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Semi-crystalline feedstock for filament-based 3D printing of polymers

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 Progress in Polymer Science 118 (2021) 101411

Contents lists available at ScienceDirect

Progress in Polymer Science

journal homepage: www.elsevier.com/locate/progpolymsci

Semi-crystalline feedstock for filament-based 3D printing of polymers

Dries Vaes, Peter Van Puyvelde∗
Department of Chemical Engineering, KU Leuven, Celestijnenlaan 200F box 2424, Leuven 3000, Belgium

a r t i c l e i n f o a b s t r a c t

Article history: Additive Manufacturing (AM), and more specifically Fused Filament Fabrication (FFF), allow the produc-
Received 18 August 2020 tion of highly customized parts, provide enormous freedom-of-design and can lead to material savings
Revised 11 January 2021
due to the layer-by-layer material deposition that is inherent to this family of production processes.
Accepted 26 April 2021
FFF utilizes both amorphous and semi-crystalline thermoplastic filaments as feedstock materials, offering
Available online 2 May 2021
a wider range of materials compared to some other polymer-based additive manufacturing techniques.
Keywords: However, the current trend where FFF, and AM in general, are changing from a technique for rapid proto-
Additive manufacturing typing to the production of fully functional parts designed for high-end applications creates the inevitable
Fused filament fabrication need to incorporate more engineering and high-performance thermoplastics, which are most often semi-
Fused deposition modeling crystalline polymers, into the material palette. Crystallization provides semi-crystalline polymers with
Semi-crystalline polymers some distinct features that set them apart from their amorphous counterparts, yet it also can present
Polymer crystallization
difficulties regarding their processing. Understanding of the behavior of semicrystalline polymers during
FFF processing is thus a prerequisite to exploit their full potential. This review provides a broad overview
of FFF processing of semicrystalline polymers. Particular focus lies on the impact of processing conditions
and feedstock modifications, such as the incorporation of fillers or the formation of blends, on crys-
tallinity as well as the microstructure of printed parts, the impact of microstructure on the mechanical
performance, and general part quality. Furthermore, attention is given to some specific phenomena that
can occur during printing of semi-crystalline feedstock filaments which have shown to strongly impact
the printing process. Examples are self-nucleation in the case of insufficient heat transfer and melting,
flow-induced crystallization due to high shear deformations upon extrusion, and the negative impact of
crystallization on chain mobility which is relevant for the development of interlayer strength and on di-
mensional accuracy due to excessive shrinkage. Finally, this review is concluded with a critical outlook
on perspectives for future research to address the current challenges that are still faced when employing
semi-crystalline polymers as FFF feedstock.
© 2021 Published by Elsevier B.V.

Abbreviations: AM, additive manufacturing; FFF, fused filament fabrication; 3D,
three-dimensional; CAD, computer-aided-design; SLS, selective laser sintering; SLA,
stereolithography; UV, ultraviolet; MEAM, material extrusion additive manufactur-
ing; FDM, fused deposition modeling; STL, standard tessellation language; Tliquefier ,
liquefier temperature; Tg , glass transition temperature; Tm , melting temperature;
Tbuild plate , build plate temperature; Tenvironment , environmental temperature; vprint ,
print speed; vfeed , filament feed rate; ∅filament , filament diameter; ∅nozzle , print nozzle
diameter; ABS, acrylonitrile butadiene styrene; PLA, polylactic acid; PCL, polycapro-
lactone; PEEK, polyetheretherketone; PP, polypropylene; PVDF, polyvinylidene fluo-
ride; PA, polyamide; PEI, polyetherimide; PPS, polyphenylene sulfide; PVA, polyvinyl
alcohol; POM, polyoxymethylene; TPU, thermoplastic polyurethane; PET, polyethy-
lene terephthalate; PEKK, polyetherketoneketone; IM, injection molding; DSC, differ-
ential scanning calorimetry; XRD, X-ray diffraction; WAXS, wide angle X-ray scatter-
ing; SAXS, small angle X-ray scattering; PP-g-MA, polypropylene-graft-maleic anhy-
dride; PE-g-MA, polyethylene-graft-maleic anhydride; PP/E, polypropylene/ethylene
copolymer; LLDPE, linear low density polyethylene; PS, polystyrene; MCC, micro-
crystalline cellulose; SDCNF, spray-dried carbon nanofibers; MAPP, maleic anhydride
polypropylene; LDPE, low density polyethylene; HDPE, high density polyethylene;
UHMWPE, ultra high molecular weight polyethylene; PHA, polyhydroxyalkanoate;
LMW, low molecular weight; PEG, polyethylene glycol; PBAT, polybutylene adipate-
co-terephthalate; TCP, tricalcium phosphate; HA, hydroxyapatite; CF, carbon fiber;
MWCNT, multiwalled carbon nanotubes; pHMGCL, polyhydroxymethyl glycolide-
co-caprolactone; PVP-VA, polyvinylpyrrolidone-vinyl acetate; PEO, polyethylene ox-
ide; PTT, polytrimethylene terephthalate; PTTIS, polytrimethylene terephthalate-co-
isophthalate-co-seacate; SA, sebacic acid; PHA-g-MA, polyhydroxyalkanoate-graft-
maleic anhydride; CNT, carbon nanotube; PBT, polybutylene terephthalate; PBS,
polybutylene succinate; PEO-g-MA, polyethylene-1-octene-graft-maleic anhydride;
FSC, fast scanning chip calorimetry; FTIR, Fourier transform infrared spectroscopy;
MAF, mobile amorphous fraction; RAF, rigid amorphous fraction; TPHU, thermoplas-
tic polyhydroxyurethane; β , nozzle angle; Ts , self-nucleation temperature; PC, poly-
carbonate; FIC, flow-induced crystallization; De, Deborah number; Wi, Weissenberg
number; τd , disentanglement time; τR , Rouse time; τs , characteristic relaxation time
for molecular stretch; γ˙ , shear rate; Wio , Weissenberg number related to molecu-
lar orientation; Wis , Weissenberg number related to molecular stretch; tR , reptation
time; Rg , radius of gyration; Ds , center of mass diffusion coefficient; χ , interpenetra-
tion depth; M, molecular weight; tw , weld time; σ , fracture strength of a polymer-
polymer interface; σ∞ , fracture strength of virgin material; σ0 , strength developed
due to wetting; K, constant; D, polymer diffusion coefficient; t, time; ψ (t ), diffu-

https://doi.org/10.1016/j.progpolymsci.2021.101411
0 079-670 0/© 2021 Published by Elsevier B.V.
D. Vaes and P. Van Puyvelde
1. Introduction
1.1. Additive manufacturing
An astonishing average annual growth rate of worldwide rev-
enues produced by all Additive Manufacturing (AM) products and
services of 26.7 % over the past 31 years and a dramatic increase in
AM-related research and patent applications clearly illustrate the
profound economic and scientific impact of AM technologies [1,2].
The progressively growing interest in AM by both industry and
government, as well as the general public, is reflected in increas-
ing investments in the field [2,3]. Additive Manufacturing, often
termed 3D printing, is defined by the ISO/ASTM 52900 terminol-
ogy standard as ‘a process of joining materials to make parts from
3D model data, usually layer upon layer, as opposed to subtractive
manufacturing and formative manufacturing methodologies’ [4].
This layer-by-layer production process results in an immense
freedom-of-design and potential customization, as it permits the
fabrication of almost any complex design or geometry by imposing
far fewer design constraints compared to subtractive techniques
[5]. The possibility to directly produce parts from computer-aided-
design (CAD) models or even 3D scans provides AM production
processes with another benefit compared to traditional manufac-
turing technologies, since expensive tooling, such as molds, is no
longer necessary [6,7]. The redundancy of part-specific tooling, of-
ten associated with high investment costs and long lead times, al-
lows to considerably reduce the time-to-market of complex parts
produced with AM and favors on-demand manufacturing [5,7,8].
Furthermore, AM technologies lead to significant material savings
compared to subtractive manufacturing, having the potential to ap-
proach zero waste manufacturing [8–10]. Since AM printed parts
can be produced in their final or near final state, as it is, for exam-
ple, feasible to design and construct shapes that would otherwise
require assembly of multiple parts if manufactured with traditional
techniques, additional processing can be minimized [5,8].
However, besides the interesting possibilities opened up by the
inherent characteristics of AM processes, these technologies still
face some major issues. First of all, AM techniques are mainly fo-
cused on low-volume batch production of customized parts, since
it is very difficult to achieve economies of scale due to a large
cycle time and low build speed, especially when compared with
more conventional mass production technologies such as injection
molding [1,5]. It should be noted that certain complex design fea-
tures such as overhangs and undercuts require the deposition of
an additional structure to support the subsequent layers of these
printed features. These support structures, often fabricated from
a secondary, sacrificial material, then need to be removed during
post-processing. Water-soluble support materials can be washed
away in a lye bath, while non-soluble supports are removed by
breaking and peeling away the support material from the printed
model [5]. The characteristic layer by layer construction typically
results in parts with inferior, anisotropic mechanical properties due
to weak interlayer boundaries or porosity, which becomes even
more challenging with multi-material AM systems [1,5,11]. More-
over, there exists a trade-off between build time and layer resolu-
tion: a higher resolution strongly increases the required build time,
yet greatly improves surface quality [5]. When surface quality is in-
adequate, post-processing techniques, such as coatings or solvent
sion initiation function; φ (t ), wetting distribution function; σd , strength developed
through diffusion; aT , shift factor; T, temperature; T0 , reference temperature; WLF,
Williams-Landel-Ferry; C1 , C2 , WLF constants; σweld , weld strength; σUT S , ultimate
tensile strength of bulk polymer; t̄R , time-average reptation time; HIPS, high-impact
polystyrene; PLM, polarized light microscopy; SEM, scanning electron microscopy.
∗
Corresponding author.
E-mail address: peter.vanpuyvelde@kuleuven.be (P. Van Puyvelde).
2
Progress in Polymer Science 118 (2021) 101411
Fig. 1. A schematic representation of the working principle of the Fused Filament
Fabrication process together with some of the key process parameters.
treatments, can be utilized. A sufficiently small layer resolution
and proper dimensional accuracy are imperative to ensure optimal
part quality and functionality [1]. AM techniques have nonethe-
less been adopted in many fields of industry, including automo-
tive, aerospace and aviation, medicine, construction, and electron-
ics [12,2].
Additive Manufacturing actually refers to a whole family of pro-
duction techniques that follow the general layer by layer fabri-
cation approach and can be subdivided into different categories
based on the type of material used. Metals, ceramics and polymers
make up the three main material groups utilized with AM tech-
niques. Within the group of polymer-based processes, the three
primary technologies are Selective Laser Sintering (SLS), during
which a part is produced from a polymer powder bed by scanning
with a laser beam, Stereolithography (SLA), a process in which a
part is constructed from a bath of liquid photosensitive resin that
is cured by scanning with a (UV) laser, and Fused Filament Fabri-
cation (FFF), which will be the scope of this review article [1,7].
1.2. Fused filament fabrication
Polymer melt extrusion techniques such as Fused Filament Fab-
rication make up one of the most widely used and rapidly growing
AM technologies [13]. Fused Filament Fabrication or Material Ex-
trusion Additive Manufacturing (MEAM) was patented under the
registered trademark Fused Deposition Modeling (FDM) by Scott
Crump and his company Stratasys, Inc. in 1989 [14]. As any other
AM technique, manufacturing an object using FFF starts from a 3D
model, created by CAD software or from a 3D scan. The 3D model,
usually in the form of an .STL file, is converted using preprocess-
ing software. This software slices the 3D model into separate cross-
sectional layers and defines the path that should be followed dur-
ing printing. What is eventually obtained is a file with instructions
for printing that can be passed on to the FFF device [15]. The FFF
technique utilizes thermoplastic polymer filament which is fed us-
ing a pinch roller mechanism into the print head that consists of
a heated liquefier, where the polymeric feedstock is molten, and
a print nozzle. During heating, the solid portion of the filament
exerts pressure to push the polymer melt through the liquefier
and eventually the smaller print nozzle. Whilst extruding the poly-
mer melt, the print head travels in the xy-plane following the pre-
defined path while moving on a gantry via stepper motors. The
first extruded layer is deposited onto a heated build plate. Once
this layer is completed, the build plate moves down by one layer
height, and the process is repeated, creating the 3D object layer by
layer [6,13]. A schematic representation of the working principle of
the FFF process is depicted in Fig. 1, which also shows some of the
D. Vaes and P. Van Puyvelde Progress in Polymer Science 118 (2021) 101411

Table 1
A general overview of the process parameters and design considerations associated with the FFF process, summarized from [6,13,15–20].

Process parameter Definition and typical set point Effect on printing process and part quality

Liquefier Temperature of the liquefier section of the print head,
temperature which should be set high enough above the material’s
(Tliquefier ) glass transition temperature (Tg ) for an amorphous
thermoplastic or high enough above the melting point
(Tm ) for a semi-crystalline material to sufficiently reduce
the polymer’s viscosity.
Build plate Temperature of the build plate which acts as a substrate
temperature onto which the part will be printed. Typically set slightly
(Tbuild plate ) above the material’s Tg .
Environmental Often referred to as envelope temperature. Printing can
temperature occur with or without environmental control, often
(Tenvironment ) assisted by fans to control airflow. Typically set above the
material’s Tg .
Print speed (vprint ) vprint is the speed at which the print head travels while
& Filament feed depositing extruded material. If too slow, fabricated
rate (vfeed ) layers may be prone to overheating. When moving too
fast, mechanical vibrations may decrease part accuracy.
vfeed is the velocity at which the feed mechanism takes
up filament to be fed to the liquefier and should be
matched to vprint .
Filament diameter The diameter of the feedstock filament. FFF systems
(∅filament ) typically use either 1.75 mm or 2.85 mm diameter
filament.
Print nozzle The diameter of the exit of the print nozzle, typically
diameter (∅nozzle ) ranging between 0.2 and 0.8 mm.
Layer thickness The thickness of one layer deposited in the xy-plane.
Typical layer heights range from 100 to 400 m.
Infill density and The percentage of the internal structure that is filled
pattern with extruded polymer. Often the internal structure is
deposited with a specific pattern, e.g. a honeycomb
structure, which minimizes part density, while retaining
sufficient strength.
Raster angle If straight roads are used as infill pattern, their
orientation relative to the x-axis of the build plate is
defined as the raster angle.
Build orientation The orientation of the part on the build plate. Possible
orientations are face-up, edge-up and up-right.
Air gap The space between adjacent roads. When printing at a
positive air gap, two adjacent roads do not touch, while a
negative air gap indicates the distance between the
centers of two adjacent roads is smaller than the road
width.
Part location The location of the printed part on the build plate
surface.
If Tliquefier is set too low, nozzle blockage can occur. A
higher Tliquefier has been shown to increase layer
adhesion, as well as the width of the deposited roads,
which increases stiffness and strength and decreases
porosity.
Ensures sufficient adhesion of the part onto the build
plate during printing, which prevents detachment of the
part and warpage.
Affects part cooling and thus counteracts warpage and
deformation as a result of a build-up of residual stresses
and can improve interlayer bonding.
If vprint is too low compared to vfeed , ’over-extrusion’
occurs, leading to expansion of the extruded filament
diameter. The opposite case, termed ’under-extrusion’,
will lead to stretching of the extruded filament. Both
phenomena can lead to process failure.
Strong deviations in filament diameter can lead to
inconsistent extrusion. Thicker filament is less prone to
buckling.
A smaller nozzle diameter improves part resolution, yet
results in an increase in the required build time, as the
overall material flow rate is reduced.
Thicker layers result in poorer part accuracy and surface
finish. Decreasing layer thickness improves interlayer
bonding and thus part strength.
Printing with lowered infill density requires less material
and reduces build time.
The raster angle influences part strength with parts built
with raster angles 0°/90° having optimal mechanical
properties.
The optimal part strength is obtained with a face-up
orientation, while an up-right orientation produces the
weakest parts, as, in this case, the interlayer bonds lie in
the loading direction.
Zero or positive air gap setting produces parts with
optimal dimensional accuracy. A negative air gap
improves tensile strength, as this means the extruded
material is pushed in the voids between the roads which
increases interlayer bond strength.
Since environmental temperature and convective cooling
rate can fluctuate across the build environment, part
cooling and interlayer bonding will be influenced by the
part location.

key process parameters that can be chosen or adjusted when using
this technique. Table 1 provides a general overview of the process
parameters and design variables associated with the FFF process
and their effect on printed part quality, necessary to understand
further discussion about the topic. This is, however, a condensed
summary, as this is already extensively reviewed in literature and
does not fall within the main scope of this article [6,13,15–20].
Compared to the other main polymer-based AM techniques, FFF
is a rather inexpensive, simple and flexible process [5,10]. Although
FFF does not offer an extensive material palette, it still provides
the opportunity to process a much wider range of materials than,
for example, SLA, which is limited to photopolymers only. Further-
more, it can be stated that the FFF technique requires far less en-
ergy for printing, especially compared to SLS, which operates using
a high intensity laser [8]. Main drawbacks of FFF include the of-
ten inadequate mechanical properties due to insufficient interlayer
bonding, poor surface quality and limited part resolution [5,8,10].
FFF utilizes both amorphous and semi-crystalline thermoplas-
tic polymers as feedstock. The two most commonly used feedstock
materials are, by far, acrylonitrile butadiene styrene (ABS) and
polylactic acid (PLA), which are amorphous and semi-crystalline,
respectively, and are considered commodity plastics [1,15,21]. As a
result of an ongoing trend where FFF, and AM in general, is shifting
from a technique for rapid tooling or prototyping to production of
fully functional parts with applications in, for example, medicine
or automotive industry, the necessity to incorporate more engi-
neering and high-performance thermoplastics in the current ma-
terial palette has become ever so eminent [2]. Most of these en-
gineering and high-performance plastics are semi-crystalline poly-
mers, which exhibit some distinct characteristics important for
their processing compared to amorphous thermoplastics [1]. It is,
therefore, imperative to fully understand their behavior during
printing to optimally exploit their use in functional parts and high-
end applications.

3
D. Vaes and P. Van Puyvelde
1.3. Advantages and disadvantages of semi-crystalline polymers
The formation of densely packed and ordered crystalline regions
is what sets semi-crystalline polymers apart from their amorphous
counterparts. This process of crystallization provides these thermo-
plastics with a typical lamellar morphology consisting of polymer
chains packed parallel to each other with disordered or amorphous
regions in between these lamellae. Semi-crystalline polymers are
generally opaque as a result of this crystalline morphology [22]. In
terms of mechanical properties, these crystalline regions do pro-
vide increased toughness and wear resistance, as well as stiffness
and strength, although amorphous polymers possess superior im-
pact resistance [22,23]. Whereas amorphous thermoplastics gradu-
ally soften when heated above the material’s glass transition tem-
perature, which corresponds to the temperature at which a sud-
den change in molecular mobility occurs and the polymer tran-
sitions from a glassy, brittle state to a more rubbery state, the
crystals in semi-crystalline polymers stay in their orderly packed
lamellar structure up until their melting point at which they can
pass to the liquid state [24,25]. In general, semi-crystalline poly-
mers can thus be employed at higher service temperatures com-
pared to amorphous thermoplastics, which typically experience a
dramatic reduction in mechanical properties at Tg [23,26]. Besides
an improved thermal stability in most cases, the semi-crystalline
morphology additionally provides these materials with excellent
chemical resistance and biocompatibility, as noncrystalline regions
are known to be preferentially biodegraded or attacked by sol-
vents and chemicals [24]. Since polymer chains are packed to-
gether more tightly in these crystalline regions, the density of
semi-crystalline polymers increases with a higher degree of crys-
tallinity. However, as a result of this dense packing upon crystal-
lization, semi-crystalline thermoplastics do suffer far more severely
from shrinkage upon cooling compared to amorphous polymers,
which can lead to serious implications for the transformation of
semi-crystalline polymers into functional parts that require a spe-
cific dimensional accuracy [24,26]. Some of the differences be-
tween amorphous and semi-crystalline polymers have been illus-
trated with their application in the SLS process, showing higher
relative densities and strengths close to fully dense parts, yet con-
siderably stronger shrinkage for the studied semi-crystalline poly-
mer compared to the amorphous material tested [27].
1.4. Applications of semi-crystalline polymers within FFF
Semi-crystalline polymers thus possess some interesting advan-
tages over their amorphous counterparts which can be exploited in
the production of parts with FFF using these materials as filament
feedstock. This is reflected in the many applications that make use
of semi-crystalline polymers with the FFF process. The applications
are mainly situated within three fields, including medicine, elec-
tronics, and aerospace and automotive, and illustrate the vast range
of possibilities for the use of semi-crystalline thermoplastics to-
gether with the FFF technique.
1.4.1. Medicine
Due to their excellent biocompatibility, semi-crystalline feed-
stock materials have already proved their versatility to be em-
ployed in various medical applications. Polylactic acid (PLA), a
biodegradable polymer, offers the advantage that its degradation
products naturally occur in the human body and can be re-
sorbed again through the metabolic pathway [28]. Hence, it has
been extensively adopted to produce porous scaffolds for tissue
engineering applications utilizing FFF [29–33]. Polycaprolactone
(PCL), another polyester with superior biocompatibility and slow
biodegradability, has found a similar use as a material for scaf-
fold manufacturing [34–39]. Besides the production of scaffolds,
4
Progress in Polymer Science 118 (2021) 101411
both PLA and PCL have been utilized in the fabrication of im-
plantable medical devices for controlled drug delivery through FFF
[40–43]. Polyetheretherketone (PEEK) is a high-performance semi-
crystalline thermoplastic which is biologically inert and is pro-
posed as a viable alternative for precious metals in the produc-
tion of implants [44]. Applications of FFF printing of PEEK in the
medical field include the production of scaffolds [45], invertebral
lumbar cages [46], customized dentistry parts [47] and cranial im-
plants [48,49]. Even polypropylene (PP), a semi-crystalline com-
modity plastic, has been studied as a possible material for cranial
implants [50].
1.4.2. Electronics
Typically, applications within the field of electronics do not re-
quire pure semi-crystalline thermoplastics, yet they often employ
fillers or nanoparticles which are added to the polymers to ob-
tain a composite feedstock material to be processed into structural
electronics with FFF. Some possible applications of these materials
include the formulation of a conductive filament consisting of PLA
with conductive carbon black or graphene as a filler, which enables
the production of a whole range of functional electronics using an
FFF printer [51,52], as well as the formulation of conductive PLA
filament by addition of Cu micropowder [53]. A nano-composite
filament of polyvinylidene fluoride (PVDF) with multi-walled car-
bon nanotubes and BaTiO3 has been found to possess enhanced
dielectric properties for the fabrication of energy storage devices
such as capacitors [54]. PLA has been blended with several elec-
trically conductive and active materials to produce an anode and
cathode for a fully printed lithium ion battery through FFF [55].
Furthermore, polyamide (PA) 6 has been studied for printing in
radio-frequency/microwave electronics applications [56], while PP
has been proposed as a possible material to be used for high- and
medium voltage insulation systems [57].
1.4.3. Aerospace and automotive
The use of FFF for the production of functional parts instead of
prototyping in the aerospace and automotive industries is far less
widespread compared to other polymer-based AM techniques such
as SLA or SLS, let alone AM with metals or ceramics, yet it has
been proposed as a viable alternative to other techniques which
could lead to a transition away from FFF as a tool for prototyp-
ing [58,59]. The main polymer that is currently used for FFF ap-
plications in aerospace is Ultem, which is the trademarked name
for polyetherimide (PEI), an amorphous specialty polymer certi-
fied by the US Federal Aviation Administration [60]. However, high-
performance semi-crystalline thermoplastics such as PEEK and
polyphenylene sulfide (PPS) have proven their worth in aerospace
and automotive applications before and most likely will be em-
ployed with FFF more frequently in the future for these applica-
tions [61].
2. Semi-crystalline feedstock materials for FFF
Table 2 provides an overview of the main semi-crystalline
feedstock materials that are commercially available [62]. These
polymers can be subdivided into three categories according to
their performance characteristics and properties. These categories
include commodity polymers, engineering polymers and high-
performance polymers. Polypropylene (PP), polycaprolactone (PCL),
polylactic acid (PLA) and polyvinyl alcohol (PVA) all fall under
commodity feedstock polymers. The category of semi-crystalline
engineering plastics for FFF is comprised of polyoxymethylene
(POM), thermoplastic polyurethane (TPU), polyethylene terephtha-
late (PET), and polyamides (PA) such as PA 6 and PA 12. Lastly,
commercially available high-performance thermoplastic filament
feedstock includes polyvinylidene fluoride (PVDF), polyphenylene
D. Vaes and P. Van Puyvelde Progress in Polymer Science 118 (2021) 101411

Table 2
The main semi-crystalline feedstock polymers for FFF that are commercially available, taken from Senvol Materials Database [62].

