Polymer 228 (2021) 123926

Contents lists available at ScienceDirect

Polymer
journal homepage: www.elsevier.com/locate/polymer

4D printing: Fundamentals, materials, applications and challenges

Aamir Ahmed a, Sandeep Arya a, *, Vinay Gupta b, Hidemitsu Furukawa c, ***, Ajit Khosla c, **
a
Department of Physics, University of Jammu, Jammu, Jammu and Kashmir, 180006, India
b
Department of Mechanical Engineering, Khalifa University of Science and Technology, Masdar Campus, Abu Dhabi, 54224, United Arab Emirates
c
Department of Mechanical System Engineering, Graduate School of Science and Engineering, Yamagata University, Jonan 4-3-16, Yonezawa, Yamagata, 992-8510,
Japan

A R T I C L E I N F O A B S T R A C T

Keywords: 4D printing refers to single-material or multi-material printing of a device or object that can be transformed from
4D printing a 1D strand into pre-programed 3D shape, from a 2D surface into preprogramed 3D shape and is capable of
Soft robotics morphing between different dimensions. Such transformations are facilitated by, e.g., heating, light, or swelling
Active origami
in a liquid, electrochemically and by programming different sensitivity to, e.g., swelling into various parts of the
Hydrogels
Polymers
designed geometry. These techniques offer adaptability and dynamic response for structures and systems of all
Smart materials sizes, and promises new possibilities for embedding programmability and simple decision making into non-
SMPs electronic based materials. Potential applications include; robotics-like behavior without the reliance on com­
plex electro-mechanical-chemical devices as well as adaptive products, garments or mechanisms that respond to
user-demands and fluctuating environments. In this paper, we have discussed fundamentals and laws governing
4D printing, materials that are employed in 4D printing along with applications such as soft robotics and
challenges that need to be overcome for 4D printing to evolve as a mainstream manufacturing technology.

1. Introduction
The history of 4D (four-dimensional) printing starts with the de­
velopments and advances in the 3D (three dimensional) printing tech­
nology. Therefore, it is very important to know about some history about
3D printing technology which eventually led to the introduction of 4D
printing. A brief knowledge about 3D printing, its history, printing
techniques, etc. Will help the reader in better understanding the concept
of 4D printing and its evolution. 3D printing is a technique of layer-by-
layer printing simple or complex structures using computer aided design
(CAD) under the control of a computer. The 3D printing saw its boom
when a patent filed by Chuck Hull (of 3D Systems Corp.) for the ster­
eolithographic process met a huge interest in the world [1]. But the term
3D printing was associated later to the adhesive jetting technology uti­
lizing powder bed in MIT (Massachusetts Institute of Technology) [2].
There is also another term called additive manufacturing (AM) or Rapid
Prototyping (RP) used for 3D printing on the industrial scale. The 3D
printing technology is currently used by media and consumer commu­
nities in the form of various printings such as stereolithography (SLA),
selective laser sintering (SLS), fused deposition modeling (FDM), jet 3D
printing (3DP), selective laser melting (SLM), direct ink writing (DIW),
electron beam melting (EBM), etc. [3,4] Due to the attainment of high
speed, high accuracy, low cost of production, 3D printing has attracted
immense interest from the industrial giants and academic institutions.
3D printing is multidisciplinary and involves the collaboration of
various fields of science and technology such as material science, me­
chanical engineering, data processing, etc. The developments in 3D
printing in recent years have enabled researchers to create complex
shapes that were impossible to produce using the old traditional tech­
niques [5–12]. The researchers have been successful in creating
remotely actuated robots [13,14], designs using algorithms and machine
learning [15–21], multi-material (bioinspired) designs [22–28], micro­
environments for tissues [29,30], and drug delivery systems using the
3D printing technology [31,32].
In 3D printing, fused deposition modeling (FDM) and stereo­
lithography (SLA) are the most commonly used techniques. In FDM,
molten material is deposited on a bed layer-by-layer using a heated
nozzle, whereas the SLA uses a laser for printing. The other commonly
used techniques for 3D printing are powder bed fusion, material extru­
sion, binder jetting, material jetting, sheet lamination process, vat

* Corresponding author.
** Corresponding author.
*** Corresponding author.
E-mail addresses: snp09arya@gmail.com (S. Arya), furukawa@yz.yamagata-u.ac.jp (H. Furukawa), khosla@yz.yamagata-u.ac.jp (A. Khosla).

https://doi.org/10.1016/j.polymer.2021.123926
Received 12 March 2021; Received in revised form 27 May 2021; Accepted 29 May 2021
Available online 6 June 2021
0032-3861/© 2021 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
A. Ahmed et al.
photopolymerization process, and directed energy deposition [7]. There
has been a huge advancement in research and development in 3D
printing and it is used by researchers for its ability to print complex
structures. But still, it is not ready to be used at large scale due to its slow
cycle time [6]. Also, the lack of printing material having high perfor­
mance adds to the barrier in 3D printing technologies. Moreover, in 3D
printing, the main focus is on the fabrication of structures that are
mostly static using a single or more materials. Hence, the applications
where a dynamic function is needed, the 3D printing cannot meet the
demands. Such dynamic functions include self-folding packages [33],
wind turbines which are adaptive [34], and soft grippers for surgical
applications [35]. Research conducted by Momeni et al. discovered that
the use of shape memory polymers (SMP) greatly improves the me­
chanical and structural properties of wind turbine blades [34]. These
SMPs based blades were fabricated in one print cycle for which we
require an additional dimension to 3D printing i.e. time. The introduc­
tion of a new dimension in 3D printing introduced a new era of printing
called Fourth-dimensional printing (4D printing). This paper is divided
into various sections and we will first discuss the 4D printing-basics,
materials, techniques used. And then is the latter part of the paper we
will focus on its application and future scope.
2. 4D printing
It was during TED conference at MIT in 2012, Skylar Tibbits showed
how there occur transformations in a static printed object (by 3D
printing) over time [36]. It has been seen that a simple 3D structure can
be transformed with time into a more complex structure [37]. This result
into a new era of printing involving a new dimension in 3D printing i.e.
time, and this was given a separate name of 4D printing technology. The
fourth dimension is the time, and we can say in a simple way that the 4D
printing is 3D printing with an extra dimension of time added to it. Or
we can say the changes in the 3D printed materials with time result in
the 4D printed materials. And after that speech by the Tibbits, the 4D
printing started to gain its popularity among the researchers and engi­
neers of various disciplines. The first research paper on 4D printing was
published in 2013 (a year from the TED speech). In this research work,
the concept of printed active composites (PACs) was used to transform a
printed sheet into a complex structure with the help of shape memory
effect (SME) [33]. Since then, the research in 4D printing has increased
exponentially all over the world. One of the basic characteristics of the
4D printing is that it is not static and can reshape with time with the
pre-programmed command from the computer.
Many definitions have been formulated for 4D printing. The earlier
being that 4D printing is simply 3D printing with time [37–39]. But the
definition that clearly explains the 4D printing is “4D printing is the
evolution in the shape, property, and functionality of a 3D printed
structure with time when it is exposed to heat [40,41], light [42,43],
water [38,44], pH [45], etc.” Another definition that can beautifully
sum the 4D printing is “4D printing is the creation of objects which alter
their shape when removed from a 3D printer. These objects
self-assemble when exposed to the water, heat, and air, etc. due to the
chemical reaction of material used”. 4D printing is a combination of 3D
printer, smart material, and a well-programmed design [46–50]. In 4D
printing, with changes in the environment, various metamaterial
structures are generated. Currently, the majority of research going on in
4D printing focusses on the shape-changing ability such as elongation,
bending, corrugation, and twisting of 4D printed materials. These abil­
ities make the 4D printed materials a perfect suite for making toys [51],
robots [52], lifters [53], microtubes [54], and lockers [55].
If we want to look more deeply into the developments of 4D printing
as compared to some other major emerging technologies in the world,
then we have to take a look at the Gartner hype cycle [56]. The Gartner
hype cycle shown in Fig. 1 [57], is an evaluation done on some major
emerging technologies in the world and how they would align with the
new business trends and applications in the next 5–10 years. Form the
2
Polymer 228 (2021) 123926
Fig. 1. Gartner hype cycle plotted for the year 2018. Reproduced from
Ref. [57] with permission. Copyright 2018, Wiley-VCH Verlag GmbH & Co.
KGaA, Weinheim.
hype cycle, 4D printing is in the stage of trigger innovation, and in the
next 10 years, it will see an increase in the expectation and development
and will be a mainstream research area during these 10 years.
Another way of justifying this claim of the hype cycle is to look at the
publications and citations of the research papers regarding 4D printing
technology. The data collected for the publications and citations for the
years 2013–2018 is shown in Fig. 2 [57]. From the two plots in Fig. 2(a)
and (b), it is quite clearly evident that the citations have increased
theatrically than the publications which itself is an indication of the
popularity of the subject.
Moreover, if we take a look into Fig. 3 [57], the USA is leading all the
countries in the world for publications in 4D printing which is then
followed by China, Singapore, and England (Fig. 3(a)) and if we take a
look at the different techniques used in 4D printing, FDM is the most
popular technique used in most of the publications (Fig. 3(b)).
When compared to 3D printing, 4D printing offers various advan­
tages such as fast growth of smart and multi-materials [58], more flex­
ible and deformable structures, and can add more potential applications
to both 4D and 3D printing. According to the most recent available
report, the research publications on 4D printing is increasing after every
year. Table 1 shows the data regarding publication during the last 10
years.
It also offers better efficiency, quality, and performance when
compared to traditional techniques where the 4D printed structures can
self-enhance their properties and behavior. The low utilization of ma­
terials in 4D printing contributes towards maintaining the sustainable
development [59]. The development of softwares like Kinematics (by
Nervous Systems) and Project Cyborg (by Autodesk Research) made the
printing of 4D structures easier [60]. Using these softwares, the designer
can visualize the structure before printing which results in the efficient
fabrication of the 4D structures [61].
2.1. Factors responsible for 4D printing
The 4D printing relies mostly on the five factors and all the five
factors must be kept in view while performing 4D printing. These five
factors are-the AM process, the material used for printing, stimuli,
mechanism of interaction, and modeling [62].
The first aspect is the AM process used for printing. The AM process
enables the production of printing material form the digital information
provided by the computer and this does not require any intermediate
tool. There are various AM processes such as stereolithography (SLA),
selective laser sintering (SLS), fused deposition modeling (FDM), jet 3D
printing (3DP), selective laser melting (SLM), direct ink writing (DIW),
electron beam melting (EBM), etc. and almost all of the process can print
A. Ahmed et al. Polymer 228 (2021) 123926

Fig. 2. Comparison of the publications (a) and citations (b) of articles for 4D printing from 2013 to 2018. Reproduced from Ref. [57] with permission. Copyright
2018, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fig. 3. Comparison of the publication by countries (a) and techniques (b)used in 4D printing from 2013 to 2018. Reproduced from Ref. [57] with permission.
Copyright 2018, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Table 1
Number of publications related to 4D printing published every year.
Year 2011 2012 2013 2014 2015 2016 2017 2018 2019

Publications 1392 2437 3529 3744 3263 4902 4687 5970 7031

Fig. 4. Diagrammatic representation of the factors responsible for the 4D printing.

