JOM, Vol. 70, No.

3, 2018
https://doi.org/10.1007/s11837-017-2730-y
Ó 2018 The Minerals, Metals & Materials Society

ADDITIVE MANUFACTURING OF COMPOSITES AND COMPLEX MATERIALS

An Overview on Additive Manufacturing of Polymers

IWONA JASIUK ,1,3 DIAB W. ABUEIDDA,1 CHRISTOPHER KOZUCH,1

SIYUAN PANG,1 FRANCES Y. SU,2 and JOANNA MCKITTRICK2

1.—Department of Mechanical Science and Engineering, University of Illinois at Urbana Cham-

paign, 1206 West Green Street, Urbana, IL 61801, USA. 2.—Department of Mechanical and
Aerospace Engineering and Materials Science and Engineering Program, University of California,
San Diego, 9500 Gilman Dr., La Jolla, CA 92093-0411, USA. 3.—e-mail: [email protected]

We present an overview on additive manufacturing (AM), also called three-

dimensional printing, with a focus on polymers. First, we introduce the AM
concept. Next, we outline several AM processes, including their advantages
and limitations, and list common polymers that are used in commercial
printers. Then, we state various AM applications and present two examples.
We conclude with a global view of the AM field, its challenges, and future
directions.

composites.5 They are materials of choice for rapid

INTRODUCTION TO ADDITIVE
prototyping and play a leading role in advancing
MANUFACTURING
3D printing of multifunctional and multiphase
Additive manufacturing (AM), commonly called materials.5
three-dimensional (3D) printing, is a group of AM is a bottoms-up manufacturing approach that
rapidly evolving technologies that are revolutioniz- prints objects one layer at a time from a 3D
ing fabrication. AM is defined as the ‘‘process of computer model. This process can freely tailor the
joining materials to make parts from 3D model data, shape and local material properties as the material
usually layer upon layer, as opposed to subtractive is deposited a small amount (voxel) at a time. Since
manufacturing and formative manufacturing a single instrument can print a wide range of
methodologies.’’1 shapes, changes in design are straightforward; i.e.,
The concept of additive manufacturing is not new, they involve reprogramming but no retooling.
as its roots lie in the 1860s, with patents appearing Designs can be e-mailed across the globe and
steadily since the 1950s.2 Modern AM dates back printed locally, saving time and transport costs.
30 years, when the first commercial printer was Parts can be printed on demand with no need for
sold in 1988. However, it is only in the last several storage. Thus, AM offers a new paradigm in design,
years that the field has grown rapidly, from niche manufacturing, and distribution.
manufacturing to a global presence. This sudden
rise can be attributed to expired patents, govern- AM TECHNOLOGIES
mental focus, and wide availability of low-end 3D
Several AM processes are currently available
printers.3 According to the Wohlers Report 2017, the
commercially, with each having its advantages
3D industry grew at a rate of 17.4% and was worth
and limitations. AM technologies can be classified
over US $6 billion in 2016.4
into the following seven process categories:1
Metals, polymers, ceramics, and composites can
be used for 3D printing. While most industrial and 1. Binder jetting
scientific interest is focused on metal printing, due 2. Directed energy deposition
to its high-end technological applications, polymer- 3. Material extrusion (fused deposition modeling,
based AM methods are most mature (representing fused filament fabrication, 3D bioprinting)
the earliest AM processes), and polymers surpass 4. Material jetting (inkjet printing)
all other material categories in terms of materials 5. Powder bed fusion (selective laser sintering,
used per year.4 Polymers include thermoplastics, selective laser melting, electron beam melting)
thermosets, elastomers, hydrogels, polymer 6. Sheet lamination (laminated object manufactur-
blends, biological systems, and polymer-based ing, ultrasonic additive manufacturing)

