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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.
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
KEYWORDS
M. ZAREK ET AL.
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
4H IIEMA
.
2H IBDL
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.
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
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
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
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melting
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.
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.
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.
M. ZAREK ET AL.
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].
References
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