Accepted Manuscript

Title: Polymers for additive manufacturing and 4D-printing:

materials, methodologies, and biomedical applications

Authors: Carmen M. González-Henrı́quez, Mauricio A.

Sarabia-Vallejos, Juan Rodriguez-Hernandez

PII: S0079-6700(18)30128-X
DOI: https://doi.org/10.1016/j.progpolymsci.2019.03.001
Reference: JPPS 1130

To appear in: Progress in Polymer Science

Please cite this article as: González-Henrı́quez CM, Sarabia-Vallejos MA, Rodriguez-
Hernandez J, Polymers for additive manufacturing and 4D-printing: materials,
methodologies, and biomedical applications, Progress in Polymer Science (2019),
https://doi.org/10.1016/j.progpolymsci.2019.03.001

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 Polymers for additive manufacturing and 4D-printing: materials,
methodologies, and biomedical applications

Carmen M. González-Henríquez1,2*, Mauricio A. Sarabia-Vallejos3,4, and Juan Rodriguez-

Hernandez5*

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Universidad Tecnológica Metropolitana, 1Facultad de Ciencias Naturales, Matemáticas y del Medio Ambiente,

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Departamento de Química, P.O. Box 9845, Correo 21, 7800003, Santiago, Chile, 2Programa Institucional de Fomento a la
Investigación, Desarrollo e Innovación, Ignacio Valdivieso 2409, San Joaquín, Santiago, Chile.
*Email: carmen.gonzalez@utem.cl

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Pontificia Universidad Católica de Chile, 3Escuela de Ingeniería, Departamento de Ingeniería Estructural y
Geotecnia, 4Instituto de Ingeniería Biológica y Medica, P.O. Box 306, Correo 22, 7820436, Santiago, Chile.

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5Instituto de Ciencia y Tecnología de Polímeros-Consejo Superior de Investigaciones Científicas (ICTP-CSIC),
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Departamento de Química y Propiedades de Polímeros, Juan de la Cierva 3, 28006, Madrid, España.
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*Email: jrodriguez@ictp.csic.es
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Graphic Abstract
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Abstract

Additive manufacturing (AM), also known as additive manufacturing, permits the fabrication of
fully customized objects with a high level of geometrical complexity at reduced fabrication time
and cost. Besides metals and ceramics, polymers have become a widely researched class of
materials for applications in AM. The synthetic versatility and adaptability, as well as the wide
range of properties that can be achieved using polymer materials, have rendered polymers the most

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widely employed class of materials for AM methodologies. In this review, the basic principles,
considering the printing mechanism as well as the advantages and disadvantages, of the most

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relevant polymer AM technologies are described. The particular features, properties and limitations
of currently employed polymer systems in the various AM technology areas are presented and

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analyzed. Subsequently, 4D printing, that is the fabrication of 3D printed structures that are cabable
to change with time, is discussed. A brief description of the polymeric materials and technologies

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under development for 4D printed structures as well as the different shape changes explored are
presented. Finally, based on the characteristics of the polymers employed for each technology
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illustrative examples of the principal applications are discussed.
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Keywords: polymers in additive manufacturing, stereolithography, fused deposition modeling, laser
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sintering, thermoplastics, photopolymerization

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Contents
1. Introduction to additive manufacturing (AM)
2. Brief summary of the AM technologies
2.1. Material extrusion
2.2. Powder bed fusion
2.3. Vat Photopolymerization processes

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2.4. Material jetting
2.5. Binder jetting

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2.6. Sheet lamination (Laminated objected manufacturing, LOM)
2.7. Directed energy deposition (DED)

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3. Polymers employed in material extrusion
3.1. Fused deposition modeling (FDM)
3.2. Bioplotting

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4. Polymers for stereolithography (SLA)

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4.1. Photosensitive resins and photopolymerization processes: free radical and cationic
photopolymerizations.
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4.1.1. Free-radical photopolymerization
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4.1.2 Cationic photopolymerization

4.2. Materials employed for SLA
4.2.1. Polymers
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4.2.2. Ceramic and metal composites

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5. Powder-based AM
5.1. Selective laser sintering (SLS): polymer powder and composites
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5.1.1. Polymer and polymer blends employed in SLS

5.1.2. Composites prepared using micro/nano fillers.
5.2. Binder jetting: polymer powder and composites
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5.2.1. Binder and powder

5.2.2. Mechanical properties of inkjet additive manufacturing parts fabricated using
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binder jetting
6. Polymeric materials employed in 4D printing
6.1. 4D printed Hydrogels
6.2. Shape memory polymers
6.3. Elastomer actuators

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 6.4. Active composites
6.5. Areas of application of 4D printing
7. Overview of the most relevant applications of AM fabricated polymeric parts
7.1. Biomedical applications
7.1.1. Anatomical models for pre-operation
7.1.2. Implants and scaffolds

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7.1.3. Cartilage and tendon regeneration
7.1.4. Bone regeneration
7.1.5. Antimicrobial implants supports

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7.1.6. Biodegradable platforms
7.2. Fabrication of elastic devices

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7.3. Piezoelectric composites
7.4. AM of high strength materials

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7.5. Thermal and electrically conductive polymeric materials
7.6. Objects with tunable dielectric permittivity
7.7. Optical components
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7.8. Magnetic 3D printed objects
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7.9. Microfluidic devices

7.9.1. Microvalves
7.9.2. Bioanalytic purposes
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7.9.3. Lab-on-a-chip
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7.10.3D printed microfluidic reactors for catalysis

7.11.Mechanochromic Materials
8. Conclusions and remarks
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 Abbreviation list

ABS: Acrylonitrile-butadiene-styrene LOM: Laminated objected

AUD: Aliphatic urethane diacrylate manufacturing,
AM: Additive Manufacturing HPHT: High-pressure high-temperature
ASTM: American Society for Testing LPS: Liquid phase sintering

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and Materials MC: Merocyanine
BAPO : Bisacrylphosphrine oxide ME: Material Extrusion
BMSC: Bone marrow stem cells MIP-SL: Mask-Image-Projection-based

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BNNTs: Boron nitride nanotubes Stereolithography
CAD: Computer-aided design MJM: Multi-jet modeling

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CFRTPCs: Continuous fiber reinforced MPP: Multiphoton polymerization
thermoplastic MRI: Magnetic resonance imaging
CLIP: Continuous liquid interface MWCNTs: Multi-walled carbon

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production nanotubes
CNFs: Carbon nanofibers N OCT: Optical coherence tomography
PA: Polyamide
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CNTs: Carbon nanotubes
CT: Computed tomography PAA: Polyacrylic acid
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DEAs: Dielectric elastomer actuators PACs: Printed active composites

PAEK: Polyaryletherketones
DED: Directed energy deposition
PBF: Powder bed fusion
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DLP: Digital light processing

PC: Polycarbonate
e-3DP: Embedded additive
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PCL: Polycaprolactone
manufacturing
PCL-TMA: Polycaprolactone
EAA: Epoxy aliphatic acrylate
trimethacrylate
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EAPs: Electroactive polymers

PDMAEMA: Poly(dimethylaminoethyl
FDM: Fused deposition modelling
methacrylate)
GFRP: Glass fiber reinforced polymer
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PDMS: Polydimethyl siloxane

HA: Hydroxyapatite
PDO: Polydioxanone
HAP: Hydroxyacetophenone
PEDOT:PSS: Poly(3,4-
HIPS: High impact polystyrene
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ethylenedioxythiophene):polystyrene
HDPE: High-density polyethylene
sulfonate
LFDM: Low-temperature fused
PEEK: Polyetheretherketone
deposition manufacturing
PEGDMA: Poly(ethylene glycol)
LOC: Lab-on-a-chip
dimethacrylate

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 PEI: Polyetherimide
PET: Polyethylene terephthalate
PETA: Pentaerythritol diacrylate
PGA: Polyglycolic acid
PHA: Poly(hydroxyalkanoate)
PHBV: Poly(hydroxybutyrate–co-
hydroxyvalerate)
PLA: Poly lactic acid
PMMA: Poly(methyl methacrylate)
PP: Polypropylene
PPF: Poly(propylene fumarate)
PPSF: Polyphenyl sulfone
PS: Polystyrene
PSLA: Projection-based SLA
PTEGA-DMA : Poly(tri(ethylene
glycol)adipate) dimethacrylate
PTHFDA : Poly(tetrahydrofuranether
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diacrylate)
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PTMC: Poly(trimethylene carbonate)
PU: Polyurethane
PVA: Poly(vinyl alcohol)
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PVAc: Polyvinyl acetate
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PVB: Polyvinyl butyral
PVDF: Polyvinylidene fluoride
RP: Rapid Prototyping
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SAN: Poly(styrene-co-acrylonitrile)
SSLA: Scanning-based SLA
SCM: Shape Changing Material
SMA: Shape Memory Alloys
SMC: Shape Memory Ceramic
SMG: Shape Memory Gel
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SMH: Shape Memory Hybrid
SMM: Shape Memory Material
SMP: Shape Memory Polymers
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SLA: Stereolithography
µ-SLA: Micro stereolithography
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SLS: Selective Laser Sintering
SP: Spiropyran
SSS: Solid state sintering
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µTAS: Micro total analysis system
TGME: Triethylene glycol methyl ether
TPE: Thermoplastic elastomers
TPO: Phosphineoxide
TPU: Thermoplastic polyurethane
elastomer
TPGDA: Tripropylene glycol diacrylate
TMTPA: Trimethylolpropane triacrylate
UHMWPE: Ultra-high molecular weight
polyethylene
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1. Introduction to additive manufacturing (AM)

The ISO/ASTM standards define the term additive manufacturing (AM), colloquially known as 3D
printing, as the “process of joining materials to make parts from 3D model data, usually layer upon
layer, as opposed to subtractive manufacturing and formative manufacturing methodologies” [1]. It
has to be clarified at this stage that there are a number of different subtypes of additive
manufacturing including 3D printing, but also rapid prototyping and direct digital manufacturing

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(DDM). The term “subtractive manufacturing” refers to traditional manufacturing methodologies
such as casting, forming, molding, and machining. These techniques usually, correspond to

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complex processes that require tooling, machinery, computers, and robots, among others, to develop
three-dimensional parts. As will be discussed later in this review, AM dramatically reduces or

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completely avoid the use of tools, permits to fully customize designs by simply modifying the 3D
model in the software and reduces the cost during the prototyping step.

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AM has been evolved during the last 30 years, not only in the field of business but also in the daily
life of consumers [2], nowadays is possible to acquire 3D printers for home-use at accessible prices.
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This rapid evolution generates a pressing need for the development of novel techniques for AM
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processes including rapid prototyping, rapid manufacturing, rapid tooling, freeform fabrication,
additive fabrication, additive techniques, layer manufacturing or solid freeform fabrication.
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In this context, Campbell and Ivanova [3] mentioned in 2013 that AM can be considered as a
disruptive technology that offers a new paradigm for engineering design and manufacturing which
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could have significant economic, geopolitical, environmental, intellectual property, and security
implications. Similarly, the Royal Academy of Engineering [4] declared that “Additive
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manufacturing is not only a disruptive technology that has the potential to replace many
conventional manufacturing processes but it is also an enabling technology allowing new business
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models, new products and new supply chains to flourish”. This disruptive potential associated with
AM technology is mainly caused by two characteristics. First, it enables the direct production of 3D
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printed physical and functional objects from digital design data, which entails the generation of
customized products that can be easily manufactured without incurring high manufacturing costs.
Second, on the consumer side, AM allows private and industrial users to design and produce their
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own goods [2], supporting Toffler's [5] idea of the rise of the ‘prosumer’, which increases the
competitive threat proposed by AM technologies to the established firms [6].
Companies operating in the additive manufacturing market today can be divided according to their
area of expertise, for example, software, raw material, hardware, and service bureau. Whereas
companies such as Autodesk or Shapeways are specialized in one area, i.e. software development in
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the case of Autodesk and Service Bureau for Shapeways, others like Sculpteo extend their business
to cover the entire production chain. The last case includes widely known companies such as
Stratasys, 3D Systems, Envisiontec or EOS [7]. In Figure 1 the areas of application with the
corresponding percentage of additive manufacturing usages, subdivided into different areas
according to the function that each manufacturing-related company is shown. As can be observed,
rapid prototyping with nearly 25% of the total is by far the most important application of additive

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manufacturing today. However, the percentage devoted to product development as well as direct
manufacturing is increasing and clearly indicates a transition from limited use of additive
manufacturing only for prototyping purposes to a wide range of applications.

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Fig. 1. Percentage of additive manufacturing application according to the manufacturing function used in the
surveyed companies [7], Copyright 2017 (Adapted with permission from Wiley-VCH publishers).
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AM working principle
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As depicted in Figure 2, the process of AM can be divided into 8 different steps. First of all, a 3D
model is designed by using a specialized computer-aided design (CAD) modeling software (Step 1)
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[1]. The file obtained is subsequently converted to an appropriate format for printing (Step 2) and
then transferred to the AM machine (Step 3) where it is digitized and sliced into a number of
consecutive layers. The machine is then set up to adjust the printing conditions (Step 4) that
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depending on the printing methodology employed includes an energy source (temperature, laser
intensity, etc.) or z-resolution (provided by the layer thickness). Other parameters also related to the
respective AM technique are the exposure time in the case of stereolithography (SLA) or the nozzle
material flow in the case of fused deposition modeling (FDM). When the optimal experimental
conditions are carefully chosen, the AM system prints the layers in a build, adding each new layer
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on top of the prior (Step 5), this is the reason for the terminology “additive manufacturing”. The
final steps involve the removal of the previously printed parts (Step 6), a post-processing stage in
which the supporting material is removed (Step 7), leading to the finalization of the part (Step 8)
obtaining a printed structure ready to be applied for which was designed.

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Fig. 2. Steps involved in the fabrication of a cup by AM [1], Copyright 2015 (Reproduced with
permission from Springer Nature Switzerland AG).
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Advantages of AM in comparison to other fabrication technologies

AM offers important advantages over other currently employed technologies [8]. This method
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permits the fabrication of fully customized products with a geometrical complex structure (internal
or external) in an economic manner (mostly for limited productions). Some reports established that
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AM corresponds to a cost-effective method in comparison, for instance, with plastic injection

molding for targeted production runs ranging from 50 to 5000 units. Other studies estimate that AM
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is highly competitive with plastic injection molding for targeted fabrications below 1000 items [9].
The basis of the low production cost is related to the no requirement of molds, costly tools, milling,
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and sanding processes.

Another crucial advantage is related to the design process involved in the printed parts. Designs can
be easily created, personalized, and modified according to any requirement of the consumer. They
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also provide the possibility of sharing the design, so that manufacturing process can be easily
carried out in many different places simultaneously. As a matter of fact, this methodology allows
the quick fabrication of prototypes with different versions for lab testing without the need for costly
and complex retooling processes. Moreover, replacement parts can be printed by third-party
producers utilizing the original designs provided by the manufacturer. As a result, a stock inventory
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is not required, reducing additional costs if finished goods remain unsold. Finally, it is worth
mentioning that AM offers important developments for manufacturing processes, particularly in
their environmental implications. This technique is more efficient in terms of feeding materials
usage and permits an environment-friendly design. Typically, less energy is required for AM in
comparison to subtractive processes for small production runs and do not need chemicals during the
manufacturing process and allow, in most of the cases, the reuse of the feeding material [8].

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Applications of AM parts

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The range of applications of AM fabricated parts has been gradually enlarged and today a wide
range of application fields are taking advantage of the benefits in the use of AM. As depicted in

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Figure 3, AM parts can accomplish the requirements of many different industrial areas including
textiles, aerospace, automotive, furniture, electronics, jewelry, sports, tooling, mold making,
toys/collectibles industry, and more recently has been implemented in biomedical applications for

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their use among others in the preparation of implants/prosthetics, dental, and surgical devices

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[8,10]. In particular, as will be depicted in the last section of this review, 3D printed parts are ideal
in the biomedical area because it is possible to fully customize and perfectly adapt the printed
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device according to each patient or to a precise surgeon needs.
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Fig. 3. Utilization of additive manufacturing across various industries [3], Copyright 2013 (Reproduced
with permission from Cognizant Communication Corporation).

However, it is worth mentioning that the range of applications has evolved during the last decades.
As an example, the AM application timeline suggested by Mawale et al. [11] in the year 2013 is
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shown in Figure 4. According to this timeline, a clear evolution from rapid prototyping (RP) to
series production can be observed. Currently studied application fields include aerospace, medical
devices, implants, or nano-manufacturing. The future of AM should, according to Mawale et al., be
directed towards the efficiency of the manufacturing processes with the finality to decrease the price
of the 3D printed parts. In terms of applications, future studies still require further investigation in
several fields, including the development of biomedical devices, in-situ bio-manufacturing or in the

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fabrication of full body organs.

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Fig. 4. AM timeline for different applications [11], Copyright 2016 (Adapted with permission from
SAGE Publications).
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From 3D to 4D printing
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4D printing was initially considered as a methodology that connects additive manufacturing with
time. In fact, in the pioneer works reported in 2013 [12–17], the strategy proposed involves the
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design of a 3D printed part able to suffer a controllable shape change. A general definition of 4D
printing was reported by Momeni et al. [17] which describes this process as a targeted evolution of
the 3D printed structures, in terms of shape, properties, and functionality. According to the Atlantic
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Council of the United States, 4D printing can be defined as “additive manufacturing of objects able
to self-transform, in form or function, when are exposed to a predetermined stimulus, including
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osmotic pressure, heat, current, ultraviolet light, or other energy sources” [18–20]. Thus, 4D
printing is the programmable dimension of a 3D printed area capable of altering the functionality of
an existing material or material hybrids engineered to self-assemble at precise locations and shapes.
As depicted in Figure 5, 4D printing is a promising technology for multiscale engineering of high
complexity structures having sizes from the sub-micrometric up to the meter range [21]. 4D printing

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implies changes in shape and functions thus introducing unprecedented additional levels of feature
complexity unable to be achieved by any of the currently available manufacturing processes such as
focused ion beam or mechanical machining. More interestingly, based on the wide range of 3D
printer resolutions from micrometer to centimeter or even higher scales, 4D printing offers a
potential extension for the production of a wide variety of features with complex shapes.

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Fig. 5. Manufacturing process by complexity and scale of the feature [21], Copyright 2017 (Reproduced
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with permission from Springer Nature Switzerland AG).

While both processes are closely related and begin with a 3D modeling and a printing step, several
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key differences can be found between 3D and 4D printing. As depicted in Figure 6, additive
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manufacturing involves the use of one (but can be more than one) material by means of a 3D
printer, resulting in a static structure. In contrast to the simplicity of additive manufacturing, 4D
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printing requires additional conditions to be met. First of all, 4D printing needs a multi-material
additive manufacturing facility since the differences in the material properties (such as the swelling
ratio or on the thermal coefficient) are at the base on the shape changes. The second condition to be
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fulfilled is the use of mathematical modeling in order to predict the changes to be produced and to
consider it during the design in order to achieve the desired final shape. The third requirement for
4D printing is a precise stimulus that will be essential in order to trigger morphological changes.
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Typical stimulus employed include heat [22,23], light [24], water swelling, [25,26] or mixtures of
these last mentioned [16,27]. Finally, the fourth main condition necessary to achieve an efficient 4D
printing process is related to the interaction mechanism. It is essential to know the exact process

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(duration of the stimulus, the intensity, for example, stimulus timing, among others) and eventually
the order in the application of the stimulus if more than one is applied [24].

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Fig. 6. The general scheme of additive manufacturing and 4D printing considering both materials and
processes [17], Copyright 2017 (Adapted with permission from Elsevier Science Ltd).
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Taking into account the aspects mentioned above, a comparison between the two technologies can
be established as depicted in Table 1, focusing on the materials, the design of the printer, the
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changes produced in the object and the application pursued [12]. Firstly, smart materials together
with a smart design are crucial in 4D printing. On the one hand, 4D printed structures require a
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thorough design that accounts for deformations of the object, i.e. digital information of the response
is required. On the other hand, 4D printing requires smart materials, able to expand, flexure and/or
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deform in response to a particular stimulus. As will be detailed in section 6, these materials include
polymers able to modify their structure in response to UV rays, temperature, or water absorption,
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just to mention a few [13,15,18,28–32]. Secondly, printers require modifications (modified nozzles,
different lasers or binders depending on the methodology employed) that enable multi-material
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additive manufacturing. Finally, it is worth mentioning that 4D printing enlarges the range of
applications of additive manufacturing to those areas in which a dynamical configurational change
is required.
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Table 1. Comparison between 3D and 4D printing technology [12], Copyright 2015 (Adapted
with permission from Mary Ann Liebert Inc. Publishers).
Additive manufacturing 4D printing
Materials Thermoplastics Self-assembled materials

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Metals Multimaterials
Ceramics Designed materials
Biomaterials or nanomaterials

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Design 3D digital information (scanning, 3D digital information for change
drawing) (deformation)

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Printer 3D printer Smart 3D printer
Multimaterial 3D printer

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Change As printed Changed after printing in shape, color,

Applications Jewelry, toys, fashion, entertainment,

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Dynamically changing configuration for
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automobile, aerospace, defense, all applications by additive
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biomedical devices, etc. manufacturing

Zhou et al. [33] reported classification of the different approaches to achieve shape switching in a
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reversible and in a controlled manner. According to the authors, the modification of the shape of the
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object can be divided into four different classes:

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a) Self-assembly of elements
The self-assembly of different elements or even components is an interesting alternative to prepare
structures with high complexity [34]. Self-assembly involves the additive manufacturing and
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automatic assembly upon applying the appropriate conditions and may be combined with other
mechanisms which will be described later [13].
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b) Deformation mismatch
4D structures obtained by a deformation mismatch are induced by the differences in any physical
property, for instance, due to a different thermal expansion coefficient or swelling ratio between the

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components of a 3D printed part. Particularly, upon heating, a piece of bi-layered beam tends to
bend toward one direction if each layer has a different coefficient of thermal expansion [35].
In practice, the stimulus may not be applied uniformly throughout the whole piece of a material due
to various reasons such as gradient temperature or solvent absorption, etc. This stimulus could result
in buckling or in other related instability phenomena [36,37]. It is worth mentioning that, for
instance, in the case of solvent absorption, there are three types of solvent transport formats, highly

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uniform such as hydrogel in water [38], gradient transition such as polyurethane (PU) in water [37]
and sharp transitions such as poly(methyl methacrylate) (PMMA) in ethanol [36].

