Emrah Celik

Additive Manufacturing
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Emrah Celik

Additive
Manufacturing

Science and Technology

Author
Prof. Emrah Celik
Department of Mechanical and Aerospace Engineering
University of Miami
1251 Memorial Drive
Coral Gables 33146
USA
[email protected]

ISBN 978-1-5015-1877-5
e-ISBN (PDF) 978-1-5015-1878-2
e-ISBN (EPUB) 978-1-5015-1098-4

Library of Congress Control Number: 2020939278

Bibliographic information published by the Deutsche Nationalbibliothek

The Deutsche Nationalbibliothek lists this publication in the Deutsche Nationalbibliografie;
detailed bibliographic data are available on the Internet at http://dnb.dnb.de.

© 2020 Walter de Gruyter GmbH, Berlin/Boston

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To mom, Adile
Preface
Additive manufacturing (also known as 3D printing) is a disruptive technology to
manufacture different types of engineering materials layer by layer, in compliance
with a previously designed and tessellated CAD model. Additive manufacturing of-
fers cheaper and mobile manufacturing due to the elimination of large stocks of
raw materials, semimanufactured parts, labor costs, and allowance to mobilize the
printer to the desired location. Besides, due to its difference from conventional
methods, it yields zero production wastes or scraps, thanks to its additive nature,
rather than subtracting material. Today, 3D printing is pacing toward being a facile,
homemade manufacturing method, owing to the rapid spreading of 3D printers all
around the world.
Despite its unique capabilities and advantages over traditional manufacturing,
additive manufacturing techniques still possess significant deficiencies such as fab-
rication speed, limited number of materials, high cost, weak interface and fatigue
performance, and the low reproducibility of material properties. These issues that
need to be resolved completely or minimized are extensively described throughout
the book and possible remedies are pointed out. In addition to its benefits and limi-
tations, future trends of additive manufacturing according to the author’s perspec-
tive and how it will further transform our life will be discussed in this book.
The goal of this book is to provide students, researchers, as well as practicing en-
gineers who would like to gain deeper knowledge on current additive manufacturing
technologies. This book extensively investigates the theoretical concepts as well as
practical considerations of various additive manufacturing methodologies. In this re-
gard, it uniquely combines the underlying science and the state-of-the-art technology
aiming to help the readers understand the fundamental concepts and inform them
about the latest developments in each manufacturing categories.
The structure of this book was organized in such a way that this could be used as
an educational tool for an individual as well as a textbook for additive manufacturing
curriculum. The first chapter of this book provides an introduction to the concept of
additive manufacturing and briefly describes the seven major categories of this tech-
nology. This chapter also describes the benefits of additive manufacturing as well as
the limitations forbidding it from replacing the conventional manufacturing technol-
ogies. Brief history of the additive manufacturing since its inception is also described
here to show the readers the development pace and the trends to predict the future of
additive manufacturing.
The remainder of the chapters are mainly categorized by the type of materi-
als on which additive manufacturing technologies are applied. Being the most
commonly used material type, the book starts with polymers in Chapter 2, where
additive manufacturing of thermoplastic, thermosetting, and elastomeric poly-
mers are described separately. Similarly, Chapters 3, 4, and 5 investigate addi-
tive manufacturing of other engineering materials: polymer composites, metals,

https://doi.org/10.1515/9781501518782-202
VIII Preface

and ceramics, respectively. The performance of each type of material system is com-
pared and contrasted against each other by considering different aspects of material
performance including manufacturability, cost, mechanical performance, and thermal
resistance. Existing material repository for each section as well as the utilized manu-
facturing technology are described extensively in these chapters to educate the reader
on why and how certain material selection is preferred for various applications.
Chapter 6 investigates the use of additive manufacturing on tissue engineering
applications. A specialized version of additive manufacturing known as bioprinting
is described in detail. Its transformative potential and its applicability on various
tissues/organs and current success stories are explored. The effect of bioprinting
feedstock materials (bioink) on bioprinting quality is evaluated and the currently
used bioink materials are described. In addition to the benefits and the current ad-
vancements of bioprinting, limitations and the great challenges that are ahead of
bioprinting field are evaluated in detail.
The true benefit of additive manufacturing lies behind the manufacturing of
complex structures that have enhanced performance and/or reduced weight over
the unoptimized legacy parts. In other words, if topology is optimized in a way to
improve the components that work better than the original design, additive
manufacturing can be used to fabricate these concept designs no matter how com-
plex they are. Chapter 7 describes the topology optimization concepts, their bene-
fits, and integration into additive manufacturing world.
Chapter 8 discusses the advanced concepts in additive manufacturing field,
which has significant potential to transform manufacturing technologies in gen-
eral. These concepts involve additive manufacturing of nonconventional materials
such as thermoelectric systems. Thermoelectric materials convert heat into elec-
tricity; therefore, additive manufacturing of these systems will make a great im-
pact in our daily life, considering the tremendous amount of waste heat. Hybrid
manufacturing that uniquely combines multiple materials or multimanufacturing
systems is also explored in this chapter. Lastly, additive manufacturing of smart
manufacturing is described in Chapter 8 using 4D printing technology. Smart ma-
terial manufacturing using 4D printing is described as the time-dependent trans-
formation of additively manufactured structures in a predicted way. The book
ends with the unique technology to pave the way for the development of future
concepts such as adding another dimension/functionality on additively manufac-
tured systems.
Additive manufacturing is a technology transforming the design concept on
manufacturing process. The impact of this technology will be further enhanced in
near future as the existing technologies are advanced, manufacturing costs are re-
duced, and novel concepts are integrated on it such as smart manufacturing and
artificial intelligence on material development and processing steps. This book in-
volves the theoretical concepts, latest technologies, and the future trends of addi-
tive manufacturing. Therefore, it is hoped that this book will help the students or
 Preface IX

individuals who want to contribute to the additive manufacturing field whether as

a user or developer, both of whom are much needed elements to continue the ad-
vancement of this technology in the future.
Contents
Preface VII

1 Introduction 1
1.1 A disruptive technology, additive manufacturing 1
1.2 Advantages of AM over traditional manufacturing 2
1.2.1 Greater design ability 3
1.2.2 No tooling 3
1.2.3 On-demand manufacturing 4
1.2.4 Rapid prototyping 4
1.2.5 Customization 4
1.2.6 Minimal material waste 4
1.2.7 Low cost for small number of parts 4
1.3 Classification of AM technologies 5
1.3.1 Vat polymerization 5
1.3.1.1 Stereolithography 7
1.3.1.2 Digital light processing 7
1.3.1.3 Continuous liquid interface production 7
1.3.1.4 Volumetric Vat manufacturing 8
1.3.2 Material jetting 9
1.3.3 Binder jetting 10
1.3.4 Material extrusion 11
1.3.4.1 Fused filament fabrication 11
1.3.4.2 Paste extrusion 12
1.3.5 Powder bed fusion 14
1.3.6 Directed energy deposition 15
1.3.7 Sheet lamination 16
1.4 Timeline/history of AM 19

2 Additive manufacturing of polymers 22

2.1 Classification of polymers 22
2.1.1 Thermoplastics 23
2.1.2 Thermosets 23
2.1.3 Elastomers 23
2.2 Selection of polymers for AM 24
2.3 AM of thermoplastic polymers 25
2.4 AM of thermosets 27
2.4.1 AM of photosensitive thermosets 27
2.4.2 AM of heat-sensitive thermosets 29
2.5 AM of elastomers 29
XII Contents

3 Additive manufacturing of polymer composites 31

3.1 Additive manufacturing of powder-doped polymer
composites 31
3.2 Additive manufacturing of short fiber-doped composites 34
3.2.1 Short fiber reinforced thermoplastic composites 35
3.2.2 Short fiber reinforced thermoset composites 35
3.3 Prediction of mechanical properties of short fiber reinforced
composites 38
3.4 Alignment of short fibers within additively manufactured
composites 40
3.5 Additive manufacturing of continuous fiber reinforced
composites 41
3.6 Mechanical performance comparison of additively manufactured
polymer composites 45

4 Additive manufacturing of metals 47

4.1 Feedstock material fabrication for powder bed fusion 48
4.2 Feedstock materials used in metal AM 51
4.2.1 Titanium and titanium alloys 53
4.2.2 Aluminum alloys 53
4.2.3 Other metals 54
4.3 Design considerations in metal AM 54
4.3.1 Void formation 54
4.3.2 Residual thermal stresses 55
4.3.3 Surface roughness 55
4.3.4 Postprocessing 55
4.3.4.1 Stress relief 56
4.3.4.2 Heat treatment 56
4.3.4.3 Hot isostatic pressing 56
4.3.4.4 Machining and surface treatments 56
4.4 Mechanical properties of additively manufactured metals 57

5 Additive manufacturing of ceramics 61

5.1 Powder-based ceramic additive manufacturing 62
5.1.1 Binder jetting of ceramics 63
5.1.2 Powder bed fusion of ceramics 64
5.2 Slurry-based ceramic additive manufacturing 66
5.2.1 Vat polymerization of ceramics 66
5.2.2 Direct writing of ceramics 67
5.3 Bulk solid-based technologies 69
5.3.1 Sheet lamination 70
 Contents XIII

5.3.2 Fused filament fabrication 71

5.4 Additive manufacturing of polymer-derived ceramics 73
5.5 Mechanical properties of AM ceramics 74

6 Bioprinting 78
6.1 Bioprinting methods 78
6.2 Bioink types used in bioprinting 81
6.3 Bioprinting applications 82
6.3.1 Bioprinting of blood vessels 84
6.3.2 Skin bioprinting 85
6.3.3 Cartilage printing 85
6.3.4 Cardiac tissue bioprinting 87
6.3.5 Kidney tissue bioprinting 88
6.4 Challenges and limitations of bioprinting functional organs 88
6.5 Bioprinting in cancer research 89

7 Topology optimization 92
7.1 Topology optimization for additive manufacturing 93
7.2 Topology optimization methods 96
7.3 Solution of topology optimization problem using ANSYS finite
element software 99

8 Advanced concepts in additive manufacturing 101

8.1 Hybrid additive manufacturing 101
8.1.1 Additive/subtractive hybrid manufacturing 101
8.1.2 Additive/additive hybrid manufacturing 102
8.1.3 Hybrid additive manufacturing/scaffolding technologies 104
8.2 Additive manufacturing of thermoelectric materials 106
8.3 Four-dimensional printing with smart materials 113
8.3.1 Four-dimensional printing materials 114
8.3.1.1 Four-dimensional-printed hydrogels 114
8.3.1.2 Shape-memory polymers 115
8.3.1.3 Elastomer actuators 117
8.3.2 Applications of 4D-printed structures 117

References 121

Index 135
1 Introduction

1.1 A disruptive technology, additive manufacturing

Additive manufacturing (AM) is a revolutionary technology, which is based upon

building three-dimensional (3D) objects by adding successive layers of material.
Different types of materials can be fabricated with this technology, including poly-
mers, metals, ceramics, composites, or biological materials. Since AM allows fabri-
cation of parts in complex geometries without the use of any tooling, early use of
AM focused on visualization models in the form of rapid prototyping. Due to the
significant improvement in material library and the quality of the fabricated parts,
AM has recently been used to fabricate end products in aerospace, dentistry, medi-
cal implantation, automotive, and even fashion design.

Additive Manufacturing

CAM Tool path

STL File 3D Printer Altered Part Quality
Software Commands File
CAD Control &
Model Inspection

CAM Tool path

CNC Machine Altered Part
Software Commands file
Subtractive Manufacturing

Figure 1.1: Additive versus subtractive manufacturing. Figure was reprinted from [1].

Unlike traditional subtractive manufacturing, AM is the process of joining materials

to make objects layer by layer. In the past century, subtractive manufacturing has
made a great impact on fabrication and prototyping since it was first introduced.
Now, manufacturing industry is on the verge of a new revolution due to the new de-
sign and fabrication opportunities offered by AM. Figure 1.1 shows the major differ-
ences between the subtractive manufacturing and AM technologies. Subtractive
manufacturing, as its name implies, involves removing sections from a material by
machining or cutting it away. It can be performed manually or via computer numeri-
cal control (CNC) machining. AM is also a computer-controlled process but unlike
subtractive manufacturing, it adds successive layers of material to create a 3D object.
Traditional subtractive manufacturing, in general, has benefits of cost per part
(especially for a high-scale manufacturing), speed, component strength, and

https://doi.org/10.1515/9781501518782-001
2 1 Introduction

material selection. New AM technologies however quickly close the gaps in these
areas and bring up a new design space involving on-demand fabrication, creation,
customization, and complexity redefining current manufacturing.
As it will be described in the next section, there are many AM technologies devel-
oped for different manufacturing purposes. Despite their differences, all AM methods
share common processing steps as illustrated in Figure 1.2. The AM process starts with
the design of the component using a 3D computer-aided design (CAD) modeling soft-
ware. The model can also be constructed via reverse engineering using a 3D scanner
or photography. Once the computer model is created, it is transferred into a slicing
software where 3D model is digitally converted into serial 2D sections format. The AM
equipment then reads this data and lays down successive layers of liquid, powder,
sheet material, or other forms layer-by-layer to fabricate a 3D object. Minimum layer
thickness dictates the manufacturing quality and it depends on the machine and AM
process type selected. Finally, additively manufactured object is removed from the AM
instrument and, if desired, postprocessing such as cleaning, sanding, coating, paint-
ing, compacting, or heat treatment is applied to enhance component performance or
esthetic appearance. Postprocessing may involve the use of other machines and tools.

Step 2. Slicing into AM format

Step 3. Material deposition

Step 1. CAD modeling

Additive
manufacturing

Step 4. Postprocessing

Figure 1.2: Main processing steps of additive manufacturing: CAD modeling, AM format slicing,
material deposition, and postprocessing.

1.2 Advantages of AM over traditional manufacturing

AM finds unique applications in vast variety of fields including electronics, aero-

space, automotive engineering, and even fashion design as shown in Figure 1.3.
This is due to the advantages of AM over traditional manufacturing technologies.
These benefits are summarized as follows:
 1.2 Advantages of AM over traditional manufacturing 3

Electronics

Transportation

Biomedicine
Design
Fashion
Architecture

Figure 1.3: Various applications of additive manufacturing. Concrete printing (architecture) [2],
transportation, [3], and fashion [4] application images were reprinted with permission.

1.2.1 Greater design ability

AM systems allow fabrication of moving parts (hinges, chains, etc.) in a single print
process, and complex structures are unachievable with the traditional manufactur-
ing. In addition, due to the flexibility of design, traditional constraints of
manufacturing are eliminated and number of parts in the design can be reduced.
Redesign process can be done digitally on the CAD model and the new part can be
fabricated in a short period of time. Since AM is a user-friendly technology and not
labor intensive, the designers are not limited to only engineers but variety of mak-
ers such as architects, artists, and even students adopt this technology in making
things. Therefore, AM technologies have created a new design space and found a
great interest in the community we live in.

1.2.2 No tooling

In AM, unlike many traditional manufacturing techniques, jigs, fixtures, or molds are
not required to secure and shape the parts being made. The components are fabri-
cated directly on a printbed or an already-fabricated part. This is a huge cost-saving
avenue of AM considering expensive tooling of traditional manufacturing systems.
4 1 Introduction

1.2.3 On-demand manufacturing

Parts can be fabricated anytime as soon as the CAD model is prepared. These CAD
models can also be sent digitally and the manufacturing can be done at home or
remote locations near consumers eliminating the transportation of the fabricated
parts.

1.2.4 Rapid prototyping

Compared to the conventional techniques with more geometric limitations, AM can

produce models quickly, in hours instead of weeks. The makers/designers can test
the prototypes quickly to save significant amount of time in the design process to
achieve the final product.

1.2.5 Customization

Every part can be fabricated differently with the AM process without adding the
cost of fabrication. The customization can be particularly useful for the biomedical
applications, where each part can be fully customized for different patients and
their special requirements.

1.2.6 Minimal material waste

Since AM technology is based on adding material to build the 3D object rather than
material removal, it uses the exact amount of material to produce parts and there is
usually no waste of material. Support material and extra powder used during the
process can often be recycled and reused for the production of the next part. This
would reduce material cost due to material waste and waste removal. This would
also minimize the environmental implications stemming from the waste in conven-
tional manufacturing.

1.2.7 Low cost for small number of parts

With the advancement of technology, AM systems are becoming more affordable

and more portable compared to the traditional manufacturing systems. Low invest-
ment costs of the AM machines attract more interest on these systems. The cost of
fabrication depends highly on the number of fabricated parts and complexity.
Usually, traditional manufacturing is beneficial for fabrication of high number of
 1.3 Classification of AM technologies 5

geometrically simple parts, whereas AM becomes highly competitive or even cheaper

for manufacturing of low number of parts with high complexity.

1.3 Classification of AM technologies

There are numerous AM technologies used for the fabrication of different materials.
In 2010, the American Society for Testing and Materials (ASTM) group, formulated a
set of standards that classify the range of AM processes into seven major categories
as shown in Figure 1.4 [5]. Each of these seven methods significantly varies in their
method of layer-by-layer AM. Each of these categories is explained as follows.

Additive manufacturing classification

Vat polymerization Sheet lamination

Material jetting Directed energy deposition

Binder jetting Powder-based fusion
Extrusion

Figure 1.4: ASTM classification of additive manufacturing technologies.

1.3.1 Vat polymerization

Vat polymerization (a.k.a Vat photopolymerization) is a 3D printing technology,

which relies on selectively curing a liquid photopolymer contained in a vat (or tank)
by a light source. Light is used to cure or solidify the resin where required, while a
platform moves the built object downward (or upward) after each new layer is cured.
The process continues curing the photopolymer layer by layer until building of a 3D
physical object is completed. After completion, the resin in the vat is drained and the
object is removed. Usually, photopolymerized samples are postcured under ultravio-
let (UV) light to achieve complete curing and maximum strength.
The majority of the photocurable resins consist of mixtures of monomers com-
bined with oligomers (a few units of monomers) and photoinitiators. As shown in
Figure 1.5, oligomers and monomers are disconnected in uncured liquid photopoly-
mer resins. As UV light is applied on these photopolymers, photoinitiators are acti-
vated and cross-link the monomer and oligomer units. This chemical process,
known as photopolymerization or photocuring, transforms liquid photopolymers
into solid components.
6 1 Introduction

Active
UV light photoinitiators
Inactive
photoinitiators

Figure 1.5: Schematic of photopolymerization process.

Depending on the type of photoinitiator and the polymerization process, there are
two major photopolymerization types: (1) free-radical polymerization and (2) ionic
photopolymerization. Free-radical photopolymerization is commonly used in photo-
polymerization-based AM technologies (Vat polymerization, material jetting). Free-
radical photopolymerization process takes place in multiple steps including activation
of the photoinitiator upon exposure to radiation within an appropriate wavelength
range, formation of free radicals by reacting the photoinitiator and monomer mole-
cules, and the propagation by forming long polymer chains to cross-link. In the final
step, cross-linking process or photopolymerization is terminated where polymeriza-
tion comes to an end, usually by one of three mechanisms, including recombination
(two chains combine), disproportionation (canceling of one radical by another with-
out joining), or occlusion (free radicals become trapped by the polymer network) [6].
The most widely used UV-curable resins are based on acrylate, which show high reac-
tivity and short reaction times (fraction of a second), and these resins are available in
wide range of different monomer and oligomer types [7].
Although free-radical polymerization is the most commonly used photopolyme-
rization process, ionic curing systems are finding increasing applications in AM.
The same photopolymerization steps, photoinitiator activation by UV light, propa-
gation, and termination steps, exist in ionic photopolymerization process. The dif-
ference, however, is that in ionic curing process, instead of free radicals, reactive
ions are the cross-linking agents for the monomers and oligomers. The termination
takes place when the ion is neutralized or stabilized. Ionic photopolymerization has
distinct advantages over free radicals including no inhibition with oxygen, minimal
sensitivity to water, and the ability to polymerize vinyl ethers, epoxides, and other
heterocyclic monomers that do not polymerize by a free-radical mechanism [7].
There are four classifications for Vat polymerization technologies. Although the
main concept of the polymerization is the same in all of these techniques, differences
in the type of light source and the curing process for the polymer material lead to this
classification. The operation principles of the three major Vat polymerization techni-
ques are as illustrated in Figure 1.6.
 1.3 Classification of AM technologies 7

Mirror
(A) Light source (B)

Liquid
photopolymer

Platform
SLA DLP CLIP
Vat

Figure 1.6: (A) Schematic of part fabrication in Vat polymerization technology and (B) different
types of Vat polymerization process (SLA, DLP, and CLIP).

1.3.1.1 Stereolithography
Stereolithography (SLA) is the oldest AM technology. As a result, it is widely adopted
by AM community today. In this method, a focused UV laser beam is directed on pho-
tosensitive resin using motor-controlled mirrors. As the light contacts the liquid resin,
chemical reaction takes place curing the resin and creating a solid layer of the desired
3D object.

1.3.1.2 Digital light processing

This Vat polymerization technique differs from SLA since the light is projected on
liquid polymer in terms of a 2D image rather than rastering a focused beam. A digi-
tal projector is used to reflect the image over the resin curing the entire 2D layer.
Since the entire layer is solidified at once, digital light processing (DLP) process can
achieve faster print times compared to SLA process. A modified version of DLP pho-
topolymerization has been developed recently where DLP projector is replaced by a
liquid crystal display (LCD) screen. This screen acts as a mask for the UV light com-
ing from an array of light emitting diodes (LEDs) shining through the LCD screen.
Similar to the projector, photopolymerization of 2D layer occurs at once resulting in
higher speeds compared to SLA. Using LCD screens instead of projectors have sig-
nificantly reduced the cost and sizes of the projector-based DLP technology.

1.3.1.3 Continuous liquid interface production

Continuous liquid interface production (CLIP) is a relatively recent technology in-
troduced by Carbon3D, in 2015, as a novel concept using an oxygen-permeable bot-
tom plate to help speed up the printing process [8]. In SLA and DLP processes, the
solidification process occurs at the very bottom of a vat with a clear bottom win-
dow. To eliminate the resin to adhere the window surface, the platform is moved up
and down creating significant suction to break the adhesion between the object and
the window. Recent developments by Carbon3D company and the creation of the
8 1 Introduction

CLIP process have resulted in inhibiting the solidification of the resin within a cer-
tain zone around the clear bottom of the vat, which eliminates this suction force. In
CLIP technique, part of the vat bottom is transparent where UV light beam shines
through using an LCD screen. While the object is lifted slowly, resin flows under
and maintains contact with the bottom of the object. An oxygen-permeable mem-
brane lies below this resin field and creates a dead zone where photopolymerization
is inhibited. This liquid interface prevents the resin from attachment of the cured
object to the bottom plate. Unlike standard SLA and DLP, the 3D printing process is
continuous and therefore much faster. Continuous printing process makes CLIP as
one of the fastest AM method. However, similar to all other Vat polymerization tech-
niques, postprocessing is necessary to clean the printed part and fully solidify it via
additional postcuring process.

1.3.1.4 Volumetric Vat manufacturing

In 2017, volumetric Vat AM was introduced where photopolymerization is per-
formed in a 3D form rather than traditional layer-by-layer fashion [9]. Volumetric
Vat manufacturing is similar to the computed tomography (CT) technique where a
series of X-ray scans are acquired at different orientations and these 2D images are
then processed with a computer algorithm in order to reconstruct the 3D image of
the object. Unlike CT imaging, in volumetric Vat 3D printing, 3D CAD model is
input as the initial step and this model is converted into 2D projections at different
orientations using tomography algorithms. When all these projections are displayed
into a homogeneous volume of absorbing material, the cumulative absorbed dose
distribution due to the projections reproduces the shape of the 3D object inside the
material [10]. When the light is projected in 3D volume at different intensities
(different doses), the photopolymer where a high dose of light is applied will solidify
whereas other locations will remain below the solidification threshold. Therefore, in
volumetric Vat process, light is projected in 3D increasing the speed of the photopoly-
merization significantly. This technique is still under development stage and better
control of the light projection and the photopolymerization processes are expected in
near future.
Vat polymerization is advantageous over other AM techniques since it is capa-
ble of fabricating parts at a high resolution down to the nanoscale level. It is also
capable of fabricating large parts using vats with big volumes. Near-transparent ob-
jects can also be fabricated with this technique, which are usually not possible with
other AM technologies where interface region between the layers leads to high level
of light diffraction. Disadvantages include applicability of this technology to only a
limited number of UV-curable resins that are not very robust materials in terms of
durability, strength, or stability. In addition, this technique usually needs a post-
curing process under UV light to complete the curing process. Some photocurable
resins have health implications; hence, special gloves and ventilation are needed
 1.3 Classification of AM technologies 9

for the printing and postprocessing steps for these toxic materials until full curing
is achieved. Depending on the geometry of the part, support structures may be re-
quired which adds to the material waste and the fabrication time.

1.3.2 Material jetting

Material jetting is a 3D printing manufacturing technique which is similar to the

standard inkjet document printing process. However, instead of dispensing ink
onto a paper, photopolymer or wax material is sprayed (or jetted) onto a build tray.
As the polymer resin droplets are deposited to the build platform, they are cured
and solidified using UV light. The process continues to deposit material layer by
layer until the 3D object is created. The material jetting process allows fabrication
of different materials within the same object. Figure 1.7 shows the schematic of ma-
terial jetting process along with example parts fabricated with this technology.

(A) (B)

UV light Inkjet nozzles

Build Support
material material

Platform

Figure 1.7: (A) Schematic of material jetting technology and (B) fully colored parts fabricated by a
material jetting system. Image was reprinted with permission from Stratasys.

Material jetting processes require support, which is often 3D printed simultaneously

from a dissolvable material. The support material is then removed during the post-
processing step. Depending on the type of the support material used and the sup-
port removal technique, there are two patented technologies; polyjet printing (PJP)
and multijet printing (MJP) used by Stratasys and 3D Systems companies. In polyjet
technology, the support material is a combination of propylene, acrylic monomer,
polyethylene, and glycerin [11]. To remove support material, pressurized water is
sprayed over the part and the remaining support material is removed chemically
by dipping the part into chemical solvent. On the other hand, MJP technology uses
10 1 Introduction

meltable paraffin wax as the support structure. To remove the wax support, the
printed sample is heated in an oven over melting temperature of the wax followed
by wiping out of the wax material out of the sample.
Material jetting 3D printing technology is a great choice for making realistic pro-
totypes, providing an excellent level of details, high accuracy, and smooth surface
finish. Material jetting allows a designer to print a design in multiple colors and with
a number of materials in a single print. These manufacturing systems offer wide
range of materials and their combinations to choose from, including rigid to rubber-
like materials, opaque to transparent materials, and materials with acrylonitrile buta-
diene styrene-simulating performance. The main drawbacks to printing with material
jetting technologies are the high cost of the UV-activated photopolymers and the deg-
radation of the mechanical properties of these materials over time.

1.3.3 Binder jetting

Binder jetting is an AM process where a binding material is sprayed (or jetted) over
powder particles to bond them to form a 3D object one layer at a time. Schematic of
the AM process is shown in Figure 1.8. Metals and ceramics in powder form are
commonly used materials in binder jetting process. During the binder jetting pro-
cess, inkjet nozzles (similar to the paper inkjet printers) on the printer head spray
droplets of a binding material on the powder printbed and bond the powder par-
ticles in these areas together. When the layer is complete, the build platform moves
down and another powder layer is spread over the printed surface. The process is
repeated until the entire part is complete. Some printed parts such as sand-casting
cores and molds are typically ready to use after binder jetting process. However, a
postprocessing step is required for most applications. This is because binder jetted

Leveling roller
Printed part

Building stage
Feeding stage

Figure 1.8: Schematic of binder jetting technology.

 1.3 Classification of AM technologies 11

parts have poor mechanical properties and a high porosity when they come out of
the printer. In terms of post-processing, metallic parts are sintered at a high temper-
ature enhancing the adhesion between the metal particles or infiltrated with a low-
melting temperature metal such as bronze [12]. Ceramic parts also usually undergo
similar sintering and infiltration postprocessing steps to enhance their mechanical
strength and reduce porosity stemming from the removal of the binder material.
Acrylic coating application on the printed parts is also a common practice to im-
prove visualization and vibrancy of the colors in multicolor printed parts.
Binder jetting is a great choice for the applications requiring appealing aesthetic
properties and parts for visualization such as architectural models, toys, and figur-
ines since this technique can produce full color 3D-printed parts at a high resolution
similar to the material jetting process. The low cost of the powder material feedstock
and the high speed of the process are the major benefits of this technology. Binder
jetting is generally not suited for functional applications due to the brittle nature of
the parts; however, metal-based binder jetting parts have relatively good mechanical
properties if the infiltration and/or sintering postprocessing steps are taken. Since
the printing process takes place at room temperature in binder jetting, dimensional
distortions and warping due to thermal stresses are not a problem in this process. As
a result, the build volume of binder jetting machines are larger compared to the all
other AM technologies. This allows manufacturing of multiple parts and large objects
such as casting molds. Similar to the powder bed fusion systems, binder jetting re-
quires no support structures since the surrounding powder provides the necessary
support.

1.3.4 Material extrusion

According to ISO/ASTM definition: “material extrusion, is an additive manufacturing

process in which material is selectively dispensed through a nozzle or orifice” [13].
Material extrusion is the most commonly adopted AM technology due to the simplicity
of this technique, wide range of material selection, low cost of the printer instrument
and the feedstock materials, and the functionality of the printed parts. Although there
are various different extrusion processes, all of these can be categorized into two
major groups: fused filament fabrication (FFF) and paste extrusion.

1.3.4.1 Fused filament fabrication

In this technique, a filament preform of thermoplastic material is inserted in an ori-
fice where it is melted and extruded through a nozzle. Once deposited, it cools
down rapidly and solidifies into a single line (a.k.a road) as shown in Figure 1.9A.
The nozzle and/or the printing platform can move in x-, y-, and z-axes simulta-
neously to deposit material into 3D geometry matching the digitally designed CAD
12 1 Introduction

Filament moving
(A) mechanism (B) Ink

Dispenser
Deposited
material
Heated
Printed extruder
part

Direct write (DW )

Fused filament fabrication (FFF )

Figure 1.9: Schematic of extrusion technology: (A) fused filament fabrication (FFF) and (B) direct
write (DW).

drawing. Most desktop AM machines currently in use are of this type and this is the
AM process when most people refer to 3D printing due to its common adoption.