(Published online January 25, 2018) 275

276 Jasiuk, Abueidda, Kozuch, Pang, Su, and McKittrick

7. Vat photopolymerization (stereolithography, 3. Resource efficiency: printing on demand, pro-

digital light processing, two-photon polymeriza- duction is closer to the consumer; parts can be
tion) printed on site; less need for transport or large
inventories; reduced shipping costs.
Table I describes four AM processes commonly used 4. Material efficiency: sustainability, material is
for polymers and summarizes their advantages and used as needed, less material waste; light
disadvantages. It also lists representative polymers weight, new materials, less fuel consumption.
used in these processes. 5. New business models: prototyping, shorter time
to market, small series, customized parts, sim-
SELECTED POLYMERS USED IN AM plified supply chain.
Next, for reference, we present properties of the
Thus, AM offers numerous advantages, while bear-
following selected commercial AM polymers:
ing in mind that it is not a preferred manufacturing
ABS_M30 and polycarbonate (PC) printed by fused
approach for all applications.
deposition modeling (FDM) method, PA 2200
printed by selective laser sintering (SLS), Protogen Limitations of AM technology include:38
O-XT 18240 and WaterClear Ultra 10122 printed by
stereolithography (SLA), and FullCure 720, Vero, 1. Small-scale production: not designed for mass
Tango Black Plus, FullCure 980, Tango, and RGD production, as traditional manufacturing meth-
525 printed by inkjet printing (Polyjet). These ods perform faster at lower cost and yield better
properties, listed in Table IIa and b, were taken material quality.
from manufacturers’ (DSM, EOS, Stratasys) data- 2. Limited knowledge of AM processes and materi-
sheets.31–37 Interestingly, most of these datasheets als: processing parameters are not yet well
only report mean values. The material properties of understood; no standards controlling quality;
3D printed parts depend on printing conditions properties of AM materials are not well charac-
(e.g., speed, power, temperature, process). terized.
FullCure 720 has the greatest tensile strength 3. Imperfections: inferior mechanical properties
under 5.08 mm/min strain rate in the printing due to defects and anisotropy; rough surface
direction. The Tango family has the lowest tensile finish, variation in material properties and
strength but superior elongation to break. Water- dimensions of printed polymer parts; depen-
Clear, FullCure 720, and Vero have similar superior dence on processes used.
mechanical properties including high tensile 4. Cost: high-quality printers and AM materials
strength, flexural strength, and elastic modulus. are expensive, slow speed of deposition (there
PA 2200 has the lowest elastic modulus among the are physical limits on increasing these speeds),
stiff materials. ABS_M30 has the highest impact need for postprocessing, higher costs for large
resistance and hardness. The density of all the production.
materials is around 1 g/cm3, with PA 2200 being the Most of these limitations are due to the fact that AM
lightest. PC is a high-temperature polymer with the is still a developing technology.
largest heat deflection temperature (HDT) and
highest glass-transition temperature (Tg). APPLICATIONS OF AM
ADVANTAGES AND LIMITATIONS OF AM AM technology has numerous applications span-
ning various industries. Examples include:
There are numerous advantages of AM technol-
ogy over traditional manufacturing methods which 1. Prototyping (fabrication of parts to test de-
have brought it to the forefront of scientific, indus- signs; the primary original goal of AM).
trial, and public attention:38,39 2. Aerospace (more robust, efficient, and lighter
parts, e.g., fuel nozzles, thrust chambers;
1. Design flexibility: geometric freedom, complexity mainly metals, flame-retardant polymers; Boe-
is for free, can create complex parts that cannot ing 787 has thirty AM parts).
be made by traditional manufacturing methods, 3. Space (lightweight and high-strength struc-
allows new and better designs of components tures).
with fewer parts and less material, reduced 4. Automotive (prototyping, tooling, customized
need for assembly and lower weight; can print cars, e.g., Bentley Motors; less potential for
materials with varying properties for new func- mainstream production due to very large vol-
tionalities. umes).
2. Production flexibility: fast prototyping, changes 5. Energy (harvesting, storage, e.g., photonics).
in design are easy (no need for retooling when 6. Architecture (prototypes of buildings; 3D
the design is changed); ideal for custom-made printed structures: buildings, bridges).40
parts; simpler production process since complex 7. Dentistry (orthodontics, e.g., custom-made
parts can be printed in single pieces, more crowns, implants, clear custom-made
flexible process (no setup time, less assembly braces).41
time, fewer production steps, more flexibility).
Table I. Selected polymer AM processes, their description, advantages and disadvantages, and materials used

