AIAA SciTech Forum 10.2514/6.

2020-2233
6-10 January 2020, Orlando, FL
AIAA Scitech 2020 Forum

Carbon Nanotube Enhanced Shape Memory Epoxy for

Improved Mechanical Properties and Shape Recovery

Siddhant Datta1, Aditi Chattopadhyay2

1,2
School of Engineering for Matter, Transport and Energy, Arizona State University, Tempe, Arizona, AZ-85287,
USA

Todd C. Henry3 and Asha J. Hall4

3.4
Vehicle Technology Directorate U.S. Army Research Laboratory, Aberdeen Proving Ground, MD, 21005, USA

* Corresponding author: sdatta10@asu.edu

Downloaded by UNIVERSITY OF TEXAS AT AUSTIN on May 30, 2020 | http://arc.aiaa.org | DOI: 10.2514/6.2020-2233

Abstract

This paper focuses on the processing and fabrication of carbon nanotube (CNT) based electro-
active shape memory epoxy nanocomposites for improvement in mechanical properties and
shape recovery behavior. Electro-active shape memory specimens have been fabricated by
soaking CNT membranes in shape memory epoxy (SME) through a specialized fabrication
process developed in-house. The improvement in dynamic mechanical properties of the
baseline SME using CNT membranes is demonstrated using single-cantilever dynamic
mechanical test setup and is correlated with the microstructure through scanning electron
microscopy characterization. For the CNT-SME, the improvement in storage modulus in the
range of 30-90ׄ°C was found to be 60% and 82%, respectively In addition, the electrical
actuation of the CNT-SME is demonstrated using a 10V DC supply and the shape recovery
response is characterized.

I. Introduction
Shape memory polymers (SMPs) have recently gained increasing popularity and a great deal of interest in the
scientific community for their versatile applicability, ranging from light-weight morphing structures in space to micro-
actuators in unmanned aerial vehicles (UAVs) [1-3]. These materials are stimuli responsive and can be formed into a
primary shape, reformed into a stable secondary shape, then actuated through external stimuli (e.g. thermal, electrical,
chemical etc.) to recover their primary shape. In comparison to shape memory alloys, SMPs possess many advantages
including excellent processability, light weight, and great flexibility in terms of material design [4,5]. To perform the
mechanical act of fixing and recovering deformation, the polymer basically consists of two phases, a fixed phase and
a reversible phase. Crystalline, glassy state, entanglement networks or crosslinking networks can be used as fixed
structures to memorize original shapes. The thermally reversible phase is generally designed to manifest a large drop
in the elastic modulus upon stimulation through the shape recovery temperature (TS) [3,4]. The melting temperature
of a crystalline phase or the glass transition temperature of an amorphous phase can be used as T S. Upon actuation
shape recovery is accompanied by a large change in elastic modulus (~ 2 GPa to 0.002 GPa), low recovery stresses (~
1 to 10 MPa), large recovery strains (> 300%), and thermal hysteresis [6].
Among the many SMPs, shape memory epoxy (SME) have found the broadest applications because of their ample
degree of freedom in property design. Design variables include various types and molecular weights of soft segment,

1
ORAU Post-Doctoral Fellow (US Army Research Lab), School for Engineering of Matter, Transport and Energy,
ASU
2
Regents’ Professor, Ira A. Fulton Professor of Mechanical and Aerospace Engineering, School for Engineering of
Matter, Transport, and Energy, ASU. AIAA Fellow
3
Multi-functional Structures and Dynamics Team, Mechanics Division, Vehicle Technology Directorate U.S. Army
Research Laboratory
4Prognostics and Diagnostics Team Lead, Mechanics Division, Vehicle Technology Directorate U.S. Army Research

