Virtual and Physical Prototyping

ISSN: 1745-2759 (Print) 1745-2767 (Online) Journal homepage: http://www.tandfonline.com/loi/nvpp20

4D printing shape memory polymers for dynamic

jewellery and fashionwear
Matt Zarek, Michael Layani, Shira Eliazar, Nicola Mansour, Ido Cooperstein,
Efrat Shukrun, Atara Szlar, Daniel Cohn & Shlomo Magdassi
To cite this article: Matt Zarek, Michael Layani, Shira Eliazar, Nicola Mansour, Ido Cooperstein,
Efrat Shukrun, Atara Szlar, Daniel Cohn & Shlomo Magdassi (2016): 4D printing shape memory
polymers for dynamic jewellery and fashionwear, Virtual and Physical Prototyping, DOI:
10.1080/17452759.2016.1244085
To link to this article: http://dx.doi.org/10.1080/17452759.2016.1244085

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Published online: 13 Oct 2016.

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Date: 26 October 2016, At: 04:14

VIRTUAL AND PHYSICAL PROTOTYPING, 2016

http://dx.doi.org/10.1080/17452759.2016.1244085

4D printing shape memory polymers for dynamic jewellery and fashionwear

Matt Zareka*, Michael Layanib*, Shira Eliazarc, Nicola Mansoura, Ido Coopersteina, Efrat Shukruna, Atara Szlara,
Daniel Cohna and Shlomo Magdassia,b
a

Casali Center of Applied Chemistry, Institute of Chemistry, The Hebrew University of Jerusalem, Jerusalem, Israel; bSchool of Materials Science
and Engineering, Nanyang Technological University, Singapore; cThe Jewelry & Fashion Design Department, Bezalel Academy of Arts and
Design, Jerusalem, Israel
ABSTRACT

ARTICLE HISTORY

4D printing is a novel approach that enables dynamic functionality in ordinary static object. We used a
methacrylated semicrystalline polymer to print objects exhibiting thermally triggered shape memory
behaviour. By exploring various molecular weights, it was found that a methacrylated
polycaprolactone polymer with a number average molecular weight of 10,000 g mol1 exhibited
the best thermal and mechanical behaviour. The effect of dyes addition to the ink formulation on
the photopolymerisation and on the printing processes was evaluated. The ink was utilised for
demonstrating fabrication of dynamic jewellery and a shoe accessory by Digital Light Processing
printing.

Received 30 August 2016

Revised 27 September 2016
Accepted 29 September 2016

Introduction
4D printing has been defined as an additive manufacturing process which constructs a physical object that is
responsive to environmental stimuli and results in a
physical, chemical or shape change, through the dimension of time (Raviv et al. 2014, Tibbits 2014). Within this
field, there are further classifications that categorise 4D
printing according to the environmental stimuli, material
composition and the 3D printing apparatus (Khoo et al.
2015). The interest in 4D printing is kindled by the implications for different responsive structures, for example
robotics (McEvoy and Correll 2015), printable actuators
(Bakarich et al. 2015), medical devices (Saatchi et al.
2015, Gao et al. 2016) and is applicable in various industries such as textiles (Hu et al. 2012), defence (Felton et al.
2014) and aerospace (Leng et al. 2011).
Shape memory polymers (SMPs) enable a unique
implementation of 4D printing. SMPs are a group of
materials that can retain a metastable shape while simultaneously being able to revert to a latent permanent
shape, encoded into the polymer architecture (Lendlein
and Kelch 2002). Different stimuli have been explored
for the triggering mechanism, including light, magnetic
fields, pH and most broadly, temperature (Berg et al.
2014). Temperature-trigged SMPs exploit the thermal
transitions of polymers, either the glass transition temperature or melting temperature, and their associated