Process Description Advantages Disadvantages

Powder bed fusion 1. A roller or blade is used to deposit a thin layer - Excess powder serves as - Expensive, high material
(PBF) of powder on a build plate support, so no support waste9
6
2. Laser fuses certain areas in the powder structures required - Few compatible materials10
3. Build plate is lowered by the height of the - Superior mechanical - Rough or grainy surface
powder layer properties7,8
4. Repeat steps 1–3 for height of part
5. Excess powder is removed
Typical materials Polystyrene, polyester, polyamide 11 and 12, polypropylene, polyurethane, polyetheretherketone (PEEK)

Material jetting 1. Liquid polymer is jetted onto a build plate in - Manufacture multimaterial - Weak mechanical properties15
droplets parts11 - Adverse environmental ef
2. Ultraviolet (UV) source cures the polymer - Low residual stresses12 fects16
An Overview on Additive Manufacturing of Polymers

3. Build plate is lowered or print head is raised by - High dimensional accuracy13,14

the height of the droplet layer
4. Repeat steps 1–3 for height of part
5. Support material is removed
Typical materials Acrylates, acrylics, polylactic (PLA), epoxies, starch

Vat photopolymer- 1. Build plate is positioned on top of a vat of - High resolution to build time - Relatively expensive due to
ization photopolymer ratio17 requirement for vat
2. UV source below vat cures certain areas in thin - Good durability18 change20,21
layer contacting the build plate - Can produce multimaterial - Requires support material
3. Build plate is raised by thickness of cured layer parts, but it is difficult19 - Cannot create parts with en
4. Repeat steps 1–3 for height of part closed volumes due to liquid
5. Support material is removed environment22
Typical materials Acrylates, acrylics, epoxies

Material extrusion 1. Thermoplastic filament is passed through a - Can be optimized for strong - Low resolution and poor sur
heated print head as the print head moves over material properties23–25 face finish require significant
certain areas of a build plate - Low costs of machines26,27 postprocessing28,29
2. Once the layer is complete, either the print - High residual stresses30
head or build plate moves by height of layer
3. Repeat steps 1 and 2 for height of part
4. Support material is removed
Typical materials Acrylonitrile butadiene styrene (ABS), PLA, acrylics, polycarbonate (PC), polyetherimide (PEI), high impact polystyrene
277
278 Jasiuk, Abueidda, Kozuch, Pang, Su, and McKittrick

Table II. (a) Mechanical properties of selected AM polymers31–36

Tensile
ultimate Tensile Flexural Flexural
Generic strength modulus Elongation strength modulus
name Process (MPa) (MPa) at break (MPa) (MPa) Sources
ABS_M30 Acrylic FDM 28 2180 2% 48 1760 Ref. 34
PC Polycarbonate FDM 42 1958 2.5% 68 1800 Ref. 35
PA 2200 Polyamide 12 SLS 42 1650 4% 1500 Ref. 33
Protogen Epoxy resin SLA 42.2–43.8 2180–2310 8–16% 66.7–70.5 1990–2130 Ref. 32
WaterClear Acrylic SLA 56 2880 7.50% 84 2490 Ref. 31
FullCure 720 Acrylic Polyjet 60.3 2870 15–25% 75.8 1718 Ref. 37
Vero Acrylic Polyjet 49.8–55.1 2192–2710 15–25% 74.6–83.6 1983–2276 Refs. 36 and 37
Tango Digital material Polyjet 1.8–2.4 45–55% Ref. 36
Tango plus 980 Digital material Polyjet 0.8–1.5 170–220% Ref. 36
RGD 525 Acrylic Polyjet 70–80 3200–3500 10–15% 110–130 3100–3500 Ref. 36

(b) Properties of selected AM polymers31–36

IZOD
Generic impact HDT HDT Density Rockwell
name Process (notched) (J/m) (°C(@66 psi)) (°C(@264 psi)) Tg (°C) (g/cm3) hardness
ABS_M30 Acrylic FDM 128 96 82 108 1.04 109.5
PC Polycarbonate FDM 73 280 261 322 1.2
PA 2200 Polyamide 12 SLS 0.93 75
Protogen Epoxy resin SLA 0.2–0.22 53–56 46–47 57–59 1.16 86–88
WaterClear Acrylic SLA 25 47 43 44 1.13 87
FullCure 720 Acrylic Polyjet 39.6 45–50 45–50 48–50 81
Vero Acrylic Polyjet 37.5–42.5 45–50 45–50 48.7–62.7 81
Tango Digital material Polyjet –10.7 1.14–1.15 60–62
Tango plus 980 Digital material Polyjet 1.12 26–28
RGD 525 Acrylic Polyjet 14–16 63–67 55–57 62–65 1.17–1.18 78–83