Laboratory

Copyright © 2020 by the American Institute of Aeronautics and Astronautics, Inc. All rights reserved.
 type of hard segment, and soft segment/hard segment composition. Depending on the molecular design, SME could
be crystalline or amorphous showing the actuation temperature in a broad range of -20 to 120 °C [7]. Although a
multitude of studies have been published in literature on SMPs and their reinforcement with dispersed carbon nanotube
(CNTs), there has not been significant research done on the use of CNT membranes (buckypaper) in SMPs. Recently,
buckypaper-based nanocomposites have received extensive recognition for the versatility they offer in a variety of
applications such as gas sensing, strain sensing, super capacitance, fuel cell electrodes, fire retardant coatings, artificial
muscles, EMI shielding and self-heating hybrid composites [8-10]. Buckypapers are also known to provide significant
increase in electrical and thermal conductivity in addition to improved elastic stiffness and strength in host polymer
matrices [11]. There is a lack of experimental evidence in explaining the mechanisms that govern the improvement in
mechanical properties and shape recovery response achieved using nano-reinforcements such as CNTs in SMPs.
This paper focusses on developing a CNT buckypaper based shape memory epoxy (CNT-SME) polymer
nanocomposite that can change shape using resistive heating and shows improved static and dynamic mechanical
properties. The CNT-SME nanocomposite possesses tunable damping properties (storage and loss modulus) and can
Downloaded by UNIVERSITY OF TEXAS AT AUSTIN on May 30, 2020 | http://arc.aiaa.org | DOI: 10.2514/6.2020-2233

switch configuration between the deformed geometry and fixed geometry through application of DC voltage. The
CNTs offer a stick-slip mechanism at the SME/CNT interface which allows for efficient energy dissipation and
improved damping characteristics that are of immense benefit to applications in UAVs. The shape morphing capability
will be made energy efficient and the microstructure of the buckypaper-SME is developed with the goal of attaining
significantly improved static and dynamic mechanical properties, thermal and electrical properties, in addition to high
shape recovery efficiency.
II. Fabrication and Experimental details
Materials and Fabrication
The materials used in this paper include multiwalled carbon nanotubes (MWNTs) and monomers for the synthesis
of SME. The shape memory epoxy is synthesized using three types of monomers purchased from Sigma Aldrich Inc.,
and the process is adopted from Xie et al. [1]. The three monomers used are Epon 826, neopentyl glycol diglycidyl
ether (NGDE) and hardener Jeffamine D-230, which were mixed in the molar ratio 0.01: 0.01: 0.01 and degassed for
15 mins at 2% vacuum. The degassed mixture was then poured into Teflon coated silicone molds and cured at 100°C
for 3 hours to obtain neat-SME specimens as shown in Fig 1. This molar ratio results in an actuation temperature of
50°C.
Since SME is not electrically conductive, MWCNTs (from US Research Nanomaterials Inc.) were integrated
within the SME in the form of membranes (buckypaper) to increase its conductivity and enable, resistive heating. The
buckypapers were manufactured in-house using the slurry compression method shown in Fig 2., described in detail in
authors’ previous work [8]. For the fabrication of buckypaper-SME nanocomposites with high MWNT content (for
high thermal and electrical conductivity), buckypaper was sandwiched between two rectangular pieces of bleeder cloth
and the SME was poured over the bleeder cloth surface and spread using a hand layup tool. This allowed the SME to
permeate into the porous buckypaper. Both sides of the buckypaper were impregnated using this layup method and
specimen was cured for a period of three hours at 100ᵒC. The process followed for resin impregnation was not vacuum
assisted to avoid any alteration to the buckypaper’s MWNT network, since resin penetration under higher pressure
can lead to displacement of CNT bundles.
Experimental Characterization
The quality of resin impregnation and CNT/SME interfacial interaction in CNT-SME nanocomposites was
determined by cross-sectional examination using SEM. For the shape-recovery function, the CNT-SME specimens
were prepared by applying silver paint electrodes to obtain minimum contact resistance. The as-prepared specimens
were then resistively heated to 50 °C using a 10V DC supply and manually deformed into a 180° configuration and
cooled to fix the deformed shape. Following this, the shape recovery response was recorded by passing 10V DC as
the specimen regained its original memorized shape.
Dynamic mechanical analysis (DMA) was conducted using Q800 DMA (TA Instruments) in a single cantilever
test set-up. The unsupported length was always 18.2 mm due to the fixture with a specimen thickness and width of
approximately 1.2 mm and 11 mm respectively. A sinusoidal strain was applied to the beam at a magnitude of 250 µε.
Each test was run with a temperature ramp of 2°C/min from 30 °C to 90 °C while discrete frequencies 1, 5, 10, 15,
20, 40, 60, and 80 Hz were interrogated. Dynamic measurements of storage modulus, loss modulus, and loss factor
(E’, E’’, 𝜂) were recorded at the defined frequency and temperature measurements.