4D printing; shape memory

polymers; polycaprolactone;
textiles; jewellery

change in modulus spanning orders of magnitude,

across those transitions. While much work has been
reported on this large group of materials, direct 3D printing SMPs was only recently reported (Zarek et al. 2016,
Ge et al. 2016). The advantages of 3D printing compared
to alternative SMP processing technologies are clear, in
view of simplicity, resolution and complexity of structures, cost and freedom of design. Notwithstanding the
recent developments in 3D printing, great progress has
been made in achieving attractive cyclical shape
memory behaviour and uncovering the near-universal
mechanism in cross-linked semicrystalline polymers
(Chung et al. 2008, Zhou et al. 2014).
An interesting semicrystalline polymer, which is the
focus of this work, is polycaprolactone (PCL) a tough
thermoplastic polyester prepared by the ring-opening
polymerisation (ROP) of -caprolactone (Woodruff and
Hutmacher 2010). It is used widely in medical
devices, polyurethane compositions and in the modelling and hobby community (Lipson and Kurman 2013).
Its attractiveness for the latter applications largely
stems from its low melting temperature (about 60C)
and its low specific heat, which translates into facile
handling. Therefore, PCL is one of the more common
materials used in fused deposition modelling processes
(Lipson and Kurman 2013). Digital Light Processing
(DLP) is a very appealing technology, which is considered to have the highest printable resolution

CONTACT Daniel Cohn

danielc@mail.huji.ac.il; Shlomo Magdassi
magdassi@mail.huji.ac.il
Supplemental data for this article can be accessed at 10.1080/17452759.2016.1244085.
*
Matt Zarek and Michael Layani contributed equally to this work.
2016 Informa UK Limited, trading as Taylor & Francis Group

KEYWORDS

M. ZAREK ET AL.

compared to other additive manufacturing approaches,

whereby the 3D object is constructed layer by layer by
photopolymerisation of a liquid resin. In order to
enable photopolymerisation of PCL, we synthesised
PCL-dimethacrylate by covalent attachment of methacrylate groups to the terminal groups of the polymer
chains (Zarek et al. 2016). For the shape memory
behaviour, it is a prerequisite that the PCL retains crystalline domains during photopolymerisation. As a consequence, the molecular weight is high and the
polymer is solid at room temperature, thus printing
must be performed while using molten PCL-dimethacrylate. Conventionally, polymers are classified as
either thermosets or thermoplastics. In this work, the
precursor oligomer is thermoplastic, which enables
printing it in its melt form and therefore the resulting
printed structures are made of a thermoset polymer.
We note that the PCL-dimethacrylate reported here is
a model material, and the shape memory behaviour
it demonstrates is obtainable in a variety of semicrystalline thermosets. 3D printed structures fabricated
with this type of polymer can be heated above the
melting temperature of the crystalline domains and
deformed into a metastable temporary shape, and
once cooled below the transition temperature, yield a
4D object. The programming step can be repeated
with different temporary shapes while the permanent
shape is determined by the pre-designed print file.
So far we reported 3D printing SMPs for prototypes of
medical devices and electronics (Zarek et al. 2016), and
to our best knowledge until now it has not been
applied to consumer goods and jewellery. Loh et al.
(2016) discussed multiple strategies to incorporate
SMPs in consumer products and Hu and coworkers
(2012) have reported on the incorporation of SMPs
within fabrics. We expect that adoption of 4D printing
will enable the fabrication of dynamic consumer products, as will be demonstrated here by moving jewellery
and responsive shoes. We therefore evaluated PCLdimethacrylate precursors with various molecular
weights, combined with various functional dyes for 4D
printing that can be utilised by product designers to
greatly expand their capabilities in what are known as
static objects.