8. Medicine (implants, prosthetics, scaffolds, de- smart materials (e.g., 4D materials that can change
vices, e.g., hearing aids, printed tissues and shape when subjected to moisture, heat, or other
organs, drug delivery, models for surgery external factors),46 architectured materials (e.g.,
planning; soft electronic materials for sensing). cellular materials, metamaterials), biomaterials
9. Nanotechnology (nanodevices, new nanocom- (e.g., materials for implants, dental applications,
posite materials).42 scaffolds for tissue engineering), biological materi-
10. Education (outreach for K-12, design projects, als (tissues, organs), and others.47
training of workforce). Next, we present two examples to illustrate the
11. Food (design of foods into complex shapes, e.g., applications of AM and challenges in 3D printing of
chocolate).43 new materials, one involving cellular materials and
12. Cultural heritage (preservation, restoration, a second using two-phase composite materials.
replicas of art and architecture).44
13. Consumer goods, e.g., clothing (smart clothing, Architectured Cellular Material
custom-made shoes).45
Our interest was to explore experimentally the
14. Art (new forms and designs).
structure–property relations of cellular materials
15. Jewelry (new designs).
based on triply periodic minimal surfaces (TPMS).48
Applications of AM technology are evolving and TPMS are infinitely continuous surfaces that divide
expanding, and some have yet to be imagined. space into two congruent intertwined regions and
have zero curvature at every point (Fig. 1). These
EXAMPLES OF 3D-PRINTED ARCHITEC- structures do not have sharp corners or joints,
TURED MATERIALS which reduces stress concentrations, allowing them
to carry greater loads prior to failure. Such surfaces
AM technology is ideally suited to create new appear naturally (e.g., soap bubbles). AM technol-
materials with superior, often multifunctional prop- ogy is well suited to manufacture such TPMS foams.
erties. Examples, with a focus on polymers, include We fabricated TPMS structures with primitive
printing of electronic materials (soft electronics), (Fig. 1a) and IWP-CM (Fig. 1b) geometries by the
An Overview on Additive Manufacturing of Polymers 279

Fig. 1. TPMS structures made of PA 2200: (a) primitive foam, (b) IWP-CM foam, (c) scanning electron microscopy, (d) micro-computed
tomography.

SLS method using a Formiga 100 3D printer (EOS, One of the challenges faced in 3D printing using
Germany). The SLS technique was selected so that the SLS process is the difficulty of removing the
the TPMS structures could be built with no support powder from structures with small openings. This
material, which would have been required if using scenario was faced when the IWP structure was 3D
other techniques for creating structures with over- printed at high relative density. Furthermore, the
hangs. The base material was PA 2200, a thermo- Formiga 100 3D printer produces layers of thickness
plastic based on polyamide 12 (Table IIa and b). 0.1 mm, limiting the minimum size of the 3D-
Processing parameters included layer thickness of printed specimens. Figure 1d shows a micro-com-
0.1 mm, laser power of 30 W, and build temperature puted tomography (micro-CT) scan image of a local
of 172.5°C. Figure 1c shows a scanning electron cross-section of a primitive foam fabricated from PA
microscopy image of the surface of the 3D-printed 2200, where microvoids can be seen along the
PA 2200 structure with partially sintered particles thickness. Such voids (defects) negatively affect
(powder) with diameter of around 45 microns. Cubic the mechanical response of the 3D-printed
specimens were fabricated with several densities structure.
and 15 mm side lengths of the unit cell. The printed Next, we tested the TPMS foams in compression.
sample size was 4 9 4 9 4 unit cells, resulting in We used the Ashby diagram of uniaxial elastic
60 mm 9 60 mm 9 60 mm samples, as shown in modulus versus density and superposed on it the
Fig. 1a and b. The relative density of the foams two TPMS foam types, for comparison with other
ranged from 8% to 25%, corresponding to wall materials.48 Ashby diagrams allow one to visualize
thickness from about 0.1 mm to 1.1 mm. the relationships between materials and
280 Jasiuk, Abueidda, Kozuch, Pang, Su, and McKittrick

