Materials and Design 135 (2017) 26–36

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Materials and Design

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Adaptive metamaterials by functionally graded 4D printing

M. Bodaghi, A.R. Damanpack, W.H. Liao ⁎
Smart Materials and Structures Laboratory, Department of Mechanical and Automation Engineering, The Chinese University of Hong Kong, Shatin, N.T., Hong Kong, China

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• Fabricating adaptive metamaterials by

functionally graded 4D printing tech-
nology
• Building performance-driven function-
ality directly into SMPs by FDM
• Designing adaptive metamaterials by
self-folding/coiling capabilities
• Characterizing self-folding in terms of
printing-speed and liquefier-temperature
• Developing FEM simulations with materi-
al and geometric non-linearities

a r t i c l e i n f o a b s t r a c t

Article history: This paper shows how fused decomposition modeling (FDM) as a three-dimensional (3D) printing technology
Received 20 July 2017 can engineer adaptive metamaterials with performance-driven functionality built directly into materials. The tac-
Received in revised form 26 August 2017 tic is based on an understanding of thermo-mechanics of shape memory polymers (SMP) and fabrication concept
Accepted 30 August 2017
behind FDM as well as experiments to explore how FDM can program self-foldable metamaterials. Self-folding
Available online 1 September 2017
mechanism is investigated in terms of fabrication parameters like printing-speed and liquefier-temperature
Keywords:
that affect layer-by-layer programming process and shape-change. It can be called a functionally graded 4D print-
Material programming ing so that the structure is fabricated additively and programmed functionally. A finite element (FE) formulation
4D printing based on the non-linear Green-Lagrange kinematic relations coupled with a robust SMP constitutive model is
SMPs established to describe material tailoring in fabrication stage and deformation. Governing equations with mate-
Self-folding/coiling rial-geometric non-linearities are solved by implementing iterative Newton-Raphson method to trace large-de-
Experimental demonstration formation non-linear equilibrium path. FDM and FE solution are then applied to digitally design and fabricate
FE analysis straight/curved beams as structural primitives for adaptive metamaterials that show 1D/2D-to-2D/3D shape-
shifting by self-folding or/and self-coiling. Finally, it is experimentally shown that the 4D printed metamaterials
have great potential in mechanical/biomedical applications like structural/dynamical switches, self-conforming
substrates, self-tightening surgical sutures, self-conforming splints and self-coiling/deploying stents.
© 2017 Elsevier Ltd. All rights reserved.

1. Introduction of the epoch [1]. It has drawn considerable attention in scientific/public

Additive manufacturing (AM), also known as three-dimensional
(3D) printing, has been identified as the second industrial revolution
⁎ Corresponding author.
E-mail address: whliao@cuhk.edu.hk (W.H. Liao).
community and even allowed anyone to be a designer. 3D printers can
fabricate complex and intricate components with significant reduction
in manufacturing time/cost and material wastage. AM techniques avail-
able commercially encompass PolyJet or stereolithography (STL) of a
photo-polymer liquid, material extrusion according to ISO/ASTM
52900 [2] or Stratasys fused deposition modeling (FDM) of polymeric