1.3.4.2 Paste extrusion

This method is commonly known as direct write (DW), liquid deposition modeling
(LDM), or robocasting. In this extrusion method, viscous paste-like material is ex-
truded through a nozzle (or tip). Unlike the melting-based extrusion (FFF), in DW,
material is a viscous fluid, not solid when deposited on the printbed. This method
relies on the fluid’s yield stress to form self-supporting structures. Fluid viscosity
and yield strength are adjusted using rheological modifiers such as nanoclay [14]
and fumed silica [15]. The fluid can be extruded via pressure controlled or displace-
ment-controlled system as shown in Figure 1.9B. In displacement-controlled extru-
sion, a stepper motor precisely moves the piston plunger downward toward the
printbed extruding the material. In the pressure-controlled systems, a pump is uti-
lized to apply pressure directly on the material to push it toward the nozzle.
Pressure level or the microstep number of the stepper motor is adjusted to control
the speed of the extrusion.
In DW, rheological properties of the extruded material determine the printability.
Highly viscous pastes are preferred as the printing materials since these materials
can resist deformation after printing and they can hold shape. In DW, shear thinning
is a commonly observed behavior as shown in Figure 1.10A, where material viscosity
is decreased as a function of shear rate. In shear thing behaving materials, during
extrusion, material viscosity drops significantly, and material can be extruded into
an intended geometry at high flowability. After extrusion, material viscosity is recov-
ered (preferably at high speed), and the extruded material can hold its shape under
 1.3 Classification of AM technologies 13

(A) (B) Storage modulus (G’)

Modulus (G′, G″)

Shear-thinning fluid
Solid-like
Viscosity

Loss modulus (G″)

Modulus Liquid-like
crossover
Newtonian fluid Shear yield
stress

Shear rate Shear stress

Figure 1.10: Rheology considerations in DW; (A) comparison of a Newtonian fluid and
shear-thinning fluid and (B) typical variation of loss and storage moduli as a function of shear rate
during extrusion.

gravitational force without sagging. During the extrusion process, shear rate (_γ) is
maximal at the walls of the extruder and can be estimated as follows:

4Q_
γ_ max = (1:1)
πr3
where r is the nozzle radius, and Q_ is the volumetric flow rate, calculated as Q_ = Sr2 ,
with S as the printing speed. Typical values of the shear rate during DW process are
50–100 s−1. In Newtonian fluids, however, viscosity is constant and does not vary
as a function of the shear rate.
Printability and the rheology relationship can be better identified by quantify-
ing the storage and loss moduli of the DW extruded materials. The storage modulus
(G′) relates to the material’s ability to store elastic energy, and the loss modulus (G′′)
is the material’s ability to dissipate stress through heat. Figure 1.10B is a representa-
tive plot for a viscous, shear thinning paste material indicating the variation of stor-
age and loss moduli as a function of shear stress. In Figure 1.10B, storage modulus is
higher than the loss modulus under low shear conditions and therefore the material
shows solids-like elastic behavior. On the other hand, under high shear, loss modulus
can be higher which indicates a liquid-like behavior of the printed material. At the
crossover (or gelation) point, storage, and loss moduli are equal and at this point ma-
terial yield stress can be measured. High yield stress is preferred for extruded materi-
als since these materials are able to resist deformation and keep their shapes without
sagging. However, higher extrusion pressures/forces are required to push these mate-
rials with high yield stress through nozzle orifices.
In DW method, entire printed structure is deposited at room temperature which
significantly reduces the dependence of the mechanical properties on thermal print-
ing history and spatial heating path [16]. Wide range of materials can be additively
fabricated via DW. Thermosetting polymers and thermoset composites, ceramics and
14 1 Introduction

ceramic composites, and conductive metal inks (copper, silver, etc.) are printable
with this method. After printing, postprocessing is usually required to enhance me-
chanical strength of the components. Curing is performed at 100–200 °C for thermo-
set materials. Similarly, heat treatment is necessary for ceramic-based pastes but
at elevated 1,000–1,500 °C to facilitate the sintering of the ceramic particles.
Postprocessing is usually omitted for printed conductive inks since the applica-
tions are limited to planar geometries [17] and high strength is not necessary. DW
technique widens the applicability of AM to liquid-based materials, composites,
and ceramics. Compared to filament based FFF technique, DW is relatively new
and still under development. Currently, it is limited to smaller volumes and
height-limited structures. Fabrication of taller 3D structures requires feedstock
with extremely high viscosity and yield strength or using support structures.

1.3.5 Powder bed fusion

Powder bed fusion is an AM method where a heat source is used to melt and fuse the
powder particles together to form a 3D object. As shown in Figure 1.11A, a thin layer
of powder is spread over the build platform and heat is directed on the selected re-
gion to fuse powder in these areas together. Afterwards, the platform is moved down
and another layer of powder is spread across the previous layer using a roller, and
the heat-induced powder fusion process is applied again on this layer. The process
continues until the entire model is built. After the fabrication is complete, unfused
powder is removed and the printed part is detached from the build plate.

Mirror
Heat source (B)
Leveling roller
(A)

Printed part (C)

Building stage Feeding stage

Figure 1.11: (A) Schematic of powder bed fusion technology, (B) laser sintering in progress, and (C)
octopus figurine fabricated via powder bed fusion (SLS).
 1.3 Classification of AM technologies 15

The heat source facilitating the fusion process can be a laser, an electron beam, or
a heat lamp. Ceramics, polymers, and metals can be fabricated in 3D geometry with
this technology. Powder bed fusion is remarkable at producing overhangs and down-
ward facing surfaces where support structures are not needed as the unbound/unfused
powder act as integrated support structure. Cost of powder feedstock and the powder-
based fusion machines have reduced significantly over the recent years. In addition,
this technology allows recycling of the unfused powder provided that the powder con-
tamination and degradation are closely monitored to achieve the desired part quality.
Selective laser sintering (SLS) and selective laser melting (SLM) are the most commonly
used powder-based fusion technologies. In SLS, powders are heated near the melting
temperatures leading to partial melting and sintering together as shown in Figure
1.11B. Figure 1.11C represents an octopus figurine fabricated with the SLS process. In
SLM, however, material is heated above its melting temperature and complete melt of
the powder is achieved creating a homogenous, nonporous structure.
There are multiple limitations of powder bed fusion technologies. First, high tem-
peratures and heat introduced into the part may cause warpage and residual thermal
stresses. In addition, powder bed fusion is one of the slowest AM techniques since it
commonly includes powder preheating (to speed up the process/enhance powder
fuse), vacuum generation, and material cooling off period. Postprocessing also is com-
mon adding to the manufacturing time and cost. Since the parts are made by fusing
material powder together, surface quality depends on the grain size of the powder and
would be very similar to manufacturing processes like sand or die casting. [18]. The
parts are manufactured over a build plate; hence, support removal postprocessing is
necessary. Since material melting is necessary (partially or fully), this technique uses
significant amount of energy to create parts compared to other AM techniques.

1.3.6 Directed energy deposition

Directed energy deposition (DED) is a process where metal wire or powder is melted
onto a build plate or an existing part using an energy source as shown in Figure 1.12A
schematically. A typical DED system consists of a nozzle mounted on a multiaxis arm
inside a closed frame, which deposits melted material onto the workpiece surface,
where it solidifies. These robotic arms allow to build objects very quickly from multiple
directions as long as the built location is within the reach of the arm. Therefore, the
process is similar in principle to the material extrusion AM technique, but unlike FFF,
filament is melted right at the deposition surface. In addition, nozzles of DED systems
can move in multiple directions, up to five different motion axes are utilized compared
to only three for most FFF machines. Material deposition can be accomplished in DED
process at a high speed and therefore, this process is claimed to be the fastest AM tech-
nology [19]. Fully dense parts in complex geometries can be achieved using robotic
arms and no support is required for overhanging features. In addition, DED process
16 1 Introduction

(A) High-energy (B)

laser

Material nozzle

Manufactured
part

Platform

Figure 1.12: (A) Schematic of DED additive manufacturing process and (B) metallic parts fabricated
via DED technology. Published with a permission from AddUp/BeaAM Inc.

can effectively be used to add metal materials to existing metal parts, which makes
this technique preferable for welding and repair applications.
Different metals can be 3D printed through DED AM technique including alumi-
num, copper, titanium, tantalum, copper nickel alloys, and steel alloys. The main
drawback with this process is the poor surface finish resulting from the melt pools.
As the metal melt pools cool down, they leave a very rough surface finish and for
this reason, most DED parts require postprocessing steps, usually in the form of sec-
ondary machining to improve surface finish. Since the DED process involves local
heating of the object at elevated temperatures, thermal stresses are commonly ob-
served. To alleviate these stresses and thermally induced implications, hot isostatic
pressure and heat treatment postprocessing steps are usually taken. Figure 1.12B
shows the DED process performed on different metallic parts by AddUp/BeaAM Inc.

1.3.7 Sheet lamination

Sheet lamination is an AM process which is significantly different from the other AM

processes since the material feedstock is not a liquid resin, a filament, or powder.
However, as the name implies, sheets of material are laminated or bonded together
building up a 3D component. The process can be applied to a variety of different mate-
rial types including paper, PVC polymer, metal, or ceramic. As shown in Figure 1.13A,
material sheets or foils are bonded together initially and 2D outline of the desired
part is obtained by cutting the laminate using a laser or blade. Alternatively, material
can be machined away using conventional CNC milling. After cutting (or machining)
 1.3 Classification of AM technologies 17

Mirror (B)
(A) Cutting laser

(C)
Roller

Platform

Sheet material

Figure 1.13: (A) Schematic of sheet lamination technology, (B) aluminum heat exchanger fabricated
via sheet lamination technology, (C) x-ray image of the aluminum heat exchanger showing internal
channels. Images were reprinted with permission from [20].

process, the next sheet is placed on the top of the existing piece. Sheet placement,
bonding, and cutting process continue until the desired 3D object is created.
If paper sheets are used as a feedstock, bonding is achieved with an adhesive or
glue, whereas for PVC sheets, a thermoplastic polymer melting is used to bond the
sheets together. In metal lamination, a localized energy source, laser or ultrasonic
waves are used to bond a stack of precision cut metal sheets to form a 3D object.
Ultrasonic bonding which is also known as ultrasonic AM or ultrasonic consolidation
is the most commonly used metal sheet lamination technique. By applying ultrasonic
wave and mechanical pressure on sheet metal stacks at room temperature, the con-
tacting interface surfaces of stacked sheets are bonded by diffusion in atomic scale
rather than melting. This process is great for making low cost, full color prints which
does not require high geometrical complexity. The process can also be used to fabri-
cate parts with internal structures without using a support structure. Additionally,
this process is extremely useful for metal printing processes where the thermal stress
of melting metal powder would be problematic such as powder bed fusion methods.
Thermal stress is minimal in sheet lamination process; however, in order to further
reduce thermal residual stress that might take place during bonding, an external cool-
ing procedure is applied for a short period time between the lamination of each layer.
Compared to other AM technologies, sheet lamination is less commonly utilized
due to the high cost of the sheet lamination systems, very specialized applications,
and limited geometrical freedom of parts fabricated with this technology. An alumi-
num heat exchanger block with an internal channel is shown in Figure 1.13B.
Internal channels can be fabricated in any layer and at different complexity as
shown in Figure 1.13C. This figure represents an X-ray image of the sheet laminated
18 1 Introduction

Table 1.1: Comparison of AM technologies.

AM method Materials Resolution Advantages Disadvantages

Vat UV Curable – µm Excellent surface Limited mechanical

polymerization Photopolymers quality, high properties, aging
(Acrylates/Epoxides) resolution, no
porosity, isotropic
properties

Material UV Curable – µm Fast, allows Low viscosity ink

jetting Photopolymers multimaterial, required
(Acrylates/Epoxides) multicolor printing

Binder jetting Starch – µm Fast, allows Limited mechanical

PLA multimaterial printing properties, rough
Metals surfaces
Ceramics

Powder bed Thermoplastics (PA, – µm Best mechanical Rough surfaces,

fusion PA, PEEK) properties, less thermal stress in
Metals (stainless anisotropy, applicable the printed part,
steel, titanium) to broad range of poor powder
materials reusability

FFF Thermoplastic – µm Compact, inexpensive Limited materials,

polymers (ABS, PLA, D printers, good high temperature,
nylon, PC, PETG, resolution porosity, and
PEEK) anisotropy

Direct write Thermosets (epoxy,  µm– cm Broad range of Low surface quality,
cyanate ester, materials, room temperature
bismaleimide) printing
Composites
Hydrogels
Biomaterials

Sheet PVC – µm Low cost, low thermal Limited geometrical

lamination Paper stress freedom
Sheet metals

Directed Metals (aluminum, – µm Fastest AM Poor surface finish,

energy copper, titanium, technology requires
deposition tantalum, copper, postprocessing,
nickel, and steel thermal stresses in
alloys) the parts
 1.4 Timeline/history of AM 19

component illustrating the ability for complex internal flow paths, which are impos-
sible with traditional manufacturing methods.
As described earlier, each of the seven AM technologies is unique in terms of
the underlying technology to fabricate 3D objects layer by layer. Each method offers
certain benefits and limitations in terms of applicable materials, cost, resolution,
speed, build volume, and so on. Table 1.1 summarizes each seven categories com-
paring and contrasting the major properties of each AM techniques.

1.4 Timeline/history of AM

To understand the future of AM technology, it is essential to look back at the history

of AM and how it transformed our lives through its development. Although it all
started 40 years ago, this technology has already revolutionized the manufacturing
industry, biomedicine, architecture, automotive, and aerospace industry, in short,
everything. Figure 1.14 summarizes some of the important milestones of the AM
technology since the first patent was filed in 1984. Description of these major events
is given and also briefly described as follows:

History of additive manufacturing

SLA is First kidney First UAV

invented First SLM printed First leg printed First meat is
printer prosthesis printed

84 88 95 98 02 04 08 10 11 14 18 Future

First inkjet First car

FDM is printer Rep-rap printed First print
invented project in space

Figure 1.14: Timeline of additive manufacturing technology development.

– The idea of AM was conceived in 1970s with the development of computers,

CAD systems, laser technology, and micron-resolution motors. However, time-
line of AM really starts with the first patent filed by Charles W. Hull in 1984 on
SLA process. This technology was then commercialized when he founded 3D
Systems company in 1986.
– In 1988, 3D Systems developed the STL file format for CAD models for slicing off
the 3D models into 2D layers. Since then, STL file format has been considered to
20 1 Introduction

be the main file format for layer-by-layer manufacturing (AM) users and greatly
assisted for the merge of AM technologies.
– In 1988, Scott Crump invented FFF technology using wax and a hot glue gun.
This extrusion technique was named as fused deposition modeling (FDM) and
patented by the company Stratasys founded by Scott Crump, which later be-
came one of the largest AM companies in the world.
– In 1989, initial patent was awarded for powder bed fusion technologies of SLS,
SLM, and electron beam melting (EBM) based on the work at the University of
Texas at Austin. Although the patent was awarded in 1989, SLM and DMLS were
developed in Germany as a part of a project between the Fraunhofer Institute,
EOS, and others in 1995 [21]. These technologies dramatically changed the AM
especially for the metallic materials.
– First commercial binder jetting machines came out after 1994. MJP process was
introduced by 3D Systems and in 1996. In 1998, polyjet technology was devel-
oped by Objet [22]. These binder jet technologies lead to multicolor, very realis-
tic prints at a high resolution and made a significant impact on AM industry.
– In 2002, AM was applied on biomedicine by 3D printing a miniature kidney
model. This functional kidney was capable of filtering blood and producing
urine in an animal model. After 17 years, in 2018, 3D-printed kidney saved the
life of a 2-year-old boy as the surgeons used the 3D-printed kidney model to
perform the organ transplant [23].
– Implementation of AM on biomedical field expanded dramatically after 2000s.
In 2003, Thomas Boland from Clemson University patented the use of inkjet
printing for cells and cell constructs [24]. This process allowed the deposition
of cells into organized 3D matrices placed on a substrate.
– In 2005, Adrian Bowyer at the University of Bath started the replicating rapidly
(RepRap) project to make the FFF technique available to everyone, and created an
open-source 3D printer that was capable of RepRap itself, at least partially [25].
Because of this open-source design along with the expired patents, new AM com-
panies emerged reducing the machine cost and rapidly increasing the progress in
the AM technologies.
– In 2008, the first prosthetic leg was used by a person. All parts of the prosthetic
(leg, knee, foot, and socket) fabricated additively without any assembly needed.
– In 2010, entire body of a car, including its glass panel prototypes, was fabri-
cated with AM processes. This first additively manufactured car, named Urbee,
was the result of a collaboration between Winnipeg engineering group, Kor
Ecologic, and Stratasys [26]. In 2014, Oak Ridge National Laboratories (ORNL)
designed and additively manufactured Shelby Cobra electric car using FFF
technology. The car was manufactured using a big area AM 3D printer devel-
oped by ORNL and Cincinnati Inc.
 1.4 Timeline/history of AM 21

– In 2011, the University of Southampton engineers additively fabricated the first

unmanned air vehicle (UAV). Entire structure of this UAV including wings, con-
trol surfaces, and access hatches was additively manufactured.
– In 2014, the first object was printed in space. The International Space Station’s
newly installed 3D printer made history by manufacturing the first object ever
additively manufactured in space. NASA’s FFF 3D printer was developed under
a contract with the Made In Space startup company, which was founded in
2010. The purpose of the 3D printer was to experiment with the possibility of
manufacturing crucial replacement parts on the station, foregoing the expense
of shipping them via rocket.
– In 2018, Italian bioengineer Giuseppe Scionti developed a technology to gener-
ate fibrous plant-based meat analogs using a custom AM system based on DW
method. Additively manufactured samples had matching texture and nutri-
tional values to those of natural meat [27]. This was a breakthrough application
for the implementation of AM on food industry and a big step toward resolving
hunger in the world.

Looking back the timeline of AM and what has been accomplished in the past
40 years is overwhelming. It has changed the manufacturing industry and trans-
formed our lives. So, what lies ahead of us? What is the future of AM technology? It
is difficult to predict the future but based on the trend line of this technology, it is
certain to say that it will grow bigger, further replace the traditional manufacturing
systems, and change our world for better.
2 Additive manufacturing of polymers

2.1 Classification of polymers

Polymers are a class of engineering materials that are composed of chains of repeat-
ing chemical units called monomers. In fact, the word “Polymer” is derived from
two Greek words, “Poly” and “Mer,” which mean “many” and “units,” respectively [28].
Repeating units or monomers can be just a few atoms or they might be complicated
ring-shaped structures containing many more molecules. Natural polymers such as
proteins, cellulose, enzymes, starches, and nucleic acids are found in living organisms
and they perform important biological functions. Other natural polymers are derived
from plants and animals and these natural polymer materials include wood, rubber,
cotton, wool, leather, and silk. It was, however, a different type of polymers, nonnatu-
ral, or synthetic ones, which revolutionized our world in the past 50 years. Synthetic
polymers such as plastics, rubbers, and epoxies are synthesized from petroleum-
based organic molecules. These materials can be produced inexpensively, and their
properties can be engineered to be superior to their natural counterparts. In many
applications, metal and wood parts have been successfully replaced by synthetic
polymers that provided lower cost, lightweight, and corrosion/chemical resistance
advantages. Polymers can be classified into three major groups according to their
molecular orientation as shown in Figure 2.1. As a result of their unique micro-
structure, each group of polymers, thermoplastics, thermosets, and elastomers
possesses different physical behaviors. Details of each category and the AM tech-
nologies to fabricate these materials are described in the next section.

Polymers

Thermosets Thermoplastics Elastomers

Heat Thermoplastic Thermoset

Light
sensitive elastomers elastomers
sensitive

Figure 2.1: Classification of polymeric materials.

https://doi.org/10.1515/9781501518782-002
 2.1 Classification of polymers 23

2.1.1 Thermoplastics

Thermoplastic polymers have linear or slightly branched molecular structures as

shown in Figure 2.1. Molecules in a thermoplastic polymer are held together by rela-
tively weak intermolecular forces. As a result of these weak interactions, thermo-
plastic materials soften when exposed to heat and then return to their original
condition when they are cooled down. Thermoplastics have a wide range of appli-
cations since they can be shaped easily and repeatedly by simply a heating process.
Some applications of these polymers include toys, food packaging, thermal insula-
tion, machine parts, and credit cards.

2.1.2 Thermosets

Unlike thermoplastics that are held together by weak intermolecular forces, thermo-
set polymers are formed by cross-linked monomer chains. During the curing pro-
cess, thermoset resin (usually in liquid form) is mixed with a catalyst, or an
external energy is applied to start a chemical reaction cross-linking the monomer
chains together irreversibly. Three-dimensional cross-linking network between the
polymer chains restricts the motion of the chains and leads to a rigid material that
does not softens or melts under heat-like thermoplastics. There are two main types
of thermosetting polymers: heat-sensitive and light-sensitive thermosets. For heat-
sensitive thermosets, thermal (heat) energy is applied to cross-link the polymer
chains. For light-sensitive resins, however, light (UV, visible, etc.) is used for the
external cross-linking energy as described in Vat polymerization section in
Chapter 1. Since cross-linked or cured thermosets do not melt when heat is applied,
these materials are ideal for applications where structural rigidity at high temper-
atures is required. Thermoset polymers are usually stronger than the thermoplastics
and more resistant to elevated temperatures. Thermosets usually have excellent
aesthetic appearance and are cost-effective materials compared to thermoplastics.
However, thermosets are not recyclable since they cannot be reformed back to their
liquid form unlike thermoplastics, which can be melted and reformed to the new
configurations for recycling purposes.

2.1.3 Elastomers

Elastomers are cross-linked polymers. However, unlike thermoset polymers, cross-

linking density is very low (Figure 2.1). Therefore, the polymer chains still have
some freedom to move, but are prevented from permanently moving relative to
each other by the strong bonds (cross-links) between the molecules. As a result of
24 2 Additive manufacturing of polymers

this microstructure, elastomers can be stretched easily and they can rapidly return to
their original dimensions when the applied stress is released. As shown in Figure 2.1,
elastomers can also be subclassified as thermoplastic and thermoset elastomers.
Thermoplastic elastomers melt when heated similar to thermoplastics and therefore,
they are commonly used in thermal manufacturing processes, such as injection mold-
ing, since heat can be used to shape these materials. Thermoplastic polyurethanes
(TPUs) are major group of thermoplastic elastomers and used for various applica-
tions, including the production of foam seating, seals, and gaskets. Thermosetting
elastomers do not show melting or softening under heat. Rubbers are the most com-
monly used materials for this elastomer type due to their flexibility and durability.
Rubbers are widely used for the manufacture of tires, tubes, hoses, window profiles,
gloves, balloons, conveyor belts, and adhesives.

2.2 Selection of polymers for AM

The ability of melting and shaping polymers under heat is an important selection
criterion for AM of polymers as described in the previous section. However, in addi-
tion to melting ability and response to heat, there are different parameters influenc-
ing the material selection process as shown in Figure 2.2.

Ease of printing

Visual quality Elongation at break

Selection
Maximum stress Melting temperature
criteria

Material cost Layer adhesion

Glass transition temperature

Figure 2.2: Physical properties of polymers affecting their selection process.

– Printability: The polymer selected for AM should have consistent flow during
AM. In addition, it should adhere strongly to the printbed and the previously
printed layers for structural strength and geometrical accuracy during the
printing process.
 2.3 AM of thermoplastic polymers 25

– Mechanical performance: Mechanical strength, stiffness, elongation at break,

and impact resistance are important parameters defining the usage of additively
manufactured part. Different polymers have different mechanical responses to
different loading conditions. Selecting the correct type and classification of poly-
mers will have significant effect on the functionality of the manufactured part.
– Visual quality: Polymers can have variety of aesthetic appearances. Although
surface finish of the additively manufactured part strongly depends on the fab-
rication method and process parameters, selection of the polymer type, color,
and microstructure will also alter the visual quality of the part.
– Resistance to moisture absorption: Unlike metals and ceramics, polymer mate-
rials absorb moisture in humid environments. Absorption of moisture can lead
to defects during the AM process. Some polymer materials (i.e., nylon) may re-
quire special storing requirements due to their high affinity to moisture absorp-
tion. In addition to manufacturing defects, moisture can lead to warpage,
hygromechanical stresses, and cracking on the printed parts.
– Material toxicity: Toxicity of polymers used in AM is a growing concern. Some
polymers, especially thermosetting resins, may contain toxic compounds.
During curing process, these chemicals may create toxic fumes and also leach
from the additively fabricated part into aqueous media. If the additively fabri-
cated part is not fully cured, these may compromise the part biocompatibility.
Nontoxic, biodegradable polymers are preferred for their safety and environ-
mental benefits. Polylactic acid (PLA) is a biodegradable thermoplastic poly-
mer, and it is the most commonly used polymer material for AM.

2.3 AM of thermoplastic polymers

PLA, acrylonitrile butadiene styrene (ABS), polyethylene terephthalate glycol, high-

density polyethylene, polycarbonate (PC), and nylon are the most commonly used
thermoplastic polymers in AM. These polymers have low-melting temperatures, and
therefore, they can be additively fabricated using FFF technique as discussed in
Chapter 1. For higher temperature applications, special thermoplastic materials hav-
ing high-melting temperatures such as polyetherimide (ULTEM), polyether ether ke-
tone (PEEK), and polyetherketoneketone (PEKK) are preferred. As shown in Table 2.1,
melting temperatures of these polymers would reach up to 400 °C. In addition, these
polymers mark high glass transition temperatures compared to the conventional
polymeric materials. Glass transition temperature is an important physical property
for the end use of polymers. Above this temperature, polymer physical behavior
changes from glassy (or crystalline) state to a rubbery state. Therefore, maximum op-
eration temperatures of polymers are designed not to exceed the glass transition tem-
peratures. High-performance polymers described earlier require special printing
systems to melt and extrude them on the printbed.
26 2 Additive manufacturing of polymers

Table 2.1: Thermal properties of common thermoplastic materials for AM.

Polymer AM Extruder Max. service Cost CTE Reference

type method temperature temperature ($/kg) (µm/m°C)

PLA FFF –  –  []

ABS FFF –  –  []
PC FFF –  –  []
PET FFF –  –  []
PVA FFF –  –  []
ULTEM FFF – . – . []
PEEK FFF –  – – [–]
PEKK FFF –  – – [, ]
Nylon FFF/SLS – – – – [, ]
Polyimide SLA/DW – – > . [–]
Epoxy DW – – – – []
Cyanate ester DW –  > – [, ]

In addition to FFF extrusion, thermoplastics can also be additively manufactured

using powder bed fusion methods. Nylon is the most commonly used polymer mate-
rial for selective laser sintering (SLS) powder bed fusion technique dominating
nearly 90% of the SLS manufacturing [29]. Different materials including polystyr-
enes and polyaryletherketones are also used in small amounts in SLS. Unlike FFF,
only a limited number of thermoplastic materials can be fabricated using SLS
method. Particle shape, powder distribution, thermal, rheological, and optical re-
quirements must be considered and only a particularly controlled property combi-
nation leads to successful SLS implementation [30]. The extent of the material
properties required for successful SLS process limits the available materials to only
a few successful thermoplastics so far. Table 2.1 shows the glass transition and
melting (printing) temperatures of the common thermoplastic materials used for
FFF and SLS additive manufacturing processes.
Ultimate tensile strength and elastic modulus are the major properties regard-
ing the mechanical performance of polymers. Figure 2.3 summarizes these proper-
ties for the additively manufactured thermoplastic polymers. As shown in this
figure, there is wide range of variation in the previously published results, which
indicates the effects of printing parameters, material composition, and environ-
mental parameters on the mechanical properties. High temperature thermoplastic
materials such as ULTEM and PEEK provide higher strength than the other addi-
tively manufactured materials. However, the material cost and the need of special
printing systems to melt them at higher temperatures are the disadvantages of these
material systems.
In addition to tensile strength and elastic modulus, elongation at break and frac-
ture toughness are also important mechanical properties for certain applications.
 2.4 AM of thermosets 27

120

100 PEEK

80
Strength (MPa)

ULTEM
60
Nylon PC
PLA
40

20 ABS

0
0 1 2 3 4 5
Elastic modulus (GPa)

Figure 2.3: Tensile mechanical properties of additively fabricated thermoplastic polymers.

Polyamides such as nylon and PC are reported to show high elongation at break
among thermoplastics materials and reach over 25% [41]. Despite their superior frac-
ture resistance, ease of fabrication and low cost, nylon is susceptible to moisture ab-
sorption and special care must be taken to keep the material feedstock in dry
condition prior to AM. Manufacturing with moist nylon filament or powder feedstock
can lead to defects in manufactured parts. In addition to nylon and PC, ABS has also
been reported to have high elongation (~20%) at fracture in certain studies [42, 43].
However, tensile strength of ABS is lower than the other commonly used thermoplas-
tic polymers.

2.4 AM of thermosets

Thermosets are highly cross-linked polymers. Cross-linking can be carried out by ap-
plying ultraviolet (UV) light on photopolymer resins or by heating thermally curing
resins. Photopolymers are generally fabricated via Vat polymerization techniques or
material jetting where UV light is used for material curing. Thermally activated/cured
thermosets are generally printed using direct write extrusion process.

2.4.1 AM of photosensitive thermosets

Typical photopolymer materials used in Vat polymerization are composed of

monomers, oligomers, photoinitiators, epoxies, and a variety of other additives in-
cluding inhibitors, dyes, toughening agents that adjust the printability and physi-
cal properties of photopolymers [6]. Photosensitive resins have been reported to
28 2 Additive manufacturing of polymers

have two primary drawbacks that have prevented their more widespread usage as
production materials: sensitivity to water/humidity and tendency to age. Several
studies have shown that mechanical properties of additively manufactured parts
fabricated via Vat polymerization change over time under a variety of environ-
mental parameters such as temperature, moisture, and UV exposure [44–46].
Similarly, researchers have also characterized mechanical properties of photocur-
able thermosets fabricated via material jetting process. Results indicate that parts
have considerable variability in tensile and compressive properties [47] and ex-
hibit anisotropy. Similar to the parts fabricated via Vat polymerization, material
jetted parts have also been reported to have time dependent mechanical proper-
ties due to the effects of aging [48]. This indicates that aging is independent of
fabrication method but takes place due to the change of polymer molecular struc-
ture and the degree of polymer cross-linking.
Considering the complexity of the photopolymer chemistry and the variety of
these resins for different manufacturers, it is difficult to make a generic compari-
son for mechanical performance of these systems. However, tensile mechanical
properties of selected photosensitive thermosets are given in Figure 2.4 to show
the distribution of these properties in the previously published studies. This figure
also shows that mechanical properties of the additively manufactured parts de-
pend not only on the additive manufacturing method but also on the chemical
structure of the polymer. Same AM technology such as material jetting can be
used to fabricate both soft (Durus, Stratasys) and stiff (High temp., Stratasys) pho-
topolymers using the same printer.

120
Direct write
Cyanate ester [1]
100 Material jetting
SLA
Polyimide [1]
Strength (MPa)

80
High temp. [2]
Epoxy [2] Epoxy [2]
60
Epoxy [3]
Epoxy [2] Epoxy [2]
40
Epoxy [2]
20 Durus [2]

Tango black [2]

0
0 1 2 3 4 5
Elastic modulus (GPa)

Figure 2.4: Tensile mechanical properties of additively fabricated thermoset polymers.

