MRS Communications (2023) 13:357–377

© The Author(s), 2023

https://doi.org/10.1557/s43579-023-00352-3

Prospective

From resin formulation and process parameters to the final mechanical

properties of 3D printed acrylate materials
Laura Schittecatte and Valérie Geertsen, Université Paris‑Saclay, CEA, CNRS, NIMBE, LIONS, 91191 Gif‑sur‑Yvette, France
Daniel Bonamy, Université Paris‑Saclay, CEA, CNRS, SPEC, 91191 Gif‑sur‑Yvette, France
Thuy Nguyen, Léonard de Vinci Pôle Universitaire, Research Center, 92916 Paris La Défense, France; Université Paris‑Saclay, CEA, CNRS, SPEC, 91191 Gif‑sur‑Yvette,
France
Patrick Guenoun , Université Paris‑Saclay, CEA, CNRS, NIMBE, LIONS, 91191 Gif‑sur‑Yvette, France
Address all correspondence to Patrick Guenoun at [email protected]

(Received 5 January 2023; accepted 23 February 2023; published online: 7 April 2023)

Abstract
Photopolymerizable resins are increasingly used to generate complex 3D printed parts through stereo lithography, digital light processing (DLP) and
liquid crystal display (LCD) 3D printing. Many challenges relating to the resin chemistry and printing parameters still exist and must be addressed
in order to entirely control the properties of parts after printing. This work reviews the current knowledge and describes the potential of DLP/LCD
methods for printed acrylate resins, as well as the steps necessary to achieve a better control over the mechanical properties of printed materials.

Introduction biocompatibility for bioengineering ­applications[10–12] and

The development of additive manufacturing as we now know dentistry,[13–15] their optical properties,[16] or their ability to
it has been a long process, its conceptualization dating back to respond to stimuli (4D printing).[17,18] Additionally, these mate-
the 1940s. It was in the 1970-1980s that the idea of spatially rials can present a range of mechanical properties. They can be
solidifying a polymer with light was first introduced: Dr. Hideo either soft or stiff, which is of great interest, especially in the
Kodama described a rapid prototyping technology based on a aerospace,[8] energy, and construction industries.[19,20]
laser process in a patent that was abandoned after one year. In Many publications are devoted to the relationship between
1984, a trio of researchers from the French National Center for the final mechanical properties of objects and their process-
Scientific Research (CNRS) and the Cilas/Alcatel company filed ing routes.[12,21–28] However, between both the formulation
another patent describing the layer-by-layer surface photopo- of the resin and the printing process itself, many intercon-
lymerization of an object also using a laser, and they printed a nected parameters must be taken into account. This review
small staircase to prove the concept. Three weeks later, Chuck aims at establishing a consensus of the state-of-the-art from
Hull filed a separate patent also to build small objects layer-by- all these different studies, results and viewpoints. This will be
layer but using UV light.[1] The French patent was abandoned achieved by analyzing the chemistry of acrylate resins, through
for a lack of industrial interest, whereas Chuck Hull developed methods such as fourier transformed infrared (FTIR), rheol-
the invention into a company and introduced the term ‘‘stereo- ogy, differential scanning calorimetry (DSC) or UV–visible
lithography’’ (SLA) in 1986.[2,3] Digital light processing (DLP) spectroscopy. The resulting mechanical properties of printed
­technology[4] was only introduced in the beginning of the 2000s, parts will also be investigated through mechanical constants
followed by liquid crystal display (LCD) printing.[5] presented in Table I, all of which are defined in the hypothesis
Today, the layer-by-layer printing of objects with photopo- of isotropic materials and linear elastic fracture mechanics
lymerization is dominated by these three technologies: SLA, (brittle fracture).[29]
DLP and LCD. Currently, SLA printing is more widely used
in scientific fields and laboratories,[6–9] whereas DLP and LCD
printings are more common for home use. Different types of 3D printers
All three technologies rely on the photopolymerization of a As mentioned in the introduction, the 3D printing vat photopo-
liquid resin at the bottom of a fluid reservoir. Most resins are lymerization principle was introduced many years ago and has
composed, at least in part, of acrylate species, the polymeriza- therefore been widely described in the literature.[2,30] Today,
tion of which is fast at ambient temperature. The formulation of three technologies for the 3D printing of photopolymerization
these resins is crucial as it affects every step of the process from resins—SLA, DLP and LCD—are mainly used, each differing
the printing parameters to the properties of the final object. by their illumination process.
New printable polymer materials are emerging every year. SLA (for stereolithography) photopolymerization makes use of
They can be distinguished by their different properties: their a laser with a given spatial resolution that locally polymerizes the
Vol.:(0123456789)