http://dx.doi.org/10.1016/j.matdes.2017.08.069
0264-1275/© 2017 Elsevier Ltd. All rights reserved.
 M. Bodaghi et al. / Materials and Design 135 (2017) 26–36
filaments and selective laser sintering (SLS) from metallic or polymeric
powders.
Metamaterials as a class of multi-scale structures exhibit thermo-
mechanical properties that are not found in the nature. Their unusual
characteristics arise from their structure and geometry rather than the
matter of which they are composed [3]. In recent years, 3D printing
technology has demonstrated great potential in fabricating metamate-
rials. For instance, employing Object350 Stratasys 3D printer based on
the PolyJet technology, Wang et al. [4] introduced dual-material auxetic
metamaterials composed of elastic joints and stiff walls without insta-
bility during deformation. Computational results from COMSOL finite
element (FE) software and mechanical testing indicated that the dual-
material auxetic metamaterial has distinctly different auxeticity and
mechanical properties form traditional single-material auxetic meta-
materials. In another research work [5], they fabricated metamaterials
with micro-structured reinforcement embedded in soft polymeric ma-
trix. Simulations conducted by ANSYS FE code and uniaxial tension
tests revealed that dual-material designs exhibit strain-stiffening fea-
tures. Using SLS technology for printing Nylon-based rubber-like mate-
rials, Rafsanjani et al. [6] proposed 2D metamaterials that exhibit multi-
stability in response to tension. The results from ABAQUS FE and me-
chanical tests revealed that multi-stable responses were triggered by
snap-through buckling. Mousanezhad et al. [7] investigated 2D auxetic
metamaterials with structural hierarchy fabricated by Eden260V
Stratasys 3D printer based on PolyJet technique. Simulations from
ABAQUS FE code and experiments showed that Poisson's ratio was de-
ceased by hierarchy-dependent elastic buckling introduced at early
steps of compression. Che et al. [8] proposed methods of small geomet-
ric variations to tune the deformation sequence of 2D metamaterial
with multiple stable states fabricated by PolyJet Object260 3D printer.
There was a good agreement between experimental data and those
from analytical solutions and ABAQUS FE code. Naddeo et al. [9] pre-
sented experimental validation of an algorithmic procedure, running
in ANSYS FE code, able to replace continuous mass of a 3D convex
solid with a cancellous bone-inspired space frame organized for having
fibers oriented according to boundary conditions. A cubic unit cell was
designed and sized to analyze mechanical performances of the new po-
rous material. The numerical results obtained from a unit-cell-based
analysis were compared with experimental tensile tests on metallic
3D printed cubic specimens confirming validity of the beam element-
based metamaterial. Recently, Bodaghi et al. [10] studied hyper-elastic
behaviors of soft metamaterials fabricated by FDM 3D printing technol-
ogy in the large-strain regime experimentally and numerically. Results
revealed that unit-cell shape, direction, type and magnitude of loading
had significant influences on anisotropic response of metamaterial
and its instability.
The 3D printed metamaterials reviewed above all are static and in-
animate. Recently, some researchers have employed 3D printing com-
bined with smart materials to offer an innovative method for crafting
active structures [11,12] and metamaterials [12–15]. It is called 4D
printing where a capacity for movement is latent within the 3D printed
structure. 4D printed structures are able to actively transform configura-
tions and evolve over time in response to surrounding stimuli. Among
active materials, shape memory polymers (SMPs) [16–19] and hydro-
philic polymers have been used because of their capability to produce
shape change subjected to an external stimulus such as heat and humid-
ity fields. For instance, Mao et al. [13] introduced a 2D metamaterial lat-
tice with shape-changing feature via printing SMPs and hydrogels by
PolyJet Objet260. The 4D printed structure expanded by immersing in
water with low and high temperatures, cooling down, drying and then
shrinked upon putting in high-temperature water. Bodaghi et al. [14]
proposed a self-expanding/shrinking 2D metamaterial lattice by print-
ing fibers of SMPs into flexible matrix using PolyJet Object500 3D print-
er. The metamaterials needed to be programmed through a heating-
loading-cooling-unloading process after fabrication. Recently, Ding et
al. [15] printed self-foldable metamaterials consisting of stiff and soft
27
polymers by inducing a compressive strain during photo-polymeriza-
tion in PolyJet process.
Although it would be straightforward to program 3D printed ob-
jects/metamaterials for simple shape change and/or function, it might
be a significant challenge for complicated changes/functions. Further-
more, it is difficult to perform manipulations needed to program mate-
rials manually in certain situations on large or small scales or in remote
locations such as in space or inside human-body.
This paper aims at demonstrating an approach to design and manu-
facture adaptive metamaterials enabled by functionally graded (FG) 4D
printing technology without application of any programming process
and external manipulation. The approach is based on an understanding
of thermo-mechanics of SMPs and FDM printing technique. Five param-
eters as material/surface of platform, its temperature, printing speed,
liquefier temperature and delay time for printing each layer are as-
sumed as effective parameters that may influence material tailoring. Ex-
periments are conducted to explore self-folding features in terms of
relevant fabrication parameters as well as theoretical framework to de-
scribe phenomena/mechanisms. It is experimentally shown that FDM
printing can program SMPs during fabrication in a graded manner for
desire functions. An FE formulation on the basis of the non-linear
Green-Lagrange strains coupled with a robust SMP constitutive model
is developed and solved implementing iterative incremental Newton-
Raphson technique. It is then applied to explore mechanisms behind
FG 4D printing and structural shape-change during activation. The
printing method and FE solution are then employed to digitally design
and fabricate self-foldable straight and curved beams as structural prim-
itives for adaptive metamaterials. The feasibility of 1D/2D-to-2D/3D
shape-shifting by self-folding or/and self-coiling features is shown, ex-
perimentally and numerically. Finally, some experiments are conducted
to demonstrate the potential applications of adaptive metamaterials in
mechanical and biomedical engineering devices like structural/dynam-
ical switches, conformal substrates, surgical sutures, stents and splints.
2. Concepts and models
The functionally graded 4D printing concept is developed here based
on an understanding of the FDM printing technology and shape memory
effects. The approach also includes experiments to show its feasibility as
well as a mathematical modeling to describe the mechanism behind it.
2.1. FG 4D printing concept
The main idea is combination of FDM printing method with SMPs to
create potentials in the design and development of adaptive metamate-
rials. SMPs have capacity of retaining a temporary shape and recovering
to original shape when subjected to environmental stimulus like heat.
III
IV
II
Strain
V
I
Temperature
Fig. 1. Schematic of the shape memory effect in the strain-temperature plane.
28 M. Bodaghi et al. / Materials and Design 135 (2017) 26–36
Fig. 1 displays a standard step-by-step thermo-mechanical protocol of
programming for SMPs in the framework of a strain-temperature
phase diagram. It starts at a strain/stress-free state at a low temperature
less than transition temperature, T = Tl b Tg, where SMP is stable in a
glassy phase. It is then heated above the transition temperature range,
T = Th N Tg (step I). Next, SMP stable at rubbery phase is loaded mechan-
ically to achieve a maximum strain, εm (step II). The strain is kept fixed
and the material is cooled down to the low temperature, Tl, (step III). In
this step, the rubbery phase gradually converts to the glassy phase
memorizing inelastic strains. SMP is finally unloaded while a pre-strain
remains in the material, εp (step IV). For the sake of activation, SMP is
heated to the high temperature, Th, that relaxes strain and recovers
the permanent shape (step V). This is known as a free-strain recovery.
Now the scope is to implement the above programming protocol dur-
ing printing process. Among various standard 3D printing technologies,
FDM technology applies a similar thermo-mechanical procedure on the
material during fabrication. Fig. 2 displays a schematic of the base of
FDM procedure. The printer performs hot extrusion of a polymeric fila-
ment through a circular nozzle. The material is heated inside liquefier in
temperature Tln that is above its Tg and then deposited onto the platform
by the printer head moving at speed Sp. In fact, the material with high
temperature is stretched that is similar to the heating-loading process de-
scribed above (steps I and II). After deposition, the printed layer cools and
solidifies and bonds with the platform that is again similar to the step III in
Fig. 1. Once a layer is completed, the build platform advances downward
and printing head proceeds to deposit the next layer. Finally, the thermo-
mechanical programming protocol is completed by mechanical unloading
through removing the printed object from the platform, like step IV.
Therefore, it can be found that FDM has potential to fabricate 3D SMP
architectures and impose inelastic pre-strain that may drive shape
memory effects in a prescribed way. In this respect, some printing pa-
rameters are supposed to be effective on SMP programming process.
For instance, printing speed may have a key role in determining pre-
strain value. It would reasonable that more speed provides more me-
chanical loading that may induce more pre-strain, see Fig. 1, step II.
While all layers are printed with the same printing speed, their surface
experiences different thermal/connection conditions. For example,
while the lower layer, as the first printing layer, is deposited on the
stiff polymeric printer bed, other layers above it are laid on the already
printed SMP layers, see Fig. 2. Thus, platform material/surface condi-
tions may be important and affect bonding and fixed strain conditions
