4D Soft Material Systems

Giulia Grassi1(B) , Bjorn Sparrman2 , Ingrid Paoletti1 , and Skylar Tibbits2

1 Material Balance Research, ABC Department, Politecnico di Milano, via Ponzio 31,
20133 Milan, Italy
[email protected]
2 Self-Assembly Lab, Massachusetts Institute of Technology, 265 Massachusetts Avenue,

Cambridge, MA 02139, USA

Abstract. This work introduces multi-material liquid printing as an enabling

technology for designing programmed shape-shifting silicones. The goal of this
research is to provide a readily available, scalable and customized approach at pro-
ducing responsive 4D printed structures for a wide range of applications. Hence,
the methodology allows customization at each step of the procedure by intervening
either on the material composition and/or on the design and fabrication strategies
for the production of responsive components. A significant endeavour is initiated
to develop and engineer two different material systems that enable shape-shifting:
silicone-ethanol composites and polyvinyl siloxane swelling rubbers. The printed
samples successfully comply with the expected swelling behaviour through a
variety of printed test patterns.

Keywords: 4D printing · Responsive material systems · Shape-shifting silicones

1 The Dance of Agencies

Polish scientist and philosopher Ludwik Fleck (Fleck 1979), introduced a vision of
research practice in which the active part of the researcher deals with setting up the
material assemblage, and the passive part consists in observing what material will do
and how they will perform. Those phases are repeated by the researcher in a loop where
the steps of human passivity can be seen as material activity, in a “dance of human
and non-human agency in which activity and passivity on both sides are reciprocally
intertwined.”
Material agency denotes the possibility that things can act on their own which con-
tributes to a broader challenging of the boundaries between ontological categories (Van
Oyen 2018). In recent years we have experienced a fertile generation of architecture
focused on material systems, such interplay of material innovation, advanced material
processes and emerging fabrication technologies is increasingly expanding our under-
standing of material practice (Perez 2011). A material is nowadays perceived as the
active generator of design (Grassi et al. 2021), made possible through techniques like
4D printing which allow designers to fully exploit material engineering and fabrication
techniques to produce responsive material systems.

© The Author(s) 2022

P. F. Yuan et al. (Eds.): CDRF 2021, Proceedings of the 2021 DigitalFUTURES, pp. 201–210, 2022.
https://doi.org/10.1007/978-981-16-5983-6_19
202 G. Grassi et al.

In this research, 4D printing design strategies, such as shape-shifting multi-material

bi-layers, are coupled with Rapid Liquid Printing, a printing technique which entails
physically drawing three-dimensionally in a gel suspension, with the aim of investigat-
ing soft responsive material systems. Contemporary explorations on the aesthetics of soft
spaces and architectures have been exploring silicone as a soft, transparent and flexible
rubber, e.g. for inflatables structures such as “Liquid Printed Pneumatics” (Sparrman
et al. 2019). Hence silicone is a valuable material for this investigation, thanks to its
elasticity, enabling kinetic morphable shapes. Taking advantage of the inherent material
properties by distributing the actuation throughout the surfaces, the self-transforming
process eliminates the need for external forces, actuators, or human/robot intervention
during the shape-shifting process. Moreover, silicone possess strong bonding characteris-
tics, flexibility (a wide array of shore hardness availability), bio-compatibility, versatility,
fire resistance and durability.

2 4D Rapid Liquid Printing

Previous research on 4D printing typically relies on the use of high-end multi-material

printers (such as Stratasys Connex 500), which employ their own proprietary materials,
or custom lab-engineered material properties. As a result, experimentation on active
materials is difficult for designers to access and scale towards applications. A novel
printing technique called Rapid Liquid Printing (RLP) (Hajash et al. 2017), spatially
extrudes two-part liquid materials immersed within a tank of gel, avoiding the need for
scaffolding. In this study we demonstrate that, by utilizing such technology coupled
with multi-material extrusion, it is possible to print silicone-based responsive material
systems that can self-transform.
This project investigates two main research questions:

• Which silicone-based composite materials can be used to achieve a shape-shifting

response through Rapid Liquid Printing (RLP)?
• Which design strategies and fabrication procedures are needed to create a responsive
material system with RLP?

