Additive Manufacturing 24 (2018) 606–626

Contents lists available at ScienceDirect

Additive Manufacturing
journal homepage: www.elsevier.com/locate/addma

Review

Additive manufacturing — A review of 4D printing and future applications T

⁎
A. Mitchell , U. Lafont, M. Hołyńska, C. Semprimoschnig
Materials' Physics and Chemistry Section (TEC-QEE) European Space Research and Technology Centre (ESTEC), European Space Agency (ESA), Netherlands

A R T I C LE I N FO A B S T R A C T

Keywords: 3D printing will revolutionize the manufacturing industry. Significant advances in computer aided design, ad-
3D/4D printing ditive manufacturing and materials science have opened up the possibilities of self-assembly systems, self-
Shape memory materials healing and material property alterations. Printing layer by layer allows complex geometries to be built, pre-
Self deployable structures viously difficult under conventional manufacturing routes. This paper is a review of the current materials
Space applications
available for 3D printing that enable the emergence of 4D printing, a ‘smart material’ that responds in a pro-
grammed way to an external stimuli. The outlook is towards potential space applications, in all areas including
deployable structures, antennas and medical supplies.

1. Introduction with deployable solar panels, composite hinges and antennas. The use
of shape memory materials in additive manufacturing has been wide-
Additive manufacturing or 3D printing is a technique in which spread to date. Several reviews have been written showing the multi-
complex structures can be built layer by layer. Stereolithography was functionality of shape memory polymers (SMP) and shape memory
first developed by Charles Hull in 1983 and since then with the expiry polymer composites (SMC). Yangju Liu gives a review specifically on
of earlier patents, it created an enormous drive for innovation of new SMPs and SMPCs in the aerospace sector, such as on hinges, reflector
technologies and materials for additive manufacturing. A future outlook antennas, lunar habitats morphing structures and truss booms [5].
suggests there will be significant investment into the 3D printing Thermoplastics are said to lose their shape recovery capabilities after
market in the next 10 years. [1] Additive manufacturing has created an several cycles, and so using thermosets are becoming more popular,
impact in all industry sectors, including aerospace, construction, med- with high stiffness, and environmental durability for space structures.
ical and military. 3D printing provides flexibility in design, significant Shape memory materials (SMM) can recover their shape after de-
material savings, as well as customisation and individualism. formation, due to an applied stimulus. This is commonly known as the
Additive manufacturing has gained significant ground over recent shape memory effect (SME). Superelasticity in shape memory alloys
years. Low et al, provide a comprehensive review of all 3D printing (SMA) and viscoelasticity in shape memory polymers are usually ob-
techniques currently available [2]. Table 1 summarises the main tech- served. Shape memory hybrids (SMH) and shape memory composites
nologies and their advantages. As described by the Royal Academy of are also emerging. With the development of 4D printing and the rapid
Engineering, ‘it is not only a disruptive technology, it has the potential to growth in additive manufacturing, SMM have significant potential in
replace many conventional manufacturing processes, but is also an enabling several industries. SMPs have the advantage of being light weight with
technology, allowing new business models, new products and new supply a greater tendency for strain recovery, than SMAs. They can also be
chains to flourish’ [3]. 3D printing not only allows consumers to design activated by various stimuli simultaneously. In addition to multiple
and produce their own goods, products can be designed without sig- stimuli for activation, SMPs can be biocompatible and biodegradable,
nificant waste. Now with the emergence of ‘4D printing’, additive thus tailored depending on the needs of application. For instance a
manufacturing will have a fundamental influence on the economy and thermoplastic polyurethane SMP as an open cell foam was designed for
society in the next decade [3,4]. space applications and biomedical uses [6].
4D printing enables the use of ‘smart materials’ that can transform
in a pre-programmed way in response to an external stimuli. This is 1.1. Shape memory polymers (SMPs) and 3D printing
known as ‘4D printing’, with the fourth dimension referring to time. The
applications of self-transforming structures are evident across all in- Shape memory polymers are able to transform to their original
dustries, in medical, defence and in aerospace sectors, such as in-space shape from one or several distorted shapes, once stimulated by

⁎
Corresponding author.
E-mail address: Adam.mitchell@esa.int (A. Mitchell).

https://doi.org/10.1016/j.addma.2018.10.038
Received 14 September 2017; Received in revised form 13 April 2018; Accepted 22 October 2018
Available online 28 October 2018
2214-8604/ © 2018 Elsevier B.V. All rights reserved.
 A. Mitchell et al.

Table 1
A Summary of the main 3D printing techniques.
3D Printer Process Material Adv/Disadv Companies

Material Extrusion Fused Deposition Modelling (FDM) / Fused The material in filament form is extruded through Thermoplastic Filaments typically Adv: Low cost, simplicity, Low FDM: Stratasys, Ultimaker,Makerbot,
Filament Fabrication (FFF) a nozzle at temperature and deposited onto a ABS, Nylon, PLA, PC, maintenance, CC: Large Zortrax, BEEVERYCREATIVE,
Contour Crafting (CC) heated build plate, and then deposited layer by Composites, Nano-fillers. construction Markforged
layer. CC: Concrete, soil, Disadv: Voids, difficult to print CC: Contour Crafting Corporation
CC: Using high pressure and large nozzles, complex structures, Accuracy is
materials can be extruded for large structures. low.
Vat Photopolymerization Stereolithography (SLA) A platform moves downwards after each layer of Liquid Photopolymers (acrylic or Adv: High accuracy- microns, SLA – 3D Systems, Formlabs, DWS
Digital Light Processing (DLP) liquid resin is cured. SLA– cured with a laser. DLP- epoxy based) Disadv: Limited materials to use. Systems
cured with a projector, Relatively Expensive, Requires DLP- EnvisionTEC, B9Creations
significant support structures
Sheet Lamination Laminated Object Manufacturing (LOM) Continuous layers in sheet form are cut using a Polymer composites, ceramics, Adv: High Speed, Low Cost EnvisionTEC, Mcor Technologies,
mechanical cutter or laser and then bonded paper, metal-filled tapes. Disadv: Depending on the
together. material post processing might be
needed, limited material use
Ultrasonic additive manufacturing (UAM) A rotating Sonotrode applies ultrasonic vibrations Metals - aluminium, copper, Adv: Low temperature Fabrisonic
to a foil, creating a roughening friction between the electronics, polymers and other processing, allows electronics,
foil and to the material being welded. This materials can be embedded sensors and polymers to be
displaces the surface oxides and other embedded
contaminates, under a compressive force the Disadv: Early stages of

607
materials are then bonded. A CNC stage allows for development. More research
selective removal and machining to final needed into Titanium, stainless
dimension steel.
Material Jetting InkJet Printing (IP) MJ – cured with UV light. DOD: milled to form, ceramics, metals, polymers Adv: Fast and efficient, produces DOD: Solidscape
Material Jetting (MJ) NPJ: Cured with heat, complex structures. Precision MJ: 3D Systems, Stratasys
Drop on Demand (DOD) Material is supplied though a nozzle and deposited Disadv: NPJ: XJET
NanoParticle Jetting (NPJ) in the form of droplets onto a build plate. This High Maintenance
solidifies, and continuous layers are printed.
Binder Jetting Binder Jetting (BJ) Powder base and liquid binder are used. The Gypsum, sand, metal, ceramic, Adv: Fast, simple and relatively ExOne, 3D Systems
powder is spread evenly and the binder glues to the polymers cheap
desired shape. Disadv: Powder form only,
mechanical properties relatively
weak.
Metals: Powder Bed Fusion Selective Laser Melting (SLM), Selective Laser The laser melts a powder bed, after each layer the SHS: Nylon, DMLS,SLS,SLM: Adv: No support structure SLM / DMLS: SLM Solution,
(PBF Sintering (SLS), Selective Heat Sintering, (SHS), powder is spread uniformly by a wiper and the Stainless steel, Titanium, needed, the integrated powder Renishaw, Concept-laser,
Electron Beam Melting (EBM), Direct Metal process repeats. The Z-axis is lowered after each Aluminium, Cobalt Chrome, Steel provides this. Large range of SLS: 3D Systems, Sintratec, Sinterit,
Laser Sintering (DMLS) print. EBM requires the use of a vacuum. SLS -Plastic material options EOS P Systems,
EBM: Titanium, Cobalt Chrome, Disadv: High power usage, Size EBM: Arcam
Stainless Steel, Aluminium, limitations, Powder grain size
Copper. very important, effects surface
finish.
Direct Energy Deposition (DED) Laser Engineered Net Shaping (LENS), Directed A nozzle combined with a multi-axis arm deposits Metals: Cobalt Chrome, Adv: Used for repair work of LENS: Optomec
Light Fabrication (DLF), Direct Metal Deposition melted material onto a specified surface. The Titanium, Polymers and Ceramics structures, Multiple axis,
(DMD), 3D Laser Cladding, nozzle can move in multiple directions and is not possible. flexibility,
fixed to a specific axis. Upon deposition the Disadv: Limited material use,
material is melted via a laser or electron beam. Post processing may be needed.
Additive Manufacturing 24 (2018) 606–626
A. Mitchell et al. Additive Manufacturing 24 (2018) 606–626