3
A. Ahmed et al.
a 4D material as long as the material used for printing is compatible with
the printer.
The next factor is the material used for printing which must be
responsive to the stimuli while being sandwiched layer-by-layer. These
materials are also known as programmable materials or smart materials
(SMs). The type of these smart materials determines the kind of stimuli
that will be used and the response of these materials towards the stimuli
will determine the self-transformation ability of the material.
The third aspect or factor is the stimuli that will be used while 4D
printing. The stimuli used can be physical, chemical, and biological. The
physical stimuli include light, moisture, magnetic and electric energy,
temperature, UV light, etc. The chemical stimuli include the chemicals,
pH level, use of oxidant, and reductant. And the biological stimuli
include the enzymes and glucose. With the introduction of stimulus,
physical or chemical changes such as relaxation of stress, motion of
molecules, phase changes are produced in the structure which result in
the deformation of the structure.
The fourth and fifth factors are the mechanism of interaction and
mathematical modeling. When a stimulus is applied to smart material,
not all materials can undergo the required transformation. We need to
provide the interaction mechanism such as mechanical loading or
physical manipulation mechanism which will plan the sequence of shape
change. After providing the interaction mechanism, the mathematical
modeling is required to plan out the duration for which the stimulus will
act upon the smart material. In Fig. 4, a diagrammatical representation
of all the factors responsible for 4D printing is shown.
In the light of the factors responsible for 4D printing, the 4D printing
can be summed up as “The stimulus is applied on the smart material
using a suitable interaction mechanism and mathematical modeling
during an AM process which results into a 4D printed structure”.
2.2. Laws of 4D printing
F. Momeni and J. Ni formulated three laws that govern the shape
changing behavior of all 4D printed structures [63]. These laws provide
better understanding of physics behind the shape changing ability of 4D
printed structures. These laws are stated as;
2.2.1. First law
The first law states that, “all the shape changing behaviors such as
coiling, curling, twisting, bending, etc. of multi-material 4D structures are due
to the relative expansion between active and passive materials”.
2.2.2. Second law
The second law states that, “there are four physical factors behind the
shape changing ability of all multi-material 4D structures i.e., mass diffusion,
thermal expansion, molecular transformation, and organic growth”. All
these factors lead to the relative expansion between active and passive
materials, which results in shape morphing under a stimulus.
Due to absorption or adsorption of stimuli (water or ion), there occur
a change in the mass of the structure. This transport of matter eventually
leads to the relative expansion of the material thus, resulting in shape
deformation. The mass change can also occur when the stimuli used is
electrical, thermal, chemical, light, etc. The thermal expansion can
cause deformations in structure, because with an increase or decrease in
temperature there occur an increase or decrease in average distance
between atoms and molecules resulting into relative expansion. Thermal
expansion can also result when the stimuli used in electrical, light, and
UV because all of these can change the temperature of structure. When
the mass and temperature of the structure are constant, relative
expansion can occur in the structures due to molecular transformation.
Electric field, magnetic field, light, mechanical force, etc. can cause
molecular transformation in such cases. For example, on applying an
electric or magnetic field, the dipoles in the material will be aligned
according to the direction of field applied resulting in the transformation
of molecules. Similarly, the application of mechanical tension on
4
Polymer 228 (2021) 123926
polymers will cause the chains to be aligned in a particular direction and
exposing a photo-sensitive material to UV light will result in trans-to-cis
conversion. Organic growth is an increase in length and weight of a
living organism over a period of time [64]. Due to an increase in weight
and length there will occur a relative expansion of active and passive
materials resulting in shape changing behavior. The organic growth can
be mostly triggered in living organisms using electrical stimuli. But
besides this we can also use heat, water, pH, mechanical force, etc.
Organic growth is used in describing the shape changing behavior of
cells, tissues, scaffolds, stents, organs, etc. developed in 4D bioprinting.
2.2.3. Third law
The third law of 4D printing states that, “time-dependent shape-
morphing behavior of nearly all multi-material 4D printed structures is gov­
erned by two “types” of time constants”. These constants can be equal,
large, and can vanish with respect to other depending upon the stimulus
and material used for 4D printing. A mathematical bi-exponential for­
mula for fourth dimension was also derived that can be used in future
modeling of 4D structures by incorporating it in software and hardware.
2.3. Type of materials used in 4D printing
In 3D printing, due to recent developments, we have been able to
place materials more precisely and flexibly which has helped a great
cause in 4D printing [65]. The materials used for 4D printing are
generally called Smart Materials as they have the ability to change their
properties over time [60]. These materials can respond to the external
stimulus and possess behaviors like self-assembly, self-healing, shape
memory, and self-capability [66]. 4D printing not only uses materials
capable of shape change, but also produce color change when exposed to
UV and visible light. In this section, we will discuss the type of smart
materials used in 4D printing based on their response to the stimuli.
2.3.1. Materials responsive towards moisture: hydrogels
Materials that are responsive towards moisture or water have
attracted huge interest due to a wide range of applications. These ma­
terials are also called Hydrogels as they possess an extraordinary ability
to respond towards the water or moisture. They are actually a class of 3D
networks of polymer chains formed by crosslinking which can expand
up to 200% of their original volume after contact with the moisture.
Hydrogels also possess a high capability of printing as various structures
were developed using hydrogels capable of folding, bending, stretching,
and geometrical expansion. These are highly biocompatible and easy to
print when used with direct ink writing [67]. But the only problem is
their slow reverse response so, one has to wait hours before they dry and
shrink. To overcome this, the hydrogels need to be programmed so that
anisotropy will be added to their swelling. A research group of Gladman
et al. combined cellulose fibrils with the hydrogen ink and these were
aligned due to the development of shear forces produced because of the
contact between the print bed and hydrogel ink [68]. Due to this
alignment, the transverse swelling became four times the longitudinal
swelling which allowed to program the 4D printed structure. Another
group Mao et al. confined the hydrogels in one direction using stiff
materials which resulted in an anisotropic swelling of the hydrogel [65].
Zhang et al. fabricated films from stearoyl esters (CSEs) cellulose and
these hydrophobic films showed a more precise and faster response than
the earlier ones [69]. Normally, hydrogels are put into the water and
they absorb the water until their saturation point is reached. But the
problem with this mechanism is that it limits the intermediate control­
ling ability of hydrogels. To overcome this, we can control the temper­
ature of the aqueous medium. This was demonstrated by Breger et al.
when they fabricated the microgripper joint using (poly-­
N-isopropylacrylamide-co-acrylicacid) pNIPAM-AAc hydrogels [35].
When the temperature of water in which the gripper was immersed was
changed, reverse actuation was possible. G.M. Spinks et al. also printed
4D material using Alginate/pNIPAM ICE gel inks [70]. To stop
A. Ahmed et al.
over-swelling, the application of hinge designs was also demonstrated
by Tibbits et al. They made a self-folding structure from PolyJet printers
which stopped to fold at some angles which were pre-programmed to
avoid the excessive swelling [51].
2.3.2. Materials responsive towards temperature: thermo-responsive
These are the smart materials that are responsive to the heat or
temperature stimuli. The changes in the shape of these materials with
respect to the thermo stimuli are mainly due to two mechanisms: the
shape change effect (SCE) [71], or the shape memory effect (SME) [72].
SME is the transformation of a deformed (plastic) materials into its
original shape using external stimuli [73,74]. Those smart materials
which show SME effect are called shape-memory materials (SMMs) and
these are classified as shape memory polymers (SMPs), shape memory
alloys (SMAs), shape memory ceramics (SMCs), shape memory hybrids
(SMHs), and shape memory gels (SMGs) [34]. SMMs are further divided
as one-way, two-way, and three-way materials depending upon the
number of shape transformation. In one-way SMMs, the initial shape
cannot be regained after deformation whereas in two and three-way
SMMs the original shape can be regained after deforming into a tem­
porary shape via an intermediate shape [75]. Depending upon the
environmental conditions, the SMMs can also exhibit SCE along with
SME. Out of various types of SMM, the SMPs are mostly used by the
researcher all because of their easy to print property. The SMPs are able
to recover their original shape after being deformed using the right
stimulus [76]. The SMPs have a characteristic glass transition temper­
ature (Tg) which is usually higher than the temperature at which they
are mostly operated. Above Tg, and at specific thermal and mechanical
conditions they are programmed and when cooled they possess a tem­
porary shape which is free from any external loading. And when the
temperature is again raised above Tg, they retain their original shape
[77]. This is due to the reason that below Tg, the internal energy of
polymer chains is low and they cannot move freely resulting in the
material being glassy and rigid.[78] But above Tg, the energy is provided
to the polymer chains causing their movement as a result the material
becomes rubbery and prone to deformation and manipulation [79,80].
Ying et al. fabricated an SMP ball using the SLA printing technique and
the ball had the capability to transit between a flat plane and its original
shape with high durability [81]. An SMP flower that can bloom upon
heating was fabricated by Ge et al. [82] and the same technology is also
used to fabricate smart grippers. Also, Bodaghi et al. found that an SMP
can be preprogrammed using heat in the FDM printers [77,83]. The
SMPs have been modified by the researchers in order to make use of
their special characteristics for printing applications i.e., thermoset and
thermadapt SMPs [84–89]. The SMPs possess two or three intermediate
states and there is a possibility of maintaining an intermediate state
which is stable as well. Another SMM that is widely used in 4D printing
is SMA having shape changing capability dependent upon the change in
temperature [90]. SMAs have a characteristic temperature called
transformation finishing temperature above which they have a high
yield strength and Young’s modulus of elasticity i.e., above this tem­
perature they are super-elastic [90]. Nitinol (Nickel–Titanium) is the
most used SMA owing to its good SME properties, high strain and
strength, stable cyclic properties making it more bio-compatible and
actuation suitable [91–93]. Ni–Mn-Ga based alloy (SMA) has been
investigated for printing 4D parts using binder jetting technique where
the printed parts showed reverse shape transformation ability upon
cooling and heating [94]. SMA based on Cu have also been explored for
4D printing as they can efficiently withstand post-printing processes and
are cost-effective. Despite not being so popular as an SMA due to their
poor ductility, various research works have been conducted using these
Cu-based SMAs [95–97]. Another class of SMAs based on Iron (Fe) have
also been explored for 4D printing (using SLM printing technique) and
they are cheap and possess pseudo elastic strains [98]. SMAs have
mostly been investigated for their application in the field of biomedicine
such as orthopedic, orthodontics, surgeries, physiotherapy, etc. [99]
5
Polymer 228 (2021) 123926
Also, in the past few years the number of publications and patents filed
using SMAs have increased [99]. The major limitation of using SMAs in
4D printing is their high cost. Also, the SMPs are more flexible, lighter,
biocompatible, and consume less energy than SMAs [100–102]. To
overcome the limitations with SMPs and SMAs, shape memory com­
posites (SMCs) were developed by integrating SMP with SMA, or SMP
with a reinforcing fibre [103]. The reinforcing fibre can be a long fibre,
short fibre, nanoparticle, nanofiber, etc. With better mechanical prop­
erties and high deformation driving force [103]. In addition to these,
SMHs are the smart materials obtained by combining SMAs, SMPs, and
hydrogels. These can be responsive towards temperature, pressure, and
multi-stimuli at a time.
In case of SCE materials, the deformation is proportional to the
stimulus applied or we can say that the deformation is varying between
the extreme states [71]. When the material is thermally responsive, the
SCE takes place in the bi-layer structures. The structure bends as the
stress is experienced while maintaining the same interface area between
the layers. A graphene-based structure was fabricated by Hu et al. and
they demonstrated how it changes into a flat sheet on heating and re­
tains its original cylindrical shape when cooled down [104]. A sharp
change in temperature is required to bring such drastic changes in the
shape.
2.3.3. Materials responsive towards the light: photo-responsive
Light also acts as an indirect stimulus for the deformation of smart
materials. When an area of a smart material that is responsive to the
light (also called photo-responsive material) is exposed to the light, it
will absorb the light which will eventually produce the heating phe­
nomenon in it. And as explained earlier, heat acts as a stimulus for the
deformation of smart materials, hence a shape change occurs in the
photo-responsive material. That is the reason why light acts as an in­
direct stimulus because it does not bring the change directly like heat
and moisture. A sequential self-folding structure was demonstrated by
Liu et al. where the light is absorbed by the joints and they get heated up
resulting in the shape change [105]. The rate at which heat is absorbed
by the joints depends upon the source of the lights used and the color of
the joints. In another work by Kuksenok et al. the light was used in a
different way to bring deformation in the photo-responsive material.
They infiltrated a chromophore (photo-sensitive) into some specified
locations of a polymer block (gel) so that only those locations get
deformed when light is made incident on the structure [106]. There
have been some other reports as well where a UV light (weak) and
visible light were used to deform the 4D structure [107].
2.3.4. Materials responsive towards the electric energy: electro-responsive
Electricity is also an indirect stimulus like light, as it has also been
proved to show heating effect due to the resistive nature of material
through which it passes. Hence, such materials that undergo deforma­
tion due to their responsive behavior towards the electric current are
called Electro-responsive materials. Miriyev et al. made an artificial
muscle from a mixture of ethanol and silicon elastomer. Current when
passed through the muscle results in the evaporation of ethanol due to
which its volume increases and this eventually led to the deformation or
expansion of the muscle [108]. The absorption or desorption of water in
polypyrrole (PPy) can be controlled with the electricity and this concept
was used by Okuzaki et al. to make microrobot (origami) using PPy.
When the robot was kept in humid conditions, due to the absorption of
moisture a voltage was developed which drives its head forward. But the
tail of the robot follows the head when the desorption occurs and the
voltage was absent [109].
2.3.5. Materials responsive towards magnetic energy: magneto-responsive
The magnetic field or the magnetic energy is again an indirect
stimulus that can bring deformation in the smart materials. And those
materials which are used to print 4D structure because of their defor­
mation response towards magnetic energy are called Magneto-
A. Ahmed et al.
responsive materials. It was Breger et al. who achieved a remote-control
mode using magnetic nanoparticles in microgripper (printed from
hydrogel). When a magnetic field was applied to the printed structure, it
began to show response which can be controlled by a remote [35]. The
4D printed structures using magneto-responsive materials have a huge
potential in the field of metal and polymer printing with only one
drawback that the size of the print must be light in weight so that it
would be affected by the magnetic field.
2.3.6. Piezoelectric materials
Piezoelectric materials can produce a charge when mechanical stress
is applied to them. The effect of producing electric charges by the action
of a mechanical force is called Piezoelectricity. Piezoelectric materials
can also be used for the 4D printing applications as they can deform
under the influence of a mechanical force. The phenomenon is simple,
the stress will be applied and charges will be produced which will
eventually bring changes in the structure (as the charge can produce
deformation).
2.3.7. Materials responsive towards pH
These are the smart materials that can respond towards the pH value
and undergo changes in shape and volume according to the pH value
[110–112]. The deformation in shape in respond to different pH values
make them suitable for 4D printing technology. Polymers that are pH
responsive have been used in 4D printing such as polyelectrolytes, as
they can receive or donate protons on pH value change due to the
presence of an ionizable side group. When a proton is released, polymer
chain stretches due to electrostatic repulsion causing a deformation in
the structure and when a proton in accepted, the structure neutralizes.
Polyelectrolytes contain polycations or polybases (such as ammonium
salt) as the functional group and polyanions or polyacids (carboxyl or
sulphonic groups) as the ionizable side chains. The side chains release
the proton at higher pH values (stretch) and accept proton at lower pH
values (neutralize). Whereas the functional group release the proton at
lower pH and accept the proton at higher pH values [113–119].
pH-responsive materials have found applications in drug delivery [116,
120,121], soft robots, actuators [110], valves, biocatalysts and colloid
stabilization [115,122]. A diagrammatic representation of the type of
materials used in 4D printing is shown in Fig. 5.
In Fig. 6 [33,82,123,124], some of the 4D printed structures fabri­
cated from hydrogels, photo-responsive, thermo-responsive, electro, and
magneto responsive materials have been diagrammatically shown. The
Fig. 5. Schematic representation of the types of materials used for 4D printing.
6
Polymer 228 (2021) 123926
research work in 4D printing based on these smart materials will be
discussed in the other sections of this paper. It must be noted that smart
materials can be responsive towards one or two stimuli. For example,
SMPs can be responsive towards temperature, light, and electric energy
whereas composite materials can be responsive towards different
stimuli.
2.4. Properties of 4D printed materials
4D printing after its advent has been discussed to have various ap­
plications in different fields of research and technology. This technology
has dramatically reduced the volume used for storage in printed struc­
tures and also opened various aspects for the transformation in the
printed structures and devices [125]. We can directly produce the
complex structures from a 3D printer or we can first produce simple 3D
structures and then assemble them to produce an overall complex
structure [71]. The 4D printing has simply made the printing dynamic
where the researchers have the choice to choose different methods and
materials as per the requirement. In contrast, 3D printing was static
where the same material was used for various applications. Due to its
dynamic features, the researchers have focused their work towards the
4D printed structures. When we look deep into these 4D printed struc­
tures, we find that their ability to self-assemble and self-repair also adds
to their potential for various applications. For example, they can be used
to build surgery devices that can penetrate the body and then
self-assemble at the required location, etc. [71] The three properties of
the 4D printed structures that have made these structures more viable in
their application are: self-assembly, self-adaptability, and self-repair.
2.4.1. Self-assembly
This is the ability of a smart material to assemble form individual 3D
printed structures and then become a complex 4D structure. This ability
of 4D printed materials can prove very helpful when used in harsh
environmental conditions such as space. Such 4D printed materials can
be used for transportation to the Space Stations. Also, this ability can be
used for satellite and antennae construction i.e., its parts can self-
assemble in the space [62]. Moreover, we can create self-assembled
building making use of this property of the 4D printed materials. Such
structures can be made with small labor force and prove to be of huge
help in war situations [126]. We can also remove some errors or defects
in the construction by using 4D printed structures. Such structures can
be introduced into the defected area where they can self-assemble and
A. Ahmed et al.
remove the defect. Also, if bending or joint is required in a certain part of
a building, we can introduce a 4D printed material there which we
already know can act as joint as well as bend. Raviv et al. believe that the
wastage of energy, money, materials, etc. must be removed by using
smarter construction materials and techniques. Their argument can be
made true by using smart materials (4D printed) programmed by com­
puters for construction which will increase the speed and accuracy of the
construction [127]. But it must be noted that the self-assembly property
of the 4D printed materials will not be efficient for every purpose. This
property will prove to be helpful where such an operation is required
[128].
2.4.2. Self-adaptability
The 4D printed structures can adapt to the environment and condi­
tions, and make necessary changes in the structure. For example, a
certain 4D printed material may assemble quickly in some conditions
whereas it may take a larger time to assemble in some other conditions.
This may be termed as the self-capability of that particular material.
Also, some materials as discussed earlier change their shape and struc­
ture upon cooling and heating. This may be regarded as their self-
capability to adjust as per the situation. This property of the 4D prin­
ted materials can prove very helpful in designing medical devices and
tissues which need to be self-adaptive. Moreover, this property can also
be exploited in electromechanical systems. Again, we need to find the
areas where such an application is needed and only then this property
can prove to be useful.
2.4.3. Self-repair
Correcting the errors and defects on its own is the property of the 4D
printed materials that can be very useful in various applications. This
property is generally termed as self-repair. For example, the applications
where we require self-healing (pipes), recycling, etc., various self-
repairing 4D printed materials can prove to be very helpful [127].
Self-healing inks (hydrogels) have already been manufactured and there
are more areas we need to find where we can exploit the self-repair
property of these materials for more application purposes [129]. And
there is no need to mention again that we need to find the applications
where self-repairing is required for better results with this property of
4D printed materials.
7
Polymer 228 (2021) 123926
Fig. 6. Diagrammatic representation of 4D
printed materials using (a) photo-responsive
material (Reproduced from Ref. [123] with
permission. Copyright 2017, Wiley-VCH
Verlag GmbH & Co. KGaA, Weinheim), (b)
electro-responsive material, (Reproduced
from Ref. [82] under creative commons li­
cense (CC-BY 3.0). Copyright 2016, Springer
Nature), (c) SMP based electric circuit with
its d) on and off response (Reproduced from
Ref. [124] with permission. Copyright 2015,
Wiley-VCH Verlag GmbH & Co. KGaA,
Weinheim.), and e) folding process of a 4D
printed cube (Reproduced from Ref. [33]
with permission. Copyright 2013, AIP
Publishing).
3. 4D printing techniques
4D printing as we know is the advancement of already existing 3D
printing. The techniques used in 4D printing are the AM printing tech­
niques. In this section, we will briefly discuss about the different printing
techniques used in 4D printing.
FDM is the printing technique in which the material to be printed is
extruded out through a nozzle and gets hardened on a substrate. The
nozzle is supported by a motor which allows it to move in X and Y axis.
When a 2D layer is printed on a substrate, the nozzle is moved upwards
in Z axis and another layer is printed over the already printed layer. In
this a way, a layer-by-layer addition is done till a final 3D or 4D printed
structure is obtained. FDM is used widely for both 3D and 4D printing-as
it is cost-effective when it comes to maintenance and consumables used.
FDM technique has been modified regularly to make it compatible for
printing new materials. For example, Tian et al. [130] developed a new
FDM technique for 3D printing of composites like continuous
fiber-reinforced thermoplastic composites (CFRTC). This new technique
made use of two inputs for material (as the material to be printed is a
composite), one nozzle for extrusion, and this method proved useful
while printing a structure requiring high mechanical properties. Boda­
ghi et al. [83] studied on the application of FDM printing for SME ma­
terials. They performed simulations and also printed structure capable of
SME using FDM printing. FDM is used widely is 4D printing and also
research is being carried out to make it more effective and compatible
with new materials.
SLA (Stereo lithography) is another printing technique that is used in
4D printing technology. In this technique, a light sensitive material
(photopolymer) is used that gets solidified when exposed to light.
Various radiations such as UV light, visible light, X rays, electron beam,
etc. can be used to solidify the material. But on a commercial scale only
UV and visible lights are used [131]. The mechanism is simple i.e.; the
light falls on the material and creates a curing reaction due to which the
molecules of resin bind together forming a solid structure. Upon curing,
the viscosity of photopolymer increases and are converted into gel which
eventually converts into a solid cross-linked polymer [131]. SLA has
been successfully employed to fabricate complex and difficult structures
efficiently. Also, materials have been developed that are compatible
with SLA printing technique.
A. Ahmed et al.
The first innovative work in 4D printing was done using SLS printing
where Stratasys Connex printer and UV light was used [51]. In this
method, a laser beam is used to scan the powder-based material
layer-by-layer [132]. This technique can be used to print different ma­
terials such as wax, polymers, metals, and ceramics [133–135]. Poly­
urethane, PCL, Polyetheretherketone (PEEK), and polyamide are the
polymers that mostly printed using SLS technique. Another laser-based
technique used in 4D printing is SLM. The only difference is that the
powder is fully melted in SLM and there is no requirement of
post-printing processes [136]. Also, the speed of beam and intensity of
laser can be adjusted as per the requirement. SLM is mostly used to print
SMAs.
Directed energy deposition (DED) is another type of additive
manufacturing process. It is mostly used to print metal parts, but can be
used for polymers and ceramics as well [137]. In this technique, a hear
source is used on the nozzle arm to melt the material post extrusion and
material is printed as wire or powder jet. Printed structures having shape
memory behaviors have been printed using DED [138–141]. In addition
to these, inkjet printing has also been popularly used for 4D printing
[142]. In this technique, structural data from a computer is constructed
layer-by-layer as small ink drops extrude out of nozzle [143]. The inkjet
printing has been successfully applied for printing cost-effective elec­
tronic components and devices, where Polyethene terephthalate (PET)
and Polyethylene naphthalate are the most commonly used polymeric
substrate [144]. The wearable devices like sensors, displays, energy
devices, etc. have been fabricated usng inkjet printing technique [145].
This technique is also very useful for bioprinting of cells, tissues, and
origami structures [146,147]. Some other used techniques are DIW
printing and projection micro stereolithography (PμSL) mostly used for
bio-medical applications of 4D printing. DIW is similar to FDM printing
technique and can be used to print wide range of materials. Thermo­
plastics, hydrogels, sol-gel oxides, polyelectrolytes, etc. can be used as
inks in DIW.
4. 4D printing of different materials: research work
As already discussed in the earlier section of the paper that most of
Fig. 7. Diagrammatic representation of various 4D printing techniques along
with the stimulus and potential applications. Reproduced from Ref. [57] with
permission. Copyright 2018, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
8
Polymer 228 (2021) 123926
the 4D printed structures are fabricated using the already available 3D
printing techniques such as selective laser sintering (SLS), fused depo­
sition modeling (FDM), stereolithography (SLA), jet 3D printing (3DP),
direct ink writing (DIW), selective laser melting (SLM), etc. In Fig. 7
[57], all these 4D printing methods along with the stimulus and po­
tential applications are diagrammatically represented. It was Zhao et al.
who argued that it is not necessary that only 3D printing techniques can
produce 4D structures. By controlling the parameters of printing very
precisely, deformations can also occur in a single, non-active material
over time [148]. Hence, we can print 4D structures using any printing
technique where dynamic changes in the shape and functions of the
materials can be made possible. In this section, the focus will be on 4D
printed structures that have been fabricated using different materials
and printing techniques.
4.1. 4D printing using multi-materials
The “multi-materials” is a combination of various polymers having a
particular geometric structure which has been printed using some 3D
printing technique. The printing of multi-materials is a very difficult task
and there are only a few printers available that can print these multi-
materials. All of these multi-material printers are ink-jet printers and
there are only two printers that are commercially available i.e., PolyJet
Connex series by Stratasy and ProJet MJP series by 3D systems. These
printers only work with the company inks based on photopolymer
resins. There is also an alternate technique of DIW printing which can be
used for printing multi-materials. DIW was built as a technique in which
a ceramic ink was used to fabricate complex ceramic structures [149].
The ink coming out of a nozzle can immediately retain its shape which is
a plus point of DIW printing that can be exploited for multi-material
printing applications. When multiple nozzles consisting of different
inks (hydrogels, sol-gel, etc.) are used in DIW printing, a multi-material
structure can be printed. The principle that governs the 4D printing
using multi-material structures is very simple. Internal stress needs to be
created in some locations of a printed structure and when the stress is
released, the structure will undergo more shifting in the shape in a
predictable manner. The internal stress that we require here can be
generated using the swelling of hydrogels or using SMPs. We will discuss
both procedures of stress generation in multi-materials structures (for
4D printing) along with the different printing techniques used.
4.1.1. Multi-material 4D printing using hydrogels
Using Stratasy Connex 500 printer, Tibbits and his group of re­
searchers printed 4D structures using a moisture responsive material
over a plastic base [51,126]. The material expanded when exposed to
the moisture or water due to the formation of a hydrogel on contact with
the moisture. This expansion resulted in deformations which resulted in
a 4D printed structure as shown in Fig. 8 (a,b,c) [38]. And by the vari­
ation in the distribution of materials, the angle as well as the length of
the printed structures can be tuned. The group of researchers used this
method to create a sinusoidal wave, a hyperbolic surface, and trans­
formed letters “MIT” into “SAL” as shown in Fig. 8 (d,e,f).
But the limitation with this method was that the structure degraded
with many folding and unfolding cycles. Also, there was only a 30%
expansion of the material using this method. In order to overcome these
limitations, a more robust material was required which should not
degrade with time and also provide more expansion. The answer was the
multi-material application and Naficy et al. printed a 3D structure using
two different hydrogel inks (multi-material) [150]. The structure formed
was responsive towards both moisture and temperature and could also
sustain reversible shape deformations. The two hydrogel inks were
prepared from poly (N-propylacrylamide) (NIPAM) which was
thermos-responsive and poly (2-hydroxyethyl methacrylate) (HEMA)
which was non-responsive towards heat. And polyurethane was used as
a swelling modifier. The structures were constructed using the DIW
printing technique along with some UV exposure. By hydration and a
A. Ahmed et al.
Fig. 8. 4D printed structures using hydrogels by the research group of Tibbits. (Reproduced from Ref. [38] under creative commons license (CC-BY 3.0). Copyright
2015, Springer Nature).
Fig. 9. a) DIW printed structure using two hydrogel inks i.e. NIPAM on the top layer and HEMA on the bottom layer, b) the demonstration of printing (left) and shape
change (right). Reproduced from Ref. [150] with permission. Copyright 2016, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
change in temperature, the structure showed significant and reversible
deformations and bending which is illustrated in Fig. 9 [150]. More
complex structures can be fabricated using this multi-material printing
approach as this method provides more freedom and flexibility in the
deformation process.
The 4D printing based on multi-materials has its limitations such as
low response speed of hydrogels, loss of mass during cycles, instability in
the shape of the structure, etc. These limitations can be overcome by
making some changes in the hydrogels using the latest technology [151,
152]. But these techniques are not easy to carry out and require
expertise and may prove to be expensive. Mulakkal et al. [1563 developed
a composite (cellulose-hydrogel) ink by joining a cellulose pulp fiber
with carboxymethylcellulose (CMC) hydrocolloid. The hydrogen
bonding between CMC, cellulose fiber, and water was ensured by adding
clay platelets to the ink. The structures printed using this ink showed
reversible shape transformation upon hydration and dehydration.
4.1.2. Multi-material 4D printing using SMPs
SMPs; as already discussed are used mostly by the researchers for
printing 4D structures. These can be used to construct multi-materials
based 4D structures owing to their more robust nature and a broad
range of mechanical properties [153]. As compared to hydrogels, the
SMPs can be programmed into several temporary shapes and they can
retain their original fabricated shape irrespective of the number of de­
formations. Whereas, the hydrogels can only transform between two
shapes (defined during the fabrication step) no matter how refined they
9
Polymer 228 (2021) 123926
are. This essential feature of SMPs distinguishes it from the hydrogels
[154]. SMPs are also favored over SMAs owing to their wide Tg range of
− 70 to 100 ◦ C [155], low cost and toxicity, and easy manufacturing
[156]. Among other SMMs, the SMPs ae preferred for 4D printing due to
their faster response rate, easy printing, and dominant response strain
[157].
One of the early 4D printed structures based on SMPs was recorded
by Ge et al. using PACs [33]. This work has already been mentioned in
the earlier part of the chapter where a discussion was made on SMPs.
The 4D printed structure along with various deformations (bend, twist,
fold, etc.) is shown in Fig. 10(a) and Fig. 10(b) [33].
Moreover, many other active devices can be produced by simply
integrating PACs with other structures. An active origami for 3D struc­
ture creation can be enabled by using PACs as hinges. This was actually
done and various origami structures were built which folded into a
pyramid, a box, an airplane, etc. [89] Active hinges can also be printed
by simply changing the behavior of SMPs and this was demonstrated by
Mao et al., the method was easy and simple to perform [55]. Due to the
time-dependent behavior of hinges, the structure was sequentially
activated when a uniform temperature was applied. Such materials that
can be exploited using temperature, heat, moisture, etc. to form hinges
are called Digital SMPs. The name digital SMP was used to refer to a
mixture of two materials i.e., tango black and Vero white compatible
with Objet Connex 260 (a multi-material 3D printer). Materials with
different Tg can be used for the fabrication of hinges, and a sequential
folding can be obtained when we use materials with higher values of Tg.
A. Ahmed et al. Polymer 228 (2021) 123926