Tg Tm Tliquefier Tbuild plate vprint

Class Polymer [°C] [°C] [°C] [°C] [mm/s] Main properties

- Recyclable, tough, flexible, low density, food safe

Commodity PP 10 130 200 80 20 and chemically inert.
- - - -
170 250 100 35
- Biodegradable, mainly biomedical applications.
PCL 60 60 130 30 20
- - -
170 45 40
Biodegradable, easy to print, does not require
PLA 55 150 180 20- 30 heated build plate.
- - - -
66 160 230 60 80
Mostly utilized as water-soluble support material,
PVA 85 150 190 35 40 biodegradable once dissolved in water.
- - - -
200 225 60 100
- Good thermal and chemical resistance, great
Engineering POM 60 165 210 100 30 dimensional stability, difficult adhesion of first
- - - layer.
175 225 110
- High wear and abrasion resistance, high elasticity,
TPU 44 185 195 40 10 low temperature flexibility, high impact
- - - - - resistance, excellent chemical, solvent, oil and
16 220 250 80 40 ozone resistance.
Recyclable, high heat resistance and strength,
PET 62 255 275 60 30 excellent dimensional stability.
- - - -
83 300 120 80
High strength, toughness and impact resistance,
PA 48 220 220 80 30 sensitive to moisture uptake, great wear
6 & & - - - resistance.
& 45 178 275 130 50
12
- High chemical resistance, high continuous use
High- PVDF 40 173 245 90 25 temperature up to 150 °C, not hygroscopic,
performance - - - - - resistant to nuclear and UV radiation, great wear
- 177 265 110 40 resistance.
25
Excellent chemical resistance, insoluble in any
PPS 85 285 315 120 20 known solvent under 200 °C, exceptional strength
- - - and stiffness up to elevated temperatures,
345 160 35 inherent flame resistance.
Easier to print than PEEK, continuous service
PEKK 162 335 345 120 20 temperature up to 260 °C, outstanding
- - - mechanical, thermal and chemical resistance,
375 140 50 inherent flame resistance.
Continuous service temperature up to 260 °C,
PEEK 143 343 375 130 10 outstanding mechanical, thermal and chemical
- - - resistance, inherent flame resistance.
410 145 50

sulfide (PPS), polyetherketoneketone (PEKK) and polyetherether-
ketone (PEEK). In what follows, studies of both commercial and
non-commercial semi-crystalline homopolymers and their appli-
cation in the FFF process will be thoroughly reviewed. The main
aim is to elucidate the link between process parameters, part
crystallinity and final printed part quality. Furthermore, semi-
crystalline copolymers, blends and composite feedstock for FFF will
be reviewed in terms of their crystallization behavior. Fig. 2 pro-
vides an overview of the relative representation for each semi-
crystalline polymer or polymer class in the literature that is dis-
cussed in this section.
2.1. Polyolefins
2.1.1. Polypropylene
Low cost and superb chemical resistance are what sets poly-
olefins, such as polypropylene, apart from other more commonly
used commodity plastic feedstock materials, including PLA and ABS
[63]. Polyolefins are generally not widely offered by many suppli-
ers nor applied with FFF, mainly due to their excessive shrinkage.
Within this polymer class, PP has been the subject of most re-
search and applications concerning FFF, as is apparent from Fig. 2.
These studies are recorded in Table 3. Commercial PP filaments are
usually modified to greatly suppress crystallization in order to en-
hance printability [64]. Very few studies focused on neat PP and
mainly investigated the use of PP blends, composites or copoly-
mers.
Wang et al. studied the effect of process parameters, such as
Tliquefier , vprint and layer thickness, on the resulting crystallinity of
samples printed with a commercial PP filament, which was also
compared to that of parts produced through injection molding
(IM). Differential Scanning Calorimetry (DSC) demonstrated a clear
distinction in thermal behavior between the printed and IM parts
which can be observed in Fig. 3. Whereas IM parts solely exhib-
ited a single endothermic melting peak around 165 °C attributed
to the melting of characteristic α -crystal in isotactic PP, printed

5
D. Vaes and P. Van Puyvelde Progress in Polymer Science 118 (2021) 101411

Table 3
Studies involving PP.

Evaluation of Mechanical Heat treatment or adaptations

Study Material Print settings crystallinity testing to printing process

Chatham, 2019 [64] PET/PP/PP-g-MA • Tliquefier : 270 °C DSC Tensile None.

blends • Tbuild plate : 110 °C tests
• vprint : 15 mm/s
Das, 2020 [70] PP/hydrocarbon resin • Tliquefier : 180 °C DSC Tensile Annealing at 120 °C for 24 h
blends • Tbuild plate : 120 °C tests in a convection oven.
• vprint : 17 mm/s
Harris, 2019 [71] ABS/PP/PE-g-MA • Tliquefier : 185 - 205 °C DSC Tensile, Screw-based extrusion system.
blends • Tbuild plate : 25 - 75 °C compres- Thermal aging for 3 or 6 days.
• vprint : 5 mm/min sion and
flexural
tests
Jiang, 2020 [73] PP T30S • Tliquefier : 230 °C DSC & XRD Tensile None.
homopolymer & PP • Tbuild plate : 80 °C (SAXS & and
T30S/PS 5250 blends • vprint : 60- 180 mm/s WAXS) impact
tests
Jin, 2020 [72] PP/E random • Tliquefier : 210 - 250 °C DSC & XRD Tensile None.
copolymers RD208CF (sample-dependent) (WAXS) tests
& RP220M blended • Tbuild plate : 120 °C
with 6 amorphous • vprint : 15 mm/s
PP-based polyolefins,
LLDPE and
β -nucleating agent
and commercial PP
filaments
Kaynak, 2018 [74] Neat PP/E random / DSC Tensile None.
copolymer & tests
composite material
with MCC
Nogales, 2019 [67] PP Smartfil filament • Tliquefier : 235 °C In-situ XRD / None.
• Tbuild plate : 100 °C (SAXS &
• vprint : 20 mm/s WAXS)
Shmueli, 2019 [68] Isotactic PP • Tliquefier : 230 °C In-situ XRD Three- None.
• Tbuild plate : 60 °C (SAXS & point
• vprint : 20 mm/s WAXS) bending
tests
Spiegel, 2020 [78] PP-1-butene & / DSC / None.
PP-1-hexene
synthesized
copolymers
Spoerk, 2017 [75] • Tliquefier : 210 °C DSC Tensile None.
PP/perlite/amorphous • Tbuild plate : 70 °C tests
polyolefin
composites
Spörk, 2017 [76] Glass-filled PP / DSC Tensile None.
tests
Wang, 2017 [65] PP homopolymer • Tliquefier : 200 - 250 °C DSC & XRD Izod None.
filament Moplen • Tbuild plate : 130 °C (WAXS) impact
HP741T • vprint : 45 mm/s tests
• Layer thickness: 0.1 -
0.3 mm
Wang, 2019 [77] PP impact copolymer • Tliquefier : 200 °C DSC / None.
composite with • Tbuild plate : 120 °C
SDCNF & MAPP • vprint : 45 mm/s
Wang, 2018 [66] PP homopolymer • Tliquefier : 200 - 250 °C DSC Tensile None.
filament Moplen • Tbuild plate : 130 °C and
HP741T • vprint : 45 - 90 mm/s flexural
• Layer thickness: 0.1 - tests
0.3 mm
Zander, 2019 [69] PP/PET & PP/PS • Tliquefier : 260 °C DSC Tensile None.
blends from recycled • Tbuild plate : 100 °C tests
plastics • vprint : 50 mm/s

parts presented two additional endothermic melting peaks. These
two peaks are due to melting of β - and β ’-crystals around 145 and
150 °C, respectively, where the formation of β ’-crystal is mainly a
result of the DSC test itself, during which β -crystal recrystallized
into a more stable β ’-crystal structure before thermal transition
into α -crystal. It should be noted that the peak at 120 °C corre-
sponds to the thermal transition of a proprietary ingredient in the
PP employed in this study. These results were also corroborated by
X-ray Diffraction (XRD), more specifically Wide Angle X-ray Scat-
tering (WAXS), which showed clear peaks in the scattering inten-
sity of the printed parts associated with the formation of β -crystal.
This formation is favored by addition of a so-called β -nucleating
agent and by crystallization temperatures between 100 and 140 °C.
Samples printed at Tliquefier of 200 °C therefore possessed a higher
β -crystal content, since in this case, with a Tbuild plate of 130 °C, the
part will reach an average temperature ideal for β -crystal growth.
When Tliquefier is increased to 250 °C, the average temperature will
consequently rise as well, and the formation of α -crystal is favored.

6
D. Vaes and P. Van Puyvelde
Fig. 2. An overview of the relative percentage of representation of each semi-
crystalline polymer or polymer class in literature across the articles referenced in
Section 2.
Fig. 3. DSC analysis on PP samples fabricated through injection molding as well
as FFF as performed by Wang et al. (2017). [65], Copyright 2017. Reproduced with
permission from Elsevier Science Ltd.
Furthermore, Wang et al. observed a higher degree of crystallinity
for parts printed with smaller layer thickness, explained by the
longer build time required for parts with reduced layer height.
Hence, these parts stay on the heated build plate for a longer pe-
riod of time. The heated build plate has been shown to induce an
annealing effect thus increasing the degree of crystallinity. In terms
of mechanical properties, an increased β -crystal content leads to
improved impact strength, yet tensile strength and elastic modulus
are negatively impacted [65,66].
Through a combination of in-situ small and wide angle X-ray
scattering (SAXS/WAXS) during printing of isotactic PP, Nogales
et al. (2019) were able to gain insight into the development of
crystallinity over the course of the FFF process and at different
locations along the printed sample. From their measurements, PP
was found to crystallize in its α -crystal form. Furthermore, no ori-
entational effects were present as printing occurred at a shear rate
of approximately 100 s−1 and the feedstock molecular weight was
insufficient to induce this phenomenon. In the study, from top to
bottom, the free surface of the top layer, three points in the bulk
of the top layer, the welding zone between the top layer and the
underlayer, and one point directly below the welding zone were
scanned with in-situ SAXS/WAXS. A typical sigmoidal crystalliza-
tion curve was observed for the bulk positions, as well as the free
surface and welding zone, starting from 0 % crystallinity thus a
fully amorphous state and gradually increasing the degree of crys-
tallinity. The position in the underlayer on the other hand behaves
differently as here crystalline phase is already present at the be-
7
Progress in Polymer Science 118 (2021) 101411
Fig. 4. The variation in degree of crystallinity of isotactic PP across the printed top
layer as observed by Nogales et al. (2019). [67], Copyright 2019. Reproduced with
permission from American Chemical Society.
ginning of the measurement. Fig. 4 clearly demonstrates the varia-
tion of crystallinity across the printed layer. Starting from a lower
crystallinity at the free surface of the top layer, the crystallinity
achieves a maximum value of around 32 % for the middle of the
bulk of the top layer, and then further decreases in the welding
zone. As can be noticed, the crystallinity in the position in the un-
derlayer is very similar to that of the corresponding point in the
top layer. Limitations on spherulitic growth imposed by interfaces
are the main reason for a reduced crystallinity in the welding zone
and top surface [67].
Furthermore, Nogales et al. (2019) studied differences in crys-
tallinity at distinct positions along the top layer. For the position
closest to the edge, a typical sigmoidal crystallization curve is ob-
served, whereas for the other positions crystallization occurs ear-
lier the further away the position is located from the edge. The
most significant difference in crystallinity is found in the position
closest to the edge compared to the other positions. This is at-
tributed to the slower print speed at the position closer to the
edge, since here, the print head starts decelerating to change its
movement direction. It is therefore assumed that singular condi-
tions in terms of momentary speed or local thermal conditions can
lead to local changes in crystalline microstructure [67]. Shmueli
et al. (2019) utilized in-situ SAXS/WAXS as well to study isotac-
tic PP during FFF. However, their feedstock material possessed a
higher molar mass which gave rise to significant orientational ef-
fects and the typical shish-kebab crystalline microstructure asso-
ciated with flow-induced crystallization [68]. The phenomenon of
flow-induced crystallization and its relationship to the processing
of semi-crystalline feedstock materials in FFF will be extensively
discussed in Section 3.2 of this article.
PP blends for FFF have been the subject of studies by sev-
eral authors. Chatham et al. (2019) investigated a PP/PET blend,
where both phases are able to crystallize. Printed blends exhib-
ited a higher degree of crystallinity of the PP phase compared to
the feedstock filament, which is ascribed to the prolonged time
above Tg and Tm of the printed sample compared to rapid wa-
ter bath quenching of the filament. The addition of PP-graft-maleic
anhydride (PP-g-MA) compatibilizer was found to lead to a phase
separation which promotes crystallization and thus printed sam-
ples with higher compatibilizer content revealed a higher degree
of crystallinity of both phases with respect to the as received, un-
blended homopolymers [64]. Zander et al. (2019) produced PP/PET
blends as well, yet utilized recycled materials for blending. Two
distinct melting points of both crystallizable phases were observed
indicating immiscibility of the two phases. A lower crystallization
temperature of the PP phase was detected with increasing PET con-
tent. Moreover, the addition of compatibilizers, which possess a
plasticizing effect, resulted in a likewise decrease in crystallization
D. Vaes and P. Van Puyvelde
temperature. Across all investigated blends, Zander et al. (2019)
discovered a reduced relative crystallinity of each polymer phase,
especially when the polymer was the minor component [69]. Das
et al. (2020) studied blends of PP with both fully and partially hy-
drogenated hydrocarbon resins. Due to excellent solubility of the
resins in the PP matrix, one single melting endotherm can be ob-
served. Furthermore, the onset of melting is shifted to lower tem-
peratures, while crystallization is delayed by increasing the resin
content. Although addition of the resins reduces crystallization of
the PP matrix, the overall degree of crystallinity is not drasti-
cally impacted up until 20 wt% of resin. The degree of hydrogena-
tion of the added resin can impact the crystallization behavior as
well, since the extent of hydrogenation influences the intermolec-
ular interactions in the PP matrix. It was found that PP blended
with partially hydrogenated hydrocarbon resin exhibits smaller
spherulites and a higher degree of crystallinity compared to the
blends with fully hydrogenated resin. Blends with partially hydro-
genated resin therefore possess greater elongation at break, as well
as tensile strength and modulus. Moreover, Das et al. (2020) an-
nealed their printed blends and found a clear increase in the de-
gree of crystallinity, which results in a material with improved ten-
sile strength, yet reduced toughness and elongation at break [70].
ABS/PP blends compatibilized with polyethylene-graft-maleic an-
hydride (PE-g-MA) were investigated by Harris et al. (2019) and
were found to exhibit a reduction in both Tg of the ABS phase and
Tm of the PP phase compared to the neat homopolymers. Addition-
ally, an increased Tbuild plate , Tliquefier and aging time were identi-
fied as possible reasons for an increase in Tm of the PP phase [71].
Jin et al. (2020) blended two PP/E random copolymers with sev-
eral additives, such as a β -nucleating agent, different amorphous
PP-based materials and linear low density polyethylene (LLDPE).
A higher β -nucleating agent content did not alter crystallinity nor
tensile strength or elastic modulus. Since β -crystal formation only
progresses between 100 and 140 °C, the cyclic reheating of de-
posited layers inherent to the FFF process promotes βα -transition
which explains the negligible effect of the nucleating agent con-
centration. However, blending with amorphous PP considerably de-
creased the degree of crystallinity due to a dilution effect. Further-
more, the elastic modulus decreased as well, since the amorphous
PP is much softer. The effect of amorphous PP addition is further
enhanced by increasing the concentration of amorphous PP. The
addition of LLDPE, on the other hand, was found to affect crys-
tallinity and mechanical properties to a lesser extent [72].
PP composite materials consisting of a PP polymer matrix com-
bined with several fillers such as polystyrene (PS) [73], microcrys-
talline cellulose (MCC) [74], expanded perlite [75], glass bubbles
and microspheres [76], spray-dried carbon nanofibers (SDCNF) and
maleic anhydride PP (MAPP) [77], have been reported as PP-based
feedstock. These fillers clearly affect crystallization behavior by act-
ing as nucleating agents for crystallization. This is reflected in an
increased crystallization temperature and degree of crystallinity of
these composite materials compared to the neat PP matrix mate-
rial [73–77].
Furthermore, Spiegel et al. (2020) synthesized PP-1-butene and
PP-1-hexene copolymers as possible feedstock materials to be ap-
plied within the FFF process. Copolymerization has been found
to decrease the degree of crystallinity with increasing monomer
content, which could provide enhanced printability by reducing
shrinkage [78].
2.1.2. Polyethylene
Polyethylene polymers are typically classified into different
types according to their molecular architecture. The main commer-
cial PE polymers are low density polyethylene (LDPE), linear low
density polyethylene (LLDPE), high density polyethylene (HDPE)
and ultra high molecular weight polyethylene (UHMWPE) [79].
8
Progress in Polymer Science 118 (2021) 101411
Among the already very few studies that are reported concerning
PE as feedstock material for FFF, even less authors have looked into
the crystallization behavior of these polymers and its relation to
the printing process. Table 4 summarizes these studies.
Chong et al. (2017) investigated the possible use of recycled
HDPE as feedstock filament and concluded excessive warpage and
adhesion problems impose serious difficulties when printing this
material [80]. In a similar way to the ABS/PP/PE-g-MA blend, Har-
ris et al. (2020) produced an ABS/HDPE/PE-g-blend to print with
a screw-based extrusion mechanism. DSC analysis on the blend
showed a significant drop in melting enthalpy compared to neat
HDPE, which indicates the presence of considerably strong inter-
molecular interaction between blend constituents [81]. Further-
more, it was found that the addition of fillers to produce PE com-
posite materials such as UHMWPE filled with hydroxyapatite or
recycled HDPE filled with activated carbon leads to a decreased
degree of crystallinity of the polymer matrix with increasing filler
content [82,83]. Combined with an observed reduction of the melt-
ing point of UHMWPE, this could facilitate its processing [82].
2.2. Polyesters
2.2.1. Polylactic acid
As was already mentioned, polylactic acid or PLA is one of the
most extensively applied FFF feedstock materials and is, by far, the
most commonly utilized semi-crystalline polymer for this technol-
ogy [84]. This is also reflected in the vast number of studies that
focus on PLA, which are tabulated in Table 5. Fig. 2 clearly demon-
strates the large share of PLA in semi-crystalline polymer literature
concerning FFF. One of the main reasons for the popularity of PLA
is its origin as it is produced from renewable resources in the form
of carbohydrate-rich crops rather than petroleum, which besides
drastically lowering its environmental impact, also provides it with
excellent biodegradability [84–86].
Several authors have investigated the impact of the FFF print-
ing process on PLA crystallinity and thermal properties when com-
pared to those of the feedstock filament. Most studies conclude
that the crystallinity of printed samples is higher than that of the
filament. This could be attributed to slower cooling rates associ-
ated with the printing process compared to relatively faster cooling
upon extrusion of feedstock filament [87,88]. However, Lay et al.
(2019) explain that this is a result of the thermal cycling expe-
rienced by the printed polymer as the temperature rises above
the cold crystallization temperature of PLA when the print head
is close to sample and then drops down below this temperature
when the nozzle moves away. These repeated heating and cool-
ing cycles induce more nucleation which leads to the formation of
smaller crystals instead of allowing a single crystal to grow [89].
Moreover, Levenhagen et al. (2017) postulate the possibility that
the higher crystallinity of a printed sample compared to that of
the filament feedstock is a consequence of high shear rates that
are applied to the PLA chains upon extrusion through the print
nozzle, which could lead to shear-induced crystallization [90], a
phenomenon that is thoroughly described in Section 3.2. It should
be noted that the printed part’s degree of crystallinity can signif-
icantly impact PLA hydrolysis and its progress, as the crystalline
phase absorbs much less water and thus diffusion of water into the
PLA polymer is limited by the crystalline phase. Hence, hydrolytic
degradation can be slowed down by increasing the degree of crys-
tallinity [91]. On the other hand, some authors find very low, al-
most negligible degrees of crystallinity in FFF samples, which are
almost amorphous. They assume the cooling rates during the print-
ing process are too fast to allow for crystallization to occur, since
PLA typically possesses fairly slow crystallization kinetics [92–96].
Generally, the degrees of crystallinity of investigated PLA FFF sam-
ples reported in literature significantly vary among the different
D. Vaes and P. Van Puyvelde
Table 4
Studies involving PE.
Study Material Print settings
Bin Md Ansari, 2019 [82] UHMWPA/hydroxyapatite / DSC
composite
Chong, 2017 [80] Recycled HDPE / DSC
Chong, 2020 [83] Recycled HDPE and / DSC & XRD (WAXS) /
HDPE/PP mixed with
activated carbon
Harris, 2020 [81] ABS/HDPE/PE-g-MA blends • Tliquefier : 185 - 205 °C
• Tbuild plate : 25 - 75 °C
• vprint : 5 mm/min
Fig. 5. Comparison between the DSC thermograms of a printed PLA sample and
the PLA filament material as studied by Cuiffo et al. (2017). [101], Copyright 2017.
Reproduced with permission from MDPI.
studies. This is most likely caused by the great variation in cool-
ing rates and thermal history experienced by the printed polymer
in each of these studies, which are obviously linked to print set-
tings and the employed FFF printer. Furthermore, the properties of
the feedstock material can also considerably impact crystallization
behavior. Especially commercial filaments often contain various ad-
ditives and fillers, including pigments. This results in varying crys-
tallization behavior among PLA filaments from different suppliers
[97,98], yet even filaments from the same supplier but with dif-
ferent pigmentation have been proven to possess different degrees
of crystallinity when printed with identical print parameters, indi-
cating that crystallinity is color-dependent [99,100]. Typically, upon
heating during DSC analysis, FFF printed samples demonstrate an
exothermic cold crystallization peak due to incomplete crystalliza-
tion of the printed PLA and self-nucleation when heated above
the glass transition temperature, which again can be attributed to
the slow crystallization kinetics of PLA [92,94,95,101]. Furthermore,
FFF printing has not been found to impact the glass transition
temperature of PLA in a significant way [31,92,101,102]. Similarly,
the melting temperature remains relatively unchanged [31,102], al-
though Cuiffo et al. (2017) have observed a decrease in melting
temperature of about 10 °C after printing as is shown in Fig. 5.
They further detected a double melting peak at 150 and 155.1 °C,
respectively, which can be attributed to the formation of two dif-
ferent crystalline phases, namely α and α ’, which is an imperfect,
metastable α form that is sometimes also termed the δ form and
that can be formed during thermal cycling and crystallization of
PLA at high supercooling from the melt [101]. A phenomenon that
was also discovered by other authors [103,104].
The printing process parameters need to be considered care-
fully as they are known to determine the thermal history that
9
Progress in Polymer Science 118 (2021) 101411
Evaluation of Heat treatment or adaptations to
crystallinity Mechanical testing printing process
/ None.
/ None.
None.
DSC Tensile, Screw-based extrusion system.
compression and Thermal aging for 3 or 6 days.
flexural tests
the printed part is subjected to and the resulting part crystallinity.
Several print settings have been systematically varied to elucidate
their respective impact on the crystallization behavior of PLA dur-
ing the FFF process. One of the main process parameters is the liq-
uefier temperature of which literature reports varying effects on
part crystallinity. Benwood et al. (2018) discovered no significant
impact of the liquefier temperature on both the degree of crys-
tallinity and the mechanical strength of printed PLA parts [103].
However, Drummer et al. (2012) report an overall clear increase
in crystalline content with increasing Tliquefier [87], while Kaygusuz
et al. (2019) detected an inverse trend as they noticed a slight
decrease in the degree of crystallinity when printing at higher
Tliquefier [105]. This could possibly be explained by the fact that the
cooling rates experienced by layers deposited at higher Tliquefier are
generally higher and therefore could be too high to allow for suffi-
cient crystallization to occur [106].
Another parameter that has been proven to clearly impact PLA
crystallization behavior during printing is the build plate temper-
ature. A definite increasing trend in crystallinity with increasing
build plate temperature was observed by Benwood et al. (2018).
The increased degree of crystallinity also manifested itself in im-
proved mechanical properties such as tensile and flexural strength
and moduli [103]. Furthermore, increasing Tbuild plate results in a
transition from α ’ to α crystals [103,104]. Vanaei et al. (2020) re-
ported a positive impact on part crystallinity with increased build
plate temperature, which was reflected in improved ductility of the
printed part [107]. Harris et al. (2019) have also noticed the ef-
fectiveness of Tbuild plate as a process parameter to enhance crys-
tallinity. According to them, a higher Tbuild plate , as well as an en-
vironmental temperature set sufficiently high above the polymer’s
Tg , restricts the deposited polymer melt from cooling down too
rapidly and thus facilitates crystallization and leads to improved
mechanical properties [108]. Wang et al. have noticed a similar
trend in their work since samples printed at increased Tbuild plate
exhibited higher degrees of crystallinity and less cold crystalliza-
tion. They attribute this to an annealing effect by the heated build
plate that keeps the printed polymer above its Tg for an adequate
amount of time [109,110]. Moreover, samples printed at higher
Tbuild plate attained greater α -crystal content as the annealing ef-
fect allows for crystallization in this crystalline form. The improved
impact strength of parts printed at higher Tbuild plate is however
not linked to a higher degree of crystallinity or greater α -crystal
content, yet it is connected to the specific crystalline morphology.
This morphology is a direct result of the cyclic heating and cool-
ing experienced by the printed polymer each time the print head
passes and moves away. These rapid heating and cooling cycles in-
duce more nucleation events and the formation of smaller crystals.
Although it is possible that annealing into larger crystals can occur
due to the heat transferred from the build plate, the cyclic tem-
perature fluctuation is the most dominant factor that determines
the resulting crystalline morphology and consequently the printed
part’s mechanical properties, as a morphology with smaller crys-
D. Vaes and P. Van Puyvelde Progress in Polymer Science 118 (2021) 101411

Table 5
Studies involving PLA.