temperature, moisture [7] or by light activation using irradiation [8]. martensite domains. Haberland et al. observed that after cyclic testing
Alternatively the SMPs can be magnetically induced by incorporating the SLM NiTi had a more stable recovery compared to the con-
nanoparticles into thermoplastics [9]. SMPs are frequently used due to ventionally made material, as the irreversible effects were less. Analysis
their biodegradability and biocompatibility, whilst being derived from after every cycle shows recoverable deformation due to pseudoelasti-
low-cost and renewable resources. SMPs have found many uses in city, but also some irreparable damage. However overall the SLM ma-
biomedical applications [10–13], micro electromechanical systems and terial demonstrates slightly greater maximum strains and recoverable
self-deployable structures [5]. A potential disadvantage for SMPs is deformation compared with that of the conventional NiTi [20]. Sa-
their low tensile strength and stiffness, in comparison to SMAs [14]. ghaian looked at the effects of Ni content on the shape memory prop-
However, many shape memory nano-composites are being developed to erties of NiTi alloys, and found the composition greatly influences its
help improve their conductivity, electrical response and mechanical behaviour. With an increase of Ni content, the strength of the material
properties [15]. increases while the recoverable strain decreases [21]. Saedi et al.
SMPs that are heat responsive are characterized by the chemical and showed the benefits of heat treating the sample after SLM fabrication.
physical cross-linking and changing sectors related to a transition Samples were kept in a furnace for 5.5 h at 950 °C and then quenched,
temperature, which can be the glass transition temperature (Tg). For an which allowed the second phases on the grain boundaries to be dis-
SMP after each phase transition temperature one shape can be pro- solved and restructured within the grains, increasing the strength of the
grammed. To activate the SMPs the original shape is deformed under fabricated part, achieving better shape memory and superelasticity
stress above its Tg. If this applied stress remains constant when the [22]. A disadvantage of these shape memory alloys can be the low
polymer is cooled below the glass transition temperature, the SMP will transformation temperature. A new Cu-Al-Ni wire is available, although
remain in the deformed manner until it is heated above its Tg again. yet to be produced by SLM, it exhibits good shape recovery and a high
Meng has shown that SMPs have distinct advantages of low density transformation temperature, up to 250 °C, suitable for space applica-
and high elastic deformation, although the small recovery stress re- tions [23]. Extensive research into a new 4D printed multi-functional
stricts the size of the components, as larger components will not be able material at NASA’s Jet propulsion Laboratory is under way. The me-
to recover under their self-weight [16]. Photo-responsive SMPs have tallic space fabric seen in Fig. 1 has four important functions; re-
some advantages in contrast to heating as a stimulus, such that other flectivity, passive heat management, foldability and tensile strength.
materials surrounding the SMP are not exposed to temperatures needed These fabrics have potential use in deployable structures, antennas,
to activate the SMP. In using the correct wavelength, light polarization spacesuits or for shielding spacecraft. Elahinia et al manufactured a
direction and intensity, control can be achieved without heating [17]. porous NiTi implant using Electron Beam Melting (EBM), which has
Shape memory is governed by chemical composition, the processing potential uses for bone fixation and in minimising invasive surgery
methods and material layout. This control to 3D print each layer allows [24–26]. Fatigue plays a vital role in the use of SMAs, such that it could
for the production of complex geometries with multi-materials, creating limit its use for repeated actuation or continuous thermal loading ap-
multi-functional parts. In general compared to thermoplastics, ther- plications. The build-up of irrecoverable strain determines the resi-
moset materials have a broader thermal usage range and enhanced lience and service life of the SMA, as during each transformation grain
mechanical properties. SMPs have many advantages over SMAs, such as refinement, dislocations and new grain boundaries emerge [27–30].
a high strain recovery, low density, cost, simple processing, bio- A novel multi-functional panel, designed for aerodynamic surfaces
compatibility and biodegradability. Shape memory alloys, for metallic as an anti-ice system is presented by Ferro et al. [31]. The design
components, are a smart material that can directly convert thermal produced via SLM provides significant weight savings and improvement
energy into mechanical work, a shape memory effect, as discussed in thermal efficiency.
below [18].
2. 4D printing polymeric structures
1.2. Shape memory alloys
Recent advancements in Polyjet 3D printing, namely from Stratasys,
Extensive studies in recent years on the shape memory effect of utilizing UV curable resins to deposit layer by layer multi-material
SMAs have been published. A shape memory alloy (SMA) can have both parts, has created a new platform for 4D stimuli responsive printed
mechanical and thermal memory. The shape memory effect found in materials. The following paper focuses on the recent developments in
metals is due to two different crystalline phases in the SMA, the mar- 4D printing and the capabilities of the current 3D printers, with a future
tensite low temperature phase and the high temperature phase auste- outlook to possible applications. Just recently 3D4MD, a medical 3D
nite. Of particular interest is using additive manufacturing techniques printing company, completed in space medical manufacturing, printing
to create metal alloys. Meier successfully produced shape memory ac-
tuators using Nickel-Titanium (NiTi) parts by means of selective laser
melting (SLM). Several benefits are evident in using SLM, for example,
NiTi is notoriously difficult to machine, with the significant heat gen-
eration during tooling it will have an impact on the surrounding mi-
crostructure. Less waste is also produced, and fewer thermomechanical
treatments are needed. A disadvantage with shape memory alloys is
that during each phase transformation cycle, microstructural defects
and dislocations evolve [19]. As reported by Meier, fracture strains and
stresses are lower for SLM NiTi compared to the conventional hot
worked and straight annealed NiTi. The transformation temperature
will be influenced by a shift in the Ni/Ti ratio, such that an increase of
0.1% of Ni content decreases the transformation temperature by 10 K
[19]. Haberland et al have demonstrated that the manufacture of pre-
cise intricate complex shapes of NiTi with functional shape memory
characteristics and pseudoelastic behaviour is possible by SLM [20].
Upon functional shape memory behaviour NiTi experiences damaging Fig. 1. Metallic 'space fabric' was created using 3D printed techniques that adds
effects during cyclic loading. These are caused by dislocations leading a different functionality to each side of the material (https://www.jpl.nasa.gov/
to irreversible strains, by dislocation plasticity and stabilization of news/news.php?feature=6816).

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A. Mitchell et al. Additive Manufacturing 24 (2018) 606–626

