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4D printing with spin-crossover polymer composites
Mario Piedrahita-Bello, José Elias Angulo-Cervera, Rémi Courson, Gábor
Molnár, Laurent Malaquin, Christophe Thibault, Bertrand Tondu, Lionel
Salmon, Azzedine Bousseksou
To cite this version:
Mario Piedrahita-Bello, José Elias Angulo-Cervera, Rémi Courson, Gábor Molnár, Laurent Malaquin,
et al.. 4D printing with spin-crossover polymer composites. Journal of Materials Chemistry C, Royal
Society of Chemistry, 2020, 18 (8), pp.6001-6005. �10.1039/d0tc01532f�. �hal-02570972�
COMMUNICATION
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Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
4D Printing with Spin-Crossover Polymer Composites
Mario Piedrahita-Bello,
a,b
José Elias Angulo Cervera,
a,b
Rémi Courson,
b
Gábor Molnár,
a
Laurent
Malaquin,
b
Christophe Thibault,
b
Bertrand Tondu,
b
Lionel Salmon,
*,a
Azzedine Bousseksou
*,a
A stereolithographic 3D printing method was used to fabricate spin
crossover-polymer composite materials with various shapes and
sizes (up to several cm). The thermomechanical properties of the
polymer and the stiumuli-responsive properties of the filler are
preserved in the composite - affording for a new approach of 4D
printing.
Three-dimensional (3D) printing, also called additive
manufacturing, consists to fabricate objects from a 3D
computer model by joining materials, as opposed to
subtractive/formative manufacturing approaches. In the past
decades, numerous 3D printing technologies have been
developed to pattern complex shapes with various object sizes,
printing resolution and fabrication speed.
1-2
In general, 3D
printing is achieved layer-by-layer using either ink deposition or
laser-writing process, though other approaches are also
employed. Yet, in each case, one of the main bottlenecks is the
limited number of advanced materials, which can be 3D printed
for specific applications.
3
In this context, 3D printing of smart, stimuli responsive
materials has received increasing attention in the past few
years.
4-6
These materials allow for the evolution of the shape
and/or functionality of the 3D printed object with time when
exposed to a stimulus, such as light irradiation, solvents,
electric/magnetic fields, pH or heat. To differentiate these
objects from “static” 3D printed structures, they were coined
with the term “4D printing”, wherein the fourth dimension
refers to time.
7
Among the different materials used for 4D
printing, shape memory polymers, liquid crystal elastomers and
hydrogels have been the most popular, with associated polyjet
printing and extrusion printing methods. The envisioned
applications of 4D printing comprise smart valves, grippers,
drug delivery systems, self-healing and adaptive structures, soft
robots and so forth.
4-7
A straightforward way to introduce novel functionalities
and/or enhance properties of existing 3D printing materials is
the use of printable polymer composites.
8
This approach has
allowed, for example, to reinforce the polymer matrix, to
improve/adjust its dielectric permittivity, electrical
conductivity, thermal diffusivity/stability, hydrophilicity as well
as to confer it with magnetic or piezoelectric properties.
Perhaps not surprisingly, polymer composites have received
also much attention for 4D printing applications.
5
Obviously, the
key challenge here is to ensure 3D printability of the composite
material without compromising the original properties of the
constituents.
In this Communication, we describe a novel approach for 4D
printing, based on spin crossover - polymer nanocomposites.
Spin crossover (SCO) is a phenomenon that occurs in some
transition metal complexes wherein the spin state of the
complex changes reversibly from the low spin (LS) to the high
spin (HS) state due to an external stimulus such as a variation of
temperature/pressure, magnetic or electric fields, vapour
adsorption or light irradiation.
9-10
The spin crossover effect is
accompanied by a significant change of magnetic, optical,
electrical and mechanical properties. The latter property is used
in SCO based mechanical actuators, wherein the volumetric
strain can reach 15 %.