Heat treatment or
Evaluation of adaptations to printing
Study Material Print settings crystallinity Mechanical testing process

Akhoundi, 2020 [116] High temperature • Tliquefier : 210 - 250 °C DSC & XRD (WAXS) Tensile tests Annealing for 1 h in an oven
PLA • Tbuild plate : 65 °C at 110 °C.
• vprint : 40 mm/s
Askanian, 2018 [112] PLA • Tliquefier : 210 °C DSC Tensile tests None.
• Tbuild plate : 50 °C
• vprint : 50 mm/s
Benwood, 2018 [103] PLA filament • Tliquefier : 190 - 230 °C DSC Tensile, flexural & Annealing for 1 h in an oven
Polymaker • Tbuild plate : 45 - 105 °C Izod impact tests at 80 and 100 °C.
• vprint : 50 mm/s
Bhandari, 2019 [117] PLA & PLA/CF • Tliquefier : 210 °C DSC Tensile tests Annealing for 30 minutes, 4
filament 3DXTECH • Tbuild plate : 55 °C h or 8 h in an oven at 90
• vprint : 30 mm/s and 120 °C.
Cicala, 2018 [97] Commercial PLA • Tliquefier : 210 °C DSC Tensile tests None.
filaments • Tbuild plate : 50 °C
• vprint : 35 - 45 mm/s
Cuiffo, 2017 [101] PLA filament • Tliquefier : 229 °C DSC / None.
NatureWorks • vprint : 90 mm/s
Dichtl, 2017 [92] PLA filament • Tliquefier : 257 °C DSC / None.
Makerbot
Drummer, 2012 [87] PLA Biomer • Tliquefier : 215 – 235 °C DSC Tensile tests None.
L9000/β -TCP • Tenvironment : 40 °C
composites
Esposito Corcione, 2019 [29] PLA 4043D/HA • Tliquefier : 180 °C DSC Compression tests None.
composites • vprint : 30 mm/s
Gao, 2019 [123] PLA/talc & PLA/CF • Tliquefier : 230 °C DSC Tensile tests None.
composites • Tbuild plate : 60 °C
• vprint : 90 mm/s
Gkartzou, 2017 [126] PLA/lignin • Tliquefier : 205 °C DSC Tensile tests None.
composites • vprint : 20 mm/s
Gonzalez-Ausejo, 2018 [113] PLA and PLA/PHA • Tliquefier : 195 - 200 °C DSC Tensile tests None.
blend filaments • Tbuild plate : 65 °C
• vprint : 50 - 70 mm/s
Gonzalez-Ausejo, 2018 [91] PLA and PLA/PHA • Tliquefier : 195 - 200 °C DSC Tensile tests None.
blend filaments • Tbuild plate : 65 °C
• vprint : 50 - 70 mm/s
Guessasma, 2020 [106] PLA/PHA blend • Tliquefier : 190 - 255 °C DSC Tensile tests None.
• Tbuild plate : 65 °C
• vprint : 150 mm/s
Harris, 2019 [108] PLA • Tliquefier : 210 °C DSC Tensile tests Commercial FFF printer
• Tbuild plate : 40 - 80 °C adapted with
• Tenvironment : 22 - 80 °C environmentally controlled
chamber.
Kaygusuz, 2019 [105] PLA filament • Tliquefier : 190 - 260 °C DSC & XRD (WAXS) Tensile tests None.
Ookuma & • Tbuild plate : 60 °C
PLA/PHA blend • vprint : 50 mm/s
Lay, 2019 [89] PLA • Tliquefier : 210 °C XRD (WAXS) Tensile & Izod None.
• Tbuild plate : 70 °C impact tests
• vprint : 60 mm/s
Lee, 2019 [111] PLA filament • Tliquefier : 210 °C XRD (WAXS) Tensile tests Commercial FFF printer
MonoPrint • Tbuild plate : 45 °C equipped with controllable
• vprint : 30 mm/s cooling air flow system.
Lee, 2019 [30] PLA Ingeo • Tliquefier : 210 °C DSC & XRD (WAXS) Tensile, None.
4032D/Ti • Tbuild plate : 90 °C compression &
composites • vprint : 30 mm/s Charpy impact
tests
Levenhagen, 2017 [90] PLA 4043D/LMW • Tliquefier : 190 °C DSC Tensile & T-peel None.
PLA bimodal • Tbuild plate : 70 °C tests
blends • vprint : 60 mm/s
Liao, 2019 [104] PLA 4043D • Tliquefier : 180 °C XRD (WAXS) Tensile tests Heat treatment in an oven
• Tbuild plate : 40 - 80 °C at 120 °C for 10 minutes.
Marat-Mendes, 2018 [98] PLA DoWire & BQ • Tliquefier : 205 - 215 °C DSC Tensile tests None.
commercial • vprint : 40 mm/s
filaments
Nor Ashikin, 2020 [102] Commercial PLA • Tliquefier : 190 °C DSC / None.
filament, PLA Ingeo • Tbuild plate : 70 °C
2002D & PLA/PEG • vprint : 60 mm/s
blend
Patanwala, 2018 [124] PLA/MWCNT • Tliquefier : 210 °C DSC & XRD (WAXS) Tensile tests None.
composites • Tbuild plate : 50 °C
Prasong, 2020 [120] PLA/PBAT blends & • Tliquefier : 210 °C DSC Tensile & Charpy None.
PLA/PBAT/talc • Tbuild plate : 45 °C impact tests
composites • vprint : 25 mm/s
(continued on next page)

10
D. Vaes and P. Van Puyvelde Progress in Polymer Science 118 (2021) 101411

Table 5 (continued)

Study Material Print settings Evaluation of Mechanical testing Heat treatment or

crystallinity adaptations to printing
process

Rasselet, 2019 [122] PLA/PA 11/Joncryl • Tliquefier : 210 °C DSC Tensile tests None.
blends • Tbuild plate : 60 °C
• vprint : 65 mm/s
Ravi, 2017 [31] PLLA PL-32 • Tliquefier : 210 °C DSC / None.
• vprint : 10 mm/s
Senatov, 2016 [32] PLA & PLA/HA • Tliquefier : 180 - 210 °C DSC Compression tests None.
composites • vprint : 30 mm/s
Shmueli, 2019 [114] PLA 4043D Natural • Tliquefier : 200 - 245 °C In-situ XRD / None.
filament • Tbuild plate : room T - 60 °C (WAXS) & DSC
• vprint : 20 mm/s
Song, 2017 [88] PLA filament • Tliquefier : 220 °C DSC Tensile, Gradual heating from room
IMAKR • vprint : 60 mm/s compression & temperature to 60 °C over
fracture tests 30 minutes, holding the
sample at 60 °C for 5 h and
slow cooling to room
temperature over 12 h.
Spina, 2019 [99] PLA Onyx Black & • Tliquefier : 210 - 220 °C DSC Compression tests None.
Crystal Clear • Tbuild plate : 40 °C
filament • vprint : 30 - 60 mm/s
Srinivas, 2018 [115] Commercial PLA • Tliquefier : 200 °C DSC & XRD (WAXS) / None.
grades with • vprint : 20 - 50 mm/s
varying molecular • Tenvironment : 70 °C
weight and
L-enantiomeric
purity
Vanaei, 2020 [107] Commercial PLA • Tliquefier : 200 - 230 °C DSC Tensile tests None.
filament • Tbuild plate : 50 - 100 °C
• vprint : 20 - 60 mm/s
• Layer height: 0.1 - 0.3 mm
Verbeeten, 2020 [94] PLA filament • Tliquefier : 200 °C DSC Tensile tests None.
Orbi-Tech • Tbuild plate : 50 - 60 °C
• vprint : 9 - 35 mm/s
Wach, 2018 [95] PLA filament • Tliquefier : 195 - 255 °C DSC & XRD (WAXS) Tensile & flexural Annealing for 10 to 70
Finnotech • Tbuild plate : 55 °C tests minutes at 85 and 95 °C.
• vprint : 45 mm/s
Wang, 2019 [121] PLA/TPU blends • Tliquefier : 210 °C DSC Tensile & Izod None.
• Tbuild plate : 60 °C impact tests
• vprint : 30 mm/s
Wang, 2017 [110] PLA Ingeo 4032D • Tliquefier : 200 °C DSC & XRD (WAXS) Izod impact tests None.
• Tbuild plate : 30 - 160 °C
• vprint : 90 mm/s
Wang, 2018 [109] PLA Ingeo 4032D • Tliquefier : 200 °C DSC Flexural tests None.
• Tbuild plate : 30 - 160 °C
• vprint : 90 mm/s
• Air gap: -0.04 - 0 mm
Wang, 2020 [119] PLA/nanocellulose • Tliquefier : 200 °C DSC Flexural tests None.
& PLA/PEG/ • Tbuild plate : 30 - 160 °C
nanocellulose • vprint : 90 mm/s
composites • Air gap: -0.04 - 0 mm
Wijnen, 2018 [96] PLA 4043D / XRD (WAXS) / Annealing from 0 to 4 h at
NatureWorks 50 and 90 °C.
Wittbrodt, 2015 [100] Differently colored • Tliquefier : 190 - 215 °C XRD (WAXS) Tensile tests None.
PLA filaments from • Tbuild plate : 60 °C
Lulzbot
Yu, 2017 [125] PLA/graphene & • Tliquefier : 190 - 210 °C DSC Tensile & flexural None.
PLA/CNT • Tbuild plate : 40 - 50 °C tests
composites • vprint : 40 mm/s
Yu, 2019 [118] PLA/talc • Tliquefier : 210 °C DSC & XRD (WAXS) Flexural tests Heat treatment for 30 or
composites • Tbuild plate : 60 °C 120 minutes at 60 or 100 °C.
• vprint : 40 mm/s

tals is associated with improved impact strength [110]. Not only
the build plate and environmental temperature can be employed
to regulate the cooling rate experienced by the printed polymer,
but this can also be effectively controlled by forced-air cooling.
Lee et al. (2019) observed some, although limited, degree of crys-
tallinity in PLA parts printed without air cooling, yet, if forced-
air cooling was utilized, the FFF samples were found to be almost
completely amorphous as the applied air flow rates led to rapid
solidification of the extruded PLA which completely prevents crys-
tallization [111].
The deposition strategy during printing can also impact the re-
sulting part crystallinity. However, Askanian et al. (2018) did not
observe any significant influence of both build orientation and
raster angle on the degree of crystallinity in their parts. This is
mostly likely due to the fact that their parts were all located very
closely to the build platform [112]. Gonzalez-Ausejo et al. (2018),
on the other hand, discovered a distinct difference in part crys-
tallinity between dumbbell specimens printed flat or up-right onto
the build plate. The flat, horizontally printed sample possessed a
higher crystalline content as it is in closer contact with the heated

11
D. Vaes and P. Van Puyvelde
build plate, which induces both a higher crystallization rate and
crystalline content, while a sample printed vertically only contacts
the build plate at one end and only over a small contact area. This
leads to a strong thermal gradient in the up-right printed part.
As a consequence, the part will exhibit an overall lower degree of
crystallinity compared to the horizontal part as well as a gradient
in crystallinity with the side that directly makes contact with the
heated build plate attaining a greater crystallinity compared to the
other end [91,113]. A similar gradient in crystallinity in vertically
printed specimens was also observed by Drummer et al. (2012)
[87]. Vanaei et al. (2020) found that the degree of crystallinity
could be enhanced by increasing the layer thickness [107]. Shmueli
et al. (2019) utilized in-situ WAXS to investigate the effect of the
printing orientation on the cooling rate and resulting crystallinity
by comparing a part printed with layers parallel to the incident
beam with one that is printed by depositing the layers perpendicu-
lar to the X-ray beam. Moreover, thermal imaging was employed to
monitor the thermal history of the point of interest in both printed
samples. Cooling occurs exponentially with time for both orienta-
tions with temperature dropping below Tm in just a few seconds.
Overall, the parallel oriented structure cools down at a slower rate
than the perpendicular one, as during printing of the former the
nozzle passes by the point of interest more frequently and the ex-
posed area for heat loss is greater for the perpendicular orienta-
tion. The larger heat retention associated with the parallel direc-
tion results in a delayed onset of crystallization, yet crystallization
occurs at higher temperatures and for prolonged times thus the
resulting degree of crystallinity is considerably higher compared to
the other orientation [114]. Sufficient heat retention has likewise
been proven to enhance crystallinity by Srinivas et al. (2018). Their
samples consist of PLA and polyvinylalcohol (PVA) support material
that is water soluble, which allows them to probe the crystallinity
of single PLA layers in the printed sample. They observed the high-
est degree of crystallinity for PLA layers located in the middle of
the printed specimens as the surrounding PVA material acts as an
insulator which maintains the temperature in the PLA material suf-
ficiently high to facilitate crystallization. The top layers possessed
the lowest degree of crystallinity, since this location is more prone
to external heat loss. Furthermore, two different print speeds were
compared. A lower vprint definitely promotes crystallization in all
printed layers, which, according to the authors, is most likely due
to the longer time that the heated nozzle resides at a certain loca-
tion for slower print speeds. Srinivas et al. (2018) also investigated
the effect of the material properties of the PLA feedstock, including
the molar mass and enantiomeric purity. They discovered a higher
molar mass or D-enantiomeric content reduce the crystallization
rate and crystalline content [115]. A higher stereoregularity, i.e. a
smaller fraction of D-stereochemical centers in PLA, allows for eas-
ier arrangement and packing of polymer chains and thus facilitates
crystallization upon cooling [102].
The often quite low degree of crystallinity of PLA samples af-
ter printing can be further increased through an annealing or heat
treatment procedure. Depending on the annealing temperature and
time, the samples can recrystallize to a certain extent. This is
reflected in the absence of a cold crystallization peak upon re-
heating of the sample in DSC and a clearly increased degree of
crystallinity in the annealed samples [95,104,116–118]. Akhoundi
et al. (2020) furthermore observed a distinct color change in their
printed samples from transparent to white upon annealing, which
clearly indicates crystallization occurred [116]. Moreover, the en-
hanced crystalline content due to annealing was found to signif-
icantly influence the mechanical properties, as both tensile and
flexural strength and modulus as well as impact strength were
drastically increased after heat treatment [95,103,116]. Liao et al.
(2019) annealed printed PLA samples at 120 °C for merely 10 min-
utes and observed a complete transition of the metastable α ’-phase
12
Progress in Polymer Science 118 (2021) 101411
formed during printing to the thermodynamically stable α -phase
[104]. A similar transition from disordered α ’ to ordered α crystals
was also detected by Bhandari et al. (2019) [117]. The extent of this
transition clearly depends on the annealing temperature as sam-
ples annealed at 100 °C attained a higher α -phase content com-
pared to those annealed at 80 °C as was demonstrated in the study
of Benwood et al. (2018) [103]. However, an annealing temperature
that is too low does not affect the crystallinity of the printed parts
in any way. Song et al. (2017) performed annealing at 60 °C and
did not observe a significant impact on part crystallinity [88]. Fur-
thermore, Wijnen et al. (2018) showed that annealing at 50 °C did
not alter the final degree of crystallinity of their printed parts even
at prolonged annealing times, yet annealing at 90 °C did increase
the crystalline content of the almost amorphous printed parts up
to 20 % [96]. Besides a sufficiently high annealing temperature, the
annealing time is also a key parameter to determine the final ex-
tent of crystallization as was demonstrated by Wach et al. (2018)
[95].
Both Gonzalez-Ausejo et al. (2018) and Kaygusuz et al. (2019)
investigated blends of PLA and polyhydroxyalkanoate (PHA) as pos-
sible FFF feedstock materials. Thermal analysis revealed two glass
transition temperatures and two melting temperatures: one for
each of the two semi-crystalline phases, indicating that the blend
components are immiscible, which will lead to phase separation in
the melt. Furthermore, Gonzalez-Ausejo et al. (2018) detected an
increased melting enthalpy for the blend compared to neat PLA.
The addition of PHA thus affects crystallization as PHA acts as a
nucleating agent which causes a uniform distribution of small crys-
tallites in the polymer, leading to improved mechanical properties,
such as tensile modulus and strength [113]. Kaygusuz et al. (2019)
additionally found that blending PLA with PHA resulted in a de-
creased glass transition temperature due to a plasticizing effect of
the PHA phase. They also noticed a relatively large cold crystal-
lization peak corresponding to the PLA phase during DSC analy-
sis of the blend, which indicates a rather low crystallinity of the
PLA phase. On the other hand, no cold crystallization peak was de-
tected for the PHA phase, implying its crystallinity is high [105].
Levenhagen et al. (2017) produced bimodal PLA blends by blend-
ing a commercial PLA grade with several low molecular weight
(LMW) synthesized PLA components. They found that the addition
of LMW components can alter the crystallization behavior of PLA,
depending on the concentration of the LMW additive. For example,
the additive with the lowest molecular weight that they investi-
gated led to an enhanced crystallization at lower concentrations
due to a plasticizing effect which aids polymer chains in their or-
ganization into crystals, yet at higher concentrations chain orien-
tation is hindered and crystallization is prevented, since the ad-
ditive then acts as a solvating agent [90]. Blending of PLA with
polyethylene glycol (PEG) has been shown by Nor Ashikin et al.
(2020) and Wang et al. (2020) to decrease the glass transition
temperature and the cold crystallization temperature of the PLA
phase, as well as promote the overall crystallization rate. PEG acts
as an effective plasticizer and thus improves molecular mobility
of the PLA chains [102,119]. Printing with PLA blended with poly-
butylene adipate-co-terephthalate (PBAT) was investigated by Pra-
song et al. (2020). In terms of crystallization behavior, the addition
of PBAT clearly retarded PLA crystallization [120]. Similarly, Wang
et al. (2019) have detected a decreased glass transition temperature
and crystallinity of the PLA phase in their blends consisting of PLA
and thermoplastic polyurethane (TPU), since the added TPU pre-
vents the PLA chains from crystallizing [121]. Rasselet et al. (2019)
produced PLA/PA 11 blends for FFF printing with Joncryl, a chain
extender, as a compatibilizer. Blending PLA with PA 11 improves
crystallinity as the PA 11 domains essentially function as nucle-
ation sites. However, the addition of Joncryl has a negative impact
on the crystallization ability of the PLA phase, reflected in stronger
D. Vaes and P. Van Puyvelde
cold crystallization upon reheating and a reduced degree of crys-
tallinity with increasing Joncryl content. PLA modified with Joncryl
compatibilizer attains a branched structure, which lowers molecu-
lar mobility and prevents the polymer chains from packing during
crystallization upon cooling [122].
PLA has been used as a polymer matrix material in a vast array
of studies involving composite material feedstock for FFF. Drum-
mer et al. (2012) mixed PLA with tricalcium phosphate (TCP) for
scaffolding applications, yet did not focus on the effect of TCP
filler on crystallization kinetics of PLA [87]. Hydroxyapatite (HA) is
another commonly used ceramic filler material. Esposito Corcione
et al. (2019) did not observe a substantial effect of the HA filler
on Tg or Tm of the PLA matrix material, which already possessed a
very low degree of crystallinity. Yet the addition of HA filler made
the PLA matrix material fully amorphous [29]. However, Senatov
et al. (2016) describe a decrease in cold crystallization tempera-
ture upon addition of HA, which they attribute to the nucleating
ability of the HA particles. Additionally, the glass transition tem-
perature is shifted to a higher temperature as the filler particles
can impede molecular mobility [32]. PLA/Ti composites were in-
vestigated by Lee et al. (2019). They observed a slight increase in
Tg in the composite material compared to neat PLA due to reduced
mobility of the polymer chains caused by interference with the Ti
particles. The crystallization temperature decreased with increas-
ing Ti content, which illustrates that the Ti particles act as nucle-
ating agents, which eventually results in a decreased crystalliza-
tion capacity, leading to a reduced crystalline content. As a result
of this heterogeneous nucleation, a higher number of incomplete
crystals are formed which melt at higher temperatures. This ex-
plains the increase in Tm upon addition of Ti particles [30]. Bhan-
dari et al. (2019) studied the effect of annealing on PLA/carbon
fiber (CF) composite specimens after printing and observed that
the addition of CF slowed down crystallization of the PLA ma-
trix [117]. In the work of Gao et al. (2019), utilizing CF as a filler
did not considerably alter the crystallization behavior of the PLA
matrix material, which could be explained by the poor interfacial
interaction between PLA and CF [123]. Multi-walled carbon nan-
otubes (MWCNTs) were found to not significantly affect PLA crys-
tallinity by Patanwala et al. (2018) [124]. Yu et al. (2017), on the
other hand, did notice an effect of adding MWCNTs to a PLA ma-
trix. An increasing MWCNT content led to a decreased crystalline
content, most likely due to molecular mobility being impeded by
the MWCNTs. Yu et al. (2017) studied the impact of graphene as
filler as well and found similar results [125]. Lignin was added to a
PLA matrix by Gkartzou et al. (2017) to produce a bio-based ther-
moplastic feedstock material for FFF. The incorporation of lignin in
the PLA polymer did not significantly affect Tg , Tm or the obtained
crystallinity [126]. Another bio-based composite investigated by
Wang et al. (2020) includes nanocellulose filler in a PLA matrix.
Nanocellulose was found to not considerably influence PLA’s Tg .
It does, however, effectively function as a nucleating agent which
profoundly enhances crystallization rates [119]. Talc has been ob-
served to be an excellent nucleating agent which provides the PLA
material with considerable crystallization ability. The addition of
talc results in a significant increase in crystallinity [118,120,123].
2.2.2. Polycaprolactone
Due to its excellent biocompatibility and biodegradability, poly-
caprolactone (PCL) is most extensively used as a FFF feedstock
polymer for biomedical applications, mainly for the production of
scaffolds for tissue engineering. Studies involving PCL are listed in
Table 6.
Some authors found no significant difference in crystallinity be-
tween raw PCL pellets, PCL filament feedstock or printed scaffolds
[36,39]. However, the work of Liu et al. (2018) demonstrated a
definite change in crystalline morphology due to the FFF print-
13
Progress in Polymer Science 118 (2021) 101411
ing process, which became clear as a dramatic reduction of the
spherulite size in the printed samples compared to the PCL fila-
ment [127]. Using a screw-based extrusion system, Liu et al. (2018)
proved that the crystalline morphology, and consequently the me-
chanical performance of printed parts, can be tailored by tuning
the processing parameters. A higher screw rotational speed as well
as lower liquefier temperatures induced smaller spherulite sizes
and a higher crystalline volume fraction, which was reflected in an
increased tensile strength and modulus for these printed samples
[128]. Northcutt et al. (2018) determined that the filament feed
rate has a negligible impact on the crystallization kinetics of the
printed PCL [129]. PCL has been proven to be affected by chain ori-
entation and shear-induced crystallization during FFF processing by
several authors [127–129], which will be dealt with in more detail
in Section 3.2.
Dunaev et al. (2018) studied the application of a polyethylene
glycol-polycaprolactone-polyethylene glycol (PEG-PCL-PEG) triblock
copolymer in FFF utilizing screw-based extrusion. Recorded ther-
mograms of distinct printed layers revealed very similar cooling
rates and thus crystalline fraction for the different layers [35]. Both
neat PCL as well as polyhydroxymethyl glycolide-co-caprolactone
(pHMGCL) copolymers were manufactured into scaffolds by Seyed-
nejad et al. (2011). Scaffold crystallinity seemed to be very similar
to that of the non-extruded materials. The degree of crystallinity
was furthermore lowered when reducing the caprolactone ratio in
the copolymer [38].
Polyvinylpyrrolidone-vinyl acetate (PVP-VA) was blended with
polyethylene oxide (PEO) and PCL by Fuenmayor et al. (2018) to
produce solid dosage forms for drug release using FFF. The ternary
blend exhibited an endothermic melting peak coming from the
PCL fraction, as well as one smaller melting event related to the
melting of PEO [41]. Patrício et al. (2014) produced PCL/PLA blends
for scaffold manufacturing. DSC analysis demonstrated two distinct
melting peaks, one for each semi-crystalline blend constituent,
which suggests PCL and PLA are immiscible. The crystallinity of
the blend was lower compared to neat PCL by incorporation of
PLA. Furthermore, the printed scaffolds attained a higher degree
of crystallinity compared to the raw blend material as the cyclic
heating followed by slow cooling during FFF processing enables
crystallinity development [37]. A higher degree of crystallinity of
printed scaffolds compared to that of the feedstock material was
also observed by Dávila et al. (2016) [34].
Dávila et al. (2016), furthermore added β -tricalcium phosphate
(β -TCP) as a filler to a PCL matrix. The resulting composite ma-
terial showed an increased crystallization temperature and degree
of crystallinity due to the nucleating effect of the β -TCP reinforce-
ment [34]. The crystallization kinetics of both neat PCL as well as
glass-filled PCL were studied by Pires et al. (2018). Glass fillers pro-
duced a crystalline morphology with smaller spherulites and led
to an increase in crystallization temperature and rate, again illus-
trating a heterogeneous nucleation effect. However, the degree of
crystallinity for the glass-filled PCL composite was lower than that
of neat PCL. Smaller amounts of fillers can lead to enhanced crys-
tallinity due to a nucleation effect, while a larger amount of fillers
actually hinder molecular mobility and thus crystallization [130].
Zhao et al. (2020) similarly demonstrated the nucleating possibil-
ities of starch fillers added to a PCL matrix, which led to an in-
creased crystallization temperature and rate [131].
2.2.3. Other polyesters
Besides PLA and PCL, some other polyesters have also re-
ceived their, albeit rather limited, share of attention in litera-
ture. Table 7 provides an overview of the studies involving these
other polyesters. The most widely used consumer polyester is
polyethylene terephthalate (PET). As was already discussed in
Section 2.1.1 from the point of view of PP, PET has been blended
D. Vaes and P. Van Puyvelde Progress in Polymer Science 118 (2021) 101411

Table 6
Studies involving PCL.