splints and surgical tools, finger splints and other dental tools aboard Fig. 2. The lengths of the cables are critical to ensure the correct stiff-
the ISS [32]. Precise laser scan measurements can be made on earth and ness is achieved, as too short and the structure will not support itself.
the 3D file is directly sent to the ISS for printing. With 4D printing now Rodriguez demonstrated a 3D printing method for shape memory
a viable option, printing transformable stents such as that by Zarek [33] constructions with electrically and thermally responsive behaviour,
is a future possibility in space. Stratasys direct manufacturing has built using bio-originated composites. Rodriguez presents a novel thermoset
the first 3D printed parts to function on the exterior of a satellite. Six composite ink allowing tuneable structures [42]. Fig. 3 describes the
satellites will be launched in 2018 as part of NASA’s COSMIC-2 project. development and manufacturing process Rodriguez used. Table 2
The antenna arrays are a critical part of the satellite, which were pre- summarises the current literature on 4D printed materials, naming the
viously made from astroquartz. Using FDM and a high strength en- additive manufacturing route, the materials used, the stimulus and 4D
gineering grade thermoplastic, a light weight replica was built. To application.
protect the polymer from atomic oxygen and UV an astronautical paint Fig. 3a presents Rodriguez’s work, the chemical structures for
was used to form a glassy layer, capable of reflecting a high percentage epoxidized soybean oil and bisphenol F diglycidyl ether BFDGE-. The
of solar radiation [34]. carbon nanotubes were dispersed within the resin resulting in non-
Significant advances in computer aided design, additive manu- Newtonian inks as depicted in Fig. 3c. Rodriguez used two routes after
facturing and materials science have opened up the possibilities of self- 3D printing. The first route in Fig. 3e involves thermally curing at 80 °C
assembly systems, self-healing and shape changing properties. To build for 16 h and then post curing at 150 °C for 2 h. In the second method as
a large scale structure one can either build block by unconnected block shown in Fig. 3f after folding the part, it is subjected to curing initially
or use programmable structures, to print a single shape changing at 80 °C for 4 h followed by full curing (Fig. 3g) at 80 °C for 12 h with a
structure that can morph into the desired construct with various hinges post cure at 150 °C for 2 h. The two methods join in Fig. 3h, where the
or electronics embedded. An example in a space environment would be 3D printed structure is heated to 80–100 °C for 5 min and programmed;
a tensegrity structure that could reconfigure itself into a satellite once by applying an external stress to deform the structure and hold the
reaching orbit. Campbell et al have combined nano-technology with 4D desired shape until the temperature decreases to 20 °C. The new shape
printing, creating a material which changes properties in response to will recover to the original shape by heating above the Tg. This method
electromagnetic waves. This could be extremely useful in sensing, of ‘4D’ printing with shape memory polymers opens a window for the
eventually testing blood pressures or insulin levels, or in space the development of much more complex structures, multi-functional and
surface of a satellite could change the absorptivity or emissivity of a multi thermal shape recovery profiles. Possible applications of such
material when needed [35]. devices include electrical interconnects and thermal sensors. Rodriguez
Similar to a pixel in 2D, a voxel is a unit of graphical information demonstrates the difficulty in ensuring the resin completely cures using
that defines a point in three-dimensional space, as described by Kurman photochemical processes, with the potential to lead to poor aging.
as building blocks, just like biological life [36]. A voxel can be pro- Another issue is in achieving an ink that has a long pot-life, which is
grammed to be a sensor, a conductor or insulator, whichever is required able to meet the printability requirements, and achieve key properties
for the application. If the same voxels are programmed together to such as stiffness, conductivity and shape memory [42].
make a system, it can be reversed, i.e. disassembled, and reused to build Rodriguez incorporated carbon nano-fillers to tailor the mechanical
something else, thus surviving and manufacturing in remote locations properties to increase the Tg and improve the conductivity. The added
becomes manageable. Extensive research is going into shape shifting carbon nano-fillers, increased the viscosity of the base resin, and in-
materials, medical devices, self-healing surfaces and structures which troduced shear thinning behaviour. This is important because it enables
can self-assemble in any environment. printing at low pressures, where shear forces surround the ink inside of
the nozzle. It is important that the storage modulus is less than the loss
2.1. Stimuli: temperature modulus meaning the ink has shear thinned and flows, which is needed
for shape fixity for room temperature printing, otherwise the ink will
Ge, Tibbits et al have used an inkjet based 3D printer to pattern SMP quickly solidify after exiting the nozzle. Rodriguez also measured the
hinges in an elasticated structure, with a UV photocurable thermoset increase in electrical conductivity, and as expected the conductivity
resin [4,37,38]. Zarek et al have also printed SMP devices using ste- increased in the SMP, with increased additions of 0.6–5.6 vol % CNT
reolithography [39]. For deployable applications, tensegrity structures (carbon nanotubes) increased the conductivity from 0.0001 to 0.4 S.
are suitable. For example in many biological organisms, muscle-skeletal cm−1 respectively. The conductivity was used to turn on low power
systems and cells can be seen as tensegrity structures. They are based on electronics. The 5.6 vol % SMP was connected to a 9 V power source but
a structural principle, described as ‘isolated components in compression, not in physical contact. The experiment was conducted in an oven set at
inside a net of continuous tension, in a way that the compressed members, 85 °C and upon heating the SMP recovered its original design to connect
struts, do not touch each other, and the pre-stressed tensioned members, the circuit, lighting the LED, as shown in Fig. 4 [42].
cables, delineate the system spatially’ [40]. Tensegrity structures can be Shape memory polymers have the advantages of high strain re-
used in communications applications such as antennas, solar arrays or covery [4], cost effective and simple shape programming procedures.
in various other deployable structures, having advantages of reducing Yu demonstrated that high precision complex deformations are possible
the risk of failures of deployment i.e. less joining mechanisms, saving with SMPs, which can be used to make sensors, actuators and biome-
weight and space in the materials used. In comparison to other de- dical devices [7,43]. The polymers used to create the 3D SMP shape are
ployable systems tensegrity systems do not need to lock the deployed characterised below. Fig. 5c summarises the seven epoxy polymers glass
shape, as self-stresses provide the stability. The same principles still transition temperatures. The materials used here are from Stratasys
apply in printing high precision structures on a small scale to providing digital multi-material Objet Connex 260 printer, labelled as 1–7 epoxy
large scale shelters. Liu has 3D printed thermally responsive SMPs to SMP.
create actively deployable tensegrities [41]. The struts are printed using The SMP was modelled using CAD, with each active hinge having a
the SMP Verowhite with the Objet 260 Connex 3D printer, having a Tg different Tg. The radius of each hinge is 5 mm, the helical line thickness
of 60 °C. The composition of Verowhite is described in Table 2. The is 0.8 mm and the depth is 6 mm. The gap between the bordering helical
struts are heated to 65 °C and deformed into a flat shape, and cooled to lines is 5 mm. As labelled in Fig. 6, polymer 1 has the lowest Tg, 32 °C
10 °C, allowing the structure to be flat packed. The elastic cables are allocated to hinges 1 and 2. Polymer 7 has the highest Tg 65 °C, de-
printed using a Fused Filament Fabrication printer with Filaflex which signated to hinges 8 and 9. Hinges 3–7 are assigned with polymers 2–6,
are attached to the struts. The connected system is then heated back with an ascending rise in Tg. The structure after printing is heated and
above the Tg of Verowhite and the structure transforms as seen below in then deformed into a straight design in hot water at 100 °C. The sample

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 Table 2
A review table for 4D printed materials and potential applications.
Authors Year 3D Printer Material Stimulus 4D Application
Published
A. Mitchell et al.

Dan Raviv, Skylar Tibbits Active Printed 2014 Stratasys Connex 500 multi-material 3D printer, UV Hydrophilic acrylated monomers, UV curable. (Vinyl Water Multiple hinges, folds and
Materials for Complex Self Evolving photopolymerizing caprolactam 50%, Polyethylene 30%, Epoxy diacrylate curls from a flat sheet.
Deformations oligomer 18%, Iragcure 819 1.9%, Wetting agent 0.1%)
Qi Ge Active origami by 4D printing 2014 Stratasys Objet Connex 260, UV Photopolymerizing Tangoblack: A rubbery material at room temperature - Temperature Hinges, box, plane etc from a
polymerised with an ink containing urethane acrylate oligomer, flat sheet.
Exo-1,7,7-trimethylbicyclo [2.2.1] hept-2-yl acrylate,
methacrylate oligomer, polyurethane resin and photo initiator.
Verowhite: a rigid plastic at room temperature polymerised with
an ink containing isobornyl acrylate, acrylic monomer, urethane
acrylate, epoxy acrylate, acrylic monomer, acrylic oligomer and
a photo initiator.
Tibbits, Mcknelly 4D printing and Universal 2014 Stratasys Multi-Material Connex, UV curable Hydrophilic acrylated monomers, UV curable. (Vinyl Water Folds and curls from a
Transformation caprolactam 50%, Polyethylene 30%, Epoxy diacrylate printed flat sheet
oligomer 18%, Iragcure 819 1.9%, Wetting agent 0.1%)
Haberland, Meier Structural and functional 2014 Realizer SLM 100, SLM solutions GmbH different NiTi powder ratios. Particle size 25-75 micron. Temperature Actuators, Truss structures,
properties of NiTi shape memory alloys medical implants, bone
produced by Selective Laser Melting reconstruction.
Kai Yu, Yiqi Mao Controlled sequential shape 2015 Stratasys Objet Connex 260. Deposits ink at 70oC, UV Epoxy based UV curable SMP Temperature Multiple hinges, each with a
changing components by 3D printing of shape photopolymerizing different Tg
memory polymer multi-materials
Yang, Chen 3D Printing of Shape Memory Polymer 2015 Makerbot Replicator 2X (Makerbot Industries LLC). Extruder DiAPLEX MM-4520 pellets from SMP Technologies, Temperature Grips, foldable flowers
for Functional Part Fabrication Temperature - 220oC. Build Plate Temperature - 45°C. Speed thermoplastic polyurethane elastomer (TPU)
while extruding −90 mm/s
Zhang, Yan Smart three-dimensional lightweight 2015 Makerbot Replicator 2X (Makerbot Industries LLC). Nozzle PLA supplied by Makerbot Company Temperature Heat shrinkable pattern

610
structure triggered from a thin composite sheet temperature 230°C, building speed 90 mms−1 transformations
via 3D printing technique
Bakarich 4D Printing with mechanically robust 2015 3D - Bioplotter (EnvisionTEC). Dymax Bluewave 75 Rev 2.0 Ionic covalent entanglement (ICE) hydrogel. Formulation: Water Hydrogel-based sensors,
thermally actuating Hydrogels UV light curing spot lamp Range of Poly(N-isopropylacrylamide) (PNIPAAm) hydrogel valves
pre cursor solutions with NIPAAm concentrations between 10 to
20%.
Lantada, Romero, 2015 SLA-3500 laser stereolithography from 3D systems Shape memory epoxy from Accura 60 Temperature Micro claw, active springs
Qi Ge Multimaterial 4D Printing with Tailorable 2016 Microstereolithography. CEL5500 LED Light Engine from Methacrylate based monomers and crosslinkers, Photo initiator- Temperature Springs, grippers, stents
Shape Memory Polymers Digital Light Innovation. A translation stage LTS300 from PhenyIbis (2,4,6-trimethylbenzoyl) phosphine oxide. Photo
Thorlabs, A stepper motor from SparkFun Electronics absorber - Sudan I and Rhodamine B.
Yang, Chen 3D printing of variable stiffness hyper- 2016 Makerbot Replicator 2X (Makerbot Industries LLC). SMP DiAPLEX MM-4520 pellets from SMP Technologies, Temperature SMP/ABS ball joint robotic
redundant robotic arm extruder Temperature: 250oC. ABS extruder temperature: thermoplastic polyurethane elastomer (TPU). Acrylonitrile arm
230°C. Build plate temperature 110°C. Speed while extruding butadiene styrene
120 mm/s
Gladman, Matsumoto Biomimetric 4D printing 2016 ABG 10000 Aerotech Hydrogel composite ink: stiff cellulose fibrils in a soft acrylamide Water For tissue engineering,
matrix, mimics the composition of plant cell walls. They are biomedical devices, soft
printed using a viscoelastic ink containing an aqueous solution robotics
of N,N-dimethlyacrylamide, photoinitiator, nanoclay, glucose
oxidase, glucose, nanofibrillated cellulose.
Yu, Yang 3D printing of shape memory composites 2016 SL200 Stereolithography Zrapid Tech, horizontal resolution Polyacyrylate-co-epoxy particles dispersed in epoxy resin. Temperature Actuators, Hinges
with epoxy acrylate hybrid photopolymer 40um and vertical resolution 1 μm. Scanning speed 6000 mm/s
Saedi Thermomechanical characterization of Ni- 2016 Phenix PXM 3D Systems NiTi Powder Temperature Actuators, Truss structures,
rich NiTi fabricated by selective laser melting medical implants, bone
reconstruction.
Naficy 4D Printing of reversible shape morphing 2016 Extrusion printer with two linear actuators (Zaber T-NA08A50- Polyether based polyurethane (PEO-PU). UV initiator: α- Hydration and Hydrogel Hinges, box
hydrogel structures S-KT03U) mounted on a Sherline 8020 CNC milling stage. A ketoglutaric acid. Crosslinking agent: N,N'- temperature
Dymax Bluewave spot light UV 300-450 nm next to the printing methylenebisacrylamide (BIS). Monomers: 2-hydroxyethyl
for curing. methacrylate or N-isopro-pylacrylamide.
(continued on next page)
Additive Manufacturing 24 (2018) 606–626
 Table 2 (continued)

Authors Year 3D Printer Material Stimulus 4D Application

Published
A. Mitchell et al.