in the first layer during cooling and solidifying. Regarding thermal sur-
face conditions, temperature of build platform may also affect bonding
conditions and pre-strain value in the first layer deposited on it. Fur-
thermore, the first layer and layers above it, except the end layer, are
Liquefier
Extrusion nozzle Printing direction
Upper layer Molten material
(end layer)
Re-heated zone
Middle layers Solidified material
Lower layer
(first layer)
Build platform
Fig. 2. FDM printing process.
heated by the hot extruded material when the machine is depositing
the next layer above them, see Fig. 2. This extra heat definitely affects
the pre-strain value and reduces it. Therefore, the nozzle temperature
takes account into a significant parameter affecting the pre-strain.
Moreover, the temperature of the layer that is being heated is another
parameter. This temperature is directly related to the delay time be-
tween printing each layer. On the other hand, the upper layer as the
end layer never gets any heat since the nozzle leaves it at the end of
printing stage so that its pre-strain might be the highest one.
Finally, it can be concluded that printed layers may be programmed
in different manners and get various values of pre-strain. Also, five pa-
rameters as material/surface of platform, its temperature, printing
speed, nozzle temperature and delay time for printing each layer can
be considered as effective parameters that may influence pre-strain
values in printed layers. From literature terminology, this printing pro-
cess can be called functionally graded 4D printing. The 4D printing pro-
cess could program SMPs during fabrication inducing pre-strain. On the
other hand, this programming could be done in functionally graded
manner. While inelastic material property like pre-stain may change
layer-by-layer gradually, there are five parameters to control and pro-
gram the object for desire functions. In this research, FDM printing tech-
nology is implemented to fabricate adaptive metamaterials with
performance-driven functionality built directly into the materials.
2.2. Materials and printing
In this study, polyurethane-based SMP filaments with a diameter of
1.75 mm and glass transition temperature of 60°C is employed (SMP
Technologies Inc., Tokyo, Japan). All SMP samples are manufactured by
a New Creator Pro desktop 3D printer developed by FlashForge. New Cre-
ator Pro is a low cost desktop printer that extrudes filaments with a
0.4 mm nozzle size. It can be controlled with any open-source software.
In this work, Craft-Ware software is utilized to produce G-code files
from STL files and to command and control the procedure parameters
of liquefier temperature and printing speed. As default, liquefier temper-
ature is set as 230°C while temperatures of build platform and chamber
remain as room temperature, 24°C. Also, the printing speed and layer
height are set as 20 mm/s and 0.2 mm, respectively. Thermo-mechanical
properties of the printed SMPs are identified by a dynamic-mechanical
analyzer (DMA, NETZSCH, Model 242). To this end, a beam sample is
printed with the dimension of 15 mm (length) × 1.6 mm (width)
× 1 mm (thickness). DMA test is carried out in an axial tensile way with
frequency of force oscillation 1 Hz and heating rate 5°C/min ranging
from −20 to 90°C. Applied dynamic stress to static stress is around 1.5.
The temperature-dependent results in terms of storage modulus, ES, and
tan (δ) are presented in Fig. 3. As it can be found, the storage modulus
in glassy phase, e.g. in Tl =20°C, is around ESg =1656MPa while it reduces
drastically to 3.18MPa at rubbery phase, e.g. in Th =90°C. A high ratio of
storage modulus downfall equal to 520 is observed. Using the formula
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
for Young's modulus defined as E ¼ ES 1 þ ð tanðδÞÞ2 , Eg = 1657 MPa
Fig. 3. DMA measurement results for the 3D printed SMP in terms of tan (δ) and storage
modulus.
 M. Bodaghi et al. / Materials and Design 135 (2017) 26–36
and Er =3.26 MPa can be calculated from the DMA test. The prominent
peak in the graph of tan(δ) associated with the glass transition tempera-
ture is read as Tg =60°C. Henceforward, sub-scripts ‘g’ and ‘r’ signify the
glassy and rubbery phases, respectively.
Next, Young's modulus (E), Poisson's ratio (ν) and thermal expan-
sion coefficient (α) of the 3D printed SMPs in glassy and rubbery phases
are specified. To this end, a sample is printed based on the geometry and
dimensions characterized by the ASTM D638 standard [20]. For tensile
tests at low and high temperatures, a Tinius Olsen® H5kS machine
(Tinius Olsen, Horsham, PA, USA) with a 5 kN load-cell and a home-
made thermal chamber is utilized. Material properties extracted from
thermo-mechanical tests are presented in Table 1. The results show
that there is an excellent agreement between measured Young's modu-
lus from DMA and tensile tests. Also, it is observed that, while Poisson's
ratio has an increasing trend during phase transformation from glassy to
rubbery, thermal expansion coefficient does not change so that it is the
same at both phases.
2.3. Feasibility demonstration
In this section, feasibility of fabricating adaptive SMP metamaterials
by FG 4D printing is demonstrated experimentally. Metamaterials are
designer matter with exotic thermo-mechanical characteristics general-
ly adjusted by their architecture rather than their chemical composi-
tions. They comprise an arrangement of mechanical elements with
tunable behaviors. SMP straight and curved beams as structural primi-
tives for metamaterials are fabricated by FDM printing method. Geom-
etry and dimensions of a typical printed curved beam with L mean
length, b width, h thickness, R mean radius and opening angle of θ are
shown in Fig. 4. A Cartesian coordinate system (xi, i = 1, 2, 3) is located
on the mid-plane of the curved beam. Among five parameters that
may affect pre-strain regime in the 4D printed objects, the effects of
the printing speed, Sp, and nozzle temperature are examined here. It
should be noted that, the nozzle temperature is unknown while tem-
perature of liquefier, Tln, is known and controllable by the Craft-Ware
software. Therefore, the effect of nozzle temperature is investigated
through temperature of liquefier.
Four straight 1D beams with L = 15, b = 1.6, h= 1 mm , θ ≅ 0 are fab-
ricated by printing parameters of Sp = 30 , 40 mm/s and
Tln = 210 , 230°C as shown in Fig. 5a. The print raster is assumed to be
along the length direction, x2 direction. In order to activate the printed
objects, they are heated by immersing into hot water with a prescribed
temperature of 90°C that is 30°C more than Tg = 60°C. All the following
samples are also activated by the same method and with the same tem-
perature. The configurations of the elements after hating-cooling pro-
cess are presented in Fig. 5b. Their geometric parameters, L′ , θ′,
measured in the x2 − x3 plane are also included in Fig. 5b.
The preliminary conclusion drawn from Fig. 5 is this primitive is able
to change its configuration over time in the presence of hot water as a
heating source. It means they are already programmed and pre-stained
during fabrication and are able to react to changes in the environment to
evoke the shape-memory effect. When the primitive printed in the
x1 − x2 plane is exposed to high temperature, it shrinks and bends to
form a curved beam in the x2 − x3 plane and remains folded permanent-
ly, see Fig. 5b. It can be considered as a self-folding 1D-to-2D process
that may enable pre-designed planar templates to transform into 3D
structures. This self-bending observed is due to an unbalanced pre-
strain induced during fabrication and deposited along x2 direction. In
Table 1
Thermo-mechanical material properties of the 3D printed SMP.
Parameter Glassy phase Rubbery phase
E (MPa) 1660 3.3
ν 0.35 0.4
α(10−4K−1) 1 1
29
Fig. 4. Illustration of the 4D printed primitive.
fact, unbalancing in pre-strain distributed through the thickness leads
a mismatch in free-strain recovery inducing curvatures. It can also be
concluded that pre-strain may have an increasing trend through the
thickness upward from the lower to the upper layer that may enable
the overall shape to be changed toward the upper layer. Fig. 5 reveals
that printing speed and liquefier temperature have significant effects
on pre-stain regime through the thickness direction. It is found that
any increase in the liquefier temperature has a negative effect on the
pre-strain. This is in accordance with what has been explained in
Section 2.2. The hotter the liquefier, the less the pre-strain. It is also
seen that enhancing printing speed increases the pre-stain value and
consequently bending deformation. It is reasonable since more speed
provides more mechanical loading that induces more pre-strain, c.f.
Fig. 1. Therefore, it can be called a functionally graded 4D printing so
that the structure is fabricated additively and programmed functionally.
Next, it is needed to explore the pre-strain regime in the 4D printed
primitives for enhancing design capabilities.
2.4. Theoretical modeling
Adaptive structures like metamaterials fabricated by FG 4D printing
method can be designed based on the theoretical understanding of the
programming mechanism and thermo-mechanical behaviors of the
printed elements. This section is dedicated to develop constitutive
modeling and mathematical formulation to describe thermo-mechani-
cal mechanisms behind programming in fabrication stage and deforma-
tion during activation.
2.4.1. SMP phase transformation
A robust phenomenological constitutive model basically presented
in Refs [21,22]. is reformulated here to estimate SMP phase transforma-
tions during thermo-mechanical loadings in a straightforward manner.
SMP materials show a combination of glassy and rubbery features.
The volume fractions of the glassy and rubbery phases are defined as:
Vg Vr
ηg ¼ ;η ¼ ð1Þ
V r V
where V represents the total volume of the SMP while Vg and Vr are vol-
umes of the glassy and rubbery phases, respectively. Since the summa-
tion of these volume fractions should be unity, i.e. ηg + ηr = 1, the
rubbery volume fraction can be expressed in terms of glassy one as:
ηr ¼ 1−ηg ð2Þ
that means there is just one independent volume fraction. As a generally
well-known assumption, ηg and Vg are considered to be dependent only
on temperature variable, T:
ηg ¼ ηg ðT Þ; V g ¼ V g ðT Þ ð3Þ
30 M. Bodaghi et al. / Materials and Design 135 (2017) 26–36

