEAMA 90 blends revealed 85 % shape recovery.

The shape memory feature was enhanced with the addition of GNP. The shape memory behavior was

experiential by first bending samples in U-shaped, followed by quenching to room temperature to obtain

temporary shape and lastly reheating it. The value of Ttrans was taken 60 C i.e. melting temperature (Tm)

obtained from DSC studies (Fig. 6) [24, 25]. Consequently the nanocomposite samples exhibited shape
Fullerenes, Nanotubes and Carbon Nanostructures

recovery when a surface temperature of 60 C was applied. The shape recovery phenomenon is shown in

Fig. 7. In PU/PEEAMA/GNP 1-5 nanocomposite, the original shape of samples was nearly 95-96%

recovered within 7-10 s. At a temperature below Tm (40 C), shape recovery rate was lower (Fig. 8). The

shape memory nanocomposite gained high shape recovery rate at 50 C and the rate was maximum at 60

C. Moreover favorable mechanical properties were significant to reveal heat induced shape memory

behavior in GNP-based nanocomposite.

4. Conclusions

Graphene nanoplatelet was used as an effective reinforcement to induce shape recovery and enhanced

mechanical properties in PU/PEEAMA/GNP 1-5 nanocomposite. The materials were fabricated using

melt technique. The blend of polyurethane and poly(ethylene-co-ethyl acrylate-co-maleic anhydride) was

physically interlinked with functional graphene nanoplatelet. Better interaction among the blend

components resulted in gyroid pattern. The interaction and self-assembled morphology was responsible

for the enhanced Youngs Modulus and tensile strength of nanocomposite with GNP loading. The

9
ACCEPTED MANUSCRIPT
 ACCEPTED MANUSCRIPT

nanocomposite samples also exhibited heat stimulated shape recovery phenomenon. The original shape of

the nanocomposite sample was almost 96% recovered at 60 C.

Fullerenes, Nanotubes and Carbon Nanostructures

10
ACCEPTED MANUSCRIPT
 ACCEPTED MANUSCRIPT

References

1. Al-Hartomy, O., Al-Ghamdi, A., Said, S. F. A., Dishovsky, N., Mihaylov, M., Ivanov, M. and Zaimova,

D. (2015) Comparison of the Dielectric Thermal Properties and Dynamic Mechanical Thermal Properties

of Natural Rubber-Based Composites Comprising Multiwall Carbon Nanotubes and Graphene

Nanoplatelets. Fuller. Nanotub. Carbon Nanostruct., 23(12): 1001-1007.

2. Cataldo, F., Ursini, O. and Angelini, G. (2009) MWCNTs Elastomer Nanocomposite, Part 1: The
Fullerenes, Nanotubes and Carbon Nanostructures

Addition of MWCNTs to a Natural Rubber-based Carbon Black-filled Rubber Compound. Fuller.

Nanotub. Carbon Nanostruct., 17(1): 38-54.

3. Cataldo, F., Ursini, O. and Angelini, G. (2009) MWCNTs Elastomer Nanocomposite, Part 2: The

Addition of MWCNTs to an Oil-extended SBR-based Carbon Blackfilled Rubber Compound. Fuller.

Nanotub. Carbon Nanostruct., 17(1): 55-66.

4. Mutlay, . and Tudoran, L. B. (2014) Percolation behavior of electrically conductive graphene

nanoplatelets/polymer nanocomposites: Theory and experiment. Fuller. Nanotub. Carbon Nanostruct.,

22(5): 413-433.

5. Wu, S., Shi, T. and Zhang, L. (2015) High Concentration and Stable Aqueous Dispersion of Graphene

Stabilized by a New Amphiphilic Copolymer. Fuller. Nanotub. Carbon Nanostruct., 23(11): 974-984.

6. Anwar, Z., Kausar, A., Rafique, I. and Muhammad, B (2015) Advances in Epoxy/Graphene

Nanoplatelet Composite with Enhanced Physical Properties: A Review. Polym. Plast. Technol. Eng.,

DOI:10.1080/03602559.2015.1098695.

11
ACCEPTED MANUSCRIPT
 ACCEPTED MANUSCRIPT

7. Ahmad, N., Kausar, A. and Muhammad, B. (2016) Structure and Properties of 4-Aminobenzoic acid

Modified Polyvinyl chloride and Functionalized Graphite-based Membranes. Fuller. Nanotub. Carbon

Nanostruct., DOI: 10.1080/1536383X.2015.1118620.

8. Manvi, G. N., Singh, A. R., Jagtap, R. N. and Kothari, D. C. (2012) Isocyanurate based fluorinated

polyurethane dispersion for anti-graffiti coatings. Prog. Org. Coat., 75(3): 139-146.

9. Yang, H. Y., Zhang, X. M., Duan, L. J., Zhang, M. Y., Gao, G. H. and Zhang, H. X. (2013)

Environmental PH-responsive fluorescent PEG-polyurethane for potential optical imaging. J. Appl.

Fullerenes, Nanotubes and Carbon Nanostructures

Polym. Sci., 129(2): 846-852.