Fig. 10. (a) represention of the fabrication mechanism of SMP with (b) various deformation operations. Reproduced from Ref. [33] with permission. Copyright 2013,
AIP Publishing).

In the case of 4D printing involving SMPs, a number of programmed
steps involving cooling, heating, loading (with fixtures and jiggs), stress
application, etc. are usually employed. A direct 4D printing process
involving SMPs was reported by Ding et al. [40] In their work, the
research group demonstrated a new technique of printing in which they
combined the steps involved in printing with the programming step. As a
result, when an external stimulus (part of programming) like heating
was applied, a direct change was observed in the shape and structure of
the printed material. In this work, a multi-material comprising of an
elastomer and an SMP was utilized. The bonding between the elastomer
and SMP was strong enough to build a strain in the laminate. The strain
was locked by the SMP and when the temperature was increased above
Tg, the strain was released which resulted in the bending of structure.
The bent structure along with some other shapes (flower, dome, helix)
that was built using this technique is shown in Fig. 11 (I) [40]. But all the
shapes that were built using this SMP-based technique were irreversible
and we know that in 4D printing the focus is more on an operation where
we can achieve reversible operations.
Hydrogels; as already known can exhibit the reversible change in
structure. But the problem is that they are soft and here we require a
robust material. To overcome this difficulty, Mao et al. combined the
hydrogels with SMPs to produce a robust and reversible shape-changing
multi-material. The shape change in this printing technique was due to
the swelling mechanism of hydrogels, whereas the temperature response
of SMPs helped in locking the shape by regulating the time required for
shape change i.e., the shape remained unchanged when the temp was
constant. The mechanism of printing with this technique along with the
shapes that were fabricated is shown in Fig. 11 (II) [158]. But again this

Fig. 11. (I) Direct 4D printing using multi-material based on an elastomer and an SMP, a) Direct printing mechanism, b),c), and d) different shapes printed using this
technique (Reproduced from Ref. [40] under creative commons license (CC-BY 3.0). Copyright 2017, Springer Nature), (II) 4D reversible printing using muti-material
comprising hydrogel and an SMP, e) fabrication mechanism, f), and g) different shapes fabricated (Reproduced from Ref. [158] under creative commons license
(CC-BY 3.0). Copyright 2016, Springer Nature).

10
A. Ahmed et al. Polymer 228 (2021) 123926

method also had some limitations as the accuracy speed was quite low i.
e., full actuation requires 10–20 h. This actuation speed can be increased
by improving the hydrogel ink making procedure, but then the hydrogel
inks which are customized may not work in the multi-material printers
(already discussed that these printers are only compatible with the
company made inks). As most of the multi-materials are printed using
ink-jet printer so, another drawback with multi-material based 4D
printing is that the properties cannot be tuned beyond the capability of
the ink or resin used. And due to these limitations, the wide range ap­
plications of these multi-material 4D printed structures are constrained.
Hence, we have to move towards single material printing to increase the
range of applications of 4D printed structures.
4.2. 4D printing techniques using a single material
Despite the limitations with multi-material based printed structures
these were employed largely in the earlier era of the 4D printing tech­
nology. The reason being the fact that the earlier research conducted in
the field was mostly by scientists and engineers. They applied the ma­
terials that were already being used in 3D printing techniques. But later
on, the application of different materials started to increase when the
material scientist gained interest in the field. And an alternative
approach was formulated for 4D printing where the structure was
directly printed form the active or smart material. These active materials
can be SMPs and hydrogels which resulted in the application of single
(active) materials for 4D printing. We will discuss the techniques as well
as single materials that are used for printing 4D structures.
devices [124], jewelry and fashion wears [160]. Various photocurable
resins such as tart-butyl acrylate-co-di (ethylene glycol) acrylate,
epoxy-acrylate hybrid, and soya bean oil epoxidase acrylate have suc­
cessfully been applied for printing 4D structures via SLA printing [161].
The 4D printed structures mentioned above have one limitation i.e.,
they can only transform between two shapes; permanent and temporary.
So the focus of researchers went towards fabricating structures that can
switch between multiple shapes and are called multiple SMPs [154]. The
multiple SMPs are easy to construct by simply programming polymers
for a broad range of temperatures (Tg) as they can switch shapes be­
tween these temperature ranges [162]. Yu et al. used Gray 60 photoc­
urable resin to print a multiple SMP based structure in Objet Connex 260
printer [163]. The transition temperature range of Gray 60 is about
40 ◦ C–80 ◦ C, thus providing a wide temperature range to switch between
multiple shapes. And a printed structure with triple shape trans­
formation performance was fabricated as shown in Fig. 13 [163].
By introducing the SMPs hinges, the rotation was also introduced
into the structures. Moreover, the triple-SMPs based printed structure
enabled the researchers to produce multiple shape-changing structures
easily and with only one SMP. The above remarkable results were ob­
tained by utilizing traditional layer-by-layer SLA and DLP printing. As
we already know that the layer-by-layer printing mechanism is time-
consuming and laborious. To overcome the time consumption an ul­
trafast digital 4D printing technique was developed by Huang et al.

4.2.1. Photo-sensitive materials based 4D printing

Photo-sensitive or photo-responsive resins are naturally responsive
to the temperature (discussed earlier). And the 3D printed structures
using these resins possess the SME. The structures using these resins are
mostly printed by SLA and DLP printing techniques. Hence, SMPs based
on these resins can be used for 4D printing. And it was Cohn et al. who
first attempted to print a structure based on photo-responsive SMPs
[124]. They used a photo-sensitive material PCLDA (polycaprolactone
dimethacrylates) based SMP to fabricate a complex structure. The
printing technique used by the group was SLA (printer Picoplus39,
Asiga) and they successfully printed various geometries using the above
SMP. In Fig. 12 [124], the setup and the various complex geometries
printed by the group are shown. Moreover, the structures built using
these photocurable SMPs can be used for surgical, electronic, and
Fig. 13. A triple shape changing structure built using Gray 60 resin as multi
common product applications. These applications can be achieved by
SMPs. Reproduced from Ref. [163] with permission. Copyright 2015, Elsevier.
integrating the printed parts with medical devices [159], electronic

Fig. 12. Diagrammatic representation of the photocurable resin based SMP used for 4D printing (SLA), along with the a) mechanism, and b), c), and d) various
complex geometries constructed using the given technique. Reproduced from Ref. [124] with permission. Copyright 2015, Wiley-VCH Verlag GmbH & Co.
KGaA, Weinheim.