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Downloaded by UNIVERSITY OF TEXAS AT AUSTIN on May 30, 2020 | http://arc.aiaa.org | DOI: 10.2514/6.2020-2233

Fig 1. Neat shape memory epoxy specimens

Table 1. Specimen dimensions tested using single-cantilever dynamic mechanical test-setup

Sample Width, mm Thickness,
mm
SME1 11.07 1.29
SME2 10.3 1.35
SME 3 10.15 1.4
SME 4 10.8 1.18
SME-CNT1 10.94 1.16
SME-CNT2 10.8 1.26
SME-CNT3 10.51 1.11
SME-CNT4 10.1 1.18

III.Results and Discussions

Microstructure Analysis
Buckypaper membrane manufactured using the slurry compression method is shown in Fig 2 along with an SEM
scan of the microstructure. The as- formed buckypapers obtained from this technique showed uniform thickness and
a robust structure with an average density of 0.42 g/cc and a porosity of 82%. Qualitative evaluation of surface
smoothness and structural homogeneity was performed using the SEM micrographs of the buckypaper surface. The
low magnification SEM images showed a uniform, crack free and stable structure composed of highly entangled
MWNTs. Uniformly distributed and randomly oriented MWNT bundles and the absence of larger voids (as seen in
Fig 2) suggest homogeneity in microstructure and isotropic material properties. Mainly two types of pores were
observed in the SEM micrographs of buckypaper, the first type is the intra-bundle pores, these are present within a
CNT bundle and the second type is of the inter-bundle pores present between CNT bundles. The uniformity in
thickness was evaluated using SEM micrographs of buckypaper cross-section and th average thickness of the
membranes was found to be 498.06 μm with thickness of samples varying in the range of ±28𝜇𝑚 from the average
value. The nano-porous microstructure allows for full through-thickness SME resin penetration for fabrication of the
CNT-SME nanocomposite with high CNT/SME interfacial interaction. The average electrical conductivity of the as-
formed buckypaper was measured using a 2-probe method and was found to be 13.228 x 103 S/m. After being
impregnated with SME to form the buckypaper nanocomposite the conductivity value dropped to 2.124 x 10-2 S/m.
Fig. 3a shows the buckypaper-SME nanocomposite and the SEM micrographs of CNT-SME cross-section for
evaluation of resin impregnation quality are shown in Fig 3b. Areas for analysis were picked from the low
magnification cross-sectional image (38x) and are represented by small blue boxes. High magnification SEM images
at different depths from the top surface reveal full penetration of the SME through the thickness of buckypaper and
good impregnation quality. The DMA characterization was conducted to better understand the interfacial
interaction/adhesion between SME resin and the embedded CNT buckypaper.

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Downloaded by UNIVERSITY OF TEXAS AT AUSTIN on May 30, 2020 | http://arc.aiaa.org | DOI: 10.2514/6.2020-2233

Fig 2. Buckypaper membrane manufactured using the slurry compression method with SEM scan of the nano-
porous microstructure

(a) (b)
Fig. 3a. Electro-active buckypaper-SME nanocomposite specimens; Fig 3b. SEM micrographs of buckypaper-
SME cross-section for evaluation of resin impregnation quality

Shape Recovery Response of CNT-SME

The shape recovery response of the 180° deformation specimen of electro-active CNT-SME is shown in Fig 4.
The 10V DC electricity is applied at the silver paint electrodes on the specimen surface and it can be seen that the
CNT-SME specimen with 180° deformation is able to change shape to its original (memorized) configuration within
10 s. Initially the specimens take approximately 5s to attain uniform resistive heating, following which the shape
recovery response happens at an accelerated rate. The specimens showed good consistency and repeatability for the
electro-active shape recovery response as determined by 12 separate tests.