 2.5 AM of elastomers 29

2.4.2 AM of heat-sensitive thermosets

Heat-sensitive thermosets can be additively fabricated via direct write extrusion

without the assistance of UV light exposure if the viscosity of the material is suffi-
ciently high. To adjust viscosity, liquid thermoset resin is mixed with rheology
modifiers such as clay or silica nanoparticles. In addition, UV light can be assisted
to further enhance the solidification process during direct write printing [49]. In
this case, photosensitive compounds must be added into the thermoset resin.
Direct write manufacturing of different types of thermoset resins such as epoxies
[14, 16], cyanate esters [40], and polyimides (Kapton) [50] have been reported in
literature. Tensile mechanical properties of some of these notable studies are
shown in Figure 2.4.

2.5 AM of elastomers

Elastomers are weakly cross-linked polymers that can be stretched extensively under
mechanical loads. AM of these material systems finds growing applications in various
fields due to their unique deformability, fracture resilience, electrical, and thermal
insulation properties. As shown in Figure 2.1, there are two classes of elastomer poly-
mers: thermoset elastomers and thermoplastic elastomers. As the name indicates,
thermoplastic elastomers behave similar to thermoplastic polymers as they are soft-
ened and melted under heat. Thermoset elastomers behave like thermosets since
these polymers can be cured/solidified by applying light or heat that irreversibly
cross-link the polymer chains. Photocurable elastomers therefore can be manufactured
via Vat polymerization (SLA, DLP, CLIP) and material jetting processes similar to photo-
sensitive thermosets. Various commercially available thermoset elastomer resins have
been developed, including PDMS [51], Carbon EPU40, Stratasys TangoPlus, Formlabs
Flexible, and Spot-A-Elastic [52]. Despite the high resolution printing with these UV-
curable resins and Vat polymerization technology, maximum elongation at break has
been limited to 170–220% in these AM techniques, currently [52]. As an alternative to
Vat polymerization and material jetting, direct write techniques were also used for dif-
ferent types of elastomers without the need of UV curing. Direct write AM can be applied
to any highly stretchable elastomer such as ecoflex by which 900% elongation at break
has been reported in literature [53]. Although this technique offers flexibility in terms of
the variety of applicable elastomeric material, part complexity and geometric resolution
in this method are reduced compared to photopolymerization methods as discussed in
Chapter1. Figure 2.5 presents examples of flexible elastomers fabricated by Formlabs Inc.
via Vat polymerization showing the high flexibility and high-dimensional accuracy.
The second class of elastomers, thermoplastic elastomers, are also commonly
used for AM applications. These materials are easily melted within the print head
and fabricated with FFF method. TPU is the most commonly used elastomer for this
30 2 Additive manufacturing of polymers

Figure 2.5: Three-dimensional-printed structures made with Formlabs elastic resin using Vat
polymerization technology. Figures were reprinted with permission from Formlabs Inc.

process and high (700%) elongation at break for this material was reported in liter-
ature [54]. In addition to the high degree of stretchability, elastomers fabricated
with this technique possess high dimensional accuracy (0.1–0.2 mm) as dictated by
the FFF technology.
3 Additive manufacturing of polymer composites

For rapid prototyping of an actual model or for applications where the components
are under low level of mechanical loading, neat thermoplastic and thermoset poly-
mers are ideal material choices. However, if higher mechanical strength is neces-
sary for structural applications or multifunctionality of the additively manufactured
part is required, polymer composites are preferred choice. Polymer matrix can be
infused with powders, short fibers, and continuous fibers for this purpose. The clas-
sification of additively manufactured polymer composites according to the dopant
or reinforcement material type is shown in Figure 3.1. Each category will be exam-
ined in the following section and comparison will be made regarding the additive
manufacturing methods and the physical properties for each composite group.

3.1 Additive manufacturing of powder-doped polymer composites

Infusing polymers with materials in powder form is commonly used for composite
manufacturing. These doping materials can be in nanoscale such as carbon nano-
tubes (CNTs), quantum dots, and graphene platelets. It can also be low aspect ratio
materials in microlength scale such as carbon black (CB) and metallic and ceramic
powders. Powder doping of polymers allow tailoring of various material properties
of printed parts including electrical conduction, shape memory, dielectricity, piezo-
electricity, optical properties, and thermal conduction. Powder-doped composites
can be fabricated by a wide range of additive manufacturing methods including ex-
trusion methods (FFF, direct write), Vat polymerization, binder jetting, material jet-
ting, and powder bed fusion due to the small size of the powder-based additives
and the ease of mixing these materials with polymer matrix.
Arguably, the most common and beneficial usage of powder doping on polymer
composites is adjusting the electrical properties of polymer composites. As a result,
many researchers have investigated the effects of different dopants on electrical prop-
erties of additively manufactured polymer structures. CNTs have been reported to have
high electrical conductivities similar to those of metals. Recently, Chizari et al. [55] fab-
ricated highly conductive CNTs/PLA (polylactic acid) nanocomposites used for additive
fabrication of conductive scaffold structures. A ball milling mixing method was used to
disperse the multiwalled CNTs (MWCNTs) at high concentrations (up to 40 wt.) in PLA.
Postiglione et al. also used PLA/MWCNT nanocomposite for additive manufacturing of
conductive 3D structures using a direct write method [56]. They reported a percolation
threshold concentration of 0.67% CNTs with a conductivity of 10 S/m, and the highest
conductivity was obtained with 5 wt.% MWCNT with 100 S/m.
Graphene is a 2D nanomaterial that attracts a growing interest in advanced
manufacturing. Graphene has low resistivity, high thermal and electrical conductivity,

https://doi.org/10.1515/9781501518782-003
32 3 Additive manufacturing of polymer composites

Polymer composites

Short fiber
Powder Continuous fiber
reinforced composites
reinforced composites reinforced composites

Figure 3.1: Classification of additively manufactured polymer composite materials.

and optical transparency. Multiple studies have used graphene to fabricate conductive
FFF filaments, and highly conductive (166 S/m) graphene-PLA FFF filaments were
successfully fabricated [57]. High cost of graphene, however, is the biggest concern
for wider application of these feedstock materials.
CB is another conductive filler material used for the additive fabrication of poly-
mer composites. CB is produced from the incomplete combustion of heavy petroleum
products such as coal tar and therefore, it is readily available and inexpensive [58].
Low cost, chemical stability, and high conductivity make CB one of the most popular
conductive additives. Kwok et al. prepared conductive polypropylene (PP)-based ther-
moplastic composites suitable for electrical circuit printing using FFF-based 3D print-
ing. High conductivity (~200 S/m) was achieved with composites containing a high
percentage loading of CB filler (≥30 wt%) [57]. The authors also showed that additively
manufactured composites containing over 25% CB by weight were suitable for fabrica-
tion and repair of the practical size electrical circuits.
Similar to electrical conductivity, thermal conductivity of polymer composites
can also be enhanced significantly by addition of conductive micro/nanomaterials.
This is due to the fact that within the material, heat can be transferred by electrons
that are also the carriers of electric current.

k = ke + k L (3:1)

where κ is total thermal conductivity, κe is the electronic contribution, and κL the lattice
contribution on heat conduction within a material. As electrical conductivity of a mate-
rial increases, electronic contribution in eq. (3.1) and therefore, thermal conductivity
increases as well. Recent studies have shown that conductive dopants (CNTs, gra-
phene, CB, copper, bronze, magnetic iron, and stainless steel) in powder form can sig-
nificantly enhance thermal conductivity of polymer composites [59, 60]. Therefore,
conductive material doped polymer composites can transport heat more effectively
compared to undoped polymers and provide uniform temperature distribution between
the print layers. As a result, thermal stresses, warpage, and spatial inconsistencies that
 3.1 Additive manufacturing of powder-doped polymer composites 33

occur due to the high temperature gradients can be minimized in components fabri-
cated with these high thermal conductivity materials.
Piezo electric materials can convert compressive and tensile stresses into an
electric charge, or vice versa. These materials find various applications ranging from
speakers and acoustic imaging to energy harvesting and electrical actuators.
Piezoelectric materials can be fabricated in different geometries by machining and/
or mechanical dicing using saws. These conventional fabrication methodologies
limit the size and shape complexity of piezoelectric elements. In addition, brittle pie-
zoelectric materials would be extremely difficult to shape into 3D geometries using
these fabrication techniques. To address these issues, Kim et al. [61] have demon-
strated a novel tool for fabricating 3D piezoelectric materials that relies on piezoelec-
tric nanoparticles embedded in a photocurable Poly(ethylene glycol) diacrylate
(PEGDA) polymer. Barium titanate nanoparticles (BTO) were chemically modified
with acrylate surface groups, which formed direct covalent linkages with the polymer
matrix under light exposure. In this study, piezoelectric polymer composites were
fabricated in complex 3D geometries (mushroom, cross, tapered cantilever, and mi-
crotubule structures) using SLA Vat polymerization technique. Doping with 10 wt%
loading of the chemically modified BTO nanoparticles resulted in the piezoelectric co-
efficient of ∼40 pC/N, which was found to be higher than the samples fabricated
using unmodified BTO nanoparticles and CNTs.
Nanomaterials can also be used to adjust optical properties of the additively
manufactured polymers. Depending on their size and environment, zero-dimensional
nanoparticles absorb light at different frequencies. As a result, these nanomaterials
have found common use for their rich-coloring effects by different industries includ-
ing cosmetics, food, and clothing. Recently, carbon quantum dots (CQDs) having 2–3
nm size were used to alter optical response of photocurable additive manufacturing
resins [62]. As shown in Figure 3.2, statue of liberty figures were fabricated using SLA
method by mixing CQD nanoparticles with clear SLA resin and laser solidification
into specified geometries. Optical response of the nanoparticle doped and undoped
(neat) and control samples to UV light were measured as shown in the figure.
As it will be discussed in the next section in more detail, doping materials in
powder form either do not have high aspect ratios required for mechanical strength
enhancement or do not possess reinforcing capability due to their nanoscale sizes
(i.e., CNTs). Therefore, instead of these nano/microscale doping materials, short and
continuous fiber reinforcements in larger scale are preferred to enhance strength and
stiffness (modulus) of polymer composites. Although enhancing tensile strength
and stiffness of polymers using micro/nanoscale reinforcements directly is not a via-
ble option, CNTs can be used indirectly to enhance the mechanical strength of addi-
tively manufactured polymers. Sweeney at al. [63] described the use of CNT-coated
thermoplastic filaments to increase the strength of the printed parts in FFF process.
In this method, thermoplastic filaments are coated with a thin CNT layer by dipping
these filaments into MWCNT ink prior to the 3D printing process. These CNT-coated
34 3 Additive manufacturing of polymer composites

(A) (B)

Figure 3.2: Change of optical properties in additively manufactured photopolymer: (A) SLA printed
the Statue of Liberty of CQD doped and undoped (right) photopolymer (the scale bar is 5 cm) and
(B) comparison of the specimen with the US dime. Figure was reprinted from [62].

filaments are then extruded via FFF to fabricate the components. Since the CNTs are
at the surface of the filament, during the extrusion process, they are deposited at the
interface of the printed roads. As the microwave heating is applied on the printed
materials, CNTs respond to these microwaves within polymers that cause local melt-
ing at the interface region between the printed layers. This facilitates material diffu-
sion in these areas and strengthens the adhesion between the layers. Since these
regions are the weakest sections in components fabricated via FFF method, local
melting at these areas has been shown to increase fracture and tensile strength of the
3D-printed materials. This method is also named as locally induced RF welding.

3.2 Additive manufacturing of short fiber-doped composites

Additive manufacturing of short fiber reinforced polymer composites (SFRPCs) are

gaining growing interest in composite manufacturing since the complex structural
parts can be manufactured without the need of special manufacturing tools.
SFRPCs can be manufactured with the same experimental procedures used for the
fabrication of neat and/or powder-infused polymers. In addition to the ease of
manufacturing, short fiber reinforcement can significantly increase mechanical
properties of polymers such as tensile strength, modulus of elasticity, and fracture
toughness unlike the powder-based reinforcements. Processing and additive
manufacturing of short fiber reinforced composites depend highly on the types of
 3.2 Additive manufacturing of short fiber-doped composites 35

polymer matrix: thermoplastic and thermoset polymers. Therefore, each composite

type will be investigated separately.

3.2.1 Short fiber reinforced thermoplastic composites

Additive manufacturing of thermoplastic materials using FFF manufacturing is a

well-established technology, and it offers high-resolution and low-cost investment
benefits as discussed in Chapter 1. Multiple studies exist in literature where chopped
polymer [64, 65], glass [66, 67], and carbon [68, 69] fibers were mixed with thermo-
plastic polymer resins such as PLA and ABS to prepare composite filament feedstock
for FFF process. Short fiber reinforced composites were then fabricated by melting
these filaments and extruding them on the printbed using FFF. Carbon fiber is the
most commonly used fiber reinforcement type due to its high strength, chemical and
temperature resistance, and low density. Previous studies performed on short carbon
fiber reinforcement have shown significant increase in tensile strength and elastic
modulus of composites compared to the neat, unreinforced thermoplastic matrix.
Enhanced stiffness (modulus) is especially important since the material distortion
and warping is significantly lowered in short fiber reinforced stiff composites during
3D printing process [70].
Although short fibers could be well oriented in the matrix as shown in Figure 3.3,
and high fiber volume ratio (~40%) could be achieved, maximum tensile strength of
the composites fabricated in these studies is below 100 MPa range (less than the un-
reinforced, thermoplastic PEEK polymer, see Figure 2.3). The major reasons behind
the low strength observed in short fiber reinforced thermoplastic composites are the
porosity between the printlines (unavoidable in FFF process) and poor fiber-matrix in-
terfacial adhesion as evidenced by the protruding carbon fibers shown in Figure 3.3.
The comparison of FFF-printed specimens to the compression molded samples by
Tekinalp et al. [69] shows that tensile strength and modulus of additively manufac-
tured composites reinforced with well-aligned fibers enhance as a function of fiber
content; however, these mechanical properties do not exceed those fabricated via com-
pression molding where fibers are randomly aligned (Fig. 3.4).
Short fiber reinforced thermoplastic filaments are commercially available today.
These filaments can be used in any FFF type 3D printing system provided that the
nozzle size and the fiber volume fraction are selected properly to prevent clogging of
the extruder with the short fibers during the printing process.

3.2.2 Short fiber reinforced thermoset composites

As described in the previous section, weak adhesion between the short fiber rein-
forcements and thermoplastic polymer is the main cause of low strength in these
36 3 Additive manufacturing of polymer composites

(A) (B)

500μm 150μm

(C) (D)

Triangular gap
among beads

50μm 50μm

Figure 3.3: Fracture surface SEM micrographs of FFF fabricated materials: (A)–(B) neat ABS and
(C)–(D) carbon fiber reinforced composite (figure was reprinted with permission).

composites. To enhance adhesion between fiber reinforcement and the matrix, fibers
are often coated with a few manometers of thick surfactant layer that is commonly
known as sizing. This coating, usually polymer, chemically couples the matrix and
the fiber creating a strong adhesion between these two components. Sizing chemistry
is well developed for coupling carbon fibers and thermoset resins where liquid resin
can wet the fiber surface and facilitate the chemical adhesion process. Additive
manufacturing of liquid thermoset polymers can be achieved using direct write
 3.2 Additive manufacturing of short fiber-doped composites 37

(A) (B)
90 20
18
80
Tensile strength (MPa)

Tensile modulus (GPa)

16
70 14
60 12
10
50 8
40 Compression molded 6 Compression molded
4
30 FDM printed FDM printed
2
20 0
0 10 20 30 40 0 10 20 30 40
Fiber loading (wt%) Fiber loading (wt%)

Figure 3.4: Comparison of FFF fabricated, carbon reinforced thermoplastic against compression
molding: (A) tensile strength comparison and (B) tensile modulus comparison. Figure was reprinted
with permission from [69].

method as described in Chapter 1. Direct write additive manufacturing of carbon fiber

reinforced epoxy thermoset composites were introduced in 2014 by Compton et al. [16]
for the first time. However, in this study, short fibers did not enhance the tensile
strength of the fabricated composites, which was probably due to the weak adhesion
between the thermoset matrix and the unsized fibers used in the composite. Recently,
Pierson et al. performed direct write manufacturing to fabricate carbon fiber/epoxy
composites where carbon fibers were sized for epoxy resin [71]. In this study, tensile
strength of 127 MPa was reached by using only 5.5% carbon fiber by volume as rein-
forcement. This was 236% increase in strength and 259% increase in elastic modulus
compared to the unreinforced epoxy. In addition, comparison of the same material
type fabricated via compression molding showed that additively manufactured sam-
ples showed 30% higher tensile strength and 47% higher elastic modulus. As shown
by the SEM images in Figure 3.5, direct write process leads to the alignment of carbon
fibers along the printing direction unlike compression molding where fibers are ran-
domly aligned. In this study, the authors also observed that fiber aspect ratio, fiber vol-
ume fraction, and orientation significantly affect the mechanical properties (strength
and modulus). The relationship between the fiber morphology and the mechanical
properties are described in the next section in more detail.
In addition to carbon fiber, short Kevlar fibers were also used as reinforcements
to additively fabricate thermoset composites by direct write method [64]. This study
showed that composite strength and modulus increased as a function of Kevlar
fiber volume fraction. In addition to the strength and modulus, elongation at break
of the composites was also increased due to the high flexibility of Kevlar (aramid)
fibers. Therefore, additively manufactured Kevlar reinforced composites have high
potential for applications where higher fracture toughness and impact resilience
are needed along with high strength and stiffness.
38 3 Additive manufacturing of polymer composites

Figure 3.5: SEM micrographs of the fractures surfaces: (A-C) random fiber alignment within
compression molding sample and (D-F) uniformly aligned short carbon fibers in 3D-printed
composite. Image was reprinted with permission from [71].

Maximum fiber loading in all of these additively manufactured thermoset com-

posite studies described earlier were limited to maximum of 5.5% by volume. It was
reported that exceeding carbon fiber over 5.5% results in discontinuous flow, nozzle
clogging, and inability of fabrication. Developing novel additive manufacturing
technologies to fabricate short fiber reinforced composites with high fiber load-
ing will make a tremendous impact for the adaptation of these materials at wider
scales.

3.3 Prediction of mechanical properties of short fiber reinforced

composites
For composite systems where short fibers are perfectly aligned, elastic modulus can
be predicted by the well-known Halpin–Tsai analytical model [14, 72, 73] as follows:

ð1 + 2sηL f ÞEm ðEr =Em − 1Þ

EL = and ηL = (3:2)
1 − ηL f ðEr =Em + 2sÞ
 3.3 Prediction of mechanical properties of short fiber reinforced composites 39

where s is the aspect ratio of the fibers, f is the fiber volume ratio, and Er and Em are
the elastic moduli of the reinforcement and matrix, respectively. The elastic modu-
lus (ER) of a material with randomly oriented fibers can be obtained by the modulus
in longitudinal and transverse directions as follows:
3 5
ER = EL + ET (3:3)
8 8

where ET is the elastic moduli in longitudinal and transverse directions and ob-
tained by

ð1 + 2ηT f ÞEm ðEr =Em − 1Þ

ET = and ηT = (3:4)
1 − ηT f ðEr =Em + 2Þ

According to these models, modulus in longitudinal direction increases by increas-

ing the aspect ratio of the fiber and the fiber volume ratio within the composite. In
transverse direction, however, fiber aspect ratio has no effect on the composite
modulus. Strength predictions can also be made using models described in [72, 73].
The ultimate strength of a material with aligned fibers is obtained as follows:
8 σm
>
> fs pffiffiffi + ð1 − f Þσm , s < sc
< 3
σL =  pffiffiffi  (3:5)
>
> σ 3 Þ
: f σr 1 − r + ð1 − f Þσm , s ≥ sc
4sσm

where sC is the critical aspect ratio of the fibers, f is the fiber volume ratio, and σr
and σm are the ultimate strengths of the fiber reinforcement and the matrix, respec-
tively. For strength calculations, critical aspect ratio (sC ) plays an important role.
Critical aspect ratio (sC ) is defined as follows:
pffiffiffi
σr 3
sc = (3:6)
2σm

The strength of a material (such as that fabricated by compression molding) with

randomly oriented fibers is calculated using the directional strengths as follows:
3 5
σR = σL + σT (3:7)
8 8

where σT is the strength in transverse direction and is obtained by

 
f
σT = σm pffiffiffi − f + 1 (3:8)
3
These analytical formulations indicate that if a fiber aspect ratio is below a critical
value (sc), fiber strength does not contribute to the composite strength. This agrees
well with the concept that the increase in aspect ratio results in an increase in strength
40 3 Additive manufacturing of polymer composites

and explains why tensile strength cannot be enhanced using powder reinforcements
with low aspect ratio as described in the previous section. Experimental validation of
the predictions above was performed recently by Pierson et al. [14] as shown in
Figure 3.6 where the experimental results for composites were both fabricated by addi-
tive manufacturing and compression molding techniques. Experimental test results
for the compression molded composites where fibers are randomly aligned closely
match the random fiber orientation predictions as shown in this figure. The authors
also observed that strength and modulus of the composites fabricated with additive
manufacturing was lower than those predicted according to the analytical models de-
scribed earlier. This mismatch can be due to the fact that analytical models given in
eqs. (3.2)–(3.8) assume perfect alignment of fibers within the composite. As shown in
SEM images, high degree of fiber alignment was observed in the additively manufac-
tured composites; however, fibers were not perfectly aligned in these material sys-
tems. Fiber misalignment as well as printing defects such as voids could lower the
strength and stiffness of the additively manufactured thermoset composites.

(A) (B)
12 250
AM experiment AM experiment
Alighned fiber prediction Aligned fiber prediction
10 CM experiment CM experiment
Tensile strength (MPa)

200
Elastic modulus (GPa)

Random fiber prediction Random fiber prediction

8
150
6
100
4

2 50

0 0
0 1 2 3 4 5 6 0 1 2 3 4 5 6
Carbon fiber volume fraction (%) Carbon fiber volume fraction (%)

Figure 3.6: Experimental and analytical model comparison of additively manufactured and
compression molded epoxy-carbon fiber thermoset composites for (A) elastic modulus and
(B) ultimate tensile stress. Image was reprinted with permission from [71].

3.4 Alignment of short fibers within additively manufactured

composites
Mechanical performance of SFRPCs strongly depends on the fiber length (or aspect
ratio) and the alignment of these short fibers within the fabricated composite struc-
ture. Theoretical [74, 75] and the experimental [14] studies have shown recently that
if the short fibers are well aligned, mechanical performance can be enhanced signifi-
cantly in the alignment direction. In addition to the mechanical properties, thermal
and moisture absorption properties of the composites can also be manipulated/
 3.5 Additive manufacturing of continuous fiber reinforced composites 41

enhanced by aligning fibers in specified orientations. Therefore, controlling the fiber

alignment has been investigated by many researchers due to its significant impact on
the physical properties of the additively fabricated materials. Different techniques
can be used to perform the alignment of short fibers in 3D printing technologies such
as applying electrical/magnetic field or shear induced fiber alignment. Each of these
methods is briefly explained later.
External magnetic and electric fields have been applied to manipulate fiber align-
ment in the liquid resin during stereolithography process. Nakatomo and Kojima used
magnetic field to align ferromagnetic γ-Fe2O3 fibers within a polymer [76]. For electrical
field alignment, conductive whiskers were used instead of ferromagnetic fibers. When
the electric field is applied on the photopolymer filled with the whiskers, a moment is
created on the whiskers which align them along the electric field in the liquid photo-
polymer [77]. Fiber alignment by electrical and magnetic field application during addi-
tive manufacturing requires advance mathematical understanding of the forces
generated from external forces, and these methods are limited to certain type of materi-
als (i.e., magnetic or conductive materials). In direct write additive manufacturing of
fiber reinforced polymer composites, fibers are suspended in a viscous polymer me-
dium and are forced through a converging nozzle aligning along the fluid flow direc-
tion due to shear forces between fibers and nozzle walls. Simulation studies carried out
by Lewicki et al. [78] and Yang et al. [79] suggest that internal surface-to-volume ratio
of the nozzle and rheology properties of the continuous phase fluid are two important
factors to achieve efficient shear alignment in extrusion. In other words, fiber align-
ment takes place naturally in direct write fabrication if these parameters are optimized.
Significant effort is ongoing to optimize process parameters and develop better
strategies to enhance fiber alignment in additive manufacturing. Manipulating fiber
orientation in the desired directions and achieving high degree of fiber alignment
(>90%) will dramatically alter mechanical, thermal, and electrical properties of poly-
mer composites and hence make a great impact in additive manufacturing of these
materials.

3.5 Additive manufacturing of continuous fiber reinforced

composites

Reinforcing composites using short fibers is capable of enhancing strength, stiff-

ness as well as fracture resistance provided that the fibers are well aligned in the
printing direction and high fiber volume ratios are achieved. The enhancement in
strength and stiffness increases as the aspect ratio (s) of the fiber reinforcement in-
creases as shown in eq. (3.5). Therefore, if high strength is needed as that of metal-
lic parts, continuous fiber reinforcement should be considered.
FFF technique has been applied by multiple researchers to fabricate continuous
fiber reinforced polymer composites, recently. In these studies, different types of
42 3 Additive manufacturing of polymer composites

fibers (glass, carbon, and Kevlar) were used to reinforce thermoplastic nylon poly-
mer using commercially available MarkForged 3D printer [80, 81]. Strength and
modulus of composite samples significantly increase as the fiber loading amount is
increased in composite. In these studies, maximum strength and modulus enhance-
ment was obtained in the longitudinal (0°) direction along which fibers are depos-
ited. Cross-hatch deposition (±45°) of fibers resulted maximum elongation at break
for the same amount of fiber loading [80]. Figure 3.7 represents four types of dog-
bone specimens fabricated for mechanical characterization: unreinforced nylon,
carbon fiber composite reinforced in uniaxial print direction, Kevlar reinforcement
in uniaxial print direction, and Kevlar reinforcement in cross-hatch (±45°) array.

Nylon Nylon/C-fiber Nylon/Kevlar Nylon/Kevlar

unidirectional unidirectional +45–45

Figure 3.7: Three-dimensional-printed continuous fiber reinforced composites. Unreinforced nylon

and composites reinforced with uniaxial carbon fibers, uniaxial Kevlar fiber, and cross-hatched
Kevlar fiber. Matrix material is nylon in all composites.

In order to estimate the elastic modulus of the continuous fiber reinforced compo-
sites along the fiber direction, the rule of mixtures is commonly utilized. Prediction
of elastic moduli for the rule of mixture is reported as follows:

Ec = Er f + ð1 − f ÞEm (3:9)

where E and V represent elastic moduli and fiber volume fraction, respectively.
Indices r, m, and c correspond to fiber reinforcement, matrix, and composite, re-
spectively. Similarly, composite strength (σc ) can also be predicted from the rule of
mixture equation as follows:

σc = σr f + ð1 − f Þσm (3:10)
 3.5 Additive manufacturing of continuous fiber reinforced composites 43

The rule of mixtures model predicts that the strength and modulus of additively man-
ufactured composites increase significantly as the fiber volume fraction increases.
High volume fractions (~40%) can be achieved with dual nozzle commercial FFF sys-
tems where the first nozzle is used for fiber deposition while the second nozzle is
used to extrude thermoplastic polymer, which solidifies and encapsulates fiber rein-
forcement right after deposition. In-nozzle impregnation methods have also been
used recently where fiber bundle and thermoplastic melt are mixed within the ex-
truder and deposited on the surface using a single nozzle. The schematic of in-nozzle
impregnation process is shown in Figure 3.8. Similar to the dual nozzle extrusion,
high fiber volume fraction was also reported with this method [82, 83].

(A) (B)
Thermoplastic resin filament Twisted jute yarn

Reinforcing fibers Drive gear

Printer head Carbon-fiber tow 10 mm

Preheater

Heater (c)
Nozzle
z Printer
y nozzle
x Carbon FRTP
Hot table
Continuous fiber composites

Figure 3.8: FFF printing of continuous fiber composites by in-nozzle impregnation: (A) schematic
and (B) fiber bundles used in FFF; and (C) photograph of the 3D printing process. Figure was
reprinted with permission from [83].

Continuous fiber reinforcement offers significant improvement in mechanical properties

compared to discontinuous fibers. However, compared to the additive manufacturing of
powder and short fiber reinforced composites, additive manufacturing of continuous
fiber composite systems possesses additional difficulties such as controlling the dual
material feeding, slicing for multimaterial system, and weak bonding between the fibers
and the thermoplastic polymer. Surface modification of carbon fiber bundle with meth-
ylene dichloride and PLA particles [82] improved adhesion and increased tensile and
flexural strength. Oztan et al. [80] also reported that microstructural defects in FFF pro-
cess can significantly reduce the strength and stiffness of the composites. It has been
also shown that optimizing the additive manufacturing process parameters (i.e., print
temperature, layer thickness, hatch spacing, number of fiber layers, etc.), thermal treat-
ment of the printed samples and postpressure treatment could reduce manufacturing
defects and improve mechanical performance of these composite materials [81, 84].
44 3 Additive manufacturing of polymer composites

As discussed in short fiber composite section, thermoplastic polymers weakly

adhere on reinforcing fibers. Recently, additive manufacturing of continuous fiber
reinforced epoxy (thermoset) composites has been introduced by Hao et al. [85]. In
this study, a carbon fiber bundle is pulled through an epoxy resin pool and this
wetted fiber tow is then extruded on the printbed using a 2-mm printing nozzle.
Tensile strength of 792.87 MPa and elastic modulus of 161.4 GPa could be achieved
in this study. Ming et al. [86] used a similar system with a difference of initial im-
pregnation step as shown in Figure 3.9A. In this work, a 3K carbon fiber tow was
impregnated with E-20 epoxy resin at 130 °C. Lowered resin viscosity at high tem-
perature and fiber tow pulling process with multiple rollers helped the penetration
of the resin into the fibers. This fabricated filament was then fed into a heated
printer head where the fiber filament moves through a viscous epoxy resin at 130 °C
(similar to the wetting step) and printed on the sample surface (Figure 3.9B) where
the resin cools down becoming more viscous which results in enhanced shape sta-
bility. After curing at 160 °C, unprecedentedly high tensile strength and modulus of
1,476.11 MPa and 100.28 GPa were achieved in this study.

Figure 3.9: Additive manufacturing of continuous carbon fiber reinforced thermoset composites.
Figure was reprinted from [86].