As shown in Fig. 1, a three-axis grantry-style CNC machine has been equipped with
the two-part pneumatic deposition system and a tank of gel which serves as a suspension
medium. The pneumatic deposition system consists of two cartridges filled with two-
part liquid material (1:1 ratio) that is pushed out by a compressor conveying through
a static mixer. Different nozzles can be employed depending on the printing diameter
(or line spacing) and printing speed. These factors are influenced by the viscosity of the
liquid printing material and its curing time (thus printing time for the overall piece or
set of prints). Multi-material Rapid Liquid Printing was achieved by swapping material
cartridges throughout the printing process.
 4D Soft Material Systems 203

Fig. 1. Machine setup for RLP

3 Shape-Shifting Silicones

By exploiting bi-layer compositions and multi-material printing it is possible to mix

the silicone matrix with a responsive material coupled with a passive silicone layer.
We analyzed the state of the art and possible applications of two material systems with
shape-shifting abilities. These have been tested for feasibility, first in terms of desired
adaptive behavior as well as machine compatibility. The two material systems are:

• Silicone bilayers of stimuli responsive material systems (active response) tested by

mixing a platinum catalyzed silicone with a phase changing material in order to make
the composite thermostrictive (ehanol)
• Silicone bilayers as passively activated rubbers (passive response) achieved by printing
bi-layers of oil swelling polyvinyl siloxane (PVS) with various oil contents and Young
modulus

Hereby we consider as an active transformation when the shape-shifting is triggered by

a change in the external environment, whereas a passive transformation is generated by
internal forces due to chemical reactions.

3.1 Ethanol-Based Active Responsive Material System

The first material system that was tested for printing was a compound of silicone and
ethanol. While undergoing phase change from a liquid to gas when reaching the boiling
point, ethanol expands. This composite material has been shown to combine high actu-
ation stress and expansion of up to about 900% (Miriyev et al. 2017). After activation,
the component reverses to the previous state once the heat source is removed. Previous
studies include projects developed at IAAC (Institute for Advanced Architecture of Cat-
alonia), So.ar (Abasova et al. 2019) and Pneu.flex (Jose et al. 2018). These investigated
204 G. Grassi et al.

the potential of cast mixtures of silicone and ethanol heated through a coiled Nichrome
wire for fabricating responsive skins. Other significant studies have been conducted at
Columbia University, at the Creative Machines Lab. They have 3D printed composite
materials with the purpose of creating soft actuators (Miriyev et al. 2019) with custom
shapes, however in a small scale (the build plate is 406 × 406 × 76 mm). Moreover, the
system doesn’t allow for growing in height with the print, because of the liquid nature
of silicone, despite UV curing. On the other hand, RLP allows larger scale, due to the
bigger size of the tank and tanks to the support given by the gel.

3.1.1 Material Testing

For the material system we tested different compositions starting from cast samples. As
described in the literature (Miriyev et al. 2017, 2018a, 2018b; Jose et al. 2018), 20%
vol. ethanol in the mixture allows for the optimal expansion rate of the compound. We
tested 10, 20 and 30% weight (slightly higher than % in vol. because the specific gravity
of ethanol is 0.8), where 30% left the specimens wet while not exhibiting an increase in
expansion. We cast a few samples of bi-layers made of a passive layer (plain silicone)
with an active one, composed of silicone and ethanol, which starts responding to heat
at 40 °C. Upon heating, the stress mismatch between the two layers initiates the shape-
change. The samples were heated with a heat-gun and the response was approximately
within one minute. Two different silicones have been employed as a matrix: Smooth On
Sorta Clear and Polytek PlatSil Gel-25. The cast samples with Polytek silicone achieved
a more dramatic bending radius because of the lower Shore hardness of the material.
Figure 2 displays a printed bi-layer strip (10 cm length, 3 cm width) which is actuated
through a heat-gun in 1 min and 40 s. The two layers are printed starting from the lower
one and swapping cartridges to change material. In this phase it is crucial to carefully
consider the single layer height, thus the two layer distance, in order to print the second
layer on top of the first one. To ensure adhesion, when the first layer starts to cure (but is
not yet fully cured), the second has to be pushed into the first layer by setting the layer
distance lower than the layer height. This approach takes into account the viscosity and
the thixotropy of the material and most importantly, the curing time.