Evaluation of Mechanical Heat treatment or adaptations

Study Material Print settings crystallinity testing to printing process

Dávila, 2016 [34] PCL CAPA 6505/β -TCP • Tliquefier : 105 °C DSC & XRD / Screw-based extrusion system.
composites • vprint : 12 mm/s (WAXS)
Dunaev, 2018 [35] PEG-PCL-PEG block copolymer / DSC / Screw-based extrusion system.
Fuenmayor, 2018 [41] PVP-VA/PCL/PEO blends • Tliquefier : 150 °C DSC / None.
• Tbuild plate : 50 °C
• vprint : 10 mm/s
Hutmacher, 2001 [36] PCL • Tliquefier : 120 °C DSC Compression None.
• Tenvironment : 25 °C tests
Liu, 2018 [127] PCL CAPA 6500 • Tliquefier : 110 °C In-situ XRD / Screw-based extrusion system.
• vprint : 0.1 mm/s (WAXS)
Liu, 2018 [128] PCL CAPA 6500 • Tliquefier : 90 - 130 °C XRD (WAXS) Tensile tests Screw-based extrusion system.
• Screw rotational
speeds: 2.5 - 10 rpm
Northcutt, 2018 [129] PCL Makerbot filament • Tliquefier : 90 - 140 °C Raman / Printing directly onto moving
• vfeed : 0.18 - 0.31 spectroscopy conveyor belt.
cm/s
Patrício, 2014 [37] PCL and PCL/PLA blend / DSC Compression None.
tests
Pires, 2018 [130] PCL and PCL/glass composite / DSC & XRD / None.
(WAXS)
Seyednejad, 2011 [38] PCL and pHMGCL • Tliquefier : 50 – 110 °C DSC / None.
• vprint : 350 - 500
mm/min
Zein, 2002 [39] PCL • Tliquefier : 125 °C DSC Compression None.
• Tenvironment : 25 °C tests
Zhao, 2020 [131] PCL Perstorp 6800/starch / DSC Tensile tests None.
composites

Table 7
Studies involving other polyesters.

Evaluation of Heat treatment or adaptations

Study Material Print settings crystallinity Mechanical testing to printing process

Chatham, 2019 [64]
Diederichs, 2019 [133]
Gnanasekaran, 2017 [137]
Ou-Yang, 2018 [138]
Wu, 2017 [135]
Wu, 2017 [136]
Yu, 2017 [134]
Zander, 2018 [132]
Zander, 2019 [69]
Zhou, 2019 [139]
PET/PP/PP-g-MA • Tliquefier : 270 °C DSC Tensile tests None.
blends • Tbuild plate : 110 °C
• vprint : 15 mm/s
PTT blends • Tliquefier : 290 °C DSC Tensile, flexural & Izod None.
• Tbuild plate : 55 °C impact tests
• vprint : 40 mm/s
PBT/CNT and • Tliquefier : 240-260 °C DSC & XRD (WAXS) / None.
PBT/graphene • Tbuild plate : 70 °C
composites • vprint : 20 mm/s
PBS/PLA blends • Tliquefier : 190 °C DSC Tensile & Izod impact None.
• Tbuild plate : room tests
temperature
• vprint : 25 mm/s
PHA/MWCNT & PHA-g- / DSC / None.
MA/MWCNT-COOH
composites
PHA/wood flour & / DSC & XRD (WAXS) Tensile tests None.
PHA-g-MA/wood flour
composites
Synthesized PPTIS / DSC Tensile, flexural & Izod None.
copolymer impact tests
Recycled and • Tliquefier : 270 °C DSC Tensile tests None.
commercial PET • Tbuild plate : 30 °C
PP/PET & PP/PS blends • Tliquefier : 260 °C DSC Tensile tests None.
from recycled plastics • Tbuild plate : 100 °C
• vprint : 50 mm/s
PBS HX-E201/Talc • Tliquefier : 135 °C DSC Tensile & flexural tests None.
composites • Tbuild plate : 95 °C
• vprint : 30 mm/s

with PP and certain compatibilizers to produce FFF feedstock
[64,69]. Zander et al. (2019) utilized both recycled PET and PP as
blend components. The resulting blends exhibited a cold crystal-
lization peak of the PET phase which becomes more pronounced
with higher PET content. However, the addition of compatibilizers
reduced the extent of PET cold crystallization as well as the crys-
tallization temperature, the latter is most likely due to a plasticiz-
ing effect of the compatibilizer, which facilitates crystallization and
chain mobility [69]. Furthermore, in earlier research, Zander et al.
(2018) compared commercial and recycled PET in terms of pro-
cessing routes, such as injection molding, filament extrusion and
FFF printing, as well as different cooling methods. Recycled PET
filament and printed samples demonstrated higher crystallization
temperatures. Moreover, it was found that the initial filament crys-
tallinity only slightly impacts the crystallinity of the final printed
part, as the FFF process is believed to heat the feedstock suffi-

14
D. Vaes and P. Van Puyvelde
ciently high above the crystallites’ melting temperature. The crys-
tallinity of a part printed with recycled PET was however consid-
erably higher compared to that of a sample printed with commer-
cial PET. This could be either explained by the already lower ini-
tial degree of crystallinity of the commercial PET or by the po-
tentially higher molecular weight of the commercial PET material
[132].
Polytrimethylene terephthalate (PTT) was modified by some au-
thors for potential application as FFF feedstock. Diederichs et al.
(2019) aimed at improving the printability of PTT by blending
with a chain extender and an impact modifier. The addition
of both components to PTT did not alter the melting tempera-
ture, yet resulted in a decreased degree of crystallinity, which
reveals the impact of both additives on the rearrangement of
PTT polymer chains as they interrupt the crystallization process
[133]. PTT-based copolyesters, polytrimethylene terephthalate-co-
isophthalate-co-seacate (PTTIS), were synthesized by Yu et al.
(2017) with varying mole percentages of sebacic acid (SA). Up to
1 mol % of SA, both Tg and Tm were found to increase with in-
creasing molar fraction of SA, while the crystallization temperature
followed an opposite direction. However, above 1 mol % of SA, the
trends are reversed. SA impacts the crystallization behavior of the
PTTIS copolyester in two ways: it serves as a longer chain to aid
crystallization and it can distort the regular packing of the poly-
mer chains thus retarding crystallization. Which of the two effects
is dominant clearly depends on the mole percentage of SA upon
synthesis [134].
Wu et al. (2017) filled polyhydroxyalkanoate (PHA) and maleic
anhydride-grafted polyhydroxyalkanoate (PHA-g-MA) with multi-
walled carbon nanotubes (MWCNTs) and chemically modified
MWCNTs with carboxyl functional groups (MWCNTs-COOH), re-
spectively. The glass transition temperature experienced an in-
crease with greater MWCNT or MWCNT-COOH content, as a higher
filler content will restrict macromolecular movement to a larger
extent. However, at too high filler concentrations, agglomeration
will counteract this effect. Both the melting point and degree of
crystallinity were also reduced by increasing the filler content. Due
to the formation of chemical bonds via a condensation reaction
between the MA group of PHA-g-MA and the COOH group of the
MWCNTs-COOH, the restriction of molecular mobility is even more
severe, resulting in the highest Tg and lowest degree of crystallinity
[135]. In later work, Wu et al. (2017) utilized identical matrix ma-
terials that were filled with wood flour to obtain composite feed-
stock. Similarly as in their earlier work, Tg increased, while Tm and
the degree of crystallinity were reduced by increasing the wood
flour content in the composites [136].
To create conductive polymer nanocomposites, Gnanasekaran
et al. (2017) added carbon nanotubes (CNTs) and graphene as fillers
to a polybutylene terephthalate (PBT) matrix. Both fillers result in
a higher crystallization temperature of the PBT matrix, yet CNTs
have been found to possess a stronger nucleation ability compared
to graphene. However, this effect levels off upon reaching a cer-
tain filler content. Furthermore, the melting point of pure PBT was
uncovered to be lower than that of the composite materials, most
likely due to a broad crystalline lamellae size distribution in the 3D
printed composite samples. On the one hand, addition of CNTs as
well as graphene leads to an enhanced degree of crystallinity com-
pared to pure PBT. On the other hand, for the PBT/CNT compos-
ite materials the degree of crystallinity reaches a maximum value
at a certain filler content. When increasing the filler content even
further, the crystalline content again decreases. A possible expla-
nation for this phenomenon is the fact that a large number of nu-
cleating filler particles can impede polymer chain movement and
thus crystal formation. Additionally, a larger filler content can lead
to agglomeration of filler particles, which again can negatively im-
pact crystallization [137].
15
Progress in Polymer Science 118 (2021) 101411
Polybutylene succinate (PBS) blended with PLA was employed
as a feedstock material in the study by Ou-Yang et al. (2018).
The utilized PLA material was amorphous. Compared to neat PBS,
blending with PLA led to a decrease in the melting point, yet a
slight increase in crystallization temperature during cooling was
observed. This is an indication that the PLA phase or the interface
between the two blend components may induce a nucleation ef-
fect. Furthermore, since the PLA material is amorphous, the crys-
talline content of PBS in the blend was reduced by increasing the
PLA fraction as a result of a dilution effect [138]. Zhou et al. (2019)
produced talc-reinforced PBS composites for FFF printing. The ad-
dition of talc resulted in an increased crystallization temperature
as a result of the heterogeneous nucleation effect induced by the
filler. The composite feedstock materials also exhibited two en-
dothermic melting peaks during DSC analysis, which are attributed
to a melting-recrystallization-remelting phenomenon [139].
2.3. Polyamides
Polyamides (PAs) are commonly referred to as nylons, which
are further classified in different types according to their chemi-
cal structure [26]. The most widely investigated polyamides for FFF
are nylon 6 and nylon 12. The studies dealing with polyamides are
summarized in Table 8.
Lay et al. (2019) compared the properties of FFF printed and
IM parts of PA 6 to those of parts manufactured from PLA and
ABS. Nylon 6 exhibited far more severe water absorption, a typ-
ical phenomenon for polyamides. However, the PA 6 parts pos-
sessed a higher degree of crystallinity than the PLA parts. It was
also found that the FFF process enhanced the crystalline content as
printed parts showed a higher degree of crystallinity compared to
IM parts, most likely due to the molecular orientation in the print
nozzle. Furthermore, PA 6 parts typically displayed greater tensile
strength and modulus as well as elongation at break than the more
commonly used PLA and ABS. The impact strength of ABS, how-
ever, was still the highest due to its amorphous character, yet ny-
lon 6 clearly possesses significantly better impact resistance than
PLA [89].
The effect of the atmosphere in which polyamides are printed
was illustrated in the study by Lederle et al. (2016). Printing of
a nylon copolymer in air seemed to result in a higher degree of
crystallinity compared to printing in an inert nitrogen gas atmo-
sphere. Crystallization appears to be limited and mechanical prop-
erties such as tensile strength are improved due to the absence
of moisture in the very dry nitrogen atmosphere [140]. Gao et al.
(2019) found no significant influence of the liquefier temperature
on the degree of crystallinity, yet a slightly reduced degree of crys-
tallinity for higher build plate temperatures when printing a ny-
lon 10/12 copolymer [141]. Moreover, the cooling rate that the ex-
truded polymer experiences after printing has been proven by de
Jager et al. (2020) to be of key importance to control part crys-
tallinity. By minimizing the difference between the extrusion tem-
perature and the environment, the printed polymer is subjected to
far slower and more gradual cooling rates that will result in more
crystal perfection [142].
Post-printing heat treatments have been proven to be effec-
tive means to relax residual thermal stresses and allow for further
crystallization. Tempering in a convection oven at 135 minutes for
3 hours at a heating rate of 3 °C/min was employed by Knoop
et al. (2015) on FFF printed nylon 12 samples. A DSC analysis on
the virgin PA 12 material demonstrated two distinct endothermic
melting peaks, which reflect the two typical crystalline phases for
PA 12, namely the α -phase and γ -phase. When heating the tem-
pered material in DSC, the degree of crystallinity was obviously
enhanced. Furthermore, it was found that the heat treatment led
to larger crystallites in a more ordered arrangement, which leads
D. Vaes and P. Van Puyvelde Progress in Polymer Science 118 (2021) 101411

Table 8
Studies involving PA.

Evaluation of Heat treatment or adaptations

Study Material Print settings crystallinity Mechanical testing to printing process

Boparai, 2016 [146] Recycled Nylon / DSC / None.

6/Al2 O3 composite
de Jager, 2020 [142] PA 12 filament • Tliquefier : 230 °C DSC & XRD (WAXS) / Slow cooling after printing at
Breathe3DP • Tbuild plate : ambient 2 °C/min or rapid cooling with
or 120 °C air.
• Tenvironment : ambient
or 120 °C
Gao, 2019 [141] PA 10/12 • Tliquefier : 200 - DSC Tensile tests None.
260 °C
• Tbuild plate : 25 - 70 °C
Jia, 2017 [145] PA 6/PEO-g-MA and PA • Tliquefier : 240 °C DSC & XRD (WAXS) Tensile & flexural tests None.
6/PEO-g-MA/PS blends • Tbuild plate : 80 °C
• vprint : 30 mm/s
Knoop, 2015 [143] FDM Nylon 12 / DSC Tensile, compression & Tempering at 135 °C for 180
Stratasys, Inc. flexural tests. minutes in convection oven at
heating rate of 3 °C/min.
Kumar, 2017 [147] PA 12 2200 from SLS / DSC Tensile tests None.
mixed with WC
Lay, 2019 [89] Nylon 6 • Tliquefier : 250 °C XRD (WAXS) Tensile & Izod impact None.
• Tbuild plate : 140 °C tests
• vprint : 60 mm/s
Lederle, 2016 [140] Nylon copolymer • Tliquefier : 263 °C DSC & XRD (WAXS) Tensile tests Printing in air and nitrogen
Taulman 910 • Tbuild plate : 50 °C gas atmosphere.
• vprint : 30 mm/s
Liao, 2018 [148] PA 12 Vestamid • Tliquefier : 250 °C DSC Tensile, compression & None.
L1670/carbon fiber • Tbuild plate : 120 °C impact tests
composites • vprint : 30 mm/s
Rahim, 2015 [149] PA 12 2200/ZrO2 /HA • Tliquefier : 230 °C DSC Tensile tests. None.
composites & PA • Tbuild plate : 110 °C
commercial filament • vprint : 90 mm/s
Taulman 618
Rahim, 2017 [150] PA 12 2200/ZrO2 /HA • Tliquefier : 200 °C DSC & XRD (WAXS) Tensile, flexural & Izod None.
composites • Tbuild plate : 110 °C impact tests
• vprint : 20 mm/s
Tantillo, 2019 [144] Markforged Tough • Tliquefier : 275 °C DSC Tensile, flexural & Annealing of printed samples
Nylon 6 copolymer • Tbuild plate : 80 °C Charpy impact tests with varied time, temperature,
• vprint : 50 mm/s pressure and cooling rate.
• Tenvironment : 40 °C
Vaes, 2019 [151] PA 6/66 random • Tliquefier : 220 - FSC / Simulation of in-situ measured
copolymers 260 °C thermal history in FSC to
• Tbuild plate : 40 - replicate printing process and
110 °C assess resulting crystallinity.
• vprint : 5.5 - 11 mm/s

to an increased energy required for melting as stronger molecu-
lar forces are acting between the chains in this ordered structure.
Tempering also benefited both tensile and flexural strengths and
moduli [143]. Likewise, Tantillo et al. (2019) found a higher degree
of crystallinity after annealing heat treatment [144].
Blending PA 6 with polyethylene-1-octene-graft-maleic anhy-
dride (PEO-g-MA) and polystyrene (PS) was discovered to impact
the overall crystallization of the PA 6 material by Jia et al. (2017).
The crystalline morphology of PA 6 demonstrated two phases,
namely the thermodynamically stable α -phase and the metastable
γ -phase. The addition of PEO-g-MA hinders regular packing of PA
6 molecular chains and decreases their mobility. Therefore, the for-
mation of metastable γ -phase is favored by higher PEO-g-MA con-
tent, accompanied by a decreased amount of α -phase. The addi-
tion of PS enhances PA 6 chain mobility due to its low viscos-
ity thus promoting the formation of thermodynamically stable α -
crystal. Although the amount of α -phase is increased by including
PS in the blend, the PA 6 content is further reduced with increas-
ing amount of PS and chain arrangement is still non-uniform thus
leading to a lower degree of crystallinity with increasing PS con-
tent [145].
Fillers are often mixed in a polyamide matrix to produce rein-
forced composite feedstock filament for FFF. Several authors have
reported studies on PA composite filaments with fillers such as
alumina (Al2 O3 ) [146], tungsten carbide (WC) [147], carbon fiber
[148], zirconia (ZrO2 ) and hydroxyapatite (HA) [149,150]. The gen-
eral trend with addition of nanofillers is an increased crystalliza-
tion temperature due to the fact that the fillers act as a nucleating
agent, yet a decreased degree of crystallinity as a result of the hin-
dering effect of nanoparticles on the chain movement, often also
reflected in an increased glass transition temperature. The incor-
poration of fillers in the polymer matrix likely destroys crystal per-
fection and thus produces smaller crystallites compared to those in
pure PA, demonstrated by a lowered melting point [146–150].
By recording the thermal history of deposited layers during FFF
using infrared thermography and implementing the resulting ther-
mal profiles in a Fast Scanning Chip Calorimetry (FSC) device, the
effect of several printing parameters as well as the feedstock’s
molecular weight on the attained crystallinity could be distin-
guished by Vaes et al. (2019). The results indicate that during the
initial phase of printing associated with high heating and cooling
rates due to the cyclic deposition of new layers onto the monitored
layer, already a substantial portion of the degree of crystallinity has
been obtained. Furthermore, a higher build plate temperature, sig-
nificantly heated above the utilized PA 6/66 copolymer’s Tg , was
found to considerably enhance the degree of crystallinity, most
likely due to an annealing effect induced by the heated build plate.
This effect is also reflected in a slightly higher degree of crys-

16
D. Vaes and P. Van Puyvelde
tallinity in a layer printed closer to the build plate, which results in
a gradient in crystallinity when moving away from the build plate.
The influence of Tbuild plate completely overshadowed the possible
impact of changing both Tliquefier and vprint on the attained crys-
tallinity. Furthermore, reducing the molecular weight of the nylon
feedstock proved to substantially increase the total degree of crys-
tallinity. This methodology thus allows to monitor the local degree
of crystallinity as a function of the experienced thermal history at
different points in time [151].
2.4. High-performance thermoplastics
2.4.1. Polyetheretherketone
A remarkable thermal and chemical resistance combined with
excellent mechanical properties make polyaryletherketones, such
as PEKK and PEEK, interesting feedstock materials for high-end ap-
plications and functional parts [61]. PEEK is by far the most exten-
sively used and studied material for FFF within this polymer fam-
ily, as is reflected by Fig. 2. Several studies have investigated the
effect of printing process parameters on the final part crystallinity
and resulting mechanical properties of PEEK parts and are summa-
rized in Table 9.
Of all printing parameters, the liquefier temperature has been
found to impose the strongest influence on crystallinity during
printing, since an increased Tliquefier provides the printed PEEK
with more energy and additional heating time to crystallize or can
lead to deterioration of polymer chains which facilitates crystal-
lization. Hence, this results in a higher degree of crystallinity of
the printed part. Both tensile strength and Young’s modulus fol-
low the trend of crystallinity, whereas a higher crystallinity dras-
tically lowers breaking elongation [152–154]. Print speed on the
other hand was identified to have an almost negligible effect on
part crystallinity by some authors, where differences in mechan-
ical performance of parts manufactured at different print speeds
are connected to a higher degree of porosity and defects induced
by the printing process, which is enhanced by higher print speeds
[46,152]. However, Wang et al. (2019) noticed a reduced crys-
tallinity at higher print speeds, which they attributed to shorter
contact times [153]. Samples printed in a temperature-controlled
environment exhibit higher degrees of crystallinity with increas-
ing Tenvironment , where crystallinity grows from 17 to 31 % for a
PEEK sample printed at Tenvironment of 25 and 200 °C, respectively,
as was studied by Yang et al. (2017). Similar results were obtained
by Wang et al. (2019) who showed a considerable enhanced crys-
tallinity by printing in a heated chamber [155]. Dependent on the
value of Tenvironment relative to PEEK’s Tg , the printed sample ex-
periences either non-isothermal (Tenvironment < Tg ) or isothermal
crystallization (Tenvironment > Tg ), where the latter provides more
energy and time to improve the crystallinity of the PEEK sam-
ple, thus resulting in a higher degree of crystallinity. Similarly as
for Tliquefier , tensile strength and Young’s modulus increase corre-
sponding to a higher degree of crystallinity associated with higher
Tenvironment . Young’s modulus can even achieve values similar to
those for molded PEEK, whereas the tensile strength of printed
samples still lies below that of molded parts due to defects caused
by printing [154].
Typically, printed PEEK samples exhibit cold crystallization
when heated in DSC as a result of incomplete crystallization due
to the rapid cooling rates in the FFF process. Hence, the degree of
crystallinity of printed parts is, in general, considerably lower com-
pared to that of the filament feedstock material due to possible
orientation effects upon feedstock filament extrusion [46,153,156].
However, Basgul et al. (2018) did not observe a significant dif-
ference in crystalline microstructure between the filament feed-
stock and printed parts, and furthermore, the top and bottom lay-
ers of the printed parts with reference to their location relative
17
Progress in Polymer Science 118 (2021) 101411
Fig. 6. The temperature variations in the heat treatment methods investigated by
Yang et al. (2017). [154], Copyright 2017. Reproduced with permission from Elsevier
Science Ltd.
to the build plate showed a negligible difference in crystallinity
[46]. Using a screw-based extrusion mechanism, Tseng et al. (2018)
printed with PEEK in pellet form and noticed a substantially higher
crystallinity of the printed parts compared to the pellet feedstock
material, probably due to stretching and alignment effects in the
extruder mechanism during printing, reaching a degree of crys-
tallinity in the printed parts close to the maximum value of 35 to
39 % for PEEK [157]. These effects will be discussed in more detail
in Section 3.2.
Annealing as a post-printing heat treatment has been proven to
be an effective way to further increase printed part crystallinity
and allows for relaxation of residual thermal stresses. The in-
creased degree of crystallinity is reflected in a reduced cold crys-
tallization peak upon reheating in DSC which decreases for higher
annealing temperatures, as well as a shift in Tg towards a higher
temperature due to a weakened mobility of the polymer chains as
they are more anchored in crystalline regions. Annealed samples
even exhibited two endothermic melting peaks: one corresponding
to secondary crystallization of a minor phase during annealing and
the other corresponding to the regular melting peak of the major
phase. As a result of increased crystallinity and relieved thermal
stresses, both tensile and impact strength and Young’s modulus are
enhanced, yet breaking elongation is considerably reduced, result-
ing in a significant loss of ductility [152,155,157,158]. Yang et al.
(2017) also investigated the effect of other heat treatments besides
annealing on the resulting printed part crystallinity and mechan-
ical performance. The temperature variations in the different heat
treatment methods are displayed in Fig. 6. Among these heat treat-
ment methods, furnace cooling and annealing result in the highest
degree of crystallinity, followed by tempering, where the cooling
down stage before heating might impact crystal size and struc-
ture and therefore lower the final crystallinity. Both air cooling
and quenching lead to far lower degrees of crystallinity as here,
the printed parts are cooled down too rapidly to allow for suffi-
cient crystallization. The trend in crystallinity is also reflected in
terms of mechanical properties, such as tensile strength and elas-
tic modulus. However, furnace cooling, which results in quite a
high degree of crystallinity, produces parts with tensile properties
that are rather comparable to parts produced with air cooling. This
is a direct consequence of the slow cooling stage during furnace
cooling, which will lead to shrinkage distortion and a build-up of
residual thermal stresses and therefore, weaker mechanical perfor-
mance [154].
Some authors have made interesting modifications to the gen-
eral FFF setup for PEEK printing which directly affect part crys-
D. Vaes and P. Van Puyvelde Progress in Polymer Science 118 (2021) 101411

Table 9
Studies involving PEEK.