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c) Bi-stability
Shape changes based on bi-stability involve structures with zero, two, or more freedom degrees

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which present a stable geometry. These types of structures feature the interesting ability to change
reversibly from one stable geometry to other if the appropriate stimulus is applied.

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d) Shape memory effect
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The fourth approach for 4D printing, and most extensively employed, involves the use of stimulus-
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responsive polymers. Several critical reviews devoted to stimulus-responsive materials have been
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reported during the last decade [39–41]. While a comprehensive overview of shape-memory
polymers is outside the scope of this review, a brief overview of the different stimulus-responsive
materials is depicted in Figure 7 [40]. Stimulus-responsive polymers are able to alter their physical
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and/or chemical properties when exposed to a particular stimulus which could include pH change,
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solvent, moisture (chemo-responsive materials), electrical (electro-responsive materials), heat

(thermo-responsive materials), stress/pressure (mechano-responsive materials), magnetic field
(magneto-responsive materials), and light (photo-responsive materials), etc.
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According to the classification provided by Sun et al. [40] in Figure 7, two different behaviors can
be observed in polymeric materials able to change their shape. On the one hand, the so-called shape
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changes materials (SCM), which instantaneously modify their structure by using the appropriate
stimulus. An illustrative example of these materials are the piezoelectric polymers that reversibly
change their shape upon application of an electrical field [42]. Also, liquid crystals and, in
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particular, nematic liquid crystals, are able to instantaneously change their shape as a result of the
parallel arrangement of the molecules along a particular direction [43]. On the other hand, an
alternative group of materials is those in which upon a stimulus produce a temporary shape change
that can either return to the original one by applying the appropriate stimulus or remain in the non-

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equilibrium shape. This kind of materials, known as shape memory materials (SMM), have been
classified into five different families being the most important ones the shape memory polymers
(SMPs) and shape memory alloys (SMAs) [41,44,45]. However, as reported by Huang et al. [39],
SMPs have several important advantages over SMAs that made this material the most appropriate
for 4D printing. First of all, polymers are easier to manipulate and their properties can be tailored
using simpler strategies in comparison to SMAs [46,47]. Secondly, SMAs are heavier and present a

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significantly lower recoverable strain (above one order of magnitude lower) in comparison to SMPs.
Moreover, SMPs shape recovery can be triggered by using different stimuli (heat, humidity, pH or light)
or even a combination of more than one [48–50]. Finally, a wide variety of SMPs are biocompatible or

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even biodegradable [51–53], characteristics that open the use of these materials for, among others, many
different biological purposes [54]. In spite of the few drawbacks, the advantages mentioned above are at

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the origin of the large expansion in the development of these materials. As a result, a variety of SMPs
has been developed and reported in the recent literature [55–57].

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Fig. 7. Classification of the various types of SRMs focusing on the materials able to modify their shape, i.e.
shape change materials (SCM) and shape memory material (SMM) [40], Copyright 2012 (Adapted with
permission from Elsevier Science Ltd).

Finally, it is worth mentioning that in addition to the materials employed, in 4D printing the shape-
shifting processes could generate different features including bending, folding, twisting, and non-
linear expansion/contraction depending on the structural design employed. In Figure 8, are depicted

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illustrative examples of shape-shifting that can occur starting from 1D, 2D, and 3D structures to
produce a wide range of structures.

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Self-bending [13,25]
Linear expansion/contraction [25,58]
Self-folding [13,25] Self-folding [13,59]

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2D-to-3D self-folding to make a
Flower-like 3D structure obtained by Helical structures with different degrees of
truncated octahedron [19]
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Self-bending [60] Bending [23] spiral by 2D–to-3D twisting [23]
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Global and local shrinkage and bending for 3D-to-3D alterations by using two
3D to 3D self-bending in a prosthetic finger [61] different stimuli [24]

Fig. 8. Shape-shifting types and dimensions in 4D printing [17], Copyright 2017 (Adapted with permission from Elsevier Science Ltd.

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2. Brief summary of the AM technologies

ASTM International criteria classify polymer AM technologies into seven different categories: (a)
material extrusion, (b) powder bed fusion, (c) vat photopolymerization, (d) material jetting, (e)
binder jetting, (f) sheet lamination, and (g) directed energy deposition [62,63]. Figure 9 shows a
diagram in which the different additive manufacturing methodologies are organized according to
several parameters: state of fusion, material feedstock, material distribution, and the AM principle.

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While it is true today that a wide variety of materials is being used in AM ranging from
thermoplastics or photopolymers to ceramics or metallic powders, we will center our attention on

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those techniques which employ exclusively polymeric materials and composites. Among these
methods, material extrusion, powder bed fusion, and vat photopolymerization have extensively

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employed polymeric materials. For this reason, this chapter will extensively describe the polymers
utilized in these three methodologies and will briefly analyze the materials employed in the rest of

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AM methodologies.

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Fig.9. Overview of single-step AM processing principles divided according to polymer material properties
[64], Copyright 2018 (Adapted with permission from Elsevier Science Ltd).

2.1. Material extrusion

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Without any doubt, the most extended AM technology is the material extrusion (ME) methodology,
in which the material is selectively dispensed through a nozzle over a movable platform (build
stage) [65]. In general, any polymer or polymer-based material, which can be fused at an adequate
temperature (without degradation), is a potential candidate to be employed in ME. By maintaining
the pressure applied and the nozzle speed constant, the material deposited will have a constant
cross-sectional diameter. As shown in Figure 10, the material (or materials, if a supporting material

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is required) is deposited on a support as required by the design. Once a layer is completed, the
machine moves the nozzle upwards or move the platform downwards (typically 100-300 m), so

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that a new layer can be created onto the previous one. The steps of a common extrusion-based
system include [1]: (1-2) loading and melting of the material; (3) application of pressure to move

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the material through the nozzle; (4) extrusion; (5) plotting according to a predefined path; (6)
bonding of the material to itself or secondary build materials to form a coherent solid structure, and
(7) inclusion of support structures which enable complex geometrical features.

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Fig. 10. Schematic illustration of a typical extrusion-based AM process[66], Copyright 2014 (Adapted
with permission from Emerald publishing).
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There are two primary approaches when using extrusion processes. The first technology was
initially developed and patented by Stratasys Inc., a company founded by Scott and Lisa Crump in
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the late 1980s [67]. In this case, the material is molten inside a heated nozzle channel permitting
flow out through the nozzle and bonding with the neighboring material before solidifying (Figure
10). This approach, known as FDM is, due to the cheap components employed, the most extended
AM technology and currently largely employed to fabricate low-cost 3D printers.

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The second approach uses flowable slurries as material for the extrusion and usually carried out
without heating. This alternative has been employed, for instance, to extrude food substances [68],
or to print, biomaterials loaded with living organisms including cells, among others. Commercially
available biomedical cell printers use this approach, that has larger-diameter nozzles to minimize
shear loading on the cells as they are deposited to enhance cell viability [69] in comparison to those
available for FDM.

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FDM present several advantages including the non-requirement of chemical post-processing as it is
the case for resins to completely cure, the low price of both the machine and materials resulting in a
cost-effective process, fast-printing, easy-to-use and widely available, just to mention few of them

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[70,71]. There are, however, disadvantages in the use of this technology such as the lower
resolution both in x-y and z-axis limited by the nozzle dimensions, the low fabrication speed even

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working in the sparse mode (that limits the amount of plastic to be deposited) and the anisotropy of
the fabricated parts [72]. Also, FDM has some limitations related to material compatibility and

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geometrical complexity of the part. Furthermore, the accuracy of the printed part depends on several

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experimental conditions including the volumetric flow rate of the extruded filament (extrusion rate),
which is determined by the pressure drop over the extruder, that depends on the liquefier geometry,
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filament feed rate, friction, and the heat transfer dynamics. Some material properties, such as
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viscosity and compressibility, are temperature dependent [73] therefore requiring some additional
optimization. After extrusion, the new bead may also expand, spread (if printed on something) and
needs to be merged with previously extruded roads. Finally, is possible that the printed object can
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warp after or during the printing process due to cooling effects [73].
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The most common polymeric materials used in this type of process are amorphous thermoplastics
such as polylactic acid (PLA) and acrylonitrile butadiene styrene (ABS). On the one hand, PLA is a
plastic derived from cornstarch, that has a relatively low melting point (150 °C-160 °C), which
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requires less energy to print than other materials and provides a distinct advantage for off-grid
applications [74–76]. On the other hand, ABS can be either synthesized by mechanical mixing of
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the styrene-acrylonitrile copolymer with butadiene, or by grafting styrene and acrylonitrile onto
polybutadiene with processing temperatures between 176 and 260 °C [77]. This makes ABS
extremely versatile, allowing the material to be tailored to many applications. For example, Clark et
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al. recently fabricates 3D energetic films using various concentrations of ABS binder combined
with a mixture of Al + MoO3 + KClO4 [78].
However, as will be thoroughly discussed later there are many other materials available on the
market such as polycarbonate (PC), polyetherimide (PEI), polyphenyl sulfone (PPSF), polyamide

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(PA), high impact polystyrene (HIPS), high-density polyethylene (HDPE), polycaprolactone (PCL),
PC-ABS blends, polystyrenes (PS), thermoplastic elastomers (TPE), polyaryletherketones (PAEK),
water-soluble poly(vinyl alcohol) (PVA), polyvinyl butyral (PVB) and polyvinyl acetate (PVAc),
among others [79]. The original feedstock material used in FDM processes are commonly
homopolymers, however, the incorporation of metallic or ceramic particles it is widely utilized
nowadays. Some selected applications, which uses polymer or composites, are depicted in Table 2.

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Table 2. Illustrative examples of applications according to the material type, using extrusion
additive manufacturing.

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Material Type Applications Reference

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Semi-crystalline PU Capable of retain good shape memory
[80]
characteristic
Polyvinylidene fluoride (PVDF) based Energetic materials (combustible), which

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[81]
filament prepared with a 20 % mass loading improves their ability to be integrated into a
of H3 micron size aluminum.
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system as multifunctional material.
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PVDF fabricated under different processing Piezoelectric material based on
[82]
parameter, including in-situ electrical poling. microstructure arrangement.
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Composite materials containing varying

blends of a tough alginate/poly(acrylamide)
Development of bio-inspired structures
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ionic covalent entanglement hydrogel and an [83]

such as artificial tendons.
acrylated urethane-based UV-curable
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adhesive material.
Commercial open-source RepRap (Lulzbot Mechanical properties of various FDM
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TAZ 3.1 and 4) mixture with Ninjaflex,
SemiFlex, HIPS, T-Glase, polycarbonate,
Nylon, and ABS.
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printing materials to promote the open-
[75]
source development of RepRap additive
manufacturing

Fabricate a variety of resistors, inductors,

Conductive thermoplastic filament made of and capacitors. Create complex, three-
carbon-black, graphene, and copper as dimensional circuits composed of either [84]
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conductive fillers embedded or fully-printed electronic

components.

2.2. Powder bed fusion

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Powder bed fusion (PBF), also called Selective Laser Sintering (SLS), was first commercialized by
Deckard and Beaman at DTM Corporation [65]. As it is schematically shown in Figure 11, in SLS
a thin layer of powder is sintered or fused by the application of a laser beam. The fabrication
process occurs as follows: the chamber, filled with nitrogen or argon in order to avoid eventual
oxidation and/or degradation, is heated just below the melting point of the material. The pre-heating
of powder bed (that should be uniform over the entire surface) is crucial for two reasons. First, this

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temperature will limit the amount of laser power required to consolidate the material, therefore,
avoiding material degradation. Second, large thermal cycles of heating and cooling have associated
expansion and shrinkage, which prone to produce undesirable warping of the printed part.

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The powder from a reservoir is deposited on the top of the build platform using a counter-rotating
roller, then the layer is selectively fused using a laser beam according to the CAD file. There also

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exists a second deposition method in which the powder is gravity fed from cassettes which are
racked into a layer by a blade. The build platform is then lowered a certain extent, which depends

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on the desired layer thickness, finally, the laser is applied again to fuse the next layer. This process
is repeated until finishing the printed part.
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For consolidation, as described by Kruth et al. [85] the powder consolidation (also known as a
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binding mechanism) can occur through three main different strategies in the case of polymers, i.e.
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Solid state sintering, liquid-phase sintering (partial melting) and full melting. Solid state sintering
(SSS) is a process that occurs below the melting temperature of the material and involves the
creation of necks between the micrometer size powder particles. These necks are created by volume
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diffusion, grain boundary diffusion or surface diffusion and grow with time. Liquid phase sintering
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(LPS) and partial melting describe a process wherein the polymeric material is only partially
melted. As a result, the melted material is able to spread between the solid polymeric microparticles
due to capillary forces. The melted material is usually known as a binder and the remaining solid
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material as a structural material. Full melting describes a process that involves the complete melting
of the particles and is applied to obtain fully dense 3D printed parts.
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As will be described later both amorphous thermoplastics and (semi-)crystalline thermoplastics

have been widely employed for SLS [85].
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Fig. 11. Schematic setup of the Selective Laser Sintering process [86], Copyright 2017 (Adapted with
permission from Elsevier Science Ltd).

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In a typical SLS process, a laser beam scan across a thin layer of powder and locally melts the
powder through to the layer below [85,87]. Although the process is conceptually simple, there are

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many highly dynamic and transient physical phenomena involved because of the extremely high
heating and cooling rates [5, 20–22], e.g. melting and partial vaporization of powders, flow of the
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molten material, powder ejection and re-distribution, rapid solidification, non-equilibrium phase
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transition, etc. Accordingly, the relevant control parameters include, in addition to the material
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properties, the bed temperature, laser energy density or layer thickness [91,92].
SLS technology has several advantages, for example, permits the use of a wide range of materials as
well as recycling of unused powder. Secondly, SLS does not require the use of support structures
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during the printing process, required in many other additive processes such as FDM since the part is
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supported by the surrounding unfused powder. Finally, SLS produces parts that are tougher and
more stable than those obtained for instance by SLA.
It is important to mention that the accuracy of this process is limited by the size of particles of the
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material, i.e. ~50-80 m. Moreover, the process requires a constant and uniform temperature close
to the melting point in the entire chamber. Finally, as has been mentioned before, oxidation needs to
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be prevented typically using an inert gas atmosphere.

Using these techniques, several structures, with complex architectures, were investigated for their
mechanical properties using a wide range of 3D printable materials. A particularly interesting
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example is the performed by Murr et al., in which oxide particles inks synthesized through of
mixing of the polylactic-co-glycolic acid copolymer (PLGA, 85:15 PLA-PLG by mass) and Fe2O3
or NiO powders. These structures can store high elastic strain energy, which is important for
mechanical energy storing applications. Additionally, the combination of high ductility, high yield

24
strength and high strain hardening of the metallic structures lead to high absorbed plastic energies
(at 50 % strain) ranging from 35-118 MJm-3 [86].

2.3. Vat Photopolymerization processes

Vat photopolymerization is an additive manufacturing process in which a liquid photopolymer in a

vat is selectively and spatially cured by light-activated polymerization [65]. Chuck Hull, in the mid-

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1980s, was the pioneer in using UV curable materials, which when exposed to a scanning laser,
produced solid polymer patterns. More interestingly, he found that by curing layer after layer, a

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solid 3D part could be fabricated [93]. He co-founded 3D Systems Inc. in 1983 and patented the
first commercial stereolithography (SLA) machine, which was released to the market in the year

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1987 (model SLA-1). Many of the lithography-based AM approaches (e.g. SLA, digital light
processing (DLP) and multiphoton polymerization (2PP)) can be grouped into this category.

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(i) Stereolithography

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The SLA system uses coherent light sources (usually lasers emitting in the UV range) to induce
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polymerization and crosslinking of a liquid resin. One of the advantages of this technique is the
high spatial resolution provided by the spot size of the focused laser beam.
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As mentioned above, the principle of SLA is based on a photopolymerization process which enables
the conversion of a liquid monomer/oligomer mixture to a solidified polymer, typically by using
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UV light, the irradiation activates the photoinitiator present in the mixture which triggers the
polymerization reaction in those areas directly exposed [94]. A platform is required (Figure 12) to
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anchor the AM part and support the overhanging structures. When the layer is finished the platform
moves downwards, a new layer of liquid resin wets the part and the process is repeated again [95].
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When the process is finished, the excess of resin is drained (can be reused) and the part washed
typically using ethanol [70,71]. The speed required to fabricate the part prevent from complete
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conversion of the photopolymerization reaction and usually, a post-curing step is carried out.
It is worth noting that the main time-consuming step in SLA is not the laser-scanning itself, but the
deposition of the new layer of photosensitive material. Here, the viscosity of the material plays an
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important role. Very often nonreactive additives or solvent must be used to decrease the viscosity of
the photopolymer resin.
There are two different main SLA techniques distinguished by their patterning process (Figure 12)
[96]:

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• Scanning-based SLA (SSLA) or direct writing. In SSLA a laser beam with small diameter
(∼0.1 mm) scans large areas by small rotations of a mirror (Figure 12a).
• Projection-based SLA (PSLA) that is also called a maskless or dynamic mask method. PSLA
uses a dynamic mask for generating 2D patterns with micrometer-scale resolution (Figure 12b).

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Fig. 12. Schematic diagrams of the approaches to photopolymerization processes: (a) SSLA and (b) PSLA

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[1], Copyright 2015 (Adapted with permission from Springer Nature Switzerland AG).

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The depth of cure, which ultimately determines the z-axis resolution, is controlled by the
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photoinitiator concentration, the laser exposure conditions (wavelength, power and exposure
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time/velocity) and the eventual incorporation of dyes, pigments or other added UV absorbers. The
photo-induced layer thickness typically varies between 50–200 µm.
The step size of the printing process is selected based on the balance between decreased build times
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and enhanced resolution. A newer version of this process has been developed with a higher
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resolution and is called micro stereolithography (µ-SLA) [97]. Among the drawbacks, it is worth
mentioning that the mechanical stability of the printed objects with SLA is lower in comparison, for
instance, with those obtained by selective laser sintering (SLS). Also, there are still remaining
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issues about the biocompatibility of the materials employed for SLA printing [98].
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(ii) Digital light processing (DLP)

This technique also utilizes light to selective crosslink a photoresin in a layer-by-layer fashion to
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build a free-standing object. Different from SLA, each layer is exposed not point-by-point but rather
all-at-once with a selectively masked light source. The build time is considerably shorter than SLA
and accordingly, is less affected by oxygen inhibition (the layer resin being polymerized is always
on the bottom of the vat and not in direct contact with the air). In addition to nonfilled
photopolymers, slurries containing, for example, ceramic or metal particles can be also processed

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with DLP [99] which allows to easily produce mixtures of polymeric and inorganic phases. In this
case, the photosensitive polymer matrix acts as a binder material, while the fillers are usually
photochemically passive. Peterson et al. [100] study and quantify the changes in crosslinking
density in a commercial resin (G+ yellow), whose elastic modulus and offset compressive yield
strength is affected by the light intensity. Thus, the impact of heterogeneous and graded materials
was demonstrated by increasing the strain-to-break of octet truss structures to exceed the values

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achieved by uniformly increasing the light intensity. A large variety of examples using this
technique have been reported during the last decade. For instance, Patel et al. [101] reported a
family of highly stretchable and UV curable (SUV) elastomer systems, which was prepared by

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mixing a monofunctional monomer consisting of epoxy aliphatic acrylate (EAA), and a difunctional
cross-linker consisting of aliphatic urethane diacrylate (AUD) diluted with 33 wt% of isobornyl

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acrylate, whose 3D printed structures were immersed in a silver dispersion. The SUV elastomer
system reported in this paper significantly enhanced the capability of the DLP-based additive

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manufacturing for fabricating soft and deformable 3D structures and devices including soft robots

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and actuators, flexible electronics, and acoustic metamaterials among others. Another interesting
example is the reported by Pekkanen et al. [102] that employed supramolecular polymers to
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generate well-defined 3D printed parts, hierarchical structures and scaffolds with gradient
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properties/tuned surface provides as an avenue for developing next-generation biomedical devices

and tissue scaffolds.
Conductive complex structures composed of photoresin and multi-walled carbon nanotubes
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(MWCNTs) were reported by Mu et al. [103]. In this study, the concentrations of MWCNTs, as
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well as the printing parameters, were investigated to yield optimal conductivity and printing quality,
demonstrating that these compounds could be used as a hollow capacitive sensor, electrically
activated shape memory composites, and stretchable circuits. In addition, mechanical tests showed
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that the addition of MWCNT could slightly increase the modulus and ultimate tensile stress while
decreasing slightly the ultimate stretch, indicating that the new functionality is not obtained at the
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price of sacrificing mechanical properties.

(iii) Continuous liquid interface production (CLIP)

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This technique corresponds to a variation of vat photopolymerization, it was reported first by

Joseph DeSimone, Edward T. Samulski, Alexander and Nikita Ermoshkin and was originally
patented by EiPi Systems Inc. Nowadays, the main producer of this kind of 3D printers is the
company Carbon3D Inc. This technique uses an oxygen permeable film to inhibit polymerization at

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the surface close to the UV sources (persistent liquid interface) [104,105], creating a “dead zone”
preventing the resin from attaching to the window. As a result, one of the main differences between
SLA and CLIP is the time required for printing. The CLIP technique corresponds to a continuous
method which is faster than the step-by-step procedure of SLA. A prototype of microneedle arrays
of a wide variety of sizes, shapes, and compositions with modular control over each design factor
was developed by Johnson et al.[106]. In this case, trimethylolpropane triacrylate (TMTPA) and

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biocompatible materials such as poly(ethylene glycol) dimethacrylate (PEGDMA),
polycaprolactone trimethacrylate (PCL-TMA), and polyacrylic acid (PAA) were utilized to
fabricate biocompatible microneedles to demonstrate the wide range of materials that can be

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utilized within this platform for encapsulating and controlling the release of therapeutic drugs.