Fig. 2. Multimaterial 3D-printed composites with soft and stiff phases: (a) a no network composite, (b) a single network composite with soft
network and stiff inclusions, (c) a single network with stiff network and soft inclusions, (d) an interpenetrating network with soft frame, and (e) an
interpenetrating network with stiff frame.

properties.49 For stiffness versus density diagrams, once the sample was of a certain size, leading to
the most desired space in the Ashby diagrams is the lower properties than reported in Ref. 36. This grid
top left corner, corresponding to stiff and light of support material was printed to allow material
materials. The TPMS foams performed well, con- expansion under the high temperature conditions
sidering that they were made of a material with (heat deflection temperature of 63°C to 67°C) for
defects (Fig. 1). Further advancements in AM tech- which RGD525 is designed. Unfortunately, the
nology, particularly in terms of the quality of printing algorithm is not adjustable, and the result-
printed materials, may help materials scientists ing samples had support material printed within
and engineers reach that desired, still empty, space them.
in the Ashby diagram. More broadly, a variety of factors have been found
to affect the mechanical properties of 3D printed
Two-Phase Composite Materials materials. For example, for the jet printing process,
Mueller et al.50 investigated the effect of the print
Our second example involves a study of two-phase location on the print bed, temperature of the print
composites with different arrangements of soft and surface, UV intensity, part orientation, expiration
stiff polymer phases to investigate the effect of the date of materials, and cleanliness of print head
connectivity between the phases on the mechanical nozzles on the dimensions and mechanical proper-
properties of their composite. The five material ties of parts tested in tension. The dimensions of
models (Fig. 2) included: (a) a composite with two printed parts were significantly affected by nozzle
discontinuous phases (a checkerboard), (b) a com- blockages, with the part being smaller and lighter
posite with one continuous phase (either stiff or when printed using a clean nozzle. Material prop-
soft) and one discontinuous phase (either soft or erties were also affected by the presence of support
stiff), and (c) a composite with two continuous material. Increased storage time was found to
(interpenetrating) phases, again two versions with correspond to a weight gain, likely due to absorption
the second model having the materials reversed. of water from humidity. Thus, it is recommended to
The 3D composites were printed with 1:1 volume print samples within the same batch to ensure
ratio of two phases using an Objet350 Connex3 consistent mechanical properties. Other factors that
(Stratasys, Poway, CA, USA). The layer thickness may affect the properties of the print are the
of the Connex3 is 30 microns in digital material strength and calibration of the ultraviolet (UV)
mode, and the system allows printing of multiple source within the printer and the amount of light
materials simultaneously. Proprietary photocur- exposure of the sample during or after printing.
able materials were used, with RGD525 as the Increased light exposure results in stiffening of the
stiff material and TangoBlackPlus as the soft resulting printed part.
material. Specimens were printed within the same The two examples above involved printing at
batch using the matte finish setting, with specimen centimeter scale. Architectured materials can also
size of 1.27 cm 9 1.27 cm 9 1.27 cm. After print- be printed at smaller scales, down to nanoscale,
ing, the support material was removed by water jet which creates further opportunities to manufacture
and samples were left to dry overnight. materials with new, as yet undiscovered, proper-
There were several challenges in the manufac- ties.51–54 Another related extension is to apply
turing of the samples for this project. It was topology optimization to tailor not only the geome-
discovered that an internal grid of support material try of a part but also the spatial material composi-
was printed within the volume of the composites tion for optimal part performance.
An Overview on Additive Manufacturing of Polymers 281