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 Table I.  Table of the different mechanical constants of 3D printed materials analyzed in this review.
Constant Name Definition Characterization Technique

σy Yield tensile strength Maximal amount of stress a material can with-

stand before exhibiting a plastic deformation
(unit: N/m2). Constraint at which the material
no longer deforms in an elastic manner, The
stress writes σ = F/A with F the force applied
(N) and A the area of the loaded sample (­ m2)

εy Yield tensile strain Relative elongation at the yield tensile stress

Static tensile test scheme.[29]
(%), Elongation ε = l −l l0 , with l the length of
0

the sample during the test and l0 the initial

length
σUTS Ultimate tensile strength Maximal amount of stress a material can with-
stand before breaking (unit: N/m2)
εUTS Ultimate tensile strain Elongation at the ultimate tensile strength σUTS
(%)
σf Breakage tensile strength Tensile stress at material breakage (unit: N/m2)a
εf Breakage tensile strain Elongation at material breakage (%)
E Young’s modulus Characterizes the stiffness of a material submit-
ted to a uniaxial stress in the linear elastic
regime. Defined as the ratio of the stress ( σ )
to the strain ( ε ) in the linear tensile elastic
domain (unit: Pa), e.g. via a static tensile
test.[29]
E′ and E′′ Storage and loss modu- Dynamic determination at a given frequency
lus is possible by Dynamic Mechanical Analy-
sis (DMA) where the storage (E′) and loss
modulus (E′′) are measured. They correspond
respectively to the stored and dissipated
energy for viscoelastic materials.[29],b

DMA (Dynamic Mechanical Analysis) principle.[29]

KIC Toughness Ability of a material to resist fracture propaga- Wedge spitting test, Compact Tension…
tion (unit: J/m2)
H Hardness Ability of a material to resist to permanent Indentation hardness test, scratch test, Vickers Hard-
deformation, such as scratching, cutting, abra- ness test…
sion, indentation or penetration (unit: N/m2)
a
The yield strength, ultimate tensile strength and breakage tensile strength are different for ductile materials (materials able to deform plasti-
cally). However, the acrylate resin polymers studied in this review are brittle materials, thus, the yield tensile strength and breakage tensile
strength are equal in most cases.
b
Some articles make use of static tensile test experiments to determine Young’s modulus, while others make use of dynamic mechanical analysis
(DMA) to determine the so-called storage modulus.

resin [Fig. 1(a)]. The object is polymerized point-by-point along printing is the hatching of the laser beam (distance between the
the laser path. This technique is repeatable and enables the printing center of two laser scans), which can limit the resolution.[2,32]
of rather large objects, although it is very time consuming because DLP photopolymerization solves the problem of the slow
it is a point-by-point process.[31] An important parameter in SLA point-by-point printing by projecting the laser as an entire 2D
design onto a ­layer[33,34] [Fig. 1(b)]. Here, the printing speed

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 Prospective

can be as fast as 0.5 to 15 mm/s[35] and with a resolution of

about 100 µm.[31,34] The main inconvenience of DLP is that
Rn • +Mn → RMn+1 •
only small objects can be printed (due to the reduction of the and the termination:
projector size to ensure high precision).[2] Additionally, possi- RMn • +RMm • → unreactive species
ble optical distortions due to the projector must be addressed.
where I refers to the photoinitiator that produces radicals (R•)
In LCD printing, an LCD screen is placed directly under
under the action of UV light, M refers to the monomer, RM
the resin vat [Fig. 1(c)], where direct contact of the screen on
refers to a chain radical and ­RMn refers to a polymer of n mon-
the vat avoids optical distortions. The printing is also layer-
omers. The vinyl double bond (C = C) is converted into a single
by-layer and the resolution depends on the screen pixel size,
bond during polymerization.[38–40] This allows the determina-
and normally a resolution of 50 to 150 µm can be reasonably
tion of the degree of polymerization by quantifying the amount
expected with LCD technology.[36,37] However, it is possible
of double bonds that were converted. As a result, chemists use
to go beyond this resolution with newer software develop-
the term double bond conversion while physicists tend to speak
ments. For example, LCD allows printing not only in black or
of the degree of cure. The base acrylate resin can be modified
white pixel, but also with different grey levels, enabling very
by changing the photoinitiator concentration, its nature, or even
high resolution (some publications claim a 10 µm in-plane
by using different types of acrylate monomers. The resin for-
­r esolution [35]). Finally, the loss of light energy due to the
mulation directly modifies the resin reactivity.
absorption of the screen must be emphasized; approximately
To compare and evaluate the different formulations and resin
90% of the light is absorbed by the LCD screen.[31] Moreover,
reactivity, P.F. Jacobs proposed a specific law in 1992 based on
the direct contact of the screen with the vat bottom hinders
energetic considerations. Jacobs used the Beer-Lambert law to
control of the oxygen level at the polymerization site, which
describe the exponential decrease of the light energy into the
may cause many printing failures.
resin with the depth z:
Although the same photochemical polymerization reac-
tion occurs in all three of these techniques, the resin must be (1)
 