Duigou 3D printing of wood fibre biocomposites 2016 Prusa i3 Rework, maximum printing area 19 × 19cm2. Nozzle Supplied by ColourFabb woodfill fine - a mix of poly(lactic acid) Water Actuators, Hinges
temperature-210°C. Heating plate 70°C. Printing speed 18 mm/ & poly(hydroxyalkanoate) reinforced with recycled wood fibres.
s.
Nadgorny Three-dimensional printing of pH 2016 Makerbot Replicator 2 × . 1.75 mm inlet diameter. Nozzle (poly(2-vinylpyridine) (P2VP pH Flow regulating devices,
responsive and functional polymers on an temperature- 220°C. Platform temperature 90°C, speed catalytic supports
affordable desktop printer 100 mm/s.
Zarek 4D printing of shape memory based 2016 Freeform Pico 2 SLA Digital Light Processing printer. The Semicrystalline methacrylated polycaprolactone (PCL) Temperature Medical devices
personalized endoluminal medical devices wavelength of the UV-LED light source was 405 nm.
Wei Direct-Write fabrication of 4D active shape 2016 Microdepositing robot I&J2200-4 I&J Fisnar, a dispensing Semicrystalline thermoplastic PLA pellets 4032D from Magnetic field, Medical devices,
changing structures based on a shape apparatus HP-7X EFD, two 365 nm UV LEDs Natureworks LLC, Fe3O4 nanoparticles 30 nm average diameter Temperature
memory polymer and its nanocomposite
Rodriguez Shape-morphing composites with 2016 Air powered fluid dispenser Ultimus V EFD, Printed using x-y-z Varying ratio s of Epoxidized soybean oil (ESBO), with Temperature Medical device, conductive
designed micro-architectures 3 axis positioning stage ABL 9000 Aerotech Bisphenol F diglycidyl ether. Incorporated carbon nanofibers hinges
Bodaghi Self expanding / shrinking structures by 2016 Polyjet Objet 500 Connex, Jets microscopic layers of liquid Tangoblack plus is a soft and flexible material obtained in Temperature Self-expanding/shrinking
4D printing photopolymer directly onto a build platform at 70°C, cured with polymerization of an acrylic oligomer, 2-Propenoic acid, 1,7,7- structures
UV light trimethylbicyclo[2.2.1]hept-2-yl ester, exo-, photo initiator,
xylenes (o-, m-, p- isomers), benzyl alcohol, acrylic acid ester,
propylene glycol monomethyl ether acetate, isoamyl acetate, n-
Butyl acetate, carbon black, ethylbenzene, citral, dipentene, 2,6-
Di-tert-butyl-p-cresol, geraniol. Verowhite is a stiff material
obtained in polymerization of an acrylic monomer, 2-Propenoic
acid, 1,7,7-trimethylbicyclo[2.2.1]hept-2-yl ester, exo-, acrylic
oligomer, photo initiator, titanium dioxide, acrylic acid ester,
propylene glycol monomethyl ether acetate, phosphoric acid
Coulais 2016 Materialise PolyvinylSiloxane, polyurethane Pressure Mechanical Metamaterials

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Combinatorial design of textured mechanical
metamaetrials
Liu 2017 Objet 260 Connex, and a Fused Filament Fabrication printer Verowhite Plus, and digital materials DM9895 and DM8530. Temperature Tensegrity deployable
Programmable deployment of tensegrity HYREL Fort he FFF printer a rubbery material Filaflex was used, a structures
structures by stimulus-responsive polymers thermoplastic elastomer base polyurethane.
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A. Mitchell et al. Additive Manufacturing 24 (2018) 606–626

Fig. 2. Deployment of 6-strut spherical tensegrity [41].

Fig. 3. Ink development and manufacturing process [42].

is immediately transferred to an environment where the temperature is Current developments in 3D printing permit the exact assignment of
10 °C, enabling all hinge sections to transfer to the glassy state, the multiple materials at micrometre resolution. Qi Ge directly printed a
temporary programmed shape, and is held for approximately 10 min. composite that specifies the fibre architecture, shape size and orienta-
The shape recovery occurs when the SMP is subjected to temperatures tion, to control the anisotropic thermomechanical behaviour of that
above its Tg, as depicted in Fig. 7. composite [38]. Within the 3D printed construct it is the glass fibres
Zhang utilises the internal strain when PLA materials are 3D that exhibit the shape memory effect [45–49]. The 3D printer used was
printed. The flat strips produced transform into a 3D shape once cooled, an Objet Connex 260, Stratasys, depositing polymer ink at 70 °C, to a
and upon heating reverse back to the initial shape, such that the pre- thin film, and then UV photo-polymerising the film layer by layer. The
vious formation is a result of thermal elastic deformation through resolution is 32–64 micron. The matrix material was an elastomer, and
cooling (See Figs. 8 and 9) [44]. the fibres a glassy polymer with thermomechanical shape memory

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Fig. 4. Electrical conductivity of the composite SMPs [42].

behaviour. The elastomeric polymer used had a Tg of -5 °C and so be- composites can also be printed as hinges attached to stiff plastic plates
haved as a rubbery solid between 10–100 °C with a modulus of 0.7 MPa that are not intended to deform.
at 15 °C. The glassy fibres had a modulus between 3.3 MPa-13.3 MPa, Bodaghi proposes a self-expanding/shrinking mechanism by multi-
depending on the temperature. The composite layer was printed 2 mm material 4D printing [52]. The developed process creates self-ex-
thick with a single row of fibres, volume fraction 0.28. The shape panding/shrinking planar and tubular structure. It is experimentally
memory effect was achieved by deforming the samples at 60 °C which is shown that the printing process introduces anisotropy into the printed
above the Tg of the digital material fibres, and then maintaining the parts. The printed design is two straight parallel beams that are cen-
applied stress on the sample while cooling to 15 °C at a rate of 2 °C/min. trally clamped, and the parts produced are able to bend in two opposite
At 15 °C the sample is held for about 5–10 min . The strain is recovered directions. The design utilizes the glassy and rubbery phases of the
by heating the sample 2 °C/min up to 60 °C. Different fibre orientations SMPs with varying Tg. The rubbery phase would be dominant above the
result in different shape memory behaviours. As shown in Fig. 10, by glass transition temperature, and the main actuation mechanism relies
varying the fibre orientation the original shape can take many forms. on carefully positioned SMP fibres at low and high temperatures. The
The extent of the shape deformation is governed by the composite design was modelled using finite element method (FEM), utilizing the
geometries and properties, the applied mechanical load and thermal thermo-mechanical behaviours of the SMP materials. The equations of
history. Ge shows that printing fibres at different angles into bilayer the printed structures are derived based on the non-linear Green-La-
strips leads to a variation in curvature upon activation [38]. The strip grange strain tensor and solved by FEM, with an iterative incremental
with the fibres orientated at 30° coils into a helix, (Fig. 10c), references Newton Raphson scheme, and then verified by experimental data. To
[50,51] describe this in further detail. The fibres in b–d have alter- attain the shape memory effect, the same programming of the polymer
nating regions of segments, one with fibres vf = 0.25 (volume fraction) composite as previously discussed after printing is applied. First the
and one without vf = 0. The fibres are orientated so that they are in the composite is heated above its Tg, of both SMP materials inducing a
top layer with zero in the bottom layer of the strip. Two layer thermo-elastic strain. The structure is then stretched to get a

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Fig. 5. Thermodynamic properties of the SMPs (a) temperature dependent storage modulus (b) temperature dependent tan δ (c) The SMP Tg summary [7].

opening the tubular structure, and with further heating, shrinks to

maintain its original diameter.
Bodaghi uses a Polyjet system Objet 500 Connex. The 3D printer
uses layers of liquid photopolymer directly onto a build platform at
70 °C, and instantly cures them with UV light. A combination of two
materials are used to produce the composite part - TangoBlackPlus and
VerowhitePlus. The composition of these polymers is described in
Table 2 by Qi Ge. The Objet 500 can combine both materials with
varying ratios to get a new digital material, such that in this study
Fig. 6. SMP component, each active hinge is formed of a different polymer [7]. TangoBlackPlus and VeroWhitePlus are mixed to create low and high
glass transition temperatures, 30 °C and 60 °C, respectively, known as
determined strain. The composite structure is then fixed in this strain DM9850, DM9885 and DM8510 in the printer material library. The
state and cooled to below the Tg (lower than the Tg’s of both SMP digital materials were analysed via DMA and the Tg for DM9850,
materials). The polymer in the rubbery phase gradually turns into a DM9885 and DM8510 was 18, 31 and 64 °C, respectively.
glassy state creating the first temporary shape. The mechanical con- To measure the anisotropy in the printed parts, 12 different thermo-
straint is released, and during unloading elastic strains are recovered mechanical parameters were measured. Six samples of each type of
while large pre-strains remain in the polymer composite. Upon heating polymer printed in different orientations were tested. The samples were
the pre-strain releases and the permanent strain is recovered (stress- prepared according to the standard ASTM D638. The tensile and
free strain recovery). The composite is heated and thus expands thermo-mechanical data, showing the Young’s and shear moduli and

Fig. 7. Snapshots of the free shape recovery process [7].