Experimental procedures
Preparation and characterisation of the
methacrylated resin precursor
For the various methacrylated PCL precursors for DLP
3D printing, we used the raw polymer or prepared
PCLs with specific molecular weights. We obtained

PCL-diols with number average molecular weights of

4000 g mol1
(Perstorp,
Cheshire,
UK)
and
10,000 g mol1 (Sigma-Aldrich, Israel). The PCL precursors of 6000 and 8000 g mol1 were synthesised as
follows: 40 g of PCL 4000 g mol1 was charged to a
three-necked flask and dried under vacuum for 2 h at
120C with magnetic stirring. Following this, nitrogen
gas was introduced to generate an inert atmosphere
and 1:100 mole ratio of stannous octoate to PCL was
added as catalyst. Stannous octoate was purchased
from Sigma-Aldrich, Israel. We added the corresponding amount of -caprolactone, with no excess (SigmaAldrich, Israel) for the ROP, to obtain molecular
weights of 6000 and 8000 g mol1. The reaction was
conducted at 145C for 3 h. For the methacrylation of
the different hydroxyl-terminated PCL segments, the
reaction vessel was cooled down to 85C. The PCLdiols with 4000 and 10,000 g mol1 molecular
weights were methacrylated as well, after the same
drying process, as reported above for the two-step
reaction. For the set of four precursor materials, the
PCL was methacrylated at 85C in the presence of catalyst stannous octoate at the mole ratio of 1:100 to the
PCL. We added isocyanatoethyl methacrylate (Tokyo
Chemical Industries) at a 2:1 mole ratio to PCL and
ran the reaction for 1.5 h. Chloroform (Biolabs, Israel)
was added using 1 mL of solvent per gram of PCL.
The solution was poured into cold petroleum ether
(Biolabs, Israel) and precipitated. The solid polymer
was recovered and left to dry in the fumehood
overnight.
The degree of methacrylation of the PCL-methacrylates was assessed by 1H NMR spectroscopy. The molecular weight of the prepared PCLs was evaluated by Gel
Permeation Chromatography (GPC) using a 2690 separation module containing Styragel columns and a chloroform eluent (Waters Corporation). The calibration curve
used polystyrene standards. Proton Nuclear Magnetic
Resonance (1H-NMR) was conducted on a Bruker
500 MHz spectrometer using deuterated chloroform
and Tetramethylsilane as the solvent and internal standard, respectively. Scans were performed at 500 MHz resonance frequency with the spectral width of 10 KHz. To
determine the degree of methacrylation, the signal
intensities of the methyl protons in the methacrylate
group were compared to the protons on the ethylene
glycol initiator, in the case of PCL 10,000 g mol1 and
butanediol initiator for the materials initiated with PCL
4000 g mol1. In the former case, there was a correction
to remove the contribution of two methacrylate protons
that overlap with the initiator. For PCL 10,000 g mol1,
the following signals were used: =CCH3 (methyl
protons in the methacrylate group, = 1.9 ppm, MC3),

VIRTUAL AND PHYSICAL PROTOTYPING

CH2CH2 (protons in the initiator, = 4.2 ppm, MC4),

and =CH2 (methylene protons in the methacrylate
group, = 5.6 and = 6.1 ppm, MP1 and MP2, respectively). The degree of methacrylation was calculated as
follows, with the coefficient present to normalise the
result.
4
IMC3
D=
.
6 IMC4 IMP1 IMP2
For the calculation of the degree of methacrylation of
PCL 4000 g mol1, we compared the relative area of
the characteristic peak of the protons on the butanediol
initiator (BDL, = 3.4 ppm) and the protons on the terminal methacrylates (IEMA, = 6.0 ppm). The degree of
methacrylation was calculated by
D=

4H IIEMA

.
2H IBDL

coated layer. Once the layer was completely solid, it

was registered as the minimum time required to
obtain a solid layer, for that specific dye concentration
and layer thickness.

3D printing method
The 4D printed parts were printed on PICO Plus39
(385 nm UV source) and PICO2 (385 and 405 nm UV
source) printers (Asiga, Australia), each equipped with a
custom temperature-controlled resin bath. The baths
are made of aluminium, having internal fluid channels
for water circulation, which enables temperature
control. The resin bath has a Teflon film (CS Hyde, USA)
clamped at the bottom of the aluminium frame. Prior to
printing, the resin is heated until it is melted in the bath.
Typical printing parameters for a magenta-coloured
resin are: Bath temperature of 80C, layer thickness of
100 m, burn-in time of 8 s and exposure time of 10 s.