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(iv) Two-photon (2PP) and multiphoton polymerization (MPP)

MPP has a wide variety of applications in different research areas such as photonic, microelectronic

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or micromechanics based on its unique resolution ranging from 0.1-5m. However, in spite of the
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impressive resolution usually, only small parts in the millimeter size range are produced. Another
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still current limitation is that the monomer types that can be employed are limited to acrylates [107].
While this is, in general, true, some reports have been published in which MPP has been employed
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to prepare photosensitive modified gelatin in the presence of living cells [108] or organic-inorganic
hybrid systems based, for instance in sol-gel composites based on Zr [109]. This technique shares
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common features with SLA but it is based on lasers which emit in the NIR spectrum, radiation
which tends generally to scatter less that UV and can, for instance, permeate through living tissues
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without denaturing proteins. The 2PP manufacturing technique is based on two-photon absorption
when the beam of an ultra-fast laser is tightly focused into the volume of a transparent
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photosensitive material, the polymerization process can be initiated by nonlinear absorption within
the focal volume. By moving the laser focus three-dimensionally through the material, 3D
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structures can be fabricated distinguishing from the other layer-by-layer additive manufacturing
methods. The term “multiphoton” is related to the simultaneous absorption of three or more photons
that can also occur (although with very low probabilities) and contribute to photo-cross-linking
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[107]. 2PP is thus an AM method that can be also found in the literature under the names of direct
laser writing two-photon, laser scanning lithography two-photon lithography, two-photon-absorbed
photopolymerizations multiphoton-excited microfabrication or 3-D multiphoton lithography.

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An application example of this technique was reported by Wolfersberger et al., in which the
immobilization of streptavidin on polymer-nanodots through biotin-binding affinity is achieved
[110]. Thus, nanoscopic well-defined structures capable of selective binding of any possible protein
via streptavidin-biotin coupling may find application in in-vitro sensing such as lab-on-a-chip
devices with a well-controlled surface area. Additionally, Wollhofen et al. create a 3D platform for
protein assays [111] using the MPP technique. Thus, a photoresist used for the protein-repellant

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scaffolds consists a monomer mixture of poly(ethylene glycol) diacrylate (PEGDA)-
pentaerythritol diacrylate (PETA) at a ratio of 4:1 and the binding pins were composed with PETA-
2-carboxyethyl acrylate (CEA) at a ratio of 9:1.

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For additional information about 2PP and related MPP, the readers are referred to recent excellent

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and more complete reviews [107,112,113].

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2.4. Material jetting

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Material jetting is an additive manufacturing process in which droplets of build material (such as
photopolymer or thermoplastic materials) and support material are selectively deposited. Figure
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13a shows a schematic description of the material jetting setup. The material jetting method creates
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3D objects in a similar way than two-dimensional ink-jet printers do. The material is jetted onto a
build platform (using either a continuous or Drop on Demand (DOD) approach), where it solidifies
permitting to build the model layer-by-layer. The material is deposited from a nozzle which moves
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horizontally across the platform, finally, the layers are cured using UV light. This technique has
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some limitations due to the narrow window process of the ink-jet actuator. However, multi-actuator
jetting systems are novel methods which allow the printing of materials with, for instance, different
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viscosities and/or electrical properties.

To build freestanding objects from two fundamentally different materials (i.e. metals and
polymers), multiprocess additive manufacturing uses a robot to transfer the object between two or
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more different AM machines during fabrication [114]. Particularly, tripropylene glycol diacrylate
(TPGDA) was mixed with triethylene glycol methyl ether (TGME), a high boiling point solvent, in
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order to create a jettable support material. TGME was found to be an effective additive which can
be considerable reduce the mechanical properties of the cured TPGDA structure by forming a
porous structure [115].

2.5. Binder jetting

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Binder jetting is an additive manufacturing process in which a liquid bonding agent is selectively
deposited to fuse powder material. Figure 13b shows a schematic diagram of the set-up of this
technique. In this process, the delivery of the binding agent is accomplished through a DOD
printhead by deposition of picoliter-sized droplets of the liquid binder. The speed of the droplets
impinging the powder bed surface might have a significant effect on droplet spreading and
absorption dynamics, which finally is directly related to the quality and integrity of the fabricated

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parts [116].
Some studies mix this technology with the application of different methods like molten bronze
infiltration. Particularly Cordero et al., form and densify a rapidly-solidified ferrous powder mixed

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with a polymeric liquid bonding agent. In this article, the structural evolution of the powder during
an infiltration heating cycle was evaluated using X-ray diffraction, electron microscopy, and

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thermal analysis. The mechanical properties of the infiltrated material were evaluated using
hardness and bending tests [117].

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Fig. 13. Schematic set-up of the techniques a) Material jetting and b) Binder jetting [118], Copyright 2017
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(Adapted with permission from Springer Nature Switzerland AG).

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2.6. Sheet lamination (Laminated objected manufacturing, LOM)

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This technique was firstly designed by Helisys Inc. in 1991. In the year 2000, this company was
sold, and Cubic Technologies bought the patents. LOM consists of an AM process in which sheets
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of material are bonded together to form an object – building part – from engineering materials such
as ceramics and composites. Thus, paper, metals (less common), fabrics, synthetic materials and
composites [119], are sequentially laminated, cut, and pasted together layer by layer to build an
object (Figure 14a). However, LOM has important disadvantages including the limited number of
available materials, the low resolution, and the high anisotropy of the resulting parts. In spite of this,

30
probably one of the major issues in LOM processes is related to roller heat, which normally is not
adequate for bringing parts together in order to fully consolidate and cure the materials. Sonmez and
Hahn [120] studied heat transfer and stress in LOM processes via modeling of numerical analysis
based on the thermomechanical behavior of the laminate during the LOM processes. These models
permitted to understand the relationship between temperature and stress distribution within the
laminate. Recently, a new method called laser-assisted AM for continuous fiber reinforced

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thermoplastic (CFRTPCs) was proposed and evaluated by Parandoush et al. [121], with the
motivation of reducing the waste associated with LOM. The authors proposed using prepreg
composed of glass fiber/Polypropylene composites (unidirectional and bidirectional). A successive

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layer of narrow prepreg tape was heated using CO2 laser and bonded by a compaction roller to form
a laminated 3D object.

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LOM has been utilized to fabricate 3D parts with various thermoplastics, including PMMA and PC,
as well as polymer-based composites. For instance, Klosterman et al. [122,123] and more recently

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Zhong et al. [124] used this method to create ceramic (SiC/SiC) and polymer matrix (glass/epoxy)

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composites. Thermo-laminated woven fiberglass/epoxy material, as one of glass fiber laminate
materials, were made from woven glass fiber fabric impregnated with an epoxy resin binder, which
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is manufactured under pressure and heat. The glass fiber laminate has as major advantages high
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mechanical strength, good corrosion resistance, sound flame and humidity resistance, etc. Chen et
al., study the quasi-static and dynamic properties of this materials, founding that fiberglass/epoxy
laminate was sensitive to the strain rate in term of the tensile strength, failure strain and Young
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modulus [125].
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Carbon nanotubes (CNTs) and boron nitride nanotubes (BNNTs) as functional composites for
possible space structures were developed by Ashrafi et al. [126]. These materials are dispersed in
epoxy for fabrication of glass fiber reinforced polymer (GFRP) laminates. The improvement in
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structural performance suggests BNNT-modified resins may be a simple and effective way to
improve fiber reinforced polymer laminates and particularly applicable to wet layup or prepreg
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approaches where nanofiller filtration is not an issue. Lionetto et al. revealed that the aluminum-
composite interface is characterized by present carbon fibers in direct contact or even embedded in
aluminum, whose surface presents pores and crevices due to the pronounced plastic deformation of
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the Al interfacial area. The film used to promote the adhesion of hybrid metal-composite joint was a
technical thermoplastic, Polyamide 6 (PA6) with 100 m thickness [127].
LOM has been shown to be capable of creating complex 3D microfluidics through the assembly of
a stack of polymer sheets with features generated by laser micromachining and by bonding the

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sheets together with adhesive. A six-layer ELISA lab-on-a-chip (ELISA-LOC) was fabricated with
an acrylic (PMMA) core and five PC layers micromachined by a CO2 laser with simple microfluidic
features including a miniature 96-well sample plate [128].

2.7. Directed energy deposition (DED)

DED is an additive manufacturing process in which focused thermal energy (e.g., laser or plasma

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arc) is used to fuse materials together, for build net-shape components or prototypes, by melting
them using a material wire or powder which is extruded from a nozzle as they are being deposited

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layer-by-layer (Figure 14b). However, the DED processes are predominantly used with metals as
titanium alloy [129–131], steel [132], nickel-based superalloy [133] and aluminum alloy [134].

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A
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Fig. 14. Schematic diagram of the set-up of the techniques a) Sheet lamination and b) Directed energy
deposition [118], Copyright 2017 (Adapted with permission from Springer Nature Switzerland
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AG).
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In Table 3 are summarized the main advantages and drawbacks for all the AM approaches depicted
above
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 PT
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Table 3. Summary of advantages and disadvantages of the different AM processes [135], Copyright 2017 (Adapted with permission
from Elsevier Science Ltd).
Process Advantages Disadvantages

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Material Extrusion Low cost of the entry-level machines. Low level of precision and long build time.

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A variety of raw materials are available. Unable to build sharp external corners.

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Versatile and easy to customize. Anisotropic nature of a printed part.
Powder Bed Fusion Support is not required for polymer powder. Rough surface finish for the polymer.

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Both polymer and metal powder can be recycled. Relatively slow build rate.
High part complexity and a wide range of materials. Expensive machines.
ED
Vat High-resolution and accuracy, good surface finish. Require support.
Photopolymerization High fabrication speed. Require post-processing to remove support.
Low-imaging specific energy. Require post curing for enhanced strength.
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A wide range of materials.

Material Jetting High resolution and accuracy. Post-processing may damage thin and small features.
E

Multiple materials with low waste. Support materials cannot be recycled.

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Binder Jetting Large number of potential materials. Rough or grainy appearance.

Support structures are included in layer fabrication. Poor strength.
Low-imaging specific energy. Post-processing required.
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Sheet Lamination High fabrication speed. High material waste.

No support structures are needed.
Low warping and internal stress.
Multi-materials and multi-colors are possible.
Difficult to remove support trapped in internal cavities.
Thermal cutting produces noxious fumes.
Possible warpage of lamination as a result of the heat of the
laser
33
3. Polymers employed in material extrusion

3.1. Fused deposition modeling (FDM)

As has been mentioned above, FDM is an AM process in which the layers are formed by extrusion
of a solid plastic filament which passes through a nozzle/print head that melts and extrudes it [136].

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To be used for FDM, the printing material must be able to flow, after fusion, and then solidify.
Amorphous thermoplastic polymers are the ideal materials for this application due to their low
thermal expansion coefficient, glass transition temperature and melting temperature, properties

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which can reduce internal stresses caused during cooling (such as warping for example). A wide
range of polymers are commercially available nowadays, PLA and ABS being the most common.

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Nevertheless, other polymers have been equally employed in FDM processes such as PC, including
PC-ABS blend and medical grade PC, PCL, PA/Nylon, PPSF, or HDPE [1]. Additionally, HIPS,

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thermoplastic polyurethane (TPU) elastomer, polyethylene terephthalate (PET) also have been used
to fabricate parts with this technique for some novel applications.
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As it has been mentioned above, for thermoplastic polymers FDM works better with amorphous
A
polymers rather than with highly crystalline polymers that, as will be depicted, are more suitable for
M
SLS processes. The reason for this relies on the fact that amorphous polymers extrude better than
crystalline ones due to a gradual variation of the viscosity as a function of the temperature. As a
result, the pressure conditions required to extrude these materials are easier to modulate by finely
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tuning the temperature of the nozzle. In contrast, crystalline polymers present a clear phase
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transition upon heating due to the fusion of the crystalline domains. In this case, a homogeneous
extrusion process are difficult to control.
While this is the general rule, it is also true that several crystalline polymeric materials, like PCL
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(FDA approved, biocompatible and extensively employed for biomedical purposes) are currently
being employed in FDM processes via few variations of the setup. For instance, Zein et al. [137]
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employed FDM to generate scaffolds using a bioresorbable PCL-based polymer with different
geometrically consistent honeycomb-like patterns with controllable porosity and channel size. The
scaffolds were fabricated using variable filament circular cross-section (Figure 15) and their
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mechanical properties were tested. Another example of the preparation of PCL 3D structures for
biomedical applications was reported by Szojka et al. [138]. They designed and produced
biomimetic 3D printer meniscus scaffolds, using small porous PCL blocks that mimic the
circumferential and radial type I collagen orientation found in the native meniscal tissue.

34
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Fig. 15. Scaffolds prepared by Zein et al. using PCL in an FDM 3D printer [137], Copyright 2002
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(Reproduced with permission from Elsevier Science Ltd).

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In addition to the build material in some cases, due to the geometrical design of the part to be
printed, the printing process requires the incorporation of a support material that must be easily
removed when the part has been finished. For instance, Stratasys developed a series of support
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materials: SR-20TM for ABS and PC-ABS, SR-30 TM for ABS, SR-100 TM for PC and SR-110 TM for
nylon, among others. However, there are two main materials commonly employed in FDM: PVA,
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which has an approximate printing temperature of 170-190°C and HIPS. The first one has been
utilized due to its water-solubility, biocompatibility, mechanical flexibility, and low cost compared
with other materials with similar characteristics. The second corresponds to a dissolvable material
that is commonly employed in conjunction with ABS parts due to its similar properties. It should be
noted that HIPS can be dissolved in Limonene, whereas ABS in acetone [139,140].

35
 In addition to the pure polymers described above, other polymer-based materials have been
equally employed in FDM:

a) Polymer blends

Blending is an easy method for creating materials that combine the properties of two or more
polymers. An illustrative example is the commercially available UltemTM 9085 which is a blend of

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PEI resin (Tg= ~216 °C) and PC (Tg= ~147 °C). This blend has a lower Tg (~ 186°C) compared to
PEI due to the addition of PC in the mixture, Figure 16 shows the structure of the polymer blend.

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This material has unique characteristics, making it, among others, in OSU 55/55 compliant for
aerospace and confined space applications, due to their interesting properties as a flame retardant.

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UltemTM 9085 present an improved ductility, flowability, transparency, and possess acceptable
mechanical properties such as high strength and stiffness. Additionally, it has good chemical
resistance to several solvents [141].

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Ultem 9085:

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Polyetherimide resin (PEI)
+
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Polycarbonate (PC)
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Fig. 16. Chemical structure of UltemTM 9085 composed of a blend of PEI resin and PC. (Photograph source
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https://dutch.alibaba.com/g/ultem-pei.html)

b) Microscale composites
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Microscale composites have been typically prepared using both microparticles and ceramic
powders, fibers or piezoelectric materials [142]. For instance, metal-polymer composites, composed
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of a mixture of iron microparticles (~10 m in diameter) or copper microparticles (10 and 45 m

diameter) were incorporated separately in ABS powder. These composites were obtained varying
volume fractions of the metal powders with the aim of producing appropriate feedstock filament for
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FDM processing. Nikzad et al. [142] reported that these composites presented an improved storage
modulus and thermal conductivity as well as a reduced thermal expansion coefficient. Other
microparticles employed include iron, used to increase the thermal conductivity [143], Al or Al2O3

36
which reduces the frictional coefficient [144] or ceramic particles to prepare materials with
improved dielectric permittivity [145], among others.

c) Nanocomposites

Similar to the microscale composites, several authors employed nanoparticles (NPs) to produce
materials with improved characteristics. For example, Perez et al. [146] explored the effect that

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produces the addition of reinforcing nanomaterials on the mechanical properties and fracture
surface characteristics of ABS. Thus, tensile test results evidenced that NPs reinforced ABS with 5

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wt% nanotitanium dioxide (TiO2) exhibited an increase of 13.2 % in the tensile strength compared
with unfilled polymer segments. However, all printed composite parts showed reduced elongation

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and embrittlement when nanoparticles were added.
Finally, CNTs and even graphene have been equally incorporated in thermoplastic filaments and
employed for FDM printing. Rymansaib et al. [147] prepared carbon nanofibers (CNFs) and

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graphite flake microparticles that were added to PS with the aim of making new conductive blends.

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The PS/CNF/graphite (80/10/10 wt%) composites provide good conductivity and a stable
electrochemical interface with the well-defined active geometric surface area. The printed
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electrodes possess a stable interface to the PS shell, good signal to background voltammetric
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responses, and are reusable after polishing. Similar studies were carried out by Lewicki et al. [148],
whose AM CNFs exhibit highly orthotropic mechanical and electrical responses as a direct result of
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the alignment of the fibers.

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3.2. Bioplotting

The term “bioplotting” was first introduced by Landers and Mülhaupt [149] in the early 2000s.
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They defined bioplotting as a type of AM technology which can be used for cell/organ printing via
the deposition (layer-by-layer) of living cells, encapsulated into a proper support matrix (typically
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biodegradable polymers), with controlled architecture and defined placement in the mild condition
[150,151]. The materials used in 3D bioplotting are known as bioinks and are intended to create
tissue-like micro-, macro- and meso-structures which can be used in biomedical or tissue
A

engineering applications. This methodology is currently being applied for regenerative medicine to
address the need for suitable tissue and organs for transplantation. The method involves additional
complexities such as the correct choice of support material, cell types, growth and differentiation
factors, and technical challenges related to sensitives of the living cells, etc. However, in spite of the
great benefit of using this technique, some limitations are currently under investigation.
37
The first step necessary for carrying out the bioplotting methodology is to design the CAD model
which will be used for printing the part, this can be accomplished via several medical imaging
techniques such as computed tomography (CT), magnetic resonance imaging (MRI), optical
coherence tomography (OCT), among others. Once the model is obtained, it becomes necessary to
choose the materials which will be used in each part and, also, to define the most appropriate
printing path in each case depending on the needs and cell characteristics. A schematic description

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of the strategy developed for 3D bioprinting is depicted in Figure 17 [152]. This methodology can
also be used for printing heterogeneous organs which possess a different kind of cell types. The
definition of the printing path is crucial because, in some cases, cell differentiation can only be

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achieved in certain topological and chemical environments, some examples (ear cartilage, kidney,
and tooth) are depicted in Figure 18. In this case, the hydrogels are working as cell-laden vehicles,

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which also serves as support for achieving an optimal cell growth and differentiation if it is
necessary. Once the printing process is finished, in some cases, subsequential post-processing is

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needed in order to extract the supporting part. Then, the tissue/organs can be implanted directly on

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the patient and either permit the cells to grow freely or can be cultured externally in order to
generate artificial tissue or organs that will be implanted later.
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Fig. 17. Schematic representation of the 3D bioplotting technique [152], Copyright 2016 (Reproduced
with permission from Springer Nature Switzerland AG).
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Fig. 18. CAD model acquisition and generation of the printing path for different types of organs. Photographs
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of the final 3D printed parts are depicted [152], Copyright 2016 (Reproduced with permission from
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Springer Nature Switzerland AG).

The chemical composition of the cell-laden support plays a key role in the process. For instance,
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gelatin/alginate hydrogels were studied by Pan et al. [150]. In this article, different crosslinking
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methods (alginate with CaCl2 and gelatin with glutaraldehyde) and their effect on scaffold
architecture, porosity, interconnectivity, pore size, and pore distribution, were described. These
results demonstrated that the material has potential as a scaffold with the ability to encapsulating
EP

cell or drugs. In a typical bioplotting process, a solution mixture of cells and pre-hydrogel is filled
into a syringe with a micro-nozzle. The syringe is connected to a pressurized air system or a stepper
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motor to press the plotting-ink through the micro-nozzle and, in this way, controllable deposit
filaments of cell/material. Some recent advances in this technique permit to deposit different
materials and immobilized cell types, which build up porous scaffold structures (Figure 18). The
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disadvantage of using this method is the shear stress generated from the variably sized nozzles,
which may impact negatively on cell viability during the printing process [153].
In addition to the alginate/gelatin, other types of materials utilized using bioplotting technology are
PLGA, tricalcium phosphate (TCP), collagen, chitosan or collagen alginate-silica composites coated
with hydroxyapatite (HA), among others. Guo et al.[154], studied the effect of PLGA composition
39
on scaffold biodegradation performance, mechanical properties, and water adsorption capacity,
using five different types of PLGA with variable molecular weight. This research was mainly
focused on optimizing printing protocol and scaffold characteristics in order to repair osteochondral
defects. Similar studies were carried out by Idaszek et al. [155], using ternary composites scaffolds
composed by PCL, TCP, and PLGA. The objective of this study was to develop a material for bone
and cartilage regeneration compatible with FDM and bioplotting techniques.

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4. Polymers for stereolithography (SLA)
As it has been introduced before, SLA is a manufacturing process which consists in the curing or

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solidification of a photosensitive liquid polymer (resin) by using a UV laser. The photosensitive
resin is comprised of three major components:

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(a) A photoinitiator, which absorbs the light and generates the active species.
(b) A reactive multifunctional monomer/oligomer. The backbone can vary in structure and

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weight and is designed to confer specific mechanical, physical or chemical properties of the
polymerized material.
(c) N
A reactive diluent which has the role of adjusting the viscosity of the mixture; it also
A
participates in the polymerization reaction.
Eventually, flexibilizers, stabilizers and UV absorbers composites can be also incorporated into the
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mixture. Most materials used are conventional epoxy, acrylate resins, or thermoplastics elastomers
[156].
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4.1. Photosensitive resins and photopolymerization processes: free radical and cationic
photopolymerizations.
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There are two common types of photopolymerization reactions used in SLA [157], i.e. free radical
polymerization and cationic polymerization.
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4.1.1. Free-radical photopolymerization

In free radical photopolymerization, the UV radiation produces a homolytic cleavage (single/double

A

bond) on the photoinitiator, thus forming two radicals. Then, the reaction is followed by the
propagation or transference step, i.e. the incorporation of monomeric units to the polymer backbone

40
or transferring of the radical to a different growing chain. Finally, the polymerization terminates by
any of the three following possible mechanisms.
(a) Combination: Two chains couple together to form one long chain. This termination mode can
be easily monitored via the molecular weight of the propagating species.
(b) Radical disproportionation: A hydrogen from one chain is abstracted to another, producing a
polymer with an unsaturated terminal group and another with a saturated one.

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(c) Combination of an active chain end with a radical (photoinitiator).
According to this last termination type, it is important to differentiate between two different kinds
of photoinitiators, i.e. Type I and II. Type I photoinitiators are unimolecular free-radical generators,

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i.e. upon the absorption of the UV-light, a specific bond undergoes homolytic cleavage to produce
free radicals. The most common type I photoinitiators are hydroxyacetophenone (HAP) or

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phosphineoxide (TPO). In contrast, type II photoinitiators require a co-initiator to trigger the
polymerization, usually alcohol or amine. The absorption of the UV light causes an excited electron

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state which will abstract a hydrogen from the co-initiator by splitting a bonding pair of electrons.

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There are several factors which determine the resolution achieved by the SLA technique including
the type of initiator, the concentration, and the molar absorption coefficient, and others which are
A
directly related to the polymerization kinetics like the presence of oxygen, the temperature or the
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UV light intensity.