Additive manufacturing of continuous fiber reinforced thermoset composites is at

its infancy and more work is necessary for fabrication of composite structures with
high mechanical performance. The proof-of-concept studies described earlier show
the challenges and limitations of this additive manufacturing technology. It is how-
ever clear that this active area of research will gain more popularity in the near fu-
ture due to superior mechanical properties of additively manufactured continuous
fiber reinforced composites reported in these recent studies.
 3.6 Mechanical performance comparison 45

3.6 Mechanical performance comparison of additively

manufactured polymer composites
Polymer composites can be additively manufactured using different types of reinforce-
ments. Micro/nanoscaled dopants in powder form can be utilized to alter especially
thermal and electrical properties of polymers. Polymer additive manufacturing meth-
ods such as Vat polymerization, extrusion, and material jetting can be applied for fab-
rication of these composites. Similar techniques can be used for fabrication of SFRPC.
Short fibers provide enhanced strength, stiffness, impact resistance, and reduced
warpage. Continuous fiber reinforced composites however are preferred for higher
strength applications. Currently, extrusion based additive manufacturing is the only
suitable method for the additive fabrication of these systems. Although the fabrication
of these composites is more challenging compared to discontinuous reinforced compo-
sites, they offer significantly higher mechanical performance. Figure 3.10 shows the
comparison of the strength and elastic modulus properties of selected studies on addi-
tively manufactured, short, and continuous fiber composites.

1,600

1,400

1,200 Continuous fiber

thermosets
Strength (MPa)

1,000
Continuous fiber
800 thermoplastic

600

400

200
Short fiber thermoset
0
0 50 100 150 200
Elastic modulus (GPa)

Figure 3.10: Strength versus modulus comparison of additively manufactured fiber reinforced
composites.

As shown in this figure, continuous fiber reinforced composites are significantly

stronger and stiffer compared to short fiber composites. In addition, mechanical
performance of thermoset composites exceeds those of thermoplastic matrix com-
posites. However, there are only a limited number of studies regarding the additive
manufacturing of thermoset-based composite materials. Figure 3.11 shows how
46 3 Additive manufacturing of polymer composites

1,600

1,400

1,200
Thermoset composites

1,000
Strength (MPa)

800

600

400

200
Thermoplastic composites

0
0 10 20 30 40 50 60
Fiber volume fraction (%)

Figure 3.11: Variation of strength as a function of fiber volume fraction.

tensile strength polymer composites vary as a function of fiber volume fraction and
polymer matrix type. In this chart, short and continuous composites are grouped
together under two main categories of thermoset and thermoplastic composites. It
is clear from the figure that thermoset composites provide higher strength for the
same amount of fiber volume content compared to thermoplastic composites. The
main reason behind this result is the weak adhesion between the fibers and the
thermoplastic matrix as described previously. In addition, direct write additive
manufacturing of thermoset composites results less defects and porosity compared
to FFF process used for thermoplastic manufacturing. As discussed in the previous
section and implied in Figure 3.11, short fiber reinforced thermosets have high po-
tential for strength enhancement. The fiber volume fraction however is limited to
5–6% in the state-of-the-art studies. Therefore, future efforts for composite additive
manufacturing must focus on increasing the fiber volume fraction in short fiber re-
inforced thermoset composites, enhancing the fiber–matrix adhesion in thermo-
plastic composites and optimization of the process parameters in continuous fiber
reinforced thermoset composites.
4 Additive manufacturing of metals

Polymers and polymer composites form the majority of the feedstock materials used
in additive manufacturing (AM) today. AM of metals, however, is gaining an in-
creased popularity due to the unmatched mechanical performance of metals and
their higher service temperatures over polymers. In addition, manufacturing of
metal feedstock materials is based on well-established technologies providing low-
cost benefits. The sale of metal AM systems marked a remarkable (~80%) increase
in 2017 compared to 2016 as reported by Wohlers Associates Inc. [87], the company
offering strategic advice on AM. Rapid increase on AM of metals is driven by the
improved metal processing technologies such as higher part quality, enhanced fab-
rication speed, and lowered cost of metal additive machines.
Additively manufactured metals can be used in numerous fields including dental,
aerospace, biomedical, and automotive industries. Additively manufactured, biocom-
patible metals such as Ti-6Al-4V are preferred in orthopedics where patient-specific im-
plants can be fabricated. In addition, the capability of fabricating these implants with
controlled porosity has benefits of matching the mechanical properties of implants to
those of the native joints and bone ingrowth allowance to improve their functionality.
Aerospace is also one of the leading industries promoting the new technologies for ad-
ditively manufactured metals due to the possibility of fabricating lightweight compo-
nents in complex geometries leading to significant amounts of weight reduction. In
automotive industry, AM is mainly preferred for rapid prototyping and the concept de-
sign stages rather than the end part manufacturing. AM, however, is preferred for
manufacturing of numerous components in luxury vehicles and the automobiles that
are customized for the user with the limited number of productions. In addition, for
highly complex parts justified by a substantial vehicle improvement, AM can be the
preferred choice over the traditional manufacturing. The number applications and the
users of additively manufactured metal components are on the rise in various fields
due to the recent developments of this technology.
As described in Chapter 1, different methods can be used for metal AM. Powder
bed fusion, direct energy deposition (DED), binder jetting, and extrusion are some of
these major metal AM techniques. The market breakdowns for the metal printing
technologies used during 2019 are shown in Figure 4.1 as reported by Aniwaa [88].
DED uses powder or wire metal feedstock and this technique is preferred to fabri-
cate large parts due to its high deposition speed. DED using wire is faster than the pow-
der feedstock and large components can be fabricated. Low resolution is the downside
of this metal fabrication technique. Extrusion involves mixing metal powders (up to
60–70%) with thermoplastic material and extrusion of the prepared filaments using
FFF method. Although simple and cost-effective, high-grade metallic properties (me-
chanical, thermal, and electrical) cannot be achieved with these metal–polymer com-
posites fabricated via FFF. Binder jetting can be used to fabricate metal parts with high

https://doi.org/10.1515/9781501518782-004
48 4 Additive manufacturing of metals

Others
Extrusion
4%
10%

Material/binder jetting
16%

Direct energy deposition

16%

Powder bed fusion

54%

Figure 4.1: Market breakdown in metal additive manufacturing technologies [89].

resolution. This technique, however, is a multistep process, including printing, binder

removal, and sintering process. Porosity and shrinkage of the component after sinter-
ing are also other disadvantages of this process in metal printing. Powder bed fusion is
by far the most commonly used metal AM technology covering more than half of the
metal manufacturing industry as shown in Figure 4.1. Powder bed fusion is preferred
over the other metal additive methods due to its versatility, repeatability, usability of
the fabricated parts without postprocessing, and the availability of large range of pow-
der feedstock. This book will therefore focus on the powder bed fusion in the remain-
der of this chapter, and the current status of this technology will be described.
Metal powder bed fusion technologies can be classified into two main groups ac-
cording to the type of the energy source for coalescing metal powders: laser-assisted
manufacturing and electron beam melting. In laser-assisted manufacturing, high
power laser sinter is used to partially or fully melt the powder feedstock for part form-
ing. Electron beam melting technology uses electron beam energy source instead to
melt the metallic powders in vacuum to form layer-by-layer deposition. Whether a
laser or an electron beam source is used for the manufacturing process, powder bed
fusion requires high-quality powder feedstock to manufacture metallic components
having the desired performance. The next section describes the common technologies
used for preparing metallic powder feedstock for powder bed fusion process.

4.1 Feedstock material fabrication for powder bed fusion

The quality and the performance of additively manufactured components depend

strongly on the quality and the cost of the metal powders used in powder bed fusion.
 4.1 Feedstock material fabrication for powder bed fusion 49

The powders must meet the rigorous requirements of chemical composition and mor-
phology. In addition, microstructural composition makes a great impact on the physi-
cal properties of the manufactured parts. In general, metallic powders must be free of
any contamination to maximize the quality. Upper limits of the contaminants of the
metallic powders used for AM are specified in ASTM standards F42.05 on Materials and
Processes [90]. As an example, ASTM standard mandates that the oxygen and nitrogen
content of finished Ti-6Al-4V products to be lower than 0.2 and 0.05 wt%, respectively
[91]. In addition, powder bed fusion methods require the powder to have excellent
flowability, which dictates that the powder must have spherical shape and the particle
sizes must be reasonably large. The flowability of the powder decreases with a decrease
in particle size. However, geometric resolution and surface quality diminish as the
powder size is increased. Therefore, spherical metallic powders with low contamina-
tion and good flowability are the desired feedstock materials for metal AM.
To fabricate metallic powders in spherical shapes to be used for powder bed fusion
feedstock, four major processing routes are preferred. These are water atomization, gas
atomization (GA), plasma atomization, and plasma rotating electrode process (PREP).
Atomization in powder manufacturing refers to a separation process where bulk liquid
is broken down into small droplets. This concept is used in all of the spherical powder
fabrication techniques where solid metal in wire or powder form is melted and con-
verted to metal droplets that solidify into a spherical shape as it cools down. In water
atomization processes, the liquid alloy free falls through the atomization chamber. It is
then rapidly cooled down and atomized by the water jets around the chamber. As the
metal droplets solidify, fabricated powder is collected at the bottom of the chamber
and dried. Due to the high cooling rates, metal powder produced with this method is
typically coarse, highly irregular in morphology that reduces both packing and flow-
ability properties [92]. In addition, metal oxidation is a great concern that does not
only influence the powder flow behavior but also impacts the melt pool, and conse-
quently, changes the bulk material composition and the mechanical properties of the
fabricated parts. Therefore, water atomization is not suitable for reactive materials
such as titanium, and it is mostly applied in steel powder production.
To overcome the limitations of water atomization that yields low spheroidicity
and applied only to nonreactive materials, GA is preferred as the feedstock fabrica-
tion method for powder bed fusion. GA process is similar to water atomization;
however, liquid metal is atomized by high pressure jets of gas instead of water dur-
ing the atomization process (Figure 4.2A). Inert gas (nitrogen or argon) is generally
used to reduce oxidation and contamination of the metal. Due to the lower heat ca-
pacity of the gas (compared to water), the metal droplets cool down more slowly
and therefore more spherical powder particles are obtained. Although interstitial el-
ements can be well controlled in gas-atomized powders, there are still potential
contamination risks that can originate from the ceramic crucibles and atomizing
nozzles used in this technique [92]. Electrode induction melting GA (EIGA) can lower
this contamination issue. In EIGA process, metal bar is melted by an induction coil
50 4 Additive manufacturing of metals

Ar
(A) Melt (B) (C)
liquid Electrode

Plasma Titanium
Melt torches spool
powder Motor Melt
Argon powder
Fixed
tungsten
electrode

Vacuum
Powder

Powder Hopper
Vacuum
pump

(A) (B) (C)

200 μm 200 μm 50 μm

Figure 4.2: Schematics of the atomizing processes and SEM micrographs of Ti-6Al-4 V spherical
powders fabricated by (A) gas atomization, (B) plasma rotating electrode process and (C) plasma
atomization. Reprinted with permission from [94].

prior to entering the atomization chamber and a film of molten metal flows down-
ward into a gas stream for atomization. Since metal feedstock does not come in con-
tact with either crucible or electrode during atomization process, contamination is
minimized. Internal voids within individual particles that contain trapped argon are
another concern for gas-atomized metal powders [93].
Plasma atomization resembles the EIGA process since a metal wire is used as the
metal feedstock as shown in Figure 4.2C. However, this metal wire is fed into a hot
zone and melted by plasma torches unlike induction coils used in EIGA process.
Molted wire is broken into metal droplets that would cool rapidly. Similar to the EIGA
process, plasma-atomized metal powders have high purity since the liquid metal
does not contact any other crucible or electrode that may contaminate the powder
before solidification. In general, the yield of fine powder using the plasma wire atom-
ization technique is significantly higher than that of conventional GA processes. The
plasma-atomized powder has very good sphericity and fewer satellites particles than
the gas-atomized powder. However, porosity due to trapped gas during atomization
still exists in plasma-atomized powders [93]. In addition, the feedstock must be in
wire form, which would increase the fabrication cost and reduce applicability of this
method on wider range of metals and alloys. Recently, a new plasma atomization
technology (a.k.a. plasma spheroidization) has been developed where metal powders
are used as feedstocks rather than metal wires. In this technique, the particle sizes do
 4.2 Feedstock materials used in metal AM 51

not change during powder plasma atomization but rather irregular particles are con-
verted into spherical powders. Plasma-atomized particles typically have high spheroi-
dicity as the other atomized powders shown in Figure 4.2, and the impurity level of
the plasma spheroidized powders is largely determined by the quality of the feed-
stock powder. Using powder feedstock instead of wire and minimal amount of satel-
lite in the fabricated powder are advantages of this technique. High investment cost
of plasma atomization is the main drawback in this method.
In order to fabricate spherical metal powders with the utmost purity, PREP, is
preferred. In this method, as its name indicates, a metal rod electrode rotating at a
high speed is melted by the tungsten-tipped cathode (Figure 4.2B). The molten liquid
is then spun off from the electrode surface to form droplets because of the generated
centrifugal force. These droplets solidify during the flight of these particles and form
spherical metal powders. Metal powders fabricated with PREP technique has high pu-
rity as the liquid metal has no contact with other metals or crucibles. In addition,
these powders have minimal gas pores compared with the other production methods,
which use the high pressure gas. In addition, liquid metal droplets fly radially
away from the metal surface under the effect of a centrifugal force, and there-
fore the chance of collisions of droplets and particles to form satellites is very
low [93]. High cost and low yield of powder fabrication are the downsizes of
this fabrication technique. Yield is low since the fabricated powder is usually
too coarse for powder bed fusion AM applications. Increasing the rotation
speeds of the metal electrode reduces the particle size but may create dynamic
forces and balancing issues as reported in [95]. Comparison of the powder
manufacturing technologies is given in Table 4.1, where major properties of
these techniques are summarized.
New powder production methods are currently under development to obtain,
high purity and low-cost feedstock fabrication. Electrolytic methods, metallother-
mic processes, and the hydride–dehydride process are some of these techniques
with high potential to be considered as cost-effective alternatives for metal powder
production [96].

4.2 Feedstock materials used in metal AM

Common materials used in AM of metals are steel (stainless and tool), aluminum,
titanium, and its alloys as well as Ni-based alloys (Inconel) and other metallic mate-
rials. Figure 4.3 shows the breakout percentages for the current usage of these met-
als in AM industry. Stainless steel and titanium-based materials mark the majority
of the metallic material used by AM applications currently.
Steel is the most commonly used engineering material as of today. Similar to the
conventional manufacturing, steel is also the most commonly used metallic material in
AM as shown in Figure 4.3. Excellent mechanical properties make these materials the
52 4 Additive manufacturing of metals

Table 4.1: Summary of metal powder processing technologies (modified from [92]).

Manufacturing Particle size, Advantages Disadvantages Metal types

process µm

Water atomization – High throughput Low spheroidicity Nonreactive

Range of particle Satellites present
sizes Wide PSD
Feedstock in ingot Low yield in – µm
form

Gas atomization – Wide range of Satellites present Ni, Co, Fe, Al
materials Wide PSD Ti (EIGA)
Feedstock in ingot Low yield in – µm
form
High throughput
High spheroidicity

Plasma – High purity Feedstock in wire or Ti, Ti-Al-V

atomization High spheroidicity powder form
High cost

PREP – Highest purity Very low yield Ti, Exotics

High spheroidicity High cost

Tool steel
4%

Aluminum
15%
Stainless steel
50%

Inconel
8%

Titanium
23%

Figure 4.3: Commonly used metals in powder bed fusion AM [97].

 4.2 Feedstock materials used in metal AM 53

desired material choice for AM applications. In addition, metal additive technologies

are suitable for the fabrication of various types of steels. Austenitic stainless steels
(i.e., 316 L) are the most commonly used steel type in AM. However, maraging steel,
precipitation hardenable stainless steels, martensitic cutlery grade, and tool steel (H13)
have also been investigated. Mechanical properties of steels depend strongly on their
microstructure, which can be tailored by controlling the process parameters such as
the cooling rate, the temperature gradients, and the elemental composition. Therefore,
metal AM offers producing metallic parts with unique microstructures and mechanical
properties by the precise control of the process parameters during manufacturing.

4.2.1 Titanium and titanium alloys

Titanium (Ti) and its alloys are gaining popularity in AM due to their excellent strength,
lightweight, and biocompatibility. As a result, these metals have already found numer-
ous applications in automotive, aerospace, and healthcare industry. In addition, high
material costs, difficulty in manufacturing these materials via conventional processing
make these materials excellent candidates for specialized AM applications. Pure Ti and
Ti-6Al-4V alloy have been widely used in commercially available powder bed fusion
technologies. Although to a lesser degree, other titanium alloys have also been investi-
gated including Ti-24Nb-4Zr-8Sn and Ti-6Al-7Nb for biomedical applications, and Ti-
6.5Al-3.5Mo-1.5Zr-0.3Si for aerospace applications [96].

4.2.2 Aluminum alloys

Unlike steel and titanium, conventional manufacturing of aluminum (i.e., casting, ma-
chining etc.) is relatively easy and cost-effective. Therefore, AM of aluminum parts has
lower commercial advantage compared to steel and titanium. In addition, aluminum
alloys are known to be challenging materials for AM due to their poor flowability dur-
ing recoating process in powder bed fusion. These materials also reflect laser highly
during laser based fusion process [96]. All of these manufacturing difficulties and the
commercial disadvantages limit the use of aluminum in this field. However, low cost
and lightweight of aluminum make it and its alloys an attractive option for AM. High
thermal conductivity of Al reduces thermally induced stresses, thus also reducing the
need for extensive support structures. In addition, the high thermal conductivity allows
for higher processing speeds. By the development of new AM technologies overcoming
the difficulties of aluminum AM and with more aluminum powder suppliers, it is ex-
pected that aluminum will be among the key AM materials in the shift toward larger
batch production of mass goods [98].
54 4 Additive manufacturing of metals

4.2.3 Other metals

High performance metals other than steels, aluminum, and titanium have also been
under investigation by AM community. Ni-based superalloys are the major metals
among these used for high-temperature applications, such as Inconel 625 and Inconel
718, and NiCoCr for biomedical applications [96]. In addition, invar (nickel–iron) al-
loys have been used for applications requiring a low coefficient of thermal expansion
in powder bed fusion.
High entropy alloys are defined as metallic alloys that contain three or more multi-
principal elements, with equal, or near equal atomic percentages [99]. High entropy
alloys are solid solution alloys with a single crystal structure and present special me-
chanical and chemical properties such as combination of high yield strength and duc-
tility, microstructural stability, and high mechanical strength at elevated temperatures,
high resistance to corrosion, and oxidation. As a result, these materials have found sig-
nificant interest in AM community. Powder bed fusion has been used to manufacture
various different types of high entropy alloys including FeCoCrNi, AlCoCrFeNi, and
CoCrFeMnNi [99–101]. In these studies, superior strength and ductility of these materi-
als have been reported due to the formation of single-phase solid-solution state.

4.3 Design considerations in metal AM

Unlike conventional manufacturing, several process-related conditions must be taken

into account in AM of metals. These are void formation, residual stresses, surface
roughness, and the postprocessing. Each of these parameters can significantly alter the
mechanical performance of the manufactured parts, and therefore they must be care-
fully assessed and optimized. Following section describes these process parameters
and their effects on the performance of the additively fabricated metal parts.

4.3.1 Void formation

Spatter ejection (powder jump) takes place when a metal powder flies out of the
laser’s path, lands back on certain parts of the fabricated material contaminating
the powder bed, and therefore affecting the build quality of a layer. This is more
pronounced if the laser intensity is very high. In addition to the spatter, using high
laser intensity will lead to higher melt pool dynamics and reduced density originat-
ing from pores formed due to entrapped gas [96]. These pores have generally spher-
ical shape, as they are formed during evaporation of material. On the other hand, if
the laser intensity (power) is too low, the metal powders may not fuse adequately,
and these loose powders can create voids within the printed part. These pores form-
ing as a result of unmolten material have irregular-shaped voids. Irregular-shaped
 4.3 Design considerations in metal AM 55

voids lead to higher stress concentrations than the spherical voids and act as crack
initiation sites during mechanical testing. Therefore, irregular-shaped voids are
considered to be more deteriorating on mechanical properties than the spherical
ones as these voids can lead to premature material failure.

4.3.2 Residual thermal stresses

During metal 3D printing, pristine alloy feedstock is exposed to a series of process-

ing steps, including rapid melting and fast solidification, which can lead to thermal
stress in the finished part [102]. When this residual stress exceeds the strength of
the printing material or substrate, defects, such as cracking in the part or warpage
of the substrate, can occur. Residual stress can be minimized by postheat treatment
and optimizing the printing process parameters. Thermal stresses are also material
dependent, and therefore, different metals (aluminum, steel, titanium) can show
different levels of sensitivity to volumetric changes under the same thermal condi-
tions leading to different amounts of residual thermal stresses.

4.3.3 Surface roughness

Surface roughness is a defect affecting the quality, aesthetics as well as the me-
chanical performance of printed parts. Although surface roughness may not affect
the static mechanical performance of the additively manufactured parts, it can be
detrimental in fatigue type of loading conditions as it will be explained later. It is
therefore a common practice to mechanically or chemically reduce the surface
roughness in additively manufactured components. Powder size, cooling rate, and
spatter can affect the surface roughness.

4.3.4 Postprocessing

Postprocessing may be applied on the fabricated metallic components to reduce thermal

stresses, reduce porosity, optimize grain microstructure, and reduce surface roughness.
Therefore, unlike polymer AM, postprocessing procedures are commonly performed on
additively manufactured metals while keeping the parts connected to the build platform.
ASTM has recently reported the postprocessing conditions to standardize the postpro-
cessing for metals manufactured via powder bed fusion in ASTM F3301 standard [103].
56 4 Additive manufacturing of metals

4.3.4.1 Stress relief

As described earlier, residual stresses can be detrimental for static and dynamic me-
chanical properties of additively manufactured metallic components. These stresses
must be relieved before the part is removed from the build plate to avoid the warp-
age and/or cracking of the parts. Stress relieving is achieved by inserting the entire
build plate in an oven. Temperature and the duration of the stress relief process are
specified for different metals in the ASTM F3301 standard.

4.3.4.2 Heat treatment

In addition to the stress relieving, heat treatment such as aging and solution an-
nealing are performed on the fabricated to optimize the grain microstructure and
improve the mechanical properties of the parts. Heat treatment may distort the di-
mensions of the parts, and therefore, it is usually applied prior to the final surface
finishing and machining.

4.3.4.3 Hot isostatic pressing

Hot isostatic pressing (HIP) is defined as the simultaneous application of high tem-
perature and pressure on metallic components to reduce porosity within these parts.
Temperature control is provided by a furnace, which is located within a pressure ves-
sel. Inert gas is used during the HIP process to apply uniform isostatic pressure that
forces internal voids to collapse and densify the material. Eliminating defects and
voids in HIP process significantly improve mechanical properties of the metallic com-
ponents. HIP process is a well-established process for a wide variety of materials
such as titanium, steel, aluminum, and superalloys. HIP process is commonly used
on additively manufactured components and near theoretical densities can be
achieved by complete elimination of porosity within the fabricated parts.

4.3.4.4 Machining and surface treatments

Mechanical machining of the fabricated metal parts may be required to ensure di-
mensional accuracy of the finished part. In addition, surface finishing might also
be required to improve the surface quality, reduce surface roughness, clean internal
channels, or remove partially melted particles on a part. As discussed earlier, sur-
face roughness is not only detrimental for the aesthetics of the additively fabricated
part but also significantly lowers the fatigue mechanical performance of the compo-
nent. Surfaces of the fabricated parts can also be treated chemically or coated to
improve physical appearance and functional properties such as reactivity, biocom-
patibility, corrosion, and wear resistance.
 4.4 Mechanical properties of additively manufactured metals 57

4.4 Mechanical properties of additively manufactured metals

As described earlier, there is a strong correlation between the process-dependent

microstructure and the mechanical properties of the additively fabricated metals.
Figure 4.4 summarizes the relationship between the AM process parameters, micro-
structure, and the mechanical performance of the fabricated parts. Process parame-
ters such as laser intensity, laser scan speed and direction, powder type, and
morphology and postprocessing operations all determine the final product micro-
structure. Grain size and orientation, porosity, roughness, and density are the mi-
crostructural properties characterized for additively manufactured metals. As a
result of these microstructural characteristics under the selected process parame-
ters, mechanical properties are determined. Strength (tensile, yield), hardness,
elongation at break, and fatigue limit are the major mechanical properties identify-
ing the structural performance of the fabricated parts.

‒ Powder properties (purity, ‒ Grain size ‒ Yield strength

moisture level, size, shape) ‒ Grain orientation ‒ Ultimate strength
‒ Print properties (pressure, ‒ Pore size ‒ Elongation
laser power, scan speed) ‒ Pore shape ‒ Fatigue strength
‒ Postprocessing (HIP, heat ‒ Roughness ‒ Toughness
treatment, surface finish)

Process parameters Microstructure Mechanical properties

Figure 4.4: Relationship between the process parameters, microstructure, and mechanical
properties of additively manufactured metals.

Several metallurgical processes play important roles in forming the ideal microstruc-
ture in additively manufactured parts for the intended application. Grain refinement,
precipitation hardening, solid-solution strengthening, and age hardening are some of
these processes defining the final microstructure, and therefore, the mechanical
properties of the fabricated metal. Selecting the right elemental composition of the
metal feedstock and controlling process and postprocess conditions are the active
areas of research, and it is out of the scope of this book. Excellent studies exist to
further understand the strengthening mechanisms in metals [104, 105] and the rela-
tionship between the microstructure and the mechanical properties in additively
manufactured metallic components [96].
Porosity is a key parameter affecting the mechanical performance of metal
structures. As described previously, pores (or voids) facilitate crack initiation and
propagation and may significantly deteriorate the mechanical performance of addi-
tively manufactured components. Not only the total porosity but also the pore size
distribution and pore shape determine the final mechanical properties. Therefore,
58 4 Additive manufacturing of metals

minimizing the porosity is one of the primer goals in metal AM. Recent advance-
ment in metal AM technology allows fabrication of metallic parts with a density
over 99.5% for different metals. This can be further increased and thermal stresses
forming during the fabrication process are minimized by HIP and thermal anneal-
ing postprocessing operations.
As a result of minimizing porosity and optimizing the AM process parameters,
fabricating metallic parts having comparable static mechanical strength to the con-
ventional manufacturing methods is achievable for different metals. In fact, static
strength can be even higher in additively manufactured parts compared to those
fabricated via conventional means (i.e., casting) since finer grains are obtained in
AM [96]. Strength, however, is highly anisotropic in AM as the grains are preferen-
tially oriented and elongated in the printing direction. In general, higher strengths
are reported in the printing direction compared to the orthogonal directions. Static
mechanical properties of selected metals are given in Table 4.2.
As shown in this table, the static strength for additively manufactured metals
can match or even exceed their conventionally manufactured counterparts.
Elongation at break and ductility of the additively manufactured metals have usu-
ally high variation and strongly depend on the process conditions and postprocess-
ing operations. Residual stresses, oxygen content, and porosity are reported to be
major factors reducing ductility in additively manufactured metals [96]. Ductility,
however, can be enhanced, if needed, by heat treatment that reduces the thermal
stresses and help reorganization of the grain microstructure.
Fatigue strength of metals is an important parameter determining their durabil-
ity under dynamic loads. Similar to the static strength, fatigue performance of me-
tallic components is affected by the microstructure including the grain size and
orientation, defects, and porosity. However, unlike static strength, fatigue strength
depends on the surface finish and roughness of these components. Surface defects,
unmelted metal particles on the surface and high surface roughness can increase
stress concentration and initiate crack formation at the surface significantly reduc-
ing the fatigue performance of the fabricated component. Reducing surface rough-
ness by machining, sand blasting, and polishing can significantly improve the
fatigue properties. In addition, HIP and thermal treatment processes can further en-
hance the fatigue performance of the fabricated parts by minimizing the porosity
and tailoring the grain microstructure, respectively. It is shown in Table 4.3 that
performing postprocessing operations on the fabricated specimens can enhance the
fatigue strengths of additively manufactured metals to match cast and wrought
materials.
In summary, metal AM is gaining a rapid popularity due to the recent advance-
ment in this technology and better control of the manufacturing process parameters.
As a result, mechanical performance of these materials can approach, and sometimes
exceed the static mechanical properties obtained for similar materials processed con-
ventionally. Weak fatigue performance, lower ductility, high variability of results
 4.4 Mechanical properties of additively manufactured metals 59

Table 4.2: Static mechanical properties selected metals fabricated via powder bed fusion (PBF) or
conventional (cast, wrought) manufacturing (redrawn according to [96]).

Metal type Process Postprocess Yield Ultimate Elongation Ref.

strength tensile (%)
strength

L-Stainless steel Wrought Annealed    []

PBF No    []
DED No    []

 Stainless steel Wrought Annealed    []

LBM No   . []

-PH precipitation Wrought Sol. treated , ,  []

and aged

Hardening steel PBF Sol. treated  ,  []

Ni- Maraging PBF No , , . []

steel

H High-speed DED No , ,  []

steel

AlSi Cast No    []

PBF No    []

AlSiMg Cast No    []

PBF No   []

AlMgSiCu PBF HIP –  – []

ALMg.Sc.MnZr PBF Aged    []

Ti Sheet No    []

Ti-Al-V PBF No   . []

Cast No  ,  []
Wrought Sol. treated , ,  []
and aged
PBF No , , . []
PBF Heat treated , , . []
(in situ)
DED No  , . []

Ti-.Al-.Mo- PBF No , , . []

.Zr-.Si
60 4 Additive manufacturing of metals

Table 4.3: Fatigue strengths of selected metals fabricated via powder bed fusion (PBF) or
conventional (cast, wrought) manufacturing (redrawn according to [96]).