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Fig. 8. The initial shape of the 3D printed composite sheet. (b) The final flower 3D printed shape after thermal mechanical treatment, (c) A complex lightweight
structure after removal of the paper [44].

Poisson’s ratio are different in three directions at the glassy phase whilst materials molecules are arranged in a systematic way, developing
they become similar at the rubbery phase [52]. crystallites once cooled below the Tg, thus they are more susceptible to
Ding et al. have recently developed an alternative way to generate thermal shrinkage than amorphous materials [59]. Due to the thermal
the shape change in 3D printed materials using the Stratasys multi- sensitivity of the material Yang proposes a cooling mechanism designed
material J750 printer. Different to other printed shape memory poly- for the 3D printer to reduce the shrinkage. Although it is not needed
mers, the as printed shape is temporary, and the permanent shape with ABS or PLA as the heat transfer from the printed structure to the
evolves over time with temperature. By printing a bi-layer, a stiff SMP external environment is adequate to lower the temperature of the ex-
with an elastomer, the coefficient of thermal expansion mismatch truded material. For the SMP, to cool it below the Tg upon extrusion,
causes the material to bend. A printed internal compressive stress can extra air circulation is needed. To help the filament feed in properly one
be generated into the elastomer part that is controlled by the layer roller is activated by a motor and the other on the extruder material. To
printing time, light intensity and curing time. Once off the build tray, ensure the roller temperature stays below the materials Tg is essential,
the 3D printed part upholds its shape, until heated above its glass otherwise the feed becomes blocked and immovable. Yang used an
transition, where it transforms into the programmed shape. The tem- infrared thermometer (accuracy+-1.5 °C), and if the temperature ex-
perature increase reduces the internal strain within the part. This pro- ceeded the Tg of the polymer, the printing process was paused. Yang
cess has multiple advantages, allowing a structure to be printed and also studied the relationship between part density and the extruded
stored, to be assembled on demand. A single rod can be transformed temperature and found SMP structures with greater density produce
into a structure, enabling assemblies much greater than the build tray to larger recovery stress during shape recovery. As the nozzle scanning
be produced. Significant savings are reported, in terms of time and speed increased, the part density dropped slightly when tested at
material usage, when printing a part flat packed, which can later be 30–150 mm/s. The build plate temperature is also vital in any print, and
transformed [53,54]. so it is recommended for any SMP material printing that the build plate
Thermoplastic filament is used extensively with fused deposition temperature should be set to the Tg of the material [55]. A nozzle
modelling (FDM). The cost effective, reliable and simple process makes scanning speed while extruding of 60 mm/s allows little room for error.
FDM 3D printers hugely popular for small co-operations and home If printing too slowly the SMP could dissipate heat and the printed layer
users, thus an extensive amount of research is going into developing is soft and unstable, whilst if printing too fast, the extrusion may not be
new materials for FDM printers [55–57]. Steven et al. mixed radiation sufficient. Another important part to note is the increase in surface
sensitizers with an acrylate copolymer SMP and developed the material roughness of the printed parts when the extruder temperature is in-
for FDM [58]. Most notably Yang has investigated the use of SMPs with creased.
FDM printing [55]. The SMP material used were DiAPLEX MM-4520 The polyurethane SMP filament used in Takeda’s study was from
pellets from SMP Technologies. The 3D printer used in this study was a SMP Technologies Inc, and an ABS filament from KYORAKU Co. Ltd,
Makerbot Replicator 2x (Makerbot Industries, LLC). The material was both with a diameter of 1.75 mm [60]. The Tg of the SMP filament is
extruded at 220 °C and the build plate temperature was 45 °C. The SMP 55 °C. The 3D printer used in this study was made by Genkei LLC, and
is a thermoplastic polyurethane elastomer. Chen investigated the the printing conditions for the SMP were; thickness of the layer 0.2 mm,
polymer shrinkage of injection moulded materials. The crystalline nozzle temperature 185 °C, bed temperature 80, 90 and 100 °C and

Fig. 9. Fig. 13 (a–c) Helical structures with varying degrees of spiral. (d–e) corrugated structures by bidirectional folding of printed composite sheets. Scale bar is
2 cm [44].

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Fig. 12. An example of the joint designed. The black springs represent the rigid
bars and disks, the red springs represent the links that cause the joint to fold
[62] (For interpretation of the references to colour in this figure legend, the
reader is referred to the web version of this article).

curable polymer that increases in size in the presence of water [62]. The
polymer in the presence of water becomes a hydrogel increasing in size
up to 200%. It is formulated with hydrophilic acrylated monomers.
Certain crosslinks after polymerisation modify the polymer from water
soluble to water swellable. The stiff black materials in Fig. 12 have a
Fig. 10. (a) – shows the original strip (b–d) shows the variation achieved with
2 GPa elastic modulus and a Poisson ratio of 0.4, whereas the hydro-
different fibre orientations.
philic red material has an elastic modulus of 40 MPa when dry and
5 MPa after water absorption, with a Poisson’s ratio of 0.5.
printing rate- 120, 420, 1080 mm/min. The elastic modulus of the SMP Three different designs were utilised, the first was linear stretching
and ABS samples were 1.42 GPa and 1.72 GPa, respectively. Takeda where the shape can alter its length when exposed to water. By ad-
also found that the greater the print bed temperature, the greater the justing the ratio of expanding material to the rigid portions, the per-
yield stress of the sample [60]. centage of linear expansion is controlled. Ring stretching is the process
Yang et al, combined the SMP with ABS or PLA for dual extrusion, by which each ring is printed with a double layer, and once exposed to
with an FDM 3D printer. Yang designed a ball joint as depicted in water one layer of the ring forces the other into the desired shape.
Fig. 11. The SMP is the bottom component, spherical cap, and the ball Finally a folding method was utilised, following the same logic, by
and socket ABS [61]. printing a rigid and expanding material together various folds and de-
When heated above the Tg, the SMP becomes soft and easily de- signs can be created [63].
formed, and the ball joint can be moved. If the SMP is heated above its Tibbits et al have designed self-evolving structures such that specific
Tg, it will tend to recover to its memory shape. The component can be materials react to varying stimuli and change shape with time. The
heated directly with embedded wires or indirectly from an external main research directions are electro-magnetic motor driven engines,
source. temperature changing materials, electroactive polymers, pressurized
fluids and light. Using these specific hydrophilic materials, reversibility
2.2. Stimuli: water could be an issue, and further work is needed to investigate multiple
cycles and material degradation [63].
Raviv and Tibbits used a Stratasys Connex 350 multi-material 3D Tibbits placed rigid discs at each hinge to control the angle of the
printer, to print a combination of a rigid plastic with a hydrophilic UV

Fig. 11. (left) Components of the ball joint (right), the movement caused by heating the SMP. [61].

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Fig. 13. Printed joints demonstrating the calibration and precision needed for
self-transformation [63].

Fig. 15. Snapshots showing the transformation from a flat 3D printed structure
to a curve crease origami structure [63].

Fig. 16. The transformation showing dynamically curved and parted field after
being subjected to water [63].

with expanding material deposited on a specific side of the strip, with

longer strips naturally creating more curvature. Attractor points were
used that influence the placement of expandable material, as well as the
rotation of the x and y directions [63]. Material degradation over time
remains an issue, also the ability to control directionality and reversi-
bility.
Fig. 14. Snapshots showing the transformation from a flat 3D printed structure Mao demonstrated a two component design by 3D printing, using
to a precise Octahedron [63]. two stimuli responsive polymers, an SMP and a hydrogel [64]. The
hydrogel swells in water and is the driving force for the shape change,
bond, so the diameter and spacing between the disks dictate the angle. whilst the temperature of the SMP dictates the time of the shape
The discs once collided stop moving, and halt the expanding material. change. Hydrogels are typically soft with a Young’s modulus of a few
The further the discs are apart, the greater the angle of curvature. Once tens to hundreds of kPa, thus integrating with a stiffer SMP removes
the 3D structure is printed, it is immersed in water, warmer water in- some design constraints.
creases the speed of transformation [63]. Fig. 13 demonstrates the ca- Duigou et al printed natural fibre bio-composites (hygromorph),
libration and precision needed for self-transformation. Fig. 14 shows with a bilayer microstructure, using FDM. The bilayer bio-composites
the transformation of a flat 3D structure into an Octahedron. are actuated by a water gradient. The printing thickness controls the
Tibbits also looked at the potential for flat sheet transformations. In stiffness and swelling capability, due to the differences in porosity of
Fig. 15 concentric circles were generated with expanding material se- the microstructure. An increase in the filament width improved the
parated by rigid material. The rings were manufactured by alternatively porosity but lowered the cohesion between the materials, resulting in
placing expanding material above or below the rigid surface, creating reduced tensile stress and increased water uptake [65]. A biodegradable
mountain and valley folds. Trial and error was needed, to calculate the seaweed based material has been used for filaments in FDM 3D
force for transformation. Too much material tore the shape, and too printing, or a plant based latex material for use in medical tools [66].
little meant little strength and the fold was not possible.
Surface curling is also possible by depositing larger areas of ex-
2.3. Stimuli: mechanical
pandable material without the use of constraints, as seen in Fig. 16. The
deposited expandable material was kept thin, but the length and width
With 3D printing, complex geometries can be realized with relative
of it increased to create the curling affect. Vertical strips were created
ease in comparison to conventional manufacturing methods. Coulais

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drops encapsulating other droplets are printed in water, these adhere to

each other, and upon changes in the environment due to pH or tem-
perature, the droplets are released [75–78].