11
A. Ahmed et al. Polymer 228 (2021) 123926

[164] In this technique, they fabricated a flat 2D sheet of poly (HEMA)
hydrogel by exposing it to light and a pixelated polymer network was
built in the sheet. The step-wise layer-by-layer addition reduces the
printing speed and hence a continuous printing process will enhance the
printing speed. This can be achieved using ultra-fast 4D printing. In this
technique, stress is introduced into a 2D polymer network which then
transforms into a 3D structure. The stress is relieved upon heating,
exposing to light, etc. and the structure further develops with time
resulting in a 4D structure. The stress can be introduced into the 2D
polymer network by dispersion in water converting it into 3D structure.
When the 2D sheet is immersed in water, variable internal stress created
between the pixels leads to swelling, and conversion from 2D to 3D
structure took place. The parameters of the geometry of this 3D structure
can be easily tuned by the light exposure and this will result in different
3D shapes sensitive to light pattern. In Fig. 14 [164], a complete dia­
grammatic representation of the whole process is shown; (a) with the
formation of 2D sheet, (b) production of pixelated network, (c) con­
version of a 2D sheet into the 3D structure, (d) tuning of geometry with
light exposure, (e) various 3D shapes obtained upon using a different
light pattern, and (f) the printed shape can be further deformed using
proper UV monomer system. The process of ultra-fast 4D printing can be
summed up as; printing of hydrogel as a 2D sheet which then transforms
into a 3D structure upon the application of various stimuli. The tech­
nique utilizes the responsive behavior of hydrogels towards different
stimuli and as a result, multi-shape printed structures are fabricated with
just one single printing. The method is simple, fast, and requires no
viscous resins. Moreover, this method takes 1 min to complete the
printing and prove very helpful in designing complex structures. Similar
light sensitive technique has also been reported for printing 4D polymer
network structures [165].
relatively poor performance as compared to thermoset SMPs when it
comes to the ability of maintaining fixed shape and recovering the
original shape. But printing thermoset SMPs using the FDM printer is not
quite an easy job. But when Yang et al. reported a series of Diels-Alder
thermoset resins which can easily recover their shape [166], this
dilemma of printing thermoset SMPs using FDM printers was over. These
SMP materials had a great adhesion among the layers and also possess
low anisotropy. But the only problem with these Diels-Alder resins was
their low transition temperature which restricts their application of
being used as SMPs.
On the other hand, Wei et al. used dichloromethane, poly (lactic
acid), and benzophenone to make a UV cross-linkable ink that can be
easily printed using DIW printing [167]. The moment ink came out of
the nozzle it was fixed as a printed structure due to the rapid evaporation
of dichloromethane. The cross-linking between poly (lactic acid) chains
was triggered further when it was exposed to a UV light, which
enhanced the shape memory behavior of the printed structure. Also, the
introduction of Fe3O4 particles produced a remote actuation feature in
the structure which will prove helpful in developing intravascular stents.
In Fig. 15 [167], the whole research work is shown in a diagrammatic

4.2.2. FDM or extrusion-based printing

It was discussed in the earlier part of the paper that the FDM printing
is the most common and famous printing technique used by the re­
searchers for printing 4D structures. The reason is; it is simple, cheap,
and has high printing speed relative to other discussed techniques.
Similar to FDM is the DIW, both these techniques are used for extrusion-
based printing. The DIW has the advantage that it can be used to print
various materials. The setup is simple in both the techniques, the ma­
terial (to be printed) extrudes from the nozzle and immediately get
fixed. Then more material is added layer-by-layer until the final required
structure is obtained. The printing process of both the methods is quite
the same and despite having advantages over one another, structures
printed with both techniques have been reported. A report where
polyurethane as SMP was printed using an FDM printer has already been
Fig. 15. DIW printing; a) printing mechanism, b) bending in presence of
discussed in Fig. 6(a) [123]. In this work, a thermoplastic SMP (carbon
magnetic field, and c) application as intravascular stents. Reproduced from
black) was printed and as we know that thermoplastic SMPs have
Ref. [167] with permission. Copyright 2017, American Chemical Society.

Fig. 14. The diagrammatic representation of the ultra-fast 4D printing technique. Reproduced from Ref. [164] with permission. Copyright 2016, Wiley-VCH Verlag
GmbH & Co. KGaA, Weinheim.

12
A. Ahmed et al.
representation; (a) with the printing process and (b) intravascular stent
application.
DIW printing can also be used to print hydrogels. The research work
of Gladman and his group have already been discussed in the earlier
section (hydrogels) of this paper. They produced a composite hydrogel
ink made of acrylamide matrix with fibrils cellulose embedded in it. This
ink was then successfully printed into a complex structure with different
shapes and geometries [44]. Poly (2-vinylpyridine) (P2VP) was printed
using FDM technique where the printing ability and mechanical prop­
erties were enhanced by adding a thermoplastic polymer i.e., acryloni­
trile–butadiene–styrene (ABS) to it [168]. The printed structures were
responsive towards pH after printing process and acted as hydrogels.
Okwuosa et al. [169] developed a method of printing enteric-coated
gastric resistive tablets. They employed a dual extrusion-based method
in which one nozzle was used to print the core and other nozzle was used
to print the shell. The core comprises of polyvinylpyrrolidone (PVP)
carrying drugs like budesonide, diclofenac sodium, and theophylline
whereas the shell is a pH responsive methacrylic acid co-polymer. Al low
pH, the shell was insoluble which inhibited the release of drug in the
gastric environment and at high pH values, the shell was soluble
releasing the drug at the intestinal site or phase. Using the
above-mentioned concept, Larush et al. [170] developed a
pH-responsive hydrogel (using acryl acid monomer) that can swell and
release drug at higher pH values.
4.3. 4D printed techniques using non-active materials
As we have observed in the case of 3D or 4D printed structures that
the stress whether intrinsic or induced in the smart materials is mostly
responsible for shifting shapes from 2D to 3D and 3D to 4D structures.
But if we look closely towards non-active materials this stress in inter­
nally existent in these materials. This internal stress is introduced into
the non-active materials during the printing or programming process.
Most of the time this internal stress is eliminated during the application
purpose of non-active materials, as this affects the performance and
stability of the product. But if this internal stress is exploited in a positive
and controlled manner, this can turn into a blessing and can prove to be
useful in achieving shape-changing geometries with non-active mate­
rials. Zhang et al. reported that internal stress is developed in the ther­
moplastic polymers like polylactic acid (PLA) and acrylonitrile
butadiene styrene (ABS) due to rapid heating and cooling during their
FDM printing. The internal stress developed was removed by heating the
polymer above its transition temperature (Tg) which resulted in the
transformation of printed structure into new shapes i.e., square or
hexagonal PLA structures were transformed into hexagons or quadran­
gles upon heating up to 90 ◦ C [171,172]. Moreover, heating of nozzle or
platform and increasing the speed of fabrication can also be used to
release the internal stress. In another work by the same group of re­
searchers, PLA strips were printed on a sheet of paper. A 3D structure
developed when the printed paper was cooled and again the flat sheet
structure was obtained on heating [172]. Zhao et al. also developed a
mechanism of transforming printed flat sheets into a complex origami
structure [148]. They used a photo-sensitive poly (ethylene glycol)
diacrylate resin to print origami structures (on exposing to light) as
shown in Fig. 16 [148]. Hence, it can be concluded non-active materials
can also be used for printing complex shape-changing structures by
having proper control over the internal stress developed in such mate­
rials. Fuwen et al. [173] printed soft robotic grippers using PLA polymer
as shape changing material. The PLA was printed as a leaf on a paper
substrate inspired by cabbage bionic leaf structure. Soft robotic grippers
were made by combining two or more bionic leaves. The bionic leaf
design has the advantage easy manufacturing, plus the reversible
deformation of leaves can be controlled by temperature.
Year 2020 also saw various research work being published on 4D
printing despite COVID-19. Cheng et al. printed shape memory co-
polyesters using 4D printing as elbow protective devices [174]. They
13
Polymer 228 (2021) 123926
applied UV assisted FDM technique to print the structure. The
co-polyester consists of PLA and poly (ε-caprolactone) along with a
functional coupling agent that can join the two segments. PLA as hard
segment provided the co-polyester good mechanical properties and poly
(ε-caprolactone) acted as the switching or shape changing segment.
Exposure to UV light provide a better bond strength between the layers
and good shape memory property. The excellent SME of the co-polyester
was characterized by three models as shown in Fig. 17(a) whereas the
ability to act as elbow protector is shown in Fig. 17(b) [174].
The UV-assisted FDM developed has the ability to fabricate more
flexible SMPs in the future. Li et al. [175] prepared a novel shape
memory polyimide (SMPI) ink that can be used for both extrusion
molding and digital light process. The ink was used to fabricate struc­
tures with good shape memory behavior which was described by
airplane, ultrasonic motor, and pagoda as shown in Fig. 18(a). More­
over, the polyimide ink was used to print self-folding box and grippers
(that can pull 15 times more weight than itself) as shown in Fig. 18(b).
Su et al. presented a novel, inexpensive, and an easy additive method
of 4D printing using polyurethane (PU) paint composite as precursor
[176]. Carboxymethyl cellulose (CMC) and SiO2 were added to the
polyurethane paint to form separate composites. CMC and SiO2
enhanced the rheological property and curing rate of polyurethane paint
without altering its shape memory properties. Also, the polyurethane
composite showed better mechanical properties as compared to pure
polyurethane and exhibited shape transformation upon heating. This
method of printing PU composites will prove useful in tissue engineer­
ing, soft robotics, etc. In Fig. 19 [176], the mechanism and 4D structures
fabricated with PU/CMC and PU/SiO2 are shown diagrammatically.
Shao et al. [177] in a novel approach fabricated 4D structure which
can be driven by electricity. The composite of silver nanowires
(Ag-NWs) and PLA was used to print the structure, where Ag-NWs were
used to ensure the electric conductivity producing heat and simulating
deformations in PLA. The 4D structure was applied as gripper in cold icy
environment and petals of flower were also printed where each petal can
be deformed separately upon applying a voltage. This work will pave
way for multi-functional application of 4D structures in different envi­
ronmental conditions and can be applicable in biomedicine, robotics,
aircrafts, etc. In soft robotics, the use of 4D printed SMPs and hydrogels
for actuation process is limited due to their slow response and inability
to exhibit reversible actuations. Thus, in soft robotics the application of
UV curable elastomers has been widely used for actuation purposes. But
these also lack application where a larger deformation is required.
Hingorani et al. [178] presented a method that can enhance the stiffness,
strechability, and durability of these UV curable elastomers by adding
mono-acrylate and urethane diacrylate to it. The structures were char­
acterized for their enhanced mechanical properties and robotic finger,
grippers, deforming lattice structures were also demonstrated.
Hoa et al. [179] argued about 4D printing of composites (4DPC)
method can be used to print twisted and curved structures. 4DPC is
similar to 4D printing with difference being that the composite material
used in 4DPC is continuous fiber composite (used in making aircrafts,
turbine blades, and automobiles) of high strength (100 MPa) and stiff­
ness (180 GPa). The shape deformation of 4DPC printed structures de­
pends upon the position, anisotropy, and stacking sequence of different
layers of composite material. Upon cooling and curing, the deformation
occurs in the structure or laminate resulting in twisted and curved
structures. Moreover, the configuration of twisted and curved laminates
was calculated experimentally and using finite element method (FEM).
Using 4DPC, Hoa et al. [180] printed the English alphabets “A”, “C”, “D”,
“I”, “N”, “O”, “R” and they were presented as “CONCORDIA”- the name
of the university as shown in Fig. 20 [180]. 4DPC has potential to be
used for printing blades of hockey sticks and turbines, and in future
more applications can be developed.
Meta-materials are known for their multi-functional properties such
as zero Poisson’s ratio, exceptional thermo-mechanical properties, and
dynamical behavior [181–186]. These are man-made materials designed
A. Ahmed et al. Polymer 228 (2021) 123926

Fig. 16. Diagrammatic representation; a) of the mechanism used to print, b) origami structures from flat shapes. Reproduced from Ref. [148] with permission.
Copyright 2016, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

14
A. Ahmed et al.
Fig. 17. Diagrammatic representation of, a) three models (kung fu panda, terracota warrior, and bird’s nest stadium) characterizing the SME properties of co-
polyester based 4D printed structures and b) representation of the application as elbow protector with software based structure (left) and real printed architec­
ture on Hulk model. Reproduced from Ref. [174] with permission. Copyright 2020, Elsevier.
by repeating unit cells to achieve such extraordinary properties. These
materials have been built using traditional 3D printing. Bodaghi et al.
[187] printed reversible energy absorbing meta-sandwiches (soft-hard)
using 4D FDM printing. They arranged elasto-plastic hard SMPs with soft
hyper-elastic polymers to attain meta-structures. The behavior of the
meta-structures was simulated accurately using FEM models for loading
and un-loading cycles, whereas the experimental studies proved the
reversible deformation behavior of the meta-structures. The novel
concept of developing reversible 4D printed structures will open a new
field of study in 4D printing and can be used for shock and impact (ac­
cidents) protection applications.
The application of thermoplastic polymers with shape memory
properties in 4D printing is a widely discussed topic and various research
works have also been done on them. But Goo et al. [188] developed a
method of using single thermoplastic polymer (ABS) having no shape
memory property in 4D printing. The anisotropy was developed in the
polymer by programming the printing paths purposely and the thermal
deformations were produced in the structure as a result of anisotropy. A
metal extrusion printer was utilized for printing the structures. The
structures after thermal deformation were irreversible and can be used
for applications requiring permanent deformation. This method can be
used for 4D printing of various polymer with no shape memory property
and would help to increase the horizon of the materials used in 4D
printing. In order to enhance the structural strength and accuracy of
deformation in 4D printed structures, Yu et al. [189] developed a
composite of PLA and carbon fibre reinforced PLA (CFPLA). The struc­
ture printed using this composite was demonstrated to have better
structural strength and possess accurate deformations.
He et al. [190] introduced a concept of 4D food printing where the
color of the food can change with storage time. The mashed potato (MP)
or purple sweet potato puree was 4D printed (dual extrusion printer) and
demonstrated to show spontaneous color change with change in pH and
potato flake content. The rheological properties, printing performance,
moisture distribution, and texture properties of MP showed a significant
change with pH and potato flake content variation. The work will pro­
vide a new way of printing colorful foods and change the concept of
single food printing to multiple-food printing using 4D printing. In
another work, soy protein isolate (SPI) with k-carrageenan (CAR) and
vanilla flavor (VNL) was used in 4D printing of food product that can
change its flavor upon exposure to heat in a microwave oven [191].
Different flavors of the product at different heat radiation of oven were
reported by using electronic nose and tongue over time.
Choong et al. [192] described a high speed 4D printing of SMPs using
nano-silica (SiO2). The SMP used was tBA (tert-butyl
15
Polymer 228 (2021) 123926
acrylate)-co-DEDGA and the printing method applied was UV-based DLP
printing. The addition of SiO2 to SMP reduced the printing of each layer
from 4s to 0.7s and further enhanced the mechanical properties of SMP.
Nano-silica used here acts as a “super-catalyst” which enhances the
photo curing rate of SMP when exposed to UV light eventually resulting
in increased printing speed. This method will introduce speed and better
mechanical properties to 4D printed SMPs.
The extensive application of cellulose compounds in 4D printing led
to the evaluation of using computational ultra-sonication microstruc­
tures in 4D printing by Oladapo et al. [193] The microstructures are
designed such that they can change their shape with time as a response
to the moisture. The cellulose specimen was extracted, analyzed, and it
was found that hydrogels between the pulp tissues provide ideal and
accurate distribution of fibers providing adequate roughness. And the
leakage potential developed after hydration and dehydration affects the
shape memory of cellulose.
Thus, the discussion makes it clear that the 4D printed materials are
printed using techniques like SLA, DIW, FDM, and ultra-fast 4D printing.
Using these techniques, we can fabricate 4D structures composed of
multi-materials, single-active materials, and non-active materials.
Further modification in the printing techniques can give complex and
structures with more deformations and bends. So, there is always a
window for modifications and experimentation in the printing methods
of 4D structures. That is probably one of the reasons why many re­
searchers, engineers, material scientists, etc. are interested in this field
of research. The freedom of trying different stimuli, materials, com­
posite materials, printers, modifications has opened various fields of
applications in 4D structures.
5. Applications of 4D printing
In this section, we will discuss some areas of research where the
application of 4D material has proved useful. So that the reader will be
introduced to such various fields and maybe in the future, he/she will
produce some extraordinary results. The 4D printing technology is only
in its initial stages of development, but it has already gathered huge
interest from various fields of research and technology. The US army has
already started a program in three different universities to develop 4D
printed materials which can be helpful in the field of defense and pro­
tection. For example, 4D printed coating of defense vehicles which can
adapt to the different environmental conditions and change their shape
accordingly. The uniform of a soldier made of 4D printed material which
can alter its shape after coming in contact with a sharp object. The self-
assembled 4D printed materials can prove to be game-changing in case
A. Ahmed et al. Polymer 228 (2021) 123926