Fig. 5. Exprimental illustration on the concept of the functionally graded 4D printing: (a) straight beam printed with different printing speed and liquefier temperature, (b) configuration of
the printed beam after heating-cooling process.

The volume fraction of the glassy phase can be determined accord- in which α is thermal expansion vector and the expression inside the in-
ing to the nature of SMP phase transformation fitting experimental tegral follows the rule of mixture. T0 is also reference temperature.
DMA data. Considering the results presented in Fig. 3, an explicit func- Next, εin that is an unknown quantity is described based on glassy-
tion in terms of trigonometric functions is introduced to interpolate rubbery phase transformation mechanisms. During cooling, the materi-
storage modulus from DMA results as: al is frozen and the rubbery phase changes gradually to the glassy phase.
    In this respect, the strain is assumed to be stocked in the SMP in propor-
tanh a1 T g −a2 T − tanh a1 T g −a2 T h tion to the transformed rubbery phase strain. It is formulated as:
ηg ¼ −     ð4Þ
tanh a1 T g −a2 T h − tanh a1 T g −a2 T l
ε_ in ¼ η_ g εr ð7Þ
in which ai (i = 1, 2) are selected to match DMA curve.
SMP phase transformation occurs by nucleation and growth of plate- where a superposed dot denotes rating function.
let inclusions, mainly directed in the stress direction [21]. Thus, it is con- Regarding the heating, the strain stored is assumed to be released
sidered that glassy and rubbery phases are connected to each other in gradually in proportion to the volume fraction of the glassy phase with re-
series. By considering the fact that the 4D printed objects may experi- spect to the previous glassy phase and stored strain. It is stated as:
ence small strains and moderately large rotations as observed in Fig. 5,
η_ g
a general assumption of additivity of strains is adopted in the form ε_ in ¼ εin ð8Þ
ηg
 
ε ¼ ηg εg þ 1−ηg εr þ εin þ εth ð5Þ
and implies that the strain release is independent of the stress/strain state
during heating.
where ε denotes total strain vector signifying total deformation of the In order to derive stress state, the second law of thermo-dynamics in
material; εg and εr represent elastic strains in the glassy and rubbery the sense of Clausius-Duhem inequality should be fulfilled. By consider-
phases, respectively; εin is associated to inelastic strain due to phase ing ε and T as external control variables, and εg ,εr , εin and ηg as internal
transformations; and εth is called thermal strain and defined as: variables and adopting Helmholtz free energy density functions and fol-
Z T lowing standard arguments, stress quantity, σ, can be derived as:
  