3.1. Stimuli: solvent

Kokkinis printed smart key connectors, which change under an

applied stimulus. The 3D printed parts consist of bilayers which swell
when exposed to a particular solvent. Kokkinis also used a magnetically
assisted technique to attain particle alignment control, using stiff ani-
sotropic particles in a liquid resin. A low magnetic field is applied to the
printed layer before it is cured via UV [79].

3.2. Stimuli: temperature

4D printing is particularly useful for medical devices, as it allows the

deployment of printed structures, in otherwise inaccessible places.
Zarek has presented a shape memory endoluminal device. The 4D
Fig. 17. Metacube reveals its precisely programmed surface texture under printed stent is deformed into a temporary shape, inserted into the body
uniaxial compression [67]. where it transitions to its original shape with an increase in tempera-
ture. Customized stents can be produced for each patient, minimizing
migration issues [33].
has designed a series of deformed cubic building blocks, whereby the
A review of the current 4D printing processes for biomedical devices
internal structure of the blocks is anisotropic such that each block can
is given by Gao et al [75]. Poly(N-isopropy-lacrylamide) (PNIPAAm)
be orientated independently to give intricate constructions [67]. The
has been extensively researched for its use in drug delivery and tissue
deformed blocks fit together like a jigsaw puzzle, in such a way that
regeneration. A bi-layered build using PNIPAAm and a water insoluble
upon compression they arrange themselves into a programmable shape.
polymer poly(ε-caprolactone) (PCL) will fold and unfold at certain
The design of frustration free mechanical metamaterials is shown in
temperatures, for drug release [75].
Fig. 17.
Wei et al incorporated magnetic iron oxide Fe3O4 nanoparticles into
a SMP. These nanoparticles are then remotely heated by alternating
2.4. Stimuli: pH magnetic fields, allowing the self-heating process for 4D shape chan-
ging transformation. Wei successfully printed the PLA nanocomposite
Nadgorny using FDM, printed a pH responsive polymer (poly(2-vi- ink using a direct-write printing technique, and produced a self-ex-
nylpyridine) (P2VP), which has a globule to coil transition upon pro- pandable intravascular stent, which could be magnetically guided and
tonation below pH 4.0. The addition of ABS considerably improved the remotely actuated, as shown in Fig. 19 [80].
mechanical stability of the P2VP. Nadgorny also functionalized the pH Naficy et al developed a series of hydrogel inks for 3D printing,
responsive polymer to become a hydrogel [68]. producing hinges capable of reversible shape deformation. The printed
hydrogels were responsive to hydration and temperature. Once the
3. 4D bioprinting cube is immersed in water, the hydrogel swells and transformation
begins. However, if the temperature increases above 32 °C, the structure
Bioprinting is an exciting prospect in the medical field. Bioprinting unfolds [81].
can be defined as ‘additive three-dimensional fabrication of tissues and Self–healing materials is an exciting prospect. To 3D print a material
organs using cells, biomaterials and biological molecules’ [69]. Several which can self-heal has countless applications. Self–healing mechan-
publications have been produced in the area of 4D printing with various isms inspired by nature are being mirrored into hydrogels, to mimic
activation methods, such as solvents, temperature and pH. human skin. Taylor et al discuss self–healing hydrogels. Covalent re-
Analysing and simulating natural events is fundamental in devel- actions in hydrogel self–healing mechanisms often require the condi-
oping new materials and processes. An example is the study of Gladman tions used for polymerisation, such as pH or UV light. Extensive re-
et al, who developed a hydrogel composite ink mimicking the structure search has been conducted on polymers which self–heal to an applied
of plant cell walls. The ink contains stiff cellulose fibrils within a soft stimulus. An overview of potential self–healing polymers, their effi-
acrylamide matrix. By positioning the cellulose fibrils they were able to ciency and whether they could be used for 3D/4D printing is sum-
control the swelling and elastic anisotropies. Various structures can be marised here [82]. The Aerospace Engineering group from Bristol
created depending upon the printed angle of the bilayers, as shown in University in collaboration with ESA is developing a self–healing skin
Fig. 18 [70]. for spacecraft. This exciting research can protect the satellite surface
For a comprehensive review on bioprinting Li et al, discuss the fu- from high velocity micrometeoroids and could potentially increase the
ture outlook, and the potential applications in biomedicine [71]. Xu lifetime of an earth-orbiting spacecraft. The composite laminate in-
et al developed a new thermal responsive thiol-ene-functionalized corporates glass filaments containing an epoxy resin and curing agent.
polybutadiene rubber [72]. The hydrogel is processed into a spiral-like Upon fracture these chemicals are released and react to solidify the
structure, and upon heating to 60 °C transforms into a temporary shape. crack or prevent further fracture [83].
Poly(N-isopropylacrylamide) (Pnipam) is a thermo-responsive material, Tibbits et al discuss the future capabilities of 2D bio printing with
where the polymer chains become hydrophilic when the environmental DNA, with the potential use for environmentally responsive materials,
temperature is decreased to less than the critical solution temperature such as materials reacting to sunlight, pollution, or a person’s touch
[73,74]. Chen et al used a crosslinker 4-hydroxbutyl acrylate (4HBA) to [84]. Qi Ge presents an alternative method in multi-material 4D
produce a pNIPAM-OH hydrogel. At 40 °C the flat printed hydrogel printing, using highly tailorable methacrylate SMPs with micro-ste-
shifted upwards producing a tubular structure. 4D bioprinting can reolithography. Qi Ge produced medical stents programmed into a
precisely control drug delivery where foldable or unfoldable bi-layered smaller diameter shape, recovering to the original form with an in-
structures can be produced which react to temperature. For example oil creased diameter upon heating, designed to swell in a narrowed artery.

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Fig. 18. Biomimetric 4D printing – flower design with different orientations. (scale bars 5 mm, inset- 2.5 mm [70].

Springs and multi-material grippers, where the actuation rate is also focusing on reducing the reliance on Earth in order for deep space ex-
controlled by the recovery temperature, are produced, with carefully ploration to become self-sustainable. In-house recycling of feedstock
designed structures, using multiple SMPs with varying Tg’s, as shown in material for 3D printing is needed to achieve this, which might include,
Fig. 20 [85]. for example, multi-material 3D printing of small satellites consisting of
metallic and electronic parts. Another objective would be to use a
planetary body or asteroid’s available resources for additive construc-
4. Potential 4D applications tion [86] (Fig. 21).
NASA’s in-space manufacturing team has developed a phased
In-space manufacturing is fundamental for future space missions. It technology roadmap from Earth-based manufacturing technologies to
will deliver cheaper launch costs and provide on-demand tools for long exploration-based, through to the year 2040, potentially focusing on
duration missions without the need to resupply from Earth. Recently, Mars, whilst ESA also considers a lunar base as a next step [87]. ESA
3D printing in microgravity was conducted on board the International have established a partnership with manufacturing technology centre
Space Station (ISS), demonstrating the printing of acrylonitrile buta- (MTC) based in Coventry the UK national centre for additive manu-
diene styrene (ABS) using fused deposition modelling (FDM). While facturing. Prototypes can be produced with state–of-the-art facilities to
detailed analysis of how ABS and other thermoplastics behave in mi- test their suitability for space applications. Research into additive
crogravity with long term exposure is still needed, (compared to the manufacturing will help to develop and promote green technologies. As
discontinuous parabolic flights, with the stop–start style of printing has already been seen, a huge reduction of waste compared to con-
currently being tested), Zero-G 3D printing on board the ISS is a proof ventional manufacturing methods, a reduction of manufacturing steps,
of concept for additive manufacturing and future deep space missions. energy consumption and overall environmental footprint. All compa-
It provides the first step inspace manufacturing for future materials and nies have responsibility to consider the materials that are taken to
more complex structures involving metals. In-space manufacturing is

Fig. 19. Direct-Write printing of 4D active

shape changing architectures by c-PLA/Fe3O4
ink: (a) optical image of the c-PLA/Fe3O4
composite ink depositing from a 150 um mi-
cronozzle to create a self-supported multilayer
composite tubular structure. (b–c) SEM image
top and side view of the printed composite. (d)
Printed composite cylinders of various sizes.
(e) Illustration of the responsive behaviour of
the composite cylinder under a constant mag-
netic field. (f) Snapshots of the remote actuated
4D shape-changing performance of a nano-
composite cylinder in a 30 kHz alternating
magnetic field [80].