Preparation of the print formulation

We prepared resins for DLP printing by compounding
the methacrylated PCL with a photoinitiator, polymerisation inhibitor and dye. For the characterisation of the
thermal and mechanical properties, the samples were
prepared as (all reported as weight/weight) 96.8%
methacrylated PCL, 3% 2,4,6-trimethylbenzoyl-diphenylphosphineoxide (TPO) as photoinitiator (BASF,
Germany), 0.1% of vitamin E (Ahava, Israel) to prevent
premature cross-linking, and 0.1% dye. The dye concentration was similar for the printing of the shoe-heel and
various rings while changing the type of dyes. The
dyes used were as follows: Magenta (Toner EO2, Clariant,
Germany), Yellow (Toner 3GP, Clariant, Germany), Orasol
Orange G (BASF, Germany) and green (Green 201 Teal,
Johnson Mattley, Netherlands).

Analysis of dyes
For evaluation of the different dyes, we compared three
dyes, magenta, yellow and orange at concentrations of
0.04 and 0.20 wt%. The rest of the additives were
added in the same concentrations as reported above.
Each ink loaded with a different dye was bar coated
(RK Print-Coat Instruments) three times at thicknesses
of 40, 50, 60, 70, 90 and 150 m, using different bar
rods. Soon after coating (on PET substrates) the ink
was exposed to UV LED flashlight (395 nm, 8 W cm1)
at constant height at exposure times of 1, 5, 7, 10,
15, 17, 18, 20 25, 27, 28 and 30 s. After exposure, the
layer was examined if completely polymerised. In the
case where there was still liquid within the layer, the
next exposure time was examined with a freshly

Mechanical and thermal characterisation of

printed structures
For testing the mechanical properties, we printed standard dog-bone coupons, ISO 527-2/1BB (Thingiverse.com, thing:190386). The mechanical tests were
conducted with an Instron 4500 Universal Testing
Machine with a custom heating apparatus according to
the protocols described by Lendlein et al. (2005). The
thermal characterisation of the precursor and printed
samples of all the molecular weights was conducted on
a Mettler-Toledo TA-400 Differential Scanning Calorimetry (DSC) calorimeter with history erase from 10C to
80C. The heating programme was as follows: heat to
80C at 10 K min1, followed by cooling rate of
2 K min1, with a 5 min pause at 10C, followed by
heating to 80C at a rate of 4 K min1. All comparisons
were based on the second heating run.

Preparation of CAD models

The jewellery and shoe accessory were designed in
Rhino3D (Robert McNeel & Associates) and Solidworks
(Dassault Systmes, France), respectively.

Results and discussion

Effect of molecular weight on thermal properties
To evaluate the effect of molecular weight on the crystallinity, which in turn sets the shape memory behaviour,
we prepared a family of PCL-dimethacrylates with
various molecular weights. The preparation of these