εth ¼ α r þ α g −α r ηg ðT Þ dT ð6Þ
T0 σ ¼ σg ¼ σr ð9Þ
 M. Bodaghi et al. / Materials and Design 135 (2017) 26–36 31

in which Heating:

σg ¼ Cg εg ; σr ¼ Cr εr ð10Þ ηg
εin ¼ εkin ð17Þ
ηkg
and C represents elasticity stiffness matrix defined as:
Finally, by considering updated values for inelastic strain, the stress-
2 3
1−ν ν ν 0 0 0 strain relationship (Eq. (12)) can be updated and unified for heating and
6 ν 1−ν ν 0 0 0 7 cooling processes as:
6 7
6 ν ν 1−ν 0 0 0 7
6 ð1−2ν Þ 7  
E 6 0 0 0 0 0 7
C¼ 6 7 σ ¼ Cu ε−β εkin −εth ð18Þ
ð1 þ νÞð1−2ν Þ 6
6
2
ð1−2νÞ
7
7
6 0 0 0 0 0 7
6 2 7
4 5
ð1−2νÞ where Cu and β called unified parameters need to be set for heating and
0 0 0 0 0
2 cooling as:
ð11Þ
8  −1
>
> _
< Cu ¼ I þ Δηg Sr Ce Ce ; β ¼ 1 Tb0
Eq. (9) is consistent with the fact that stress evolutions of each phase ηg ð19Þ
> _
are equal in the series model. : Cu ¼ Ce ; β ¼ ηk
> TN0
g
Next, in order to derive constitutive stress-strain relationship for
SMP materials consists of glassy and rubbery phases, strains from Eq.
(10) are substituted into Eq. (5) that yields: Eq. (18) reveals that the developed constitutive model for SMPs
looks like a linear thermo-elastic model with non-linear material prop-
σ ¼ Ce ðε−εin −εth Þ ð12Þ erties and having inelastic strains known from the preceding time step.

in which 2.4.2. Equilibrium equations

The deformation of the 4D printed objects are expressed in terms of
  −1 the Green-Lagrange strain vector accounted for small strains and mod-
Ce ¼ Sr þ ηg Sg −Sr ð13Þ erately large rotations. The non-linear strain-displacement kinematic
relations can be expressed in a matrix operator form as:
is called an equivalent stiffness matrix and looks like Reuss formula in  
1
the general theory of homogenization. Also, S denotes the compliance ε¼ DL þ DN u ð20Þ
matrix defined as C−1. 2
From a computational point of view, the non-linear SMP behavior
where u indicates generalized displacement vector defined as:
during heating/cooling can be treated as an explicit time-discrete
stress/strain-temperature-driven problem. The time interval [0, t] is 8 9
< u1 =
partitioned into sub-increments and the discretized problem is solved
u ¼ u2 ð21Þ
over a general interval [tk, tk + 1]. For notation simplicity, the variables : ;
u3
with superscript k are associated to the preceding time-step whereas
the ones without superscript are referred to the current step k + 1. It and ui (i = 1, 2, 3) represents displacement components of a generic
is assumed that control variables ε (or σ), T and ηg at time t as well as point within the printed object domain along xi (i = 1, 2, 3) axes,
the solution at time tk are known. The evolution Eqs. (7) and (8) for respectively.
the inelastic strain during cooling/heating can be discretized by implicit Denoting partial differentiation with respect to the spatial coordi-
backward-Euler integration scheme as: nates xi (i = 1,2,3) as:

εin ¼ εkin þ Δηg εr ð14aÞ ∂ ∂ ∂

¼ ∂1 ; ¼ ∂2 ; ¼ ∂3 ð22Þ
∂x1 ∂x2 ∂x3
Δηg
εin ¼ εkin þ εin ð14bÞ DL and DN known as linear and non-linear operator matrices are de-
ηg
fined by:
where 2 3 2 3
∂1 0 0 ∂1 u1 ∂1 ∂1 u2 ∂1 ∂1 u3 ∂1
60 ∂2 07 6 ∂2 u1 ∂2 ∂2 u2 ∂2 ∂2 u3 ∂2 7
6 7 6 7
60 ∂3 7 6 ∂3 u1 ∂3 ∂3 u2 ∂3 ∂3 u3 ∂3 7
Δηg ¼ ηg −ηkg ð15Þ DL ¼ 6
60
0 7; DN ¼ 6 7
6 ∂3 ∂2 7
7
6 ∂2 u1 ∂3 þ ∂3 u1 ∂2
6 ∂2 u2 ∂3 þ ∂3 u2 ∂2 ∂2 u3 ∂3 þ ∂3 u3 ∂2 7
7
4 ∂3 0 ∂1 5 4 ∂1 u1 ∂3 þ ∂3 u1 ∂1 ∂1 u2 ∂3 þ ∂3 u2 ∂1 ∂1 u3 ∂3 þ ∂3 u3 ∂1 5
By using Eqs. (10) and (12) to substitute εr and σ, and preforming ∂2 ∂1 0 ∂1 u1 ∂2 þ ∂2 u1 ∂1 ∂1 u2 ∂2 þ ∂2 u2 ∂1 ∂1 u3 ∂2 þ ∂2 u3 ∂1

some mathematical simplifications, the inelastic strain (Eqs. (14a) and ð23Þ
(14b)) can be updated explicitly for cooling and heating processes in
stress and strain control manners as: It can be shown that variation of strain field is derived as:
Cooling:
δε ¼ ðDL þ DN Þδu ð24Þ
εin ¼ εkin þ Δηg Sr σ for stress control mode ð16aÞ
Equations of equilibrium as well as the corresponding boundary
conditions are derived in a straightforward manner from the principle
 −1  
εin ¼ I þ Δηg Sr Ce εkin þ Δηg Sr Ce ðε−εth Þ for strain control mode
of the minimum total potential energy as:

ð16bÞ δU−δW ¼ 0 ð25Þ

32 M. Bodaghi et al. / Materials and Design 135 (2017) 26–36

in which variations δU of the strain energy and δW of the work done by They all are defined as:
the external loads need to be substituted with their definitions in terms
of stresses, forces, virtual strains and virtual displacements. ðDL ΨÞT Cu ðDL ΨÞT dV
K0 ¼ ∭ V  
Starting from the variation of the strain energy 1
KL ¼ ∭V ðDL ΨÞT Cu ðDN ΨÞT þ ðDN ΨÞT Cu ðDL ΨÞT dV
2
1
δU ¼ ∭V δεT σ dV ð26Þ KN ¼ ∭V ðDN ΨÞT Cu ðDN ΨÞT dV
8 29 8 9
< Q1 = < Q i−1 = ð33Þ
Fm ¼ Q 2 ; Q i ¼ ⋮ ; i ¼ 1; 2; 3
and using stress definition (Eq. (18)), it can be rewritten as: : ; : ;
Q 2 ui−20
  Fkin ¼ β∭ V ðDL ΨÞT þ ðDN ΨÞT Cu εkin dV
δU ¼ ∭ V δεT Cu ε−β εkin −εth dV ð27Þ  
F th ¼ ∭V ðDL ΨÞT þ ðDN ΨÞT Cu εth dV

where V signifies the volume of the printed structure. The potential en- It should be mentioned that, εkin and εth are known variables through
ergy of external loads can be also expressed as: the SMP element that are held into the volumetric integrals. In this re-
spect, T is assumed to be constant through the element volume while
δW ¼ δuT Q ð28Þ the Gauss-Legendre numerical integration method is implemented to
calculate the integral including εkin along xi (i = 1, 2, 3) coordinates. A
3 × 3 ×3 discrete grid Gauss points having 3 points along each xi axis is
where
considered in this study. Finally, in order to construct global FE
8 9 governing equations, Eq. (32) is assembled for all elements that results
< Q1 = in:
Q ¼ Q2 ð29Þ
: ;     
Q3 k
K0 þ KL U þ KN U U ¼ Fm þ Fin þ Fth ð34Þ

denotes point forces in the xi (i = 1,2,3) directions. Eq. (34) represents a non-linear set of equations due to geometrical
non-linearity. Consequently, an iterative solution procedure such as
2.4.3. FE methodology Newton-Raphson technique [23] is implemented to solve the problem
In this division, a Ritz-based FE solution is developed to predict func- in a step-by-step mode. By knowing temperature T, mechanical loading
tionally graded 4D printing process and thermo-mechanical behaviors Fm and inelastic strain field εkin from the previous load-step, new value of
of 4D printed metamaterials. A 20-noded quadratic serendipity hexahe- U is calculated iteratively. Afterwards, the strain and stress state can be
dron element with 3 degrees of freedom (i.e. ui (i =1,2, 3)) per node is computed using Eqs. (30), (20) and (18), respectively. Finally updated
proposed for the present problem. Considering quadrilateral shape inelastic strains at all Gauss points are calculated through either Eqs.
functions ψi(x1, x2, x3) (i = 1…20) [23], the displacement vector u can (16a) and (16b) or (17) for cooling or heating process.
be approximated in terms of nodal-mechanical variables as: It should be noted that, in the printer nozzle, the polymer melt is
under stress, with part of the deformation energy being stored elastical-
u ¼ ΨU ð30Þ ly. As the polymer melt leaves the nozzle, stresses are relaxed and the
elastically stored energy is released, leading to radial expansion of the
in which Ψ and U are elemental interpolating matrix and generalized melt referred to as die swelling. The phenomenon may affect pre-strain
nodal displacement vector defined as: regime induced by 4D printing process. For predicting die swelling and
investigating its effects on pre-strain regime, viscoelastic-based SMP
2 3 constitutive model should be developed, even though it is beyond the
ψ 0 0 objective of the present work. For more details on modeling of visco-
Ψ ¼ 0 ψ 05
4
elasticity in SMPs and die swelling, one may refer to [24–26].
0 0 ψ
ψ ¼ fψ1 ⋯ψ20 g
ð31Þ 3. Adaptive metamaterials: design-fabrication-simulation
0 ¼ f8
0⋯09 g 8 9
< u1 = < ui−1 =
U ¼ u2 ; ui ¼ ⋮ ; i ¼ 1; 2; 3 In this part, the developed computational tool is first implemented
: ; : ;
u3 ui−20 to describe thermo-mechanical mechanisms behind SMP material tai-
loring during fabrication stage. It is then applied to digitally design
primitives fabricated by FG 4D printing for adaptive metamaterials
where ui−j (i = 1…3;j = 1…20) are mechanical nodal variables.
By substituting the discretized displacement field (Eq. (30)) into the
strain field (Eq. (20)) and its variation (Eq. (24)) and subsequent results
into the virtual energies (Eqs. (27) and (28)) and the principle of
minimum total potential energy (Eq. (25)), FE governing equations for
a generic element can be derived as:

ðK0 þ KL ðUÞ þ KN ðUÞÞU ¼ Fm þ Fkin þ Fth ð32Þ

where K0 represents the constant stiffness matrix while KL and KN are

linear and quadratic stiffness matrices which are dependent on the
nodal displacements. Also, Fm , Fkin and Fth are load vectors induced by
mechanical loading, SMP phase transformation and thermal loading
due to temperature change from a reference temperature, respectively. Fig. 6. Model prediction for Young's modulus and comparison with experimental DMA data.
 M. Bodaghi et al. / Materials and Design 135 (2017) 26–36 33

Table 2 and Table 2 also reveal that the 4D printing process with parameters
Predictions for pre-strain (%) regime of the SMP beam printed in various printing speeds of Sp = 40 mm/s , Tln = 230°C and Sp = 30 mm/s , Tln = 210°C induces
and liquefier temperatures.
similar pre-strain into the beam structure and results in nearly similar
Location Sp = 30 mm/s Sp = 40 mm/s configuration after activation. Finally, it can be concluded that control
Tln = 210°C Tln = 230°C Tln = 210°C Tln = 230°C of printing speed and liquefier temperature may allow the realization
of self-folding 3D structures. The pre-strain regime and its values re-
Upper layer 30.5 15 37 31.3
Middle layers 25.3 10.1 29 24 ported in Table 2 may serve as benchmark data to researchers dealing
Lower layer 20 5.6 21 17 with design, simulation and fabrication of FG 4D printed object. From
a technical viewpoint, objects printed with high temperatures may
have a strong interface bonding. Therefore, the following results are
that can reveal self-assembly functions. Finally, several 3D adaptive printed with fabrication parameters of Sp = 40mm/s and Tln = 230°C.
metamaterials with shape-shifting features that illustrate broad poten-
tial applications are presented. 3.2. Primitives for adaptive metamaterials