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Fig. 20. 3D printed multi-material grippers (a) Multi-material grippers with different designs (b) the as printed shape and temporary shape after programming. [85].

space, to manage any residual waste and polluting substances [88]. The is generated by photodissociation of molecular oxygen by intense UV
immediate focus is on 3D printing plastics and metals, and the recycl- light. The collisions with a material will cause oxidation and erosion,
ability of such printed parts. Eventually the key is self-sustainment in unless they are already in their highest oxidation state. The collisions
space, in remote destinations, with large scale additive construction with hydrocarbon-based polymers like Kapton can break CeC and C–H
(contour crafting), and use of planetary resources. In 2018 NASA will bonds and cause oxidation, which results in the loss of mass and ejec-
introduce the next step into in space manufacturing and sustainability. tion of gases, such as CO2 and CO [90]. The current materials capable of
The ‘Refabricator’ can turn waste into raw materials again for re- ‘4D printing’ deliver exciting proof of concepts for future designs of
printing, all within the same unit [89]. Currently only plastic parts can satellites. Further development and qualifications are needed for their
be recycled and reused, however, by 2020 NASA wants to build a fully use in the external space environment.
integrated Fabrication Laboratory, a fully multi-material recycler that 3D printing has significantly grown over recent years such that it
includes metals. 3D printing allows us to move away from the tradi- could substitute many of the conventional manufacturing processes.
tional design for manufacturing approach and towards a design for Significant investment is predicted for the next decade in developing
need, where fewer manufacturing steps are required, using less material new materials, printers and concepts. Now with the emergence of 4D
and energy. printing and smart materials, the 3D printing industry will have a major
The requirements for materials in the space environment are sub- impact in many sectors, including the medical, aerospace and defence
stantial. Low Earth orbit (LEO) is 200–2000 km above the Earth’s sur- industries. For future deep space exploration and self-sustainability
face. A commonly used polymer on the surface of spacecraft in LEO is additive manufacturing is fundamental. Exploration will ultimately
Kapton. Kapton is a 50–150 kDA polyimide formed by the condensation produce vital infrastructure, new research and development which will
of dianhydride and a diamine monomer. It has a good resistance to UV filter into future industry. Technologies, such as life support for human
radiation and is stable between -269 to 400 °C [90]. Due to this thermal habitat, producing a closed artificial eco-system, recycling of water, O2
stability, Kapton is used as flexible film for substrates for solar arrays, and CO2. Several papers included in this review have demonstrated
thermal insulation, and spacecraft inflatable structures. After six years novel proof of concepts for 4D printing structures and medical parts,
in LEO, Kapton has the potential to degrade significantly. The main such as stents, and new drug delivery mechanisms. Exciting possibi-
causes of material degradation are the high energy vacuum UV radia- lities, such as that from Tethers and Magna Parva are emerging.
tion in wavelengths from 100 to 200 nm, temperature extremes from Tethers Unlimited is combining additive manufacturing with other
-175 to 160 °C, collisional impacts from space debris and micro- robotic technologies to enable in-orbit fabrication of large structures,
meteoroids, ionising radiation and atomic oxygen (ATOX) [91–100]. In such as trusses and antenna reflectors, termed the ‘SpiderFab process’.
LEO, ATOX is said to be the prime cause of material degradation. ATOX They are utilizing pultrusion and combining it into the additive

Fig. 21. Lunar base constructed via additive manufacturing -

An inflatable dome is extended from one end to provide a
support structure for construction. To produce a protective
shell layers of regolith are built up over the dome by a 3D
printer. http://www.esa.int/spaceinimages/Images/2013/
01/Lunar_base_made_with_3D_printing.

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manufacturing technique. Using carbon-fiber reinforced poly-

etheretherketone thermoplastics (CF/PEEK) [101], Magna Parva has
developed an in-orbit manufacturing pultrusion system that can pro-
duce large carbon composite structures in space. The pultrusion process
has been scaled down such that the equipment can be accommodated
onto a spacecraft. The project COPMA stands for ‘Consolidated Off
Planet Manufacturing and Assembly System for Large Space Structures’
[102]. By combining additive manufacturing and robotic systems, the
materials needed for manufacture in space can be launched in a com-
pact manner. The in-space manufacture can produce structures much
larger than if these were produced on Earth. Once built in space, size is
no longer an issue, much greater diameters for booms and complex
trusses can be realised, generating increased structural performance.
Manufacturing in space has the potential to save on launch once the
necessary equipment is deployed in space. Manufacturing in space
would mean complex heavy deployment mechanisms are not needed to
deploy booms or trusses, they could be manufactured in their opera- Fig. 22. 3D printed deployment mechanism for solar panels. http://www.esa.
int/spaceinimages/Images/2014/10/3D-printed_deployment_mechanism.
tional form. 4D printing requires further development, utilizing the
design of high strength composite materials and new 3D printing
technologies. A relatively new technology described as Ultrasonic Ad- (DPR), with two DPRs being accommodated on each satellite. Initially
ditive Manufacturing (UAM) has emerged. A rotating Sonotrode applies during launch the DPR is stowed away, and deployed once in orbit by a
ultrasonic vibrations to a foil, creating a roughening friction between single axis mechanism, which incorporates flexible piping for cooling
the foil and to the material being welded. This displaces the surface fluids [104]. Most conventional deployable devices are highly complex,
oxides and other contaminates, under a compressive force the materials containing numerous linkages, hinges and motors, which ultimately
are then bonded. A CNC stage allows for selective removal and ma- accompanies high cost and heavy structures. Recent developments in
chining to the final dimension. This technique works at a relatively low functional materials, give rise to lightweight, inexpensive materials
temperature, which enables other more delicate electronics and poly- capable of multiple deformations without degradation. The function-
mers to be embedded within the structure. During printing the metals ality of 4D printing allows materials to interact and adapt to changing
do not experience any alterations in grain size, precipitation or phase environments. Materials which can transform and adapt to variable
changes, and post processing is not necessary. This could create the stiffness applications have potential for deployable structures, such that
path for multifunctional materials and surfaces, combining metals, it is possible to withstand deformations at low stiffness and retain their
polymers and composites, to produce materials which are conductive, structure at high stiffness. Fig. 23 shows the Galileo System Test Bed
can change shape and sense their surroundings. Version 2 (GSTB-V2/A), a demonstrator for the Galileo global naviga-
For long duration human space exploration significant resources tion satellite system, deploying its solar arrays, a critical component for
and time are needed to solve the complex scenarios for every even- the success of the mission (Fig. 24).
tuality, including health risks, and exposure to space radiation. The Fig. 24 is an example of MARSIS boom deployment, the multi-metre
moon is not protected by an atmosphere or magnetic field, it is there- booms are released and locked into place. Low frequency radio waves
fore exposed to all radiation emitted from the sun and space environ- are sent towards the planet and will be reflected from any surface they
ment. Shielding materials and biological systems can be damaged from encounter. The importance of deployable structures to the success of a
high energy protons and charged particles. New developments for mission is unprecedented, as demonstrated by ESA’s seventh Earth ex-
shielding in remote locations is an area to consider, for spacecraft, plorer, the Biomass mission, which is set to launch in 2020. The mission
space suits and potential habitats. Other potential effects are the large will deliver essential information regarding the condition of our forests
temperature extremes or finding ideal location habitats which are often and advance our knowledge of the global carbon cycle. The biomass
lit, providing energy for solar arrays. The lunar dust was a big issue sensor orbiting at 637–666 km consists of a P-band (435 MHz) Synthetic
during the Apollo missions, it is charged electrostatically due to the Aperture Radar (SAR), which is based on a large deployable reflector
ultraviolet rays from the sun, causing photoemission, meaning the dust
assumes a positive charge, and as a result responds to any electric fields
around the environment. The abrasiveness of the dust created issues
with seals, joints, connectors, on optical surfaces and cameras etc.
Potential responsive visors, wipers or reversal electrical systems to shed
the electrical sticking of the dust could be designed.
Fig. 22 depicts a 3D printed titanium deployment mechanism for
satellite solar arrays, a lightweight version of the Adele mechanism. The
3D printed structure reduces the number of separate parts needed and
saves 80% on mass. The satellites moving mechanisms are critical for
mission success. These include solar arrays, antennas, scanning me-
chanisms and valve components for propellant systems [103]. De-
ployment mechanisms may only have to operate once or multiple times
throughout their service life. The reliability and precision of deploy-
ment is obviously very important for the success of any mission, thus
understanding how 4D printed structures behave in microgravity, their
fixity, repeatability and reversibility is a further challenge. The design
of a deployment mechanism with fewer components, may have a lower
risk of mechanical failures, and could potentially be cheaper, and
simpler to control. An example where 4D printing could eventually be Fig. 23. GSTB-V2/A deploys its solar arrays http://www.esa.int/
used in a preprogramed manner, is that of the deployable panel radiator spaceinimages/Images/2005/10/GSTB-V2_A_deploys_its_solar_arrays.