Fig. 2. Printed bi-layer activation, the transition from 0 to 3 took 1min and 40 s.
 4D Soft Material Systems 205

3.1.2 Thermo-Responsive Apertures

By exploiting the successful bending feature of activated bi-layers, more complex and
larger geometries have been printed such as the star-like aperture shown in Fig. 3.
The sample demonstrates the ability to print interesting kinetic geometries that can be
exploited for environmentally adaptive products and structures. The star-like aperture
has a diameter of 15 cm and was printed in less than 5 min. It consists of two layers
where the first is plain silicone and the second is a silicone-ethanol mixture. The planar
line spacing is 0.75 mm and the printed path has been optimized (“spiralized”) with a
script in order to result in a single continuous printed line for each layer. The layer height
is 3 mm, hence the distance between the two layers was set 1 mm apart in order to have
a 0.5 mm of superimposition through pushing downwards to ensure adhesion.
Several tests on the material composition have been performed to obtain the right
viscosity, printing time and cure time of the overall objects. Table 1 indicates values of
percentage in weight of silicone, ethanol, thickener and retarder for the active layer. The
active layer is printed by mixing the material pushed out by the two cartridges, each one
filled respectively with part A and part B, where additives are included in the same ratio
to both, to obtain the same viscosity.

Table 1. Composition of the silicone-ethanol mixture for the printed sample in Fig. 3

Gel 25 partA Gel 25 partB Ethanol Retarder Thickener

% weight 38 38 20 1 3

This composition has to be customized in respect to the printing strategy adopted,

especially with respect to the retarder, which influences the cure time. For instance, if
the same print consists of two layers with two different materials, a higher percentage
of retarder will allow it to keep the material in the fluid state (not fully cured) while
printing the second layer, which will guarantee bonding. We observed that above 5%
retarder resulted in weakened material properties or uncured parts.
The transition of the responsive element is quick at high temperatures (approximately
two minutes at 70 °C) however, if we imagine such systems to be activated through solar
heat we’d have to integrate an additive to render the composite more heat conductive, thus
transforming faster. This issue has been addressed by Xia (2020) which used diamond
nanoparticle-based thermally conductive filler to improve the actuation speed.

3.2 PVS-Based Passive Responsive Material System

Passively actuated adaptive systems represent another possibility within shape-changing

systems. Expanding upon the work of Pezzulla et al. (2015), we conducted a series of
experiments aimed at testing the swelling capacity of polyvinylsiloxane (PVS) bi-layers.
As investigated by Prof. Holmes from the MOSS Lab at Boston University, harnessing
anisotropic swelling allows for precise control over the curvature in bilayer structures.
206 G. Grassi et al.

Fig. 3. Star-like shape growing in height upon heating

3.2.1 Material Testing

PVS is a two-part silicone mixed in a 1:1 ratio. The tested specimens were cast in bi-
layers disks with two different silicones (PVS Zhermack Elite Double 32, green, and
Zhermack Elite Double 8, pink) in which one layer expands relatively to the other. The
differential swelling of the two silicones, with different Young modulus (pink silicone
has a lower Shore hardness A, in respect to the green, 8 to 32), is accomplished by the
residual polymer chains left in portions of cured elastomers. Consequently, the system
exhibits a physical transformation in response to its internal micro behavior and induced
stresses. We’ll refer to the PVS 32 green as the passive material and to PVS 8, pink, as
the active material.
Following the Timoshenko bimetal model we produced casted circular disks of 10 cm
diameter, with different thickness ratios for the two layers. Once the two-part material
cured, the samples were removed and tested for their transformation. Their final curvature
was affected both by the total thickness as well as the relative thickness of one layer to
the other.