10. Mao, H., Qiang, S., Yang, F., Zhao, C., Wang, C. and Yin, Y. (2015) Synthesis of blocked and

branched waterborne polyurethanes for pigment printing applications. J. Appl. Polym. Sci., 132(46): DOI:

10.1002/app.42780.

11. Gunes, I. S., Cao, F. and Jana, S. C. (2008) Evaluation of nanoparticulate fillers for development of

shape memory polyurethane nanocomposites. Polymer., 49(9): 2223-2234.

12. Govorin Bajsi, E., Pustak, A., mit, I. and Leskovac, M. (2010). Blends of thermoplastic

polyurethane and polypropylene. II. Thermal and morphological behavior. J. Appl. Polym. Sci.,117(3):

1378-1384.

13. Pichaiyut, S., Nakason, C. and Vennemann, N. (2012) Thermoplastic elastomers-based natural rubber

and thermoplastic polyurethane blends. Iran. Polym. J., 21(1): 65-79.

14. Kannan, M., Bhagawan, S., Thomas, S. and Joseph, K. (2012) Comparison of theory with

experimental data for nanoclay-filled TPU/PP blend. Indust. Eng. Chem. Res., 51(41): 13379-13392.

12
ACCEPTED MANUSCRIPT
 ACCEPTED MANUSCRIPT

15. Guo, Y. H., Li, S. C., Wang, G. S., Ma, W. and Huang, Z. (2012) Waterborne polyurethane/poly (n-

butyl acrylate-styrene) hybrid emulsions: Particle formation, film properties, and application. Prog. Org.

Coat., 74(1): 248-256.

16. Shah, R., Kausar, A. and Muhammad, B. (2015) Characterization and Properties of Poly(methyl

methacrylate)/Graphene, Poly(methyl methacrylate)/Graphene oxide and Poly(methyl methacrylate)/p-

Phenylenediamine-Graphene Oxide Nanocomposites. Polym. Plast. Technol. Eng., 54(13): 13341342.

17. Shefelbine, T.A., Vigild, M.E., Matsen, M.W., Hajduk, D.A., Hillmyer, M.A., Cussler, E.L. and Bates,

F.S. (1999) Core-shell gyroid morphology in a poly(isoprene-block-styrene-block-dimethylsiloxane)

Fullerenes, Nanotubes and Carbon Nanostructures

triblock copolymer. J. Am. Chem. Soc., 121(37): 8457-8465.

18. Goldacker, T. and Abetz, V. (1999) Core-shell cylinders and core-shell gyroid morphologies via

blending of lamellar ABC triblock and BC diblock copolymers. Macromolecules, 32(15): 5165-5167.

19. Corres, M. A., Zubitur, M., Cortazar, M. and Mgica, A. (2011) Thermal and thermo-oxidative

degradation of poly (hydroxy ether of bisphenol-A) studied by TGA/FTIR and TGA/MS. J. Anal. Appl.

Pyrol., 92(2): 407-416.

20. Sattar, R., Kausar, A. and Siddiq, M. (2015) Thermal, mechanical and electrical studies of novel shape

memory polyurethane/polyaniline blends. Chines. J. Polym. Sci. 33(9): 1313-1324.

21. Kickelbick, G. (2003) Concepts for the incorporation of inorganic building blocks into organic

polymers on a nanoscale. Prog. Polym. Sci., 28(1): 83-114.

22. Kong, X. and Narine, S. S. (2008) Sequential interpenetrating polymer networks produced from

vegetable oil based polyurethane and poly (methyl methacrylate). Biomacromole., 9(8): 2221-2229.

23. Zhao, X., Zhang, Q., Chen, D. and Lu, P. (2010). Enhanced mechanical properties of graphene-based

poly (vinyl alcohol) composites. Macromolecules, 43(5): 2357-2363.

13
ACCEPTED MANUSCRIPT
 ACCEPTED MANUSCRIPT

24. Hu H. J., Yang, Z., Yeung, L., Ji, F. and Liu, Y. (2005) Crosslinked polyurethanes with shape memory

properties. Polym. Int., 54(5): 854-859.

25. Zhuohong, Y., Jinlian, H., Yeqiu, L. and Lapyan, Y. (2006) The study of crosslinked shape memory

polyurethanes. Mater. Chem. Phys., 98(2): 368-372.

Fullerenes, Nanotubes and Carbon Nanostructures

14
ACCEPTED MANUSCRIPT
 ACCEPTED MANUSCRIPT
Tensile Strength Strain Youngs Modulus
Sample
(MPa)) (%) (GPa)
PU 20.1 40.4 15.5
PU/PEEAMA 50 35.8 35.1 20.1
PU/PEEAMA 70 36.1 35.5 20.9
PU/PEEAMA 90 37.1 37.2 21.1
PU/PEEAMA/GNP 1 39.4 29.2 30.5
PU/PEEAMA/GNP 3 40.5 19.9 32.5
PU/PEEAMA/GNP 5 43.7 12.3 36.9
Fullerenes, Nanotubes and Carbon Nanostructures

Table 1. Mechanical properties of PU/PEEAMA blend and PU/PEEAMA/GNP nanocomposite.