M. ZAREK ET AL.

materials involves the straightforward ROP of -caprolactone with near complete conversion of the monomer.
Particularly, using a PCL diol as the initiator for the ROP
enables, one to obtain a PCL macromethacrylate of
almost any molecular weight. The criteria for selecting
a 4D material are that the polymer molecular weight is
sufficiently high so that after cross-linking there
remains a crystallisable fraction that can actuate the
shape memory behaviour. On the other hand, too high
a molecular weight will result in too high a viscosity of
the polymer melt and therefore will not enable proper
printing. Additionally, too long PCL segments will generate thermosets with an inadequate crosslink density and,
therefore, limited recovery capability. Furthermore, one
must consider the degree of methacrylation since, as
we reported, a low degree of methacrylation could not
successfully print (Zarek et al. 2016). To investigate the
effect of molecular weight on the mechanical and
shape memory properties of the 4D printed objects, we
compared PCL 4000, 6000, 7500 and 10,000 g mol1
(all number average molecular weights).
The Tm and enthalpy of fusion values of the 3D printed
objects were determined by DSC (Table 1). It should be
noted that generally, the melting temperature is taken
as the peak of the DSC endotherm, despite the fact
that there is an actual broad melt behaviour. This is
due to the polydisperse nature of the chain lengths
and the different crystallite populations. Figure 1 shows
the melting temperature of the four different molecular
weight inks before and after 3D printing. As seen, prior
to printing, PCLDMA molecules exhibit a slight increase
in melting temperature as the chain length increases.
After photopolymerising and cross-linking the samples,
the melting point decreases for MW above
4000 g mol1. For 4000 g mol1 MW objects, there was
no melting point and, therefore, no shape memory
behaviour. As shown in Figure 2, the enthalpy of fusion
shows that there is a substantial decrease in the crystalline fraction of the polymer after cross-linking. Crosslinking imparts a molecular architecture to the polymer
network, which is also reflected by the broadening of
the melting endotherm (Liu et al. 2007). It has also

Figure 1. Melting temperature of the PCLDMA 3D thermosets

before and after 3D printing.

been shown previously that the heat of crystallisation

is practically independent of the rate of cooling (Lendlein
et al. 2005), supporting the notion that it is the molecular
architecture that defines the limits of the crystallisation. It
follows therefore that the degree of methacrylation is a
significant variable that can affect these thermal properties. A higher degree of methacrylation will constrict
further crystallite formation than lower degrees of
methacrylation. We note that the PCL 4000 g mol1
with 100% methacrylation was printable but, due to its
low molecular weight and lack of crystallisability, did
not exhibit any shape memory behaviour. When the
degree of methacrylation was reduced below 75%
methacrylation, the object was printable yet exhibited
poor shape memory properties, and when below 40%
methacrylation, the object was not printable. We did
not proceed to further analyse PCL 4000 g mol1 with
different degrees of methacrylation because of its poor
mechanical properties.

Effect of molecular weight on mechanical

properties
The printed objects were characterised with respect to
their mechanical properties above and below their
melting temperatures. Figure 3 presents the tensile
modulus and the stress at break of 3D printed dog-

Table 1. The physical parameters of 3D printed PCLDMA.

Object no.

Mn (g mol1)a

Dm (%)c

Tm (C)d

Hm(J g1)e

S4
4000a
97

>99
43
S6
6000b
>99
51
S8
7500b
88
47
S10
10,000a
a
Mn taken from manufacturer.
b
Mn was calculated by GPC and rounded to the nearest 500.
c
Degree of methacrylation was determined by 1H-NMR.
d
Tm was taken as the peak of the melting endotherm from DSC.
e
Enthalpy of melting was calculated from the integration of the
endotherm from DSC.

26
36
29

melting

Figure 2. Enthalpy of fusion of the PCLDMA 3D thermosets

before and after 3D printing.

VIRTUAL AND PHYSICAL PROTOTYPING

Figure 3. Tensile modulus (left axis) and stress at break (right

axis) of the different molecular weight 3D printed PCLDMAs
below the melting temperature.

bones below the Tm. It can be seen that increasing the

average length of the chains causes an increase in the
modulus and stress at break. As the molecular weight
increases, entanglements result and a higher stress is
required to disentangle the chains and overcome the
inter-chain secondary forces, to separate the chains.
The presence of crystalline domains, with molecules
long enough to traverse through the crystalline and
the amorphous regions further improve the strength of
the material. Above the melting temperature, there will
be no crystalline domains, and therefore the stiffness
and strength are only due to the cross-linking density
and inter-chain secondary interactions.
Figure 4 plots the values for tensile modulus and
stress at break for the same specimens above the
melting temperature. The modulus values are 12
orders of magnitude lower than the same materials at
room temperature, below their transition temperature.
It should be noted that specimens prepared with the
two low-molecular-weight polymers, as indicated by
the data in Figure 4, were brittle. Some of the samples
were damaged due to clamping and therefore were