Metal type Process Postprocess Surface Fatigue Ref.

treatment strength
at  (MPa)

 L-Stainless steel PBF No No  []

Heat treated Machined  []
HIP Machined  []

-PH Precipitation- PBF No Polished  []

hardening steel

AlSi Cast No Polished – []

PBF Stress relieved Polished  []

AlSi Mg Cast No Polished  []

PBF No No  []
PBF No Polished  []

ALMg.Sc.MnZr PBF Aged Polished  []

Ti-Al- V Wrought No Polished  []

PBF Stress relieved No  []
PBF Stress relieved Polished  []
PBF Stress relieved No  []
PBF Stress relieved Polished  []

depending on the manufacturing process, instrument, feedstock type, and other pro-
cess parameters limit wider use of these processing techniques for fracture-critical
applications. Future work is needed to understand the sources beneath these issues
and resolve them to make the metal AM a stronger alternative for the conventional
metal manufacturing technologies.
5 Additive manufacturing of ceramics

Ceramic materials possess unique mechanical, thermal, and electrical properties

that cannot be achieved with polymers and metals. These properties include high
level of hardness, excellent thermal and electrical insulation, chemical and wear
resistance, and extremely high melting point. These properties make ceramics pre-
ferred materials for applications involving harsh environments (high wear, temper-
ature, pressure, etc.). In addition, ceramics are earth abundant, natural materials
providing excellent biocompatibility, and low costs. As a result, traditional ce-
ramics derived from common, naturally occurring raw materials such as clay and
quartz sand are as old as human race. These ceramic materials have been exten-
sively used as foodware, clay brick and tile, industrial abrasives, refractory linings,
and Portland cement. In addition to these traditional ceramics, high performance
ceramics have found great usage in the recent years. High performance ceramic ma-
terials such as oxides, carbides, and nitrides exhibit superior mechanical properties
including high strength, high resistivity against high temperature, corrosion, and
oxidation. Therefore, these ceramic materials find growing interest in the fields of
aerospace, automotive, and energy conversion where components such as the gas
turbines, engines, batteries, and heat exchangers undergo high operation tempera-
tures. Fabrication of ceramic materials in complex geometries using conventional
manufacturing methods, however, is extremely difficult due to the low ductility,
high melting temperature, and high crack damage sensitivity of these materials.
AM offers new opportunities for forming ceramic materials into complex geome-
tries and allows fabrication of customized and lightweight ceramic parts via topology
optimization. This design flexibility has attracted various applications of additively
manufactured ceramics. Due to the biocompatibility of ceramics and the ability of fabri-
cating patient-specific parts, biomedical applications dominate the current usage of ad-
ditively manufactured ceramics. Biocompatible-bioinert ceramics such as alumina and
zirconia are commonly used in dental applications. Biocompatible–bioactive materials
such as hydroxyapatite or bioactive glasses are preferred in orthopedical implants
(knee, hip, spinal fusion, etc.), where bone tissue repair and growth within or around
the implant are desired. Additively manufactured ceramics used for aerospace applica-
tions include high temperature resistant, tough, and strong ceramics that are very diffi-
cult or impossible to fabricate using conventional methods. Turbine components,
spark plugs, hypersonic engines are some of these aerospace applications. Figure 5.1
represents some examples of additively manufactured ceramics used in mechanical,
aerospace and medical applications.
Ceramic additive manufacturing can be classified into three major categories
according to the type of ceramic feedstock: powder-based ceramic manufacturing,

https://doi.org/10.1515/9781501518782-005
62 5 Additive manufacturing of ceramics

(A) (B) (C)

5 mm 2 mm 2 mm

(D) (E)

1 cm

Figure 5.1: Examples of additively manufactured ceramic parts used for different applications: (A)
alumina gear parts fabricated using the LCM technique; (B) alumina turbine blade; (C) alumina
cellular cube. (A)—(C) were reprinted with permission from [136]. (D) Cranial segment fabricated via
powder bed fusion. Figure was reprinted with permission from [137], (E) SiOC-based turbine wheel.
Figure was published with permission from [138].

slurry-based ceramic manufacturing, and bulk solid-based ceramic manufacturing

as shown in Figure 5.2. Processing approaches, advantages, and disadvantages of
these fabrication methods are explained in the following section.

Ceramics feedstock for AM

Powder based Slurry based Bulk solid based

– Powder-bed fusion – Vat polymerization – Laminated object manufacturing

– Binder jetting – Direct ink writing – FFF

Figure 5.2: Classification of additive manufacturing techniques based on the ceramic feedstock type.

5.1 Powder-based ceramic additive manufacturing

In powder-based ceramic additive manufacturing, loose ceramic powders are used

as feedstock material. Ceramic powders are bonded together via spraying liquid
binder on them (binder jetting) or they are melted (partially or fully) using a laser
beam (powder bed fusion). Binder jetting and powder bed fusion are commonly
 5.1 Powder-based ceramic additive manufacturing 63

adopted technologies for ceramic additive fabrication due to their design flexibility
without the need of any support structures.

5.1.1 Binder jetting of ceramics

Binder jetting is the most commonly used additive manufacturing technology for
ceramic manufacturing. As described in Chapter 1, in binder jetting process, an ink-
jet printing head jets a binding liquid onto ceramic powder giving it a 3D shape. At
the end of the process, binder is removed, and the remaining ceramic particles are
sintered to enhance the stability and the strength of the fabricated part. Multiple
nozzles can be used to fabricate large (meters long) objects [139] or deposit simulta-
neous layers of smaller objects for mass manufacturing.
Binder jetting is an additive manufacturing technology with the benefits of
high speed, low cost, and design flexibility. This technique is used to fabricate ce-
ramics with high porosity. Porous biomedical ceramic materials find various appli-
cations, most notably in biomedical field. Components used for tissue engineering
such as tissue scaffolds, biomedical implants, and cages are commonly preferred to
be porous than solid since the porous network allows tissue and cell ingrowth in
these biomedical systems. Hydroxyapatite and calcium phosphates are such bio-
compatible ceramic materials and commonly used in binder jetting technique to
print scaffolds and implants for bone replacement.
Although porosity within additively fabricated ceramics is advantageous in
scaffolding applications, it adversely affects the mechanical performance of ceramic
materials. Voids form within the fabricated ceramic specimens due to the imperfect
packing of ceramic particles and also due to the requirement of the sacrificial
binder material that is removed during the sintering process. Porosity of 40–60% is
commonly observed in binder jetting process. Compared to metals, porosity is a
greater concern for mechanical performance of ceramics that show significantly
higher sensitivity to defects and possess very low fracture toughness. In order to
achieve high density and, therefore, high structural stability, postprocessing tech-
nologies have been developed for ceramic additive manufacturing. These techni-
ques involve infiltration of the porous parts, applying isostatic compaction prior to
sintering and liquid sintering of the binder jetted parts.
In the infiltration method, a secondary material in liquid form such as molten
metals or ceramic/metal slurries penetrates into and fill the pores of the ceramic
part. Filling the voids and densification of the ceramic component lead to signifi-
cant enhancement of mechanical performance due to the reduction of porosity.
Infiltration method has also been used to fabricate secondary ceramic materials by
the reaction between the porous ceramic preform and the infiltrated material.
Liquid silicon is one of the most commonly used infiltration materials to fabricate
reaction bonded silicon carbide ceramics. In this method, liquid silicon is infiltrated
64 5 Additive manufacturing of ceramics

into binder jetted preforms and heated to temperatures giving rise to the interaction
between the preform and the silicon and the formation of new ceramic phases such
as silicon carbide [140, 141] and titanium silicon carbide (Ti3SiC2) [142] depending
on the selected preform material.
In addition to infiltration, isostatic pressure (or compaction) is commonly used in
ceramic additive manufacturing to reduce porosity. Pressure is applied on “green”
samples prior to sintering step. It was reported that cold isostatic pressure application
performed on binder jet processed Ti3SiC2 structures before sintering resulted highly
dense (99%) ceramic structures [143]. Similarly, heat and pressure can be applied si-
multaneously in warm isostatic pressure technique. Yoo et al. [144] applied warm iso-
static pressure on alumina parts to achieve 99.2% relative density. The main limitation
of the performing isostatic pressures is the difficulty of application of this technique on
complex geometries, such as parts with internal cavities where application of pressure
can lead to undesirable deformations or material failure.
Liquid sintering has also been shown to be an effective postprocessing method to
reduce porosity within the additively manufactured ceramic structures. In liquid sinter-
ing method, secondary phases/materials are added into the ceramic mix prior to print-
ing. During the sintering process at elevated temperatures, these additives/dopants
melt and take a viscous liquid form, enhance sintering, powder bonding processes,
and minimize porosity by filling the cavities. This method has been applied by multiple
researchers to fabricate highly dense (95–98%) ceramic structures using ZnO/SiO2
additives into tricalcium phosphate (TCP) [145] and hydroxyapatite (HA)/wollastonite
additives in glass ceramic [146].
In summary, binder jetting is a flexible and a highly adopted technology for ad-
ditive fabrication of porous ceramic structures. Ceramic particles can be fabricated
into complex geometries using small amounts of organic or inorganic binders
sprayed by a printing head. Porous ceramics fabricated with technique may find im-
mediate applications without the need of any postprocessing. Achieving highly
dense ceramic components, however, requires performing postprocessing opera-
tions that can result in achieving mass densities of ceramic components similar to
the theoretical bulk ceramic values.

5.1.2 Powder bed fusion of ceramics

Powder bed fusion has similarity to binder jetting since it does not require any sup-
port material for printing process as the powder bed acts as the support for the suc-
cessive layers. Powder adhesion and the additive manufacturing are, however,
performed by melting the loose powders using a laser beam source rather than
spraying an adhesive material.
Direct sintering of ceramic powders via laser beam is difficult due to the low ther-
mal shock resistance of ceramics, poor sintering, and high cost due to the extremely
 5.1 Powder-based ceramic additive manufacturing 65

high melting temperatures of these materials. As a result, direct melting of ceramic

powders has been used only in limited number of studies. Using direct sintering, ce-
ramic parts were fabricated out of alumina [147], zirconia [148], and zirconia/yttrium
oxide (ZrO2–Y2O3) [149] powders. Large porosity, crack formation, and high surface
roughness were observed in these fabricated parts. To mitigate the issues of direct
sintering, laser microsintering method was developed recently [150], and this method
allows melting and sintering of ceramic powders in submicron length scale with a
laser. Al2O3- and SiC-based ceramics were successfully fabricated with low roughness
and at high resolution. However, this method is only applicable to small parts
(micro-millimeter scale) and not practical for fabrication of larger parts.
Due to the difficulty of direct melting or sintering of ceramic powders, an alterna-
tive powder bed fusion methodology is developed where ceramic powder is mixed
with a lower temperature melting material that is melted by the laser during the addi-
tive manufacturing process and allows the formation of 3D shape. These binder mate-
rials are also selected to be temperature shock tolerant to minimize the risk of
residual stresses and cracking during sintering. Polymers, metals, and ceramics (i.e.,
glass) can be used as the liquid-forming binder phase. If polymer (organic) binder is
utilized as the binder, this binder material is removed after the laser-sintering process
by heat, and the remaining ceramic powders are sintered in a furnace at elevated
temperatures. Inorganic binders, however, cannot be removed by firing at elevated
temperatures. These binders remain in the fabricated ceramic material or interact
with the ceramic powder and form secondary phases. If metallic binder is utilized, an
inert gas is used during the fabrication to prevent possible oxidation of the binder
material. During the preparation of multimaterial powder feedstock, the binder can
be either mixed with the ceramic powder or it can be coated directly on the surface of
the powder. It has been shown that the latter is advantageous since it results homog-
enous distribution, better sintering, and mechanical performance.
Various binders have been used in powder bed fusion fabrication including pol-
yetheretherketone, polyamide, ammonium phosphate, TCP, polycarbonate, glass,
and boron oxide. As expected, using the sacrificial binder material results in signifi-
cant porosity and these porous ceramics find wide range of biomedical applica-
tions. For structural applications, however, denser ceramics are required and
therefore densifications methods such as infiltration and isostatic compaction de-
scribed in the previous section are commonly performed on porous ceramic pre-
forms for these applications. Organic binder-based powder bed fusion process
cannot be applied to enclosed geometries since the binder cannot be drained out of
the fabricated component. In addition to porosity, low geometrical resolution and
high degree of shrinkage (during sintering and also isostatic compaction processes)
are limitations for powder bed fusion fabricated ceramics.
66 5 Additive manufacturing of ceramics

5.2 Slurry-based ceramic additive manufacturing

Slurry-based ceramic additive manufacturing techniques involves the preparation

of liquid feedstock in the form of ink or paste in which ceramic particles are dis-
persed. This ceramic-based liquid slurry can be additively manufactured via Vat po-
lymerization, material jetting, or paste extrusion techniques.

5.2.1 Vat polymerization of ceramics

In Vat polymerization, ceramic particles are contained within a photopolymer. As the

photopolymer is cured via a UV light source, ceramic material remains surrounded by
the crosslinked polymer network. The fabricated part usually goes under additional
heat treatment process for the removal of the polymer phase and sintering of the re-
maining ceramic particles. In this method, homogeneity, stability, and viscosity of the
mixture are essential to obtain the desired part quality. Ceramic particles must be well
dispersed within the photopolymer and this condition must be stable during the print-
ing process. Segregation of ceramic particles results in homogeneous part fabrication
and poor material performance. Low volume content of ceramic particles within the
composite mix increases dispersion efficiency. However, this leads to porous ceramic
network and high shrinkage that are not desirable for structural applications. Another
process parameter that needs to be carefully controlled is the mixture viscosity.
Ceramic/photopolymer mixture is desired to have low viscosity and good flow charac-
teristics that are optimized for the Vat polymerization process. In addition to viscosity,
high volume of ceramic powders may negatively affect the photopolymerization pro-
cess since the UV light may be absorbed or scattered by the ceramic particles leading
to insufficient curing.
Different types of ceramics such as SiO2, Al2O3, ZrO2, and SiC can be fabricated
with Vat polymerization technology. SLA and DLP are the major Vat polymerization
technologies used for ceramic additive manufacturing. As described in Chapter 1,
DLP involves the projection of light as a 2D layer instead of raster scanning of a
single-point-based light interaction, and therefore, DLP process significantly en-
hances the printing speed. DLP ceramic printing technique is commercialized in the
name of lithography-based ceramic manufacturing (LCM) by founding company of
Lithoz GmbH [151]. Figure 5.3 shows examples of ceramic components fabricated
via LCM polymerization.
Due to the speed and the resolution of the process, fine ceramic structures in-
cluding lattice structures [153], heat exchangers [154], and negative Poisson’s ratio
metamaterial structures [155] have been fabricated with this ceramic-additive fabri-
cation method.
 5.2 Slurry-based ceramic additive manufacturing 67

A B C

1 cm 1 cm 1 cm

D E F

5 mm 5 mm 5 mm

Figure 5.3: Images of silicon nitride-based ceramic parts fabricated via LCM additive
manufacturing: (A) gyroids, (B) impeller, (C) spinal implant (posterior lumbar interbody fusion
cage), (D) cutting tools, (E) dental two-piece implants with M1.6 inner thread, and (F) de Laval
nozzle. Figure was reprinted from [152].

5.2.2 Direct writing of ceramics

Direct ink writing is defined as the extrusion of viscous liquids (or pastes) layer by
layer to construct 3D objects. Direct write (DW) technique enables a cheaper and faster
alternative compared to the photopolymerization. In this technique, ceramic suspen-
sions compose of a ceramic powder, dispersant, polymer binder (i.e., polyvinyl pyrroli-
done and methyl cellulose) and solvent such as water. Alumina has been used
commonly in this method due to its low cost, availability, and ease of densification.
Highly loaded viscous inks can be prepared over 60% ceramic content that helps mini-
mizing the shrinkage after the sintering step [156]. Similar to all other ceramic additive
manufacturing technologies, biomedical implants have been the most common appli-
cations for ceramics fabricated with DW method. Porous ceramic structures can be fab-
ricated, which show the structural similarity to native bone. In terms of material choice
for ceramics printed via direct ink writing, calcium phosphate glasses, and HA are the
most common ceramics used to fabricate artificial bone scaffolds due to their excellent
biocompatibilities. Low resolution and high level of porosity of the fabricated part are
the major issues of the direct ink writing processed ceramics. Infiltration of metals and
molten glasses can be performed as the postprocessing operations to increase the
density and improve structural properties of these materials. Figure 5.4 represents low
and high magnification images of a lead zirconate titanate (PZT) ceramic component
68 5 Additive manufacturing of ceramics

fabricated via direct ink writing [157]. PZT is a piezoelectric ceramic, which has the abil-
ity to respond to electric field and change its shape.

(A) (B)

x
z

5 mm STMesh A2 200 μm

Figure 5.4: PZT structure fabricated via direct ink writing; (A) low magnification image of the PZT
structure and (B) SEM image showing detailed microstructure. Images were reprinted from [157].

A recent study [158] used direct ink writing to fabricate bioinspired ceramic materi-
als that could not be obtained via any other additive manufacturing technologies.
In this study, hexagonal alumina platelets (~5 μm diameter and 0.5 μm thickness)
and submicron alumina powder were mixed together and 3D printed in different
geometries. High shear stresses during the DW process yielded the alignment of the
alumina platelets perpendicular to the nozzle wall giving concentric circles of plate-
lets as shown in Figure 5.5. As the shear forces are stronger close to the nozzle wall,
platelets are well aligned at the wall vicinity and more random at the core where
yield stress is minimum. In this study, the nozzle length was found to be the most
important parameter affecting the platelet alignment. As shown in this figure, lon-
ger nozzles allowed more time for the alignment of the platelets and the core size
having randomly oriented platelets was minimized.
In addition to the control of alumina nanoplatelets, bioinspired, Bouligand meso-
structures were fabricated in this study. Bouligand structure is a helical arrangement of
successive layers as shown in Figure 5.6. And this structural arrangement is used in
many natural materials such as plywood and chitin-protein fibers in insects due to
their ability to enhance impact resistance and toughness [159]. By using this natural
observation, alumina-based ceramics described earlier in the form of Bouligand struc-
tures were fabricated via direct ink writing from alumina-based ceramics by rotating
the print direction 30 ° at each layer. Fabricating ceramic layers in the form of
Bouligand configuration enhances the fracture toughness of additively manufactured
ceramics compared to both transfilament and interfilament configurations (Figure 5.6).
 5.3 Bulk solid-based technologies 69

(A) (B) 100,000 Storage modulus (G′)

Loss modulus (G″)
10,000 Yield
point

Modulus (Pa)
1,000
Gel flowing

100
Gel at rest

10
100 1,000
Shear stress (Pa)

(C) 1 mm (D) 12.5 mm (E) 25 mm

length length length

Figure 5.5: (A) SEM image of a single alumina platelet, (B) dynamic mechanical analysis of the
printing paste showing shear thinning (C)–(E) SEM images of filaments printed using different
nozzle lengths. Partial images (A)–(E) were reprinted from [158], https://doi.org/10.1038/
s41598-017-14236-9.

This was mainly due to the enhanced resistance of the material to crack propagation as
the cracks are forced to propagate helically instead of following a straight path in
Bouligand structures as shown in this figure. Figure 5.6 also shows the additively man-
ufactured ceramic gears to demonstrate the flexibility and the resolution of the DW
technology to fabricate ceramic components.
Direct ink writing is well suited for the fabrication of porous ceramic structures
with periodic features where high surface quality is not a priority. Alignment of
micro/nanoscale constituents in direct ink writing process is a unique capability of
this technique, and this can be used to fabricate mesostructures with novel proper-
ties. However, dense engineering ceramics are difficult to process using direct ink
writing, thus limiting the applications of these ceramics.

5.3 Bulk solid-based technologies

Unlike the powder or liquid-based techniques, bulk solid-based ceramic additive

manufacturing involves the feedstock materials to be in bulk solid form such as a
70 5 Additive manufacturing of ceramics

(A) (B) (C)

Transfilament Interfilament Bouligand

(D) (E) (F)

(G) (H)

Figure 5.6: Bioinspired, Bouligand structure: microstructures of bioinspired platelet-epoxy

composites produced via robocasting of platelet pastes and comparison to natural analogues.
Schematic diagrams of the three morphologies (A) trans-filament, (B) interfilament, (C) bioinspired,
Bouligand structure, (D)–(F) SEM images of fracture surfaces of the three composites, (G) Printed
parts to demonstrate the flexibility of the technique and (H) SEM images of the microstructure of
the printed part. Scale bars 10 and 500 μm. Image was reprinted from [158], https://doi.org/
10.1038/s41598-017-14236-9.

thin layer of ceramic sheet or a filament. Sheet lamination and fused filament fabri-
cation are the manufacturing techniques using these solid feedstocks, respectively.

5.3.1 Sheet lamination

Sheet lamination uses ceramic sheet preforms as the feedstock materials. Ceramic
sheets are prepared by tape-casting method as illustrated in Figure 5.7. In tape casting,
ceramic powder is blended with a solvent, binder material, and other additives to pre-
pare a homogenized mix. This mixture is then deposited on a surface and thinned with
blades. Due to the usage of these flattening blades, this method is also known as doctor
 5.3 Bulk solid-based technologies 71

Binder Additives
Ceramic powder
Pump

Homogenizer
Slurry Mixer
Solvent

Drying

Reservior

Doctor blade region Peeling belt

Figure 5.7: Schematic of tape casting process. Figure was reprinted with permission from [160].

blading method. At the final drying step, the solvent is evaporated from the film mate-
rial. Tape casting technique is widely used for the fabrication of thin sheets not only
from ceramics but also from polymers, metals, and paper. A few micron-thin films can
be fabricated with this technique.
After completing the green ceramic sheet preparation, these sheets are rolled onto
the working platform and the excess material is removed. The next layer is then depos-
ited until the final 3D part is obtained as described in Chapter 1 in detail. After the final
layer deposition, the part is sent for binder removal and sintering at elevated tempera-
tures. Different types of ceramics have been reported to be fabricated with this tech-
nique including Al2O3, zirconia, SiC [161], piezoelectric materials [162], HA for bone
implant preparation [163], and ceramic composites including Si/SiC [164] and ZrO2/
Al2O3 [165].
High speed, applicability to different ceramic materials, and low fabrication tem-
perature (prior to sintering) are the advantages of sheet lamination. However, the re-
quirement of sheet ceramic feedstock, high porosity, and poor surface adhesion
between the layers that may cause delamination are the drawbacks of this method.

5.3.2 Fused filament fabrication

Fused filament fabrication (FFF) technique is based on melting of a thermoplastic fila-

ment and solidifying upon deposition on a printbed as described in Chapter 1. Brittle
ceramics cannot be shaped into flexible filaments as the FFF feedstock material; how-
ever, ceramic powders can be mixed with thermoplastic polymers to prepare ceramic-
72 5 Additive manufacturing of ceramics

polymer composite filaments. These highly ceramic loaded (up to 60%) filaments can
then be used to fabricate 3D structures using a conventional FFF instrument. Therefore,
the major benefit of fabricating ceramics with the FFF method is the ability of using
commonly used, low cost FFF printers rather than more expensive printing systems.
After the printing process is completed, the part is subjected to binder polymer removal
and sintering of the remaining ceramic powders to achieve densification. Similar to
other ceramic additive manufacturing technologies, ceramic FFF method has been ap-
plied for the fabrication of bioceramic scaffolds due to high porosity left behind the re-
moved polymer material. In addition, alumina, silicon nitride [166], and piezoelectric
[167] ceramics have also been successfully fabricated via FFF method. Well dispersion
of ceramic particles within the polymer is essential for the part quality and porosity. In
addition, size and shape of these particles dictate the quality of the printed part along
with the standard FFF process parameters such as rod width, layer thickness, build ori-
entation, raster angle, and porosity.
Up to this section in this book, we have investigated the additive manufacturing
technologies of ceramic materials under the three main classification of feedstock type:
powder-based, slurry-based, and bulk solid-based ceramic additive manufacturing.
Each of these technologies have certain drawbacks and benefits to be considered dur-
ing when selecting the ideal technology for the certain application. Table 5.1 summa-
rizes these commonly used additive manufacturing technologies listing the main
characteristic properties, benefits, drawbacks, and the main applications for each fabri-
cation technique in comparison.

Table 5.1: Comparison of ceramic additive manufacturing technologies (redrawn from [168]).

Feedstock AM method Resolution Speed Surface Feedstock Applications

type quality cost

Powder Binder jetting µm–mm Medium Medium Medium Structural/

based bio

Powder bed fusion µm–mm Medium Low Low Structural/

bio

Slurry Stereolithography µm Slow High High Structural/

based bio

Digital light µm Medium High High Structural/

processing bio

Direct ink writing µm–mm Medium Low Low Structural/

bio

Solid based Sheet lamination µm–mm High Medium Medium Structural

Fused filament mm Medium Low Medium Functional

fabrication
 5.4 Additive manufacturing of polymer-derived ceramics 73

5.4 Additive manufacturing of polymer-derived ceramics

Polymer-derived ceramics, as their name indicates, are obtained by transforming

preceramic polymers into ceramics. Precursor materials used for the process are
organosilicon polymers such as poly(organocarbosilanes), poly(organosiloxanes),
poly(organosilazanes), and poly(organosilylcarbodiimides [169]. Polymer-to-ceramic
transformation takes place by heating silicon-based polymers (orgonosilicon) at
about 1,000 °C under inert atmospheres and breaking of the C–H bonds. The release
of H2, CH4, or other volatile compounds results in the formation of an inorganic ce-
ramic material [170]. Figure 5.8 shows that different ceramic compounds can be ob-
tained by altering the precursor polymer. As the figure indicates, SiC can be obtained
from poly(organocarbosilanes). SixCyOz can be derived from poly(organosiloxanes)
and SixCyNz ceramic compounds can be derived from either poly(organosilazanes) or
poly(organosilylcarbodiimides).

R1
Silicon-based polymers: Si X
n
R2

R1 R3 R1 R1 R1
Si
S C Si
S O Si
S N Si N C N
R2 R4 n R2 n R2 R3 n R2 n

Poly(organocarbosilanes)
ganocarbosilanes) Poly(organosiloxanes) Poly(organosilazanes) Poly(organosilylcarbodiimides)
Poly(organosilylcarbo

ΔT ΔT ΔT ΔT

SiC SixCyOz SixCyNz

Figure 5.8: Molecular structures and the types of polymer precursors transforming into ceramic
materials. Figure was reprinted with permission from [169].

Polymer-derived ceramics have unique properties such as high chemical durability,

high creep resistance, semiconducting behavior and stability at ultrahigh temperatures
(up to 2,000 °C) [169]. Therefore, these materials find applications as temperature-
resistant materials or functional materials in micro/nanoelectronics fields. Although
polymer-derived ceramics materials were discovered over 50 years ago, their popularity
has increased dramatically after the recent developments of their additive manufactur-
ing technologies. Since the precursor materials for these materials are polymers, these
preceramic polymers can be additively manufactured into complex geometries and then
pyrolyzed to form ceramic parts. Especially Vat polymerization has been successfully
74 5 Additive manufacturing of ceramics

applied to additively fabricate these materials since photoactive thiol, vinyl, acrylate,
methacrylate, or epoxy groups can be easily attached to organosilazanes [171]. In ad-
dition, metallic precursors can be added into organosiloxane preceramic polymers to
fabricate metal-based ceramics as introduced by [172]. Figure 5.9 shows the additive
manufacturing methodology of ceramic structures in this study where the prepa-
ration of the photocurable preceramic polymer, DLP printing of this polymer and
pyrolysis steps are described to fabricate octet truss structure shaped polymer de-
rived ceramics.

(A) (C) (D) (E)

Print platform

Synthesis of preceramic Resin trough N2

polymers

(B)

LED source Final ceramic

Pyrolysis of preceramic component
DLP 3D printing polymers
Modeling

Figure 5.9: Additive manufacturing of polymer derived ceramics. (A) Precursors used in the printing
mix, (B) octet truss structure was designed using CAD software, (C) DLP 3D printing process,
(D) pyrolysis process performed on 3D-printed pre-ceramic polymer, (E) ceramic material derived
after the pyrolysis process. Figure was reprinted with permission from [172].

Figure 5.10 shows the designed and fabricated polymer-derived ceramic part in this
study before and after pyrolysis steps. As shown in this figure, complex lattice
structures can be successfully fabricated via this technology. The main benefits of
using preceramic polymers in additive manufacturing is taking advantage of using
well established, high reposition technologies to fabricate ceramic components.
Additively manufactured, polymer-derived, and metal-doped ceramics can also find
novel applications in magnetics, catalysis, MEMS, and so on. Main limitation of ad-
ditive manufacturing of polymer-derived ceramics is the high level of shrinkage
(>20%) of the printed structure during the polymer to ceramic transformation as
shown in Figure 5.10.

5.5 Mechanical properties of AM ceramics

As described throughout this chapter, high porosity is a common characteristic prop-

erty of additively manufactured ceramic parts. Depending on the manufacturing pro-
cess, fabricated parts can have the porosity range in between 20% and 60%. This high
level of porosity adversely affects the mechanical properties of ceramic parts and limit
 5.5 Mechanical properties of AM ceramics 75

(A) (B)

10 mm

(C) (D)

10 mm

Figure 5.10: (A) Octet lattice structure designed as CAD model, (B)–(C) 3D-printed polymer-derived
ceramic component before and after pyrolysis. (D) Picture of ceramic component after pyrolyzed at
1,000 °C. Figure was reprinted with permission from [172].

their usage except the applications where high porosity is desired such as biomedical
scaffolding. As a result of high porosity level, bending strength lower than 30 MPa is
commonly observed in these highly porous ceramics regardless of the ceramic type or
the fabrication method. Figure 5.11 shows a summary of the compressive strength as a
function of porosity reported by Zocca et al. [173]. It is clear that the porosity in the
ceramic parts significantly reduces the strength in these materials.
Additively manufactured ceramics used for structural applications are almost
always postprocessed and densification steps take place such as infiltration, iso-
static compaction and heat treatment of the fabricated parts as described previ-
ously. As a result, high density (>90%) can be achieved in these ceramic parts and
therefore, mechanical properties can be significantly increased. Table 5.2 summa-
rizes mechanical properties of selected ceramic materials after densification process
is applied as reported by Wang et al. [174]. It is clear from the table that strength of
the ceramic parts can be dramatically enhanced after applying the densification
process and the mechanical properties of these parts become similar to those fabri-
cated via conventional ceramic fabrication technologies. Nevertheless, in general,
mechanical properties of additively manufactured ceramics are still lower than
those fabricated via conventional methods. Both fracture strength and fracture
76 5 Additive manufacturing of ceramics

100

Compressive strength (MPa)

Farzadi 2014 Calcium sulfate P-3DP
Fielding 2012 TCP P-3DP
10 Fielding 2012 TCP + ZnO P-3DP
Kolan 2014 bioglass P-SLS
Chu 2002 HA SL
Genet 2013 HA/TCP DIW
Fu 2011 bioglass DIW
1
Franco 2011 HA/TCP DIW
Miranda 2007 HA DIW
Houmard HA/TCP DIW
Non-AM processing
0.1
20 30 40 50 60 70 80
Porosity (%)

Figure 5.11: Compressive strength versus porosity of porous ceramics fabricated via additive
manufacturing. Figure was reprinted with permission from [173].

Table 5.2: Comparison of the mechanical properties of additively and conventionally fabricated
ceramic materials redrawn according to [174].