Evaluation of Heat treatment or adaptations

Study Material Print settings crystallinity Mechanical testing to printing process

Basgul, 2018 [46] OPTIMATM LT1 medical • Tliquefier : 390 - XRD (WAXS) & FTIR Compression, None.
grade PEEK 410 °C compression-shear &
• Tbuild plate : 100 °C torsion tests
• vprint : 16.7 - 50
mm/s
Berretta, 2017 [162] PEEK 450G & CNT • Tliquefier : 365 °C DSC Tensile tests & Short None.
Plasticyl PEEK 101 • Tbuild plate : 300 °C beam stress tests
• vprint : 30 mm/s
El Magri, 2020 [152] VESTAKEEP 3300G • Tliquefier : 380 - DSC Tensile tests Annealing at 200, 250 &
PEEK 420 °C 280 °C in DSC for 2 h.
• Tbuild plate : 100 °C
• vprint : 20 - 40 mm/s
• Tenvironment : 30 °C
Gong, 2019 [158] PEEK non-medical • Tliquefier : 420 °C / Izod impact tests None.
grade • Tbuild plate : 80 °C
• vprint : 20 mm/s
Hu, 2019 [159] PEEK filament from • Tliquefier : 385 °C XRD (WAXS) Tensile and bending Print nozzle adapted with heat
Sting3D Technology • Tbuild plate : 135 °C tests collector module and
Co. Ltd. • vprint : 25 mm/s high-power heater.
• Tenvironment : 60 °C
Luo, 2018 [160] PEEK 450G • Tliquefier : 410 °C DSC Short beam shear tests CO2 laser for local heating of
• vprint : 6 mm/s printed layer during
deposition.
Rinaldi, 2018 [156] PEEK 450PF • Tliquefier : 400 °C XRD (WAXS) & DSC Tensile tests None.
• Tbuild plate : 100 °C
• vprint : 20 mm/s
Tseng, 2018 [157] PEEK 90G & 450G • Tliquefier : 370 - XRD (WAXS) & DSC Tensile & compression Screw-based extrusion system
390 °C tests using pellet feedstock.
• Tbuild plate : 280 °C Annealing of sample at 200 °C
• vprint : up to 370 for 4 h.
mm/s
Vaezi, 2015 [161] PEEK 450G • Tliquefier : 430 °C / Tensile tests None.
• Tbuild plate : 130 °C
•Extrusion flow rate:
2.2 mg/s
• Tenvironment : 80 °C
Wang, 2019 [153] PEEK 450G • Tliquefier : 380 - / Tensile tests None.
440 °C
• Tbuild plate : 280 °C
• vprint : 17 - 26 mm/s
• Layer thickness: 0.1
- 0.5 mm
Wang, 2019 [155] Apium PEEK 450 • Tliquefier : 400 °C DSC & XRD (WAXS) Tensile, compression & Three different printers are
Natural filament • Tbuild plate : 100 °C flexural tests compared. Annealing at 160 °C
• vprint : 20 mm/s for 30 minutes, followed by
• Tenvironment : ambient 200 °C for 2 h and then
or 145 °C cooling to room temperature.
Yang, 2017 [154] PEEK 450G • Tliquefier : 360 - DSC Tensile tests Several heat treatments are
480 °C applied after printing,
• vprint : 40 mm/s including: air cooling, furnace
• Tenvironment : 25 - cooling, quenching, annealing
200 °C & tempering. For details, see
text.

tallinity. Hu et al. (2019) have equipped their print head with a
heat collector module and a high-power heater. This heat collector
module plays three important roles: it reduces heat loss through
air convection, it prevents residual heat being transferred from the
nozzle to the throat pipe preventing nozzle blockage and it pre-
melts the deposited layer enhancing layer adhesion. In terms of
crystallinity, printing with the heat collector module was found to
provide the same effect as a heat treatment [159]. Furthermore,
by employing a CO2 laser with varying power, Luo et al. (2018),
were able to locally alter the temperature of the interlayer bond-
ing point between two successively deposited layers. By increas-
ing laser power, the local temperature rose from below Tg to a
value between Tg and Tm of the PEEK material. This not only re-
duced cold crystallization upon reheating of these samples in DSC
to be hardly noticeable, but enhanced the degree of crystallinity to
almost 35 % as well. Unlike environmental heat control or post-
printing heat treatments, the laser-assisted process permits very
localized control of crystallinity, which can open up possibilities to
tune part crystallinity in different regions in the printed part [160].
A local difference in crystallinity does, besides impacting me-
chanical performance, alter the visual appearance of the printed
PEEK part, which becomes apparent as a color difference, where
darker regions are more amorphous. This color difference can,
however, be eliminated through annealing [161]. It should be noted
that the addition of fillers such as carbon nanotubes can lead to
a shift of both the crystallization and melting temperature of the
PEEK material to higher temperatures as was found by Berretta
et al. (2017) [162].
2.4.2. Polyphenylene sulfide
Polyphenylene sulfide is another high-performance thermoplas-
tic with outstanding mechanical performance that combines both

18
D. Vaes and P. Van Puyvelde
Table 10
Studies involving PPS.
Study Material Print settings
El Magri, 2019 [163] PPS filament from • Tliquefier : 320 -
FILOALFA 350 °C
• Tbuild plate : 65 °C
• Tenvironment : 30 °C
Fitzharris, 2019 [166] PPS monofilament • Tliquefier : 290 °C
• Tbuild plate : 80 °C
Geng, 2018 [164] PPS A900 • Tliquefier : 285 °C
• vprint : 11.3 mm/s
Kishore, 2018 [165] PPS / DSC
excellent chemical and thermal resistance, as well as resistance
to radiation, and is more easily processed than PEEK [61]. How-
ever, studies involving PPS have been far less common compared
to those concerning PEEK. The most important studies that look
into PPS printed parts and their crystallinity are listed in Table 10.
A higher liquefier temperature was again found to increase the
degree of crystallinity as well as the tensile strength of printed
specimens [163]. Furthermore, printed samples exhibit cold crys-
tallization when reheated during DSC analysis, which reveals in-
complete crystallization during printing [163,164]. However, this
cold crystallization can be removed by annealing the printed parts
as was performed by Geng et al. (2018). First of all, parts printed
with air-forced cooling were found to be significantly less crys-
talline compared to naturally cooled samples. PPS parts printed
with air-forced cooling were annealed at distinct temperatures for
100 minutes. The cold crystallization peak diminished or even dis-
appeared and degrees of crystallinity rose with increasing anneal-
ing temperatures. Due to a higher degree of crystallinity, sam-
ples annealed at higher temperatures exhibit far greater tensile
strength and elastic modulus, yet are more brittle and have lost
ductility, also reflected in a weakened impact resistance [164].
However, higher annealing temperatures can result in oxidative
cross-linking with formation of a greater number of C-O bonds,
which is indicated by a widening of the melting peak and a dis-
coloration of the material. The oxidative cross-linking was con-
firmed by Fourier Transform Infrared Spectroscopy (FTIR) analysis
[164,165]. The higher crystallization onset temperature and peak
crystallization temperature of annealed samples indicate enhanced
crystal formation of the polymer from the melt state, which can
be explained by the introduction of new nucleation sites by the
structural change as a result of cross-linking reactions [165].
Fitzharris et al. (2019) utilized both DSC and FSC to analyze the
crystallinity of PPS material for FFF, as well as the mobile and rigid
amorphous fractions, MAF and RAF, respectively. The crystalline
morphology can be seen as a two phase system with a crystalline
and amorphous phase. The MAF corresponds to the part of the
amorphous phase that retains its full mobility, whereas the RAF
refers to chains in the amorphous phase that experience a con-
siderably decreased mobility as they are hindered by surrounding
crystalline phase. DSC was employed to check printed part crys-
tallinity, again revealing cold crystallization. Annealing studies are
performed with both DSC and FSC at 85, 90 and 95 °C, correspond-
ing to the onset, midpoint and endpoint of the glass transition of
PPS, respectively. Further annealing studies apply even higher tem-
peratures of 100, 110 and 120 °C to test possible envelope tem-
peratures of the printing process and to check whether isother-
Progress in Polymer Science 118 (2021) 101411
Evaluation of Heat treatment or adaptations to
crystallinity Mechanical testing printing process
DSC Tensile tests None.
DSC & FSC / Annealing at temperatures ranging
from 85 to 120 °C for 5 minutes in
both DSC and FSC. Successive
deposition of layers during printing
replicated in FSC.
DSC Tensile tests & Izod Both air forced cooling and natural
impact tests cooling are applied. Annealing
performed at temperatures ranging
from 130 to 240 °C for 100 minutes.
Tensile tests Isothermal annealing at 250 °C in
furnace in air for 18 h.
mal crystallization can occur. Besides reducing the cold crystalliza-
tion peak, higher annealing temperatures lead to higher degrees
of crystallinity, consequently reducing MAF and increasing RAF. To
mimic the printing process with its typical subsequent heating and
cooling cycles at high heating and cooling rates, corresponding to
the successive reheating of a printed layer by deposition of new
layers, a cyclic thermal protocol with decreasing temperatures was
applied in the FSC device. The degree of crystallinity and RAF in-
creased, and thus MAF decreased, with a growing number of cy-
cles. This allows to illustrate the effect of the thermal history ex-
perienced by the part during printing on the resulting crystallinity
[166].
2.5. Other semi-crystalline polymers
Some other semi-crystalline polymers have been studied for
their application with FFF. Table 11 sums up these studies.
2.5.1. Polyvinylidene fluoride
Polyvinylidene fluoride (PVDF) is a semi-crystalline polymer
with a piezoelectric response which can lend itself to sensing, ac-
tuation or energy harvesting applications. Momenzadeh et al. uti-
lized FTIR as a tool to evaluate the crystalline β -phase content in
processed PVDF, which is directly related to its piezoelectric re-
sponse. To investigate the effect of the different processing stages
on the β -phase content, a sample at each stage of the process-
ing route, going from the raw pellet material to extruded fila-
ment feedstock and FFF printed parts, is analyzed with FTIR. The
amount of crystalline β -phase in the printed samples was found
to be about three times that for the raw pellet material and 39
% higher than that in the feedstock filament. Both the large pres-
sure and associated stresses, as well as the higher temperatures
at the nozzle tip during FFF printing are most likely the reason
for this increased β -phase content. Furthermore, to evaluate the
effect of certain printing parameters on β -phase content, Momen-
zadeh et al. varied infill density and pattern, layer thickness and
nozzle diameter and analyzed the printed samples with FTIR. The
printed samples acquired a higher amount of crystalline β -phase
when printed with higher infill density and smaller layer thickness
and nozzle diameter. The infill pattern was found to have a negli-
gible effect [167,168].
2.5.2. Thermoplastic polyurethane
Thermoplastic polyurethanes (TPUs) combine flexible and rigid
chain segments or blocks, where the flexible segments provide the
polymer with an elastomeric character, while the rigid segments
19
D. Vaes and P. Van Puyvelde Progress in Polymer Science 118 (2021) 101411

Table 11
Studies involving other semi-crystalline polymers.

Evaluation of Heat treatment or adaptations

Study Material Print settings crystallinity Mechanical testing to printing process

Haryńska, 2019 [169] PCL-based TPU / DSC / None.

Momenzadeh, 2018 [167]
Momenzadeh, 2020 [168]
Ni, 2017 [171]
Rigotti, 2018 [172]
Schimpf, 2019 [170]
PVDF Kynar 740 • Tliquefier : 220 °C FTIR / None.
• Tbuild plate : 100 °C
• vprint : 15 mm/s
• Infill density: 75 -
100 %
• Infill pattern:
concentric,
honeycomb, rectilinear,
grid & triangles
• Layer thickness:
0.05 - 0.2 mm
• ∅nozzle : 0.2 - 1 mm
PVDF Kynar 740 • Tliquefier : 220 °C FTIR Tensile tests None.
• Tbuild plate : 105 °C
• vprint : 15 mm/s
PVA 0588 blended / DSC & XRD (WAXS) Tensile tests None.
with urea/caprolactam
or urea/formamide
mixtures
PVA Mowiflex TC • Tliquefier : 230 °C DSC Tensile tests None.
232/CNT composite • Tbuild plate : 40 °C
• vprint : 40 mm/s
Synthesized TPHU • Tliquefier : 190 °C DSC & XRD (SAXS) / Samples stored at room
filament • Tbuild plate : 50 °C temperature or at elevated
temperatures (50, 70 or 80 °C)
in oven for 24 h.

supply additional strength as a result of hydrogen bonds between
the urethane groups. A medical-grade TPU based on PCL diol has
been synthesized by Haryńska et al. (2019). Upon heating in DSC,
the material exhibited three distinct melting peaks. The first two,
at lower temperatures, can be attributed to the melting of the soft
segments, while the third one reflects the melting of the strong
hydrogen bonded chains of the hard segments. When cooled, the
sample shows two crystallization peaks, one for each segment type
[169]. Schimpf et al. (2019) synthesized thermoplastic polyhydrox-
yurethanes (TPHUs) which were found to print without noticeable
warpage and with excellent adhesion to the build plate. More-
over, annealing of the TPHU material benefited the degree of crys-
tallinity [170].
2.5.3. Polyvinyl alcohol
Poly(vinyl alcohol) (PVA) is another possible semi-crystalline
feedstock material for FFF that is water-soluble and biodegrad-
able. Ni et al. (2017) blended PVA with urea/caprolactam and
urea/formamide mixtures and found a decreasing degree of crys-
tallinity of the PVA matrix with increasing amount of added mix-
ture. Since urea, caprolactam and formamide can form hydrogen
bonds with the hydroxyl groups in PVA, intermolecular hydrogen
bonding in the PVA material is replaced by these hydrogen bonds
which inhibits crystallization. This effect is stronger at higher con-
centration of the added mixtures. The urea/caprolactam mixtures
affected crystallization ability to a larger extent compared to the
urea/formamide mixtures, as the latter form less stable hydrogen
bonds with PVA. Furthermore, the addition of the urea/caprolactam
mixture lowered the melting point of the material due to this hy-
drogen bond replacement as well as a lubricating effect, increas-
ing the intermolecular distance between the PVA molecules [171].
Rigotti et al. (2018) reinforced PVA with carbon nanotubes (CNT)
to produce composite feedstock material for FFF. The introduction
of nanofillers shows the typical increase in crystallization tempera-
ture, which indicates CNTs act as a nucleating agent, yet the degree
of crystallization is lowered with incorporation of CNTs [172].
3. Specific phenomena related to the use of semi-crystalline
feedstock for FFF
3.1. Insufficient melting and self-nucleation
The liquefier in the print head of the FFF printer serves to heat
up the incoming thermoplastic filament preferably to the set liq-
uefier temperature, Tliquefier . The feedstock material is heated by
thermal contact with the heated liquefier wall, which is necessary
to sufficiently reduce the material’s viscosity to allow for optimal
extrusion [173]. Heat is conducted from the wall of the liquefier
tube to the filament as it moves through the print head. The liq-
uefier wall itself is typically heated using a resistively heated coil
embedded in a metal block [174]. The pressure drop or extrusion
force that is required to attain a desired volumetric flow rate of
polymer extrudate is directly proportional to the polymer’s viscos-
ity. If, however, the viscosity is not adequately decreased due to
Tliquefier being set too low or due to insufficient heat transfer in the
liquefier, the required extrusion pressure or force can exceed the
maximum system pressure or extrusion force of the FFF machine.
This could lead to an inadequate extrudate flow rate or even print
nozzle clogging. The maximum system pressure or extrusion force
is related to the feedstock filament’s stiffness and geometry as well
as the maximum torque that can be applied by the driving motors
of the pinch roller wheels of the feed system [175]. Thus a certain
minimal or threshold temperature exists at which the maximum
extrusion force or pressure is reached [176,177]. This poses one of
the main rate limitations of FFF printing, since faster printing re-
quires a higher throughput rate of filament through the liquefier.
Hence, the residence time of the filament in the heated section of
the print head is considerably reduced which can lead to an insuf-
ficient reduction in feedstock viscosity and thus an increase in the
required force for extrusion [174,176]. This is illustrated by Fig. 7
where it can be clearly seen that the required extrusion force in-
creases with increasing filament feed rates. Furthermore, for all ap-
plied liquefier temperatures a maximum extrusion force is reached