Figure 4. Tensile modulus (left axis) and stress at break (right

axis) of the different molecular weight 3D printed PCLDMAs
above the melting temperature. Note the different scales compared to Figure 3.

not included in the analysis. From samples which were

analysed, some were broke on the contact edge with
the clamps, which probably led to the large variation in
the results. Figure 5 shows the strain at break of the
materials above the transition temperature. The 4000
and 6000 g mol1 are brittle with extremely poor
elongation. These properties make these two materials
poor candidates for 3D printing of complex structures
and therefore we did not continue to perform SMP
experiments with them. While the 7500 g mol1 precursor exhibited acceptable performance in terms of stiffness, strength and toughness, the 10,000 g mol1
precursor was clearly superior. Its melt viscosity was
approximately 30 Pa s and was compatible with the
DLP printer. Therefore, we proceeded with printing
the 4D apparel and accessories with PCLDMA
10,000 g mol1 material.

Influence of dyes
The natural appearance of PCL is a turbid white when it is
below its melting temperature, primarily due to light
scattering by the crystalline domains. For many commercial applications, an aesthetic consideration is important,
especially within the fashion, outerwear and jewellery
industries. Therefore, there is genuine interest in the
effect of coloured dyes, from across the colour spectrum,
on the SMP 3D printing process itself and on the appearance of the finished objects. The direct addition of a dye
in the ink formulation may affect the polymerisation and
hence the printing process by competing with the
photoinitiator through light absorption. To evaluate the
impact of the various dyes, we examined the minimal
time to cure of yellow, orange and magenta-dyed inks,
as a function of the layer thickness. These dyes were
chosen based our experience with these dyes in 3D
printing.
While the TPO photoinitiator has a broad absorbance
spectrum, the UV light source of the printer is nearly
monochromatic, at 405 or 385 nm (depending on the
printer). As can be seen in Figure S1 (see online
supplemental material at http://dx.doi.org/10.1080/
17452759.2016.1244085), the yellow, orange and
magenta dyes absorb in these wavelengths differently,
depending on their absorption extinction spectra, while
the magenta dye has the most distinct absorption in
the near UV range. These dyes act as sensitisers together
with the photoinitiator. Usually, sensitisation takes place
between the dye and the photoinitator, improving the
process of radical formation (Gruber 1992). For evaluation of dye addition effect, the inks with dye concentrations of 0.2 wt% were irradiated at 395 nm at various
film thicknesses, while evaluating the minimal time for

M. ZAREK ET AL.

Figure 5. Values of strain at break above the melting temperature as a function of PCL precursor molecular weight.

obtaining full curing (in which the layer is completely

dry) compared to blank methacrylated PCL ink with no
dyes. As shown in Figure 6, for thick layers (150m), all
the inks with the added dyes polymerised within the
first 20 s of exposure, whereas the ink without any dye
required almost 1 min for complete polymerisation.
The ink with the magenta dye required the minimal
exposure time, whereas the orange and yellow dyes
required much longer exposure time. For thin layers
(<60 m), it can be seen that the illumination intensity
is sufficient to penetrate through the whole depth of
the specimens to initiate complete polymerisation;
hence there is no difference between the minimal
exposure times. The positive effect of the magenta dye
in the thick films may result from less light absorption of
the magenta dye at 385 nm (Figure S1). The exact mechanism of the dyes function is not completely clear yet.

4D printed jewellery and fashionwear

Once we established the optimal printing conditions and
ink compositions, we performed 3D printing of a shoe

accessory and jewellery, to obtain dynamic 4D objects.