4.1.2. Cationic photopolymerization

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In this case, the photoinitiator directs the conversion of UV light into the polymerization initiating
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species; this molecule, commonly bearing a cationic and anionic pair, to form a strong acid (either a
Lewis or Brönsted acid) which triggers the polymerization. The cationic part of the photoinitiator is
EP

responsible for UV absorption, while the anionic portion is transformed into the strong acid
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41
[158,159]. Then, the polymerization mechanism proceeds in a similar way than other chain-growth
polymerizations (propagation, termination and chain transfer steps).

4.2. Materials employed for SLA

The ideal printing materials to be used in SLA should have a relatively low-medium viscosity [160],

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in order to be able to rapidly form crosslinked polymers, and therefore, relatively rigid 3D printed
parts. In the following section, some materials commonly utilized in SLA are reviewed.

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4.2.1. Polymers

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SLA is a precise, fast, and cheap technology used to fabricate 3D parts with intricated internal and
external geometries when is required. The most common polymers used in SLA to fabricating 3D

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printed parts are acrylates, in the case of free radical photopolymerization, and epoxy monomers,
for cationic photopolymerization. However, in most of the cases, the material selection is made
N
depending on the final application of the part. Photopolymerizable epoxies offer better mechanical
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properties than acrylates ones. Also, in contrast to acrylate resins, epoxy monomers have
exceptionally low volume shrinkage and good dimensional stability.
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In addition to rigid additive manufacturing objects, both elasticity and flexibility are crucial for
other purposes. SLA has been employed to produce flexible and elastic three-dimensional structures
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that, in comparison to hydrogels, presented improved mechanical resistance of the 3D printed part.
Schüller-Ravoo et al. [161] fabricated flexible and elastic poly(trimethylene carbonate) (PTMC)
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structures using a three-armed methacrylate PTMC macromer (obtained by reaction of trimethylene

carbonate, glycerol, and methacrylic anhydride). Upon seeding of bovine chondrocytes in the
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scaffolds, the cells adhere and spread over the PTMC surface. After 6 weeks of culture, cells with a
round morphology are present, indicative of the differentiated chondrocyte phenotype,
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demonstrating the presence of differentiated cells which tends to produce cartilage specific
proteoglycans and collagen fibrils of high collagen type II over type I ratio.
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Fig. 19. Left: Scaffolds µ-CT and SEM images of the PTMC resin parts. Right: a, b) alcian blue staining and

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c,d) picrosirius red staining of constructs after culturing for 3 and 6 weeks [161], Copyright 2013
(Reproduced with permission from Wiley-VCH publishers).

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There are several studies like the mentioned before, in which SLA printed parts are used in bio-
related applications. In this context, the use of biocompatible and biodegradable polymeric

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materials has been also reported for this purpose. Choi et al. [162] described a biodegradable
scaffold defined as a “gradually degraded chemically in-vivo, leaving the desired shape of the
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regenerated tissue without causing cytotoxicity”. The same group claimed that the biocompatibility
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observed indicated that “the surface of the scaffold remains chemically compatible such that cells
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can attach and grow on the scaffold without inducing any undesired reactions (or immune
responses) with neighboring tissues”.
In this context, during the last years, several biodegradable and biocompatible materials have been
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synthesized and adapted for its use in SLA. For example, Cooke et al. [163] reported a
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poly(propylene fumarate) (PPF) scaffold, accomplishing the requirements of biodegradability and

biocompatibility described by Choi et al. [162]. Another example in which PPF was used for the
fabrication of scaffolds was reported by Lee et al. [164]. Lee et al. used PPF as a biomaterial,
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diethyl fumarate (DEF) as the solvent and bisacrylphosphrine oxide (BAPO) as the photoinitiator.
After optimizing the experimental printing conditions (resin composition, critical laser exposure,
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and penetration depth) the authors succeeded in the fabrication of scaffolds with high resolution
while minimizing the overcuring of the resin. There are other materials like PCL, that possess
excellent properties as biocompatible/biodegradable support because is degraded by hydrolysis of
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the ester linkages in physiological conditions.

4.2.2. Ceramic and metal composites

43
It is difficult to obtain acceptable mechanical properties (high level of hardness, mechanical
resistance to fluid pressure, etc.) as well as thermal/electrical conductivity when using exclusively
photosensitive resins. As a result, the fabrication of composites by dispersing an additive on the
precursor resin (typically ceramic or metallic particles) has been extensively employed. For
instance, a printable diamond polymer composite was developed by Kalsoom et al. [165] for the
fabrication of low-cost thermally conducting devices. The material was developed by simply

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suspending the high-pressure high-temperature (HPHT) diamond microparticles in the
commercially available acrylate-based resin (30 % w/v). To test the thermal conductive (heat
transfer) performance of the printed sinks, a heating system, placed directly under the sink, was set

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at 100 ºC, the temperature distribution in the sink, and in the control system, was determined using
a thermal imaging camera. As depicted in Figure 20, the IR images for two heat sinks showed that

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the temperature of the composite heat sink (Figure 20d) was almost 5–8 ºC higher for all three
regions compared to the basic miicraft cream BV-001 resin (AP) heat sink (Figure 20c), thus

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demonstrating that the composite material improved the heat distribution away from the heated
surface.
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Fig. 20. (a-b) 3D printed heat sink using commercial acrylate resin and 30 % w/v composite material, (c-d)
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IR images of the polymer heat sink and composite heat sink heated for 10 min at 100 ºC [165], Copyright
2016 (Reproduced with permission from Royal Society of Chemistry Publishing).
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In addition to the incorporation of particular ceramic or metallic charges, a current challenge to

adapt additive manufacturing technology to the elaboration of reinforced composites involves the
ability to control the fiber orientation during the printing process. An illustrative example of the
efforts in this direction was reported by Martin et al. [166] and Zhou et al. [167]. Both research
groups used the bioinspiration or biomimetic approach to fabricate structures with increased
44
mechanical properties. Martin et al. created ceramic/polymer composites in which the direction of
the ceramic-reinforcing particles/fibers can be finely tuned in order to mimic the architecture of
osteons in the cortical bone, for example. Zhou et al. used a similar procedure (MWCNT embedded
in a photocurable resin) to create Bouligand-type structures which mimic chitin structuration of
crustacean exoskeletons. These two examples and a few more will be shown in detail in the
following section of this review.

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5. Powder-based AM
5.1. Selective laser sintering (SLS): Polymer powders and composites

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First of all, it is worth mentioning that the 3D printed parts fabricated using SLS can achieve similar

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mechanical properties as parts prepared by injection molding or similar forming techniques
[168,169]. However, probably one of the major advantages of SLS is related to the “a priori” great
variety of materials that could be employed, including polymers, metals, and blends (metals and

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ceramics/polymers) [97,169,170].

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Examples of polymers that could be blended are acrylic styrene (AS), PCL or PA/nylon. It is also
possible to use composites or reinforced polymers, for instance, PA with fiberglass or metal fibers,
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like copper. Here below some aspects related to the material selection will be discussed.
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Thermoplastic materials typically employed in SLS [171], could present either semi-crystalline or
amorphous characteristics. From a morphological point of view, the main difference between these
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two types is related to the molecular arrangement which acquires after solidification. Whereas, an
amorphous material has the chain molecules randomly arranged, a semi-crystalline material present
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chains and backbone interconnections with an ordered structure. The structural variation between
both confers to each type of material different thermal properties which determine, in turn, the SLS
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printing parameters. In both cases, upon heating, a glass transition temperature (Tg) is observed
[172,173]. The majority of semi-crystalline polymers have a glass transition temperature (Tg) below
or close to room temperature (between -100 °C and 50 °C) while the amorphous polymers typically
CC

employed have a Tg close to 100 °C. Moreover, semi-crystalline polymers present a melting
temperature (Tm) above 100 °C (between 100 °C and 400 °C) in which the material rapidly changes
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from a solid to a liquid form. This transition does not exist in amorphous polymers, which present a
progressively viscous behavior with no clear phase transitions [85,174,175]. When semi-crystalline
polymers are employed in SLS, the laser heats the material above the T m. In this situation, the
material remains solid until an appropriate amount of heat is absorbed transforming it into a viscous
liquid. On the opposite, amorphous polymer powders are consolidated upon heating above the T g. In

45
comparison to semi-crystalline polymers, amorphous materials are much more viscous and
therefore require larger heating to establish the appropriate particle interconnection in order to form
a stable 3D printed part [176].
In addition to the crystallinity of the polymer employed, other parameters that must be taken into
account during SLS process include particle size, powder flow, the thickness of the deposited layer,
laser power, and relative humidity, just to mention few of them [177]. For instance, the power and

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scanning speed of the laser is directly related to the mechanical properties of the 3D printed parts. In
addition to the laser intensity, decreasing the laser scanning speed leads to denser parts as a result of
the longer interaction time between the powder and the laser beam [178]. A higher laser scan speed

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results in less energy transferred to the materials [179] and therefore, low internal adherence of the
material is achieved, producing fragile 3D printed parts.

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Finally, another issue to consider in SLS is related to the shrinkage due to associated heating and
cooling processes during printing. In particular, the use of semi-crystalline polymers produces

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higher material shrinkage upon solidification than amorphous ones. In order to minimize this

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drawback, the printing chamber is typically preheated slightly below the melt transition of the
polymer, allowing the powders to be below their melting temperature during long periods of time
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(up to hours) [85].
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5.1.1. Polymers and polymer blends employed in SLS

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Nylons, in their different variants, are without any doubt the most extensively employed polymer
for SLS. An illustrative example of their use was reported by Das et al. [180], which fabricates
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scaffolds from Nylon-6. In this article, biocompatibility tests were carried out, showing that Nylon-
6 scaffolds permit cell viability during extended time periods. PCL, due to their good
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biocompatibility, bioresorbability, and processability, has found application biomedical purposes in

tissue engineering [181] or cartilage repair [182–184] among others has also been widely employed
for SLS [185]. For example, Eshraghi et al. [186] studied the mechanical and microstructural
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properties of PCL scaffolds with one-, two-, and three-dimensional orthogonally oriented porous
architectures produced by SLS (Figure 21).
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Fig. 21. Scaffolds with one-, two-, and three-dimensional orthogonally oriented porous architectures produced

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by SLS using PCL as printing material [186], Copyright 2010 (Reproduced with permission from
Elsevier Science Ltd).

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Amorphous polymers such as PC or PS have been also employed for SLS, but to a lesser extent due
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to the printing complexity involved in the process. These polymers tend to yield weaker, and more
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porous structures than the semi-crystalline polymer powders [187,188]. Although relatively brittle,
PS parts can be strengthened and toughened by substitution with either poly(styrene-co-
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acrylonitrile) (SAN) or ABS [177].

Finally, also the use of natural polymers has been explored for SLS. For instance, cellulose and its
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derivatives were used as coating materials for drug–releasing scaffolds and related biomedical
applications. It has been also projected for the incorporation into orthopedic implants prepared with
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SLS methodology. Salmoria et al. [92] reported the rapid fabrication of starch–cellulose and
cellulose acetate scaffold. As has been mentioned above, the evaluation of the laser power, laser
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scan speed and the polymer particle size influence on the scaffold properties. In particular, the
adjustment of SLS printing parameters is crucial to warrant the processability of biodegradable
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cellulose-based polymers. As depicted in Figure 22, the specimens with lower particle size
presented more sintering, higher mechanical strength and a significant level of closed pores, as
indicated by the density measurements and fractography analyses performed to the sample.
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Fig. 22. Micrographs of starch–cellulose specimen surfaces: (a) particles of 106–125 m, (b) 150–212 m;
and cellulose acetate surfaces: (c) particles of 106–125 m, (d) 150–212 m [92], Copyright 2009
(Reproduced with permission from Elsevier Science Ltd).

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Polymer blends have been employed to obtain materials with variable properties by using SLS
printing technique. Nevertheless, the examples reported in the literature are rather scarce. An
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illustrative example of this strategy was reported by Salmoria et al. [189] which prepared blends of
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polyamide (PA2200) and HDPE, with average particle sizes of 60 and 100 m. The authors
reported the formation of heterogeneous microstructures of PA2200/HDPE blend specimens with
co-continuous and disperse phases depending on the quantity of HDPE included in the blend.
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5.1.2. Composites prepared using micro/nano fillers

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A large number of studies have been made to improve the mechanical and physical properties of
polymeric parts printed using SLS methodology via reinforcing them using different fillers. For
instance, the incorporation of ceramic particles into polymers improved their mechanical properties
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and malleability [190–192]. In general, polymeric materials employed for SLS have been charged
with:
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(i) Micrometer-sized inorganic fillers such as glass beads, silicon carbide, HA, and aluminum
powder

Chung and Das [193] prepared composites of Nylon-11 filled with different fractions of glass beads
(0–30 %). The results showed that the tensile and compressive modulus increases while strain at
48
break and strain at yield decreases as a function of glass bead volume fraction. Tan et al. [194]
employed AM to overcome the limitations encountered with conventional manual-based fabrication
processes. For that purpose, the authors prepared scaffolds based on poly(ether etherketone)
(PEEK) and HA powders, physically blended, and later processed on a commercial SLS system.
PEEK has a glass transition at approximately 143 °C and melts at approximately 343 °C. Since
PEEK has a much lower melting point than HA, it is possible to induce sintering of PEEK at

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temperatures near Tg and partially expose the HA particles to the sintered PEEK matrix. However,
the laser power and bed temperature play a crucial role in the sintering process (Figure 23). PEEK
sintering is better accomplished at higher bed temperatures. The sintering process appeared to be

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more promising when the laser power and bed temperature were increased up to 12 W and 140 °C.

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Fig. 23. Micrograph of sintered PEEK specimens produced at a part bed temperature of 140 °C and laser
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powers of (a) 9 W, (b) 12 W, (c) 16 W, (d) 20 W, (e) 24W, and (f) 28W [194], Copyright 2003
(Reproduced with permission from Elsevier Science Ltd).

Xia et al. [195] selected HA as reinforcement for PCL materials for scaffolds prepared via SLS.
SEM micrographs showed that the nano-HA/PCL scaffolds exhibited predesigned, well-ordered
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macropores and an interconnected micropore network with a 130 % improvement in the
compressive strength. Human bone marrow stromal cells were seeded onto the nano-HA/PCL
scaffolds and cultured for 28 days in-vitro. As indicated by the level of cell attachment and
proliferation, the nano-HA/PCL showed excellent biocompatibility, comparable to PCL bare
scaffolds, but showing increased mechanical properties.
A brief summary of scaffold examples prepared by SLS reported in the literature is included in

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Table 4.

Table 4. Illustrative examples of polymeric materials employed for bio-related applications using

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SLS [196], Copyright 2015 (Adapted with permission from Taylor & Francis Group).
Material Physical properties Biological properties Final part Reference

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Porosity: 85 % High cell density was [184]
Pore size: 40–100 m. observed after 6 days.

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Porosity: 83 %
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Porcine adipose stem [197]
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Pore size: 300–400 cells show good
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PCL m. proliferation and

differentiation into
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osteoblasts.
Porosity: 40–84 %. A confluent cell [198]
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monolayer (elongated
morphology) could be
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observed on the
scaffold.
CP Porosity: All scaffolds facilitate [199]
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/PHBV PHBV 62.6 % cell proliferation and

CHA/PL PLLA 69.5 % ALP expression for
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LA CHA/PLLA 66.8 % SaOS-2 cells. Viability

assays on sintered
scaffolds were
performed after 3 days
of culture.

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 HA/β- Porosity: 61 % MG63 cells exhibited [200]
TCP Interconnected elongated and
macroporous network. flattened morphology
Pore size: interconnected with
0.8 – 1.2 m. micro-extensions.
Forsterite Interconnected porous Cells attached and [201]

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with network. Pore size: 0.5 spread on the
bioactive - 0.8 m. forsterite /glass

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glass scaffold surface.

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(ii) Nano-sized fillers such as clay, carbon nanofibres, nanosilica, and nano-Al2O3 particles

The impact resistance can be improved by including nanocomposites in the material matrix. For

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instance, Zheng et al. [202] prepared nano-Al2O3 particles coated with PS by emulsion
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polymerization and used them as fillers to reinforce PS based composites prepared by SLS. The
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influence of the treated and untreated NPs on the sintering behavior and mechanical properties of
the specimens were also studied. The authors found that exist many uneven holes in the untreated
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composites. In contrast, for the treated composites, due to the treated NP surface, the laser
absorbance was improved, and NPs show a homogeneous dispersion in the polymer matrix. As a
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result, a fully dense structure was obtained with enhanced mechanical properties. In particular, the
impact and tensile strength increased by 50 % and 300 %, respectively, compared with the unfilled
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PS.
Nanocomposites have been, similarly to microcomposites, employed for scaffold fabrication. For
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example, Duan et al. [199] prepared three-dimensional nanocomposite microspheres based on

calcium phosphate (Ca-P), poly(hydroxybutyrate–co-hydroxyvalerate) (PHBV) and carbonated
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hydroxyapatite (CHA)/poly(L-lactic acid) (PLLA). In Figure 24 are depicted illustrative models

and the resulting 3D printed structures. The fabricated scaffolds had controlled microstructure,
totally interconnected porous network and high porosity. According to the authors, in-vitro
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biological evaluation showed that SaOS-2 cells had high cell viability, normal morphology, and
phenotype after 3 and 7 days of culture. The incorporation of Ca-P nanoparticles significantly
improved cell proliferation and alkaline phosphatase (ALP) activity, whereas CHA/PLLA scaffolds
exhibited a similar level of cell response compared with bare PLLA.

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Fig. 24. (a-b) Schematic diagrams of the scaffold model, (c) scaffolds fabricated by SLS: (A) PHBV; (B) Ca-
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P/PHBV; (C) PLLA; (D) CHA/PLLA, (d) MicroCT reconstruction of Ca-P/PHBV scaffold [199], Copyright
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2010 (Reproduced with permission from Elsevier Science Ltd).

5.2. Binder jetting: polymer powders and composites

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In contrast to SLS, binder jetting process employs inkjet head (IJH) instead of a laser. The head
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prints a liquid binder onto a thin layer of powder following an object profile generated by the CAD-
software [203]. Two kinds of DOD heads can be used in IJH systems: piezoelectric and thermal
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(bubble-jet). Depending on the mechanism used in the drop formation process (Figure 25) different
material properties and resolutions can be achieved.
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In the thermal system, there is a heating element used as a thin-film resistor. When an electrical
pulse is applied to the head, a high current pass through the resistor and the fluid in contact is
vaporized, forming a vapor bubble over the resistor. This vapor bubble expands in the fluid
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reservoir, the increased pressure causes a droplet formation which is ejected through the nozzle. In
the piezoelectric head system, the volume of an ink chamber is changed by the application of a
voltage pulse to a piezoelectric element that is coupled, directly or indirectly, to the fluid. The
volumetric change causes pressure/velocity transients within the fluid, which produces a drop that
flows from the nozzle [204].
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Fig. 25. Schematic illustration of the operating principles of a DOD inkjet printer with a) thermal and b)
piezoelectric actuation [205], Copyright 2010 (Adapted with permission from Annual Reviews).

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The use of thermal or piezoelectric IJH depends on the desired properties intended for the final part.
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Each technique has some advantages and disadvantages which can be classified in availability,
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printing speed, the accuracy of printed parts, and functional cost. Thermal IJH has some advantages,
including availability, higher print speed, and lower cost compared with piezoelectric [151].
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However, the risk of exposing the binder to thermal stress, low droplet directionality, and non-
uniform droplet size generates considerable disadvantages compared to piezoelectric IJH [206]. The
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shear stress imposed on the binder at the nozzle tip wall can be avoided by using an open-pool
nozzleless ejection system, which can also avoid the drawback of nozzle clogging [207,208].
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As the precision of fabricated models strongly depends on the velocity, initial size, and path of the
droplets, it is essential to control these parameters, including nozzle diameter, binder properties, and
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the resonance frequency of the head [206]. Tsai et al. [209], developed a material jetting method
based on color 3D manufacturing by using multi-piezoelectric heads by optimizing the sub-system
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parameter and via the designing of a stable module.

5.2.1. Binder and powders

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Droplet generation in a DOD system is a complex process because binder must have suitable
properties to prevent spreading during the printing process. Therefore, liquid drop behavior can be
characterized by physical constants, such as Reynolds (Re), Weber (We) and Ohnesorge (Oh)
numbers. In the early 80s, the Ohnesorge number [210] was identified as an appropriate group of
physical constants which permitted to characterize drop formation, and, together with the use of the
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parameter Z (=1/Oh), it was proposed that a value of Z > 2 is suitable for stable drop generation.
Subsequently, in the year 2000, Reis and Derby [211] reported the models for different situations
(which were then replicated experimentally) in order to determine the optimum printing conditions
for particulate suspension, particularly for slurries of Al2O3 dispersed in paraffin wax. According to
this, they proposed the following range for Z, 10 > Z > 1, in order to obtain a stable drop formation.
At low values of Z, viscous dissipation prevents drop ejection, whereas at high Z values the primary

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drop is accompanied by a large number of satellite droplets due to the low viscosity of the fluid.
Another limiting factor for drop generation is the influence fluid/air interface tension at the nozzle.
A drop must have enough energy to overcome this barrier for ejection. Duineveld et al.[212]

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suggest that this lead to a minimum velocity for drop ejection, which is related to the viscosity of
the material and with the nozzle diameter.

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Finally, the mechanism that leads to the onset of splashing is also a topic of interest, the first
advances were proposed by Stow and Hadfield [213] as a critical dimensionless grouping of

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variables, depending on the Reynolds and Weber numbers. This relationship has been explored by
several authors.
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According to these equations, and the limiting values of Z, it is possible to construct a map, in an
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appropriate parameter space, with coordinates Re and We, that can be used to define fluid properties
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in DOD inkjet systems (Figure 26).

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Fig. 26. Illustration of the fluid regime properties where DOD inkjet printing is possible [205], Copyright
2010 (Reproduced with permission from Annual Reviews).