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Fig. 26. A 5 m diameter antenna reflector, designed for orbital operations. It

Fig. 24. The second MARSIS boom deployment on ESA's Mars Express 2005. has a double pantograph design to form a deployable ring. http://www.esa.int/
http://www.esa.int/spaceinimages/Images/2005/06/MARSIS_boom_2_ spaceinimages/Images/2016/11/Large_double_pantograph_reflector.
deployment_begins.
rigid structure, ensuring the membrane is tight on each vertex. Ensuring
perfect precision for multiple cycles could be challenging. If the entire
deployment process is dependent on homogenous heating from solar
flux, difficulties may arise [107].
In Fig. 26 the reflector has a double pantograph design to form a
deployable ring. The challenge is to develop a large enough reflector
which can be stowed before launch and deployed accurately to full size
to meet their strict performance requirements. The reflector was de-
veloped through ESA’s Technology Research Programme (TRP). An-
other large reflector developed through TRP, based on a carbon fibre
reinforced silicone surface, was also tested at ESA’s thermal-vacuum
chamber. The top netting supports the finely integrated metallic mesh.
A structure such as this could eventually be 3D printed and stowed in a
pre-programmed way to be deployed in space. Large antenna reflectors
can be used for Earth observation, navigation and deep space missions.
Precision is required on deployment and operational stability is needed
thereafter, as a deployment failure would result in a mission failure.
Carbon Fibre reinforced plastics tend to be used for rigid structural
members. A Reflector with a diameter greater than 5 m must have a
foldable structure, to be deployed once in orbit. For these designs the
Fig. 25. Biomass mission - Concept B deployed configuration with NG reflector
possible use of tensegrity structures becomes favourable, where no
[105].
mechanical joints are present, and thus a compression system can be
more accurately predicted than conventional hinged systems. The
(Fig. 25). The large antenna will be folded in the Vega launcher and possible modes of failure are significantly reduced from the deploy-
deployed in space. The antenna will consist of a deployable arm and ment. Sensors and actuators can be programmed into the system, en-
unfoldable reflector with a 12 m projected aperture diameter. abling a ‘smart’ structure. The Tensegrity structure, as described by
Potential applications for 3D printed programmable matter of low Zolesi [108] are ideal for space applications. With careful design, a
mass include antennas for radio communication, radar surveillance, ‘form finding’ property is enabled. Utilizing the spatial freedom of the
instrument booms, and solar sails [106]. There are typically three types bars, and flexibility of the cables, some bars contain a fixed length
of deployment systems used, inflatable or elastically deformed systems, whilst others are variable. This structure can create a ring with the
and pantographic systems. The pantographic structures are formed of cables in compression or in tension, creating different equilibrium
stiff materials with spring hinges, which use a locking mechanism after configurations. Upon Launch the tensegrity structure must be tightly
the deployment, usually triggered by pyro-mechanical cutters. If the packed, and once released into tension.
deployment velocity needs to be controlled or it needs to be reversible, ESA’s first 3D printed dual reflector antenna is shown in Fig. 27. It is
motor actuated mechanisms are used. Stiffer structures tend to need printed as one polymer type and plated with copper to certify the radio-
more stowage volume and are heavier, though they provide a higher frequency performance requirements. For further space qualification
geometrical accuracy. Examples of elastically deformed systems are the additional work is needed, to eventually build more complex geome-
coilable boom, where all parts are integrated to save mass and increase tries and target higher frequencies.
reliability. Inflatable systems are very low weight although they need In space manufacture requires alternative uses for materials at end
gas storing cylinders. Deployment modules, if 3D printed, could po- of life. All aspects of waste are considered before launch, and potential
tentially function as part of the deployment solar sail. The solar sail is recycling options studied. PEEK is a high strength thermoplastic used
printed and stowed flat, pre-programmed to react to a certain en- for demanding applications, due to its high thermal and mechanical
vironmental stimulus. With stowed solar sails, wrinkling of the mem- stability, and low levels of outgassing in a vacuum. It also has the po-
brane can be an issue, thus the deployment must be precise to provide a tential for biocompatibility; an SLS type powder based AM technology

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A. Mitchell et al. Additive Manufacturing 24 (2018) 606–626

temperature SMP. Kong and Xiao have recently reported on the poly-
imide that maintained its shape fixity and shape recovery to 100% after
1000 cycles, which was measured at up to 70 °C above its Tg (229 °C).
The TGA results stated the decomposition temperature at 5% weight
loss was 505 °C, thus demonstrating its thermal suitability for high
temperature applications [113]. To protect polymers from the en-
vironmental effects of LEO inorganic coatings are typically applied,
such as SiO2. SiO2-coated Kapton polyimide surfaces have previously
been used, as they are relatively unreactive to atomic oxygen. Also the
atomic layer deposition of Al2O3 and TiO2 onto polymer surfaces can
shield the substrate against atomic oxygen erosion and VUV-induced
degradation. However, if light does penetrate the coating through a
defect, potential volatile complexes could be released [114].
CubeSats are nanosatellites typically weighing between 1 and 10 kg.
The satellite subsystems are available commercially, and so can be
ready for launch within 1–2 years. They have potential as a means of
Fig. 27. ESA's first 3D printed dual reflector antenna. Printed as a prototype deploying small payloads, radio receivers and optical cameras. With
with one polymer type, and plated with copper to meet its radio frequency
multiple CubeSats distributed, simultaneous observations can be made
performance requirements. http://www.esa.int/spaceinimages/Images/2016/
over the same area, at a cheaper cost. ESA has begun a number of
03/3D-printed_antenna.
CubeSat missions since 2013, such as QARMAN designed to demon-
strate re-entry technologies, i.e. new heatshield materials and stabili-
is capable of manufacturing bioactive PEEK/HA structures. However, sation systems [115]. Eventually these CubeSats could be 3D printed in
the process of mixing bioactive PEEK is difficult due to the lack of space. ESA has 3D printed CubeSat structures incorporating their own
control of the bioactive phase within the PEEK matrix. A study by Vaezi electrical lines. These can be printed using PEEK and other high grade
describes an alternative method to control the bioactive phases in- thermoplastics, as they are recyclable and biocompatible [116]. A new
corporated into PEEK, using additive manufacturing and compression project Manufacturing of Experimental Layer Technology (MELT)
moulding, enabling precise control of the biological performance and consisting of The European Space Agency, Active Space GmbH, Active
mechanical properties [109]. Space SA, OHB Systems AG and BEEVERYCREATIVE is under way
Typically in spacecraft materials composites account for around [117–119]. The MELT projects aim is to produce a fully functional
17% of the total mass, and metallic materials around 63%, thus metallic electronic breadboard in a microgravity environment using high grade
materials show the biggest potential for reuse, especially aluminium engineering polymers. 3D printed CubeSats with a programmable ele-
alloys which can be optimized for additive manufacturing. Few ther- ment could be the next generation (Figs. 28–30).
moplastics are present, although PEEK is showing great promise, and Today approximately 750,000 objects larger than 1 cm are orbiting
becoming increasing popular in replacing thermoset composites Earth. Active Debris removal (ADR) is needed to stabilise the growth of
[110,111]. For example a high strength engineering-grade thermo- space debris, and any newly launched objects must comply with post-
plastic produced by FDM was used for NASA’s COSMIC-2 project. The mission disposal guidelines. At typical collision speeds of 10 km/s in
high grade thermoplastic passed all qualification tests for the exterior of low earth orbits impacts by 1 cm sized objects could completely disable
a satellite. All that was needed was a protective astronautical paint to an operational satellite, whilst debris approximately 10 cm in size could
protect it against atomic oxygen and UV [34]. Wu has characterized the lead to the complete destruction of a satellite. Each potential collision
shape memory effect in PEEK, which has a potential use in medical creates further debris increasing the percentage of further impacts,
applications [112]. These recent publications could be a step closer to leading to a self-sustaining cascading process known as the ‘Kessler
4D printing of other such devices. Polyimide is another high syndrome’. In 2015 ESA’s Integral and Cluster-2 satellites had their

Fig. 28. Several tiny satellites leaving the International Space Station’s Kibo laboratory using a small satellite orbital deployer. http://www.esa.int/spaceinimages/
Images/2015/07/CubeSats_leaving_Station.

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A. Mitchell et al. Additive Manufacturing 24 (2018) 606–626

Fig. 29. CubeSats being launched from the International Space Station's Kibo laboratory. 2014 http://www.esa.int/spaceinimages/Images/2014/10/Cubesat_
launch_from_Station.

orbits changed to ensure both satellites will re-enter the Earth’s atmo-
sphere in the next decade in a safe way. Densely populated regions at
1000 km altitude are chosen for multi-target removal missions. ESA’s e-
Deorbit will be its first launching in 2024 with an aim to remove a large
ESA owned object from its current orbit, and perform a controlled re-
entry into the atmosphere. Various autonomous guidance and capture
mechanisms have been proposed. The precision and speed are of up-
most importance, to prevent rebounding and a potential collision. In the
future robotic arms and complex deployment hinges could use 4D
printing to avoid areas of complexity with multiple hinges and potential
areas of failure (Fig. 31).

5. Conclusion

3D Printing provides an exciting future for manufacturing and

materials. Significant weight savings and complex designs can be rea-
Fig. 30. 3D printed CubeSat body, incorporating its own electrical lines. http://
lised. 4D printing is at a proof of concept stage that has taken a huge
www.esa.int/spaceinimages/Images/2017/05/3D-printed_CubeSat_body.
step forward in realising the capabilities of pre-programming matter
which react to various stimuli. The responsive materials have potential
to revolutionise aerospace, medical and defence industries in the next

Fig. 31. ESA's proposed e.Deorbit mission, using a robotic arm to catch a derelict satellite. http://www.esa.int/spaceinimages/Images/2017/01/e.Deorbit_s_robotic_
arm.

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