Fig. 4. Tests arranged in order of magnitude of curvature, from left: 14, 11, 10, 13, 18, 0, 17, 15,
12, 16

As shown in Fig. 4, the final curvature achieved after curing decreases as the overall
thickness of the disks increases. For a fixed quantity of green material, the highest
 4D Soft Material Systems 207

curvature has been achieved with the lower quantity of pink. However, the highest
curvature has been achieved with a higher quantity of pink (by weight) with respect to
the green layer. These tests have shown that the best results can be achieved having a ratio
of 2.5 between the green and the pink layer thicknesses. Assuming that the same ratio
of 2.5 could apply to the volume too, when printing, the results were achieved by either
having different layer heights or by changing the patterns (thus surface area). Viscosity
was measured and tuned through the thickener to achieve a range of 800.000–1.000.000
cP to allow printability and to influence the print speed which, for instance, has to faster
for a more liquid paste. Furthermore, a retarder was added (1–4%) in order to tune the
cure time according to the design and fabrication needs.

3.2.2 Shape-Shifting Swelling Rubbers

Initial printed experiments were conducted with two-layered simple geometries such
as rectangles and circles by varying the layers thicknesses and patterns to achieve a
gradient of curvatures accordingly to the printed tests. An interesting finding, as shown
in Fig. 6 (bottom left), was by taking advantage of the liquid phase of the silicone
(increasing the amount of retarder according to the printing time), it was also possible
to print a layer of PVS 8 (pink) underneath, on top, or inside the green layer. While the
viscosity of PVS 32 was still low, the nozzle could pass through it and print underneath
it simplifying the multi-material printing process. Indeed, in order to print a three layer
structure made of two materials, instead of swapping the cartridges two times, it was
possible to change them only once. Regarding the pattern actuation, the main direction
of the material expansion/shrinkage, and the resulting bending orientation, depended on
the main direction of the active material. For instance, as shown in Fig. 5 concentric
circles would create a positive Gaussian curvature. Other printed objects demonstrated
the ability of lattice structures to constrain the deformation of a surface (Fig. 7). While
in Fig. 8, the local curvature induced by the swelling, creates a surface change in the
regular dotted pattern on the other side of the piece, generating a morphable fur.

Fig. 5. Left: from left to right - ratio values of the green layer area over the pink are 1, 2 and 3.
Right: the ratio of the green layer over the pink is 3 and the overall thickness is reduced.
208 G. Grassi et al.

Fig. 6. Printing patterns of the active layer: from one side to two sides stripes and full layer

Fig. 7. Lattice structures used to constrain the actuation of a surface

Fig. 8. Morphable fur

4 Discussion and Conclusions

Throughout our experiments silicone exhibited extreme flexibility in terms of material
testing enabling optimization both of the mix design and of the fabrication process. As
a matter of fact, the methodology applied in this research allows for customization at
each step of the procedure by intervening either on the material composition and/or
on the design and fabrication strategies for the production of active components. This
expands the current domain of 4D printing research which has been constrained to
proprietary materials and machines or complex processes in laboratory environments
that are difficult to scale. Our approach exploits off-the-shelf two-part silicones that are
 4D Soft Material Systems 209

widely available and have a wide range of material applications, combined with a novel
form of printing to create complex and precise structural transformations. Applications
of tunable 4D printed silicones can include active hybrid material systems as sensorial-
responsive environments (Ahlquist 2019), soft shape-change tangible interfaces (Ou
et al. 2016), and wearables emotional interfaces (Farahi 2018).
Both the silicone-ethanol mixture and PVS bi-layers have proven to be feasible
materials for RLP. The main challenges for silicone-ethanol were related to silicone
porosity and ethanol volatility, which jeopardize the durability of the material system.
On the other side, PVS bi-layers tests, are not reversible once actuated. Therefore, future
works can focus on improving the durability of the material systems herein presented
and designing more complex structures.
Finally, 4D Soft Material Systems have proven to enable a wide array of kinetic
design with an easy-available material such as silicone.

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