Three different types of binders are commonly used in the inkjet additive manufacturing method:
water-based binders (e.g., ZB54, Z Corporation) [214], phosphoric acid–based/citric acid–based
binders [215], and polymer solution binders such as PVA and poly(D,L-lactic acid) (PDLLA) [216].
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Depending on the type of binder, adhesive forces or hydraulic setting reactions possess a
fundamental role. Polymeric binders have been widely used to fabricate ceramic-based parts, but
the 3D printed parts present low resolution and poor mechanical properties. However, the
development of acid binders generated 3D printed parts with improved resolution and mechanical
properties [217].
Powder flowability is also an essential parameter for additive manufacturing processes. On the one

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hand, small values of flowability decreased fabrication resolution due to insufficient recoating. On
the other hand, high flowability did not provide enough powder bed stability for additive
manufacturing. Particle wettability is another factor to consider in additive manufacturing

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processes. The binder volume deposited on the bed, binder amount absorbed by the powders, and
the particle size determines the resolution and mechanical properties of the printed parts. In the case

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of using water-based binders, the powder particle size alters the pore distribution within the bed,
influencing on drop penetration behavior [218].

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5.2.2. Mechanical properties of additive manufacturing parts fabricated using binder jetting
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Improving the mechanical properties of porous parts is a challenge in inkjet additive manufacturing.
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Sintering post-processing increases the possibility of the final part to failure due to the burnout of
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binder and, also generate dimensional changes and the printed model [219]. Therefore, the binder
concentration is usually optimized in order to prevent failure, while still providing sufficient
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mechanical stability to the 3D printed part. Zhang et al. fabricated 3D printed scaffolds (strontium-
containing mesoporous bioactive glass) which exhibited higher compressive strength (8–9 MPa)
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than the human trabecular bone (2–12 MPa) [220]. In addition, the mechanical strength of the
scaffold after soaking during 7 days in simulated body fluid (SBF) is ~7 MPa. These excellent
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results were attributed to the use of aqueous PVA as a binder, which bonds the ceramic particles
together and consequently decreases the brittleness of the scaffolds.
Similarly, Wu et al. [216] prepared porous calcium silicate (CaSiO3, CS) scaffolds with a
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controllable morphology (from cube to hexahedral) by using a 12 % PVA solution as a binder.

Besides, the authors studied the in-vivo osteogenesis by comparing it with 3D printed β-TCP
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scaffolds. The compressive strength and Young’s modulus of printed CS scaffolds were 3.6 ± 0.1
MPa and 40 ± 8 MPa, respectively. The scaffolds present an approximately pore size of 1 x 1 mm
and a porosity of 65 %. A deformation study of the scaffolds under compressive tests revealed that
CS scaffolds partially maintained their configuration in the center and collapsed at the borders,
probably due to the distribution of polymeric binder of the printed scaffolds, which could affect the

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local flexibility of the structure. By comparing the compressive strength of CS scaffolds with those
using PU foam and PDLLA as binders, an increase when using a PVA as binder solution was
observed [221].
In the case of acidic binders, Vorndran et al. [217] fabricated parts from β-TCP using phosphoric
acid as a binder. They improved the compressive strength of the materials by adjusting the ratio
between binder and powder. Compressive strengths of 3.4 and 7.4 MPa were obtained for a binder-

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to-powder-volume ratio of 2 and 4, respectively while retaining cell viability at 68 % [222].
Powder particle size and printing direction have also direct implications on the mechanical behavior
of 3D printed parts. As an example, composites of HA/PVA were used as bone tissue scaffolds

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which shown different mechanical behaviors along different printing axes [223]. The mechanical
strength for X-axis scaffolds reported was 0.76 ± 0.02 MPa, whereas this value was 0.88 ± 0.02

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MPa along the Y-axis. In order to increase the mechanical resistance several groups proposed the
use metal oxide components as reinforcement agents, this method is also recommended to improve

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the mechanical properties of bioactive ceramics, especially for hard tissues and implant applications

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[224,225]. As reported by Fielding et al. [226] the addition of SiO2/ZnO into TCP can increase the
mechanical properties of implants. They fabricated a cylindrical scaffold by binder jetting with the
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addition of SiO2/ZnO. The resulting scaffolds exhibited interconnected square channels of different
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sizes (1000 μm, 750 μm, and 500 μm), and 10.5 mm in height. The doped fabricated scaffolds,
which had less total open pore volume than the pure scaffolds, showed the greatest compressive
strength than the pure samples.
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6. Polymeric materials employed in 4D printing

As has been elaborated before, a general requirement for 4D printing is the use of one or more than
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one material with distinct physical properties which enables shape changes. Whereas a wide variety
of polymeric materials are available for additive manufacturing (as has been thoroughly revised in
the previous sections of this review), there still exist a lot of pending issues which must be fulfilled
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for the development of 4D materials. In spite of this, recent efforts to achieve complex 4D printing
architectures illustrate the progress that has been made. For example, the integration of stimuli-
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responsive materials together with the possibility to print multiple materials in a precise design
provide unique platforms to fabricate intricate 4D responsive objects. As depicted in Figure 27
(top), single and multi-material objects can be straightforwardly fabricated by additive
manufacturing and designed to react to different stimulus. In some cases, shape changes can be
achieved by using multi-stimuli arrangements. A concept design based on this methodology was

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proposed by Khare et al. [21] who proposed a design of an artificial insect that is illustrated in
Figure 27 (bottom). This ambitious complex design involves several shape types and changes
provided by different multi-stimuli combinations in order to achieve simultaneously or separately
expansion, flexibility, shrinking or morphing, with the finality to fulfill a particular desired
application.
While it is true that, due to the current development phase of 4D printing technology, the variety of

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stimuli-responsive materials and design concepts is rather limited and thus requires further
development to achieve complex architectures, in the following we will attempt to discuss the most
relevant polymeric materials employed for 4D printing.

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Fig. 27. Top: Schematic illustration of the mechanism proposed to achieve actuation and shape flexibility
using either single or multi-stimuli responsive materials. Bottom: Design of an artificial bug controlled by
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multi-stimuli activation [21], Copyright 2017 (Reproduced with permission from Springer Nature
Switzerland AG).
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6.1. 4D printed Hydrogels

Smart hydrogels based on bi-layered structures (with either only one or two layers of gels) have
been widely explored for 4D printing. In this case, the different swelling ratio between the
respective layers that is provided by a particular solvent, pH or temperature, enables

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folding/unfolding transitions of the structure [227]. The concept of self-evolving structures has been
developed using hydrophilic materials, typically hydrogels, able to swell when immersed in water,
inducing changes in the 3D printed shape (Figure 28) [25].

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Fig. 28. Top: Rendered illustration of the primitive folding. By adjusting the distances between the disks, it is
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possible to set the final folding angle. Video frames of the fabricated primitive folding in water over time are
also showed. Bottom: Fabrication parameters of bending elements [25], Copyright 2015 (Reproduced
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with permission from Springer Nature Switzerland AG).

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Gladman et al. [16] fabricated a composite hydrogel ink that mimics the structure of plant cell
walls (Figure 29). It consists of a soft acrylamide matrix reinforced with cellulose fibrils which
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possess a high stiffness. The composite is printed using a viscoelastic ink composed of an aqueous
solution of N, N-dimethylacrylamide, Irgacure 2959 as photoinitiator, nanoclay, glucose oxidase,
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glucose, and nanofibrillated cellulose (NFC). The clay particles were used as a modifier for altering
the rheologic and viscoelastic properties, to facilitate desirable printability of inks. Larger amounts
of clay lead to higher crosslink densities and, therefore, lower swelling ratios. Glucose oxidase and
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glucose scavenge the surrounding oxygen, which consequently reduces oxygen inhibition during the
UV curing process. The shape-shifting state of the material described above is irreversible. To
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achieve reversible shape-shifting behavior in hot and cold water, the poly(N, N-
dimethylacrylamide) needs to be replaced with thermo-responsive N-isopropylacrylamide.

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Fig. 29. Complex flower morphologies generated by biomimetic 4D printing. (a-b) Simple flowers composed
of 90°/0° and -45°/45° bilayers oriented with respect to the long axis of each petal, (c–f) print path (c), printed
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structure (d) and resulting swollen structure (e) of a flower demonstrating a range of morphologies inspired by
a native orchid, the Dendrobium helix (courtesy of Ricardo Valentin) (f) [16], Copyright 2016
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(Reproduced with permission from Springer Nature Switzerland AG).

6.2. Shape memory polymers

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Shape memory polymers (SMPs) are a class of stimuli-responsive materials which have shape-
shifting properties. These polymers have been attracting increasing attention from the standpoint of
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both fundamental research and technological innovations. The motivation for using SMPs in
applications is their unique ability to either transform to a transitory shape when exposed to an
external stimulus and to recover a permanent shape when the stimulus is removed. SMPs can
respond to one or several stimuli (multi-stimuli materials). Among the most extensively studied
control parameters are temperature [228–230], water [48], pH [231], pressure [232], light [233–236]

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or even, magnetic fields [237]. Figure 30 show 4D printed parts fabricated by Magdassi et al. [230]
based on SMPs which react to heat, in particular, PCL macromethacrylate was used to create
structures which revert to his original shape above its melting temperature (60 °C). The printing
process is carried out with the polymer bath heated at 90 °C using SLA technique. Figure 30
shows a scaled Eiffel Tower and a bird which were repeatedly cycled through different temporary
shapes by changing the environmental temperature. Both figures illustrate the resolution and type of

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complex structures that can be obtained with this approach. Note also that the transparency is
another mutable property of these printed structures since it is related to the crystallite melting, the
object becomes transparent depending on the thickness of the printed part.

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Fig. 30. Examples of a heat reactive SMP that reverts to its original shape when exposed to 70 °C for an
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Eiffel Tower model and a bird [230], Copyright 2016 (Reproduced with permission from Wiley-VCH
publishers).
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6.3. Elastomer actuators

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Traditional robots are designed for specific applications and are commonly built using hard
materials that cannot achieve large structural deformations or mimic a soft-body animal such as an
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octopus [238]. One important aspect of soft robotics is the emphasis on three-dimensional
structures, being a popular and emerging field that tries to capture some of the natural organism
behaviors by using mostly soft materials [25,239]. The electroactive polymers (EAPs) materials are
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an example of soft-materials which are readily controllable by electrical stimulus [240]. Upon
supplying electricity to a dielectric elastomer actuator (DEAs), the structure of the actuator will
deform, and it can generate a significant amount of strain (100 % more) [241]. As a result, the
electrical energy entered into the DEA is transformed into mechanical work. This characteristic is
particularly interesting for control and sensing since the most efficient and established controllers
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are electrical (can sense, actuate and vary their stiffness). Alternative soft-smart materials can be
controlled by other methods using such stimuli as chemical, optical or magnetic, but these are less
well established and more difficult to interface with electronic circuitry. Moreover, another
advantage of EAPs is that they offer the tantalizing potential to form arbitrary shaped actuators and
sensors through relatively straightforward fabrication methods. For instance, Rossiter et al. [239]
presented a new method to fabricate DEAs for soft robotics through an additive manufacturing

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process. This new fabrication procedure helps to address the issues faced in manufacturing DEAs
by the conventional ones as they are often difficult and labor-intensive [242]. Figure 31a shows a
proof of concept for printing soft active structures like a single thin membrane with a thick circular

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collar. Figure 31b-c shows the membrane with 0V and with 5KV applied. This result suggests that
this membrane can be utilized as an active component in an actuator.

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Fig. 31. Single printed membrane for soft DEAs using PolyJetTM technology [239], Copyright 2009
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(Reproduced with permission from SPIE Digital Library).

6.4. Active composites

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Ge et al. [22] created printed active composites (PACs, or active composites by 4D) which were
printed using a 3D multimaterial polymer printer (Objet260 Connex, Stratasys), combining both
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heat and stress to activate an SMPs to bend at different rates and directions depending on the design
of the hinges. The matrix has been designed to be an elastomeric and the fibers to be a glassy
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polymer to realize tailored thermomechanical shape-memory behavior. The combination of

elastomer and glassy polymer fibers creates a soft composite [14]. Thus, glassy polymers in the
form of fibers exhibit shape memory effects when were heated above their glass transition
temperature (Tg= 35 °C), the temperature is then decreased to 15 °C at a rate of 2 °C/min.
Simultaneously, the applied stress was maintained on the sample. At this temperature, the matrix

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was still in the rubbery state, but the fibers were in a glassy state. After holding the sample for
enough time to equilibrate the strain (5 min), it was released, and the elastic unloading was
observed, reaching a temporary shape of the 3D printed part. Finally, the sample was heated in
order to reach their original state at 60 °C (Figure 32a-b). In Figure 32b bottom is possible to
observe different geometric transformation obtained with the PAC 3D printed structure. The
different forms are created depending on the fiber orientation and location, leading to several shape-

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shifting processes such as bending, rolling, twisting and waveforms.

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Fig. 32. (a) Top: The PAC architecture made up of a top layer pure elastomeric matrix material and bottom
layer of glassy polymer and elastomeric matrix material. Bottom: strain-time of the composites; (b) The
process of activating the PAC by heating the material, applying a load to the material, allowing it to cool, and
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releasing the stress to allow the material to bend. Reheating the PAC allows the material to return to its
original flat shape [14], Copyright 2013 (Reproduced with permission from AIP Publishing LLC).
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Active composites can also be useful to design and fabricate self-assembling origami structures:
boxes, pyramids, three-hinged airplanes, and five-hinge airplanes via 4D printing techniques. Mao
et al. [243] proposed a simple alternative to create sequentially self-folding structures by additive
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manufacturing hinges with digital SMPs. A box with the six rigid sides connected by PAC hinges
was 3D printed in a flat shape (dimension is 15 mm, Figure 33a-left). The PAC hinges were pre-
programmed with definitive bending angles using the relation of PAC hinge length and applied
strain to determine the bending angle. The walls of the box should bend at a 90°, so the hinges

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required a 20 % strain while the material was heated above its Tg (Figure 33a-right). The
component managed to form the box shape with minor irregularities when straining the material
[243]. Similar methods have been used to create self-assembling and disassembling trestles, but
with different geometrical parameters for the PAC lamina and matrix laminates (Figure 33b)
[22,244]. For instance, Wu et al. [244] fabricated structures consisting in 4 identical active composite
strips connected at the center. These structures were deformed in hot water (70 °C) and then cooled

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to ~0° C. Every strip had one fiber with higher Tg (fiber 1) and twelve fibers with lower Tg (fiber
2). The volume fractions of fiber 1 and fiber 2 were 1.2 % and 14.4 % respectively. The structure
was stretched with a strain of 8% at 70 °C and then cooled to 0 °C. After releasing at the low

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temperature, the sample bent slightly with a small curvature. When heated, the strips folded and the
trestle stands up from the flat shape. If the sample heating continued, the trestle returned back to its

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flat shape. As mentioned by the authors, this design could be used as an active supporting trestle
controlled by external heating.

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Fig. 33. (a) Initial 3D printed flat surface that mimicking the USPS mailbox and right upon heating, the
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sheet folds into a box with a self-locking mechanism [243], Copyright 2015 (Reproduced with
permission from Springer Nature Switzerland AG). (b) Design of the trestle, cross-section, the
shape of the structure after programming and deformation behavior of the structure in the recovery
process [244], Copyright 2016 (Reproduced with permission from Springer Nature
Switzerland AG).
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6.5. Areas of application of 4D printing

Nowadays, in addition to those applications of additive manufacturing, there are several application

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fields in which 4D printing can be useful, including the fabrication of origami structures, 4D
nanoprinting, biomedical applications (stents, adaptive scaffolds, and tissue engineering). In Table

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5 are depicted some of the most relevant applications.

Table 5. Some of the most relevant, and potential, applications of 4D printing [17], Copyright

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2017 (Adapted with permission from Elsevier Science Ltd).

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 4D PRINTING APPLICATIONS
DEMONSTRATED APPLICATIONS POTENTIAL APPLICATIONS
Origami structures [22] Drug delivery systems [59]
Bio-Origami [26] Smart textiles [245]
Artificial Crambin protein [19] Adaptive pipes [246]
structure

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4D nanoprinting [247] Self-healing hydrogels [248]
Smart valve to control the hot [27] Self-assembly at large [19]

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and cold flow scales and in the harsh
environment

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Smart valve to control the [249] Soft robots [24,250]
acidic or basic flow
Laser-based cell printing [251] Tissue engineering [60,252,253]

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Adaptive metal-materials [23,254,255] Error-correct and self- [19]

Stent
N repairing structures
[59,254,256,257] Construction on Mars [258]
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along with contour crafting
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Smart gripper [59]

Smart key-lock connectors [31]
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Adaptive Scaffolds [241] [259]

Adaptive joints [25]
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Several applications of 4D printing strategies are based on the use of SMPs, for example, Choong et
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al., [260] developed a tert-butyl acrylate-co-di(ethylene glycol) diacrylate (tBA-co-DEGDA)

network based on a dual-component phase switching mechanism to form a single 4D printable
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SMPs using SLA. Besides, in this study, it was demonstrated the fabrication of a self-assembled
buckminsterfullerene (or C60 bucky-ball) when it was subjected to different temperatures (Figure
34).
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Fig. 34. a) Buckminsterfullerene (or C60 bucky-ball) in printing stage, (b-c) unfolded after printing, (d-h) and
recovering its original bucky-ball shape by soaking at 65 ˚C in water [260], Copyright 2017 (Reproduced
with permission from Elsevier Science Ltd).

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Others are based on the incorporation of electronic conductive polymeric materials. For example,
Sundaram et al., [261] demonstrated the fabrication self-folding electronic composites via additive
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manufacturing. Integrated electronics, with complex 3D shapes, can enable new applications in
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sensing and robotics. The parts were created without using any external processing. According to
this, Figure 35 shows an electrochemical element integrated into a spontaneously folding, fully
printed, composite, which consists of six materials that are printed simultaneously. The
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transmission through the electrochromic ink based on poly(3,4-ethylene

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dioxythiophene):polystyrene sulfonate (PEDOT:PSS) can be modulated by applying a voltage. The

stretchable printed conductor provides electrical contacts through the folded legs. Bakari et al. [262]
demonstrated a functional hydrogel-based device by the production of an artificial meniscus,
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artificial tendon and a smart valve (Figure 35 b).

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Fig. 35. a) Electrochromic element integrated into a spontaneously folding fully printed composite [261],
Copyright 2017 (Reproduced with permission from American Chemical Society

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 Publications). b) Macroscope image of a 3D printer particulate reinforced Alg/PAAm ICE gel printed
with Alg/PAAm ICE gel and Emax gradient structures [262], Copyright 2016 (Reproduced with
permission from Cambridge University Press).

7. Overview of the most relevant applications of AM fabricated polymeric parts

7.1. Biomedical applications

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Polymers are, without doubt, the fastest growing category among all the materials employed for
biomedical applications during the last decade [263]. This remarkable growth is related to the

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advantages in the use of polymers for biomedical purposes in comparison to metals. Among the
most important advantages, it is worth mentioning the biocompatibility of several polymers, as well

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as their elastic properties and bio-inertness.
The large variety of polymeric materials combined with the possibility to fabricate tailor-made

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structures by AM provide unique possibilities to employ these materials for biomedical purposes.
As a result, in recent years, medical applications have come to the fore, and are predicted to make
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up 21 % of a US $ 8.9 billion industry in the next 10 years [264]. According to this, several studies
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related to all areas of additive manufacturing linked to human health are currently being developed,
and will, therefore, encompass many different areas ranging from medical devices, implants,
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prosthetics, surgical planning, and guides, to tissue engineering and regenerative medicine, as well
as advanced pharmaceutical fabrication. In particular, some recently created journals are completely
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devoted to this kind of technologies, one case is the Journal of 3D printing in Medicine, released in
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the year 2017 [265]. AM is set to play a crucial and fundamental role in the future of healthcare.
This section of the review will be devoted to describing some of the most interesting and important
biomedical applications related to AM.
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7.1.1 Anatomical models for pre-operation

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An anatomically correct reconstruction of implants with high complexity is particularly challenging,

especially when certain anatomical landmarks are lost. Often, large experience and precise 3D
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conceptual ability are needed. CAD and CAM have been continuously improved over the past few
decades and has found its way into daily clinical work. These 3D models provide to the surgeon an
additional understanding of the patient-specific anatomy [266,267]. Msallem et al. developed a
cost-efficient protocol/workflow for performing craniofacial reconstruction using an in-house
manufactured silicon implant [268]. Other common applications for AM models in preoperative
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instances involved the cardiovascular area [269–271]. A particularly interesting case was explained
by Schmauss et al., which created an aortic model for perioperative planning of complex surgery,
commonly called frozen elephant trunk (FET) that combined conventional surgery with difficult
endovascular techniques [272]. The FET was performed on the aortic arch, which possessed
unpredictable anatomy. By using a CT reconstruction of the aorta, it was possible to manufacture a
3-D model using a high-definition color 3-D printer (Spectrum Z 510). After printing, the model

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was infiltrated using urethane resin (Por-A-Mold 2030) which confers it a flexible but tough
structure, perfect for simulating the ascending aorta part surgery of the FET. Figure 36 shows some
images of the 3-D model before and after the FET procedure. Other recently reported uses of

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additive manufacturing include planning for endovascular closure of an ascending aortic
pseudoaneurysm [273] and for complex aortic coarctation intervention [274].

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Fig. 36. Left: 3D model of the aortic arch before and Right: after FET surgery procedure [272],
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Copyright 2014 (Reproduced with permission from Elsevier Science Ltd).

Other studies also report CAD models of ear cartilage for auricular reconstruction, Berens et al.
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show a simple and low-cost protocol based on 3D printed models based on starch and silicone to
obtaining realistic cartilage framework for surgery simulation of microtia reconstruction [275]. The
results demonstrate that this procedure corresponds to a reproducible tool for simulation of auricular
reconstruction, which may be a benefit for the trainee and more experienced microtia surgeon from
the use of a patient-specific representation of costal cartilage.

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In summary, surgery simulation using 3D models is emerging as a fundamental resource for
teaching procedural techniques, in fact, cardiovascular societies are emphasizing cardiac procedural
simulation as a required part of cardiology fellowship curricula [276].