20
D. Vaes and P. Van Puyvelde
Fig. 7. The variation of the extrusion force as a function of filament feed rate for
different liquefier temperatures. [174], Copyright 2017. Reproduced with permission
from Elsevier Science Ltd.
at some point, yet for lower Tliquefier this maximum is already at-
tained at lower feed rates [174].
Indeed, it has been extensively reported in literature that of-
ten a clear discrepancy between the set liquefier temperature and
the actual extrusion temperature, i.e. the temperature of the poly-
mer extrudate, can be observed, both experimentally as well as
from results of numerical simulations. Experimental observations
of the extrusion temperature are mostly performed by either ther-
mocouple measurements [107,115,178–180] or by utilizing IR ther-
mography [[151],181–183]. Most studies have found that the ac-
tual extrusion temperature was several tens of degrees lower than
the set liquefier temperature. Sometimes a temperature difference
of almost 50 °C could even be observed [182]. The difference be-
tween the liquefier set point and the extrudate temperature was
also found to be worsened by increasing the print speed and thus
the filament feed rate, as this considerably shortens the filament’s
residence time in the liquefier [179]. Numerical models can also
be of great significance in studying the heat transfer and flow in-
side the liquefier and can be utilized as a predictive tool to ana-
lyze the liquefier’s heat transfer performance. Many authors have
modeled the internal heat transfer and flow inside an FFF print
head, although most studies focus on amorphous feedstock poly-
mers [153,174,176,180,182,184–188]. In the work of Go et al. (2017),
a heat transfer model of a FFF liquefier is constructed by finite el-
ement analysis. Fig. 8a provides a schematic overview of the lique-
fier geometry, indicating three distinct zones: (I) the liquefier tube,
(II) the constriction zone and (III) the print nozzle. The tempera-
ture distributions alongside the liquefier which are calculated from
their model are demonstrated in Fig. 8b. At higher filament feed
rates, the set liquefier temperature is clearly not able to fully pen-
etrate the core of the filament feedstock. Radial temperature gra-
dients in the material can be observed. Fig. 8c shows the polymer
feedstock temperature at the centerline of the liquefier for differ-
ent build rates at distinct distances from the liquefier inlet. There-
fore, if the feedstock material is not sufficiently heated to a desired
or adequate temperature for extrusion before it reaches the print
nozzle, the required extrusion force might become too large or the
system will clog [174].
As was mentioned before, the allowable filament feed rate and
thus print speed are directly related to the efficiency of the heat
transfer in the liquefier. Higher print speeds have been found to
lead to an increase in the required extrusion force due to a reduced
residence time of the extruded material in the liquefier. Hence,
when increasing the set Tliquefier , higher print speeds can be ob-
tained as the heat transfer will be faster in that case [176]. Heat
21
Progress in Polymer Science 118 (2021) 101411
transfer can further be improved by altering the print head design.
The liquefier section should be long enough to allow for sufficient
heat transfer, even at elevated feed rates [174,188]. The nozzle an-
gle, indicated by the angle β in Fig. 8a, is another design parame-
ter that influences the flow and heat transfer in the liquefier. An
increasing nozzle angle has been found to decrease the melting
rate [185]. Some authors have proposed or tested certain modi-
fications to the print head or print setup which could drastically
improve heat transfer. Jerez-Mesa et al. (2018) studied the effect of
the heatsink design on the liquefier temperature and found that a
helical heatsink showed optimal performance [189]. Go and Hart
(2017) were able to significantly speed up the FFF process by pre-
heating the incoming filament feedstock with a laser and hence
overcoming heat transfer related build rate limitations. Printing
with the modified setup was about 10 times faster than with a
standard commercial FFF printer [190]. Mackay has proposed to in-
corporate a torpedo, which is a design originating from IM manu-
facturing, in the FFF liquefier. This is a solid cylinder with profiled
ends that sits in the center of the liquefier tube and pushes the
melt to the liquefier wall to improve heat transfer and simultane-
ously generate heat through viscous dissipation as the melt flows
through the annular opening between the liquefier wall and tor-
pedo [173]. It should also be noted that fouling of the liquefier wall
can occur due to an accumulation of degraded material. This will
considerably lower the effective wall temperature and thus reduce
the thermal driving force for heat transfer to the feedstock filament
[182].
Most of the studies that deal with heat transfer in the lique-
fier mainly focus on amorphous feedstock materials. When heated
sufficiently above their glass transition temperature, the viscosity
of amorphous thermoplastics can be drastically reduced to allow
for effective extrusion and printing of these feedstock materials.
As mentioned in the discussion above, if heat transfer is inad-
equate and the set liquefier temperature is not achieved by the
filament, the required extrusion force or pressure drop will be
larger and in severe cases nozzle clogging can occur. However, for
semi-crystalline polymers, the material’s viscosity is only consid-
erably reduced when heated above its melting point after which
the resulting melt can be extruded. If the heated liquefier is un-
able to completely heat up the whole filament feedstock mate-
rial high enough above its melting temperature or keep the mate-
rial long enough above this temperature, some crystallites in the
semi-crystalline feedstock material may remain unmelted. These
unmelted crystallites can act as nucleation sites for crystallization
than can occur when the extruded polymer is deposited and cools
down. This phenomenon is termed self-nucleation or self-seeding.
Starting from a solid semi-crystalline feedstock material and de-
pending on the achieved self-nucleation temperature Ts upon heat-
ing in the liquefier, three distinct self-nucleation domains can be
distinguished. Fig. 9 provides a schematic molecular representa-
tion of the three self-nucleation domains denoted as DI , DII and
DIII . Domain I (DI ) or the melting domain occurs when complete
melting of the polymer is achieved and all crystalline memory of
the polymer is erased. This is the case when a homogenous melt
is formed that consists of isotropic random coils. This can only be
achieved at temperatures that are sufficiently high above the poly-
mer’s peak melting temperature when held at this temperature for
an ample amount of time. Domain II (DII ) or the self-nucleation
domain is characterized by the formation of self-nuclei. The em-
ployed self-nucleation temperature is then low enough to produce
these self-nuclei, yet still high enough to avoid annealing. The self-
nuclei originate from certain precursors. Depending on Ts , these
precursors take on different forms. For lower Ts , still within the
second domain, Ts is high enough to melt almost all of the poly-
mer, yet low enough so that some smaller crystal fragments re-
main which then act as self-nuclei. On the other hand, for higher
D. Vaes and P. Van Puyvelde
Fig. 8. The utilized liquefier geometry and results from the finite element analysis model of the liquefier heat transfer by Go et al. (2017) with (a) a schematic diagram
of the liquefier geometry, (b) the calculated temperature distributions in the liquefier for different volumetric flow rates, and (c) the polymer feedstock temperature at the
liquefier centerline for different build rates at distinct distances from the liquefier inlet. [174], Copyright 2017. Adapted with permission from Elsevier Science Ltd.
Fig. 9. The different self-nucleation domains DI, DII and DIII and their schematic
molecular representation. [192], Copyright 2015. Reproduced with permission from
Elsevier Science Ltd.
Ts in domain DII , the melt can retain some residual segmental ori-
entation, or so-called crystalline memory, which can again produce
self-nuclei. Domain III (DIII ) or the self-nucleation and annealing
domain occurs when Ts is low enough to result in partial melting
while the unmelted crystals can anneal into thicker crystals. When
a polymer sample is cooled down from a temperature within the
self-nucleation domain, the drastic increase in nucleation density
results in an exponential increase in the number of spherulites
that are formed. However, their size is reduced, since they im-
pinge on one another before growing. Thus the resulting crystalline
morphology is considerably altered by self-nucleation [191,192].
Self-nucleation drastically enhances the crystallization rate, as self-
nuclei are far more effective than any other heterogenous nucleat-
ing agent [193–195].
Very few studies concerning semi-crystalline feedstock for FFF
have considered the phenomenon of self-nucleation. Northcutt
et al. (2018) have proposed self-seeding as a possible explanation
for the observed enhanced crystallization kinetics at lower lique-
fier temperatures. Lower liquefier temperatures might not com-
pletely melt all crystallites which can then act as nucleation sites
upon cooling [129]. In the studies on PEEK by Yang et al. (2017)
22
Progress in Polymer Science 118 (2021) 101411
and Wang et al. (2019) a range of liquefier temperatures are tested
and the resulting printed part crystallinity is determined. Starting
from the lowest liquefier temperature, the degree of crystallinity
initially decreases with increasing liquefier temperature. The au-
thors explain this reduction by the incomplete melting of some
crystallites in the liquefier due to a lower and non-uniform tem-
perature inside the liquefier [153,154]. Liu et al. (2018) observed
a small amount of PCL crystal nucleation that occurred before the
polymer melt entered the nozzle section of the print head. How-
ever, this is most likely due to a partial undercooling of the PCL
melt as it travels from the extruder head to the nozzle and cannot
really be attributed to a self-nucleation effect [127].
3.2. Orientational effects and flow-induced crystallization
Once the filament feedstock material’s viscosity is sufficiently
reduced by thermal contact with the liquefier walls, the result-
ing polymer melt will be pushed into the conical constriction zone
and further through the capillary of the print nozzle for extrusion.
While the material is pushed through the print nozzle, the poly-
mer melt will experience a certain shear rate or range of shear
rates, depending on the location of the melt in the print head.
The local shear rate is directly related to the velocity of the poly-
mer melt at that location in the print head and this velocity is
directly proportional to the pressure drop between the inlet and
outlet [196]. The pressure drop that needs to be overcome for ex-
trusion is also dependent on the print nozzle design, as increas-
ing the nozzle diameter can significantly reduce the pressure drop
and thus the shear rate experienced by the polymer melt [187,197].
Moreover, the pressure drop can also slightly be altered by chang-
ing the nozzle angle, since smaller nozzle angles typically result
in a larger pressure drop [187]. Typical shear rates reported for
FFF printing vary between roughly 100 s−1 and 10 0 0 s−1 , although
sometimes even higher shear rates are mentioned in literature. A
typical apparent shear rate in the nozzle’s capillary is about 500
s−1 [129,173,177,182,197]. These shear rates lie well within the non-
Newtonian regime for all polymers. Hence, as a result of the expe-
rienced shear rates, macromolecular chains can orient and align in
the direction of flow [173,177,198].
These orientational effects can influence the microstructure of
the extrudate. For example, in the case of polymer blends that
are employed as feedstock material, the orientation imposed by
D. Vaes and P. Van Puyvelde
Fig. 10. The evolution of the blend morphology upon printing of a TPU/PLA blend as studied by Leng et al. (2019). [199], Copyright 2019. Reproduced with permission from
American Chemical Society.
the shear flow in the print nozzle can alter the blend morphol-
ogy upon deposition. Leng et al. (2019) studied a feedstock blend
of TPU and PLA in pellet form to be printed with a screw-based ex-
trusion mechanism. The morphology evolution during the printing
process is schematically visualized in Fig. 10. The initial morphol-
ogy can be seen as PLA droplets that are dispersed in a TPU ma-
trix. While flowing through the nozzle, the PLA droplets are elon-
gated. Upon extrusion through the print nozzle, the PLA droplets
are further elongated into microfibers as a result of the shear flow
deformation. Due to the formation of these PLA microfibers, the
tensile strength and Young’s modulus are considerably enhanced,
yet a good elongation at break can be retained at the same time
[199]. A similar morphological evolution was observed by Wang
et al. (2019) during their study of a PLA/TPU blend, which clearly
demonstrated elongation of the TPU minor phase into fibers upon
extrusion [121]. Jiang et al. (2020) and Zhou et al. (2017) respec-
tively studied blends of PP with polystyrene (PS) and polycarbon-
ate (PC) as minor phases. Both observed the in-situ formation of
microfibers due to the imposed shear rate upon deposition, which
are highly beneficial for the mechanical properties of the result-
ing printed part. An increased print speed was furthermore found
to significantly enhance microfiber formation as the shear flow de-
formation is more severe in that case, which was reflected in im-
proved tensile properties for parts printed at higher vprint [73,200].
Moreover, it should be noted that besides the minor phase in
blends, reinforcing fibers in composite feedstock can orient in the
direction of flow as well. The alignment and orientation of fibers
upon shear deformation in the print nozzle can also impact the
mechanical properties [201].
In general, orientation of polymer chains as a result of the
extrusion step during the FFF process can affect the mechanical
performance of the printed parts. It has been proven that if the
macromolecular chain orientation can be retained after deposition,
the resulting anisotropy in mechanical properties will lead to im-
proved mechanical properties such as elastic modulus and ten-
sile strength [113,152,154]. However, the extrusion-induced orien-
tation can also be relaxed after deposition. With increasing build
plate temperature or residence time on the build plate, polymer
chain mobility is enhanced and thus relaxation can occur more
easily, hence orientation can get lost [104]. Annealing after print-
ing can provide a similar effect [173]. Orientation and alignment
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Progress in Polymer Science 118 (2021) 101411
of chains under shear flow leads to a more ordered chain con-
figuration, which consequently can considerably facilitate and en-
hance crystallization [73,113,157,202]. Liu et al. (2018) observed the
formation of PCL crystals during FFF printing, which are oriented
parallel to the extrusion flow direction [127]. In some other work,
Liu et al. (2018) detect clear anisotropy in the extruded PCL poly-
mer when deposited from the print nozzle. This is a direct result
from the orientation imposed during shear flow upon extrusion.
Especially at lower processing temperatures, this orientation can-
not be relaxed, which is reflected in higher levels of anisotropy
in samples produced at lower liquefier temperatures. Higher lev-
els of anisotropy and crystal orientation have been found to lead
to improved mechanical performance such as an enhanced Young’s
modulus [128]. De Jager et al. (2020) reported a clear orientation
of nylon 12 polymer chains parallel to the filament direction in the
flow field during filament production. The oriented chains then act
as row nuclei for subsequent lamellar growth [142]. The set lique-
fier temperature can also impact the resulting crystalline morphol-
ogy after orientation upon extrusion as was found by Tojeira et al.
(2014). At sufficiently high Tliquefier , orientation can be more easily
relaxed due to enhanced molecular mobility thus a more isotropic
crystalline distribution is achieved. If, however, some orientational
melt memory is retained, this will impact the growth direction of
the lamellar crystals [203].
It is therefore obvious that both the crystallization rate, degree
of crystallinity and resulting crystalline morphology, as well as
the resulting mechanical properties can be influenced by the im-
posed shear flow on the polymer melt. This phenomenon is termed
flow-induced or shear-induced crystallization. Flow-induced crys-
tallization (FIC) is highly dependent on the high molecular weight
fraction of the molecular weight distribution, since only polymer
chains above a certain critical orientation molecular weight can
form oriented structures that remain stable at higher temperatures
above the melting point. These oriented structures act as precur-
sors or flow-induced nuclei, which are obviously limited in their
number, since the amount of chains above the critical molecu-
lar weight can become exhausted. The development of the ori-
ented shear-induced precursors furthermore depends on the de-
formation rate that is experienced by the polymer melt [25]. This
flow strength can be quantified by dimensionless numbers such
as the Deborah number De and the Weissenberg number W i. In
D. Vaes and P. Van Puyvelde
Fig. 11. A schematic representation of the different flow regimes and resulting crys-
talline morphologies in flow-induced crystallization. [25], Copyright 2013. Repro-
duced with permission from John Wiley & Sons, Inc.
general, the Deborah number is defined as the ratio between the
stress relaxation time and a characteristic relaxation time of the
process, while the Weissenberg number is defined as the product
of the stress relaxation time and a characteristic deformation rate
of the process, e.g. the shear rate. However, in the treatment of FIC
the two dimensionless measures of flow strength are often consid-
ered analogues [204]. Corresponding to the flow strength, which
is reflected in two characteristic time scales of the high molecular
weight fraction of the molecular weight distribution, and the de-
formation rate, three distinct regimes can be distinguished. Fig. 11
provides a schematic representation of the different flow regimes
and resulting crystalline morphologies in flow-induced crystalliza-
tion. The two characteristic time scales refer to the disentangle-
ment time of the polymer melt, τd , which is equivalent to the poly-
mer’s reptation time, τrep , and the Rouse time, τR , which is related
to molecular stretch and is sometimes also denoted as τs , a charac-
teristic relaxation time for stretch. The process of reptation will be
discussed in more detail in Section 3.3. Two corresponding Weis-
senberg numbers can be defined,
W io = γ˙ τd
and
W is = γ˙ τR
where γ˙ denotes the shear rate. W io reflects macromolecular chain
orientation, while W is corresponds to molecular stretch. In the first
regime, when γ˙ < 1/τd , no significant effect of the applied flow
is observed, and quiescent crystallization occurs. Both Weissenberg
numbers in this regime are smaller than one, W io < 1 and W is
< 1. When the applied shear rate increases, the second regime is
entered, where 1/τd < γ˙ < 1/τR . Orientational effects will only en-
hance point nucleation in this regime, meaning that besides nor-
mally observed athermal nucleation some additional nucleation oc-
curs. Due to enhanced nucleation the crystalline morphology will
consist of finer spherulites. In the second regime it also holds that
W io ≥ 1, yet still W is < 1. In the third regime, when γ˙ > 1/τd and
γ˙ > 1/τR , molecular stretch is achieved under flow which gener-
ates fibrillar nuclei, so-called shish, onto which lamellae grow ra-
dially outward, which are called kebabs [25]. The kebabs are some-
times referred to as parent lamellae, as another species of lamellae,
called daughters, nucleate on their lateral surface, as is depicted
in Fig. 12 [205]. For both Weissenberg numbers it now holds that
W io ≥ 1 and W is ≥ 1 [25]. FIC has already received its fair share
of attention concerning its occurrence in more traditional polymer
processing methods including film blow molding [206], extrusion
Progress in Polymer Science 118 (2021) 101411
Fig. 12. A schematic illustration of the typical shish-kebab crystalline morphology
with a shish, parent kebabs and daughter lamellae. [212], Copyright 2014. Repro-
duced with permission from American Chemical Society.
[207,208] and injection molding [209–211] and can be seen as a
self-reinforcement mechanism in the processing of polymer melts.
Some studies have mentioned the occurrence of FIC during FFF
processing. Jiang et al. (2020) observed a slight enhancement in
the degree of crystallinity in their PP/PS blends with increasing
print speed, as an increased flow field will lead to a higher de-
gree of orientation of the polymer chains which facilitates crystal-
lization. Moreover, some distinct shish-kebab structures were de-
tected in the PP phase, which, together with the PS microfibers
that are formed upon extrusion, lead to a highly oriented mor-
phology which results in excellent mechanical performance of the
FFF processed samples [73]. Both Nogales et al. (2019) and Shmueli
et al. (2019) have studied PP crystallization during FFF processing
by in-situ X-ray scattering. However, Nogales et al. (2019) reported
that the molecular weight of their PP feedstock material was not
(1) high enough above a critical molecular weight to allow for the
molecular segments that are oriented at a certain shear rate un-
der flow to remain oriented. Thus the oriented structures even-
(2) tually relax and break down into point nuclei. Hence, very lim-
ited or no orientation is present in their studied PP samples [67].
Shmueli et al. (2019), on the other hand, did observe clear orien-
tational effects and the formation of shish-kebab structures, since
their PP feedstock material did possess a sufficiently high molec-
ular weight. This again proves that the extrusion step during FFF
processing can impose considerable chain orientation and stretch-
ing resulting in characteristic shish-kebab structures. Shmueli et al.
(2019) furthermore report that the degree of crystallinity and the
kebab orientation are highest in the core of the deposited polymer
filament and gradually decrease toward the interlayer interface re-
gion. Due to considerably higher shear rates in the shell of the fil-
ament extruded from the print nozzle, the shish-kebab structures
appear here first before the orientation is propagated more slowly
towards the core of the filament. However, as a new filament is
subsequently extruded on top of the previously deposited filament,
the resulting increase in temperature upon deposition of the sec-
ond filament will lead to unravelling the shish-kebab structures.
Moreover, since the kebab structures are oriented perpendicular
to the layer-layer interface, they are easier to unravel, while the
shish structures are oriented parallel to the interface and hence
will be more difficult to unravel [68]. Liu et al. (2018) have sug-
gested that during their screw-based extrusion printing of PCL both
24
D. Vaes and P. Van Puyvelde
thermal-induced and shear-induced crystallization take place. The
alignment and orientation of macromolecular chains in the extru-
sion step enhance the formation of crystal nuclei. Increasing screw
rotational speeds thus strengthens this orientational effect, which
is reflected in an increased crystal volume fraction that can lead
to improved tensile properties [128]. Northcutt et al. (2018) have
also attributed enhanced crystallization kinetics of the investigated
PCL feedstock material to high wall shear rates as well as consider-
able extensional flows, which are highest in the middle of the ex-
trudate, when extruding at lower liquefier temperatures, which is
a clear indication of flow-induced crystallization. A higher Tliquefier
results in relaxation of the flow-induced structures and thus the
effect on crystallization kinetics is much less pronounced. They fur-
thermore described that the rapid cooling of the extruded melt
upon deposition can prolong the lifetime of flow-induced struc-
tures, which can then act as nucleation sites once the extrudate
reaches a temperature for spontaneous crystallization [129]. This
was confirmed in the mathematical model by McIlroy et al. (2018),
where it was found that the liquefier temperature should be suf-
ficiently low for FIC to occur, since the extruded polymer filament
should cool down below the melting temperature while the poly-
mer chains remain in their stretched conformation. Furthermore,
the model revealed that as a result of the interplay between sur-
face cooling and macromolecular stretch a boundary layer of flow-
induced nuclei exists in the outer shell of the extruded filament,
which will considerably enhance crystal growth in this region. The
core of the deposited filament, on the other hand, will experience
much slower quiescent crystallization and will crystallize much
later. As the boundary layer contains orders of magnitude more
nuclei compared to the bulk of the extruded filament, the resulting
crystalline morphology in this boundary layer will consist of much
smaller spherulites compared to those in the bulk [213].
3.3. Interlayer adhesion
Polymer specimens produced with FFF typically exhibit weaker
mechanical strength and possess lower apparent mechanical prop-
erties compared to parts fabricated using conventional process-
ing techniques such as compression molding [17] and injection
molding [65]. This is partially due to the voids and porosity that
are inherent to the FFF printing process [214]. Besides the char-
acteristic voids in between layers, additional porosity can be in-
duced by external factors such as nozzle removal from the print
surface [46]. However, the main reason for the weaker mechani-
cal performance of FFF printed parts is the insufficient adhesion
or bonding between successively extruded and adjacent roads, es-
pecially interlayer bond strength in the build direction (i.e. z-
direction) often being the weakest and most critical in terms of
mechanical strength of the full part [180]. Interlayer adhesion or
welding between deposited polymer roads is a process that is
thermally driven and consists of molecular interdiffusion and re-
entanglement of macromolecular chains across the interlayer in-
terface [198]. The extent of molecular diffusion thus depends on
the thermal history of the interlayer zone, which is highly non-
isothermal, further complicating the analysis [180,215,216]. The in-
terlayer bond quality is furthermore influenced by the growth of
the neck that is formed between the adjacent roads [180,215].
Fig. 13 shows the issue of partially fused layers and unfused lay-
ers for PEEK parts produced with FFF taken from a study by Bas-
gul et al. (2018). Additional porosity, possibly caused by nozzle re-
moval from the print surface, is depicted as well. Both the lack of
sufficient layer adhesion and printing-induced porosity will drasti-
cally reduce the mechanical performance of the parts [46].
Interlayer bonding, often termed healing, has been theoretically
described by Wool and O’Connor for the welding of isothermal
amorphous interfaces. Their model describes the healing process
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Progress in Polymer Science 118 (2021) 101411
in five steps, which are depicted in Fig. 14. During surface rear-
rangement and approach, intimate contact between the polymer
interfaces is established. In this process, all surface asperities from
bumps and surface texture are eliminated. Furthermore, strength of
the interface can only develop if one surface wets the other. Wet-
ting is assumed to occur instantaneously, which requires the in-
terface temperature to be considerably higher than the polymer’s
glass transition temperature. After wetting, healing of the polymer-
polymer interface proceeds to a mechanism of macromolecular
chain diffusion across the interface. Diffusion requires molecular
mobility which means temperature should remain sufficiently high
above Tg [217–221]. The polymer’s diffusion mechanism is gov-
erned by the process of reptation, which was described by De
Gennes and later by Doi and Edwards [222,223]. Fig. 15 shows
the theoretical concept behind reptation. In the reptation model,
a polymer chain in the melt state can be viewed as being initially
(i.e. at time t = 0) confined to an imaginary tube which represents
the topological constraints imposed by the entanglements with the
surrounding chains. Due to entanglements, the movement of the
confined chain is predominantly restricted to that along the curvi-
linear length of the tube. As the chain exhibits Brownian motion
back and forth in the tube, its ends can move freely away from the
tube. After a certain time t = t1 , the chain ends have escaped the
original tube forming the so-called minor chains, which are encir-
cled by their most probable spherical envelope to represent their
static dimensions. Over time, the length of these minor chains in-
creases until the so-called reptation time tR is reached. At tR , the
chain has completely escaped the original confined tube and has
forgotten its original configuration [219,224]. The reptation time
can be expressed by the scaling relationship
Rg 2
tR = (3)
Ds
where Rg is the radius of gyration and Ds is the center of mass dif-
fusion coefficient. Thus, the reptation time corresponds to a char-
acteristic diffusion time for a polymer to diffuse across a distance
equal to its radius of gyration [225]. Fig. 16 represents the con-
cept of molecular chain interdiffusion across a polymer-polymer
interface based on the described minor chain concept. It should
be noted that only the minor chains at one end of the interface
are shown for the purpose of clarity. Initially, at time t = 0, com-
plete intimate contact is established between the two polymer sur-
faces. At this point in time, the minor chains still have zero length
and are thus represented as dots. The chain end segments then be-
gin to reptate. With increasing time, the minor chains which have
escaped from the tube constraint will grow in length and move
across the interface over a certain interpenetration depth χ . As
the reptation time is approached, the minor chains have diffused
across an average interpenetration depth which is about equal to
the radius of gyration Rg and bulk or virgin state properties are
achieved at the polymer-polymer interface [218–220,224,225]. Dur-
ing the final step, randomization, polymer chains continue to dif-
fuse across the interface and re-entangle. However, during this
step, the mechanical properties of the interface do not further in-
crease [217,221]. As the diffusion rate is directly proportional to
temperature, the reptation time and thus the time to reach the vir-
gin state is inversely proportional to temperature [225]. It should
also be noted that the reptation time scales with molecular weight
according to tR ∼ M3.4 [22]. However, it has been shown in practice
that minor chains do not need to diffuse across a distance equal to
the radius of gyration to achieve bulk properties. Virgin state prop-
erties can be achieved at smaller interpenetration distances and
thus at times shorter than the reptation time. Therefore, achiev-
ing the maximum bond strength and full healing can already oc-
cur at a so-called weld time tw ≤ tR [224,226]. The healing model
by Wool and O’Connor based on reptation theory results in Eq. (4)
D. Vaes and P. Van Puyvelde Progress in Polymer Science 118 (2021) 101411

Fig. 13. SEM images of FFF printed PEEK layers illustrating partial fusion of layers (a) and unfused layers (b) which are both observed in one surface (a), together with clear
indications of porosity induced by the printing process (c). [46], Copyright 2018. Reproduced with permission from Cambridge University Press.

Fig. 14. A schematic representation of the five steps in the healing model proposed by Wool and O’Connor, including (1) surface rearrangement, (2) surface approach, (3)
wetting, (4) diffusion and (5) randomization. [217], Copyright 2017. Reproduced with permission from Emerald Publishing Limited.

for the time-dependent evolution of fracture stress σ of the inter-

face under isothermal conditions.
σ σ K 1/4

t ψ (t ) φ (t )
0
= + (4)
σ∞ σ∞ σ∞
In Eq. (4), σ∞ represents the fracture strength of the virgin ma-
terial, σ0 is the strength developed due to wetting, K is a constant
that is proportional to D1/4 where D is the polymer diffusion coef-
ficient, t is time, ψ (t ) refers to the diffusion initiation function to
take into account any delay in diffusion due to surface rearrange-
ment and φ (t ) is the wetting distribution function that expresses
the total fractional wetted area. Eq. (4) can be simplified to Eq. (5)
if instantaneous wetting and intimate contact are assumed.

Fig. 15. The movement of a linear polymer chain in an entangled melt through
the process of reptation. At a time equal to the reptation time tR , the chain has
completely forgotten its original configuration and has escaped the original tube
confinement. However, maximum bond strength can already be obtained at the
so-called weld time tw . [224], Copyright 2002. Reproduced with permission from
American Chemical Society.
σ = σ0 + σd = σ0 + K t 1 / 4 (5)
σd equals the contribution to the total strength developed
through diffusion. Hence, during isothermal healing, diffusion
and polymer-polymer interface bonding are proportional to t 1/4
[217,218,220,221,227]. The proposed healing model has been suc-
cessfully applied in isothermal welding studies of amorphous
polymers [218,221]. However, a lot of processes, including FFF,
are highly non-isothermal. Therefore, the proposed isothermal
model should be adjusted in order to properly analyze and
predict strength development of polymer-polymer interfaces un-
der non-isothermal and real processing conditions. Bastien et al.
(1991) have incorporated non-isothermal conditions into the weld-
ing problem by subdividing the thermal history into many step
changes, where each step is small enough to be assumed isother-
mal [228]. This model was later modified by Yang et al. (2002) who