Conventionally, jewellery and footwear have changed
over the last centuries only in style and materials, but
they have predominantly remained static objects. In
Figure 7, we present a set of temperature-responsive
rings that bloom upon heating above the transition
temperature of the printed SMP. The top row displays
the rings as they were printed, after post-processing
assembly of the ring from the various parts, and the
bottom row shows the structures in their temporary
metastable state. It should be mentioned that in this
example, the design enables blooming upon exposure
to heat, and obviously the reverse action, petal closing
is similarly achievable as shown in Figure 8. A film
showing the various rings is presented in Movie S1 (see
online supplemental material at http://dx.doi.org/10.
1080/17452759.2016.1244085).
At present, this particular implementation of the
shape memory behaviour is a one-way process and is

Figure 6. Minimum exposure time (in seconds) for film layers of

various thicknesses to cure for a set of dyes at a concentration of
0.2 wt%.

Figure 7. Photographs of a set of four shape memory responsive 3D printed flower-themed rings. The top row is the permanent shape
of the structures. The bottom row is the metastable temporary shape. On heating above the melting temperature, the shape memory
structures recover their permanent shape.

VIRTUAL AND PHYSICAL PROTOTYPING

Figure 8. The fabrication and assembly of dual colour shape memory responsive ring. Two serial print jobs were combined to the final
structure and assembled with a standard ring base.

Figure 9. Photographs of the two-state 3D printed heel attachment on a 3D printed shoe.

activated by heating. However, recent advances in SMPs

have revealed materials that are capable of cycling
between multiple metastable states (Zhou et al. 2014).
Such materials will be evaluated in our future research.
We also explored combining different printed objects
with different colours that are assembled after printing,
as seen in Figure 8.
As shown in these examples, we show how objects
that were perceived to be non-responsive can be
designed to respond to the environment (e.g. ambient
temperature of the day) and furthermore can be programmed at the whim of the user by setting
the temporary shape to ones desire. Obviously, these
types of objects can have other functionalities related
to temperature sensing with health benefits, such as prolonged exposure to sunlight, or safety alerts for cookingware that is hot, by transitioning the SMP material to its
elastic state above the melting temperature.
Besides dynamic aesthetics, we further show that
the SMP objects can also be utilised for adding functionality. Therefore, we fabricated 3D printed shape

memory material as a fashion component for multifunctional footwear. As demonstrated in Figure 9, we

printed a shoe-heel that is designed to have two
states: high and flat heel. The SMP heel is attached
proximal to the heel above the contact layer with the
floor so as not to interfere with normal gait. In the scenario where the wearer wants to raise the heel, the SMP
attachment is heated up with a standard hand dryer
and transforms to the high-heel configuration. It
should be mentioned that in this case, the whole shoe
was 3D printed, while only the heel was printed with
the SMP materials. This emphasises the versatility and
synergy of the digital world of 3D printing, when combined with advanced materials research. While we used
a PCL-based formulation that has a tensile modulus of
over 100 MPa, there are other studies that investigated
the modulus of PCLs under compression. Eshraghi and
Das (2010) reported the compressive strength of a
higher molecular weight PCL with a value surpassing
300 MPa. A future study is planned to investigate the
role nanofillers may have on the mechanical properties

M. ZAREK ET AL.

of the 3D printed SMPs. This information would be

instrumental in designing functional objects with
better load-bearing capabilities.

Conclusions
We have demonstrated that 3D printed SMPs are intriguing materials with a lot of potential for applications
that are not traditionally associated with advanced
materials research. We investigated a set of semicrystalline polymeric precursors of different molecular
weights and found that PCL with 10,000 g mol1 displayed the best mechanical properties while simultaneously being compatible with conventional 3D DLPbased printing processes. This PCL-based ink was used
to create multicoloured temperature-responsive rings
and a footwear attachment and we expect that the presented approach will provide a new tool-set and inspiration for designers.

Disclosure statement
No potential conflict of interest was reported by the authors.

Funding
This research was partially supported by the Singapore National
Research Foundation under the CREATE program: Nanomaterials for Energy and Water Management, by The FTA program
of Israel National Nanotechnology Initiative, and the Israel
Science Foundation [grant number 183/16].

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