TOPOLOGY OPTIMIZATION environmental, and security implications.71 Also, it

has been predicted that it may change the world, as
Topology optimization (TO) refers to algorithms
the World Wide Web did.68
which can generate geometries that minimize or Here are some examples of the current or pre-
maximize an objective function while satisfying one
dicted impacts of AM technologies:
or more constraints. In practice, TO is used to
design low-weight parts for a given set of boundary 1. Design: Ability to 3D-print complex shapes and
conditions, which has practical advantages for a a wide range of shapes with one piece of
wide range of industries, including aerospace and equipment with no need for retooling. New
automobiles, where weight is at a premium. TO is optimized designs are possible involving new
not a new technology, and many attribute the birth shapes, fewer parts, and tailored microstruc-
of the technology to the seminal 1988 paper by tures.
Bendsøe and Kikuchi.55 Despite this, TO remained 2. Innovation: Open nearly unlimited possibili-
relatively dormant until recently because the gen- ties for innovation in design; allow new com-
erated geometries are incredibly difficult to manu- plex shapes, new materials; stimulate research
facture via conventional manufacturing methods. on creation of new materials (e.g., architec-
The rapid expansion of AM methods changed that.56 tured structures, such as metamaterials,
AM is the perfect method to bring topologically foams).
optimal designs to life. There are now a wide range 3. Manufacturing: Versatile technique using lo-
of TO methods that have demonstrated extensive cal resources, customization, and flexibility
capabilities.57 These capabilities include optimiza- with no time or cost penalties, higher design
tion for coupled thermomechanical problems with complexity ‘‘for free,’’ reduction of assembly
embedded systems,58 design of variable-density work (fewer production steps).69,72
lattice structures,59 and advanced multimaterial 4. Distribution: Products can be printed on
optimization.60 demand with no need for warehouses, packag-
ing or long-distance transport.
SIZE IN ADDITIVE MANUFACTURING 5. Customized healthcare: Personalized medicine
(custom implants, tissue scaffolds, drug deliv-
Objects formed by AM can be of various sizes,
ery devices), dentistry (bridges, crowns,
with the limit being the printer capacity. While
braces), safety equipment (helmets).41
most commercially available printers create parts in
6. Environment: Sustainability, involve less
centimeters, sizes can vary widely. There have been
material and less waste, decrease the need
impressive reports on printing very large parts
for transport, leading to lower carbon emis-
(buildings,61 bridges,40 cars62), as well 3D printing
sions.73
at nanoscale.63
7. Education: Need for education of workforce on
Recently, nano/microadditive manufacturing
AM.74 Dissemination of knowledge to K-12
techniques have attracted increasing attention due
students, education of teachers.
to their impact on many applications, including
8. Research: Open new research directions: mod-
microelectromechanical systems, plasmonics, and
eling of 3D processes, invention of new archi-
microbiology.51 Micro-AM is based on a two-photon
tectured materials, designs of new printers
polymerization (TPP) method.53,54 TPP uses a high-
and 3D printing technologies.
intensity laser beam to draw a 3D structure inside a
9. Economy: New companies and businesses
photocurable polymer.51 The Nanoscribe (Nano-
form, new specializations and jobs are created.
scribe GmbH, Germany) printer uses 3D direct
Manufacturing may shift from few select
laser writing (DLW) based on TPP64 and allows one
countries with low labor costs to local printing,
to print feature sizes down to 100 nm.65 Unlike
impacting local and global economies.69
conventional microfabrication techniques, fabrica-
10. Infrastructure: Governments, states, compa-
tion of complex 3D structures using Nanoscribe does
nies, and funding agencies are investing to
not require expensive masks, making it an ideal
support and explore this new industry. New
technique for many high-end applications.64
centers and new companies and businesses are
being formed.74
IMPACT, ACHIEVEMENTS, AND
11. Security: Uncontrolled manufacturing of
CHALLENGES OF AM
weapons.68
The AM field has attracted interest from acade- 12. Law: New laws and regulations need to be
mia, industry, and the public due to its enormous introduced for protection of patents and other
potential, and has been hailed as a ‘‘game chan- intellectual property. Liability for the failure of
ger,’’66,67 ‘‘transformative technology,’’68 ‘‘disruptive 3D-printed parts becomes more complex.75
technology,’’68 and ‘‘new industrial revolution,’’69,70 13. Health hazards: Particle emissions from fused
among others. AM is expected to have profound filaments.76
global economical, geopolitical, social, demographic,
282 Jasiuk, Abueidda, Kozuch, Pang, Su, and McKittrick

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