11
The advantages of SCO compounds with
respect to other smart materials for the elaboration of
composite actuators are (1) the high work density, (2) the fast
switching, (3) the possibility to tune the transition temperature
and (4) multifunctionality. For our work, a key asset is the
compatibility of SCO materials with various polymers, which has
already been advantageously used for the fabrication of SCO-
polymer composite actuators.
12-15
Recently, some of us have reported the direct laser
fabrication of 2D and 3D architectures (scalable up to 500 cm
3
)
with micrometric feature resolution using a single-photon
absorption stereolithographic methodology (SLA), based on the
photopolymerization of a resin.
16
The effective polymerization
a.
Laboratoire de Chimie de Coordination, CNRS UPR 8241, 205 route de Narbonne,
F–31077 Toulouse, France. E_mail : lionel.salmon@lcc-toulouse.fr,
azzedine.bousseksou@lcc-toulouse.fr
b.
Laboratoire d'Analyse et d'Architecture des Systèmes, CNRS UPR 8001, 7 avenue
du Colonel Roche, F–31400 Toulouse, France.
Electronic Supplementary Information (ESI) available: Additional sample
characterization details. See DOI: 10.1039/x0xx00000x
COMMUNICATION Journal of Materials Chemistry C
2 | J. Mater. Chem. C, 2020, 00, 1-3 This journal is © The Royal Society of Chemistry 2020
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depth in the material allows to easily write both in thick
(maximum tested 100 μm) and thin (minimum tested 10 μm)
layers as well as to realize 3D architectures including true
freestanding structures without the need of sacrificial supports.
Here we use this methodology to 3D print SCO nanocomposites.
First, a powder sample of the [Fe(NH
2
trz)
3
]SO
4
(trz = 1,2,4-
triazole) spin crossover complex was prepared using a slightly
modified version of the synthesis proposed in ref. 17. This
complex has been chosen because of the important volume
change of its unit cell (ca. 9%) upon the SCO phenomenon, its
good cyclability and weak absorption at the SLA laser
wavelength (405 nm). Figure S1 in the Electronic Supporting
Information (ESI) shows two consecutive cycles of the thermal
variation of the magnetic susceptibility. Subsequent to a first
‘run-in’ cycle, the compound presents stable spin crossover
properties with transition temperatures of T
1/2
↑
= 67°C and
T
1/2
↓
= 56°C for the heating and cooling modes, respectively,
denoting a hysteresis loop of ca. 9°C width. Transmission
electron microscopy reveals that the microcrystalline powder
consists of ca. 1-2
m long rod-shaped particles (see Fig. S1).
Homogeneous suspensions of the particles were obtained by
mechanically mixing the powder sample (up to 20 wt%) with the
commercial DS-3000 photosensitive polymer used for 3D
printing. The SLA setup (Fig. 1) consists of galvanometric
mirrors, which move the laser beam (20 μm diameter) along the
x and y directions with a maximum writing speed of 6400 mm/s.
The sample holder and the tank are mounted on a z-axis moving
stage, which can ensure a minimum layer thickness of 10 μm.
The maximum printed object volume is 15 (x) × 15 (y) × 10 (z)
cm
3
. All the structures produced in this work were obtained
layer-by-layer using a raster scan filling procedure.
Fig. 1. Scheme of the 3D fabrication setup.
We started by 3D printing uniform structures with
homogeneous distribution of the SCO load within the whole
object. This required the assessment of the adequate laser dose
to complete the photo-polymerization for each sub-layer for a
selected thickness and selected SCO loading. Whatever the
laser dose used, above ca. 15-20 wt% SCO load it was not
possible to obtain a stable multilayer film as the sample became
too brittle (see Fig. S2). A good compromise consisted in using
15 wt% SCO complex with 5800 mm/s writing speed, z-slicing
set at 30 μm/layer and a hatching of 30 µm to avoid
overexposure and reduce the overall fabrication time (15 min
for a 1 mm thick pattern). To remove the unexposed materials
the sample was developed in an isopropanol bath under
sonication for 15 minutes. Using this procedure, 2D and 3D
shapes (square, triangle, spring, dog bone, etc.) were printed
with various thicknesses (from 100 to 1000 µm) and sizes (up to
3 cm long) (Fig. 2). The most complex 3D structures we
fabricated are helical springs of 6,6 mm length, 4,2 mm
diameter, 300 µm wire diameter, pitch size of 800 µm and coil
angle of 18 degrees. These springs were fabricated with
supporting bars of 500 µm, which were eventually removed.