3.1. Pre-strain regime prediction
The first step is to predict pre-strain value induced in all printed
layers during fabrication. In order to achieve the investigation, phase-
transformation parameters including a1 , a2 , Tl and Th presented in Eq.
(4) need to be calibrated. Using DMA results already displayed in Fig.
3, they are set as 0.15, 0.145 and 20, 100°C, respectively. Young's modu-
lus calculated from Eq. (13) is illustrated in Fig. 6 and compared with ex-
perimental data from DMA. The results reveal that the trigonometric
function is able to successfully simulate SMA phase transformation in
a smooth and gradual manner as observed in experiments.
The initial and final status of the straight beams as displayed in Fig.
5 are given as inputs and applied to FE tool. Implementing a try and
error scheme, pre-strain regime in terms of its value at lower, middle
and upper layers is computed and presented in Table 2 for various
printing speeds and liquefier temperatures. As it can be seen, pre-
strain has an almost linearly increasing trend through the thickness
upward inducing self-folding feature. During heating, the pre-strain
is released non-uniformly. This un-balancing produces bending defor-
mation and leads to self-folding. In this respect, any increase in print-
ing speed or liquefier temperature has positive and negative effects on
the induced pre-strain value and consequently structural deformation
as observed in experiments, see Fig. 5. The results presented in Fig. 5
Five 2D primitives with different shapes are proposed for designing
adaptive metamaterials with self-folding feature. First, one straight and
two curved beams with the same length, width and thickness
(L = 34, b = 1.6,h = 1 mm) and different angels of θ = 0 , 60 and 90° are
printed as illustrated in Fig. 7a. The configurations of the primitives
after hating-cooling process are displayed in Fig. 7b. The FE model is
also implemented to simulate structural deformations using pre-strain
regime reported in Table 2 for Sp = 40 mm/s and Tln = 230°C. Simula-
tions are also included in Fig. 7c. The color bar in Fig. 7c displays trans-
verse displacement (u1), along X1-direction, to maximum transverse
displacement (u1m). In this aspect, u1m is reported in Fig. 7c. The results
show that, while straight beam has a shape-shifting via self-bending
mechanism, curved beams experience both bending and cross-sectional
rotation at the same time. In fact, once activated by hot water, the free-
strain recovery stands the curved beam up while natural curvature
leads the structure to rotate along the length direction. It results in
forming a conical ring with rectangular cross-section that is oblique
with respect to the ring axial direction. From a topology point of view,
in fact, inner and outer edges of the curved beam with small and large
radii make the apex and base of truncated conical shell-like structures.
Furthermore, it is interesting to note that all beams with the same
length either in curve shape or straight transform to rings with similar
mean diameters (≅ 7 mm) so that both end edges meet each other.

(a)

(b)

(c)

u1m=0 mm u1m=17.4 mm u1m=22.4 mm

Fig. 7. Straight and curved 4D printed primitives: (a) initial configuration after printing, (b) final configuration after heating-cooling, (c) simulation.
34 M. Bodaghi et al. / Materials and Design 135 (2017) 26–36

Fig. 8. Wave-shaped (a–c) and extended wave-shaped (d–f) 4D printed primitives: (a, d) initial configuration after printing, (b, e) final configuration after heating-cooling, (c, f) simulation.

Their difference is cross-section angle with respect to the ring axial direc- will be required to print some supportive material that may affect surface
tion is measured as 22 and 31° for initial primitives printed with angels of quality and mechanical properties/strengths of the spring.
60 and 90°. Regarding simulation, it is noted that the FE model-solution is It is interesting to note that the helical is permanent shape of the self-
able to correctly replicate main characteristics observed in the experi- coiling structure. It means it is possible to program it into any other
ments. In this aspect, maximum error of 2% is achieved for mean diame- shape as a temporary shape and then achieve free shape recovery upon
ters that is acceptable. It should be mentioned that the simulations have heating. For instance, the spring as depicted in Fig. 9a is heated by im-
been performed using pre-strain information obtained from the previous mersing in hot water with temperature of 90°C and then straightened.
test (Table 2). The good qualitative and quantitative agreement obtained Next, it is kept fixed and cooled down to the room temperature followed
with the same pre-strain for both tests confirms accuracy and reliability by mechanical unloading, see Fig. 9b. It looks like a straight beam with
of the predicted pre-strains in the previous section. 54 mm length. Heating the straightened 1D beam will result in fully
These self-foldable primitives can serve as elements of adaptive shape recovery as shown in Fig. 9.
metamaterials for complicated shape-changes or complex functions. It
is worth mentioning that, while the mass of the printed elements re-
mains constant during phase transformation, the geometry and stiffness
are changed. It means dynamic properties are changed as the 4D printed
object is heated. They could be a good candidate to be employed as
adaptive structural/dynamic switches providing different tempera-
ture-dependent dynamic characteristics. For instance, they may be
promising in designing self-foldable metamaterials for affecting reso-
nance behaviors [27].
Next, another primitive with geometrical parameters of the curved
beam described above with L = 34 , b = 1.6 , h = 1 mm and θ = 60° is
printed in a symmetric wave-shaped form. In fact, it is composed of
two arcs with θ = 30°. The configurations of the sample after printing
and heating-cooling are demonstrated in Fig. 8a and b. Simulations are
also embedded in the third part of the figure. As it can be seen, the 2D
wave-shaped primitive gets into a ring shape but has a derivation along
the circumferential direction. A qualitatively and quantitatively good
agreement between experiment and simulation is also observed. The
final shape looks like a helix of helical spring. It brings the idea that the
planar wave-shaped component may be employed for designing adap-
tive metamaterials in spring shape. The wave shape template is then ex-
tended in both directions to have four segments of arcs with θ=30°. The
counterpart of Fig. 8a–c for the current example is depicted in Fig. 8d–f.
The results reveal that the extended wave-shape template transfers to a
helical spring with two coils after heating-cooling process. It can be a
Fig. 9. Thermo-mechanical programming on the self-coiling spring: (a) initial
demonstration of 2D to 3D shape-shifting by self-coiling mechanism. configuration after printing-heating-cooling process, (b) final configuration after
Thus, it can be called a self-coiling spring. Beyond self-coiling feature, a heating-straightening-cooling-unloading (the straightened beam is recovered back to
static spring could be printed directly by FDM 3D printing. However, it the spring upon heating).
 M. Bodaghi et al. / Materials and Design 135 (2017) 26–36 35

Fig. 10. 4D printed self-conforming device: (a) straightened beam and a hex key, (b) conforming to radius of 6.8 mm, (c) configuration after full shape recovery; 4D printed self-tightening
fiber: (d) straightened beam and soft polymeric substrate, (e) forming a loose knot, (f) shrinkage of the fiber by heating.