Ceramic type Manufacturing type Fracture Fracture Ref.

strength toughness
(MPa) (MPa*m/)

Aluminum oxide (AlO) Conventional – . []

Additive  – []

Additive  – []

Additive – .–. []

Zirconium oxide (ZrO) Conventional   []

Additive  – []

Additive  . []

Silica (SiO) Conventional – .–. []

Additive . – []

Silicon carbide Conventional   []

Additive  – []

Boron carbide Conventional   []

Additive .–. . []

 5.5 Mechanical properties of AM ceramics 77

Table 5.2 (continued )

Ceramic type Manufacturing type Fracture Fracture Ref.

strength toughness
(MPa) (MPa*m/)

Silicon nitride (SiN) Conventional – – []

Additive  .–. []

Aluminum nitride (AlN) Conventional  . []

Additive  – []

toughness of additively manufactured ceramics are lowered due to the unavoidable de-
fects and porosity even after performing postprocessing operations described earlier.
Additive manufacturing of ceramic materials is an active area of research due to
the superior properties of these materials over metals and polymers such as thermal
and chemical resistivity, unique mechanical properties, low cost, and biocompatibil-
ity. However, additively manufactured ceramic parts find limited applications cur-
rently since these components possess high porosity stemming from the low powder
packing density and the pore formation due to the removal of sacrificial organic ma-
terials used during the printing process. One straightforward approach to increase
the density of the powder bed is the deposition of ceramic slurries instead of dry pow-
ders. Although slurry-based ceramic AM is advantageous over powder-based fabrica-
tion, subsequent densification steps are necessary to obtain nearly pore-free parts.
Therefore, compared to polymer and metal additive manufacturing, ceramic additive
manufacturing remains as an expensive, time-consuming, multistep process which
limits the adoption of this technology by a wider AM community.
6 Bioprinting

Bioprinting can be defined as a procedure where living or nonliving biomaterials

are additively manufactured to imitate natural tissues or organs. In this regard, bio-
printing is a very promising research field for tissue engineering and regenerative
medicine, which aims at replacing a pathological or necrotic body tissue with an
artificial one. Biomaterials printed in three-dimensional (3D) geometries can also be
used to understand an underlying mechanism of a biological function (or a disease)
and test the efficacy of a drug on 3D-printed biomaterials that mimic those in vivo.
Therefore, bioprinting finds a wide range of applications today in basic research,
biomedicine, and pharmaceutical industry.
Bioprinting process starts with a computer-aided design (CAD) for the natural
tissue/organ of interest. This process is followed by the preparation of the printing
feedstock material, or bioink, which may consist of a natural or synthetic material
for the desired application. Bioink is then deposited on the printing platform or on
the existing biomaterial in a layer-by-layer fashion through a computer-controlled
algorithm. To fully understand the benefits and limitations of the bioprinting pro-
cess, it is essential to describe available bioink materials used for bioprinting, addi-
tive manufacturing procedures commonly used to deposit bioink materials, and the
functions of these biomaterials after printing for in vivo or in vitro applications.
Therefore, this chapter is structured accordingly to inform the readers the common
bioprinting methodologies, available bioinks used as feedstock material today, and
the major successful applications of this technology in biomedicine. This chapter
concludes with the limitations and challenges of the current bioprinting technol-
ogy. Reviewing the recent studies in this emerging field will guide biomedical re-
searchers to comprehend the limits of 3D printing technology and foster new
collaboration opportunities for manufacturing engineers and scientists to broaden
the extent of their research.

6.1 Bioprinting methods

Bioprinting technologies can be classified into four major categories: inkjet print-
ing, extrusion, Vat polymerization, and laser-assisted printing. Schematic represen-
tation of these techniques and the comparison of their major properties such as
printing speed, cell viability, and investment costs is shown in Figure 6.1. Brief de-
scription of each method is given later.
Extrusion is a common bioprinting technique in which biomaterials are extruded
through a nozzle of the extrusion system by a pneumatic or piston-controlled pres-
sure system (Figure 6.1A). In the deposition process, the bioink is deposited onto a
platform bed layer by layer forming a 3D structure. To obtain the structural integrity of

https://doi.org/10.1515/9781501518782-006
 6.1 Bioprinting methods 79

Figure 6.1: Commonly used bioprinting technologies: (A) extrusion bioprinting, (B) inkjet
bioprinting, (C) laser-assisted bioprinting, and (D) Vat polymerization bioprinting.

the extruded material, the bioink viscosity must be high enough to overcome the gravi-
tational forces and avoid sagging. Viscosity can be enhanced by adding a curing agent
in the bioink and initiation of the chemical cross-linking of the biopolymer within the
bioink by applying an external stimulation (thermal, light, etc.). Cross-linking process
can also take place at room temperature naturally without any intervention depending
on the curing reaction type. Extrusion process is a simple bioprinting technology that is
capable of printing highly viscous bioinks with high cell densities. Multimaterial print-
ing is also possible using multiple extrusion channels integrated on a single printing
setup. However, shear stress induced during the extrusion process may cause cell defor-
mation and damage. Therefore, cell viability may be lowered if the process parameters
such as biomaterial concentration, nozzle pressure, and nozzle diameter are not suc-
cessfully optimized. In addition, the material choice is currently limited since the bioink
material must be able to encapsulate cells through hydrogels.
Inkjet bioprinting is another bioprinting methodology which can be considered
under material jetting additive manufacturing classification described in Chapter 1.
Therefore, the bioink is sprayed (or jetted) onto a surface in a drop-on-demand fash-
ion. In this type of bioprinting, bioink deposition can be regulated by thermal or
piezoelectric actuation as shown in Figure 6.1B. In thermal actuation, heating ele-
ment near the nozzle increases the bioink temperature forming a bubble. This bub-
ble forces the bioink to move out of the nozzle orifice. In piezoelectric actuation,
however, inkjet printer utilizes piezoelectric element to generate pressure pulse,
which leads to dispensing of liquid through the nozzle orifice. Similar to the extrusion
80 6 Bioprinting

bioprinters, inkjet bioprinters are relatively cheap and simple manufacturing systems.
However, the speed of inkjet printing is much faster since multiple printheads can
work in parallel (rather than in series in extrusion bioprinting), which allows deposi-
tion of multiple cell types at high speed. Due to the precise control of the dropwise
bioink deposition, inkjet printing has high resolution (~30 µm) [184]. In addition, ink-
jet printing results in relatively high cell viability for especially piezoelectric actuation
systems. High temperature applied on bioinks in the process of thermal actuation
may cause damage and influence the activity of cells after printing. The main limita-
tion of the inkjet printing is the low-viscosity requirement of bioink (~0.1 Pa.s) [185].
This requirement makes the printing of viscous hydrogels and extracellular matrix
(ECM) rather difficult. Cell aggregation and nozzle clogging are also commonly ob-
served issues when high cell densities are used. Therefore, the printing is usually op-
erated with low-cell density bioinks to assure printability.
Laser-assisted bioprinting is a high-resolution printing technique in which cells
are deposited from the source platform to the substrate platform (Figure 6.1C). In
this technique, the laser pulse is applied on the bioink-containing cells and this
laser pulse creates a bubble. This bubble forces cells to move from the source to the
substrate platform where the cells are collected. This technique can allow deposi-
tion of individual cells in a precise way; therefore, it has superior resolution com-
pared to other bioprinting techniques. In addition, it is capable of printing highly
viscous inks without the issue of clogging since it is a nozzle-free deposition tech-
nology. Cell viability is also very high in laser-assisted printing (>95%). The main
limitation of this technology, however, is the low volume of the deposited ink, and
therefore, manufacturing process is relatively slower than the other bioprinting
methods. As a result, laser-assisted printing is preferred for printing smaller sam-
ples. High instrument cost compared to other bioprinting technologies is also an-
other drawback of this technique.
Vat polymerization bioprinting is based on the photopolymerization of a bio-
ink consisting of light-sensitive polymer. In this technique, photopolymer is selec-
tively cured layer by layer to create 3D biomaterial as shown in Figure 6.1D. Light
can be projected in terms of two-dimensional (2D) pattern (DLP) instead of raster
scanning (SLA) of the laser line by line as described in Chapter 1 in detail. This fea-
ture results in a significant increase in printing speed compared to other bioprinting
technologies. As described earlier, Vat polymerization results high resolution and
hence, biomaterials with high dimensional accuracy can be fabricated with this
methodology. In conventional Vat polymerization technologies, UV light source is
preferred due to its high energy. UV light, however, can damage DNA of cells in bio-
ink, and therefore, visible light is gaining popularity in stereolithography bioprint-
ing process. Vat polymerization-based bioprinters provide high cell viability
(>85%) since the selective cross-linking of bioink by light does not involve shear
stress to cells or high thermal loading. Bioink, however, must be transparent to
allow light to pass the material without significant scattering. To minimize light
 6.2 Bioink types used in bioprinting 81

scattering and homogenous cross-linking, cell density is usually kept at low level,
which is also another limiting factor for this biofabrication technique.

6.2 Bioink types used in bioprinting

Bioink preparation is the most important step for bioprinting. Properties of the bio-
ink such as the ink type, the concentration of the constituents, gelation time, and
viscosity can greatly affect the printability and the properties of the fabricated sam-
ples. In general, bioinks should be printable into stable 3D constructs with high
structural integrity. Bioinks must also have high level of biocompatibility support-
ing cell adhesion, proliferation, and spreading [186]. Therefore, the choice of the
suitable bioink is essential for the success of bioprinting. High level of biodegrad-
ability is another property sought for the prepared bioinks.
Hydrogels are biopolymers that satisfy these bioink requirements. Hydrogels
can be naturally derived such as collagen, gelatin, agarose, and chitosan or syn-
thetic such as polyethylene glycol (PEG) and polyurethane (PU). These biopolymers
are cross-linked by controlling the external stimuli, including temperature, pH,
light, enzymes, and ions. Cross-linked hydrogels are designed to be highly biocom-
patible and allow the cellular activities described earlier. Hydrogels can be natu-
rally derived such as alginate, gelatin, and chitosan. They can also be synthetic
such as PEG and PU based. Commonly utilized natural and synthetic bioinks are
described briefly later.
Alginate is one of the most commonly used bioink material due to its low cost,
and fast gelation process using ionic calcium compounds (CaCl2, CaCo3, and
CaSO4). High viscosity of alginate is another benefit of this bioink material. Since
alginate itself does not allow cell adhesion, it is usually mixed with natural poly-
mers such as collagen and fibrinogen to facilitate adhesion process.
Gelatin is a natural polymer obtained from the hydrolysis of collagen; hence, it
has excellent biocompatibility and biodegradability properties. Gelatin is easily
cross-linkable, soluble in water, and nonimmunogenic [187]. Despite these advan-
tages, gelatin hydrogel exhibits a relatively rapid degradation and poor mechanical
strength, restricting its use as bioink. GelMA hydrogel, a gelatin-based hydrogel
functionalized with methacrylic anhydride, has been proven to control degradation
rate and improve the mechanical strength of gelatin [188]. However, GelMA requires
photoinitiator for the cross-linking process. High concentration of the photoinitiator
and the UV emission to activate the photopolymerization can be toxic to cells [189]
and therefore their effects must be limited to maximize the cell viability.
Chitosan is a natural polysaccharide biomaterial obtained from the outer skele-
ton of shellfish or fungal fermentation [190]. It is highly biocompatible, and has an-
tibacterial properties. Chitosan is widely used in bioprinting of bone, skin, and
cartilage tissues. This bioink type, however, suffers from slow gelation time and
82 6 Bioprinting

poor mechanical properties. It can be mixed with gelatin to improve printability

and 3D construct shape fidelity [191]. Chitosan hydrogels are widely used in 3D bio-
printing, especially for the applications of bone and skin repair/replacement and
microflow channel fabrication.
Naturally derived hydrogels have been used extensively as bioinks since they
can support cell functions and have biodegradable properties. However, due to
their low viscosity, these hydrogels have generally poor mechanical properties to
support tissues; therefore, synthetic polymers such as PEG are in use for applica-
tions requiring high mechanical performance. PEG is a synthetic polymer and it has
tailorable mechanical properties required for bioprinting. It is nontoxic and bioi-
nert. Therefore, cell adhesion is poor in PEG-based hydrogels. Similar to the algi-
nate, it is commonly mixed with other active biopolymers to improve cell adhesion
properties. Pluronic is another synthetic polymer widely used in bioprinting.
Pluronic has similar properties to PEG.
The ECM is a 3D network of extracellular proteins (collagen, fibrinogen, glyco-
proteins, enzymes, etc.), and it involves numerous biological functions including
cellular growth, tissue repair, and remodeling. In bioinks, one or a mix of these pro-
teins are used to support the cellular functions during and after the printing pro-
cess. These bioinks, however, can hardly mimic the native ECM properties due to
the complexity of the native ECM structure. Decellularized ECM (dECM) is a promis-
ing candidate as a bioink precursor since it has the appropriate structure and
inductive cues to enable cellular growth and differentiation processes [192].
Decellularization agents (ionic, nonionic zwitterionic detergents, and enzymatic
and physical agents) are capable to remove cells from the native ECM to prepare
dECM compound. dECM can then be mixed with the preferred cells and used as the
bioink material mimicking the natural environments for these cells.
As described earlier, bioinks have different mechanical, biocompatibility, and
biodegradability properties and they can be either natural or synthetic biopolymers.
Native dECM can also be used as a precursor for bioinks to better resemble the mi-
croenvironment in vivo. Preparation of cost-efficient bioinks with suitable mechani-
cal and biological properties is an active area of research and it has the utmost
importance for the future of bioprinting process and tissue engineering. Table 6.1
summarizes major bioink types that are currently in use and the major properties
for each bioink type.

6.3 Bioprinting applications

Bioprinting has been used in various applications including the biofabrication of

functional artificial tissues and organs for repair or replacement. It has also been
used to additively fabricate cancer tissues with the aim of understanding the under-
lying biophysical mechanisms of the cancer-related diseases. Major bioprinting
 6.3 Bioprinting applications 83

Table 6.1: Bioink types and properties (redrawn according to [193]).

Bioink Cross-linking mechanism Bioactiveness Bioprinting technique

type

Alginate Ionic cross-linking with divalent ions; Bioinert Extrusion, laser-assisted

covalent cross-linking with PEG photo- and inkjet
cross-linking with methacrylate

Collagen Physical pH- and temperature-mediated Bioactive Laser-assisted and

cross-linking, chemical cross-linking microwave-based
with genipin/transglutaminase/lysyl
oxidase

Gelatin Physical cross-linking via temperature- Bioactive Extrusion and laser-

dependent/opposite charged polymers; assisted
chemical cross-linking with horseradish
and hydrogen peroxide after
modification with phenolic hydroxyl
group

Hyaluronic Chemical cross-linking via coupling of Bioinert Extrusion, laser-assisted,

acid tyramine/NHS/Cu(I)-catalyzed microwave-based, and Vat
cycloaddition reaction/host–guest polymerization
interactions/HA-based copolymer
hydrogels/oxidation of thiol-modified
HA/thiol-modified HA using PEG
derivatives/furan-modified HA
derivatives with dimaleimide PEG/gold
nanoparticles/photo-cross-linking of
tyramine-substituted HA

PEG Functionalized through hydroxyl end Bioinert Vat polymerization,

groups to form PEGDA, PEGDMA, n-PEG extrusion, and inkjet.
photo-cross-linkable hydrogels with
different photoinitiators: Irgacure 
( nm), LAP (visible light), VA
( nm), eosin Y (visible light),
riboflavin with triethanolamine

GelMA Chemical photo-cross-linking with Bioactive Vat polymerization,

different photoinitiators: Irgacure extrusion, and inkjet.
 ( nm), LAP (– nm),
VA- ( nm), eosin Y (–
nm), ruthenium and sodium persulfate
(– nm)

Pluronic Temperature-dependent physical Bioinert Extrusion

cross-linking, modification of
terminal hydroxyl moieties to form
photo-cross-linkable hydrogels
84 6 Bioprinting

applications regarding the functional tissues involve vascular structures and blood
vessels, neuronal tissues, cornea, cardiac tissues, skin, cartilage, and kidney as
shown in Figure 6.2. Brief explanation of the bioprinting procedures for each func-
tional tissue is described later.

Figure 6.2: Current bioprinting applications for tissue engineering in human body. Figure was
edited and reprinted with permission from [193].

6.3.1 Bioprinting of blood vessels

Blood vessels are essential components of the circulatory system allowing transpor-
tation of oxygen and nutrients to organs and tissues throughout the human body
via blood stream. Design and fabrication of artificial blood vessels are long-term
studies of tissue engineering, and it has only been successful for large artery blood
vessels due to the difficulty of fabrication of small capillaries and the mismatch in
elastic properties [194]. Recently developed bioprinting technologies such as sacrifi-
cial, embedded, hollow tube, and microtissue bioprinting have great potential to
fabricate microvascular networks with interconnected microchannels in arbitrary
geometries.
 6.3 Bioprinting applications 85

Sacrificial bioprinting involves the deposition of sacrificial hydrogel material in

the core of the bioink surrounded by the endothelial cells. After printing, sacrificial
core layer is selectively removed and the remaining cells in the shell establish the
endothelium creating the vascular pattern. This technique is the most established
bioprinting technique for blood vessel printing. However, it is limited to simple ge-
ometries and cannot be used to generate sophisticated vasculature due to the lack
of support in 3D volume. In embedded bioprinting technique, printing is performed
with a relatively long syringe tip dipped into a viscous hydrogel material rather
than on a flat printbed. Since the bioink is supported by this surrounding viscous
hydrogel material as it is extruded from the syringe, this technique can produce
freeform structures in 3D and complex blood vessels can be fabricated. Hollow tube
bioprinting is based on the deposition of the hollow blood vessel in as single step
using wet-spinning technology and, therefore, simplifies the bioprinting process.
Blood vessel printing is important not only to replace the necrotic vascular tissue,
and is also essential to make organ bioprinting possible with enclosed vascularate
with food transport for these organs. Therefore, development of new bioinks with
high biocompatibility and bioprinting of blood vessels mimicking the native tissue
will make a significant impact in tissue engineering.

6.3.2 Skin bioprinting

Skin is the largest organ in the human body, playing important functions, including
protection, temperature regulation, and sensation. Skin bioprinting has the utmost
importance for wound healing, replacement of the diseased skin tissue, and testing
of medicinal and cosmetic products in vitro. Skin has complex, nonuniform 3D archi-
tecture including proteins (collagen, elastin), cells (keratinocyte, melanocyte), and
other structures (hair follicles, sweat glands, fatty tissues, etc.). Inkjet bioprinting is
commonly used for skin printing using the mixture of collagen and the skin cells.
Artificial skin has been successfully fabricated by numerous researchers [195–198]
with matching morphology to that of native skin to facilitate the protection and bar-
rier functions. However, native skin serves several other key functions such as tem-
perature regulation (hair follicles and sweat glands), touch sensation (sensory
nerves), and skin hydration (sebaceous glands) [193]. Biofabrication of multifunc-
tional, smart skin tissues serving these functions is under current investigation.

6.3.3 Cartilage printing

Cartilage is an elastic tissue located at the joints of the skeletal system protecting
bones by providing shock absorption and cushioning. Cartilage is also the structural
component of ear and nose. Compared to the other connective tissues, cartilage has
86 6 Bioprinting

limited and slow self-repairing capability [199]. Therefore, the use of bioprinting tech-
nology has a great potential for cartilage repair and replacement. Chondrocyte cells
secrete the ECM to maintain and sustain native cartilage. Therefore, it is the main cell
type used in bioinks for the cartilage bioprinting process. However, limited availabil-
ity of this cell type resulted in the search for alternative cells including mesenchymal
stem cells (MSCs) that can be isolated from bone marrow. MSCs can differentiate into
cells of the specialized connective tissues, including bone, adipose tissue, and carti-
lage [200]. Unlike other cell types, these stem cells also reported to have less immune
rejection and therefore they have high potential in bioprinting of connective tissues
including cartilage. One of the notable studies on bioprinting of cartilage tissue using
MSCs is shown in Figure 6.3 [201]. In this study, human MSCs (hMSCs) were added
into pluronic-alginate bioink mixture and printed in the shape of an ear and nose
onto a heated stage, resulting in instantaneous solidification via the sol–gel transi-
tion of the pluronic, and the structures were then stabilized through alginate cross-
linking using CaCl2 immersion.

A B C

D E

Figure 6.3: Three-dimensional printing of cartilage tissue using alginate hybrid gel. (A) and (B)
Post-cross-linking images of a full-sized ear and nose (scale bars are 1 cm). Wide-field fluorescence
microscopy of (C) cross-hatch pattern, (D) a single fiber printed through a pipette tip, and (E) and
(F) a single fiber printed through a 30-gauge needle (scale bars are 200 μm). Figure was reprinted
from [201].
 6.3 Bioprinting applications 87

6.3.4 Cardiac tissue bioprinting

Due to the high rate of mortality, heart-related diseases remain to be a leading cause of
death worldwide. Treatment of heart diseases is rather difficult since the muscular
heart tissue (myocardium) has very limited regeneration capability in mammalians in-
cluding human [202]. Heart transplantation is the only effective treatment against
these heart diseases. However, organ availability, immune rejection, high cost, and
surgical complications are the issues of this treatment method. Therefore, bioprinting
of cardiac tissue is essential to solve existing limitations of the heart transplantation
process and therefore it has compelling benefits to the patients suffering from heart
diseases. In addition, bioprinting of in vitro heart models mimicking the structural and
functional characteristics of native heart will make tremendous impact on drug discov-
ery and development in this field. Unlike the other tissues considered for bioprinting,
the bioprinting of a functional myocardium requires alignment of cells and the contrac-
tion capability of these cells; therefore, bioprinting of heart tissues remains challeng-
ing. Significant progress has been made in lab-scale bioprinting of cardiac cells
(cardiomyocytes) loaded within bioinks. In a recent study by Noor [203], stem cells
taken from a patient are differentiated into cardiomyocytes. In this study, cardiomyo-
cytes are mixed with the hydrogel prepared from the patient’s own dECM. Endothelial
cells, cells forming blood vessels, are also added to this mixture to create artificial
heart with vascular channels similar to the native heart. The prepared bioink is
printed into heart shape with the surrounding sacrificial matrix, which provides
structural support for the printed heart. Postprocessing of the printed heart in a
bioreactor results in the cardiomyocytes to self-organize and form solid cardiac tis-
sue. The surrounding support material is then dissolved, leaving the fully printed 3D
heart model infused with major blood vessels with blood-carrying capability as
shown in Figure 6.4.
The structure and functionality of the bioprinted cardiac patches are studied
in vitro analyses, and cardiac cell morphology is assessed after transplantation,

(A) (B) (C) (D)

Figure 6.4: Bioprinting of vascularized heart in small scale. (A) The human heart CAD model. (B)
and (C) A printed heart within a support bath. (D) Blue and red dye injection into ventricles after
extraction to demonstrate hollow chambers and the septum in between them. Partial figure was
reprinted from [203].
88 6 Bioprinting

revealing elongated cardiomyocytes with massive actinin striation. Figure 6.4

shows the CAD design (Figure 6.4A) and additive manufacturing process (6.4B-C) of
an artificial heart integrated with the vascular structure (lumen). Embedded bio-
printing was used in this work in which the viscous hydrogel acts as a support ma-
terial. Figure 6.4D shows the fabricated heart with different colors representing the
blood flow within different heart sections. This proof-of-concept study as well as
the other recent research studies performed on bioprinting of cardiac tissues [204–
207] have demonstrated the great potential of the additive manufacturing technolo-
gies for personalized tissues and organs, and for the drug screening in an appropri-
ate anatomical structure and patient-specific biochemical microenvironment.

6.3.5 Kidney tissue bioprinting

Kidneys perform important functions in human body including blood filtration and
regulating pH and fluid balance. Similar to the heart bioprinting process, fabrication of
artificial kidney is an area of active research due to the high demand of kidney trans-
plant and shortage of these organs. Kidney has complex microarchitecture, which also
makes bioprinting the suitable technique for artificial fabrication of this organ. Three-
dimensional printing has been used in clinical kidney transplant surgery as an educa-
tive tool to help surgeons to determine the feasibility of transplantation and foresee the
possible complications. This technology has been applied especially during the trans-
plantation of adult kidneys to kid recipients (<20 kg) with complex structural anoma-
lies [208]. These patient-specific 3D models fabricated via additive manufacturing has
become clinically important for surgeons to perform the clinical kidney operations.
Apart from fabricating the plastic models in education, the current research on
functional kidney bioprinting mainly focuses on preparation of small-scale renal
structures such as the proximal convoluted tubules [193]. Biofabrication of these tu-
bules is extremely important for in vitro biotoxicity studies since the reabsorption
and accumulation of drugs occur mainly at this site in the kidney. Bioprinting of
fully functional artificial kidney is currently a challenging task due to the complex
microstructure of this organ and integration of vascularization. A recent study [209]
investigated the animal implantation of the bioprinted kidney tissue and observed
development of host-derived vascularization. This key study shows that formation
of new blood vessels and connecting with the host vascularization is possible for
the bioprinted kidney tissues in vivo.

6.4 Challenges and limitations of bioprinting functional organs

Bioprinting holds tremendous potential for the fabrication of artificial organs for
transplantation purposes. If succeeded, this technology will transform the tissue
 6.5 Bioprinting in cancer research 89

engineering and may provide remedy for various organ failure-related diseases we
face today. However, bioprinting functional organs have numerous limitations
and challenges to be applicable in clinical organ transplantation operations.
Native organs and tissues require vascular connections to take in oxygen and nu-
trients and dispose waste through the blood stream. Currently, bioprinted organs
lack this microvasculature formation due to its complex 3D shape and small size.
Although in situ printing and developing strategies to connect the bioprinted or-
gans with the existing vascular system of the recipient tissue provide promising
results, vascularization remains as the main challenge in functional printed or-
gans. In addition to the vascular tissue formation, bioprinted organs and tissues
also require postprinting maturation under physiological conditions prior to
in vivo transplantation. This maturation may take several weeks, and using bio-
reactors would contribute to high cost and low speed of this technology. Lastly,
biocompatibility, interaction with the neighboring tissues, viability, and functions
(contraction, sensing, communication, filtration, etc.) of these bioprinted organs
in vivo necessitate significant amount of research investment to make this tech-
nology ready for clinical trials.
Considering the current limitations and challenges of the technology, bioprinted
artificial tissues and organs will most likely find ex vivo applications in terms of ther-
apeutic test platforms. Using these artificial biomaterials mimicking the native tis-
sues and organs can help medical scientists understand the diseases mechanisms
and the efficacy of novel drugs developed against diseases relevant to these organs
and tissues. In addition, these test platforms can decrease the reliance upon animal
models saving time and cost in these studies. The following section describes one of
these major bioprinting applications in vitro; cancer bioprinting can make significant
impact in cancer treatment procedures.

6.5 Bioprinting in cancer research

Despite the rigorous research effort, cancer remains as one of the daunting chal-
lenges we face today. Cancer initiation and progression are highly dependent upon
the complex, 3D, in vivo tumor microenvironment. Commonly used in vitro tumor
modeling studies, however, are based upon planar, 2D geometries, which cannot
mimic the actual tumor initiation and progression microenvironment. These overly
simplified models also lack cell and ECM interactions existing in vivo. Therefore,
the success of cancer research studies based on simple 2D models to represent the
actual tumor initiation and progression in vivo is greatly impaired. In order to im-
prove the efficiency of existing cancer investigations, bioprinting provides a suitable
alternative in creating a more realistic 3D cancer microenvironment and offers the
controlled distribution of the tumor cells within this microenvironment [210, 211]. It
has been shown previously that replacement of 2D cancer models with 3D-bioprinted
90 6 Bioprinting

ones can lead to significant modifications on gene and protein expressions, gradient
profiling of proteins, cell signaling, morphology, and viability [212–216]. Therefore,
replicating 3D cancer microenvironment using bioprinting process has utmost impor-
tance for the future development and success in cancer research. Bioprinting tech-
nology has already been applied to various cancer applications to mimic cancer
microenvironment and better understanding the fundamental concepts for cancer
initiation and growth. The summary of all these recent studies utilizing cancer bio-
printing is shown in Table 6.2, where the cell viability levels for different methods
are reported.

Table 6.2: Recent research studies on cancer bioprinting (redrawn according to [211]).

Cancer Bioink Cell Bioprinting Reference

type viability method

Breast Mesenchymal stem cells + gelatin –% Stereolithography []

methacrylate
Breast hBMSCs + MDA-MB-/MCF- –% Stereolithography []
Breast MCF- + PEG >% Inkjet []
Breast MDA-MB-/IMR- MCTS High Extrusion []
Breast Breast adenocarcinoma + mouse macrophage >% Extrusion []
+ sodium alginate
Brain GSC + hMSCs + sodium alginate/gelatin >% Extrusion []
Brain Human glioma stem cells + gelatin/alginate % Extrusion []
Brain U glioma + pluripotent stem cell-derived N/A Extrusion []
neural organoid
Brain GAM + GBM + gelatin methacryloyl/gelatin High Extrusion []
Brain GSC + U + sodium alginate >% Extrusion []
Cervical HeLa + gelatin/alginate/fibrinogen >% Extrusion []
Cervical HeLa + gelatin/alginate/fibrinogen >% Extrusion []
Cervical HeLa +  T/ + PEGDA N/A Stereolithography []

In these studies, 3D bioprinting techniques have opened a great range of opportu-

nities, especially for in vitro monitoring of cancer progression with increased con-
trol on the ECM. Bioprinting has significantly improved biomimicry of cancer
modeling compared to conventional tissue engineering, thanks to the enhanced ac-
curacy and composition of tumor environment coupled with the availability of im-
proved vascularization [230, 231]. The major advantage of additive manufacturing
is that it allows more realistic, accurate, and facile modeling compared to well-
established 2D techniques. Recent applications of bioprinting for this purpose have
concluded appreciable results to further illuminate the cancer biology and explore
new fields such as progression of cancer, cell interactions, drug efficiency, and
 6.5 Bioprinting in cancer research 91

treatment methods. Bioprinting has been applied to only a limited variety of can-
cers: breast, brain, cervical, and ovarian as shown in Table 6.2. Implementing bio-
printing on different types of tumors and understanding the biophysical cues on
cancer initiation and progression mechanisms can significantly improve the drug
efficacy and interaction systems in future cancer studies.
7 Topology optimization

Optimizing the geometry of a structure is essential to reduce weight, material, and the
cost of the manufacturing process; therefore, it provides significant economic and envi-
ronmental benefits. Fabricating components with reduced weights without adversely
affecting their functionality is especially important for aerospace applications. Recent
advancements in additive manufacturing have made the optimization concept more
important than ever since this manufacturing process does not have the design con-
straints of the conventional manufacturing methods and it is not bound to the geome-
tries optimized in a limited design space. Geometrical optimization process involves
the search of optimum design parameters to meet the design objectives such as mass,
volume, and stress reduction while satisfying the design constraints. There are three
major concepts where geometry of the design can be optimized. These are size, shape,
and topology optimization techniques as shown in Figure 7.1.
In a size optimization process, length, width, or thickness of the components
are the design parameters and these geometrical parameters are optimized to
achieve the optimized configuration using an iterative procedure. Similarly, shape
optimization focuses on the modification of the component shape by which the
ideal component function can be obtained such as homogenously distributed stress
with minimum stress concentration.
Topology optimization, however, is the process of determining the connectivity,
shape, and location of internal and external structure of a solid domain by deter-
mining the best material distribution [233]. Therefore, topology optimization allows
the structures to attain any shape within the design space with greater design free-
dom when compared to size and shape optimization methods that deal with only
geometrical variables such as length, thicknesses, and shape of predefined compo-
nents. Topology optimization compliments the manufacturability freedom of addi-
tive manufacturing process with this design freedom capability; hence, topology
optimization finds a wide range of applications in early conceptual and preliminary
design phases where changes made on the component topology have a significant
impact on final part performance.
It is also a common practice that all of these optimization methods are used to-
gether in a multistep optimization process. In the first phase, topology optimization is
used due to its robustness and high flexibility as described earlier as an optimal con-
figuration of the structure. It is then further optimized using the size and shape optimi-
zation process in detail to achieve the final optimal design under realistic loading
configurations. The success of this design process, therefore, highly relies on the accu-
racy of the initially performed topology optimization process. In this chapter, the de-
tails and the importance of the topology optimization process are described, major
methods used in topology optimization are shown, and the topology optimization inte-
grated design process is explained using a finite element analysis software.

https://doi.org/10.1515/9781501518782-007
 7.1 Topology optimization for additive manufacturing 93

Size optimization Shape optimization Topology optimization

Figure 7.1: Structural optimization techniques. Figure was reprinted from [232].