Fig. 18. Diagrammtic representation of a) shape memory behavior of printed structures like aeroplane (top), ultrasonic motor, and pagoda using SMPI. b) appli­
cation of SMPI to print self-folding box (top) and gripper (bottom). (Reproduced from Ref. [175] under creative commons license (CC-BY 3.0). Copyright
2020, Elsevier).

of war as they can assemble in a quick time.
The 4D printed materials can amazingly influence the day-to-day life
of people. The printed products can adapt to the changing environment
conditions (humidity, temperature, pressure, moisture, etc.) keeping in
mind the user demands. Moreover, the 4D printed materials consume
less volume so their shipping and arrangement will require less space
and labor. After their usage, the products can be used to meet new de­
mands owing to their property of self-capability and self-repair. Their
application in space-related programs has a huge potential. Solar cells
and antenna used in satellites and space vehicles can be 4D printed. They
can self-assemble in space reducing labor and can also adapt to the
varying conditions of the space. Medical sciences can be a potential area
where 4D printed structures can do wonders. 4D printed stents can be
introduced into the body through a small incision and when it reaches
the desired location, external stimuli can be applied to change its shape
in order to get the required results. Also, a Nano 4D printed device can
be introduced into the body and will self-assemble when it reaches the
required location and the desired operation can be carried out. 4D