3.3. Potential applications
This section is dedicated to demonstrate potential applications of
self-folding primitives and self-coiling springs in mechanical and bio-
medical engineering devices. For example, the self-coiling spring dem-
onstrated in Fig. 9 can serve as spiral stents. In the straightened shape,
the 1D beam can be placed inside a catheter and then delivered to the
required location. Once the constraint is removed, the 1D beam may
be heated by blood temperature and mechanically self-coil. It may act
like a supporting function for opening the artery keeping blood flowing
normally or encompasses any object like a blood clot for treating stroke.
In the next example, the 1D straightened beam presented in Fig. 9b
is used as a 1D element that softens and conforms to 3D environments
upon heating. Fig. 10a displays the 1D component and a hex key with
a diagonal of 6.8 mm. The experimental results presented in Fig. 10b
and c reveal that, after warming, the 1D smart component is able to soft-
ly conform to the 3D hexagonal supporting environment. Even after
cooling, the device retains its conformed geometry and shape fixing,
see Fig. 10c. It can be found that this adaptive element has potential to
be used as flexible and conformal components for future mechanical/
biomedical devices fabricated by 4D printing technology. Motivated by
the research work of on shape memory suture [28], the feasibility of
the current 1D-to-3D self-coiling metamaterial for a similar purpose is
checked experimentally. A two-part soft polymeric substrate that
looks like tissue, (30 mm × 15 mm × 1 mm) × 2, as shown in Fig. 10d, is
loosely connected by the 1D straightened beam at room temperature,
see Fig. 10e. When the temperature is increased above the critical tem-
perature, Tg, the adaptive metamaterial is activated triggering the shape
recovery and removes the gap and tighten the tissue-like substrate, see
Fig. 10f. In fact, it acts like a self-tightening fiber. This may pave the way
for 4D printing patient-design self-tightening fibers for surgical sutures.
As a final example, straight beam element presented in Fig. 7 is used
to design and fabricate planar metamaterial (34 mm × 17.6mm × 1 mm)
by self-folding ability. It is composed of a periodic arrangement of the
six straight primitives (34 mm × 1.6 mm × 1 mm) programmed along
their length direction during printing stage as depicted in Fig. 11a.
Upon heating, the 2D lattice transforms to shape a 3D tubular
metamaterial as shown in Fig. 11b. The inner dimeter is also similar to
that of self-foldable primitive. It confirms reliability of SMP program-
ming during FG printing process so that all beam-like elements are
programed in a similar way. This 4D printed planar metamaterial with
self-folding capability may has potentials to be used as adaptive cus-
tom-designed structures that may conform to cylindrical environment
and perform supporting function. It can be used in biomedical devices
for different supporting usages like broken bones or tracheal splint.
Such a 4D metamaterial may exhibit another great potential to serve
as a self-deployable stent, see Fig. 11c and d. To this end, it needs to be
heated and rolled to get like a smaller cylinder as shown in Fig. 11d. It
is able to retain the temporary shape by fixing-cooling-unloading pro-
cess. The small tube can be stored inside a catheter and then delivered
36 M. Bodaghi et al. / Materials and Design 135 (2017) 26–36
(a) (b)
Fig. 11. 4D printed metamaterial lattice with self-folding capability: (a) after printing, (b) after heating-cooling process; 4D printed self-deploying stent: (c) another view of part b, (d)
configuration after heating-rolling-cooling-unloading (the rolled cylindrical lattice deploys upon heating).
to the required position. Once the catheter is removed, it is heated to
self-deploy and recover its original shape automatically, see Fig. 11c.
4. Conclusion
The aim of this paper was to describe functionally graded 4D printing
to fabricate planar adaptive metamaterials enabled to transform to 2D/3D
configurations by self-folding and self-coiling features. FDM printing
technology was used to program SMP materials during deposition stage
in a functionally graded manner. Experiments were conducted to explore
self-folding features characterized in terms of relevant fabrication param-
eters like printing speed and liquefier temperature. Boundary value prob-
lems were solved to describe thermo-mechanical mechanisms behind
programming during fabrication stage and shape-change during activa-
tion. In this respect, FE governing equations were derived based on the
non-linear Green-Lagrange strains and coupled with constitutive model
developed for SMP phase transformations during heating/cooling pro-
cesses. They were then solved by iterative incremental Newton-Raphson
scheme to trace non-linear equilibrium path in the large-deformation re-
gime. The understanding derived from modeling and experiments was
employed to design and fabricate straight and curved beams as structural
primitives for adaptive metamaterials that revealed 1D-to-2D and 1D/
2D-to-3D shape transformation through self-folding or/and self-coiling.
Finally, it was experimentally shown that the adaptive metamaterials
had the potential to be used in mechanical and biomedical applications
like structural/dynamical switches, self-conforming substrates, self-tight-
ening surgical sutures, self-conforming splints and self-coiling/deploying
stents. This research is likely to advance the state of the art 4D printing
and unlock potentials in the design and development of functional struc-
tures with self-folding/coiling/conforming/deploying features in a con-
trollable manner.
Acknowledgments
The work described in this paper was supported by the Research
Grants Council of the Hong Kong Special Administrative Region, China
(Project No. CUHK 14202016) and the Chinese University of Hong Kong
(Project ID: 3132823).
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