E(z) = Emax exp −z/Dp
adapted for each process. Indeed, DLP and LCD resins are where ­Dp is the light penetration depth and ­Emax is the total
more reactive than SLA resins because the power density of light exposure dose at the resin surface. ­Dp is inversely propor-
the light used is inferior.[34] Therefore, it is necessary to refor- tional to the molar extinction coefficient of the initiator and its
mulate the resins to fit each process. To do so, in the next sec- concentration. To pass the gel point, E(z) must reach the criti-
tion, we describe the use of Jacobs’ law as an efficient tool to cal threshold energy ­Ec. This occurs when z = ­Cd (cure depth).
compare resins reactivity. At this point:

(2)
 
E(Cd ) = Emax exp −Cd /Dp = Ec
The photopolymerization reaction Finally, the commonly used Jacobs’ law can be obtained
The first step of photopolymerization (or the creation of the from Eq. (2) and is written as ­follows[41]:
“green part”, that is to say the, non-post-treated sample) is  
almost always based on acrylate chemistry. Acrylates pho-
Emax
Cd = Dp ln (3)
topolymerize quickly and at ambient temperature, which makes Ec
them well adapted to 3D printing processes. Epoxy groups can
• Cd: Cure depth (µm)
also be added to generate Interpenetrated Polymer Networks
• Dp: Light penetration depth in the resin (characteristic
(IPN). In IPN systems, acrylates initiate polymerization and
length) (µm).[41]
the green part is subsequently heated to activate further epoxy
• Emax: Exposure dose (mJ.cm−2); energy received at the resin
polymerization.[14,21] However, IPN systems will not be dis-
surface during the curing.
cussed in this review.
• Ec: Critical exposure (mJ.cm−2); minimum amount of
Acrylate monomers can polymerize due to their acrylate
energy needed to start the curing process and reach the gel
vinyl functional group, which undergoes a radical polymeri-
point.[23,24,41–45]
zation. In these reactions, the photoinitiator generates radical
reactive species when excited at a specific wavelength in the
UV spectrum. These reactive species initiate the polymerization Jacobs’ law is applicable in the range ­Dp < ­Cd < ­4Dp.[41] The
of the monomers.[21] As explained by Kim et al.[38] three main semi logarithmic plotting of C ­ d versus E­ max is a straight line
steps can be distinguished in the photopolymerization reaction: known as Jacobs’ working curve [Fig. 1(d)]. One important
the initiation step: point is that Jacobs’ law gives information on intrinsic resin
parameters ­(Ec and ­Dp) that do not depend on the printer or on
I → 2R• experimental conditions.[43] However, the control of the resin
the propagation steps: reactivity is necessary to adjust the printing parameters.
Historically, Jacobs’ working curve applied for SLA print-
ing. The laser scans particular areas of the liquid resin at
R • +M → RM•

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 Figure 1.  (a) Scheme of SLA apparatus. (b) DLP apparatus (c) LCD apparatus. (d) Example of a Jacobs’ curve from Hofstetter et al. repro-
duced with a ­ uthorization[24] (e) Experimental methods to determine ­Dp and ­Ec for DLP or LCD printers.

different speeds. The higher the speed, the shorter the exposure studies are also treated, and we will precise for each case when
to UV and therefore, the thinner the final object is. The height LCD or SLA printing is concerned.
of the samples is directly measured with a caliper or a microm-
eter and corresponds to ­Cd.[23] The exposure ­Emax is obtained
with the following formula:
Influence of the resin composition
Emax =
Plaser
(4) on the mechanical properties
Hs Vs Monomer nature and functionality
where ­Plaser is the laser power, ­Hs is the hatching (distance The first step of the formulation is the selection of monomers
between laser scan lines) and ­Vs is the laser speed.[23,41,44] or a mixture of monomers and oligomers (Table II). As for
For DLP/LCD processes, ­Dp and ­Ec values are also obtained all polymerization reactions, the choice of specific monomer
by exposing a pre-determined area with the same light power (size, molecular weight, and chain rigidity when polymerized)
for different times, as illustrated in [Fig. 1(e)]. ­Cd (sample directly affects the appearance of the printed object and its
height) is also directly measured with a caliper or a micrometer, properties and, among them, its mechanical properties.
but in this case, ­Emax is obtained by multiplying the exposure Several approaches can be found in the literature to confirm
time with the light power [Fig. 1(e)].[40,46] this direct relationship between the monomer structure and the
The large differences in reactivity between SLA, DLP and final polymer properties. For example, Pooput et al. evaluated
LCD resins are due to resin formulations which have been resin reactivity via Jacobs’ curves and mechanical properties
adapted to each process.[24,41,47,48] of their DLP-printed samples via tensile tests.[49] They reported
Thus, the reactivity of the resin is driven by its very compo- that formulations with flexible chains presented lower mechani-
sition, which directly influences the final mechanical proper- cal resistance (high strain and low tensile strength) whereas
ties of the printed part. For the rest of the study, we will focus the formulations that contained rigid chains, with aromat-
on results obtained with DLP printing. A few LCD and SLA ics for example, were stiffer, due to the intrinsic structure of