15
ACCEPTED MANUSCRIPT
 ACCEPTED MANUSCRIPT

Table 2. Shape memory properties of PU/PEEAMA blend and PU/PEEAMA/GNP nanocomposite.

Fullerenes, Nanotubes and Carbon Nanostructures

Shape recovery rate Recovery time Shape Recovery

Sample
(%) (s) (%)
PU 41 18.2 82
PU/PEEAMA 50 49 16.1 85
PU/PEEAMA 70 65 15.9 85
PU/PEEAMA 90 66 15.2 85
PU/PEEAMA/GNP 1 69 10.2 95
PU/PEEAMA/GNP 3 75 8.5 95
PU/PEEAMA/GNP 5 80 7.1 96

16
ACCEPTED MANUSCRIPT
 ACCEPTED MANUSCRIPT

CH3
NCO
O
H2 N n NH2

PEGBA
NCO
TDI

O
H O
CH3 C N
N O N n H
H
Fullerenes, Nanotubes and Carbon Nanostructures

O
C N H

Hard Segment Soft Segment

Fig. 1. Preparation of polyurethane.

17
ACCEPTED MANUSCRIPT
 ACCEPTED MANUSCRIPT

Hydrogen bonding O
HO HO
C
Functional GNP

O O O
Fullerenes, Nanotubes and Carbon Nanostructures

y z
x
PEEAMA O O CH3 HO HO C
O

O H H
N N
H O
CH3 C
N O n

O
PU
C N H

Fig. 2. Interaction in PU/PEEAMA/GNP nanocomposite.

18
ACCEPTED MANUSCRIPT
 ACCEPTED MANUSCRIPT

2965 1273
3390 3033
1736 1599
% Transmittance

B
Fullerenes, Nanotubes and Carbon Nanostructures

3361 3010 2933 1246

1695 1589

3500 2500 1500 500

-1
Wavenumber (cm )

Fig. 3. FTIR spectra of (A) PU; and (B) PU/PEEAMA blend.

19
ACCEPTED MANUSCRIPT
 Fullerenes, Nanotubes and Carbon Nanostructures

E
C
A
ACCEPTED MANUSCRIPT

20
F
D
B

ACCEPTED MANUSCRIPT
 ACCEPTED MANUSCRIPT

Fig. 4. FESEM micrographs (A) PU/PEEAMA 50; (B) PU/PEEAMA 70; (C) PU/PEEAMA 90; (D)

PU/PEEAMA/GNP 1; (E) PU/PEEAMA/GNP 3; and (F) PU/PEEAMA/GNP 5 nanocomposite.

Fullerenes, Nanotubes and Carbon Nanostructures

21
ACCEPTED MANUSCRIPT
 ACCEPTED MANUSCRIPT

44 40

42
Tensile strength (MPa)

40 30

Strain (%)
38
Fullerenes, Nanotubes and Carbon Nanostructures

36 20

34

32 10
0 1 2 3 4 5
GNP content (wt.%)

Fig. 5. Mechanical properties of PU/PEEAMA 50 blend and PU/PEEAMA/GNP nanocomposite.

22
ACCEPTED MANUSCRIPT
 ACCEPTED MANUSCRIPT

60.4 oC
Heat Flow (Exo)

60.5 oC

PU/PEEAMA/GNP 1
Fullerenes, Nanotubes and Carbon Nanostructures

PU/PEEAMA/GNP 3
60.7 oC
PU/PEEAMA/GNP 5

40 50 60 70 80
Temperature (oC)

Fig. 6. DSC second covers of samples: (A) PU/PEEAMA/GNP 1; (B) PU/PEEAMA/GNP 3; and (C)

PU/PEEAMA/GNP 5.

23
ACCEPTED MANUSCRIPT
 ACCEPTED MANUSCRIPT
Fullerenes, Nanotubes and Carbon Nanostructures

Fig. 7. Shape recovery process of (A) PU/PEEAMA/GNP 1 and (B) PU/PEEAMA/GNP 5 at 60 C.

24
ACCEPTED MANUSCRIPT
 ACCEPTED MANUSCRIPT

90
PU/PEEAMA/GNP 1
PU/PEEAMA/GNP 5
75
Shape recovery rate (%)

60

45
Fullerenes, Nanotubes and Carbon Nanostructures

30

15

30 40 50 60
o
Temperature ( C)

Fig. 8. Shape recovery rate of nanocomposite at different temperature.

25
ACCEPTED MANUSCRIPT
 ACCEPTED MANUSCRIPT

Graphical abstract

O
HO HO
C
O O O
y z
x
O O CH3
O
H Interaction
CH3 HC
N O NH
HO HO C
O
O
O Functional GNP
C N H n N
PU/PEEAMA blend H
Fullerenes, Nanotubes and Carbon Nanostructures

Double gyroid structure

26
ACCEPTED MANUSCRIPT