16
A. Ahmed et al.
Fig. 19. 4D structures printed using PU composites. a) Method of preparing PU composties, b) 4D printed structures using PU/CMC composite, and c) 4D printed
structure using PU/SiO2 composite with shape memory behavior. (Reproduced from Ref. [176] under creative commons license (CC-BY 3.0). Copyright 2019, Taylor
and Francis).
Fig. 20. Diagrammatic representation. a) English alphabets “a”(I), “c” (II), “d”
(III), “i” (IV), “n”(V), “o” (VI), “r” (VII) printed using 4DPC. b) word “Con­
cordia” using alphabets printed using 4PDC. (Reproduced from Ref. [180]
under creative commons license (CC-BY 3.0). Copyright 2020, Elsevier).
printing has also gained a huge response in the field of robotics and
actuators where they can be used to advance the technology. In robotics,
the expensive materials like motors, sensors, and materials difficult to
17
Polymer 228 (2021) 123926
assemble can be replaced by the 4D printed structures. Moreover, the
application of these materials will reduce the size of the robots. Self-
healing pipes, removing errors in the construction, self-healing hydro­
gels, etc. are some of the possible applications of 4D printed materials
that are expected to come true in future time. These printed materials
can also be used in the field of sensors and printed artificial organs
[194].
5.1. Medical applications
Bioprinting is the application of the material transfer process for the
fabrication of biological materials like a cell, tissue, molecules, etc. to
accomplish the biological functions. The field of bioprinting developed
as a result of an increase in organ transplants. The supply of organs for
the transplant is low and the current tissue engineering has certain
limitations which eventually led to the development of a new branch of
tissue engineering called 3D or 4D bioprinting. Bioprinting as compared
to traditional tissue engineering has various advantages such as high
accuracy in cell positioning, fabricate tissues with high density, and can
produce large tissue-engineered products. With the advancements over
A. Ahmed et al.
the years, 3D bioprinting evolved into 4D bioprinting. The term 4D
bioprinting refers to the 3D printing of biocompatible materials that can
evolve with time after printing [195]. The evolution here refers to the
transformation of properties, shape, physical, chemical, and biological
composition of 3D structures. With the advancement in biology, the
definition of 4D bioprinting has been extended to the functional trans­
formation and maturation of 3D cells or tissues over time [44,196,197].
Thus, 4D bioprinting includes a biomaterial (that can change shape) and
the maturation of 3D printed structure using this biomaterial which is
shown in Fig. 21(a) [57].
The possibility of constructing a complex structure using 4D bio­
printing is the main reason that 4D bioprinting is being proposed as the
next-generation tissue engineering technique. Also, 4D bioprinting has
the highest resolution among all other bioprinting techniques which
allows the integration of more information and details into the tissue. 4D
bioprinting comprises focusing a pulse of laser on a cartridge resulting in
the removal of material, which is then deposited layer-by-layer on the
substrate. The properties of the materials that can be used for 4D bio­
printing must be the same as discussed earlier in the paper i.e., tem­
perature, moisture, light, electric and magnetic energy, pressure, pH,
etc. responsive. 4D bioprinting enabled the fabrication of biological
structures that can alter their shape under the influence of a stimulus. A
self-folding cell origami was developed by Kuribayashi-Shigetomi et al.
[198] using cell-laden 3D microstructures as shown in Fig. 21(b), that
self-folded into a cube. Moreover, an integrated tissue-organ printer
(ITOP) capable of printing stable human tissue of any shape was re­
ported by Kang et al. [199] The ITOP was able to fabricate cartilage,
calvarial bone, and skeletal muscle as shown in Fig. 21(c). In the
biomedical applications, 4D bioprinting has depicted a huge potential in
Fig. 21. Diagrammtic representation of bioprinting. (a) Shape-changing and maturation of 4D printed biomaterial (b) and self-folding origami which folded into a
cube, and (c) ITOP based printing of tissues and organs. (Reproduced from Ref. [57] with permission. Copyright 2018, Wiley-VCH Verlag GmbH & Co.
KGaA, Weinheim).
18
Polymer 228 (2021) 123926
drug delivery, tissue fabrication, and suitable organ regeneration and
transplantation [199,200]. Also, with the development of highly 4D
compatible biomaterials, the field of 4D bioprinting is growing as an
active field of research. Using soybean epoxidized acrylate, scaffolds
were printed that can support multipotent human bone marrow
mesenchymal stem cells (hMSCs) [161]. The scaffolds so printed were
able to recover their original shape at the body temperature of humans i.
e., 18.8 ◦ C. And the material showed greater adhesion than PEDGA and
other hMSC with no difference from PLA and PCL. To treat infants with
tracheobronchomalacia, a 3D printed tissue was developed using PCL
that could change shape under resorption conditions and tissue growth
with time [201]. The printed structure was customized for infants less
than 1 year and expands with the changes in the airway size over 3
years. And when the airways were able to function independently, the
material degraded after 3 years. The expansion and degradation of the
PCL device over time is a 4D effect thus, implying the potential of 4D
bioprinting devices that can be used for pediatric applications. In Fig. 22
[161,201], the scaffolds supporting hMSCs and PCL devices to treat
infants with tracheobronchomalacia are shown. A 4D printed model of
the brain was developed recently using near-infrared (NIR) responsive
composite material to assess the behavior of neural stem cells under 4D
transformations [202]. This is one of the fields that is growing as an
application of 4D printing where we can build models of various organs
to study their behavior and composition so that better treatment can be
made available to cure diseases in such organs. 4D printed
nano-biomedical devices can find large applications in the form of bio­
sensors, bioactuators, biorobots, etc. to monitor the physical changes in
cells and tissues.
The biorobots can be used to deliver drugs and therapeutic agents,
A. Ahmed et al.
and also perform surgeries. In the field of orthopedics, 4D printing can
prove very useful in treating abnormality taking advantage of their self-
deformation. Also, the orthopedic models developed can change their
property with respect to the stimuli applied. The orthopedic parts
developed using 4D printing are more flexible, can be an accurate
replica of the patient’s part, and complex surgeries can also be carried
successfully with these parts [161]. 4D printing has a huge potential to
develop in the field of orthopedic in the next coming years [197], where
it can improve the parts used and surgeries carried out. In the future, the
printing of heart, liver, kidney, can be made possible using 4D printing
of smart materials as these can be genetically more fit with respect to the
patient and can be flexible and self-compatible [203,204]. The skin graft
can be fabricated using 4D printing which will be of the same color as
the patient’s original skin and can be used to treat skin burns that can
grow like original skin [50,205]. 4D printed devices can be used for
target drug delivery where medication is required at a specific location.
They can contain the drug and release it when the environment of the
selected location is suitable as stimuli. Malachowski et al. fabricated
“theragrippers” that can be used for target drug delivery in the gastro­
intestinal tract [206]. Azam et al. studied the drug delivery of containers
made from polycaprolactone (PCL) and SU-8 panels, where PCL acts as
thermo-responsive material [207]. 4D-printing can be used for the
fabrication of stents with speed and accuracy. The shape memory
property of 4D printed structures also reduces the area of surgical in­
vasion, and after its implantation, it will regain its original shape.
Bodaghi et al. demonstrated the application of SMP fibers as stents [83],
and Ge et al. also fabricated 4D printed stents using high-resolution SLA
[82]. The DIW printing of PLA inks was used to fabricate 4D stents
responsive towards magnetic energy, that can be controlled and guided
remotely to the area of application [167]. The introduction of 4D
printing in scaffolds made the morphology and structure of scaffolds
reproducible and regular. HEMA, methacrylic acid (MAA), and dieth­
ylene glycol dimethacrylate (DEGMA) copolymers were crosslinked
with ethylene glycol dimethacrylate (EGDMA) to produce contact lens
using 4D printing. Triethylene glycol dimethacrylate (TEGDMA)
co-polymerized with Bis-glycol dimethacrylate (GMA) at room temper­
ature was be used as dental adhesive and composite opening a new are of
19
Polymer 228 (2021) 123926
Fig. 22. Diagrammatic representation of
scaffolds for hMSCs and PCL device for in­
fants with tracheabronchomalacia. (a) SEM
images (I) and photo images of scaffolds (II),
(b) confocal images of scaffolds on hMSCs
(Reproduced from Ref. [161] under creative
commons license (CC-BY 3.0). Copyright
2016, Springer Nature), (c) computer-based
design on the PCL device, and (d) pre and
post-operative images of the patient
(Reproduced from Ref. [201] with permis­
sion. Copyright 2015, American Association
for the Advancement of Science).
application of 4D printed SMPs in dental sciences [208]. Thus, 4D
printing has a huge potential in medical applications, where it can
improve clinical outcomes, decrease complications in surgeries, can be
used for target drug delivery, fabricating scaffolds and stents, dental
applications and provide accurate detail about the anatomy of the body
[209,210].
5.2. Application in soft robotics
In traditional robotics, hard materials like metals, hard plastics, and
ceramics are used for developing robots [120,130]. These robots are
designed for particular applications and environment, and cannot
withstand any environmental conditions. They cannot attain large de­
formations and cannot perform tasks that require flexibility [211,212].
To overcome these limitations, a field of soft robotics was developed that
can produce robot’s flexible like humans, can vary their stiffness, and
adjust to the environmental conditions [82]. Soft robotics require soft
and smart materials like electroactive polymers (EAPs). Due to these
materials, a soft interaction can develop with fragile objects which
provides a better tolerance towards damaging forces as compared to the
traditional robots. 4D printed structures suit best to the field of soft
robotics as they are flexible, deform, and can adjust to the environ­
mental changes. The actuators for soft robots can be built using 4D
printed structures. Rossiter et al. fabricated dielectric elastomer actua­
tors (DEAs) using 3D printing techniques and this resolved the problem
of time and labor consumption faced in the traditional fabrication of
DEAs [211,213]. The DEAs belongs to the group of EAP smart materials
(4D materials) that can respond to the electrical stimuli [214]. When
electric energy is supplied to DEA, it gets converted into mechanical
energy and the actuator deforms producing motion in the robot. Going
further into the research, the group produced a complex prototype of the
actuator in which the components of actuator were printed on two
membranes in a pre-strain state, and electrodes were attached on both
sides of each membrane. The actuator moved upwards when the voltage
was applied to the upper membrane and the actuator moved downwards
when the voltage was applied to the lower membrane. Another method
of using 4D printing in soft robotics is the embedding of parts into
A. Ahmed et al.
special components during 3D printing and when the object is printed,
parts can be made to self-assemble using external stimuli [215]. A fully
assembled DEA cannot be printed at a time which adds to the limitation
of this method. But in the future, the work can be done in this regard so
that the structures won’t require pre-straining and would prove to be
useful in soft robotics. Soft actuator (SA) can also prove useful in soft
robotics, and these at the same time are cheap, easy to fabricate, and
eco-friendly. In Fig. 23 [215,216], various applications of 4D printing in
soft robotics are shown diagrammatically.
Miriyev et al. fabricated a composite material that can be used as SA
[108]. The SA was made of porous silicon elastomer matrix having pores
filled with ethanol and can be printed easily with 3D printers. The SA
expanded when exposed to heat or temperature, as the ethanol evapo­
rates and thus, can lift weights and bear stress and strain. Also, the SMPs
have been applied as actuators (shape change), but due to their slow
response, they weren’t utilized much in robotics. But with the devel­
opment of 4D printing, complex structures can be fabricated using SMPs
that can be actuated through different stimuli. These can prove useful as
actuators in specific situations. Lopez et al. printed a 4D structure using
liquid crystal polymer (thermos-responsive) as a potential application in
optics [217]. MacCurdy et al. have printed a 3D hydraulic robot via
inkjet printing using non-curing liquid [14]. Pneumatic artificial mus­
cles (PAMs) are also used as actuators as they are lightweight, flexible,
expandable, and can exert large forces [218]. Yap et al. printed soft
pneumatic actuators which can be used in soft robotics. These were
printed using FDM printing, with structures being durable and actuation
more reliable and consistent [219]. Despite extensive growth and
development in 4D-printed soft robots, full and accurate control along
with modeling of these robots still remains a difficult task. This is due to
the reason that these robots possess non-linear dynamics, physical and
Fig. 23. Application of 4D printing is soft robotics. a) robotic finger [215], and b) various applications [216].
20
Polymer 228 (2021) 123926
chemical properties that can vary with time, and stiffness in materials
[220]. To achieve better control of the actuation, a closed-loop 4D
printed soft robotics has been formulated [221]. But this is also in earlier
stages of development and no promising work in this regard has been
published so far. Thus, 4D printing has a huge potential as an application
in soft robotics, but in the future, more such materials need to be
developed that can provide better actuation and control. And the actu­
ation performance and durability of 4D printed robotics is another
challenge that needs to be addressed in the future.
5.3. Application as self-evolving structures
4D printing can be used to fabricate self-evolving structures which
can attain their original shape on contact with water. These were first
developed by Raviv et al. using various multi-materials and were also
named by the research group [127]. The structure was printed using a
hydrophilic polymer over a plastic substrate, the polymer would in­
crease in volume upon exposure to the water. Many complex structures
were fabricated by the group which showed deformations like folding
and stretching. Due to the continuous wetting and drying of the struc­
tures, there occurred the mechanical degradation of the structures. But
these problems can be solved soon by exploring new multi-materials
with self-evolving capabilities. Moreover, other mechanisms besides
moisture can be explored for such materials i.e., temperature and UV
exposure. These self-evolving structures can be applicable in many
fields. For example, these structures can be assembled easily in deep
water conditions which are difficult to obtain with other structures. And
this would prove helpful while repairing parts of objects (ships, boats,
etc.) in deep water. Also, the exploration of deep-water bodies and
plants can be made more advanced using instruments with such printed
A. Ahmed et al.
parts that can be assembled in a deep-water environment. Moreover, the
diving suit used by divers in deep water can also be enhanced using such
self-evolving 4D printed structures.
5.4. Application as active origami
Origami is an art, where a piece of paper is folded into a 3D structure.
One of the key features of origami is the reduction in size which is much
explored in today’s modern world as the compacting of large-size objects
into small space is a requirement in many fields. For example, origami
can be found useful in making cartons, shopping bags, airbags of auto­
mobiles, and in electronics (Photovoltaic solar cells) where we require
small size along with shape-changing features. Traditional origami can
be expensive and hence, an idea of active origami was developed. Active
origami is the designing of an origami structure having the ability to self-
fold [89], and this will require smart materials such as SMPs,
light-activated polymers, etc. 4D printing can be useful in developing
active origami structure, as 4D printed structures can self-fold, and are
easy and cheap to print. Thus, multi-materials such as PACs can be
investigated for application as active origami. Ge et al. designed an
active origami structure using PACs hinges [33]. The flat polymer sheets
were printed with PACs hinges, and these active origami structures were
able to deform into the shape of a cube, pyramid, and an airplane. Active
origami can be further enhanced using different smart materials and
advanced computational tools and techniques that would result in more
flexible 4D printed active origami structures. Also, the printing of more
complex active origami structures can be made possible using sequential
folding, where different parts of the complex structures would not
interfere with each other during folding. Yu et al. have recently
researched on the sequential shape-changing properties of SMPs [222].
A photocurable SMP (UV) was used with SME to achieve the sequential
shape change. As the SMP is temperature responsive, the shape recovery
of SMP can be controlled. Z. Khoo et al. have been researching on 4D
printing of single and multi-material SMPs and their applications [50].
In their work, the used only SMPs as hinges for active origami as com­
parted to Ge et al. (who used SMP in an elastomeric matrix). The
advantage being that multi-material SMPs provide better shape and
design of an active origami structure. Also, an active origami structure
can respond in every direction while being programmed. Using this
approach and making suitable adjustments, the research group have
developed many active origami structures like reconfigurable origami,
multi-folding origami, etc.
5.5. Application in aerospace
In aerospace industry, the manufacturing of parts for the space
missions is very important. The parts must be produced at cheaper costs
and should last for long duration. As already discussed, the 4D printed
structures are produced at low cost and can withstand extreme envi­
ronmental conditions. Moreover, these structures can adjust and modify
with respect to the surroundings. Thus, 4D printing is finding its po­