7.1 Topology optimization for additive manufacturing

Mathematical concept of topology optimization concept was initially applied for

simple truss structures in 1904 and then applied to more complicated solid systems
such as beams [234, 235], porous, and composite structures [236]. The mathematical
concept was then integrated into numerical algorithms that lead to the develop-
ment of commercial topology optimization simulation packages in 1990s which
were suited for subtractive manufacturing. Although the mathematical principles of
topology optimization were established more than a century ago and the numerical
simulation softwares have become available in the past 30 years, the true potential
and benefit of topology optimization have been revealed with the advent of additive
manufacturing technologies, recently. AM technologies make the uncompromised
fabrication of topologically optimized components possible with their unmatched
design freedom. The general workflow of the integration of topology optimization is
given in Figure 7.2. The procedures start with setting up a CAD model of the original
design and importing the model into a topology optimization platform (software or
an algorithm). A suitable topology optimization methodology is then selected to op-
timize the geometry of the design satisfying the constraints in the optimization
study. The optimized domain can be smoothed out for the manufacturability and
aesthetic purposes. The smoothed model is then reanalyzed to check if it satisfies
the design requirements. If it fails this satisfaction, topology optimization algorithm is
modified, and the optimization process is repeated until the desired design is achieved.
Successful optimization process results in the optimized models that surpass the per-
formance of the original model. At the final stage, topology-optimized model can be
additively manufactured at high level of complexity and high performance.
Since the conventional solid component fabrication is no longer required in addi-
tive manufacturing, components with highly porous topology and complex shape
94 7 Topology optimization

CAD model Postprocessing and

import smoothing

Finite element
analysis Finite element
analysis

Homogenization
Selecting topology SIMP No
optimization method Level set
ESO/BESO Satisfactory?

Yes
Optimized geometry
satisfying the constraints

Figure 7.2: Workflow of topology optimization process for additive manufacturing.

can be achieved. In other words, topologically optimized structures with high strength
and good energy absorption properties can be obtained at significantly low density.
Therefore, mass reduction-based topology optimization finds wide range of applica-
tions especially in automotive and aerospace in which weight reduction is a highly de-
sired phenomenon. An example problem aiming to reduce component mass using
topology optimization is described in Section 7.3. In this case study problem, signif-
icant mass reduction is achieved without compromising the functionality and the
strength of the designed part.
Another important area that topology optimization has found applicability is in ad-
ditive manufacturing of the design of support structures. Support structures are sacrifi-
cial elements, which are used during the additive manufacturing to support low-
angled and overhanging sections of the fabricated parts with respect to the build
plane. Although some additive manufacturing technologies such as powder bed fusion
and binder jetting do not require support structures, supports are needed in most other
additive techniques.
Printing support structures can slow down the process and requires additional
postprocessing steps for their removal. It is estimated that 40–70% of an AM prod-
uct cost could be expended for removal of support structures as reported by Liu and
coworkers [237]. In addition, the support material may not be removed completely
in designs where these supports are inaccessible such as self-contained cavities;
therefore, extra weight will be added to the final AM part. Therefore, it is important
 7.1 Topology optimization for additive manufacturing 95

to design supports with minimum mass or optimize the part geometry in a way to
completely eliminate the need for supports.
Figure 7.3 shows some examples regarding the support design to minimize sup-
port weight. Figure 7.3A (reported by Huang et al. [238]) shows the comparison of a
straight wall support and a slim support in which the support structure is slimmed
down to save material and enhance the printing speed. Figure 7.3B shows an exam-
ple of a tree-like support pattern, where significant support material can be saved
compared to solid, straight wall support design.

(A) (B)

Figure 7.3: Topology-optimized support structures proposed for mass reduction. (A) Comparison of
the slimmed and straight wall support structures. Partial image was reprinted from [238] with
permission. (B) Tree-like support structure. Partial image was reprinted from [239] with permission.

Considering the mass reduction and maximizing the fabrication speed, overhang-free
topology optimization for completely removing the need for support structure is a
more appealing concept. However, in overhang-free topology optimization, the struc-
tural mechanical performance and even functionality of the fabricated part may be
compromised [237]. In addition, support structures may be beneficial to assist heat
transfer toward the base plate, thereby creating a uniform temperature distribution
and minimizing the occurrence of thermal-related stresses and warping. Therefore, it
would be more practical to strategically place sacrificial support material in regions
where the placement would generate significant improvement in part performance
rather than redesigning the parts to removed them completely. Selection of minimiz-
ing the support structure, complete elimination, or combining the both methods de-
pend strongly on the part design and its functionality. Regardless of the selected
methods, topology optimization plays an important role in the design process on ad-
ditively manufactured components where support structures are considered.
Although topology optimization in additive manufacturing has been mainly ap-
plied on strength-based weight minimization and the support design of the fabricated
parts, other design objectives have been implemented in topology optimization as
well. Topology optimization methods have been developed for optimizing additively
manufactured thermal systems such as heat exchangers and heat sinks based on
96 7 Topology optimization

conductive, convective, and conjugate heat transfer concepts. In these applications,

topology optimization is used to design geometries by modifying geometry-dependent
heat transfer coefficients (conductive and convective) in the system to optimize the
heat transfer in heat sinks and heat exchangers. Additively manufactured thermal sys-
tems designed via topology optimization have shown lightweight and increased ther-
mal performance compared to the conventional heat transfer systems [240]. Lange
et al. used topology optimization to design a heat sink component by maximizing the
thermal conductivity throughout the part and minimizing its weight. It was shown that
the topology-optimized heat sink was highly complex in terms of geometry, making it
impossible to fabricate via traditional fabrication technologies. It was, however, possi-
ble to successfully fabricate the optimized design via powder bed fusion additive
manufacturing evidencing the mutual importance of topology optimization and addi-
tive manufacturing. It was also experimentally validated in this study that the heat
transfer coefficient with topology-optimized design was improved compared to the un-
optimized heat sink component.
In summary, topology optimization has been applied in numerous applications
in additive manufacturing, including lightweight component design, minimizing or
completely eliminating support structures, and maximizing thermal conductivity to
achieve effective heat transfer process minimizing the thermal stresses and warp-
ing. More applications will emerge as the additive manufacturing technologies will
continue to develop and more robust topology optimization concepts and numerical
simulations will be available in the future. The major topology optimization meth-
ods currently in use are described in the next section.

7.2 Topology optimization methods

Topology optimization is a mathematical method in which the material topology is

modified to maximize the performance of the system. There are various topology opti-
mization methods such as homogenization, SIMP (solid isotropic microstructure with
penalty), ESO/BESO (evolutionary/bidirectional evolutionary structural optimization),
and level set method. The main difference among methodologies lies in the parameteri-
zation of the design space. Some of the topology optimization methods explicitly define
the design directly on the finite element domain while the others define a design im-
plicitly using a separate function from which the structure is interpreted. Regardless of
the methodologies selected, there is a generalized mathematical concept behind these
optimization methods which can be described as follows:
8
< Objective function min or max f ðxÞ
>
Constraints g ð xÞ ≤ 0 (7:1)
>
:
Variable range xmin ≤ x ≤ xmax
 7.2 Topology optimization methods 97

In this definition, design variable (x) is the vector of independent variables that de-
scribes the design. It may represent parameters such as geometry, type of material,
and distribution of material. Objective function f(x) is a function or many functions
that return values, which indicate the suitability of the design. Objective function f(x)
may represent weight, displacements in a given direction, stress, or manufacturing
cost. In structural analysis problems (stress-based optimization), maximizing the
overall stiffness of a structure or minimizing its compliance under a specific amount
of mass removal is the most commonly utilized objective function. Constraints in the
design problem are defined by the g(x) ≤ 0 function, which could be limits on mass,
volume, stresses, displacements, eigenfrequencies, heat flux, and so on, and the de-
sign space is determined by the range of the independent variable range (xmin, xmax).
The solution is sought using different governing equations that can be solved using a
generic form as follows:

K ðxÞu = F ðxÞ (7:2)

where K(x) is the stiffness matrix and F(x) is the force vector. Type of the problem
determines the governing equations. If the stress-based problem is solved in the de-
sign problem, stress–strain constitutive relationships are utilized. In a thermal con-
ductivity design problem, heat equation is used as the governing equation.
There are different topology optimization methods using these common optimiza-
tion concepts. The main goal in these methods is to determine the existence or absence
of material within a given region of a design domain. Solid-void concept is commonly
used in topology optimization methods where solid represents the existence of a mate-
rial, whereas void implies the absence of material. The main difference between the
different topology optimization methods is the type of parameterization of the design
space. Traditional methods such as homogenization and SIMP (solid isotropic material
with penalization) explicitly define the design directly on the finite element domain
while in the other methods (i.e., level set method) structure domain and boundaries
are represented based on the implicit functions rather than an explicit parameteriza-
tion of the design domain. The most commonly used SIMP and level set methods are
briefly described later.
Currently, the most widely used methods for structural topology optimization
are explicit parameterizations that are broadly classified as density-based methods.
Among all the density-based methods, SIMP is by far the most popular technique
due to its conceptual simplicity and ease in implementation. As a result, nearly all
commercial topology optimization tools utilize a density-based method [241]. The
SIMP method predicts an optimal material distribution within a given design space,
for given load cases, boundary conditions, manufacturing constraints, and perfor-
mance requirements. In SIMP method, the design variables are defined for each ele-
ment and normalized value for pseudodensity parameter ranging from 0 to 1.
98 7 Topology optimization

Density variables are penalized with a basic power law as shown in the following
equation:
 
f ρe = ρpe f0 (7:3)

where the objective function, f, is selected as the physical quantities such as mate-
rial stiffness, cost, or conductivity depending on the problem type. ρe is the density
of the finite elements used in the optimization and p is a finite penalty parameter
commonly used in the range of 1–3. For each element, the assigned relative density
can vary between a minimum value ρmin and 1, which allows the assignment of in-
termediate densities for elements (characterized as porous elements). The penalty
factor p diminishes the contribution of elements with intermediate densities (gray
elements). The penalty factor steers the optimization solution to elements that are
either solid black ( ρe = 1) or void white ( ρe = ρmin). Numerical experiments indicate
that a penalty factor value of p = 3 is suitable.
Level set topology optimization method is a recently developed, shape-based to-
pology optimization technique where implicit functions are used to define structural
boundaries rather than an explicit parameterization of the design domain. As shown
in Figure 7.4A–C, level set function is defined to represent boundaries when the level
set function is zero and it matches the initial shape contour. In this 2D domain, opti-
mization algorithm is applied to satisfy the objective function under the constraints.
Following the optimization process, the shape will evolve (Figure 7.4B–D).

(A) (B) Φ (x) > 0

Ω D

𝜕Ω Φ (x) = 0
Φ (x) < 0

(C) (D)

Figure 7.4: Level set topology optimization method. (A) and (C) Two-dimensional topologies and
(B) and (D) corresponding level set functions. Image was reprinted from [244] with permission.
 7.3 Solution of topology optimization problem using ANSYS finite element software 99

Level set optimization produces smoother boundaries compared to SIMP method.

In addition, the level set method does not use intermediate density material (gray zone)
in the design domain resulting in clear, unambiguous geometries. However, level set
method is a time-dependent (as the level set function moves along the domain with a
controlled velocity) initial value problem and therefore its accuracy is strongly depen-
dent upon the initial design, which is a major drawback of this methodology. However,
new tools are under development to reduce this dependency [242]. Level set methods
also require reinitialization during the process when the level set function is not satisfac-
tory (too flat or too steep), which adds additional computational complexity; therefore,
algorithms not requiring this process is under development to reduce the computational
cost [243].

7.3 Solution of topology optimization problem using ANSYS

finite element software
As a demonstration example for topology optimization integration in additive
manufacturing, the design process of a bracket under load is considered as shown
in Figure 7.5A. The bracket is pulled with 5,000 N from the pinholes located at the
upper right ears and the other pinholes are used as the cylindrical supports fixed in
all directions (radial, tangential, and axial). The goal of this bracket design example
is to reduce the mass of the bracket as much as possible without adversely affecting
the structural stability of the part. ANSYS finite element analysis software (R19) was
used to solve for the topology-optimized design problem where the bracket model
was imported as shown in Figure 7.5B. Static structural finite element analysis
under the loading conditions described earlier results in maximum stress of 100 MPa
in the bracket (Figure 7.5C). It is clear from this figure that the majority of the bracket
is under minimal stress (blue zones), which evidences the feasibility of topology opti-
mization implementation. In the initial topology optimization problem, as the design
constraint, mass is set to be reduced by 60%. Topology-optimized model for 60%
mass reduction is given in Figure 7.5D, where extra material not contributing the
structural stability in blue areas was removed by the topology optimization software.
Density-based (SIMP method) topology optimization algorithm was selected as the
optimization option, which achieved the optimized solution by maximizing the stiff-
ness (or minimizing the compliance) as described earlier. Optimized model was then
redrawn smoothing out the optimized geometry (Figure 7.5E) and structural finite ele-
ment analysis was performed on this model under the same loading conditions as
shown in Figure 7.5F. This figure indicates that maximum stress in the bracket re-
mained the same (100 MPa) despite the removal of 60% mass in the original design.
Therefore, in the second design iteration, design constraint was increased to 75%
reduction in mass, which resulted in the topology shown in Figure 7.5G. Similar
to the first design, the optimized design was smoothed out for the improved
100 7 Topology optimization

Figure 7.5: Step-by-step design process for the topology-optimized bracket under mechanical
loading. (A) Loading and boundary conditions for the bracket, (B) imported bracket CAD design into
ANSYS finite element software, (C) structural analysis of the original design, (D) 40% mass-reduced
model obtained by the topology optimization algorithm, (E) smoothed CAD design based on the
topology-optimized model, (F) structural analysis of the topology-optimized design, (G) 75% mass-
reduced model obtained by the topology optimization algorithm, (H) smoothed CAD design based
on the 75% mass-reduced model, and (I) structural analysis of the final design.

manufacturability and aesthetics purposes. Final design is shown in Figure 7.5H.

Finite element analysis (Figure 7.5I) performed on this design under the same
loading conditions showed only a slight increase in the maximum stress (112 MPa)
in the bracket despite the removal of large mass from the original design.
Therefore, this final design was found to be satisfactory for the amount of mass
reduction, structural stability, and manufacturability properties.
In summary, topology optimization is a unique tool to design additively manu-
factured parts with improved performance. This improvement can be reduction of
mass, redesigning the support structure and/or optimizing the mechanical, ther-
mal, and electrical properties. Development of more accurate and computationally
efficient topology optimization methods will further enhance their integration in
manufacturing of additively fabricated components.
8 Advanced concepts in additive manufacturing

8.1 Hybrid additive manufacturing

Hybrid additive manufacturing (hybrid-AM) can be defined as a multimaterial layer-by-

layer manufacturing process or integration of other manufacturing technologies with
additive manufacturing (AM). Hybrid-AM extends the design flexibility of the AM pro-
cess by adding a new dimension into the manufacturing paradigm. In other words, hy-
brid-AM uniquely combines the strength of multiple manufacturing processes or
multiple materials to enhance the part performance or functionality. Therefore, some
of the existing limitations of the conventional AM processes can be eliminated with
this approach. In general, hybrid-AM processes follow a serial order and these are not
simultaneous processes. Therefore, adverse interactions and influence of individual
events on each other are minimal. In this book, hybrid-AM technologies are considered
in terms of three major application fields: additive/subtractive hybrid-AM, hybrid-AM
of multimaterial electronic components, and hybrid-AM in tissue engineering. The ben-
efits and limitations of these methods are described in the following sections.

8.1.1 Additive/subtractive hybrid manufacturing

As described throughout this book, AM has significantly extended the design flexi-
bility of traditional subtractive manufacturing technologies. However, subtractive
manufacturing has unique benefits over AM such as better surface finish and high
speed. As a result of these distinct benefits of each manufacturing methodology,
the concept of integrating additive and subtractive manufacturing technologies
has been developed. Computer numerical control (CNC)-based digital subtractive
manufacturing techniques are well suited for this integration since both AM and
CNC manufacturing use the similar digital control platforms. Figure 8.1 shows the
concept of hybrid-AM/subtractive manufacturing where CNC milling is performed
on the surfaces of an additively manufactured part to create features with im-
proved surface quality and precision at high speed [245].
In addition to milling, other subtractive manufacturing (machining) techniques
can be integrated to AM such as turning and drilling further extending the capabili-
ties of hybrid-AM. The hybrid-AM/subtractive manufacturing has unique advantages
over traditional AM. As described, hybrid method combines the design flexibility and
the excellent surface finish of subtractive manufacturing. Stair effect, which is a com-
mon geometrical artifact in additively manufactured components, can be completely
eliminated by machining these surfaces in hybrid manufacturing. In addition, rare
materials or materials that are difficult to machine can be initially fabricated via AM
to near-net shape, and subsequent step of machining creates parts economically and

https://doi.org/10.1515/9781501518782-008
102 8 Advanced concepts in additive manufacturing

(1) Start (2) Additive process (3) Milling (4) Additive process
Z
Laser Spindle
X Y
Substrate

Workbench

(5) Milling (6) Additive process (7) Milling (8) Finish

This cycle is
repeated...

Figure 8.1: Schematic of additive/subtractive hybrid manufacturing. Image was reprinted from
[245] with permission.

with minimum waste. This is especially beneficial for rare materials with high costs.
As described in Chapter 4, dynamic strength of metals is significantly affected by the
surface roughness. Therefore, hybrid-AM/subtractive manufacturing allows fabrica-
tion of metallic components with higher dynamic strength compared to AM parts due
to the improved surface quality [246].

8.1.2 Additive/additive hybrid manufacturing

The main goal of integrating subtractive and additive technologies together is to

achieve robust and high-speed manufacturing of metals with complex geometries and
superior surface finish. Different AM methodologies can also be combined to unify the
benefits of different AM technologies in the same manufacturing system. Considering
the benefits and the limitations of the major AM technologies, an obvious choice for
this integration is combining the high-resolution, single-material AM techniques with
those having low-resolution but multimaterial capabilities. Therefore, the hybrid-AM
system would have the desired surface quality and the capability of additively fabricat-
ing multiple materials in the same setup. As an example, researchers at the University
of Texas el Paso [247] developed direct write (DW) integrated hybrid manufacturing
technology, which enabled printing of electrical circuitries onto the structure surfaces
fabricated via stereolithography (SLA). This concept was then further expanded to
fused filament fabrication (FFF) to build 3D circuit boards for a CubeSat satellite [248].
Instead of DW process, material jetting was also integrated on the FFF system to
fabricate electronic structures at high resolution (~10 µm) [249]. Therefore, addi-
tive/additive hybrid-AM technologies focus on integrating multimaterial AM
 8.1 Hybrid additive manufacturing 103

technologies such as direct ink writing and material jetting into the robust,
high-resolution AM methods such as FFF and SLA.
The most common needs and uses of the hybrid-AM/AM technologies are in elec-
tronic applications. Electronic systems usually involve the combination of metal con-
ductors, ceramic insulators, dielectric materials, polymers, and semiconductors. The
hybrid-AM enables embedding of these multimaterial systems in electronic compo-
nents with high degree of complexity realizing functional systems at reduced cost and
weight. High geometrical complexity is demanded in many automotive, medical, and
aerospace fields, which creates challenges in the production of traditional PCB-based
electronics. Figure 8.2 shows an example hybrid process combining SLA and direct ink
writing developed by Jo et al. [250] to fabricate a functional 3D-printed circuit board
(PCB) device in a complex geometry. Circuit diagram of the electronic system is
given in Figure 8.2A. As shown in this figure, the exterior wall is fabricated by

(A) (B)

6V Aduino MCU
Via hole
Battery
330 Ω M 1 kΩ LED
C Resistor Sensor
U Resistor

Upper layer Lower layer Upper layer

10 mm

(C) (D)
LED Sensor

LED

Figure 8.2: Additively fabricated printed circuit board (PCB) system. (A) Circuit diagram of a
3D-printed (B) bottom view of the PCB with an Arduino-programmed MCU, a photosensor, a battery,
resistors, via holes, and LEDs, (C) top view of the printed PCB, (D) image of the 3D PCB operation,
showing that the LED turns on when the photosensor is covered. Figure was reprinted with
permission from [251].
104 8 Advanced concepts in additive manufacturing

the SLA method photopolymerizing the liquid polymer material around the elec-
tronic components initially. The process is then paused to clean the partially
printed part and dispense interconnects using direct ink writing. Other elec-
tronic components such as battery resistors and diodes are also laid down on the
printed surfaces at this step. The SLA process then resumes to build photopoly-
mer around the electronic components embedding them within the polymer as
shown in Figure 8.2B–D.
The hybrid-AM/AM technologies developed for manufacturing of electronic com-
ponents have tremendous potential due to their design flexibility and their capability
of multimaterial fabrication with minimal material waste. The main limitation of
these methods is the intermittent process between the different manufacturing steps
leading to significant reduction of the manufacturing speed. The development of new
hybrid-AM technologies that are capable of simultaneous integration of multimaterial
AM techniques will significantly enhance the adoption of hybrid-AM technology for
various novel applications in the future.

8.1.3 Hybrid additive manufacturing/scaffolding technologies

AM plays an important role in tissue engineering since it allows successful fabrica-

tion of patient-specific 3D implant structures and scaffolds. However, the lack of
surface texture mimicking that in native tissues adversely affects the cell adhesion
and proliferation of the fabricated structures limiting the implementation of these
AM methods for certain tissue engineering applications [252]. In addition, low reso-
lution of AM technologies prevents the manufacturing of submicrometer structures
mimicking those observed in natural extracellular matrix (ECM) and hierarchical
porous architectures with multimodal pore size distributions [253]. Hybrid-AM tech-
nologies combining standard AM with cell scaffolding techniques can be used to
optimize the surface morphology of the printed structure for cell adhesion and pro-
liferation. In addition, multimaterial, multiscale (micro-nano-macro) materials can
be deposited on the printed structures further tailoring the biophysical properties of
these 3D-printed biomaterials. Electrospinning and freeze-drying are among these
scaffolding techniques that are readily applicable to AM integration.
Freeze-drying methods can be integrated into AM technologies to fabricate
structures consisting of multiscale (micro and nano) pores. Fabrication of custom 3D
architectures with multilevel pore arrangement ensures a larger surface area for cell
adhesion and proliferation [254]. Freeze-drying is a commonly used technology, which
involves freezing of the material, lowering the pressure, and finally removing the sol-
vent by sublimation. This technology can be easily integrated into DW AM to fabricate
tissue scaffolding materials in 3D geometry. In this hybrid-AM methodology, a polymer
fiber solution is dispensed at low temperature using DW AM, and then the solvent
is freeze-dried leaving the porous fiber network behind. The porosity level of the
 8.1 Hybrid additive manufacturing 105

fabricated scaffold can be controlled by simply adjusting the process parameters

such as temperature. Natural biopolymers such as 3D collagen can be used to cre-
ate hierarchical 3D scaffolds with highly porous surface that act as cell entrap-
ment system.
As an alternative route to freeze-drying, wet-spinning system can be used to manu-
facture porous fiber networks in 3D. This technique relies on collecting a solidifying
filament of polymer solution into a coagulation bath with predefined layer-by-layer
patterns [255, 256]. The produced fibers possess an enhanced biological response due
to their “spongy” morphologies. This hybrid manufacturing technique is advanta-
geous since it is a single-step process compared to the freeze-drying-based hybrid
manufacturing. However, applicability of this method to only specific biomaterials
limits its applications.
Electrospinning is one of the most common polymer fiber production techni-
ques that uses electric force to draw charged polymer solutions to produce fibers in
the range of nano- and microlength scales. AM and electrospinning can be inte-
grated together in different configurations resulting in hybrid-AM technologies.
Electrospun fibers can be deposited using sacrificial targets fabricated by AM. This
allows micropatterned scaffolds consisting of random fibers with a defined 3D sur-
face microtopography. Alternatively, melt electrospun fibers can be directly printed
on the surface similar to the FFF process. Melt electrospinning involves melting of
thermoplastic polymers during the electrospinning process rather than liquid solu-
tion of polymer materials in a solvent. Direct printing of fibers instead of using sac-
rificial targets allows the controlled single-step deposition of the fibers on the
printbed at high resolution. Recently, submicron range, uniform thermoplastic fi-
bers were additively fabricated by Hochleitner et al. [257] using melt electrospin-
ning-based hybrid-AM. Despite its high resolution and controlled microstructure,
this technique requires a sophisticated experimental setup integrated with heating
and electrical insulation, which is a major limiting factor. In addition, high heat ap-
plied on the polymer material may adversely affect the temperature-sensitive mate-
rials (i.e., collagen, growth factors, etc.)
To overcome these challenges, electrohydrodynamic jet printing (E-jetting)
technique was developed to fabricate polycaprolactone (PCL) scaffolds recently.
Ethanol targets used in this technique allow the fabrication of highly porous 3D
scaffolds with controlled filament orientation at room temperature [258]. It was re-
ported that 3D fibrous scaffolds consisting of entangled micro/nanofibers improved
cell seeding efficiency and cell adhesion compared to the scaffolds fabricated via
extrusion-based AM [252].
In summary, integration of fiber scaffolding technologies with AM techniques such
as FFF or DW creates unique scaffold structures that act as ideal cell adhesion and pro-
liferation locations for tissue engineering. Fiber-based structures fabricated in 3D ge-
ometries can mimic the native ECM topographically and spatially. The porosity, fiber
size, and orientation can be controlled by using different scaffolding technique and
106 8 Advanced concepts in additive manufacturing

controlling the process parameters. Table 8.1 presents the major hybrid-AM scaffold
fabrication technologies summarizing benefits and limitations.

Table 8.1: Summary of hybrid-AM technologies used in tissue engineering (redrawn according to [252]).

Hybrid-AM Advantages Limitations Materials Applications

method

Freeze-drying High porosity with Two-step process PLGA Bone

smaller pore size Chitosan Cartilage
Control of porosity PLLA/TCP Nerve
level Type-I collagen
PLLA/chitosan

Wet spinning Spongy fiber Limited set of PCL Bone

morphology biomaterials PCL/HA
One-step process Star poly
(ε-caprolactone)/HA

Melt Submicron fiber size Complex PCL Skin

electrospinning and micron size fiber- experimental setup Neural
to-fiber distance (heating + electrical Vascular TE
Microscale threads insulation)
consisting randomly
interwoven micro/
nanofibers

E-Jetting Different strut Difficult control of PCL Bone

morphology depending micro/nanosized
on the viscosity of strut size
target solution

8.2 Additive manufacturing of thermoelectric materials

Thermoelectric effect is an exciting concept dealing with the direct conversion of

heat energy into electricity and it has great potential to be the ultimate remedy for
waste energy recovery in general. Considering the significant amount of energy
around us ultimately goes unused in terms of waste heat, and the importance of
the waste heat recovery can be better recognized. Thermoelectricity refers to a
phenomenon by which thermal energy is converted directly into electrical energy
(and vice versa) without any moving parts or working fluids. Thermoelectric mate-
rials are able to generate electricity under a temperature differential, which ren-
ders them capable materials in reduction of the waste heat. If a thermal gradient
is introduced (e.g., engine heat on one side with ambient temperature on the
 8.2 Additive manufacturing of thermoelectric materials 107

opposing side) along these materials, an electric potential, ΔV, is created accord-
ing to the following equation:

ΔV = SΔT (8:1)

where S and ΔT are Seebeck coefficient and relative temperature, respectively. Heavily
doped semiconductors are the best thermoelectric materials that possess high Seebeck
coefficients, high electrical conductivities, and low thermal conductivities which are re-
quired to avoid the loss of temperature gradient along the material. Based on the dop-
ing type, thermoelectric material can be either p- or n-type. If a thermoelectric material
is kept under thermal gradient, in p-type material, positive charges (holes) move from
the hot side to the cold side. In n-type material, negative charges (electrons) move from
the hot side to the cold side. If both materials are connected in serial electrically and
parallel thermally, electric current flows in the system and temperature gradient is con-
verted into electrical energy as shown in Figure 8.3A. A single module shown in this
figure is capable of limited amount of electrical energy. To produce higher level of
energy, multiple thermoelectric modules are arranged in a serial connection as
shown in Figure 8.3B. Thousands of modules may be required for applications de-
manding large power needs such as NASA’s radioisotope thermoelectric generators
used for multiple space missions producing kilowatt range of electrical power.

Hot surfa
(A) ce (B)

p-Type
n-Type

+ +
–
+ + +
+ + Holes – – –
– – –
Electrons
Cold surf
ace

Electric fl
ow

Figure 8.3: Principle of thermoelectric energy generation. (A) Thermoelectric effect in p- and n-type
thermoelectric materials and (B) assembled modules in a thermoelectric generator device.

Since its discovery over 100 years ago, thermoelectricity has attracted great scientific
interest and it has been extensively investigated by numerous researchers; however, it
has found only niche applications such as deep space exploration systems by NASA as
described earlier. Fundamental challenges of thermoelectric systems limiting its use in
our daily lives are twofold: low-energy conversion efficiency and difficult multistep
process of their fabrication even for simple geometries. Conventional fabrication of
thermoelectric device is a multistep process, including powder synthesis, ingot prepa-
ration, dicing, metallization, leg dicing, and assembly (Figure 8.4) [259].
108 8 Advanced concepts in additive manufacturing

(A) (B)

Insulating Powder
substrate synthesis/ Ingot Ingot
alloying sintering dicing
Electrical n-Type p-Type
shunts

Module
Leg dicing Metallization
assembly

Figure 8.4: (A) Schematic of thermoelectric unicouple system. (B) Processing steps for the fabrication
of a conventional thermoelectric device. Image was reprinted from [259] with permission.