26
D. Vaes and P. Van Puyvelde
Fig. 16. The evolution of minor chain interdiffusion across a polymer-polymer interface over time. [224], Copyright 2002. Reproduced with permission from American
Chemical Society.
replaced the discrete isothermal step approach by Bastien et al.
(1991) by an integral of the temperature profile [224]. Ezekoye
et al. (1998) have employed the temperature dependence of the
polymer diffusion coefficient to calculate the strength development
under non-isothermal conditions. The degree of healing was found
to be directly proportional to the area under the curve of the diffu-
sion coefficient as a function of time. The temperature dependence
of the diffusion coefficient directly follows from the thermal his-
tory of the weld interface [225]. However, it should be noted that
these non-isothermal models do not consider crystallization phe-
nomena and are thus still only applicable to amorphous polymer
welding problems.
Insufficient layer adhesion remains an important issue associ-
ated with the FFF process. The analysis of the welding problem
is complicated by the highly non-isothermal character of the FFF
printing process. Studies on interlayer adhesion have been per-
formed for both amorphous and semi-crystalline feedstock mate-
rials. However, welding of amorphous polymers such as ABS in FFF
has received greater attention in literature and has been studied
more systematically and at a more fundamental level. Since the fo-
cus of this article remains on semi-crystalline feedstock polymers,
only the main studies and findings concerning interlayer adhesion
of amorphous polymers are discussed. It should be noted that most
of this discussion also applies to semi-crystalline polymers.
For amorphous polymers, interlayer adhesion is improved if
the layer-layer interface can remain above the material’s Tg for a
longer time. Above Tg , macromolecular chains retain their mobil-
ity and thus chain diffusion across the interface can take place.
It was found that an increasing liquefier temperature can extend
the time the interface temperature remains above Tg which pro-
motes intermolecular diffusion. An increased Tliquefier can further-
more induce local remelting at the interface and generally in-
creases the interface temperature. Several authors have confirmed
the positive effect of printing at a higher Tliquefier on interlayer ad-
hesion [214,215,229]. No clear trend is reported on the effect of
print speed on interlayer adhesion. Some studies report no signif-
icant impact of print speed on the extent of interlayer bonding
[216,229], while others report both positive and negative effects
of increasing print speed on welding in FFF. Abbott et al. (2018)
have described an improved layer adhesion for slower print speeds
which is contrary to what was expected. This effect is attributed
to the small cross-sectional area of the employed test specimens
that does not require long nozzle travel distances. Radiative heat-
ing due to proximity of the print head could increase the local
interface temperature thus promoting diffusion. The impact of ra-
27
Progress in Polymer Science 118 (2021) 101411
diative heat transfer is more predominant for slower print speeds
[215]. Interlayer cooling time, i.e., the time in between the depo-
sition of a new layer, is highly critical for interlayer bonding. If a
deposited layer has cooled down too much before deposition of a
new layer, interlayer diffusion will be limited. Hence, Goh et al.
(2020) report an inverse relationship between interlayer cooling
time and consequently print speed and interlayer bonding, sug-
gesting that faster printing will lead to improved interlayer adhe-
sion [17]. As a result of the relationship between interlayer cooling
time and the extent of welding, whether or not a part is printed
individually will affect the interlayer cooling time and thus the de-
veloped strength. If multiple parts are printed in the build envi-
ronment, each part is generally constructed layer-by-layer with the
print head depositing all the required material in the xy-plane for
all layers at one specific z-position after which the z-position is
changed and the process is repeated. Thus, the interlayer cooling
time can substantially increase if multiple parts are built simulta-
neously. Hence, parts that are printed individually generally exhibit
greater interlayer strength [230]. Overall, increasing layer height
will decrease the extruded layer’s cooling rate. Hence, the interface
temperature can remain higher for a longer time which enhances
strength development [17,214,215]. Increasing the build plate tem-
perature can positively impact the interlayer adhesion although to
a far lesser extent than the liquefier temperature. The build plate
temperature should lie sufficiently high above the feedstock’s glass
transition temperature to be able to contribute to welding [214].
The position of the printed part on the build plate can alter its
experienced thermal history which can affect the development of
interlayer strength. The convective air flow field in the build en-
vironment is generally not homogeneous which could lead to lo-
cal differences in part cooling rates [180]. Especially for z-oriented
parts, interlayer adhesion is critical, as under loading the interlayer
bonds in these parts will bear the applied load. Therefore, verti-
cal or z-oriented parts often possess considerably weaker mechan-
ical properties compared to parts that were printed flat or on-edge
[17,21,231].
Some authors have made successful attempts at studying and
modeling interlayer welding of amorphous polymers in FFF at a
more fundamental level. Seppala et al. (2017) have employed IR
thermography to record the thermal history of a weld region. By
converting these non-isothermal temperature profiles into equiva-
lent isothermal weld times, comparisons between different print-
ing conditions can be made. The polymer chain mobility above Tg
was related to the temperature-dependent shift factor aT (T) from
time-temperature superposition on rheological data which is de-
D. Vaes and P. Van Puyvelde
fined at temperature T in Eq. (6) as the ratio of the reptation time
at T to the reptation time at a reference temperature T0 .
tR ( T )
aT ( T ) =
tR (T0 )
The temperature dependence of the shift factors can be fitted
with the Williams-Landel-Ferry (WLF) equation:
−C1 (T − T0 )
log(aT ) =
C2 + (T − T0 )
where C1 and C2 are the so-called WLF constants. The equivalent
isothermal weld time can then be calculated. The non-isothermal
profile can be approximated as a sequence of isothermal temper-
ature steps. The reduced time for each isothermal step is equal to
t/aT and relates times at different temperatures to that at the ref-
erence temperature. The weld time tw is the sum of the reduced
times for each isothermal step from the beginning of weld forma-
tion until temperature has reached Tg . This calculation is equiva-
lent with the integration of 1/aT as is described in Eq. (8).
tT =Tg
dt
tw = ∫
0 aT (t )
It was found that the weld time was highly dependent on the
set liquefier temperature and that print speed did not really affect
weld time. Furthermore, a strong correlation between the calcu-
lated equivalent isothermal weld time and the developed strength
was observed [216]. Bartolai et al. (2018) have utilized a similar
approach by again employing IR thermography to record thermal
history. Similarly, they have used the principle of time-temperature
superposition on rheological data together with the WLF equation
in Eq. (7) to express the temperature dependence of the reptation
relaxation time. They further employed a strength prediction re-
lationship by Ezekoye et al. (1998) to predict weld strength σweld
based on the material’s bulk ultimate tensile strength σUT S , the
weld time tw , which is in this case defined as the time the weld
interface remains above Tg , and the time average reptation time t̄R .
This relation is given in Eq. (9) [232].
 1/4
tw
σweld = σUT S
t̄R
Bellehumeur et al. (2004) have predicted the neck growth and
sintering between two polymer filaments, which is attributed to
strength developed by wetting σ0 in the healing model in Eq. (4).
It was found that the liquefier temperature had a significant effect
on wetting, as the largest contribution to wetting occurred when
the temperature of the ABS extrudate lied above 200 °C, while
the environmental temperature did not considerably affect wetting
[233]. In the healing simulation by Coogan et al. (2017), a simi-
lar model to that of Ezekoye et al. (1998) is derived, where the
temperature dependence of the polymer diffusion coefficient was
calculated from rheological data. Results from the simulations in-
dicate that increased Tbuild plate , Tliquefier , vprint and layer width im-
prove weld strength as all these conditions allow for more polymer
chain diffusion to occur across the interlayer interface. Further-
more, it was found that interfacial welding in FFF follows the t 1/4
dependence stated in the healing model by Wool in Eq. (4) [217].
McIlroy et al. (2017) have studied the effect of disentanglement of
polymer chains upon extrusion through the print nozzle on the de-
gree of welding that can take place. Model predictions show that
the weld thickness typically is larger than Rg , yet not sufficiently
large enough for the polymer to fully relax. For typical print con-
ditions, entanglements do not have sufficient time to recover dur-
ing cooling. A reduced mechanical strength of the weld can thus
be attributed to disentanglement in the nozzle combined with a
delay in entanglement recovery. An increased liquefier tempera-
ture and a less entangled feedstock material can lead to thicker
Progress in Polymer Science 118 (2021) 101411
and more entangled welds as both will reduce the reptation time
which will improve mechanical performance [198]. Coogan et al.
(2020) have recently come up with the first experimentally vali-
(6) dated model which can be employed to predict interlayer strength.
The model takes into account both the impact of the contact area
between successively deposited layers as well as the extent of in-
terlayer diffusion on the developed interlayer strength for high-
impact polystyrene (HIPS) as a model material. From their devel-
(7) oped model and its experimental validation directly followed that
for the utilized HIPS material interlayer strength was mainly lim-
ited due to insufficient intimate contact whereas, for most investi-
gated processing conditions, adequate interlayer diffusion was able
to take place [234].
The main reason why fewer in-depth studies exist on interlayer
adhesion of semi-crystalline polymers in FFF is that the crystal-
lization process that takes place during cooling after deposition
considerably complicates the analysis of the welding problem. For
amorphous thermoplastics, chain mobility and diffusion are es-
sentially only dependent on temperature as decreasing tempera-
ture will lead to an exponentially increased viscosity which is re-
(8) flected in a considerably lower amount of polymer chains diffus-
ing across the interface [235]. Diffusional chain motion is consid-
ered to be negligible below Tg for an amorphous polymer, making
the polymer’s glass transition temperature the limiting tempera-
ture for healing of amorphous polymers [21]. For semi-crystalline
polymers, on the other hand, macromolecular chain mobility is
drastically lowered upon crystallization, since polymer chains will
then be embedded in the growing crystals, hindering their long-
range mobility. This means that adequate interdiffusion and inter-
layer bonding will be impeded due to the crystallization process
[173,227,236]. Barocio (2018) distinguishes three possible scenarios
concerning the welding of deposited semi-crystalline polymer lay-
ers in FFF. In the first scenario, when a printed road underneath
the newly deposited road has not yet crystallized, interdiffusion
across the interface can occur as described above and will proceed
until crystallization starts. If the time between the start of chain
diffusion after deposition of material and the initiation of crystal-
lization is sufficiently long enough (i.e. close to the reptation time),
(9) randomization across the interface can be achieved. Once crystal-
lization occurs, the crystallization front will grow in the direction
of the thermal gradients that develop during printing. The polymer
chains that have been allowed to diffuse and randomize across the
interlayer interface will then take part in the formation of crystal-
lites across that interface. The second scenario takes place when
the previously extruded sublayer is already crystallized to some
extent, but its temperature is still close to the melting point. In
that case, by depositing a new road on top of this sublayer, lo-
cal remelting can occur at the interface. This will again allow for
polymer chains to diffuse across the interface before crystallization
progresses once more along the direction of the existing temper-
ature gradients, leading to the development of crystallinity across
the layer-layer interface. In the third scenario, the previously crys-
tallized sublayer has cooled down too extensively so that local
remelting and thus interlayer diffusion cannot occur. Furthermore,
due to a large degree of supercooling induced by the cooled down
sublayer, polymer crystals will nucleate and will likely grow from
the interface into the bulk of the newly extruded layer. No crystal-
lization across the interface takes place [237]. Crystallization across
the interface should preferentially occur, since a higher degree of
crystallinity across the interface leads to greater mechanical prop-
erties [235]. Jarrousse (2005) has proposed that co-crystallization
across the interface of two semi-crystalline polymers can substan-
tially improve interfacial adhesion, which was also proven by Xue
et al. (20 0 0) [236,238]. However, for this reinforcement mechanism
to take place, a certain interdiffusion should have already occurred
before recrystallization [236]. McIlroy et al. (2017) have mentioned
28
D. Vaes and P. Van Puyvelde
that a higher degree of crystallinity at the interface, possibly due
to FIC, will lead to a larger number of available spherulites which
can form tie-chains across the weld interface. These so-called tie-
chains are polymer chains that become embedded into the crys-
talline regions on either side of the interlayer interface [198].
Among studies concerning interlayer adhesion of semi-
crystalline feedstock polymers in FFF two main groups can be
distinguished. In the first set of studies, a more qualitative ap-
proach to characterize interlayer welding is employed. The trends
that result from these studies are very similar to what has been
already established for amorphous polymers. A second group of
studies on semi-crystalline polymers try to incorporate the crys-
tallization phenomenon into their analysis of the welding problem
by investigating the effect of crystallization on chain diffusion and
by focusing on the crystalline morphology at the weld interface.
Several authors report that the printed part’s mechanical prop-
erties such as tensile strength and modulus are not just dependent
on the degree of crystallinity or resulting crystalline morphology.
Yet, the overall mechanical performance of the printed specimens
is governed by a multitude of factors such as the printing condi-
tions, the degree of crystallinity, the level of interlayer diffusion,
the multiscale interfaces between layers, residual internal stresses,
voids that act as stress concentration points, and feedstock degra-
dation phenomena [70,103,141,154]. In terms of the effect of print-
ing process parameters, several varying conditions were analyzed.
One of the most important print parameters to impact interlayer
diffusion and thus welding was found to be the liquefier temper-
ature. An increased Tliquefier will considerably facilitate chain dif-
fusion across the weld interface due to enhanced thermal mobility.
Furthermore, the time for diffusion-controlled bonding will be pro-
longed as a higher extrusion temperature will extend the time be-
fore Tg is reached and mobility is halted. A higher Tliquefier can also
induce partial remelting of the surface of the sublayer which will
lead to improved diffusion. Due to the strong temperature depen-
dence of viscosity, an increased Tliquefier will drastically reduce the
melt viscosity which will lead to more cross-flow upon deposition
thus decreasing the air gap and voids. However, the liquefier tem-
perature should not be set too high as deterioration of the polymer
feedstock material can occur which will negatively impact mechan-
ical performance [65,66,103,107,116,141,239–241]. A negative air gap
has been proven to be beneficial for interfacial strength [109]. Gen-
erally, a build plate temperature that is set sufficiently high above
the material’s glass transition temperature will shift the overall av-
erage temperature experienced by the extrudate to a higher value.
This will enhance interlayer diffusion and bond formation [94,110].
However, it has been reported that an increased Tbuild plate can lead
to an enhanced degree of crystallinity in the printed parts which
results in more crystallization-induced shrinkage, eventually im-
pairing interlayer strength [109]. Due to the poor heat conduct-
ing properties of polymers, a temperature gradient often exists in
the printed sample where the layers that are positioned closer to
the build plate remain at a higher temperature throughout the
printing process compared to layers which are deposited further
away from the build platform. Weld strength can therefore not be
uniform across the whole printed sample due to inhomogeneous
thermal history [65,242]. By printing in an environmentally con-
trolled chamber at sufficiently high Tenvironment , temperature gradi-
ents can be minimized and interlayer welding can be further en-
hanced [241]. Concerning print speed, similarly as for amorphous
polymers, contradicting results have been reported. Some studies
have observed positive effects of increasing print speed on inter-
layer adhesion, mostly attributed to the decreased interlayer cool-
ing time and thus higher average temperatures which promote
chain diffusion [94,243]. However, other authors have found that
slower print speeds enhance interlayer bonding as slower print-
ing will increase the total required printing time and thus heat
29
Progress in Polymer Science 118 (2021) 101411
exposure of the print on the heated build plate or in the heated
print environment [66,115]. Increasing print speed might also lead
to greater void formation. Furthermore, polymer chains will require
more time and energy to recrystallize at lower print speeds thus
improving bond strength [153]. Trends in interlayer adhesion re-
lated to changes in layer height have also been controversially dis-
cussed in literature, mainly due to the fact that multiple mecha-
nisms that govern interlayer bonding can overlap [240]. Some stud-
ies mention the positive effect of increasing layer height as this
minimizes heat losses and enhances diffusion [243], while other
findings indicate that the smaller the layer height, the easier it
is to achieve the same level of interlayer bonding compared to a
larger layer height and smaller layer heights also lead to increased
total printing times which again will result in prolonged heat ex-
posure of the printed part and thus allows longer times for diffu-
sion [65,66]. Build orientation and print order can both affect the
interlayer cooling time and thus the degree of welding between
successively deposited layers. A shorter time in between deposi-
tions of polymer extrudate allow for improved welding as the in-
terface remains at a higher temperature, as was already discussed
for amorphous polymers [112,123,141,244]. Besides printing condi-
tions, feedstock material properties have been found to impact in-
terlayer welding as well. A lower molar mass is associated with a
reduced viscosity and thus improved diffusion capabilities as the
timescales for interlayer bonding decrease with decreasing molar
mass. A reduced viscosity will also lead to more crossflow upon
deposition and thus reduced voids and air gap, which improves
part strength [115,240].
Fewer studies have focused on the actual effect of crystal-
lization on the diffusion phenomenon. It is generally accepted
that macromolecular chain mobility is drastically hindered or even
completely impeded upon the onset of crystallization as the at-
tachment of polymer chains to the growing crystals will prevent
their diffusion [115,117,245]. The crystallization onset temperature
will therefore dictate the thermal processing window that is re-
quired to establish sufficiently strong interlayer bonds. The inter-
face temperature should preferentially remain above the crystal-
lization onset temperature for an adequate amount of time so
that molecular diffusion can occur prior to crystallization [245]. To
achieve higher interface temperatures, especially the liquefier tem-
perature, and to a lesser extent the build plate temperature, should
be chosen high enough to ensure elevated temperatures of the
weld zone [114,245]. An increased Tliquefier can moreover lead to
partial remelting of the top surface of the sublayer which will con-
siderably benefit interlayer diffusion and bond strength [245,246].
Shmueli et al. (2019) have performed an analysis of the evolution
of the polymer diffusion coefficient with temperature in two sep-
arate studies, one focusing on PLA and the other on PP. By deter-
mining the temperature evolution of the diffusion coefficient based
on the recorded thermal history during FFF processing, an effective
diffusion length could be established over the temperature range of
interest. In the case of PLA, where the degree of crystallinity was
found to be very low, the relevant temperature range was taken
between the extrudate temperature and Tg , as the low number
of crystallites were expected to not considerably impede molec-
ular diffusion. For PP, on the other hand, the lower limit of the
temperature range was chosen to be the crystallization onset tem-
perature since PP does exhibit far greater crystallinity. When the
net diffusion length approaches the radius of gyration of the poly-
mer, complete interdiffusion is assumed to have occurred. For PLA,
it was clearly illustrated that increasing Tliquefier considerably fa-
cilitates diffusion as Rg is more easily reached at higher liquefier
temperatures. In the case of PP, diffusion lengths much larger than
Rg where reported, indicating that complete interlayer welding has
occurred prior to the onset of crystallization [68,114].
D. Vaes and P. Van Puyvelde
Fig. 17. The local crystalline morphology at the weld or fusion zone for PP samples printed at Tliquefier = 230°C with varying Tbuild plate of (a) 25°C, (b) 85°C, and (c) 105°C.
[245], Copyright 2016. Reproduced with permission from John Wiley & Sons, Inc.
Inspection of the crystalline morphology of the interlayer in-
terface can also be highly beneficial to further comprehend the
impact of crystallization on strength development in FFF. Besides
X-ray scattering, both polarized light microscopy (PLM) and scan-
ning electron microscopy (SEM) have been employed to investigate
the local variations in morphology at the weld zone. Hertle et al.
(2016) have utilized PLM to visualize the effect of the build plate
temperature, among other printing parameters, on the resulting in-
terlayer morphology as is depicted in Fig. 17. For the set liquefier
temperature, a Tbuild plate that is too low will not lead to remelting
of the surface of the sublayer as its temperature has already cooled
down too much. Therefore, incomplete intimate contact is present
in some regions which signifies that no interlayer diffusion could
have taken place at these locations. Higher build plate tempera-
tures eliminate incomplete intimate contact, yet too high Tbuild plate
can lead to dimensionally unstable conditions which is reflected in
the wavelike bonding region. As a result of the high cooling rate
due to cooling at the surface for lower Tbuild plate , a highly micro-
crystalline morphology is observed at the layer surface. While for
the lowest employed Tbuild plate large spherulites are formed in the
deposited layer at the interface and a discontinuous transition to-
wards the sublayer is detected, a higher build plate temperature
results in a continuous spherulite size gradient [245]. McIlroy et al.
(2019) have reported a difference in spherulite size between the
weld region and the bulk of the extruded roads, which can be at-
tributed to and controlled by FIC. The observed smaller spherulite
sizes at the weld region could be beneficial in terms of mechan-
ical performance as decreasing spherulite size is correlated with
more ductile behavior [247]. Nogales et al. (2019) detected a clear
change in the average interlamellar distance in the top surface of
the sublayer after deposition of a new layer on top. This increase
in long-spacing can be attributed to the partial remelting of crys-
talline lamellae upon deposition of the top layer, which facilitates
welding [67]. Wang et al. (2017) have inspected the weld region of
PLA printed specimens using SEM. The resulting micrographs are
30
Progress in Polymer Science 118 (2021) 101411
shown in Fig. 18. The difference between the samples from group
B and D is the set layer height, which is 0.2 mm for samples from
group B and 0.4 mm for those from group D. Other print settings
have remained identical. However, the SEM micrographs indicate a
clear distinction in the morphology of the interlayer zone. For sam-
ples of group B, crystals are oriented perpendicularly to the inter-
face as molecular diffusion occurs across the interface. The areas
in the welding zone are furthermore more crystalline compared to
other nearby areas due to the higher average temperature. Sam-
ples from group D, on the other hand, exhibit significantly fewer
crystals. The existence of a crystal band across the interface can be
highly beneficial to the developed interlayer strength [110].
Barocio (2018) developed a model that combines a phenomeno-
logical model for polymer diffusion with a phenomenological
model describing the crystallization phenomenon. The welding is
expressed based on a weld time of which the temperature depen-
dence is calculated from the thermal history experienced during
FFF processing. The evolution of the degree of crystallinity is mod-
eled by a polymer crystallization model which is coupled to a crys-
tal melting model. The weld time is integrated up until a critical
time is reached to obtain a degree of bonding at the interface. This
critical time corresponds to the moment where a critical value of
the degree of crystallinity is established, at which point chain mo-
bility is assumed to have become negligible due to constraints im-
posed by growing crystals. This model allows local prediction of
the degree of bonding as a function of the experienced thermal
history and the developed degree of crystallinity which are both
dependent on the processing conditions [237].
Many routes have been suggested to enhance interlayer adhe-
sion both for amorphous and semi-crystalline feedstock materials.
Although the main focus will lie on literature reported for semi-
crystalline polymers, many of these methods are also applicable
to amorphous thermoplastics. One option is applying a heat treat-
ment such as annealing to the printed part post-printing, which
has been proven to be a viable method to enhance interlayer
D. Vaes and P. Van Puyvelde
Fig. 18. SEM micrographs of the weld region in PLA specimens produced with FFF at Tbuild plate = 160°C. Spherulites are indicated by white ellipses. Sample B was printed
with layer height of 0.2 mm, while for sample D layer height equals 0.4 mm. [110], Copyright 2017. Reproduced with permission from Elsevier Science Ltd.
strength and overall mechanical performance of printed parts. This
is partially due to the fact that annealing at elevated tempera-
tures can reduce the number of voids that are present after print-
ing and that residual stresses can relax [70,116,117,164]. However,
the main effect of annealing on interlayer strength lies in the im-
proved interdiffusion and enhanced degree of crystallinity, often
reflected in an increased tensile strength and modulus and more
brittle behavior [70,116,164]. Annealing can furthermore alter the
crystalline morphology by increasing lamellar thickness and can
induce more crystal perfection [103]. It should be noted that the
chosen annealing temperature is crucial. Geng et al. (2018) have
shown that for PPS an increasing heat treatment temperature will
lead to improved diffusion and interlayer strength [164]. Bhandari
et al. (2019) report that annealing PLA printed parts below the ma-
terial’s cold crystallization temperature resulted in a slight increase
in interlayer strength due to improved diffusion across the inter-
face. Annealing above the cold crystallization temperature, on the
other hand, did not result in improved interlayer adhesion, since,
above this temperature, the considerable increase in the degree of
crystallinity will prevent or at least greatly hinder chain reptation
across the interface [117].
Besides post-printing heat treatments, some authors have em-
ployed in-process heat treatment methods to enhance interlayer
adhesion. Both controlling the build environment temperature and
convective heat flow in the build environment can influence in-
terlayer diffusion. By insulating the build environment at elevated
temperatures in a heating box, Harris et al. (2019) were able to im-
prove chain mobility by ensuring an elevated Tenvironment through-
out the whole printing process [108]. Moreover, Lee et al. (2019)
have illustrated the influence of air-forced cooling on the interfa-
cial coherence. Increased air cooling velocities lead to decreased
sublayer temperatures prior to deposition of new layers which
eventually negatively impacts interlayer adhesion [111]. Luo et al.
(2018) utilized a CO2 laser to preheat the interlayer bonding point
which improves the interlayer strength at two levels. Macroscop-
ically, if laser power is sufficient, the laser will heat up the sur-
31
Progress in Polymer Science 118 (2021) 101411
face of the previous layer creating a melt pool which adaptively
bonds with the deposited layer, while on a microscopical level, by
increasing the temperature of the interlayer bonding point above
Tg , chain interpenetration across the interface is considerably fa-
cilitated. Thus, laser power should be chosen carefully so that it
is high enough to heat up the interlayer bonding point sufficiently
high above Tg , yet not too high as this would cause degradation
of the material that actually deteriorates mechanical performance.
Furthermore, for semi-crystalline materials such as the PEEK mate-
rial employed in the study by Luo et al. (2018), local temperature
control by the laser can also be utilized to gain a local control of
the developed degree of crystallinity [160]. A similar set-up was
employed by Ravi et al. (2016) during printing of ABS. Their work
again showed the considerable improvement in interlayer strength
if the interface temperature could be increased above Tg for an ad-
equate amount of time with assistance of the laser [248]. Strie-
mann et al. (2020) influenced the interlayer temperature by apply-
ing an infrared preheating system consisting of two ceramic radia-
tors emitting long-wave infrared rays. Incorporation of the infrared
preheating system clearly benefited interlayer strength and could
be used to optimize strength development during FFF processing
[249].
By forming polymer blends, interlayer adhesion can be consid-
erably improved. Das et al. (2020) have reported the beneficial ef-
fect of blending PP with hydrocarbon resins with different degrees
of hydrogenation on interlayer strength, especially upon addition of
partially hydrogenated hydrocarbon resin which was shown to im-
prove interlayer chain entanglements and diffusion prior to crystal-
lization as a result of its excellent miscibility in the PP matrix [70].
The formulation of blends of PP random copolymers with amor-
phous PP led to improved interlayer bonding quality as was ob-
served by Jin et al. (2020). This is a result of the volume filling
effect by the amorphous PP among spherulite boundaries which
apparently strengthens the entanglements induced by crystallites
at the interface. However, addition of LLDPE drastically reduced
the interlayer bonding quality, most likely due to phase separa-
D. Vaes and P. Van Puyvelde
tion. As a result of separated PP and PE crystals occurring at the
interface, interlayer bonding quality is impaired by the existence
of hetero crystalline boundaries [72]. Plasticizers can enhance the
diffusion capability of polymer chains, meaning that the required
weld time to obtain complete bonding of two polymer interfaces
can be significantly reduced upon addition of plasticizers. Ko et al.
(2019) found improved interlayer adhesion upon addition of only
10 wt% of plasticizer [250]. Levenhagen et al. (2017) have inves-
tigated the effect of blending low molecular weight PLA additives
on the interlayer bonding quality of the PLA matrix. Linear addi-
tives with three distinct molecular weights of 8.5 k, 50 k and 100
k were utilized. The 8.5 k additive lacks the ability to form suffi-
cient entanglements across the interface thus lowering the overall
mechanical performance of the sample due to an excessive plas-
ticizing effect. The 100 k additive, on the other hand, hinders in-
terfacial adhesion due to its large polydispersity, indicating a large
portion of long chains, which actually hinder chain mobility and
interlayer diffusion and entanglements. The 50 k sample, however,
did lead to the desired effect as it dramatically improved diffu-
sion across the weld interface and was able to form sufficient en-
tanglements [90]. In later work, Levenhagen et al. (2018) studied
the effect of chain architecture of the low molecular weight addi-
tives on their ability to enhance interdiffusion. Linear chains, 3-arm
stars and 4-arm stars are compared. 3-arm stars diffuse following
a similar mechanism as linear chains. However, due to their ex-
tra arm, which acts as an additional entanglement point, interlayer
adhesion was found to be dramatically increased. A 4-arm star ex-
hibits poor diffusion and entanglement capabilities which leads to
decreased mechanical performance upon addition of this type of
additive [251]. Srinivas et al. (2020) have produced blends of PLA
with high L-enantiomeric purity with low molecular weight dif-
fusion promoting PLA additives with random enantiomeric purity
and PLA stereocomplex crystals. Poly(L-lactide) and poly(D-lactide),
the two enantiomeric forms of PLA, can co-crystallize into a so-
called stereocomplex crystal structure. The low molecular weight
additives are non-crystallizable due to their random enantiomeric
purity. Combining both additives can lead to a drastic improvement
of the interlayer strength. The plasticizing effect of the low molec-
ular weight additives clearly promotes molecular diffusion across
the interface even under the presence of nucleating stereocrystals.
The weld strength and dimensional stability is further enhanced by
the incorporation of polymer chains from either side of the inter-
face into stereocrystals [252].
Reports on the effect of the addition of fillers on interlayer
strength have been mixed. Gao et al. (2019) describe improved in-
terlayer coalescence and bonding strength upon addition of fillers
such as carbon fibers or talc when comparing tensile strength of
PLA samples with 90 ° print orientation, as in this case, the in-
terlayer weld zone is directly loaded [123]. On the other hand,
Bhandari et al. (2019) report the negative impact of the addition of
carbon fiber on the interlayer mechanical properties, which they
attribute to the increased melt viscosity and thus an increase in
the required time for wetting and reptation which is a direct re-
sult of the addition of carbon fiber [117]. Wang et al. (2016) have
devised an approach to improve weld strength by the addition of
thermally expandable microspheres, which drastically reduce voids