tential applications in the aerospace industry. International Space Sta­
tion (ISS) printed 3D structures of ABS in microgravity suggesting the
future potential of such materials in the space missions. Moreover, the
printing time is also low and they can be printed in the spacecraft thus,
reducing the reliance on earth for the components. One of the key fea­
tures in the space mission is the use of materials that are self-sustainable.
The 4D structures have the ability to self-assemble according to the
conditions and can be the game changer in such missions. Nitinol, a
shape memory alloy of nickel and titanium, is very popular in the space
industry and has been printed using 4D printing techniques. The 4D
materials can be used for manufacturing parts of the satellites, space
exploration tools that are self-sustainable. The light weight of 4D printed
structures reduces 80% mass of a component. PEEK, a thermoplastic
with efficient stability at high stress and temperature has been printed
using SLS technique and is used for manufacturing parts of the
21
Polymer 228 (2021) 123926
spacecrafts and satellites.
5.6. Application in sensors and flexible electronics
4D printing can be useful in developing sensors. As the 4D printed
structures are responsive towards moisture, temperature, stress, strain,
electric and magnetic energy, pH, etc. Thus, these can act as sensors for
these stimuli. In addition to this, the 4D printing is cost-effective and the
printed structures are light, sensitive, accurate, and highly responsive.
As a result, 4D printing will make sensors more advanced and futuristic.
SMAs not only act as actuators, but can also be used to measure tem­
perature, strain, and detect fatigue and damage inside a structure. Ul­
trasonic additive manufacturing (UAM) which combines metals and
smart materials to print intelligent structures can be used to manufac­
ture intelligent vehicles and aircraft. UAM is a type of 3D printing that
can be used to print intelligent materials i.e., 4D structures. Structures
printed using UAM have reduced mass which can be helpful in the
transportation industry. 4D printing can be used to repairs errors in the
construction, as they can be delivered to the defected site where they can
self-assemble on the application of a suitable stimulus. The self-repairing
ability of 4D printed structures can be used to develop self-healing
structures. The self-healing materials will enhance the reliability and
lifetime of the material systems [222–226]. 3D printed structures with
the capability of self-healing the cracks (developed during printing)
have been fabricated recently. Due to this self-healing capability of 4D
structures, they can be used again and again (recycled) which will help
in reducing the consumption of materials and also save the environment
from waste materials. In the textile industry, 4D printing can find its
applications where the textile would react to the changing environ­
mental conditions and morph accordingly, providing better comfort and
ventilation [67]. 4D printed textiles can also change the color and
texture of the surface according to the changing conditions. On the
surfaces of textiles like cotton, polypropylene, polywood, and polyester,
materials such as PLA, ABS, Nylon could be printed [227]. Also, in the
film and fashion industry 3D printed outfits have started to gain atten­
tion [228]. Moreover, 4D printing can enhance the quality of home
appliances making them more comfortable and adaptive to heat and
moisture. 4D printed shoes can transform according to the requirement
and environment. 4D printed wings of an airplane can adapt to different
air conditions and provide better lift and safety. 4D printed composite
springs used in automobiles as leaf springs have been demonstrated to be
equivalent to the traditional springs [230]. Using 4D printing, the blades
of wind turbine were printed requiring no conventional electrome­
chanical systems such as actuators and sensors [34]. The 4D printing of
these blades also provided more control over the system and energy
production. Also, a smart photovoltaic system was introduced by the
same research group having the capability to deform according to the
availability of the sunlight and providing an efficient solar energy pro­
duction system [231]. The fabrication of electronic circuits and devices
is another application of 4D printing. Deng et al. [232] printed an
electronic circuit with polystyrene films using SLA printing process
whereas the conductive wires were printed using DIW printing. Fabri­
cation of 3D circuits is another application of 4D printing. Zarek et al.
[124] also synthesized a flexible electronic circuit using methylacrylate
where the structure was printed using SLA and conductive ink was
printed using inkjet printing. The fabricated structure was used to light
an LED when heated above the melting temperature (Tm).
6. Challenges and future
4D printing is a new research area that came at the advent of 3D
printing technology. 3D printing itself is in the developing stage. Being a
new field of research and only in its initial stages, 4D printing has some
limitations and challenges that need to be overcome soon. The three
main challenges to 4D printing are challenges in technology, material,
and design. The technological challenges include the unavailability of
A. Ahmed et al.
3D printing technologies. 3D printers that can print 4D structures are
only available in some of the research institutes in the world. In the
current scenario, 4D printing is done using PolyJet and SLM printing
technologies to print multi-material and metallic components respec­
tively. In PolyJet printers, the material (smart) must be in the liquid
state and when exposed to UV light will result in a printed structure,
whereas in SLM a laser is used to print structure by melting the powder
particles. In both cases, the smart material has to fulfill certain criteria i.
e., must be in the liquid state and responsive towards UV light to be
printed in PolyJet and have to be in powder in order to be printed by
SLM. Thus, only a few smart materials would be printed using these
printing technologies. More technological innovation is required to
produce new printing technologies so that more smart materials can be
4D printed. The next challenge is the type and properties of materials
used for 4D printing. To print 4D structures using SMAs like NiTi,
additional care is required to print structures without defects as these
are compositional sensitive. Some smart materials can degrade with
continuous deformation, whereas some materials (hydrogels) degrade
with repeated wetting and drying. In some cases, the material had to be
mixed with some other components to make it printable. Also, the
interaction between smart materials and 3D printing technology poses a
challenge to 4D printing. Thus, more research is needed in discovering
new smart materials that can be printed directly, won’t degrade after
continuous application, and interact smoothly with 3D printing tech­
nology. Designing of the smart structures is the other challenge that 4D
printing face. The smart structure can adjust according to the environ­
ment and make the required changes, so they must be designed properly
in order to get the desired results. Smart structures can work better as an
actuator when produced in a pre-strain mode. But only a few works have
been reported where such a pre-strain mode has been achieved. Also, a
3D printing technique that can directly print the pre-strain membrane is
not available. So, there is a need to work on the designing of the smart
structures in 4D printing. Also, the impact of 4D printing on environ­
ment was not discussed so far, but in year 2020 a paper was published
which argued that the energy consumption by 4D printing of polymers
can be reduced by 37.33% [233]. It was proposed that the shape pro­
gramming and recovery temperature must be 10–15 ◦ C above the Tg, the
concentration of multi-functional crosslinkers must be increased in
materials, and the parameters influencing 4D printing must be adjusted
throughout the printing procedure to reduce the energy consumption.
Once these limitations are sorted out, 4D printing will bring a rev­
olution in the manufacturing and designing of the products in the future.
It will lower the capital requirement, reduce marketing time, make
products easily transportable, reduce the size of products, thus bringing
a new and efficient business model. 4D printed structures can find their
application in the space missions, as they can sustain harsh environment
conditions. The parts of satellites and aircrafts printed using 4D printing
can be easy to assemble in space (as they can self-assemble). And the
deformations required in space using 4D printed structures would not be
a problem. 4D printing can prove effective in simplifying the design of
3D structures. The user-responsive products that can react according to
the user requirements can be printed using 4D printing technology. They
can adjust to the environment and perform as per the requirement of
users. Also, a lot of smart materials have not been explored so far that
can further advance 4D printing and add to its potential applications.
New materials including custom textile composites, carbon fibres, and
printed wood grain would open new proficiencies in 4D printing. The
current application of 4D printing is mainly focused on its shape-
changing ability, but in future various other functions of 4D printed
structures can be discovered which will make them multi-functional.
The diverse response of 4D printed materials towards stimuli can be
explored in the future, which will again add to its multi-functional ap­
plications. According to an estimate, 4D printing will reach a global
value of 537.8 million dollars by the year 2025. Although 4D printing is
a multi-disciplinary field, in future more collaborations among its con­
stituent fields will bring more control in shape evolution of these
22
Polymer 228 (2021) 123926
structures. 4D printing will have a profound effect on our daily life in the
future.
7. Conclusion
In this paper, developments and the applications of 4D printing were
reviewed. 4D printing is an advancement of already existing 3D printing
by including time. 4D structures can deform with time depending upon
the stimuli to which they are exposed. They can respond to heat, water,
light, electric energy, magnetic energy, stress, strain, pressure, etc.
These structures can self-assemble, self-repair, and are self-compatible
with changes. 4D printing involves the use of 3D printing techniques
for printing smart materials i.e., single material, multi-material, or non-
active material. 4D printing finds its applications in medical sciences,
soft robotics, self-healing products, active origami, etc. In tissue engi­
neering, 4D bioprinting has advanced the field of tissue and organ
development for transplants. It has the potential to physically replicate
the development path of biology and bring organ printing one step
closer to reality. 4D printing has also been active in developing target
drug delivery systems. 4D printing has its limitations when it comes to
printing techniques, materials used, and designing techniques of the
structures. But there is a huge scope for 4D printing in the future, as
more smart materials can be discovered along with new and more effi­
cient printing technologies. 4D printing which is mostly confined to
structural changes can be developed to achieve multi-functional appli­
cations. Also, the range of applications of 4D printing can be expanded
in the future to various other fields. Being a multi-disciplinary research
field, it will enjoy the feature of having applications in different fields
such as engineering, material science, medical science, nanoscience, etc.
In the future as well. To conclude, one thing is certain that 4D printing
will not remain confined to shape change in the future. It will develop in
various other applications and advance as a new area of controlled smart
structure printing.
Data availability statement
The raw/processed data required to reproduce these findings cannot
be shared at this time due to technical limitations.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgement
This work was supported in part by JSPS KAKENHI Grant Number
JP17H01224, JP18H0547, JP19H01122, JST COI Grant Number
JPMJCE1314, JST -OPERA Program Grant Number JPMJOP1844, JST
-OPERA Program Grant Number JPMJOP1614, and the Cabinet Office
(CAO), Cross-ministerial Strategic Innovation Promotion Program (SIP),
“An intelligent knowledge processing infrastructure, integrating phys­
ical and virtual domains” (funding agency: NEDO) and the Program on
Open Innovation Platform with Enterprises, Research Institutes and
Academia (OPERA) from JST.
References
[1] C. Hull, C. W., U.S. Pat. 4575330, 1986.
[2] C. Bower, M. Meitl, D. Gomez, S. Bonafede, D. Kneeburg, inventors; X-Celeprint
Ltd, assignee (2016). U.S. Pat. 9358775.
[3] S.A. Tofail, E.P. Koumoulos, A. Bandyopadhyay, S. Bose, L. O’Donoghue,
C. Charitidis, Mater. Today 1 (2018) 22.
[4] S.F. Shirazi, S. Gharehkhani, M. Mehrali, H. Yarmand, H.S. Metselaar, N.A. Kadri,
N.A. Osman, Sci. Technol. Adv. Mater. 3 (2015) 16.
[5] J. Choi, O.C. Kwon, W. Jo, H.J. Lee, M.-W. Moon, Addit. Manuf. 4 (2015) 159.
A. Ahmed et al.
[6] W. Gao, Y. Zhang, D. Ramanujan, K. Ramani, Y. Chen, C.B. Williams, C.C.
L. Wang, Y.C. Shin, S. Zhang, P.D. Zavattieri, Comput. Aided Des. 69 (2015) 65.
[7] I. Gibson, D. Rosen, B. Stucker, Additive Manufacturing Technologies, Springer,
New York, NY, 2015. New York.
[8] Y.Y.C. Choong, S. Maleksaeedi, H. Eng, S. Yu, J. Wei, P.C. Su, Appl. Mater. Today.
18 (2020) 100515.
[9] G.X. Gu, M.J. Buehler, Acta Mech. 10 (2018) 4033.
[10] A. Nishiguchi, H. Zhang, S. Schweizerhof, M.F. Schulte, A. Mourran, M. Moller,
ACS Appl. Mater. Interfaces 12 (10) (2020) 12176–12185.
[11] F. Libonati, G.X. Gu, Z. Qin, L. Vergani, M.J. Buehler, Adv. Eng. Mater. 8 (2016)
1354.
[12] F.P.W. Melchels, M.A.N. Domingos, T.J. Klein, J. Malda, P.J. Bartolo, D.
W. Hutmacher, Prog. Polym. Sci. 8 (2012) 1079.
[13] S. Miyashita, S. Guitron, M. Ludersdorfer, C.R. Sung, D. Rus, in: Presented at IEEE
Int. Conf. Robotics, Automation, ICRA, May 2015.
[14] R. MacCurdy, R. Katzschmann, Y. Kim, D. Rus, in: Presented at IEEE Int. Conf.
Robotics, Automation, ICRA, June 2016.
[15] D. Brackett, I. Ashcroft, R. Hague, in: Proc. Solid Free. Fabr. Symp vol. 1, 2011,
pp. 348–362.
[16] A.T. Gaynor, N.A. Meisel, C.B. Williams, J.K. Guest, J. Manuf. Sci. Eng. 6 (2014)
136.
[17] T. Zegard, G.H. Paulino, Struct. Multidiscip. Optim. 1 (2016) 175.
[18] G.X. Gu, C.T. Chen, M.J. Buehler, Extrem. Mech. Lett. 18 (2018) 19.
[19] G.X. Gu, C.T. Chen, D.J. Richmond, M.J. Buehler, Mater. Horizons (2018) 939.
[20] G.X. Gu, S. Wettermark, M.J. Buehler, Addit. Manuf. 17 (2017) 47.
[21] B.H. Jared, M.A. Aguilo, L.L. Beghini, B.L. Boyce, B.W. Clark, A. Cook, B.J. Kaehr,
J. Robbins, Scripta Mater. 135 (2017) 141.
[22] S.Y. Hann, H. Cui, M. Nowicki, L.G. Zhang, Addit. Manuf. 36 (2020) 101567.
[23] B.G. Compton, J.A. Lewis, Adv. Mater. 34 (2014) 5930.
[24] U.G.K. Wegst, H. Bai, E. Saiz, A.P. Tomsia, R.O. Ritchie, Nat. Mater. 1 (2015) 23.
[25] G.X. Gu, F. Libonati, S.D. Wettermark, M.J. Buehler, J. Mech. Behav. Biomed.
Mater. 76 (2017), 135Addit. Manuf.
[26] G.X. Gu, M. Takaffoli, M.J. Buehler, Adv. Mater. 28 (2017) 1.
[27] G.X. Gu, M. Takaffoli, A.J. Hsieh, M.J. Buehler, Extrem. Mech. Lett. 9 (2016) 317.
[28] Y. Hu, Z. Wang, D. Jin, C. Zhang, R. Sun, Z. Li, K. Hu, J. Ni, Z. Cai, D. Pan,
X. Wang, W. Zhu, J. Li, D. Wu, L. Zhang, J. Chu, Adv. Funct. Mater. 30 (2020)
1907377.
[29] B. Holmes, W. Zhu, J. Li, J.D. Lee, L.G. Zhang, Tissue Eng. 1–2 (2015) 403.
[30] W. Zhu, B. Holmes, R.I. Glazer, L.G. Zhang, Nanomed. Nanotechnol. Biol. Med. 1
(2016) 69.
[31] J. Firth, S. Gaisford, A.W. Basit, Springer, Cham, 2018, pp. 153–162.
[32] N.A. Peppas, J.Z. Hilt, A. Khademhosseini, R. Langer, Adv. Mater. 11 (2006)
1345.
[33] Q. Ge, H.J. Qi, M.L. Dunn, Appl. Phys. Lett. 13 (2013) 131901.
[34] F. Momeni, S. Sabzpoushan, R. Valizadeh, M.R. Morad, X. Liu, J. Ni, Renew.
Energy 130 (2019) 329.
[35] J.C. Breger, C. Yoon, R. Xiao, H.R. Kwag, M.O. Wang, J.P. Fisher, T.D. Nguyen, D.
H. Gracias, ACS Appl. Mater. Interfaces 5 (2015) 3398.
[36] Skylar Tibbits, The emergence of “4D printing” | TED Talk [Online]. Available at:
https://www.ted.com/talks/skylar_tibbits_the_emergence_of_4d_printing.
Accessed 2018 Sep. 10.
[37] S. Tibbits, Architect. Des 84 (2014) 116–121.
[38] D. Raviv, W. Zhao, C. McKnelly, A. Papadopoulou, A. Kadambi, B. Shi, S. Hirsch,
D. Dikovsky, M. Zyracki, C. Olguin, S. Tibbits, Sci. Rep. 4 (2015) 7422.
[39] E. Pei, Assemb. Autom. 34 (2014) 310.
[40] Z. Ding, C. Yuan, X. Peng, T. Wang, H.J. Qi, M.L. Dunn, Sci. Adv. 3 (2017),
e1602890.
[41] A. Kotikian, R.L. Truby, J.W. Boley, T.J. White, J.A. Lewis, Adv. Mater. 30 (2018)
1706164.
[42] H. Yang, W.R. Leow, T. Wang, J. Wang, J. Yu, K. He, D. Qi, C. Wan, X. Chen, Adv.
Mater. 29 (2017) 1701627.
[43] O. Kuksenok, A.C. Balazs, Mater. Horiz. 3 (2016) 53.
[44] A.S. Gladman, E.A. Matsumoto, R.G. Nuzzo, L. Mahadevan, J.A. Lewis, Nat.
Mater. 15 (2016) 413.
[45] M. Nadgorny, Z. Xiao, C. Chen, L.A. Connal, ACS Appl. Mater. Interfaces 8 (2016)
28946.
[46] J. Choi, O.C. Kwon, W. Jo, H.J. Lee, M.-W. Moon, 3D print, Addit. Manuf. 2
(2015) 159.
[47] J.J. Wu, L.M. Huang, Q. Zhao, T. Xie, Chin. J. Polym. Sci. 36 (2018) 563.
[48] D.G. Shin, T.H. Kim, D.E. Kim, Int. J. Precis. Eng. Manuf. Green Technol. 4 (2017)
349.
[49] F. Momeni, S.M. Mehdi, N. Hassani, X. Liu, J. Ni, Mater. Des. 122 (2017) 42.
[50] Z.X. Khoo, J.E.M. Teoh, Y. Liu, C.K. Chua, S. Yang, J. An, K.F. Leong, W.Y. Yeong,
Virtual Phys. Prototyp. 10 (2015) 103.
[51] S. Tibbits, C. McKnelly, C. Olguin, D. Dikovsky, S. Hirsch, in: Proc. Of the 34th
Annual Conference of the Association for Computer Aided Design in Architecture
vol. 539, 2014.
[52] B. An, D. Rus, in: Presented at IEEE International Conference on Robotics and
Automation, 2012. USA.
[53] Y. Liu, W. Zhang, F. Zhang, X. Lan, J. Leng, S. Liu, X. Jia, C. Cotton, B. Sun, B. Gu,
T.-W. Chou, Compos. B Eng. 153 (2018) 233.
[54] K.K. Shigetomi, H. Onoe, S. Takeuchi, Han, PLoS ONE 12 (2012) 1.
[55] Y. Mao, K. Yu, M.S. Isakov, J. Wu, M.L. Dunn, H. Jerry Qi, Sci. Rep. 5 (2015) 1.
[56] M.J. Walker, B. Burton, M. Cantara, Gartner, Stamford, USA, 2018.
[57] X. Kuang, D.J. Roach, J. Wu, C.M. Hamel, Z. Ding, T. Wang, M.L. Dunn, H.J. Qi,
Adv. Funct. Mater. 29 (2018) 1805290.
23
Polymer 228 (2021) 123926
[58] M. Jacobsen, Clearing the way for pivotal 21st-century innovation, in: Giftedness
and Talent in the 21st Century, Springer, 2016.
[59] A. Subash, B. Kandasubramanian, Eur. Polym. J. (2020) 109771.
[60] S.K. Leist, J. Zhou, Virtual Phys. Prototyp. 1 (2016) 1.
[61] S. Chung, S.E. Song, Y.T. Cho, Int. J. Pr. Eng. Man-GT. 3 (2017) 359.
[62] F. Momeni, S.M.M. Hassani, N.X. Liu, J. Ni, Mater. Des. 12 (2017) 42.
[63] F. Momeni, J. Ni, arXiv preprint 2018, 1810.10376.
[64] L. Von Bertalanffy, Hum. Biol. 2 (1938) 181.
[65] M. Vaezi, S. Chianrabutra, B. Mellor, S. Yang, Virtual Phys. Prototyp. 1 (2013) 19.
[66] X. Li, S. Jianzhong, Z. Wong, Assemb. Autom. 2 (2017).