7.1.2 Implants and scaffolds

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The aim of biomedical implants is to enhance the quality of patient lives by extending the
functionality of essential body systems beyond their supposed lifespans. Many thermoplastic

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polymers have been used in the clinic for decades; including PCL, polyglycolic acid (PGA), PLA,
polypropylene (PP), and polydioxanone (PDO) [277–280]. These materials have been developed for

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multiple applications in the human body, ranging from man-made objects that provide physical
support, such as knee implants and synthetic blood vessels, to applications that improve the
functionality of human organs. For example, melt-processed polymeric screws and pins for

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orthopedic surgery based on PGA and PLA can be used for the reconstruction of the anterior

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cruciate ligament (ACL). These polymeric screws have the advantage of being bio-resorbable as
well as radiolucent and can also be fabricated via melt processing (injection molding) of
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thermoplastic polymers [281–283].
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PCL is an excellent candidate for biocompatible/biodegradable support. This polymer is degraded

by hydrolysis of its ester linkages under physiological conditions and has therefore received great
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attention for its use as an implantable biomaterial. In particular, it is especially interesting for the
preparation of long-term implantable devices. Elomaa and coworkers [284] developed a series of
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scaffolds based on photocrosslinkable PCL-based resin and applied using SLA. No additional
solvents were required during the fabrication process. Three-armed PCL oligomers of varying
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molecular weights were synthesized, functionalized with methacrylic anhydride, and

photocrosslinked, resulting in high gel-content networks. As illustrated in Figure 37, the scaffolds
precisely matched the computer-aided designs, with no observable material shrinkage. The average
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porosity was 70.5 ± 0.8 %, and the average pore size was 465 μm with high interconnectivity.
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Fig. 37. Photograph (a), μCT visualization (b) and SEM images (c-d) of a scaffold built by stereolithography

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using 1500-m macromer [284], Copyright 2011 (Reproduced with permission from Elsevier
Science Ltd).

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Another interesting example was reported by Peltola et al. using a novel antimicrobial composite

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based on a bioactive glass (BAG) and PMMA to create craniofacial reconstructions in patients with
large skull defects. According to CT and PET-CT analysis, this kind of implants seems to be a
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promising low-cost craniofacial reconstruction alternative [266].
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The most common material used for hip and knee joint implants is the ultra-high molecular weight
polyethylene (UHMWPE), which can be obtained via crosslinking by gamma irradiation.
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UHMWPE can be processed by melt compression molding or by AM [285]. UHMWPE can be

employed to create 3D printed structures using laser sintering. However initial tests evidenced that
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the material exposed to the laser beam undergone degradation in terms of chain scission, cross‐
linking, and oxidation [286].
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In contrast to these studies on the laser sintering of UHMWPE that were unable to produce
multilayer parts, Rimell et al. [287] demonstrated that by heating the powder prior to sintering is
critical to fabricating by SLS. This was carried out to minimize thermal gradients during processing
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and resultant induced strains upon cooling. The authors fabricated multilayer parts with accurate
dimensions (±0.1 mm) and significant sintering between particles and layers.
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Chitosan and bone-like nanostructures, which contain HA, have been mixed with cells and printed
successfully using the bioplotting technique. MC3T3-E1 pre-osteoblast cell-laden chitosan and
chitosan-HA hydrogels were characterized and these hydrogels were compared to alginate and
alginate-HA hydrogels. According to the results obtained cells with chitosan and chitosan-HA
hydrogels presented osteogenically differentiation after 21 days of culture. Besides, chitosan and

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chitosan-HA hydrogels exhibited good mechanical support after printing and provided highly active
cell-platforms compared to the alginate bioink [288]. Using the same printing technique, Diogo et
al, mixed alginate with β-TCP and extruded by 3D plotter [289]. Different composition of β-
TCP/alginate of 50/50 % (w/w), 30/70 % (w/w) and 20/80 % (w/w) were evaluated. As the β-TCP
contents in alginate matrix increased, the accuracy of printing increased due to an increase in the
viscosity of hydrogel composites. 50/50 β -TCP/alginate scaffolds had the highest compression

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strength and Young’s modulus and these values were higher than those of trabecular bones.
Furthermore, biological tests using osteoblast cells suggested that 50/50 β-TCP/alginate scaffolds
were promising candidates as composite scaffolds in bone regeneration applications.

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Besides implant generation, there is an enormous translational potential in the production of tissue-
engineered (TE) scaffolds using AM technologies for biomedical applications [290]. Complex 3D

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scaffolds that have a fully interconnected structure with predefined dimensions and porosity are
required for effective repair or regeneration of tissues and organs [291]. A crucial aspect for design

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TE scaffolds is to allow a suitable biological function in addition to mechanical integrity and mass

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transport (diffusion and permeability), this characteristic can be achieved by controlling the porosity
and architecture of the TE scaffold. The common AM methods have limitations when trying to
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mimic the biological function of natural tissue, due to the difficulty to finely control the scaffold
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architecture, dimensions, and porosity. SLA is an additive manufacturing process that allows
greater control of TE scaffold dimensions and features compared to other AM techniques. SLA
permits to precisely control the architecture and features of the resulting scaffold and, thus, offers
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great benefit for regenerative medicine as well as to construct repeatable identical scaffolds or to
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fabricate patient-specific templates [292]. Meyer et al. [293] synthesized soft polymers based on
photocurable α,ω-poly(tetrahydrofuranether diacrylate) (PTHFDA) resins for SLA applications.
Small bifurcated tubes (close to capillary dimensions) were printed and proved as blood supplying
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systems. Biocompatibility tests show nontoxic characteristics of the polymers, and some materials
present shape memory effects. Figure 38 (left) shows some micrographs (optical and SEM) of the
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structures printed with SLA using PTHFDA resins and their shape memory characteristics. Later,
Elomaa et al. [294] fabricated biodegradable hydrogel vessel graft scaffolds from a water-soluble
methacrylated poly(ethylene glycol-co-depsipeptide) via SLA technique. The macromer was used
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to print bifurcating tubular structures of small dimensions which presented good biofouling
properties according to endothelial cell proliferation tests performed after 10 days of in-vitro
culture. Figure 38 (right) shows fluorescence images and photographs of the hydrogel scaffolds
printed via SLA and also the models of the bifurcating vascular tubes. More recently, Akkus et al.

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[295] reported another example of SLA printed photocurable hydrogels based on chitosan and
PEGDA. Ear shaped TE scaffolds were printed using SLA, the fabricated hybrid scaffold showed
interconnected and homogeneous pore network, which together with its mechanical properties,
enhance cell adhesion on the surface and permit high-quality printability.
Finally, another interesting example was reported by Hirsch et al. [296] that carried out a surgical
reconstruction of the ossicular chain by using SLA technologies for the fabrication of the prosthesis

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based on commercial photocurable polymers. They elaborated patient-specific prosthesis which is a
potential solution for the wide range of anatomic variation encountered in the pathological middle
ear and could decrease the rate of post-operative prosthesis displacement by increasing the

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likelihood of a proper fit, in addition to decreasing surgical time.

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Fig. 38. Soft scaffolds used for vascular applications. Left: Micrographs and photographs of
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photopolymerizable PTHFDA microtubes printed via SLA which show their small dimensions and shape
memory effect. Right: 3D printed SLA hydrogel bifurcating vessel tubes based on photocurable
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poly(ethylene glycol-co-depsipeptide), fluorescence micrographs and CAD models can be observed also
[293], Copyright 2012 (Reproduced with permission from MDPI Basel), and [294], Copyright
2015 (Reproduced with permission from Royal Society of Chemistry Publishing).
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7.1.3 Cartilage and tendon regeneration

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Articular cartilage defect in the joints is a common clinical problem, which leads to articular
dysfunction, significant pain, and even disability. Its regeneration remains a great challenge for
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clinicians and researchers since cartilage lacks the ability to rapid self-healing produced by their
avascular and aneural nature [297]. The combination of endogenic bone marrow stem cells (BMSC)
with suitable biomaterials has emerged as a promising method for achieving one-step cartilage
repair using specific-patient designed tissue scaffolds created via additive manufacturing
techniques. Recently, Ao et al. [297], designed a scaffold via integration of silk fibroin with gelatin

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in combination with BMSC-specific-affinity peptide, a mixture which balances the mechanical
properties and degradation rates to perfectly match the newly formed cartilage. This biomaterial
appears to be a promising solution for knee cartilage repair and, moreover, the dually optimized
scaffold may also serve for the regeneration of other joint cartilages. Another promising method to
create complex composite tissues is the precise placement of cell-laden hydrogels in a layer-by-
layer fashion [298]. Atala et al. presented a novel method for the fabricating stable and human-scale

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patient-specific tissue constructs with any shape by printing cell-laden hydrogels together with
biodegradable polymers in integrated patterns and anchored on sacrificial hydrogels as supports.
The authors demonstrated that, by this method, it is possible to create microchannels in the scaffold

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which resulted in enhanced tissue formation since the maximum nutrient diffusion distance for cells
needed to survive without vascularity is in the range of ~100–200 µm. Cartilage structures showed

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adequate in-vitro tissue formation without necrosis after 5 weeks. Future advances in this
technology are expected to produce clinically useful tissues and organs that incorporate multiple

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cell types at precise locations to recover native structure and function. Figure 39 show some of the

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results obtained by Atala et al. including photographs of the hydrogel scaffold for cartilage
regeneration and also some in-vivo studies performed on rats.
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Fig. 39. Designed fiber bundle structure for muscle organization and final printed device (a, b and c).
Micrographs of live/dead staining of the encapsulated cells in the fiber structure which shows high cell
viability after the printing process (d, e, f, and g). Structural maintenance and host nerve integration of the
bioprinted muscle construct (in-vivo study) (h, i, and j) [298], Copyright 2016 (Reproduced with
permission from Springer Nature Switzerland AG).

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Another relevant problem to manufacture cartilage scaffolds results from the increase in the tensile
strength without compromising their soft mechanical properties. In the case of scaffolds for the
regeneration of tendons, this is a crucial aspect that needs to be considered. The tensile strength of
tendons is related to their microstructure because correspond to highly organized tissues made from
a hierarchical alignment of type I collagen fibrils which transmit force from muscle to bone. While
relatively minor tendon injuries may heal on their own, major tendon injuries result in scar

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formation which hinders mechanical performance and often results in pain and poor functionality.
Their fast regeneration is crucial in several clinical cases. According to this, Harley et al. [299]
describe the use of additive manufacturing techniques which incorporate ABS fibers into a collagen

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scaffold. Notably, the mechanical performance of scaffold fiber composites (elastic modulus, peak
stress, and toughness) could be modified by varying fiber-reinforcement geometry without affecting

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the native bioactivity of the collagen scaffold.
Visscher et al. [300] introduced an additional consideration, i.e. the scaffold contraction. For

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example, it is widely accepted that successful engineering of ear cartilage requires suitable scaffolds

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and appropriate cell sources without compromise their mechanical compliant characteristics.
Visscher et al. developed a contraction-free biocompatible scaffold for ear cartilage by using
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fibrin/hyaluronic acid (FB/HA) hydrogel combined with collagen I/III scaffold. One of the most
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interesting aspects of this study is the elaboration of a cage containing the structure of ɛ-PCL. Hsu
et al. [301] attempted to solve this problem using a different approach. They printed a compliant
scaffold through a water-based additive manufacturing technique named low-temperature fused
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deposition manufacturing (LFDM) using biodegradable PU elastic nanoparticles, hyaluronan, and

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bioactive ingredients (TGFβ3) or a small molecule drug (Y27632). The mixture of biomaterials
used to promote the self-aggregation of mesenchymal stem cells (MSCs) which generated an
appropriate release time of the bioactive ingredients, allowing to produce the matrix for cartilage
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repair. Figure 40 shows a scheme of the methodology proposed by Hsu et al. and also some images
and mechanicals studies which prove their compliant characteristic.
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Fig. 40. Schematic representation of the additive manufacturing process for (a) scaffold manufacture using

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PU/HA aqueous solutions via the LFDM system and (b) some photographs which shows their compliant
property [301], Copyright 2016 (Reproduced with permission from Elsevier Science Ltd).
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7.1.4 Bone regeneration
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Bone, although apparently a rigid material, is a dynamic tissue that is in a constant state of
deposition and resorption [302]. The purpose of a TE is to provide favorable conditions for cell
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growth and invasion while providing mechanical support until a sufficient stage of healing is
reached to try to mimic the function of bone. One of the pioneer examples was reported by
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Hutmacher et al., which created bone scaffolds by FDM with a porosity of more than 56 % and pore
sizes between 380 and 590 μm. Fibroblasts and osteoblasts were grown on these scaffolds and the
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authors observed that grew from the periphery to the center to cover the pores [303].
More recent advances in the elaboration of 3D printed bone scaffolds have been made with other
polymeric materials bearing hydroxyapatite and different polymers, like poly(ester urea),
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poly(propylene fumarate) or PCL [304–306]. These materials promote bone regeneration and are
excellent candidates for their use in orthopedic applications. In Figure 41 shows a scheme
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explaining the methodology proposed by Yu et al. (Top) and some results obtained for MC3TC-E1
cell mineralization on the scaffolds after 4 weeks of culture (Bottom). These images clearly
evidenced the increase in calcium concentration as a function of the percentage of hydroxyapatite
included in the mixture.

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Fig. 41. Top: Scheme of the methodology proposed for additive manufacturing of bone scaffolds based on
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hydroxyapatite and poly(ester urea) and Bottom: some results of MC3TC-E1 cell mineralization on the
scaffolds after 4 weeks of culture [304], Copyright 2017 (Reproduced with permission from
American Chemical Society Publications).
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Esposito-Corcione et al. [307] also used hydroxyapatite mixed with PLA to manufacture a bone
graft substitute via rapid prototyping method. Firstly, the inclusion and distribution of the
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hydroxyapatite particles were physically and chemically characterized via SEM-EDX and TGA
measurements. The mechanical properties of the material were tested via three-point bending tests.
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The composite was used to manufacture real three-dimensional maxillary sinus model by additive
manufacturing showing suitable characteristics to be used as bone scaffolds such as high
mechanical strength and appropriate microstructural porosity. Equally, Chiellini et al. [308] recently
reported biodegradable materials based on polyesters (poly(hydroxyalkanoate) (PHA)) produced by
different bacteria under unbalanced growth conditions. Particularly, poly[(R)-3-hydroxybutyrate-

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co-(R)-3- hydroxyhexanoate] was used to print bone scaffolds via AM wet-spinning system. Cell-
culture experiments employing MC3T3-E1 murine osteoblast cell line showed good cell
proliferation after 21 days of culture, and also demonstrated promising results in terms of cell
differentiation towards an osteoblast phenotype.

7.1.5. Antimicrobial implant supports

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Biomedical polymeric devices, as has been stated before, are broadly used nowadays and are
essential in the human healthcare system. There are several examples of polymeric-based

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biomedical devices, including artificial hips and knee implants or systems such as stents, heart
valves or even vascular grafts (section 7.1.2) commonly used both to improve the quality of life

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and, in some cases, increase life expectancy. In spite of this, a still remaining fundamental problem
in the employment of polymeric materials for biomedical purposes is related to material
contamination by a wide variety of microorganisms. This issue is nowadays a critical limitation for

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the use of polymeric materials in this application field. Particularly, in the biomedical area, this

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topic is important because is highly possible that bacteria could be present in the media, affecting
the integrity of the medical devices and healthcare products. This problem will also become a
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limitation in another kind of areas which employs polymers, such as food packaging, dental
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equipment or household sanitation [309].

Several research groups are currently focused on the elaboration of antimicrobial polymers [310]
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and in the fabrication of functional surfaces/materials. In this context, a recent example was
reported by Vargas-Alfredo et al., who designed an antimicrobial strategy which combines the use
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of HIPS and AM to fabricate 3D parts that, independently of the explored geometry, changes both
chemical composition and microstructure of the surface in order to improve antimicrobial activity.
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The scaffolds were fabricated by FDM methodology by using HIPS filaments. The object surface
was then modified generating 3D parts with porous surfaces by means of the breath figures (BF)
approach. BF strategy involves the scaffold immersion in a polymeric solution during a controlled
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time period. Immersion time variation allows pore size modification, the solution concentration has
also a direct influence on pore distribution. Moreover, by using polymer blend solutions of PS and
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PS-b-PAA (PS23-b-PAA18) and a quaternized PS-b-poly(dimethylaminoethyl methacrylate) (PS42-b-

PDMAEMA17), it was possible to simultaneously chemically modify the surface of the scaffold and
therefore improving their antimicrobial capacity. SEM and FT-IR were used to characterize the
surfaces (Figure 42). Finally, scaffold biological response to bacteria was explored. The porous
surfaces prepared using quaternized PDMAEMA as well as those prepared with PAA as main

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components confer antimicrobial activity to the 3D printed parts, permitting to kill S. aureus
bacteria on contact.

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Fig. 42. Left: 3D CAD model selected for surface and chemical modification. Middle: SEM images of the

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scaffold revealing the layered structure obtained via FDM, also the microstructured porous surface is

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depicted. Right: Effect of the chemical composition on the 3D printed part antimicrobial properties [310],
Copyright 2017 (Reproduced with permission from Springer Nature Switzerland AG).
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Also, SLA printing methodology has been employed as an AM method for the fabrication of
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antimicrobial objects. As an example, in a recent contribution, Garcia et al. [311] described the
fabrication of 3D printed pH-responsive and antimicrobial hydrogels with micrometric resolution.
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The hydrogels were prepared by using a photosensitive mixture of PEGDMA with variable chain
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lengths (ranging from 2 up to 14 units) and AA as a linear monomer. These mixtures result in a
wide variety of smart-hydrogels with swelling-responsive capacities depending on the monomer
composition and the type of crosslinker used during the synthesis. Moreover, to control the UV
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penetration depth, a photoabsorber (Sudan I) was employed with the finality of increase printing
model accuracy and z-axis resolution (Figure 43). Interestingly, the hydrogels described before are
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able to reversibly swell and shrink upon pH environmental changes. Also, it was demonstrated that
the swelling ratio is directly related to the amount of AA included in the monomeric feed and thus,
can be finely tuned. Finally, the antimicrobial properties of the hydrogels were characterized using
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S. aureus as a bacterial model. The authors found that all the composites, even those with a low
amount of AA units, present excellent antimicrobial properties against S. aureus.

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Fig. 43. Left: Lateral and top 3D views of the µ-CT reconstruction of the printed part. Right: Bacterial
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viability on the different hydrogels with a variable amount of AA. Fluorescence micrographs at 43X
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magnification, after 24 hours of bacterial adhesion. Green fluorescence corresponds to the emission of all
bacteria, while the red one is related to the emission of propidium iodide (dead bacteria). Scale bars
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correspond to 20 µm [311], Copyright 2018 (Reproduced with permission from American Chemical
Society Publications).
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7.1.6. Biodegradable platforms

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Biodegradable materials have been used to construct TE implants and scaffolds (tendon, cartilage,
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and bone reparation/regeneration applications) [298,301,307]. In these studies, the biodegradable

materials were used for the fabrication of TE devices with improved biocompatibility and suitable
mechanical properties. In general, the biodegradable material was used in order to provide support
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to the cells that help the innervation and vascularization processes of the affected area and reduce
the recovery time of the tissue. Finally, the scaffold is absorbed by the organism with an appropriate
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biodegradation rate that so that the tissue has the required time to regenerate. In some cases [301],
the biodegradable material may also contain bioactive substances that released help in the cell
regeneration process [312].
The porosity and microstructure of the 3D printed biodegradable platforms can be precisely
controlled via novel AM methods like mask projection micro-stereolithography (MPμSLA).

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Chartrain et al. [313] reported the fabrication of biodegradable tissue scaffolds (with 50 µm feature
sizes) using poly(tri(ethylene glycol)adipate) dimethacrylate (PTEGA-DMA). The resulting 3D
printed parts presented suitable thermomechanical properties for the fabrication of tissue scaffolds
of connective tissue and spongy bone. MC3T3-E1 mouse preosteoblasts were seeded on PTEGA-
DMA films to assess adhesion and biocompatibility, demonstrating good cell adhesion and
significantly higher cell viability in comparison to tissue culture treated PS. Moreover, hydrolysis

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studies evidenced that the material degrades relatively slow in minimum essential cell media,
providing the required time for being used as support for the growing tissue.
Other common medical uses for 3D printed biodegradable materials are the manufacture of vascular

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grafts and stents. Fisher et al. [314] developed a 3D printed vascular scaffold via digital light
processing SLA (DLP-SLA) method using PPF, a biocompatible and biodegradable polyester. The

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authors tested the printed device on mice presenting a medically common congenital heart disease,
coarctation of the aorta. A custom graft was designed to fit the specific curvature of the patient’s

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anatomy and subsequently was tested both for fit and fluid dynamics before eventual 3D fabrication

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of the customized implant. Moreover, mechanical characterizations were also carried out on the
printed material, demonstrating suitable mechanical properties to support vascular tissue growth
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both in-vitro and in-vivo. The implantation of the 3D printed grafts in mice shows long-term
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efficacy up to 6 months after surgery. Another example was reported by Cabrera et al. [315]. They
demonstrated that a commercially available thermoplastic polyester elastomer (FlexiFil) can be
used for the design and manufacture of a polymer stent via FDM techniques with mechanical
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performance comparable to conventional nitinol stents used for heart valve implantation in animal
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trials. Crush and crimping mechanical tests were conducted to validate the results predicted by the
computational model. Finally, the degradability of the polymer was tested via accelerated
hydrolysis degradations. After 8–16 weeks of implantation, the in-vivo implanted stents show fully
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integrated within the native vascular wall. Figure 44 shows some photographs of the 3D printed
stent placed inside the crimping device. Also, the self-expansion property of stent is demonstrated
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when the device is pushed out of the delivery system.

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Fig. 44. (a - b) Photographs of the crimping mechanical test. (d – h) Also, an image sequence is depicted in
which shows the self-expansion process of the FlexiFil printed stent [315], Copyright 2017 (Reproduced

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with permission from Mary Ann Liebert Inc. Publishers).

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Although the medical examples of biodegradable platforms are the most common in the literature,
there are other studies that support the possible use of these materials in other research fields. A
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notable example is the proposed by Guo et al. [316] which manufacture devices based on
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environmentally sustainable flame retardant nanocomposites via FDM technique. By controlling the
proportions in a mixture of PLA, melamine polyphosphate and Cloisite 30B (C-30B) was possible
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to create a fiber with increased flame resistance than PLA. Cone calorimetry tests revealed that
while a significant decrease in the heat release rate, accompanied by the formation of an
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intumescent char, was achieved by the addition of 1 % C-30B to the melamine polyphosphate /PLA
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blend, a very poor char, corresponding the increase in the heat release rate, was obtained with
addition of 2 % C-30B.
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7.2. Fabrication of elastic devices

Silicone, one of the most important elastic industrial material, has been formulated to have a low
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elastic modulus, high extensibility, and toughness, in addition to excellent thermal and oxidative
stability, and chemical inertness [317]. Although silicon properties have enabled a multitude of
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industrial uses to be developed for solid elastomeric structures, the handling viscous liquid silicone
still a challenge in AM technologies.
McAlpine et al. [318] reported one of the first studies in which silicon was effectively used as part
of a 3D printed functional structure. They presented a novel strategy for manufacturing biological
cells with structural and nanoparticle derived electronic elements. The fabrication of three-

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dimensional biological tissue (auricular prosthetics) interweave with functional electronic devices
was carried out via AM techniques. In their study, the presented a strategy based on additive
manufacturing of cell-seeded hydrogel matrix intertwined with a conductive solution of silicone and
silver nanoparticles which form an inductive coil antenna to read signals from cochlea-shaped
electrodes.
Angelini et al. [319] reported a method for print 3D silicone structures on self-assembled micro-

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organogels as a matrix. In Figure 45 and Figure 46 are depicted the scheme proposed by Angelini
et al. for silicone printing on the micro-organogel matrix and some photographs of the obtained 3D
silicone printed devices respectively. The rheological properties of the micro-organogel matrix

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could be tuned, leveraging the jamming transition facilitating its use for additive manufacturing of
silicone structures. Their findings demonstrated that the printed feature size can be controlled by the

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yield stress of the micro-organogel medium, enabling the fabrication of numerous complex silicone
structures with high resolution. By tuning the chemical and mechanical properties of the gel matrix,

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it was possible to create a continuous and stable deposition of silicone.