Clearly, 3D printing allows us to obtain SCO materials with
shapes, which would be extremely difficult, if not impossible, to
obtain by other fabrication methods.
Fig. 2. 3D printed SCO-polymer composite objects. Upon heating above ca. 80 °C a
reversible colour change occurs between the LS (violet) and HS (light-yellow) states.
Heating of the structures by a heat gun allowed for a visual
confirmation of the SCO phenomenon and its reversibility (Fig.
2). For a more detailed assessment of the properties of the
composite materials, we carried out differential scanning
calorimetry (DSC) and thermogravimetric (TG) measurements,
as well as thermomechanical analysis (TMA) coupled with
optical reflectivity detection (see the ESI for experimental
details). As shown in Fig. S1, the spin transition in the composite
occurs at slightly lower temperatures (T
1/2
↑
= 65°C and T
1/2
↓
=
54°C), which might be ascribed to the elastic confinement in the
polymer matrix.
18
To control the thermal stability of the printed
devices at the actuation temperatures, differential scanning
calorimetry (DSC) and thermogravimetric analysis (TGA) were
performed on both the composite, the pure complex and the
pure DS3000 resin (see Fig. S3 in the ESI). These thermal
analyses show that SCO occurs at a temperature well below any
crystalline transition of the polymer matrix, and that the
composite retains its stability up to 220°C, thus ensuring that
actuation does not interfere with the properties of the polymer
Journal of Materials Chemistry C COMMUNICATION
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matrix (Fig. S3). From the TMA analysis, the Young’s modulus of
the 15 wt% SCO composite (1.7 ± 0.2 GPa) at room temperature
is comparable with that of the pure polymer matrix (1.5 ± 0.2
GPa). Upon heating, one can observe a similar decrease of the
Young’s modulus (ca. 0.2 GPa at 90 °C) in the two samples, but
a detailed tracking reveals in the SCO composite a discontinuity
of the Young’s modulus around the spin transition
temperatures – the HS phase being considerably softer (Fig. 3).
Fig. 3. Simultaneous optical reflectivity – thermomechanical analysis of the 3D printed
SCO-polymer composite. The Young’s modulus of the pure polymer is also shown at
selected temperatures.
To demonstrate 4D printing we fabricated a 3 cm long bimorph
architecture consisting of two stacks: the pure DS-3000 polymer
and the SCO-polymer composite. Such bimorph structures are
commonly used for actuation magnification, because the
different expansion of the two strata allows for large amplitude
bending movement.
15
A common pitfall in this mechanism,
however, is delamination and our efforts were focused
therefore on ensuring strong adhesion between the two stacks.
For the 3D printing of bimorphs, the tank was divided by a PDMS
wall into two area. First, the pure DS-3000 stack (90 µm) was
printed at 200 mm/s writing speed to ensure tight adhesion
with the build platform, setting the z-slicing at 30 μm/layer and
60 µm of hatching, for an overall fabrication time of around 7
minutes. Then the build table was removed and put into an
isopropanol bath to remove the uncrosslinked polymer. The
build table was then replaced into the 3D printer to continue
the second part of the printing with the SCO material (thickness
of 150 µm) stored in the other part of the tank. In this case, the
z-slicing and the hatching parameters were fixed to 30 µm. In
order to obtain strong adhesion between the layers of pure DS-
3000 and the composite layers containing SCO material it is
necessary to elaborate the first SCO composite layers under the
same high-exposure conditions used for the elaboration of the
pure DS-3000 layers. (To illustrate this pivotal issue, Figure S2
shows a bimorph obtained using lower exposure.) Afterwards,
in order to reduce the fabrication time, the writing speed was
increased to 400 mm/s. Figure 4 shows SEM images of the
transversal section of a 3D printed bimorph pattern containing
15 wt% SCO filler. (See coupled EDX analysis in Fig. S4.). We can
clearly discern the interface between the smooth, nude DS-
3000 stack and the rough SCO/DS-3000 composite stack
containing well dispersed particles of the SCO compound. Note
the good continuity between the two layers, which is an
indispensable feature to avoid the delamination and to optimise
the performance of the bimorph actuator.