[67] Y.S. Zhang, K. Yue, J. Aleman, K. Mollazadeh-Moghaddam, S.M. Bakht, J. Yang,
W. Jia, V. Dell’Erba, P. Assawes, S.R. Shin, M.R. Dokmeci, R. Oklu,
A. Khademhosseini, Ann. Biomed. Eng. 1 (2017) 148.
[68] A.S. Gladman, E.A. Matsumoto, R.G. Nuzzo, L. Mahadevan, J.A. Lewis, Nat.
Mater. 4 (2016) 413.
[69] K. Zhang, Sci. Rep. 5 (2015) 1.
[70] S.E. Bakarich, R. Gorkin III, M. in Het Panhuis, G.M. Spinks, Macromol. Rapid
Commun. 36 (2015) 1211–1217, https://doi.org/10.1002/marc.201500079.
[71] Y. Zhou, W.M. Huang, S.F. Kang, X.L. Wu, H.B. Lu, J. Fu, H. Cui, J. Mech. Sci.
Technol. 10 (2015) 4281.
[72] M.D. Hager, S. Bode, C. Weber, U.S. Schubert, Prog. Polym. Sci. 49–50 (2015) 3.
[73] R. Li, Y. Shi, J. Liu, Z. Xie, Z. Wang, Int. J. Adv. Manuf. Technol. 5–8 (2009) 597.
[74] T. Niendorf, F. Brenne, P. Krooß, M. Vollmer, J. Günther, D. Schwarze,
H. Biermann, Metall. Mater. Trans. 6 (2016) 2569.
[75] E. Pei, G.H. Loh, Prog. Addit. Manuf 3 (2018) 95–107, https://doi.org/10.1007/
s40964-018-0047-1, 1–2, 95.
[76] W.M. Huang, Mater. Today 13 (2010) 54.
[77] M. Bodaghi, A.R. Damanpack, W.H. Liao, Smart Mater. Struct. 6 (2018), 065010.
[78] D.Q.M. Craig, P.G. Royall, V.L. Kett, M.L. Hopton, Int. J. Pharm. 179 (1999) 79.
[79] S.J. Dengale, H. Grohganz, T. Rades, K. Löbmann, Adv. Drug Deliv. Rev. 100
(2016) 116.
[80] G. Li, A. Wang, J. Polym. Sci., Polym. Phys. Ed. 14 (2016) 1319.
[81] Y.Y.C. Choong, S. Maleksaeedi, H. Eng, J. Wei, P.C. Su, Mater. Des. 126 (2017)
219.
[82] Q. Ge, A.H. Sakhaei, H. Lee, C.K. Dunn, N.X. Fang, M.L. Dunn, Sci. Rep. 1 (2016)
31110.
[83] M. Bodaghi, A.R. Damanpack, W.H. Liao, Mater. Des. 135 (2017) 26.
[84] Q. Wang, X. Tian, L. Huang, D. Li, A.V. Malakhov, A.N. Polilov, Mater. Des. 155
(2018) 404.
[85] Q. Zhang, K. Zhang, G. Hu, Sci. Rep. 6 (2016) 22431.
[86] S. Banudevi, Biochem. Physiol. 5 (2016) e154.
[87] J.E. Teoh, Y. Zhao, J. An, C.K. Chua, Y. Liu, Smart Mater. Struct. 12 (2017)
125001.
[88] Y. Liu, Some Factors Affecting the Transformation Hysteresis in Shape Memory
Alloys, Science Publisher, New York, 2010.
[89] Q. Ge, C.K. Dunn, H.J. Qi, M.L. Dunn, Smart Mater. Struct. 9 (2014).
[90] H. Tobushi, S. Hayashi, E. Pieczyska, K. Date, Y. Nishimura, Sci. Forum 674
(2011) 225.
[91] J. Van Humbeeck, Adv. Eng. Mater. 11 (2001) 837.
[92] R.F. Hamilton, T.A. Palmer, B.A. Bimber, Scripta Mater. 101 (2015) 56.
[93] B.V. Krishna, S. Bose, A. Bandyopadhyay, Metall. Mater. Trans. 5 (2007) 1096.
[94] M.P. Caputo, A.E. Berkowitz, A. Armstrong, P. Mullner, C.V. Solomon, Addit.
Manuf. 21 (2018) 579.
[95] T. Gustmann, J.M. dos Santos, P. Gargarella, U. Kuhn, J. Van Humbeeck, S. Pauly,
Shape Mem. Superelasticity. 1 (2016) 24.
[96] E.M. Mazzer, C.S. Kiminami, P. Gargarella, R.D. Cava, L.A. Basilio, C. Bolfarini,
W.J. Botta, J. Eckert, T. Gutsmann, S. Pauly, Mater. Sci. Forum 802 (2014) 343.
[97] P. Gargarella, C.S. Kiminami, E.M. Mazzer, R.D. Cava, L.A. Basilio, C. Bolfarini,
W.J. Botta, J. Eskerf, T. Gustmann, S. Pauly, Mater. Res. 35 (2015).
[98] R. Dasgupta, J. Mater. Res. 16 (2014) 1681.
[99] F. Auricchio, E. Boatti, M. Conti, SMA biomedical applications, in: Shape Memory
Alloy Engineering, Elsevier, Amsterdam, 2015.
[100] S.N.R. Kantareddy, T.W. Simpson, Z. Ounaies, M. Frecker, Proc. 26th Annu. Int.
Solid Free. Fabr. Symp. Addit. Manuf.Conf. (2016).
[101] Y. Chen, D.C. Lagoudas, J. Mech. Phys. Solid. 56 (2008) 1752.
[102] Z. Wang, C. Hansen, Q. Ge, S.H. Maruf, D.U. Ahn, H.J. Qi, Y. Ding, Adv. Mater. 23
(2011) 3669.
[103] T. Mu, L. Liu, X. Lan, Y. Liu, J. Leng, Compos. Sci. Technol. 160 (2018) 169.
[104] Y. Hu, G. Wu, T. Lan, J. Zhao, Y. Liu, W. Chen, Adv. Mater. 47 (2015) 7867.
[105] Y. Liu, B. Shaw, M.D. Dickey, J. Genzer, Sci. Adv. 3 (2017) 1.
[106] O. Kuksenok, A.C. Balazs, Mater. Horizons 3 (2016) 53.
[107] J. Wu, Z. Zhao, X. Kuang, C.M. Hamel, D. Fang, H.J. Qi, Multifunct. Mater. 1
(2018) 15002.
[108] A. Miriyev, K. Stack, H. Lipson, Nat. Commun. 1 (2017) 1.
[109] H. Okuzaki, T. Kuwabara, K. Funasaka, T. Saido, Adv. Funct. Mater. 36 (2013)
4400.
[110] B. Jeong, A. Gutowska, Trends Biotechnol. 7 (2002) 305.
[111] F. Liu, M.W. Urban, Prog. Polym. Sci. 1–2 (2010) 3.
[112] I. Roy, M.N. Gupta, Chem. Biol. 12 (2003) 1161.
[113] E. Gil, S. Hudson, Prog. Polym. Sci. 12 (2004) 1173.
[114] H.R. Almeida, M.H. do Amaral, P.A.L. Lobão, 2012.
[115] S. Dai, P. Ravi, K.C. Tam, Soft Matter 3 (2008) 435.
[116] D. Schmaljohann, Adv. Drug Deliv. Rev. 15 (2006) 1655.
[117] J. Kost, R. Langer, Adv. Drug Deliv. Rev. 24 (2001).
[118] Q. Zhang, L. Liu, H. Zhou, X. Wu, K.D. Yao, Artif. Cell Blood Sub. 3 (2000) 255.
[119] B. Hilmi, Z.A.A. Hamid, H.M. Akil, B.H. Yahaya, Procedia Chem 19 (2016) 406.
A. Ahmed et al.
[120] K.S. Soppimath, T.M. Aminabhavi, A.M. Dave, S.G. Kumbar, W.E. Rudzinski, Drug
Dev. Ind. Pharm. 8 (2002) 957.
[121] Y. Qiu, K. Park, Adv. Drug Deliv. Rev. 19 (2001).
[122] M. Nadgorny, Z. Xiao, C. Chen, L.A. Connal, ACS Appl. Mater. Interfaces 42
(2016) 28946.
[123] H. Yang, W.R. Leow, T. Wang, J. Wang, J. Yu, K. He, D. Qi, C. Wan, X. Chen, Adv.
Mater. 33 (2017) 1701627.
[124] M. Zarek, M. Layani, I. Cooperstain, E. Sachyami, D. Cohn, Adv. Mater. 28 (2016)
4449.
[125] T. Campbell, S. Tibbits, B. Garret, Sci. Am. 311 (2014) 60.
[126] R. Mutlu, G. Alici, in: Presented at IEEE International Conference on Advancd
Intelligent Mechatronics, AIM, 2015.
[127] T. Raviv, L. Striukova Sci. Rep. 4 (2014) 7422.
[128] S. Tibbits, in: Proc. 31st Annual Conference of ACADIA, 2011. Banff.
[129] S. Bauer, S.B. Gogonea, I. Graz, M. Kaltenbrunner, C. Keplinger, R. Schwodiauer,
Adv. Mater. 26 (2014) 149.
[130] C. Yang, X. Tian, T. Liu, Y. Cao, D. Li, Rapid Prototyp. J. 1 (2017) 209–215.
[131] C. Sun, N. Fang, D.M. Wu, X. Zhang, Sensor. Actuator. A 121 (2005) 113–120.
[132] P. Parandoush, D. Lin, Compos. Struct. 182 (2017) 36.
[133] M. Kang, Y. Pyo, J.Y. Jang, Y. Park, Y.H. Son, M.C. Choi, J.W. Ha, Y.W. Chang, C.
S. Lee, Sensor. Actuator. A 283 (2018) 187.
[134] T. Zhao, R. Yu, X. Li, B. Cheng, Y. Zhang, X. Yang, X. Zhao, Y. Zhao, W. Huang,
Eur. Polym. J. 101 (2018) 120.
[135] K. Shahzad, J. Deckers, Z. Zhang, J.P. Kruth, J. Vleugels, J. Eur. Ceram. Soc. 1
(2014) 81.
[136] I. Yadroitsev, P. Bertrand, I. Smurov, Appl. Surf. Sci. 253 (2007) 8064–8069.
[137] I. Gibson, D. Rosen, B. Stucker, In Additive Manufacturing Technologies. 3D
Printing, Rapid Prototyping, and Direct Digital Manufacturing, second ed.,
Springer, New York, 2015.
[138] P.R. Halani, I. Kaya, Y.C. Shin, H.E. Karaca, Mater. Sci. Eng., A 559 (2013) 836.
[139] J.J. Marattukalam, A.K. Singh, S. Datta, M. Das, V.K. Balla, S. Bontha, S.
K. Kalpathy, Mater. Sci. Eng. C 57 (2015) 309.
[140] X. Xu, X. Ling, M. Yang, J. Chen, W. Huang, J. Alloys Compd. 2 (2009) 7820787.
[141] S. Bernard, V.K. Balla, S. Bose, A. Bandyopadhyay, J. Mech. Behav. Biomed.
Mater. 13 (2012) 62.
[142] J. Bai, R.D. Goodridge, R.J.M. Hague, M. Song, Polym. Eng. Sci. 53 (2013).
[143] M.M. Mohebi, J.R.G. Evans, J. Comb. Chem. 4 (2002) 267.
[144] M.A. Riheen, T.K. Saha, P.K. Sekhar, J. Electrochem. Soc. 166 (2019) B3036.
[145] M. Gao, L. Li, Y. Song, J. Mater. Chem. C 5 (2017) 2971.
[146] M. Nakamura, A. Kobayashi, F. Takagi, A. Watanabe, Y. Hiruma, K. Ohuchi,
Y. Iwasaki, M. Horie, I. Morita, S. Takatani, Tissue Eng. 11 (2005) 1658.
[147] S.A. Nauroze, L. Novelino, M.M. Tentzeris, G.H. Paulino, Int. Microw. Symp.,
IEEE (2017) 1575.
[148] Z. Zhao, J. Wu, X. Mu, H. Chen, H.J. Qi, D. Fang, Macromol. Rapid Commun. 13
(2017).
[149] J.A. Lewis, J.E. Smay, J. Stuecker, J. Cesarano, J. Am. Ceram. Soc. 12 (2010)
3599.
[150] S. Naficy, R. Gately, R. Gorkin, H. Xin, G.M. Spinks, Macromol. Mater. Eng. 302
(2017) 1600212.
[151] Q. Zhao, J. Sun, Q. Ling, Q. Zhou, Langmuir 5 (2009) 3249.
[152] J.P. Gong, Y. Katsuyama, T. Kurokawa, Y. Osada, Adv. Mater. 14 (2003) 1155.
[153] M.C. Mulakkal, R.S. Trask, V.P. Ting, A.M. Seddon, Mater. Des. 160 (2018) 108.
[154] Q. Zhao, H.J. Qi, T. Xie, Prog. Polym. Sci. 49–50 (2015) 79.
[155] S. Erkeçoglu, A.D. Sezer, S. Bucak, Smart Drug Deliv. Syst. 1 (2016).
[156] M.D. Monzon, R. Paz, E. Pei, F. Ortega, L.A. Suarez, Z. Ortega, M.E. Aleman,
T. Plucinski, N. Clow, Int. J. Adv. Manuf. Technol. 89 (2017) 1827.
[157] J.M. Pearce, Science 6100 (2012) 1303.
[158] Y. Mao, Z. Ding, C. Yuan, S. Ai, M. Isakov, J. Wu, T. Wang, M.L. Dunn, H.J. Qi, Sci.
Rep. 1 (2016) 1.
[159] M. Zarek, N. Mansour, S. Shapira, D. Cohn, Macromol. Rapid Commun. 2 (2017)
1600628.
[160] M. Zarek, M. Layani, S. Eliazar, N. Mansour, I. Cooperstein, E. Shukrun, A. Szlar,
D. Cohn, S. Magdassi, Virtual Phys. Prototyp. 4 (2016) 263.
[161] S. Miao, W. Zhu, N.J. Castro, M. Nowicki, X. Zhou, H. Cui, J.P. Fisher, L.G. Zhang,
Sci. Rep. 6 (2016) 27226.
[162] T. Xie, Nature 7286 (2010) 267.
[163] K. Yu, M.L. Dunn, H.J. Qi, Extreme. Mech. Lett. 4 (2015) 9.
[164] L. Huang, R. Jiang, J. Wu, J. Song, H. Bai, B. Li, Q. Zhao, T. Xie, Adv. Mater. 7
(2017) 1605390.
[165] Z. Fang, H. Song, Y. Zhang, B. Jin, J. Wu, Q. Zhao, T. Xie, Matter 2 (2020)
1187–1197.
[166] K. Yang, J.C. Grant, P. Lamey, A. Joshi-Imre, B.R. Lund, R.A. Smaldone, W. Voit,
Adv. Funct. Mater. 24 (2017) 1700318.
[167] H. Wei, Q. Zhang, Y. Yao, L. Liu, Y. Liu, J. ACS Appl. Mater. Interfaces 1 (2017)
876.
[168] M. Nadgorny, Z. Xiao, C. Chen, L.A. Connal, ACS Appl. Mater. Interfaces 42
(2016) 28946.
[169] T.C. Okwuosa, B.C. Pereira, B. Arafat, M. Cieszynska, A. Isreb, M.A. Alhnan,
Pharm. Res. (N. Y.) 2 (2017) 427.
[170] L. Larush, I. Kaner, A. Fluksman, A. Tamsut, A.A. Pawar, P. Lesnovski, O. Benny,
S. Magdassi, J. 3D Print. Med. 4 (2017) 219.
[171] Q. Zhang, D. Yan, K. Zhan, G. Hu, Sci. Rep. 5 (2015) 8936.
[172] Q. Zhang, K. Zhang, G. Hu, Sci. Rep. 6 (2016) 22431.
[173] F. Hu, L. Lyu, Y. He, Int. J. Precis. Eng. Manuf. 20 (2019) 1915.
[174] C.Y. Cheng, H. Xie, Z.Y. Xu, L. Li, M.N. Jiang, L. Tang, K.K. Yang, Y.Z. Wang,
Chem. Eng. J. (2020) 125242.
24
Polymer 228 (2021) 123926
[175] X. Li, Y. Yang, Y. Zhang, T. Wang, Z. Yang, Q. Wang, X. Zhang, Mater. Des. (2020)
108606.
[176] J.W. Su, W. Gao, K. Trinh, S.M. Kenderes, E. Tekin Pulatsu, C. Zhang,
A. Whittington, M. Lin, J. Lin, Int. J. Smart Nano Mater. 3 (2019) 237.
[177] L.H. Shao, B. Zhao, Q. Zhang, Y. Xing, K. Zhang, Extreme Mech. Lett. (2020)
100793.
[178] H. Hingorani, Y.F. Zhang, B. Zhang, A. Serjouei, Q. Ge, Int. J. Smart Nano Mater.
3 (2019) 225.
[179] S.V. Hoa, X. Cai, Compos. Struct. 238 (2020) 111883.
[180] S.V. Hoa, D.I. Rosca, Mater. Today Commun. (2020) 101115.
[181] Y. Chen, T. Li, F. Scarpa, L. Wang, Phys. Rev. Appl. 2 (2017), 024012.
[182] M. Bodaghi, A.R. Damanpack, G.F. Hu, W.H. Liao, Mater. Des. 131 (2017) 81.
[183] A. Mirabolghasemi, A.H. Akbarzadeh, D. Rodrigue, D. Therriault, Acta Mater. 174
(2019) 61.
[184] X. Li, L. Gao, W. Zhou, Y. Wang, Y. Lu, Extreme Mech. Lett. 30 (2019) 100498.
[185] C. Nimmagadda, K.H. Matlack, J. Sound Vib. 439 (2019) 29.
[186] M. Moscatelli, R. Ardito, L. Driemeier, C. Comi, J. Sound Vib. 454 (2019) 73.
[187] M. Bodaghi, A. Serjouei, A. Zolfagharian, M. Fotouhi, H. Rahman, D. Durand, Int.
J. Mech. Sci. 173 (2020) 105451.
[188] B. Goo, C.H. Hong, K. Park, Mater. Des. 188 (2020) 108485.
[189] Y. Yu, H. Liu, K. Qian, H. Yang, M. McGehee, J. Gu, D. Luo, L. Yao, Y.J. Zhang,
Comput. Aided Des. 122 (2020) 102817.
[190] C. He, M. Zhang, C. Guo, Innovat. Food Sci. Emerg. Technol. 59 (2020) 102250.
[191] P. Phuhongsung, M. Zhang, B. Bhandari, Food Res. Int. 12 (2020) 109605.
[192] Y.Y. Choong, S. Maleksaeedi, H. Eng, S. Yu, J. Wei, P.C. Su, Appl. Mater. Today.
18 (2020) 100515.
[193] B.I. Oladapo, A.V. Adebiyi, E.I. Elemure, J. King Saud Univ. Eng. Sci. 2 (2019).
[194] Frost, Sullivan, 4-D printing to usher in age of low labour, fast-paced product
manufacturing. http://images.discover.frost.com/Web/FrostSullivan/NA_PR_ABr
own_D545TI_21Aug2014.pdf, 2014. (Accessed 24 November 2017).
[195] Y.C. Li, Y.S. Zhang, A. Akpek, S.R. Shin, A. Khademhosseini, Biofabrication 9
(2016), 012001.
[196] N.J. Castro, C. Meinert, P. Levett, D.W. Hutmacher, Curr. Opin. Biomed. Eng. 2
(2017) 67.
[197] B. Gao, Q. Yang, X. Zhao, G. Jin, Y. Ma, F. Xu, Trends Biotechnol. 34 (2016) 746.
[198] K. Kuribayashi-Shigetomi, H. Onoe, S. Takeuchi, PloS One 7 (2012), e51085.
[199] H.W. Kang, S.J. Lee, I.K. Ko, C. Kengla, J.J. Yoo, A. Atala, Nat. Biotechnol., 34,
312.
[200] D.A. Zopf, A.G. Mitsak, C.L. Flanagan, M. Wheeler, G.E. Green, S. Hollister,
Otolaryngol. Head Neck Surg. 152 (2015) 57.
[201] R.J. Morrison, S.J. Hollister, M.F. Niedner, M.G. Mahani, A.H. Park, D.K. Mehta,
R.G. Ohye, G.E. Green, Sci. Transl. Med. 285 (2015) 285ra64.
[202] H. Cui, S. Miao, T. Esworthy, S.J. Lee, X. Zhou, S.Y. Hann, T.J. Webster, B.
T. Harris, L.G. Zhang, Nano Research 6 (2019) 1381.
[203] H.G. Yi, H. Lee, D.W. Cho, Bioengineering 1 (2017) 10.
[204] J. Gosnell, T. Pietila, B.P. Samuel, H.K.N. Kurup, M.P. Haw, J.J. Vettukattil,
J. Digit. Imag. 6 (2016) 665.
[205] P. He, J. Zhao, J. Zhang, B. Li, Z. Gou, M. Gou, X. Li, Burns Trauma 5 (2018) 1.
[206] K. Malachowski, J. Breger, H.R. Kwag, M.O. Wang, J.P. Fisher, F.M. Selaru, D.
H. Gracias, Angew. Chem. Int. Ed. 31 (2014) 8045.
[207] Azam, K.E. Laflin, M. Jamal, R. Fernandes, D.H. Gracias, Biomed. Microdevices 1
(2011) 51.
[208] K. Gall, C.M. Yakacki, Y. Liu, R. Shandas, N. Willett, K.S. Anseth, J. Biomed.
Mater. Res. 339 (2005).
[209] S. Awasthi, N. Pandey, Clin. Epidemiol. Glob. Health 1 (2015) 24.
[210] S. Awasthi, T. Verma, M. Agarwal, J.V. Singh, N.M. Srivastava, M. Nichterd, Clin.
Epidemiol. Glob. Health 3 (2017) 107.
[211] J. Rossiter, P. Walters, B. Stoimenov, in: Proc. SPIE 7287, Electroactive Polymer
Actuators And Devices (EAPAD), 2009.
[212] S.H. Ahn, K.T. Lee, H.J. Kim, R. Wu, J.S. Kim, S.H. Song, Int. J. Precis. Eng.
Manuf. 4 (2012) 631.
[213] Y.B. Cohen, V.F. Cardoso, C. Ribeiro, S. Lanceros-Méndez, Advanced Piezoelectric
Materials, Woodhead Publishing, 2017.
[214] A. O’Halloran, F. O’Malley, P. McHugh, J. Appl. Phys. 7 (2008), 071101.
[215] L. Justin, M. Amelia, B. Christopher, in: Presented at 22nd Annual International
Solid Freeform Fabrication Symposium, 2011. Austin, TX.
[216] A. Zolfagharian, A. Kaynak, A. Kouzani, Mater. Des. 188 (2019) 108411.
[217] M. López-Valdeolivas, D. Liu, D.J. Broer, C. Sánchez-Somolinos, Macromol. Rapid
Commun. 5 (2018) 1700710.
[218] F. Daerden, D. Lefeber, Eur. J. Mech. Environ. Eng. 1 (2002) 11.
[219] H.K. Yap, H.Y. Ng, C.H. Yeow, Soft Robot. 3 (2016) 144–158.
[220] C. Della Santina, R.K. Katzschmann, A. Biechi, D. Rus, in: Presented at IEEE
International Conference on Soft Robotics, 2018, pp. 46–53. RoboSoft.
[221] A. Zolfagharian, A. Kaynak, A. Kouzani, Mater. Des. 188 (2019) 108411.
[222] K. Yu, A. Ritchie, Y. Mao, M.L. Dunn, H.J. Qi, Procedia Iutam 1 (2015) 193.
[223] S.R. White, N.R. Sottos, P.H. Geubelle, J.S. Moore, M.R. Kessler, S.R. Sriram, E.
N. Brown, S. Viswanathan, Nature 6822 (2001) 794.
[224] S.R. White, J.S. Moore, N.R. Sottos, B.P. Krull, W.A. Santa Cruz, R.C. Gergely,
Science 344 (2014) 620.
[225] X. Chen, M.A. Dam, K. Ono, A. Mal, H. Shen, S.R. Nutt, K. Sheran, F. Wudl,
Science 295 (2002) 1698.
[226] M. Röttger, T. Domenech, R. van der Weegen, A. Breuillac, R. Nicolaÿ, L. Leibler,
Science 356 (2017) 62.
[227] P. Cordier, F. Tournilhac, C. Soulie-Ziakovic, L. Leibler, Nature 451 (2008) 977.
[228] E. Pei, J. Shen, J. Watling, Rapid Prototyp. J. 5 (2015) 556.
A. Ahmed et al.
[230] S. Ramesh, C. Usha, N.K. Naulakha, C.R. Adithyakumar, M. Reddy, Mater. Sci.
Eng. 1 (2018), 012123.
[231] S.V. Huo, Compos. Struct. 210 (2019) 869.
[232] D. Deng, A. Jain, N. Yodvanich, A. Araujo, Y. Chen, proc. of Int. Symp. Flex.
Autom. IEEE (2016) 286–291.
[233] M. Han, Y. Yang, L. Li, Addit. Manuf. 34 (2020) 101223.
Mr. Aamir Ahmed is an M.Phil. student and has pursuing his research in the field of
additive manufacturing and nanomaterials.
Dr. Sandeep Arya did his PhD from University of Jammu, India. He is currently working
as a Senior Assistant Professor in the Department of Physics, University of Jammu. His
research interests include fabrication and characterization of nanostructured materials for
sensing and energy applications. He has published more than 50 refereed scientific articles
in different journals of repute.
Dr. Vinay Gupta is a visiting scientist at Khalifa University of Science and Technology,
Abu Dhabi, UAE. His interests include materials for energy applications. He has several
research publications in various reputed journals. He is a recipient of Shanti Swaroop
Bhatnagar award, one of the highest Indian science awards, for his contributions to
physical sciences in 2017. He has also received three major research fellowships; JSPS
fellowship of the Japan Society for the Promotion of Science (1998–2000), Alexander von
Humboldt Fellowship (2003–04), and Indo-USIUSSTF fellowship (2012–2013).
Prof. Hidemitsu Furukawa completed his Ph.D. in Physics in the Department of Physics,
Tokyo Institute of Technology in 1996. After this, he worked as an assistant professor in
Tokyo Institute of Technology and Tokyo University of Agriculture and Technology, an
25
Polymer 228 (2021) 123926
associate professor in Hokkaido University, and in April 2009 he was appointed associate
professor in the Department of Mechanical Systems Engineering at the Graduate School of
Science and Engineering, Yamagata University, where he set up the Soft & Wet Matter
Engineering Laboratory (SWEL). He was promoted to professor in 2012. In June 2013, he
founded the Yamagata University Life-3D Printing Innovation Center (LPIC). and became
the chair of the Center. In November 2017, he co-founded the university venture D-light
Matter Inc. and became a special technical advisor. In April 2018, he established the
YAWARAKA 3D Co-Creation Consortium and became its president. He is also a member of
the Engineering Academy of Japan and a member, a fellow of the Japan Society of Me­
chanical Engineers, a board member of the Society of Polymer Science, and a director of
the Japanese Society of Ophthalmology, and a co-chair of the Japan America Frontiers of
Engineering (JAFOE) 2018 and 2021. Prof. Hidemitsu Furukawa’s profile at Miraikan- The
National Museum of Emerging Science and Innovation. https://www.miraikan.jst.go.jp/e
n/research/facilities/SmartSoftManufacturing/.
Dr. Ajit Khosla is currently working as a professor in Yamagata University’s Department
of Mechanical Systems Engineering. Dr. Khosla received his PhD from Simon Fraser Uni­
versity in 2011, where he was awarded the Dean of Graduate Studies Convocation Medal
as one of SFU’s most outstanding graduate students in the Faculty of Applied Sciences. He
has initiated numerous research projects and developed collaborations with industry and
universities globally. Dr. Khosla’s current research program is interdisciplinary in nature
and focuses on the development of sustainable 3D and 4D printable hybrid nanocomposite
materials, with applications in sensors (physical, chemical and bio), energy storage de­
vices, energy harvesting, stretchable sensors for the Internet of Things (IoT), and soft ro­
botics. Careful consideration is given to synthesis and designing of 3D and 4D printable
hybrid materials, so that the processes involved do not compromise the natural environ­
ment, or the ability of future generations to maintain sustainable communities.