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Fig. 45. Scheme of the methodology proposed for print 3D silicone structures on micro-organogel matrices
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[319], Copyright 2017 (Reproduced with permission from the American Association for the
Advancement of Science).
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Fig. 46. Micrographs and photographs of some devices fabricated using the method proposed by Angelini

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et al. [319], Copyright 2017 (Reproduced with permission from the American Association for
the Advancement of Science).
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One of the critical issues in AM is the combination of several printing methods in order to increase
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the range of materials or even the fabrication of hybrid structures. Toyserkani et al. [320] developed
a hybrid system combining material jetting and material extrusion. The methodology reported is
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capable of printing non-Newtonian viscous silicone while increasing the fabrication velocity
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(between 10 to 20 times compared to the typical extrusion methods). Upon optimization of the
printing parameters to maximize the printing resolution a clear surface quality enhancement of the
resulting devices was observed.
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Other studies are focused on the optimization and tunability of mechanical properties of the silicone
printed devices. Lenhardt et al. [321] explored the capability to tune the stiffness of the silicone-
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based materials via careful control over their chemistry, network formation, and crosslink density of
the ink formulations. As depicted in Figure 47 (Left), Lenhardt et al described a silicone printed
silicone pneumatic actuator capable of reach fully articulated configurations. More recently,
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Magdassi et al. [101] reported the fabrication of highly stretchable and UV curable elastomers for
digital light processing based additive manufacturing using UV-curable polydimethylsiloxane
(PDMS) composites.
Plott and Shih [322] also optimize silicone printing parameters for obtaining structures with
minimal voids and high strength, elongation and fatigue life for being used as pneumatic actuators.
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In this article, experiments were performed to study effects of flow rate, layer height, and the
distance between adjacent silicone lines on the solid and thin-wall vertical layer deformation and
void generation. In Figure 47 (Right) are depicted some photographs of the mechanical
characterization performed to silicone-based foams with different internal printing structure and
chemical properties.

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Fig. 47. Left: Photographs of the pneumatic actuator with minimal voids printed with (a) silicone in non-
deformed and (b) fully articulated configurations. Right: Photographs of mechanical tests developed on
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silicone-based foams which present alterations in their chemistry and structure [321], Copyright 2017
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(Reproduced with permission from Wiley-VCH publishers), and [322], Copyright 2017
(Reproduced with permission from Elsevier Science Ltd).
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The fabrication of novel devices requires, in some cases, the development of alternative and
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innovative AM methods. For instance, Velev et al. [323] proposed a new methodology for printing
liquid polymeric solutions based on organosilicon compounds. PDMS was printed by using a
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capillary suspension ink containing PDMS in the form of both precured microbeads and uncured
liquid precursor, dispersed in water as a continuous medium. Figure 48 (Top) shows a scheme of
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the methodology proposed by Velev et al., showing both the PDMS microbeads particles mixed
with PDMS, as a liquid precursor, in suspension on air/water medium for additive manufacturing as
well as the SEM cross-section micrographies of the resulting fibers in which the PDMS crosslinked
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microparticles can be observed. The suspension possesses the mechanical characteristics needed for
direct ink writing and could be 3D printed and cured both in air and underwater, resulting in
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structures remarkably elastic, flexible, and extensible. In Figure 48 (Bottom) are depicted some of
the structures obtained via this AM proposed methodology.

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Fig. 48. Top: Scheme of the proposed methodology for additive manufacturing of PDMS microbeads
mixed with PDMS liquid precursor in suspension on air/water medium. Bottom: Some of the structures
printed with PDMS using this technique [323], Copyright 2017 (Reproduced with permission from
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Wiley-VCH publishers).
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7.3. Piezoelectric composites

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Piezoelectric devices are currently being employed for a wide variety of applications, ranging from
acoustic imaging to energy harvesting. However, conventional manufacturing processes have
limited capability to achieve complex geometries with high resolution. Moreover, mechanical stress
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caused by the traditional machining processes can result in grain pullout, strength degradation and
depolarization of the near-surface region, which finally leads to significant degradation in
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piezoelectric device performance [324]. AM is, therefore, an interesting alternative to fabricate

piezoelectric parts. Subannajui et al. [325] report a CuO semiconductor manufactured by FDM and
a sintering technique using PLA as polymeric support. The obtained 3D printed CuO semiconductor
presents an electric response to light and pressure.

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Whereas embedding electronics inside static 3D-printed structures to improve their overall
functionality has been already reported, achieving fully 3D-printed electronics able to modify the
3D structure in response to a particular stimulus is a current challenge. One of the few examples
was reported by Sundaram et al. [261] that presented a new approach for fabricating electronic
composites that can electronically fold at room temperature. For that purpose, they employed a
multimaterial additive manufacturing process based on iso-octyl acrylate oligomers partially UV

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crosslinked. The shape of the printed elements was electrically controlled providing a route to
transform planar electronics into nonplanar geometries.
Poly(vinylidene fluoride) (PVDF) is one of the best candidates to fabricate piezoelectric devices.

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Although its piezoelectric behavior is worse than some ceramics, PVDF present other advantages
including biocompatibility, toughness, flexibility, and processability. The electroactive β-phase of

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PVDF (with a planar zigzag form) is the cause of a dipole moment, which results in higher
piezoelectric and ferroelectric constants. The addition of barium-titanate NPs (BaTiO3 NPs) has

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shown to improve the ferro- and piezo-electric properties of PVDF without compromising its

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flexibility or strength. Therriault et al. [326] proposed a one-step method for print piezoelectric
components based on a solvent-assisted method using the PVDF-BaTiO3 NPs composite at room
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temperature. The authors employed a methodology based on a ball-milling using steel balls in order
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to increase the β-phase fraction in the PVDF composite via the activation BaTiO3 (BT), thus leading
to improved piezoelectric properties of the printed material. Figure 49 shows the proposed scheme
of the methodology which involves the ball-milling process and an image of the 3D printed
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piezoelectric device and its electric response to the finger-tap test. Tseng et al. [327] report a similar
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study which enhances the piezoelectric properties of PVDF composites but in this case via a corona
poling method. The piezoelectric activations of the PVDF occur when it is exposed to a high
electric field created and controlled by a charged needle which also deposits the material during the
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FDM process. The electric field promotes the alignment of PVDF molecules dipole moment,
increasing the β-phase percentage in the printed composite, and thus enhancing its piezoelectric
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characteristic.
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Fig. 49. Scheme of the proposed methodology for a one-step solvent-assisted method using PVDF-BT NPs
composite via ball-mining. Also, photographs of the resulting piezoelectric component and its response to

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finger-tap are showed [326], Copyright 2017 (Reproduced with permission from American Chemical
Society Publications).

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Other studies about 3D printed piezoelectric devices also involved the use of BT NPs. Zhou et al.

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[328] report a method for print those devices using a photocurable resin (SI500, EnvisionTec Inc.)
mixed with deagglomerated BT powder via Mask-Image-Projection-based Stereolithography (MIP-
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SL). The printed composite exhibited a piezoelectric constant and relative permittivity similar than
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commercial piezoelectric ceramics. This technique was, in turn, used to manufacture an ultrasonic
transducer with a focused piezoelectric element on one side, then, via an ultrasonic scan, it was
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successfully visualized the structure of a porcine eyeball using the ultrasonic transducer printed
using the MIP-SL technique.
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In addition to the above-reported polymers, another type of polymeric materials with piezoelectric
properties, known as piezoelectrets, have been equally explored. Piezoelectrets are polymeric films
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with electrically charged internal cavities, that result in a material with piezoelectric behavior.
These well-defined cavities can be precisely controlled via additive manufacturing methods. Pisani
et al. [329] perform a study in which ABS was chosen as a base structural material. They fabricated
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different voided structures via FDM, containing from 1 to 16 cavities with variable sizes and found
that samples with smaller cavities present decay of 11 % in the amplitude, temporal stability and
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pressure dependence of the piezoelectric effect, which is significantly lower than the other analyzed
samples.

7.4. AM of high strength materials

The most common way to enhance the mechanical properties of the 3D printed materials involves
the use of reinforced polymers, such as fiber reinforcement, either by means of carbon or glass
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fibers. Currently, some reinforced polymers are commercially available such as ABSplus-P430
developed by Stratasys, DuraForm PA (PA 12) Plastic, and DuraForm HST composite
commercialized by 3D Systems. In addition to the use of reinforced polymeric materials, [330–332]
the printing experimental parameters can be varied in order to enhance the mechanical properties of
the 3D printed materials. Finally, another alternative to improve the mechanical strength of a
particular material, involves the optimization of the design of the part to be printed varying, for

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instance, the device internal structure. According to this, several studies attempted to design
mimicking the structures frequently found in nature. As an example, Martin et al., [166] by using
3D magnetic-printing process, created an SLA-based additive manufacturing framework capable of

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printing dense ceramic/polymer composites in which the direction of the ceramic-reinforcing
particles could be finely tuned within each individual voxel of printed material. As it is shown in

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Figure 50, they were able to recreate a variety of reinforced architectures similar to those exhibited
by biological discontinuous fiber composite systems including the osteon structures within

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mammalian cortical bone, the layered nacreous shell of abalones and the cholesteric reinforced
dactyl club of the peacock mantis shrimp.
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Fig. 50. Bioinspired composites with microstructured. (a) Abalone shell exhibits a layered structure of calcite
prisms. This architecture is (b) simplified and (c) 3D magnetic printed. (d-f) The dactyl club of the peacock
mantis shrimp exhibits a cholesteric architecture. (g-i) The mammalian cortical bone exhibits concentric

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plywood structures of lamellae-reinforced osteons [166], Copyright 2015 (Reproduced with permission
from Springer Nature Switzerland AG).

Another interesting example is the so-called Bouligand or twisted plywood structure, a layered
rotated microstructure consisting of multiple lamellae of aligned collagen, elastin or chitin fibers
which progressively rotate with respect to their neighbors. Several studies evidenced that this

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structure is the responsible for the reinforcement of crack stop. Zhou et al. [167] create a
biomimetic structure based on rotated layers of MWCNT embedded in a photocurable resin printed
by electrically assisted MIP-SL technique. According to the mechanical tests performed to the

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obtained structures, the maximum load is significantly enhanced due to the fracture resistance of the
Bouligand pattern. Moreover, the authors observed that a smaller rotation angle leads to greater

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energy dissipation and impact resistance. Figure 51 shows the process proposed by Zhou et al for
the design of a Bouligand-type structure.

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Fig. 51. Schematic diagram of Homarus americanus claw microstructure consisting of a Bouligand-type
Chitin-protein fiber and schematic representation of the different alignment of carbon nanotubes by the
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rotation of the electrodes during the printing process, also surface optical microscopy images and SEM
images of fracture surface for different alignment of MWCNT are showed [167], Copyright 2017
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(Reproduced with permission from Wiley-VCH publishers).

Following a similar strategy, Börner et al. [333] created a biomimetic scaffold via FDM using
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inorganic-organic hybrid materials. The precise engineering of the interface used during the
manufacture of the bone scaffold enhanced both the elastic moduli and the toughness of the
biodegradable material composed by MgF2 NPs, a binding peptide, and a polymer conjugate,
namely MBC, in a continuous matrix of PCL. The insertion of biocompatible MgF2 NPs produced a
considerable increase in the mechanical properties of the material (mechanical tensile, compression
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and indentation properties, as well as Young´s modulus and toughness) without compromising their
degradation behavior, ion release kinetics and in-vitro cell viability. Figure 52 presents the
biomimetic structure of the material proposed by Börner et al. employed as a scaffold for bone
regeneration.

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Fig. 52. Schematic illustration of the bioinspired interface engineering and compatibilization of inorganic-
organic composite materials. Top: The scheme shows the hierarchical structure of bone and Bottom: MBC
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[333], Copyright 2017 (Reproduced with permission from Royal Society of Chemistry
Publishing).
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In addition to polymers bearing inorganic charges, thermosetting polymers with improved

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mechanical properties have been also explored for AM. An interesting example was reported by
Voit et al. [334]. They reported the fabrication of 3D printed thermosets objects involving a Diels-
Alder reversible thermoset (DART) process by using furan-maleimide polymers. The material could
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be decrosslinked and printed within a temperature range of 90 and 150 °C and recrosslinked at
lower temperatures. This process leads to high-toughness thermoplastics and increasing quality in
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part surface finish. Recently, Fang et al. [335] reported the use of resin epoxy mixed with carbon
fibers to generate thermosetting reinforced fibers for FDM printing. The devices presented superior
mechanical performance than 3D printed thermoplastic composites.

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7.5. Thermal and electrically conductive polymeric materials

Polymer for electronic purposes has experienced enormous advances during the past decade, aiming
to develop efficient, scalable, and rational processing techniques for the production of smaller,
better and faster electronic devices. The wide use of traditional silicon technology for almost all
electronic device fabrication represents a limitation due to their low flexibility and high cost.

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Polymer, on the contrary, can be easily processed and may with the advent in AM also be
incorporated into multifunctional devices. One of the first method used to develop printed
electronics at room temperature in one single step was proposed by Magdassi et al. [336]. The

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synthesized a self-sintering conductive ink based in AgNPs which are stabilized with a polymer
forming an adsorbing coated surface over the AgNPs. The sintering process was triggered due to the

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presence of a destabilized agent, which came into action only during drying of the printed pattern.
This caused the detachment of the anchoring groups of the stabilizing polymer enabling their

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coalescence and sintering.

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Lewis et al. [337] reported a new alternative approach that they called embedded additive
manufacturing (e-3DP), for fabricating strain sensors within extensible elastomeric matrices. Their
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approach involved the extrusion of a viscoelastic ink through a deposition nozzle directly into an
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elastomeric reservoir. As the nozzle moved inside the reservoir, void spaces are introduced that are
filled by a capping layer [338]. After printing, the reservoir and the filler fluid were co-cured to
form a monolithic part, while the embedded conductive ink remained fluid. Lewis et al. carried out
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mechanical and electrical tests of the e-3DP material, having a glove shape (Figure 53a) with
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embedded strain sensors and evidenced that the material remained functional after high strains
(Figure 53c) and possessed the ability to react at five different hand positions (Figure 53b).
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Fig. 53. (a) Gloves manufactured with the method e-3DP proposed by Lewis et al., (b) Resistance
reaction to five different hand positions, and (c) photographs which show their capacity to bear high strains
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[337], Copyright 2014 (Reproduced with permission from Wiley-VCH publishers).

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Recently, Vlassak et al. [339] fabricated electronic devices with sub-millimeter resolution, using
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viscoelastic UV-curable conductive hydrogels (poly(acrylamide), PAAm) mixed with an

elastomeric matrix (PDMS), both optically transparent). Similarly to Lewis et al, the authors
manufactured electric sensitive gloves exhibiting a particular electrical response depending on the
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hand position. Xia et al. [340] developed a method for creating electronic devices via SLS. For that
purpose, flexible TPU was mixed with CNTs and 3D printed. SLS provides a unique approach to
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construct a conductive segregated network of CNTs in the polymer matrix. This method produces
composites with electrical conduction seven orders of magnitude higher than conventional
injection-molded TPU/CNTs while maintaining excellent flexibility, conductivity, and durability
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after bending 1000 cycles. Finally, Areir et al. [341], published recently a study in which a protocol
for the rapid-fabrication of flexible energy storage capacitors via additive manufacturing
technology. The manufacturing of the devices was achieved via a mixture of activated carbon and
an electrolyte gel deposited over an optically transparent silicon substrate and the capacitors were
formed by multiple material layers deposited in one rapid and accurate event.
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AM allows producing electric circuits embedded in dielectric materials and opens the door to new
technologies. For example, Cummer et al. [342] designed, fabricated and tested a 3D metamaterial
using a highly conductive cooper-based polymeric filament. The resulting structures presented
dielectric permittivities 5 times higher than the commonly used parallel plates. Moreover, exploiting
the third dimension of the unit cell design space permitted to achieve enhanced electromagnetic
properties.

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In this rapidly expanding area, new methods for produce flexible and soft electronics are steadily
under development. One example was recently reported by Lewis et al. [343], which used hybrid
additive manufacturing procedure for fabricating electronic devices via a combination of direct ink

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writing of conductive ink into dielectric elastomeric materials with automated pick-and-place of
electronic components within a unique integrated manufacturing platform. As it is illustratively

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shown in Figure 54 this AM method presented the potential application in wearable electronics
with different electronic wearable devices, i.e. sense strain and pressure.

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Fig. 54. (a-c) Photographs of elbow stain sensor with a magnification of the LED response to strain, and
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(d-f) foot pressure sensor with the pressure map obtained during a step [343], Copyright 2017 (Reproduced
with permission from Wiley-VCH publishers).
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Some of these electrically conductive polymers also presented thermal response which permits the
generation of thermosensitive devices with specific shapes and structures. For example, Magdassi et
al. [230] developed heat-activated shape memory devices via additive manufacturing using SLA. In
their report, PCL was used as a base semicrystalline polymer and modified with methacrylate
groups covalently linked to the chain ends via a simple alcohol-isocyanate reaction. Figure 55
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shows both a vascular stent and a device for thermally active soft electronics printed with this
material in the temperature range of 25 °C to 70 °C.

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Fig. 55. Photographs of a 3D printed vascular stent exposed to different temperatures (from 25 °C to 70 °C)

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and a thermosensitive device designed for soft electronic applications [230], Copyright 2016 (Reproduced
with permission from Wiley-VCH publishers).

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Other studies, like the performed by Roehm and Madihally [344] or by He et al. [345], were
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focused on obtaining 3D printable thermosensitive and conductive polymers. He et al. mixed
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graphite flakes with polyamide 6 (PA6), maleic anhydride grafted poly(ethylene 1-octene) (POE-g-
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MAH) and PS were used to form fibers. Typically, the graphite flakes are naturally aligned in the
in-plane direction due to the conventional molding method, thus reducing the thermal conductivity.
He et al. used FDM to generate an orientation of the graphite flakes in the through-plane direction,
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increasing their thermal conductivity up to 5.5 W m-1 K-1.

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Tao et al. [346] reported an interesting material having anisotropic heat distribution. The material
was based on conductive poly(lactic acid) doped with graphene (G-PLA). Via a controlled mixture
of doped and undoped PLA, they were able to print materials with variable thermal conductivity
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and electrical resistivity. The temperature gradient was constructed by designing and printing items
with a quasi-continuously change of resistivity. Figure 56 shows a scheme of this innovative
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printing method as well as the thermal images of the material during voltage exposure. Depending
on the local thermal characteristics of the material it is possible to observe the anisotropic change of
the temperature gradient.
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Fig. 56. Schematic representation of the additive manufacturing method used to manufacture the anisotropic
thermally conductive materials. Thermal infrared images of the material after applying 10 V for 45 sec. (a)

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and (b) shows a graph indicating the temperature at a particular position on the sheet [346], Copyright 2017
(Reproduced with permission from Elsevier Science Ltd).

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7.6. Objects with tunable dielectric permittivity

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Dielectric materials with tunable permittivity can be used in a wide range of important scientific

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research areas and technology sectors, such as photonic crystals, electronics, and communications,
among others. AM using polymeric composites allows the fabrication of objects with complex
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geometries without the need of expensive tooling, thus making it an attractive method for creating
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dielectric materials. For example, Grant et al. [347] reported the fabrication of several composites
with variable loadings of BT microparticles embedded in a polymeric matrix of ABS. The
microwave dielectric properties of 3D-printed parts (which includes loadings up to 70 wt% of BT)
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were characterized using a 15 GHz dielectric resonator. The resulting parts presented dielectric
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microwave characteristics with relative permittivity in the range 2.6 – 8.7. Dielectric permittivities
were reproducible over the entire process and were in good agreement with those of bulk unprinted
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materials. Isakov et al. [145] fabricate meta-materials based on ABS polymeric matrix including
microparticles of different perovskite oxides such as BT, CaTiO3, and Ba0.64Sr0.36TiO3. The mixture
of these materials provided a tunable range of dielectric permittivity. In the reported study, 3D-print
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coupons were fabricated with spatially varying patterns which present different dielectric
permittivity leading to high dielectric anisotropy. Figure 57 shows the images of some printed parts
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with stripes arrangements of relatively low (ABS only) and high (dielectric ceramic/ABS
composite) permittivity materials, and also the spatial distribution of the resonant frequencies which
qualitatively represents the local dielectric permittivity of the meta-material. By designing the
structure of 3D-printed parts, the microwave operating frequency and magnitude of Mie-type
resonances could be manipulated to provide metamaterial-like characteristics.

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Fig. 57. (a) Some photographs 3D-printed parts with stripes arrangements of low and permittivity materials.
(b-c) Spatial distribution of the resonant frequencies, directly related to the local dielectric permittivity,

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showing anisotropic dielectric behavior [145], Copyright 2016 (Reproduced with permission from
Elsevier Science Ltd).

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7.7. Optical components
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Since the last years, the AM technique expands to new application fields like the manufacturing of
optic devices in research and industry. The most extended AM methods used for printing optical
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devices are FDM, multi-jet modeling (MJM), and SLA. However, independently of the method
employed a major still remaining problem is that the manufactured components exhibit a rough
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surface, which is incompatible with optic devices, and present a low transmission coefficient.
Several research groups investigated this aspect [348,349] and reduce this drawback using different
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mixtures of optically transparent thermoplastic polymers. Moreover, an optimal smooth surface can
be achieved by using robot-based polishing methods (Figure 58 a). Figures 58 b-c show the
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surface of the printed components before and after the polishing treatment, the surfaces were
obtained using white light interferometry.
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Fig. 58. (a) Photograph of the robot-based polishing treatment. The surfaces of the printed components (b)
before and (c) after treatment are depicted. Finally, (d-e) photographs of the optic device surfaces are showed

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[350], Copyright 2016 (Reproduced with permission from Walter de Gruyter GmbH).