Fig. 4. SEM images showing at different magnifications the interface of the neat polymer
and polymer composite stacks in bimorph objects.
The thermal expansion coefficients of the two strata are similar,
therefore one expects significant bending chiefly around the
spin transition temperatures (Figures 5 and S5). Figure 5a shows
COMMUNICATION Journal of Materials Chemistry C
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side-view optical images of a 1 mm thick bimorph structure at
two temperatures below (pink) and above (colourless) the spin
transition temperature. As expected, for increasing aspect
ratios, the bending amplitude also increased. The tip
displacement for a thin (0.24 mm) sample upon heating and
cooling between 15 and 120 °C is depicted in Figure 5b. One can
note the brusque movement associated with the spin transition.
The tip displacement for this 30-mm-long bimorph is ca. 4.5
mm, denoting a displacement (D)-to-length (L) ratio of D/L =
0.15. This effect was successfully repeated during twenty
thermal cycles for both aspect ratios. In order to use the
classical bilayer model to determine the mechanical and
actuating properties of our composite, a simple rectangular
bilayer object was fabricated (Fig S6). Using the classical
Timoshenko model for bilayer actuators, the total strain of the
active layer caused by the SCO phenomenon was calculated.
19,12
The linear strain of the active layer (ΔL/L) is 0.33 %. Using this
value, the volumetric work density of the actuator could be
estimated as W/V = 1.5 mJ·cm
-3
. This value determines the
maximum amount of work per unit volume that an actuator can
perform. (Further details on these calculations can be found on
the SI.) We have also included in the SI a table comparing
different bending type polymer-based, soft actuators. The
actuating performance of the present 3D printed actuator falls
between that of different systems, but remains perfectible even
in comparison with other SCO-based systems. In particular, the
use of 3D resins with higher Young’s modulus and SCO
compounds with lower transition temperature could bring
significant improvements.
Fig. 5. (a) Colour change and associated bending of a bimorph actuator (850 µm active
layer and 150 µm inactive layer) upon the SCO. (b) Actuation cycle of a bimorph actuator
(150 µm active layer and 90 µm inactive layer) upon heating and cooling.
Conclusions
Using a stereolithographic approach in conjunction with spin
crossover-polymer composites, we have 3D printed various
stimuli-responsive mono- and bimorph architectures with sizes
up to several cm and structural details down to the 80
m scale.
The objects display good thermal and mechanical properties
and afford for reversible mechanical actuation generated by the
volume change accompanying the spin crossover phenomenon.
The fabrication process developed here is straightforward,
versatile and enables the creation of arbitrary planar and three-
dimensional geometries, which are otherwise not accessible
using spin crossover complexes. This work widens the restricted
choice of materials for 4D printing and opens up prospects for a
range of applications including grippers, moving parts in
microfluidics, drug delivery, adaptive optics, and so forth.
Acknowledgment
We thank financial support from the Federal University of
Toulouse/ Région Occitanie (PhD grant of MPB), the Agence
Nationale de la Recherche (ANR-19-CE09-0008-01), the French
RENATECH network, supported as part of the MultiFAB project
funded by FEDER European Regional Funds and Région
Occitanie (Grant No.16007407/MP0011594) and the European
Commission (H2020-MSCA-RISE-2016, SPINSWITCH, No.734322
and H2020-NMBP-PILOTS-2017, HoliFAB, No.760927).
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