and thus lead to an overall improvement of mechanical properties
[253]. If the fillers incorporated in the polymer matrix are ther-
mally conductive, the average temperature in the deposited layers
is increased which facilitates bonding, as was observed by Wächter
et al. (2019) [241]. Jin et al. (2020) demonstrated the impact of
the addition of β -nucleating agent in a PP random copolymer ma-
trix on the resulting interlayer welding performance. Adding a high
concentration of β -nucleating agent was found to negatively im-
pact bond strength as a result of the β -α crystallite growth tran-
32
Progress in Polymer Science 118 (2021) 101411
sition and the existence of twin crystal structures, which possess
many crystal boundaries [72].
Other, more specific methods to strengthen interlayer interfaces
have also been reported in literature. Ultrasonic vibration was em-
ployed by Li et al. (2018) and proved to be an excellent tool to
induce increased and deeper interdiffusion and re-entanglements
across the interface, which was reflected in a reduced void frac-
tion, a more uniform distribution of stresses and clearly stronger
interlayer bonds [93]. Shaffer et al. (2014) successfully exploited
the effect of ionizing radiation as a tool to create crosslinks to en-
hance interlayer adhesion in PLA blended with radiation sensitiz-
ers. It was found that irradiation temperatures above Tg are neces-
sary to provide the polymer chains with adequate mobility in or-
der for generated radicals to find one another and create crosslinks
[254]. Shih et al. (2019) utilized cold plasma treatment to enhance
interlayer bonding in FFF parts. The treatment time was found to
be highly critical as excessive treatment exposure could lead to
deterioration of the polymer or the formation of a disproportion-
ate oxidation layer thickness which could weaken the interlayer
weld region [255]. With the incorporation of carbon nanotubes, lo-
cally induced microwave heating has been found by Sweeney et al.
(2017) to be another viable technique to strengthen interfaces in
FFF printed parts. The authors suggest that carbon nanotube coat-
ings on polymer feedstock filaments combined with this heating
method can allow FFF printed specimens to achieve mechanical
properties close to those produced with conventional manufactur-
ing techniques [256]. Peng et al. (2019) have created core-shell fil-
aments consisting of a PC/ABS core and a LDPE or HDPE shell. Due
to a lower solidification temperature of the PE shell compared to
the PC/ABS core, the PE material can diffuse over a broader tem-
perature range during cooling. Thus the enhanced diffusion com-
bined with possible crystallization of chains across the interface
can lead to improved interlayer strength [257]. Interfacial stereo-
complexation was employed as a strengthening mechanism in a
study by Srinivas et al. (2019) by alternately depositing layers of
poly(L-lactide) and poly(D-lactide). It was found that a higher con-
centration of stereocrystals was obtained when printing at lower
print speeds as this provides sufficient local heat dosage. Sufficient
heat is essential for interfacial stereocomplexation to occur as it
ensures that the deposited layer remains in the melt state, the sub-
layer becomes reheated into its melt state, and sufficient time is
given for molecular diffusion across the interface [258].
3.4. Shrinkage and dimensional stability
After extrusion onto the build plate or previously deposited lay-
ers, the molten polymer will gradually cool down and solidify.
Generally, this solidification process is associated with a charac-
teristic volume reduction or shrinkage of the extruded polymer.
This is followed by further thermal contraction as the tempera-
ture drops below the solidification temperature of the polymer.
As a result, the printed specimen’s dimensions can be reduced
compared to the original design of the part [259]. Furthermore,
thermal gradients that are inherent to the FFF process arise from
the cyclic deposition of new layers, which can increase the tem-
perature of previously extruded layers even several layers down.
Besides this, part design can lead to thermal gradients in the
printed part as well, since thicker regions will cool down more
slowly compared to thinner wall regions or protruding sections.
These temperature gradients will result in the buildup of internal
stresses within the printed part due to uneven shrinkage and ther-
mal expansion [6,175,235]. A schematic representation of the in-
ternal stresses, namely tensile and compressive stresses, that arise
within a printed layer due to inconsistent shrinkage is given in
Fig. 19. This can bring about warpage, which is often noticeable as
a distortion or curling of the edges or base of the printed specimen
D. Vaes and P. Van Puyvelde
Fig. 19. A schematic representation of the internal stresses in a printed layer, con-
sisting of tensile and compressive stresses, upon inconsistent shrinkage and thermal
contraction during cooling after printing. [235], Copyright 2018. Reproduced with
permission from Elsevier Science Ltd.
[235,259]. In severe cases, the printed part can become partially or
completely detached from the build plate due to warpage or even
delamination of printed layers and part cracking can occur [6,259].
The ability to guarantee dimensional stability of printed specimens
is obviously of great importance to ensure printed part quality.
Some examples of printed specimens which exhibit warpage and
issues with dimensional accuracy are depicted in Fig. 20 [260,261].
All polymers exhibit volume shrinkage upon cooling from the
melt state up until their glass transition temperature due to a de-
crease in both the free volume between macromolecular chains
as well as their vibrational volume [261]. However, the extent of
shrinkage is far less severe for amorphous thermoplastics com-
pared to their semi-crystalline counterparts due to the unstruc-
tured nature of their solid state. Furthermore, the solidification
shrinkage with amorphous polymers occurs at a much slower rate
[259]. Semi-crystalline polymers, on the other hand, exhibit a far
greater change in specific volume upon cooling due to crystal-
lization [261]. During crystallization, polymer chains are packed
together more tightly and efficiently compared to amorphous
regions, forming highly dense crystalline structures [24]. Semi-
crystalline polymers will thus experience far greater shrinkage due
to a considerably higher change in specific volume compared to
amorphous polymers [261]. This is illustrated in Fig. 21 where the
general changes in volume for an amorphous and semi-crystalline
polymer are compared. It can be clearly observed that the change
in specific volume for a semi-crystalline polymer, which is a result
of crystallization, is much more pronounced, reflected in greater
shrinkage [27,262].
In other polymer processing techniques such as injection mold-
ing, part shrinkage is an important phenomenon to take into ac-
count, especially when processing semi-crystalline polymers, and
has been the subject of several studies [263–265]. Furthermore, in
other polymer-based AM techniques, such as SLS, semi-crystalline
polymers have been found to exhibit more extensive shrinkage and
thus more issues with dimensional accuracy of sintered parts com-
pared to amorphous feedstock [27].
Several studies, both experimental as well as numerical, have
been performed on both amorphous and semi-crystalline poly-
mers to characterize the extent of shrinkage and warpage. Since
this review article focuses on semi-crystalline polymers, the re-
ported studies are related to this polymer class. It should however
be noted that Spoerk et al. (2020) have thoroughly described the
shrinkage phenomenon in the context of FFF in a recent review
article, which mainly focused on polypropylene [261]. This article
will try to highlight the main findings concerning shrinkage and
dimensional accuracy of FFF printed parts over the whole semi-
crystalline polymer family. Special attention is devoted to the link
between part crystallinity, FFF process parameters and dimensional
stability of printed parts.
33
Progress in Polymer Science 118 (2021) 101411
Most experimental studies are mainly looking at dimensional
accuracy in a qualitative way, although some authors quantify di-
mensional accuracy by determining the deviation in the dimen-
sions of the printed part compared to the original design’s di-
mensions. First of all, some semi-crystalline polymers are more
prone to exhibit severe shrinkage and warpage compared to oth-
ers. The extent of volumetric contraction upon crystallization is
thus dependent on the type of polymer. PLA is an example of
a semi-crystalline polymer which typically possesses fairly slower
crystallization kinetics and very low shrinkage [76,84,259]. PP, on
the other hand, is highly prone to excessive shrinkage, which,
combined with fast crystallization kinetics, can lead to severe
issues with warpage and dimensional stability during printing
[76,261,266]. In general, very few studies actually link the shrink-
age or warpage behavior of a specific semi-crystalline feedstock
material during printing to the process-induced crystallinity. The
degree of crystallinity that is achieved during printing is influ-
enced by the thermal history of the extruded polymer, which is,
in its turn, dependent on the processing conditions. It is sug-
gested that a build plate temperature above the feedstock ma-
terial’s Tg will ensure rapid adhesion of the deposited polymer
onto the build plate and will allow the extruded polymer to ac-
commodate any residual stresses due to thermal gradients, thus
leading to severely diminished warpage and dimensional distor-
tion [20,141,267,268]. Furthermore, the temperature of the build
environment can have a similar effect on the degree of warpage.
By enclosing the printer and controlling Tenvironment , uneven cool-
ing of the printed part can be counteracted [269]. With increas-
ing chamber temperature, the cooling rate of the deposited poly-
mer slows down, which impacts the crystallization kinetics. This
has been shown by Wu et al. (2014) and Hu et al. (2019) to con-
siderably improve dimensional accuracy [159,270]. Fan cooling can
also be employed to control part warpage. However, different re-
sults have been reported. The printed part cools down too quickly
if an excessively high fan cooling speed is employed, which, ac-
cording to Diederichs et al. (2019), induces warpage by causing in-
ternal stresses and impacting the crystallization rate [133]. Geng
et al. (2018), on the other hand, have described enhanced dimen-
sional accuracy and decreased warpage with air-forced cooling, as
this allows for efficient convective heat transfer within the build
environment and effective control of the temperature distribution
in the printed part [164]. Hämäläinen (2017) has illustrated the ef-
fect of printed part geometry on the extent of shrinkage and di-
mensional accuracy. Cylindrical parts exhibited far superior dimen-
sional stability compared to their cubic counterparts printed un-
der the same conditions. This is a direct result of the difference in
geometry between both parts as this influences how the internal
stresses build up in the respective specimens. Both the cubic and
cylindrical specimens were deposited using a 45 ° infill pattern, yet
with the cubic parts stress concentrations occur in the sharp cor-
ners of the cube, which lead to distortion and detachment from
the build plate. This is caused by the lengthwise shrinkage of the
polymer roads, which leads to a contractile force from corner to
corner within a layer and a net contractile force that is pointed
towards the center of the cube. However, in the cylindrical spec-
imens, no stress concentrations exist and contractile forces origi-
nating from shrinkage are evenly distributed, hence these parts do
not exhibit severe shrinkage distortion. Furthermore, thin-walled
samples were found to exhibit far greater issues with shrinkage as
these samples experience much higher cooling rates. Again, cylin-
drical thin walled samples exhibited improved dimensional accu-
racy compared to cubic samples [267].
Some authors have attempted to employ modeling to obtain
numerical simulations of the residual stresses and resulting shrink-
age and warpage in FFF printed parts. The first group of models is
designed to predict the residual stresses and part warpage through
D. Vaes and P. Van Puyvelde
Fig. 20. Some examples of printed parts which exhibit issues with dimensional accuracy due to shrinkage and warpage with (a) a distorted part printed with PLA. [260],
Copyright 2017. Reproduced with permission from International Journal of Mechanical and Mechatronics Engineering, and (b) a distorted part printed with PP. [261], Copyright
2020. Adapted with permission from Wiley Periodicals, Inc.
Fig. 21. The difference in change in volume between an amorphous and semi-
crystalline polymer, illustrating the greater shrinkage for semi-crystalline polymer
due to crystallization. [262], Copyright 2019. Reproduced with permission from El-
sevier Science Ltd.
its thermal history without including local part crystallinity or any
crystallization kinetics into the model. Yang et al. (2018) were able
to model the temperature distribution and corresponding stress
field in simulated PLA parts printed with different infill patterns.
The calculations proved that thermal gradients exist in the parts
which lead to an inhomogeneous distribution of shear stresses and
thus stress concentrations. A honeycomb filling pattern was found
to be the best in terms of stress distribution and warpage min-
imization [271]. Fitzharris et al. (2018) simulated the warpage of
two successively deposited roads onto the build plate for both PPS
and PP feedstock. Again, the warpage and residual stresses were di-
rectly linked to the temperature distribution in the modeled parts.
It was observed that higher liquefier temperatures, longer deposi-
tion paths, and slower print speeds lead to stronger thermal gradi-
ents. Furthermore, some material properties were altered to study
their influence on part warpage. Decreasing the feedstock’s coeffi-
cient of thermal expansion led to a decrease in part warpage by
the same factor, while changing thermal conductivity, heat capac-
ity or Young’s modulus did not affect warpage [272]. The results
from the models by Watanabe et al. (2016), which utilizes PP, and
Liu et al. (2015), which utilizes PLA, are very similar. Warpage and
dimensional distortion were found to be counteracted by increas-
ing layer thickness and print speed and by decreasing the lique-
fier temperature [273,274]. Gudadhe et al. (2019) have modeled
the internal stress development and warpage in HDPE rectangu-
lar bar parts. No actual crystallization kinetics were incorporated
in the model, yet the event of crystallization and the associated
abrupt change in density was modeled as a step change in the
thermal expansion coefficient. Stresses were found to be mainly
present at the edges and corners of the printed parts. A brim can
therefore be used to increase the contact area with the build plate
34
Progress in Polymer Science 118 (2021) 101411
over which the warpage forces can be spread out thus minimizing
part distortion [275]. Other models do include crystallization ki-
netics and are able to calculate the local degree of crystallinity in
printed parts based on the simulated thermal history. These mod-
els can be seen as a foundation for further modeling attempts to
predict the development of residual stresses and shrinkage start-
ing from the temperature and crystallinity distribution [276–278].
Brenken et al. (2019) succeeded in combining heat transfer anal-
ysis, crystallization kinetics, thermoviscoelasticity and anisotropic
shrinkage within one single predictive model to simulate the re-
sulting residual stresses and deformations of an FFF printed struc-
ture. This developed simulation tool set is an industrially valuable
design tool which can drastically reduce the often-employed trial-
and-error method which is very time-consuming [279].
Shrinkage of semi-crystalline feedstock in FFF printing can be
counteracted in a variety of ways. One of the most applied princi-
ples is the incorporation of fillers in the feedstock polymer, which
has been extensively reported in literature. In general, these fillers
are preferably thermally conductive as these have been proven
to reduce the time to reach thermal equilibrium in the printed
part which can minimize warpage issues [261,272]. A vast array
of fillers has been reported in literature which have been added to
study their effect on shrinkage reduction, including wood powder
[280], CaCO3 [259,280], TCP [87], WC [147], talc [120,259], perlite
[75,259], glass [76], and natural fibers, such as hemp and gypsum
[281]. The addition of fillers reduces the coefficient of thermal ex-
pansion of the polymer matrix material and is thus an effective
way to minimize shrinkage. The extent of shrinkage reduction is
typically increased by increasing the filler content [120,281,282].
However, excessive filler loading can also lead to poorer perfor-
mance due to agglomeration of filler particles [280], as well as fil-
ament instability or feeding issues [259]. Some authors have re-
ported a clear increase in the feedstock polymer’s crystallization
temperature upon addition of filler material. Thus the gap between
the melting temperature and the crystallization onset temperature
is reduced. This is beneficial for warpage control of the printed
part as the extruded polymer initiates crystallization earlier upon
cooling after deposition. Hence, the polymer crystallizes at the
beginning of the deposition, as the layer temperature decreases
quickly, so that the unfavorable effect of an abrupt change in spe-
cific volume is minimized [75,76,147]. Smaller filler sizes have been
found to have a more pronounced effect on shrinkage reduction
as the specific interfacial surface area between the particles and
the polymer matrix is larger in that case [75]. Jin et al. (2020)
added β -nucleating agent to a PP random copolymer matrix for
FFF printing. This, however, resulted in increased geometric distor-
tion due to the β -α growth transition and the complex β -α twin
crystal structure, which forms different crystal boundaries. There-
fore, the residual internal stresses cannot be homogeneously dis-
tributed anymore leading to increased warpage [72].
D. Vaes and P. Van Puyvelde
The formulation of polymer blends can be utilized as an ef-
fective way to minimize part shrinkage and warpage of semi-
crystalline feedstock materials in FFF. Chatham et al. (2019) re-
port the beneficial effect of blending two semi-crystalline poly-
mers with considerably different melting temperatures such as PP
and PET to improve dimensional stability. The higher melting PET
phase requires a higher processing temperature than what would
normally be used to extrude the lower melting PP phase. The PET
phase will thus start crystallizing at a higher temperature, while
the PP phase retains its molecular mobility until the deposited
polymer has cooled down further, which also helps molecular dif-
fusion across the interface. The high melting phase can then hold
the shape of the deposited road, which ensures geometric integrity
of the printed part, while the low melting phase minimizes print
failure by postponing shrinkage and warpage of the part [64].
Blending of PP with hydrocarbon resins was proven by Das et al.
(2020) to be able to delay the onset of crystallization of the PP
phase and increased the time the PP phase could remain in the
melt state. This allows for more time for stress relaxation and im-
proved dimensional accuracy [70]. Diederichs et al. (2019) attribute
the improved warpage in their PTT blends to a decreased degree
of crystallinity and spherulite size, as smaller crystallites will re-
duce chain movement upon cooling, thus reducing the residual
stresses [133]. PA 6 was blended with PEO-g-MAH and PS by Jia
et al. (2017). With increasing amorphous PEO-g-MAH content, the
α -crystal content decreased, while the γ -crystal content increased.
This leads to reduced shrinkage as the chains in these blends tend
to arrange irregularly after incorporation of PEO-g-MAH. Ternary
blends of PA 6, PEO-g-MAH and PS again exhibit an improvement
in shrinkage as the PA 6 content is obviously reduced with increas-
ing PS content, and although the α -crystal content is increased
upon addition of PS, the chain arrangement again becomes ununi-
form [145]. The addition of amorphous components into a semi-
crystalline matrix has been shown to reduce the degree of crys-
tallinity and thus the shrinkage due to a dilution effect [72,282].
Copolymerization is another route that is employed to slow
down crystallization kinetics and thus reduce shrinkage of a cer-
tain polymer, such as PP [261]. For example, the 1-butene and 1-
hexene copolymers synthesized by Spiegel et al. (2020) exhibit far
superior printability in terms of shrinkage and geometric stability
[78].
Dimensional changes can also occur after heat treatment
such as annealing. During annealing, preferably at a tempera-
ture that lies sufficiently high above the material’s glass transi-
tion temperature, a reorganization and densification of the inter-
nal crystal structure can occur which leads to increased shrinkage
[96,144,283]. Hu et al. (2019) were able to improve the dimensional
accuracy of their printed PEEK parts by employing their specially
designed heat collector module, which was already described in
Section 2.4.1 [159].
Peng et al. (2019) produced core-shell filaments to circumvent
the severe shrinkage that is associated with the processing of poly-
olefins such as LDPE and HDPE. These filaments consist of a PC/ABS
core and a LDPE or HDPE shell. LDPE and HDPE are generally
not easily employed as feedstock polymers for FFF due to their
excessive volumetric shrinkage upon crystallization. Incorporation
of the PC/ABS polymer core was found to considerably mitigate
the warpage deformation that is associated with shrinkage of this
polyolefin feedstock [257].
4. Conclusion and outlook
All AM processes inherently utilize a layer-wise deposition
strategy for part production starting from a 3D model. This allows
all of these techniques to considerably decrease material wastage,
provide on-demand manufacturing and great freedom-of-design,
35
Progress in Polymer Science 118 (2021) 101411
and reduce the need for additional post-processing. AM technolo-
gies such as FFF are gradually evolving from techniques for rapid
tooling and prototyping to established production processes for
highly customized and more high-end applications. FFF, being a
polymer-based AM technique, employs both amorphous and semi-
crystalline thermoplastic polymer filaments as a feedstock mate-
rial. Hence, there exists a clear need to incorporate more engineer-
ing and high-performance thermoplastics, besides the more com-
monly used commodity plastics such as ABS or PLA, into the FFF
material palette to meet the performance requirements in these
high-end applications. Most engineering and high-performance
polymers are semi-crystalline, meaning that upon cooling, the
crystallization process leads to the formation of densely packed
and ordered crystalline regions. This provides these materials with
generally improved toughness, strength and stiffness, as well as
better chemical resistance compared to amorphous polymers. Fur-
thermore, semi-crystalline polymers can typically be employed at
higher service temperatures yet exhibit far more severe shrinkage
compared to their amorphous counterparts. Semi-crystalline poly-
mers have already proven their worth in many applications utiliz-
ing FFF in fields such as medicine and electronics. It is therefore of
utmost importance to fully understand their behavior during FFF
processing. Mainly the impact of crystallization on final part qual-
ity and mechanical performance is key.
This review article therefore first provided a general overview
of the literature concerning both commonly used, as well as less
frequently employed semi-crystalline feedstock polymers for FFF
and the effect of printing conditions on their crystallization be-
havior during FFF printing. Furthermore, the impact of the degree
of crystallinity and the resulting crystalline morphology on the
printed part’s mechanical performance was highlighted. The crys-
tallization process during printing is governed by the experienced
thermal history, which is, in its turn, dependent on the process pa-
rameters. Although for some processing conditions there seems to
exist a consensus in literature on its effect on printed part crys-
tallinity, for other printing parameters conflicting results have been
reported. This variation in described results can be attributed to
many factors. The impact of a specific print setting on the de-
gree of crystallinity and crystalline morphology is mostly studied
by varying this specific printing parameter, while all other param-
eters are kept constant. This does allow to elucidate the effect of
a parameter within one study, yet, if the set of constant param-
eters differs among different studies, it becomes very difficult to
perform a one-on-one comparison between the reported results.
Furthermore, a correct choice of a specific set of constant param-
eters is highly important as the choice for the value of one pa-
rameter can overshadow the effect of the parameter that is ac-
tually the subject of the study due to the fact that multiple pa-
rameters affect thermal history simultaneously. Finally, among the
reported studies, various FFF print systems are employed, as well
as many different feedstock materials. Obviously, crystallization be-
havior is difficult to compare between semi-crystalline polymers
of different chemical nature. However, even when comparing feed-
stock materials based on the same homopolymer, great variation
in the results were observed, which can be explained by differ-
ences in molecular weight, fillers, and pigments, especially for
commercial filaments. This illustrates the need for more consis-
tent and standardized testing. This review also described many
routes to alter the degree of crystallinity utilizing both in-situ as
well as post-printing heat treatments. Furthermore, the impact of
feedstock modifications such as incorporation of fillers or forma-
tion of blends and copolymers on crystallization behavior were
reviewed.
The use of semi-crystalline polymers in FFF can bring about
specific phenomena or issues that do not occur with amorphous
polymers or at least to a lesser extent. These phenomena, which
D. Vaes and P. Van Puyvelde
can complicate the application of semi-crystalline thermoplastics
in FFF, were thoroughly reviewed in this article.
One of the main rate limiting factors in the FFF process is the
heat transfer in the liquefier of the print head. Both for amorphous
and semi-crystalline polymers, sufficient heat transfer is required
to adequately lower the feedstock’s viscosity so that optimal ex-
trusion can take place. If the viscosity could not be reduced to the
required level, extrudate flow rate and temperature can be lower
than what is established as a set point. In extreme cases, noz-
zle blockage can even occur, leading to process failure. For semi-
crystalline polymers, insufficient heat transfer can cause incom-
plete melting of the feedstock polymer’s crystallites or might not
fully erase crystalline memory in terms of residual segmental ori-
entation. These unmolten crystallites or unrelaxed oriented chains
can then act as so-called self-nuclei. This phenomenon is termed
self-nucleation or self-seeding and leads to a drastic increase in
the nucleation density and an exponential increase in the number
of spherulites, which remain small as they impinge on each other
while growing. However, hardly any study mentions the possible
occurrence of self-nucleation in the context of FFF, which opens
up possibilities for future studies to investigate this phenomenon
within the FFF process. It should be considered whether the mor-
phology that results from self-seeding can be beneficial to printed
part quality and mechanical performance. If so, studies should fo-
cus on how print settings can be changed, e.g. higher print speeds
and lower liquefier temperatures, to obtain self-nuclei and control
the extent of self-seeding. If this morphology is unwanted, noz-
zle design and print parameters can be employed to optimize heat
transfer and allow complete melting of the feedstock polymer.
Upon extrusion, shear deformation can considerably orient and
align the polymer chains in the direction of flow. If orienta-
tion can be retained after extrusion, the resulting anisotropy can
be beneficial for mechanical performance. In the case of blends,
it was furthermore found that shear deformation can alter the
blend morphology upon deposition which again has consequences
for the mechanical properties of the final printed part. However,
for semi-crystalline thermoplastics some additional phenomenon,
termed flow-induced crystallization, can occur. Both the crystalliza-
tion rate, resulting degree of crystallinity and crystalline morphol-
ogy are all affected by the imposed shear flow rate. Depending on
the flow strength, different regimes are entered. At low shear rates,
no effect of orientation exists and quiescent crystallization occurs,
whereas at increasing flow rates, chain orientation will occur. The
oriented chains can act as nuclei and will thus enhance nucleation.
At even higher flow rates, chains are not only oriented but also
stretched which creates fibrillar nuclei, called shish, onto which
lamellae grow radially outward, termed kebabs. The extent of FIC
and the resulting morphology is thus clearly dependent on the im-
posed flow strength, and additionally requires some fraction with
sufficiently high molecular weight as only polymer chains above a
critical molecular weight can retain their orientation at tempera-
tures above the melting point. The occurrence of FIC during FFF
processing has received some, yet limited attention in the litera-
ture, and requires far more extensive research. The question again
rises under which processing conditions this phenomenon can take
place and whether or not the resulting morphology can be ben-
eficial to part quality and mechanical performance. Since in tra-
ditional polymer processing FIC is considered a self-strengthening
mechanism, its use could possibly be exploited and its extent could
be tuned for its successful application within the context of FFF.
Across all AM techniques, thus including FFF, insufficient in-
terlayer adhesion between successively deposited layers remains
a major issue and has severe consequences for the mechanical
performance of printed parts. In the case of FFF, this holds for
both amorphous and semi-crystalline feedstock polymers. How-
ever, to analyze this problem for amorphous thermoplastics, a wide
36
Progress in Polymer Science 118 (2021) 101411
theoretical framework exists. This includes the isothermal healing
model by Wool and O’Connor which consists of five steps: surface
rearrangement, surface approach, wetting, diffusion through repta-
tion across the interface, and randomization. Furthermore, to an-
alyze real problems with non-isothermal temperature evolutions,
other models exist that work well to predict interfacial strength
development for amorphous polymers. Several authors have suc-
cessfully applied similar methodologies to study interlayer bond-
ing between successively extruded amorphous feedstock in FFF,
both qualitatively looking at the effect of several processing con-
ditions, as well as performing more in-depth, fundamental analy-
ses of the problem. For amorphous polymers, the diffusion phe-
nomenon, which can be described through the process of repta-
tion, is in principle only temperature-dependent, where the poly-
mer’s glass transition temperature acts as the limiting tempera-
ture, below which chain mobility is negligible. For semi-crystalline
polymers, on the other hand, the analysis of the welding prob-
lem is considerably more complicated due to the occurrence of
crystallization upon cooling which can impede molecular diffusion
as well. Thus, for semi-crystalline polymers both temperature and
crystallization can limit diffusion. However, most studies on in-
terlayer adhesion of semi-crystalline feedstock were found to only
discuss the effect of processing conditions and reported very simi-
lar results as for amorphous polymers without considering the im-
pact of crystallization on interlayer bonding. Few studies actually
took into account the effect of crystallization on the diffusion ki-
netics or looked at the crystalline morphology at the interlayer in-
terface. Hence, there still exists a large gap in the knowledge on
how and to what extent crystallization can impede chain diffu-
sion across the interface and thus limit interlayer bonding. A clear
theoretical framework should be established. More studies are re-
quired that evaluate and compare the timescales of chain diffu-
sion and crystallization and how these parameters can be tuned
by correct processing conditions. In general, molecular diffusion
should always precede crystallization as this will benefit the inter-
layer strength. Crystallization across the interface can furthermore
be exploited as an effective additional strengthening mechanism.
Semi-crystalline polymers typically exhibit far more shrinkage
compared to their amorphous counterparts due to dense packing
of polymer chains in lamellae upon crystallization. Thermal gra-
dients in the printed part that are inherent to the printing pro-
cess will lead to uneven shrinkage and thermal contraction upon
cooling which result in the buildup of residual internal stresses.
This can induce part warpage, or in severe cases, detachment
from the build plate, delamination or part cracking can occur. It
thus becomes apparent that shrinkage and thermal stresses can
severely distort the part’s dimensions and lead to issues with di-
mensional accuracy and stability. Most studies that discuss the
effect of processing conditions on dimensional accuracy of semi-
crystalline parts do not consider the effect of the resulting de-
gree of crystallinity on part shrinkage and dimensional stability.
Yet, they mostly focus on the changes in thermal gradients and
thus contractile forces with varying process parameters. Hence, the
link between crystallization and shrinkage could be more specifi-
cally highlighted in future studies. Shrinkage and issues with di-
mensional stability are mostly counteracted by either impeding
or postponing crystallization. However, it should be carefully con-
sidered if these adjustments to the crystal forming ability of the
feedstock material will not negatively impact other aspects of the
printing process such as interlayer adhesion or the final mechani-
cal properties of the printed part.
In general, semi-crystalline feedstock polymers can be highly
valuable in responding to the growing demand for more high-
performance materials to be employed in high-value applications
with FFF. However, to successfully exploit their full potential and
to utilize them as efficiently as possible, it is crucial to completely
D. Vaes and P. Van Puyvelde
comprehend and possibly alter their behavior, mainly referring to
crystallization, during FFF processing. From this review, it becomes
clear that for this polymer family, the impact of crystallization and
the resulting crystalline morphology on printed part quality, me-
chanical performance, and dimensional accuracy is often still un-
exposed. It should also be noted that PLA is the most widely stud-
ied semi-crystalline polymer in literature as it is a very common
feedstock material for FFF. However, PLA is not suitable for most
high-performance applications, while other polymers that can be
adequately employed in such applications, such as PEEK and PA,
have not received their fair share of attention in literature.
Funding
The authors thankfully acknowledge financial support pro-
vided by SIM Flanders (ICON project FLAMINCO; project number:
HBC.2017.0325) .
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared to
influence the work reported in this paper.
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