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Recently, Hong and Liang [351] proposed a new precision additive freeform optics manufacturing
(AFOM) method which used an IR pulsed laser and PDMS as printing material. Thermally curable
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silicones have several advantages, like UV stability, non-yellowing, and high transmission. Pulsed
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IR laser radiation offered a distinct advantage in processing optical silicones, as the high peak
intensity achieved in the focal region allows for curing the material quickly reducing the effect
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produced by local heating in the material. To obtain a smooth finish of the optical component, a
liquid layer of PDMS was spread on the surface and then cured via laser exposure. A schematic
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representation of this process is shown in Figure 59 (Top), photographs of the resulting lenses are
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shown also in Figure 59 (Bottom).

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 Fig. 59. Top: Schematic representation of the AFOM method. Bottom: Photographs of the resulting 3D
printed lenses by using this technique [351], Copyright 2017 (Reproduced with permission from
Springer Nature Switzerland AG).

Another common use for additive manufacturing in the optics area is the fabrication of waveguides
or light-pipes. Heinrich et al. [350] demonstrated 3D printing of a light-pipe embedded in a
supporting material (Figure 60, Top). Another example was recently reported by Hu et al. [352], in

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which a highly conductive and mechanically strong microfiber was produced by using CNTs and
NFC. The solvent exchange was performed once the NFC-dispersed CNT solution was extruded

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into the coagulation bath of ethanol, leading to the formation of a stable gel fiber. A dry CNT–NFC
microfiber could be obtained after pulling the gel fiber out to dry under tension. During the process,

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all the building blocks were highly aligned along the fiber direction, enhancing the electric and light
conductivity, as well as the mechanical strength of the fibers. Figure 60 (Bottom) shows a scheme

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of the method used to obtain the CNT-NFC composite and the resulting microfiber used as a
conductive line for LED light.
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Fig. 60. Top: 3D printed device designed for been use as a light-pipe, in images b-d are possible to observe
the shape of the laser introduced in the pipe, the shape of the extracted laser and a top view of the pipe.
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Bottom: A schematic representation of the method proposed to form CNT-NFC microfibers and photography
of the resulting microfiber as light conducting line [350], Copyright 2016 (Reproduced with permission
from Walter de Gruyter GmbH), and [352], Copyright 2017 (Reproduced with permission from
Wiley-VCH publishers).

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7.8. Magnetic 3D printed objects

Additive manufacturing technology has been applied to develop a new type of magneto-responsive
materials based on polymeric matrixes, commonly, magnetic microparticles (micro-magnets)
incorporated into the material thus allowing them to acquire magnetical properties. Polymer bonded

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magnets offer application opportunities in the sensor and electric drive technology. Via the
modification of some mechanical properties of the matrix with hard magnetic filler particles, it has

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been possible, for example, to manufacture polymer bonded permanent magnets. Huber et al. [353]
developed a new method to fabricate geometrically complex structures based on polymeric matrices

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bonded with isotropic hard magnets using AM. The NdFeB powder, included inside polyamide 11
(PA11) was mechanically and magnetically characterized. The magnetic test performance of the
materials obtained by using different fabrication methods, i.e. hysteresis curves of 3D printed and

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injection molded parts were analyzed and compared. The authors upgraded the 3D printer to a 3D

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magnetic flux density measurement system that allowed a measurement resolution of 0.05 mm
along the z-axis, permitting to print polymer bonded magnetic systems with the freedom of having a
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specific complex shape with locally tailored magnetic properties.
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Recently, Bollig et al. [354] fabricated transformer cores using FDM methods optimizing several
factors that largely determine the efficiency of a transformer, including the core material, core
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geometry, and the windings. The main goal of the core material is, therefore, to allow high magnetic
permeability in order to maximize conversion output as well as to present low magnetic coercivity.
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As a result, the hysteresis losses will be minimized displaying high electrical resistivity in order to
minimize eddy current losses. According to the authors, a donut-like toroidal geometry theoretically
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leads produced the most efficient transformer. Bollig et al. fabricated a toroidal core geometry by
FDM using a commercially available composite of PLA and a particulate phase of 40 wt% iron.
They compared the performance of identically-shaped printed and standard cores and investigated
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how the internal geometry (fill factor and fill pattern) of the printed cores affects the core
performance. According to their findings, while the fill pattern does not appreciably change the core
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performance, an increase of the filling percentage improved the magnetic performance.

Li et al. [355] also developed a novel method for the fabrication 3D printed parts based on
elastomers with magnetorheological characteristics. As schematically shown in Figure 61 the
magnetorheological hybrid elastomer comprised two types of materials. On the one hand, an
elastomer resin mixed with a UV-curable silicone sealant was used as a polymeric matrix. On the

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second hand, a magnetorheological fluid carrier (silicone grease) mixed with carbonyl iron powder
at a concentration of 30 % v/v. As observed in Figure 61, two cartridges with the
magnetorheological fluid and the elastomer resin respectively were prepared and deposited layer-
by-layer in order to form the desired architecture. Finally, UV curing was applied upon each layer
deposition to solidify the resin. The study performed by Li et al. demonstrated that the proposed
additive manufacturing technique was feasible for fabrication of magnetorheological elastomers

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with controlled microstructures and proposed their use as a tunable spring-damper element. The
compressive stiffness and viscous damping coefficient, presented a clear dependency on the
external magnetic field applied, showing a constant increase in the case of the compressive stiffness

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and a plateau stabilization in the case of the viscous damping coefficient.

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Fig. 61. A schematic diagram which explains a method developed for fabricating 3D printed parts with
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magnetorheological properties. Top: Three printing components: (1) MR fluid cartridge, (2) elastomer resin
cartridge, (3) UV curing unit. Middle: Photographs of some resulting printed parts, (a) pure elastomer, (b)
strip pattern, and (c) dot pattern. Bottom: Compressive stiffness and viscous damping coefficient of the 3D
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printed parts at different magnetic flux densities [355], Copyright 2017 (Reproduced with permission
from Elsevier Science Ltd).

7.9. Microfluidic devices

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Fluid flows at smaller dimensions (micro- or nano-sizes) exhibits unique behaviors not replicable at
macroscopic scales. Microfluidic devices (MFDs) have revolutionizing several research fields in the
last years [356]. Most of the MFDs fabrication techniques are largely constrained by the complexity
of real 3D structures, which limit researchers ability to produce fluid flow paths with nonstandard
cross sections with different sizes and directions. In this sense, AM technology brought new
possibilities and alternative routes to overcome this limitation. Actually, several research studies

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have been focused, for example, in improving the printing resolution that would allow decreasing,
for instance, the channel sizes in microfluidic devices. In a recent review, Chong et al. [357]
provided a clear view of this topic. The field of MFDs fabrication has been dominated in the last

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decade by molding approaches based on the use of PDMS and thermoplastics. This methodology
does not permit a high control of the geometrical structure of the final device. On the one hand,

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particularly, PDMS molding is a largely manual process, being hard to fully automate. On the other
hand, devices molded in thermoplastics enable higher throughput but do not necessarily improve the

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manufacturing process. The inclusion of AM technologies has recently attracted attention as an

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alternative to fabricate microfluidic systems due to its automated 3D fabrication, reduced costs, and
fast-improving resolution. In this section, we aim is to highlight some recently performed efforts in
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3D-printing of MFDs and to point out some of the most interesting applications.
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7.9.1. Microvalves
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Microfluidic systems integrating several functionalities, such as cell/tissue incubation controls,

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enzymatic processing, and biochemical analysis, are generally computer-controlled and the flow is
finelly controlled by micropumps and microvalves. Micropumps and microvalves can control
process in miniature biomedical fluid samples down to picoliter and single-cell quantities. These
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devices have already revolutionized the fields such as genome sequencing, proteomics, cell biology,
and medical diagnostics by enabling inexpensive, customizable fluid-handling automation at the
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micrometric scale [358].

For example, Au and co-workers [359] described the fabrication of diaphragm valves that can be
3D-printed by SLA technique. The valve in operation is shown in Figure 62. The diaphragm is a
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100 m thick plastic membrane with a diameter of 10 mm printed inside a chamber and that can be
pneumatically deflected by pressurization of the control valve, thus allowing to open or close the
fluid flow. By mixing, two or more of these valves is possible to create intriguing circuits with
controllable fluid flows at the micro- or nano-liter range. Another interesting example was reported
by Nordin et al. [360] that proposed a slight variation of SLA (DLP-SLA) and used high-density
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materials (PEGDA258) with excellent water stability to fabricate the parts (no-swelling or
mechanical strength degradation). These variations permitted to fabricate smaller parts with
complex structures. For example, Nordin and co-workers combined two of these valves with a
valve-like displacement chamber in order to create a compact 3D printed micropump.

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Fig. 62. Top-left: Basic valve design. Schematical diagram of a valve unit in its open and closed states, and
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micrographs in these two states. Bottom-left: Photographs of a dye-filled switch in three different actuation
states. Right: Valve control of the 3D-printed cell perfusion system which shows the circuit diagram and a
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photograph of a dye-filled switch connected to a cell culture chamber with fluorescent micrographs and plots
of indicated regions in the inset [359], Copyright 2015 (Reproduced with permission from Elsevier
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Science Ltd).

Recently, Walczak and co-workers [361] also reported the fabrication of microvalves using AM
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processes, particularly with MJP, but with a novel design of two types check microvalves based on
deflecting or hinge-fixed micro flap with 200 µm and 300 µm thickness. Opening/closing
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characteristics of the microvalves for forwarding and backward pressures were determined,
checking their proper operation. Figure 63 shows the diagrams of the two tested valves, the
corresponding simulations, and photographs of their deflection performance. The results
demonstrated a good correlation between simulated and experimental results of flap deflections
according to applied pressure.

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Fig. 63. Top: Cross-sections of tested check microvalves. Middle: Visualization of the simulation results
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(fluid velocity and von Mises stress magnitudes). Bottom: Photographs of the microvalve flap deflection for
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backward/forward pressures. Reproduced with permission from reference [361], Copyright 2017
(Reproduced with permission from IOP Publishing).
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Other studies used the innovations in MFDs fabricated via AM technologies to fabricate
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microvalves including a cellular component in its structure. Long et al. [362], for instance,
employed polyvinylpyrrolidone (PVP, water-soluble polymer), commonly used for cell separation
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purposes to mitigate the sedimentation effects in the microvalve-based dispensing system. They
described the microvalve bioprinting output in terms of printing resolution and printing consistency
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and determined the minimum cellular density required to achieve a high dispensing efficiency of >
95 %.
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7.9.2. Bioanalytic purposes

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Since the first reports in micro total analysis system (µTAS), the advances in microfabrication have
promoted a revolution in analytical and bioanalytical studies in many different areas. Examples of
these applications include the elaboration of fluidic reaction ware devices for chemical syntheses
[363], continuous flow micromixers for glucose detection using an SLA 3D printer [364], printing
of microfluidic chips for cell culture using a 3D sugar printer [365], just to name a few.
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In this context, Verpoorte et al. [366] are pioneers in the use of FDM for bioanalytical research.
They started analyzing the printing parameters used in FDM processes i.e. resolution, surface
roughness, leakage, transparency, material deformation, and the possibilities for integration of other
materials. Then, the autofluorescence, solvent compatibility, and biocompatibility of 12
representative FDM materials were tested and evaluated. The authors conclude that FDM is an
appropriate printing method for a wide range of microfluidic applications.

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Coltro et al. [367] described the use of AM technologies (FDM method using ABS) to fabricate
microfluidic devices for direct spray ionization mass spectrometry (MS) assisted by the paper tip.
Paper tips were added to the printed channel to facilitate the spray formation via the application of 4

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kV at the sample reservoir containing 0.1 % formic acid prepared in methanol. The authors
validated the method for qualitative analysis of ballpoint pen inks, caffeine, xylose, and lysozyme.

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The same research group also described the fabrication of integrated microfluidic platforms
containing microchannels and embedded sensing electrodes for capacitively coupled contactless

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conductivity detection (C4D) [368]. The sensing electrodes were printed with PLA doped with

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carbon nanotubes and then integrated on ABS printed microfluidic channels.
Finally, also a particularly interesting example of 3D printed structures for bioanalytic purposes was
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reported by Ozcan et al. [369]. This group developed a personalized food allergen testing platform,
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termed iTube depicted in Figure 64. This device runs on a cellphone camera, which imaged and
automatically carried out colorimetric assays for sensitive and specific detection of allergens in food
samples. The test and control tubes were inserted from the side of the device and were vertically
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illuminated by two separate light-emitting-diodes. The illumination light was absorbed by the
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allergen assay, inducing changes in the intensity of the acquired images. These transmission images
of the sample and control tubes could be digitally processed within 1 sec using a smart application
running on the same cellphone for detection and quantification of allergen contamination in food
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products.
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Fig. 64. A picture of the iTube platform, utilizing colorimetric assays and a smartphone-based digital reader,

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is shown [369], Copyright 2013 (Reproduced with permission from Royal Society of Chemistry
Publishing).

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7.9.3. Lab-on-a-chip

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Lab-on-a-chip (LOC) technologies have been rapidly implemented in many fields such as medicine,
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chemistry, and biotechnologies permitting to transform bulky and costly laboratory equipment onto
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small, user-friendly, easily replicable chips [356].

For instance, Gong et al. [360] used an inexpensive custom resin formulation PEGDA258, Sudan I
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and Irgacure 819, to fabricate robust membrane valves. To improve the durability the resin
composition was modified by adding a thermal initiator (Azobisisobutyronitrile, AIBN). Thus, a
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post-printing 30 minutes oven cured further the material and lead to a greater degree of crosslinking
and improved the mechanical roughness of the part. As shown in Figure 65 a, when pressure is
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applied to the control chamber, the membrane deflects downward and seals the fluid channels. On
the opposite upon removing the pressure, the valve opened and fluid could flow between the two
channels at the bottom of the fluid chamber. The central circular region in which the membrane
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contacts the bottom of the fluid chamber can be clearly seen in the same figure. They later
developed a more complex device i.e. 3-to-2 multiplexer with integrated pump and shown that it
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can also be used as a mixer.

Urrios et al. [370] used of a biocompatible transparent resin composed by PEGDA250 with small
amounts of photoinitiator (Irgacure 819) for the fabrication of bio-microfluidic devices that were
water-impermeable biocompatible, transparent and cheap. In Figure 65 b the DLP-SLA setup used
for print the MFDs is depicted. The 3D-printed devices were highly transparent and cells could be

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cultured on PEGDA250. This biocompatible SLA resin and printing process solves some of the main
drawbacks of 3D-printed microfluidic devices: biocompatibility and transparency, thus enabling the
fabrication of microfluidic biomedical devices.

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Fig. 65. (a) A CAD design of the 3D printed device, also schemes and photographs of the valve in the open
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and closed states are depicted. (b) DLP-SLA setup used for print transparent bio-microfluidic devices.
Photographs of the devices printed using this technology [360] and [370], Copyright 2016 (Reproduced
with permission from Royal Society of Chemistry Publishing).
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7.10. 3D printed microfluidic reactors for catalysis

As has been mentioned above, microfluidic devices have found applications in a wide range of
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areas including biosensing, analytical chemistry or combinatorial synthesis [371–373]. In addition

to these, microfluidic devices have been also employed for catalytic purposes, particularly for
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catalysis microfluidic reactors. These devices present several advantages in comparison to larger
scale reactions, which includes the reduction of the required volumes and, therefore, the reaction
wastes, improving the kinetics of diffusion-limited reactions or increasing temperature control
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[374].
These advantages are particularly interesting for enzymatic catalysis which is a topic that is
receiving considerable attention during the decade [375–377]. For instance, temperature control is a
critical parameter when enzymes are used in a catalytic reaction, due to their unique secondary or
tertiary structure, that may be altered upon large temperature changes, and therefore, it can shift the
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enzyme selectiveness with an appropriate substrate [378,379]. As a result, reactions catalyzed by
enzymes are typically carried out using mild reaction conditions using water as an environmentally
friendly solvent [380].
Using enzymes, Sanz de Leon et al. [381] reported the fabrication of a microfluidic lab-on-a-chip
device in which substrate surface immobilization was carried out using host-guest interactions of an
adamantane modified enzyme and a cyclodextrin (CD) modified surface (Figure 66). The authors

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employed these type of immobilizations because, in comparison to other enzyme immobilization
strategies, it becomes in an interesting alternative since the interactions formed are strong enough to
prevent enzyme release and they can be displaced and re-constructed by using the appropriate

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molecules.
The SLA printed microfluidic device was functionalized using the BF approach, allowing the

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preparation of microporous surfaces in which the cavities were decorated with CD moieties. More
precisely, the porous functional reservoir was obtained by casting a mixture of UHMWPE and a

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poly(styrene-co-cyclodextrin) (P(S-co-SCD)) in a moist environment. The catalytic activity of these
microfluidic devices surfaces was tested and remained stable during five reaction cycles.
Interestingly the microfluidic device employed for the catalytic reaction could be regenerated thus
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leaving the surface prepared for further immobilization processes.
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ABTS + H2O2
a) ABTS*
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HRP
Porous film CD
Microscope slide
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Inlet Outlet

ABTS ABTS*+
Green radical cation
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l = 405 nm

Spectrofluorometer

b) c) d) 2,0 HRP
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HRP-Ada
OD (405 nm)

1,5 Control

1,0

0,5
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C: Reaction R: Catalytic 0,0

0 50 100 150 200
control reaction Time (s)

Fig. 66. a) Scheme of the oxidation of ABTS by interaction with HRP and H2O2, b) control of the reaction
and c) green color observed as a result of the oxidation of ABTS, d) activity of the soluble HRP, HRP-Ada
and its control (OD stands for Optical Density) [381], Copyright 2017 (Reproduced with permission
from American Chemical Society Publications).
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Other groups have also employed microfluidic devices for continuous-flow organic chemistry. For
instance, Dragone et al. [382] reported the fabrication of robust and inexpensive 3D-printed reactors.
They connected the parts using standard fittings resulting in complex, custom-made flow systems. This
methodology demonstrates the versatility and convenience of using 3D-printed reactors for the synthesis
of organic compounds, using flow techniques with an in-line ATR-IR flow chamber used to monitor the
reactions in real time. As a proof of concept, they reported the use of two types of organic reactions,

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imine syntheses, and imine reductions, to show how different reactor configurations and substrates give
different products [382].

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7.11. Mechanochromic Materials

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Several natural processes which occur in living organisms rely on mechanochemical transduction,
i.e. cascades of events that translate macroscopic forces (cell stretch, for example) into chemical
reactions (inflammation processes). In contrast, few mechanochemical materials, which could

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respond in a useful and controlled manner to the exposure of mechanical stress, have been reported
so far. N
Recent advances in polymer mechanochemistry have been complemented with additive
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manufacturing systems enabling the transformation of macroscopic mechanical forces into specific
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chemical reactivity resulting in overall material color changes [383]. Peterson et al. [384,385]
described the preparation of mechanochromic 3D printed parts using FDM methodology. In their
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studies, mixtures of spiropyran (SP) and PCL polymers were employed to construct filament,
employed in turn to print both single or multicomponent tensile specimens. SP reacts upon
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stretching, i.e. the labile spiro C-O bond breaks, and the colorless SP compound is mechanically
activated into a colorful merocyanine (MC) (Figure 67).
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Fig. 67. Tensile test specimen in their initial and post elongation states showing the mechanochromism of the

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central region, and an elongated specimen showing the encased filament [384], Copyright 2015
(Reproduced with permission from American Chemical Society Publications).
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8. Conclusions and remarks

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The development of a wide variety of additive manufacturing (AM) technologies offers nowadays
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versatile platforms for tailor-made fabrication of fully-customized products in a decentralized and

cost-effective fashion. Besides its initial use limited as a tool for rapid prototyping or eventually for
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small-scale production of customized items, AM has become an interesting methodology to

fabricate components with unusual shapes in a wide variety of applications ranging from
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architecture to biomedicine.
This review provided a general and introductory overview of the most extensively employed
methodologies to fabricate AM parts using polymers as base materials. Thus, filaments, liquid
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resins or powders have been used in FMD, SLA, and SLS respectively. In addition to the extensive
evolution of the printing capabilities (resolution of the technologies, size of the printed parts, etc.)
an important focus during the last decade has been the design of novel materials adjusted for each
AM technology and adapted for a targeted application. Polymers are excellent candidates to fulfill
many different requirements. Polymers can be synthesized by many different polymerization
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approaches and can have different functional groups. Polymers can be easily be processed and
combined with micro and nano-charges that confer unique properties, i.e. increase the mechanical
properties, improve the thermal conductivity or provide an electrical response. Moreover,
biocompatible/biodegradable polymers, elastic polymers or thermoplastic elastomers are currently
being employed as materials for different AM technologies. Finally, smart polymeric materials are
at the origin of 4D printing. Shape memory polymers, hydrogels or active polymer based

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composites are currently a the center of multiple studies in which static 3D printed part are able to
change their shape thus producing novel geometries.
A concise overview of the most important areas of application including recent illustrative

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examples of novel polymeric materials developed for AM as well as their applications has been also
thoroughly described. The large amount of work and the wide range of applications of 3D printed

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polymeric parts renders a succinct overview of this topic difficult. A great effort has been carried
out to organize and classify the most relevant applications and to provide illustrations of select

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examples from recent research to offer a clear vision of the state of the art.

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Future and novel developments in terms of equipment and materials will offer new opportunities for
the use of AM printed materials for different applications of functional technical parts, medical
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parts or micro-fabrication. A final challenge that also is subject of ongoing work relates to the
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translation of AM methods to production technologies.

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Acknowledgments
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The authors acknowledge financial support given by FONDECYT Grant N° 1170209. M.A. Sarabia
acknowledges the financial support given by CONICYT through the doctoral program Scholarship
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Grant. J. Rodriguez-Hernandez acknowledges financial support from the Spanish National Science
Foundation (CSIC) and the Ministerio de Economia y Competitividad (MINECO) (Project
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MAT2016-78437-R, FONDOS FEDER). Finally, this study was funded by VRAC Grant Number
L216-04 of Universidad Tecnológica Metropolitana.
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