The fabrication and the assembly of hundreds or even thousands of modules for the
fabrication of a single device are challenging processes used in the conventional
manufacturing of these systems. In addition, conventional manufacturing is only lim-
ited to flat thermoelectric module geometries, and therefore, complex geometries such
as recently developed annular thermoelectric systems with higher efficiencies cannot
be fabricated via these conventional manufacturing techniques. AM offers a transfor-
mative potential for the manufacturing of next-generation thermoelectric systems and
overcomes some of these challenges. Extrusion, Vat polymerization, and powder bed
fusion technologies have been implemented for the AM of thermoelectric materials re-
cently. In addition to the flexibility in device size and shape, the cost and time for the
fabrication of thermoelectric systems can be reduced significantly using AM technolo-
gies since the same printing device can be used to make electrical contacts and deposit
thermoelectric materials. Therefore, the entire manufacturing process can be auto-
mated. Some of these notable works developed recently are described in more detail.
SLA technique was used by He and coworkers [260] in 2015 where p-type bismuth
antimony telluride (Bi0.5Sb1.5Te3, BST) powder was mixed with photocurable resin in
a Vat, and 3D structures were additively manufactured by curing the photopolymer
surrounding the thermoelectric powder. Fabrication steps are shown in Figure 8.5.
Custom manufacturing setup in this study allowed preparation of components highly
loaded with thermoelectric powders (up to 60 wt%). Printed components were then
thermally annealed at 350 °C up to 6 h enhancing the thermoelectric properties.
Thermoelectric figure of merit (ZT) is the most important parameter showing the con-
version efficiency of thermoelectric materials. In this study, maximum ZT of 0.12 was
achieved for the samples fabricated via SLA and annealed for 6 h.
In 2019, Oztan et al. [261] fabricated bismuth telluride (Bi2Te3) in complex geome-
tries using FFF technique in which thermoelectric material could be additively manu-
factured with the assistance of a sacrificial polymer matrix. The process starts with
 3D printing

BST
BST ≤ 5 wt%
BST Photoresins
Pore
Formlabs form 1+ SLA
(a) 3D printer Thermal annealing

Laser Amorphous
carbon and
residual
photoresins
(b)
3D fabrication
Composite resins
5 wt% < BST ≤ 60 wt%

Composite resins

Figure 8.5: Stereolithography additive manufacturing of thermoelectric materials. Image was reprinted from [260] with permission.
8.2 Additive manufacturing of thermoelectric materials
109
110 8 Advanced concepts in additive manufacturing

mixing acrylonitrile butadiene styrene (ABS) and Bi2Te3 powders and preparing a
thermoelectric filament precursor using a filament extruder as shown in Figure 8.6.
A desktop FFF printer can then be used to 3D print this filament feedstock into any
custom geometry. Similar to the SLA process, 3D-printed samples need heat treat-
ment postprocessing steps to maximize the thermoelectric performance. During post-
processing, the sacrificial ABS polymer in the printed composite is initially removed
and then the remaining thermoelectric material (Bi2Te3) is sintered below its melting
temperature (585 °C). In this study, higher ZT of 0.54 was achieved at room temperature
testing. Higher efficiency of FFF compared to the SLA method may be due to higher
amount of the thermoelectric material within the printed composites (80 vs 60 wt%)
and the heat treatment process performed at elevated temperatures (up to 550 °C),
where stronger bonding between the powders could be obtained enhancing the electri-
cal conductivity and the thermoelectric efficiency. Similar to the SLA fabrication, high
porosity was observed in the fabricated samples, which need to be minimized to im-
prove the thermoelectric conversion efficiency.

Polymer /
TE powder

Mixture Extrusion Printing

Figure 8.6: Schematic of FFF additive manufacturing of thermoelectric materials [261].

DW (paste extrusion) AM technique was also utilized to fabricate thermoelectric ma-

terials in viscous ink form in 2018 [262]. Instead of using an organic printing aide
material, this study introduced Sb2Te3 chalcogenidometallate (ChaM) ions as inor-
ganic binders to prepare printable Bi2Te3-based inks. Inorganic binder-based ther-
moelectric inks showed high level of shear thinning, and therefore, successful paste
extrusion of these materials was possible as described in Chapter 1. Paste-extruded
specimens need heat treatment to facilitate the bonding between the thermoelectric
powders and maximize the thermoelectric conversion efficiency. Homogenous ther-
moelectric properties were achieved in paste-extruded materials, and their dimen-
sionless figure-of-merit (ZT) values were 0.9 (p-type) and 0.6 (n-type), which were
comparable to the bulk material values. Main limitations in the paste extrusion of
thermoelectric materials are the requirement of postprocessing (heat treatment) of
the printed parts, and high level of shrinkage (~20%) after the heat treatment pro-
cess is implemented.
 8.2 Additive manufacturing of thermoelectric materials 111

The above challenges (high porosity, low efficiency, and requirement of

postprocessing and filament fabrication) can be overcome using powder bed fu-
sion technologies, including selective laser sintering (SLS) and selective laser
melting (SLM). Laser-based powder bed fusion of thermoelectric materials was
first introduced in 2015 by Leblanc et al., where the proof-of-concept study in-
vestigated the feasibility of rapid prototyping of thermoelectric compounds
using SLM technologies [263]. Optimizing the process parameters (i.e., laser
power) allowed them to reach the figure of merit of 0.11 in a follow-up study. A
schematic of the SLM technology used by the Leblanc group along with the fab-
ricated Bi2Te3 components is shown in Figure 8.7. In 2017, SLM was used to fab-
ricate fine (~3.4 µm) n-type Bi2Te2.7Se0.3 powder achieving maximum ZT of 0.84
[264]. This study evidenced the capability of laser bed fusion techniques to fabri-
cate thermoelectric materials with conversion efficiencies similar to those fabri-
cated via conventional techniques. Qiu et al. [265] prepared Bi0.4Sb1.6Te3 bulk
materials using slurry-based SLM technology. Slurry-based SLM process starts
with the fabrication of thermoelectric powder by thermal explosion followed by
the ball milling procedures. Some of the powder is spark plasma sintered to fab-
ricate bulk substrate material for laser sintering. The remainder of the powder is
mixed with alcohol and spread over the substrate to obtain a thin slurry layer
(~50 µm). The alcohol is then evaporated by a heater volatilizing the alcohol, and the
powder layer was laser sintered. In this study, high ZT of 1.1 at 316 K was achieved
along with the high mechanical strength of 91 MPa. Reduced grain size as well as
high density of dislocation defect resulting from rapid solidification lead to greatly

Galvo and
(A) F-theta lens
Laser (B)

5 mm
Fabricated part

Roller Loose powder

Spacer (C)
5 mm

Build plate

(D)
5 mm

Figure 8.7: (A) Schematic of SLM additive manufacturing procedure of thermoelectric materials
(B) disk-shape-printed Bi2Te3 part with 16 W laser power (relative density ∼81%), (C) disk-shape-
printed Bi2Te3 part with 25 W of laser power (relative density ∼88%), and (D) rectangular-shape-
printed Bi2Te3 part. Figure was reprinted with permission from [266].
112 8 Advanced concepts in additive manufacturing

strengthening the mechanical properties. This work provides an effective solution for
preparation of Bi2Te3-based materials with high texture, robust mechanical proper-
ties, and excellent TE performance and would be instructive for other layered struc-
ture material systems.
Similar to SLM, SLS method was also investigated for the AM of thermoelectric
components. Unlike SLM, material is partially melted in SLS as described in
Chapter 1. The fabrication of the porous TE samples of Bi0.5Sb1.5Te3 (BST) using SLS
was performed by Shi et al. [267] recently. Since the powders are partially melted in
SLS AM, this process results in porous thermoelectric structures. SLS-fabricated po-
rous Bi0.5Sb1.5Te3 was reported to have high ZT value of 1.29 at 54 °C. Since the ther-
mal conductivity is reduced significantly by the porosity as well as boundaries and
defects forming in the SLS process, higher figure of merit was achieved compared
to the bulk BST materials fabricated via conventional manufacturing methods.
In summary, AM has a significant potential as an alternative method for the
thermoelectric device manufacturing reducing the manufacturing difficulties while
minimizing material losses and providing geometric flexibility. Table 8.2 summarizes
the notable studies in which AM technologies of thermoelectric materials are re-
ported. Bismuth telluride-based thermoelectric materials have been the first choice in
these studies since, arguably, this material type is the best performing thermoelectric
material at room temperature, is cost-effective, and is well investigated previously.
Nevertheless, thermoelectric AM technology is at its infancy and novel materials, en-
hanced properties, and process optimization are well sought in the near future to fa-
cilitate the functional thermoelectric device fabrication and the wide range of use of
this technology in energy conversion applications.

Table 8.2: The comparison of research studies reported on additive manufacturing of

thermoelectric materials.

AM method Printer type Material Maximum ZT Reference

SLA Custom and commercial (Form ) Bi. Sb. Te . []
D printer
FFF Commercial D printer BiTe . []
(Ultimaker )
Paste Custom D printer Bi.Sb.Te . (p-type) []
extrusion (p-type) . (n-type)
SLM Custom D printer BiTe . []
SLM Custom D printer BiTe.Se. . []
Slurry based Custom D printer Bi.Sb.Te . []
SLM
SLS Commercial D printer Bi.Sb.Te . []
(XJRP SLS)
 8.3 Four-dimensional printing with smart materials 113

8.3 Four-dimensional printing with smart materials

The concept of 4D printing was initially introduced by Tibbits in 2013 TED talk [268].
Four-dimensional printing is defined as adding time variable to the 3D printing (addi-
tively manufacturing) where the shape, property, or functionality of a 3D-printed
structure can change as a function of time [269, 270]. In this regard, 4D printing is an
extension of 3D printing and it includes all the process steps of 3D printing: CAD
modeling, layer-by-layer fabrication, and postprocessing. In addition to these steps,
an external stimulation is applied on the 3D-printed structure to obtain predictable
changes on this structure as a function of time. Therefore, the main difference in 4D
printing compared to 3D printing is the usage of smart materials responding to the
external stimuli and achieving unique time-dependent response. A key point in 4D
printing is not achieving time-dependent changes but rather obtaining these changes
in a predictable manner. Therefore, 4D printing requires extensive mathematical
modeling to predict the precise responses of the 3D-printed smart materials. As a re-
sult of external stimulation, these smart materials used in 4D printing transform into
another stable state. Different types of stimuli can be applied on smart materials giv-
ing rise to 4D printing. As shown in Figure 8.8, external stimulation can be applied in
terms of heat, light, electricity, moisture, pH, and magnetic force. Different states of
the 4D-printed structures can be achieved as a result of the selected smart material
type, the configuration of the 3D-printed part, and the external stimulation type.
Accordingly, the structure can shift from one state to another under the correspond-
ing stimulus in a predicted way. Therefore, the fundamental building blocks of
4D printing are the smart material type, 3D printing configuration determined by the
mathematical models and stimulus.

Smart External stimulation 4D printing

materials

– Hydrogels 3D printing Math model

– Ceramics

– Alloys

– Composites
Heat
– Polymers pH
Moisture
Light
Electricity

Figure 8.8: Schematic representation of the 4D printing procedure including the smart material
and external stimulation configurations.
114 8 Advanced concepts in additive manufacturing

The application of external stimulus is necessary to trigger the changes on smart materi-
als and create altered shapes, properties, and functionalities. Heat (temperature), mois-
ture (water), light, electricity, magnetic force, and pH are the most commonly used
stimuli to fabricate 4D-printed structures. These stimuli can also be used in combination
such as simultaneous application of heat and water to achieve the desired configura-
tions. The selection of the stimulus is performed according to the specific application,
which determines the type of smart material employed in the 4D-printed structure.
As shown in Figure 8.8, the materials used in 4D printing process are categorized
similar to those in 3D printing: hydrogels, ceramics, alloys, polymers, and compo-
sites. However, these unique materials respond to external stimuli and therefore they
are “smart” materials. Material selection is one of the most critical steps in 4D print-
ing process. Smart materials used in 4D printing have different capabilities defined
by the following characteristics: self-sensing, decision making, responsiveness,
shape memory, self-adaptability, multifunctionality, and self-repair. Major types of
smart materials investigated in 4D printing are described in the next section.

8.3.1 Four-dimensional printing materials

As described earlier, 4D printing materials are able to change their properties under
external stimulus. Although there are only limited number of materials available for
4D printing compared to those available for conventional 3D printing, significant re-
search progress has been made recently to extend the list of stimuli-responsive smart
materials. Major materials used in 4D applications are hydrogels, shape-memory pol-
ymers (SMP), liquid crystal elastomers (LCE), and active composites.

8.3.1.1 Four-dimensional-printed hydrogels

Smart hydrogels used in 4D printing are based on the concept of using inactive rigid
and active soft polymers in the printed system. When a stimulus is applied on this bi-
layer material, soft hydrogel swells or shrinks in response to the stimuli, and the rigid
polymer keeps its shape. As a result, bending deformation is obtained in the structure.
If the series of these materials are connected in a predesignated way, folding and un-
folding motion can be created. There are mainly two different stimuli applied on hydro-
gel-based smart materials: moisture (water immersion) and temperature (heat).
Hydrophilic hydrogel materials are able to swell when immersed in water; therefore,
these rubber-like materials can induce significant changes in the 3D-printed bilayer
structure in the concept described earlier. Figure 8.9A shows an example of the shape-
changing capabilities of water-responsive, 4D-printed hydrogel structures presented in
a pioneering work by Tibbits [270]. In this study, hydrogel-based smart materials were
fabricated in the form of a series of hinges that transformed a linear structure into a 3D
cube when immersed in water. Water-responsive hydrogel smart materials were also
 8.3 Four-dimensional printing with smart materials 115

(A) (B)

t=0 t = 25 min

Figure 8.9: Examples of 4D printing of hydrogel materials: (A) line-to-cube transformation of a

water-immersed hydrogel structure. Partial image was reprinted from [270] with permission.
(B) Biomimetic 4D printing of a flower with multiple petals. Partial image was reprinted from [271]
with permission.

used recently to fabricate 4D-printed parts mimicking the plant cell wall structure [271]
as shown in Figure 8.9B. In this work, bilayer structure consisted of soft acrylamide ma-
terial (hydrogel) and cellulose fibrils with high stiffness (rigid layer). The composite
structure was printed via DW extrusion technique in which bilayers were oriented in
different angles with respect to the long axis of each petal (90°/0° and −45°/45°). Water
immersion created swollen form of the soft material resulting in the complex geometries
as shown in this figure.
Temperature-responsive hydrogels have also been developed as a smart material
feedstock of 4D printing. Poly(N-isopropylacrylamide), or PNIPAm, is a common ther-
moresponsive material used for 4D printing applications. When immersed in aqueous
solution, PNIPAm hydrogel becomes hydrophilic and swells at temperatures below
32 °C. Above this temperature, this hydrogel starts to dehydrate, leading to shrinkage
and shape transformation. Therefore, similar to the water-responsive hydrogel compo-
sites, if a temperature-responsive hydrogel is 3D printed along with a nonresponsive
polymer, bilayered composite hinge system can be fabricated. Wu and coworkers fabri-
cated temperature-responsive hydrogels with disproportional swelling property [272].
In other words, these composite hydrogels in aqueous medium showed bending defor-
mation at temperatures above 32 °C since the different components of the composite
result in different amounts of swelling at this temperature level. Four-dimensional-
printed composite hydrogels are also capable of reversible shape deformation in re-
sponse to both hydration and temperature-responsive hydrogels consisting of PNIPAm
as reported by Naficy et al. [273].

8.3.1.2 Shape-memory polymers

SMPs have attracted growing interest in 4D printing due to their unique ability to trans-
form their shapes when exposed to an external stimulus and to recover a permanent
116 8 Advanced concepts in additive manufacturing

shape when the stimulus is removed. SMPs differ from hydrogels since these materials
show gradual controlled transformation under stimuli making these preferred materials
for morphing structure applications [274]. An example of shape change of PCL macro-
methacrylate SMPs by varying their temperature is shown in Figure 8.10A [275]. Eiffel
tower and bird figurines were 3D printed using SLA technique using a heated Vat of
90 °C. As the temperature of the printed structure varied, different geometries were ob-
tained resulting in reversible shape change under thermal stimuli.
Multiple SMPs and/or SMPs along with materials not responding to external
stimuli can be 3D printed together in a precisely designed configuration (shape,
placement, and mixing ratio) to obtain complex geometries in these composite sys-
tems. If SMPs with different properties are used in this multi-SMP system, SMPs re-
spond differently to the external stimuli under the stimuli and therefore selective
shape change can be obtained in a precise way. Digital SMPs are the main class of
these multi-SMP systems, where SMPs with different glass transition temperatures
are used to obtain temperature-controlled shape change. An example of this trans-
formation is shown in Figure 8.10B, where a mailbox was designed with digital
SMPs responding to thermal stimulus [276]. In this application, digital SMPs were
used along with the thermally nonresponsive materials to obtain the desired config-
uration. Multistep programming of digital SMPs is also possible, where changing
the temperature in multiple steps results in multiple different configuration of the
printed structures.

A B

2 cm
t=2.5 s t=6.3 s

10 mm t=7.2 s t=11.0 s

Figure 8.10: (A) Thermally activated single material shape-memory polymers. Eiffel tower and bird
figurines respond to temperature stimulus changing their shapes. Partial image was reprinted
from [275] with permission. (B) Time lapse of the folding process of a mailbox-shaped digital SMPs.
Image was reprinted from [276].

Although thermally responsive SMPs are the most common SMP type, other SMPs re-
sponding to different stimuli also exist such as those responding to pH change, solvent,
moisture (chemoresponsive materials), electrical (electroresponsive materials), stress/
pressure (mechanoresponsive materials), magnetic field (magnetoresponsive materials),
and light (photoresponsive materials) [277].
 8.3 Four-dimensional printing with smart materials 117

8.3.1.3 Elastomer actuators

SMPs are the commonly preferred 4D printing materials due to their high elastic de-
formation, low cost, low density, and potential biocompatibility. However, most
SMPs only exhibit a one-way response, while further active responses require addi-
tional programming steps. Reversible shape change can be obtained in hydrogels
due to swelling and shrinking when the stimuli are applied and reversed. However,
the response time of hydrogels to an external stimulus is long and shape change is a
relatively slow process. LCEs are unique materials that exhibit rapid and reversible
shape changes; therefore, these materials are becoming increasingly popular as a
4D-printed smart material. Since LCEs combine the properties of highly stretchable
elastomers and self-assembly of liquid crystals, they are preferred in fabrication of
smart stretchable structures such as soft robots, implantable biomedical devices, and
systems based on artificial muscles. Shape change in LCEs is through a transition be-
tween the liquid crystal (nematic) state and the isotropic state in response to stimuli
such as light, heat, and electrical or magnetic fields. By thermal cycling above and
below its nematic to isotropic transition temperature (TNI), the LCE can alternate be-
tween its nonaligned (isotropic) and aligned (anisotropic) states, causing large and
reversible shape change [278]. Reversibility of 4D-printed LCEs under temperature
stimulus was extensively investigated recently by Kotikian et al. [279]. Figure 8.11
reported in this study represents the shape shifting process from 2D to 3D, where
3D-printed LCE polymers in 2D geometries transform into 3D cone (Figure 8.11A)
and saddle (Figure 8.11A) configurations upon increasing the temperatures over
TNI. Tremendously high out-of-plane deformation (~1628%) was observed in these
structures leading to these 3D transformations. Similarly, Figure 8.11C and D shows
isotropic shrinkage and 3D conical array expansion of LCEs under thermal stimulus,
respectively. It was also shown in this study that upon cooling, reversible shape
morphing was observed in these 4D-printed LCE materials.

8.3.2 Applications of 4D-printed structures

Predicting the exact state of the material as a result of these applied stimuli leads to
unique properties of 4D-printed structures such as self-assembly, multifunctionality,
and self-repair. Therefore, these structures possess great potential in terms of reduced
volume and transportation benefits. Smart structures can be printed in low-volume
forms such as 2D sheets or compressed structures. They can then be transformed into
larger 3D forms prior to the actual usage. Three-dimensional fabrication of these
structures at low volumes creates tremendous advantages of packageability and
transportation. In addition, 4D-printed structures can find various applications in
biomedical, electronics, and robotic fields. Biomedical devices such as stents and
adaptive scaffolds can be fabricated via these structures. These biomedical systems
can be preformed into a temporary shape, inserted into the body through a smaller
118 8 Advanced concepts in additive manufacturing

(A) (C)

(D)
(B)

Figure 8.11: Shape morphing in LCEs under external stimuli. Two-dimensional to 3D transformation
of disk-shaped LCEs (≈0.4 mm thick) into (A) cone and (B) saddle configurations. (C) Top-down
images of mesh-shaped LCEAs (≈0.5 mm thick) after printing (left) and shrinking into an isotropic
form (right) upon heating above TNI (scale bars = 5 mm). (D) Top and side views of an LCEA sheet
after printing (left) and morphing (right) into a conical array upon heating above TNI (scale bars =
5 mm). Figure was reprinted with permission from [279].

surgical incision, and deployed into its desired configuration under an external body-
induced stimulation. Targeted drug delivery is another application where the drugs
encapsulated into 3D-printed structures can only be released when reached to the tar-
geted locations in which the interaction with the targeted tissue/organ can provide
the required stimulation.
Self-assembly of 4D-printed parts can also be used in aerospace structures,
antennas, and satellites in which the smart parts are unfolded when they are in
use and folded back to minimize their volumes. Another potential application of
4D-printed parts includes self-assembling of buildings, especially in remote locations
such as those at war zones or in outer space where minimum human involvement is
preferred [280].
 8.3 Four-dimensional printing with smart materials 119

In soft robotics, 4D-printed structures can also find unique applications. Figure 8.12
shows an example of gripping motion using a 4D-printed structure as reported by
Ge et al. [281]. Since no wiring or mechanical hinges are necessary in these actua-
tors, reliability and simplicity are greatly enhanced. As a result, material cost is
reduced and if precisely controlled, these devices can be used for gentle interac-
tion with fragile objects [282].

I II III IV

Figure 8.12: Snapshots of a 4D-printed SMP gripping a bolt. Image was reprinted from [281].

Self-repair is also a notable property investigated in 4D-printed structures. Since

these structures are capable of reorganizing their structures, external stimulation can
be applied to repair the damaged zones and the functionality is retained. It was dem-
onstrated in numerous studies that materials used in 4D printing are capable for
structural restoration of damages and can be applied in various applications such as
restoration of damaged pipes in a plumbing system as well as self-healing vascular
models for tissue engineering.
In this chapter, the concept of 4D printing, material types, and major applica-
tions are described. Despite its remarkable potential due to these unique properties,
4D printing is still under development stage since its introduction in 2013, and exten-
sive research work is needed to make it an established technology desired for ground-
breaking applications.
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Index
4D printing 113 CAD 2, 19, 78, 93, 113
cages 63
active composites 114 cancer bioprinting 89
additive manufacturing of ceramics 61 carbon fiber 42
additive manufacturing of metals 47 carbon nanotube 32, 33
additive manufacturing of polymer carbon quantum dot 33
composites 31 cardiac tissue bioprinting 87
additive manufacturing of polymers 22 cartilage bioprinting 85
Additive Manufacturing of Thermoplastic casting 53, 58
Polymers 25 cell adhesion 104
Additive Manufacturing of Thermosets 27 cell viability 78
additive/additive hybrid manufacturing 102 ceramic 10, 15, 16, 61
additive/subtractive hybrid additive chemical composition 49
manufacturing 101 chemical resistance 61
Additive/Subtractive Hybrid Manufacturing 101 chemo-responsive materials 116
Advantages of AM 2 chitosan 81
age hardening 57 CNC 16, 101
aging 28 constraints 97
alginate 81 contamination 49
alumina 65, 66, 71 continuous fiber reinforced composites 41, 45
aluminum 53 Continuous Liquid Interface Production 7
ammonium phosphate 65 corrosion resistance 56
analytical model 38, 42 cost 15, 17, 26, 47, 48, 61, 64, 72, 77, 78, 92,
annular thermoelectric systems 108 117
ASTM 11, 55 creep resistance 73

BESO 96 decellularized extracellular matrix 82, 87

big area additive manufacturing 20 densification 75
Binder Jetting 10, 47, 63, 94 density-based optimization 97
bioactive 61 design 3
bioactive glasses 61 Digital Light Processing 7
bioceramic 72 direct energy deposition 47
biocompatibility 56, 61, 67, 81, 82, 89, 117 direct write 12, 13, 14, 29, 37, 41, 67, 104, 110
biocompatible 47 Directed Energy Deposition 15
biodegradability 81, 82 displacement-controlled extrusion 12
biofabrication 82 doctor blading method 71
bioinert 61 ductility 54, 58, 61
bioink 78, 79, 81
biomaterial 78 elastic modulus 37, 45
biomedical implants 63 elastomers 22, 23, 29
bioprinting 78, 82, 90 electrical aalignment 41
bismuth telluride 108, 112 electrical insulation 61
blood vessels bioprinting 84 electrode induction melting gas atomization 49
boron oxide 65 electrohydrodynamic jet printing 105
Bouligand structure 68 electrolytic method 51

https://doi.org/10.1515/9781501518782-010
136 Index

electron beam assisted manufacturing 48 Inconel 54

electron beam melting 48 infiltration 63, 67, 75
electro-responsive materials 116 inkjet bioprinting 79
electrospinning 104, 105 inkjet printing 78
elongation at break 57 ionic photopolymerization 6
epoxy 44, 74 isostatic compaction 63, 75
ESO 96 isotropic transition temperature 117
external stimulus 114, 115, 117
extracellular matrix 82 Kevlar fiber 37, 42
extrusion 47, 78 kidney bioprinting 88

fatigue 55, 57, 58 laser assisted bioprinting 80

feedstock 57, 61, 72 laser assisted manufacturing 48
feedstock materials 51 laser based fusion 53
FFF 21 laser micro sintering 65
fiber alignment 38, 39, 40 laser-assisted printing 78
fiber-matrix adhesion 46 lead zirconate titanate 67
figure of merit 108, 110, 111, 112 Level Set Method 96
finite element analysis 92 Level set topology optimization 98
flowability 49, 53 liquid crystal elastomers 114
fracture toughness 26, 77 liquid deposition modeling 12
free-radical polymerization 6 liquid sintering 63, 64
freeze-drying 104 lithography-based ceramic manufacturing 66
fused filament fabrication 11, 12, 26, 29, 34, locally induced RF welding 34
35, 43, 46, 70, 71 loss modulus 13

gas atomization 49 machining 53, 56

gelatin 81 magnetic alignment 41
gelation 81 magneto-responsive materials 116
GelMA 81 manufacturability 92
glass fiber 42 maraging steel 53
Glass transition temperature 25 martensitic steel 53
grain refinement 57 mass reduction 95
grain size 58 Material Extrusion 11
graphene 32 Material Jetting 9, 66
Material toxicity 25
hardness 57 material waste 4
health implications 8 mechanical performance 25, 26, 29, 45, 47, 54,
heat sensitive thermosets 29 55, 57, 58, 74
heat treatment 56, 58, 75 mechano-responsive materials 116
high entropy alloys 54 melt electrospinning 105
history of Additive manufacturing 19 Metal 10, 15, 16
homogenization 96 metal oxidation 49
hot isostatic pressing 56, 58 metallothermic process 51
Hybrid Additive Manufacturing 101, 104 microstructural composition 49
hydride-dehydride process 51 microstructure 57, 58
hydrogels 79, 81, 85, 114, 117 morphology 49
hydroxyapatite 61, 63, 67 multi-functionality 117
 Index 137

Multijet printing 9 randomly aligned fibers 39

multiple parts 11 rapid prototyping 47
recoating 53
natural polymers 22 residual stresses 54
Newtonian fluid 13 Resistance to moisture absorption 25
Ni-based superalloys 54 resolution 19, 47, 48, 65, 67, 72, 102
No Tooling 3 robocasting 12
nozzle impregnation 43
satellite 51
objective function 97 seebeck coefficient 107
optimization 92 Selection of Polymers for Additive
organosilicon polymers 73 Manufacturing 24
orthopaedical implants 61 selective laser melting 15, 111
overhang-free topology optimization 95 selective laser sintering 15, 26, 111
oxidation 54 self-assembly 117, 118
self-repair 117
paper 16 shape memory polymers 114
paste extrusion 12, 13, 66 shear alignment 41, 68
PCL 116 Shear rate 13
photocurable preceramic polymer 74 shear thinning 12, 13
photocurable resins 5 Sheet Lamination 16, 70
photoinitiator 5, 27 short fiber reinforced composites 34, 35,
photopolymer 80 38, 45
photo-responsive materials 116 shrinkage 65, 74, 110
photosensitive thermosets 27 silicon carbide 71
piezoelectric 33, 71, 72 SIMP 96, 97, 99
piezoelectric actuation 79 sintering 48, 63, 64
plasma atomization 49 sizing 36
plasma rotating electrode skin bioprinting 85
process 49 slim support 95
pluronic 82 slurry based ceramic additive
PNIPAm 115 manufacturing 66
Polyjet 9 smart material 113
polymer 15, 22 solid solution strengthening 57
polymer derived ceramics 73 spatter ejection 54
polyurethane 81 speed 47, 72
porosity 57, 58, 63, 64, 71, 75, 77 spheroidicity 49, 51
post process 59 spheroidization 50
post processing 54, 64, 77, 94, 111 stainless steel 51
Powder Bed Fusion 14, 47, 64, 94 stair effect 101
powder bed fusion technologies 108 stereolithography 33, 102
powder doped polymer composites 31 storage modulus 13
powder feedstock 48 straight wall support 95
powder-based ceramic AM 62 strength 45
precipitation hardening 57 streolithography 7, 19
pressure controlled extrusion 12 stress relief 56
Printability 24 subtractive manufacturing 1, 101
support 94
138 Index

support structures 11 titanium 51, 53

surface adhesion 71 tool steel 53
surface roughness 54, 55, 58, 65, 102 topology optimization 61, 93
synthetic polymers 22 Tree-like support 95
tricalcium phosphate 64, 65
tape casting 70
temperature responsive hydrogels 115 ultrasonic additive manufacturing 17
tensile strength 37 Ultrasonic bonding 17
thermal actuation 79
thermal conductivity 53 Vat Photopolymerization 5
thermal insulation 61 Vat polymerization 23, 27, 66, 78, 80, 108
thermal shock resistance 64 viscosity 79, 81
thermal stress 17, 55 Visual quality 25
thermal stresses 15, 16, 55 void formation 54
thermoelectric generator 107 Volumetric Vat Manufacturing 8
thermoelectric materials 106, 108
thermoplastic elastomers 29 warm isostatic pressure 64
thermoplastic polymer 47 warpage 15, 45
thermoplastics 22 water atomization 49
thermoset composites 46 water responsive hydrogel 114
thermoset elastomers 29 wear resistance 56, 61
thermosets 22, 23
tissue engineering 63, 78, 104 zirconia 66, 71
tissue scaffolds 63