Fig 4. Shape recovery response of CNT-SME at 10 V DC stimulation

4
 Dynamic Mechanical Analysis
The response of the storage modulus of neat SME over the temperature range 30-90°C is shown in Fig 5a. A
decrease in storage modulus from about 1.5 GPa to 17.58 MPa was observed as the temperature was ramped up to
90°C. The loss modulus response of the neat SME is shown in Fig 5b. From the loss modulus peak, the glass transition
temperature can be identified as 30-40°C depending on the excitation frequency. Compared to the neat SME, the
nanotube storage modulus response was 2.4 GPa to 32.14 MPa in the range of 30-90ׄ °C. Hence, there was significant
improvement in storage modulus, and the increase was found to be between 60% and 82% in the range of 30-90 °C.
The loss modulus peaks are also at higher temperature for the CNT-SME at 40-50°C. The loss modulus for CNT-SME
was found to be 173.13 MPa, whereas for the neat-SME was found to be 188.9 MPa. Hence there was no significant
change in the loss modulus by incorporating the CNT buckypaper in SME. The significant increase in storage modulus
in the CNT-SME without significant change in loss modulus is a highly beneficial property for damping applications
where the load-bearing capability of the material is drastically increased while maintaining energy dissipation
characteristics.
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In general, the storage modulus response and loss modulus response across the four specimens for each material
type had a similar response, the 1 Hz response can be seen in Fig 7. The storage modulus, loss modulus, and loss
modulus peak can all be seen to increase with the addition of the CNTs. The increase in dynamic mechanical properties
can be attributed to effective interfacial load transfer between the SME matrix and CNTs of the buckypaper membrane.
This is achieved due to high volume of nano-pores of the buckypaper which allow for increased interfacial interaction
between the CNT reinforcement and SME matrix, as shown in Fig 3b.
2500
Storage Modulus, MPa

2000 1 Hz
5 Hz
10 Hz
1500 20 Hz
40 Hz
1000 60 Hz
80 Hz
500

0
25 35 45 55 65 75 85 95
Temperature, deg-C
(a) Storage Modulus vs. Temperature
400
Loss Modulus, MPa

350 1 Hz
300 5 Hz
250 10 Hz
20 Hz
200 40 Hz
150 60 Hz
100 80 Hz
50
0
25 35 45 55 65 75 85 95
Temperature, deg-C
(b) Loss Modulus vs. Temperature
Figure 5. DMA response for neat shape memory epoxy

5
 3000

Storage Modulus, MPa

2500 1 Hz
5 Hz
2000 10 Hz
20 Hz
1500 40 Hz
1000 60 Hz
80 Hz
500
0
25 35 45 55 65 75 85 95
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Temperature, deg-C
(a) Storage Modulus vs. Temperature
450
Loss Modulus, MPa

400 1 Hz
350 5 Hz
300 10 Hz
250 20 Hz
200 40 Hz
150 60 Hz
100 80 Hz
50
0
25 35 45 55 65 75 85 95
Temperature, deg-C
(b) Loss Modulus vs. Temperature
Figure 6. DMA response for carbon nanotube shape memory polymer

2500 500 Ep Nano 1

Storage Modulus, MPa

Loss Modulus, MPa

Ep Nano 1
Ep Nano 2
Ep Nano 2 Ep Nano 3
2000 Ep Nano 3 400 Ep Nano 4
Ep Nano 4 Plain Ep 1
1500 300 Plain Ep 2
Plain Ep 1 Plain Ep 3
Plain Ep 2 Plain Ep 4
1000 Plain Ep 3 200
Plain Ep 4
500 100

0 0
30 40 50 60 30 40 50 60
Temperature, deg-C Temperature, deg-C
(a) Storage Modulus vs. Temperature (b) Loss Modulus vs. Temperature
Figure 7. Dynamic response comparison for neat-SME and CNT-SME nanocomposite at 1 Hz

6
 IV.Conclusions
Shape memory epoxy specimens were fabricated to achieve an actuation temperature of 50°C and were then
incorporated with CNT buckypaper membranes using a novel fabrication approach to increase electrical and thermal
conductivity. Through-thickness SME penetration was achieved through the nano-porous buckypaper membranes
which resulted in high interfacial interaction between the inherent CNTs and SME matrix. This allowed for effective
load-transfer at the CNT/SME interface and electro-active actuation could be achieved through resistive heating using
10V DC electricity. Full shape recovery in the 180° deformation specimen was obtained within 10s of DC stimulation
with consistent repeatability. Through the single-cantilever DMA testing it was found that the storage modulus of
CNT-SME nanocomposite showed an increase of 60% at RT and 82% at 80°C, compared to the baseline-SME
specimens. Although there was a drastic increase in storage modulus of the CNT-SME, there was no significant change
in the loss modulus, indicating that the CNT-SME maintained good energy dissipation characteristics with
significantly increased weight bearing capability.
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Acknowledgments

Research was sponsored by the Army Research Laboratory and was accomplished under Cooperative Agreement
W911NF-17-2-0207. The views and conclusions contained in this document are those of the authors and should not
be interpreted as representing the official policies, either expressed or implied, of the Army Research Laboratory or
the U.S. Government. The U.S. Government is authorized to reproduce and distribute reprints for Government
purposes notwithstanding any copyright notation herein.

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