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 Prospective

chains. Similarly, Zhu et al. worked on healable and recyclable studied the impact of different amounts of HDDA (di-acrylate)
DLP-printed polymer and studied the mechanical properties (Table II) on the mechanical properties via DMA studies.[59]
of resins composed of two monoacrylates: urethane monoacr- The authors observed an increase in the glass transition tem-
ylate (UMA) and acrylic acid (AA) via tensile tests.[27] They perature, ­Tg, and an increase in the storage modulus as the pro-
demonstrated that mechanical properties such as the Young’s portion of HDDA monomer increased. They explained their
modulus, the tensile strength and the glass transition tempera- observations by the fact that high HDDA content increases
ture could be tuned with different monomer ratios. Chen et al. crosslinking in the polymer network. As a result, ­Tg increased
also observed large changes in mechanical properties (e.g., due to the hampering of chain movement, and the stiffness (E)
Young’s modulus and ultimate tensile strength) depending on increased due to high chain crosslinking. Indeed, the authors
the different monomer compositions and mixtures used.[55] showed by X-ray Diffraction (XRD) that the chains were more
Indeed, increasing the proportion of harder oligomer increases packed when the HDDA content increased.[59] This might indi-
the Young’s modulus. cate the occurrence of more intense crosslinking due to the
While commercial acrylate monomers are most commonly di-functional crosslinker (HDDA). This spatial arrangement
used, some authors chemically grafted acrylate groups to generates a packing of the chains and consequently, an increase
other types of monomers. For example, Field et al. modified a in stiffness.
poly(caprolactone) with methacrylate groups. They carried out These works demonstrate that the nature of the mono-
tensile tests and observed an increase of the Young’s modulus mer and the proportion of different compounds influence the
from 0.7 to 4 MPa when the methacrylation substitution degree modulus, the ultimate tensile strength and the glass transition
doubled from 40 to 80%.[12] Chen et al. also observed a strong temperature.
increase of Young’s modulus (from 0.1 to 5.1 MPa) and of ulti-
mate tensile strength when increasing the degree of acrylation Photoinitiator
from 7 to 30% with poly(glycerol sebacate) acrylate (PGSA) Another component of high importance for the photopolym-
polymer printed with DLP.[55] erization reaction is the photoinitiator, which influences the
The crosslinking density is also an important factor that photopolymerization kinetics and printing parameters (e.g.,
influences mechanical properties. This crosslinking density is rheology, layer thickness, exposure time). In addition to that,
directly related to the number of acrylate groups in the mono- its choice appears crucial to mechanical behavior.
mer used, which is called functionality. For example, Miao For example Scherzer et al. demonstrated the different
et al. investigated the storage modulus of bio-based acrylate effects of three photoinitiators at the same concentration in an
monomers with di- or tri-functionality (BHMP2 and BHMP3 acrylate resin.[60] They shed light on the different induction
respectively) printed via DLP method.[56] The authors observed periods or conversion rates obtained depending on the nature
that the triacrylate presented a higher Young’s modulus due to of the photoinitiator.[58,60,61] Moreover, not only the nature but
its compact and crosslinked structure. In the same way, Oezkan also the concentration of the photoinitiator influences the print-
et al. worked on LCD and found that the curing performance ing parameters. Indeed, with a lower amount of photoinitia-
increased with the amount of multifunctional oligomers in the tor, longer exposure times are needed to reach the same layer
formulation.[48] Therefore, the cross-linker, which is a multi- thickness.[50] Gonzalez et al. observed very small variations in
functional acrylate, drives the network organization and thus average viscosity when increasing the photoinitiator (BAPO)
the mechanical properties. content in their formulations.[50] However, Zanon et al., used
Dietz et al. studied the influence of the chain length and of camphorquinone as a photoinitiator and they observed differ-
pendant chains of di-, tri- and tetra-acrylate monomers. They ent rheological behaviors depending on the camphorquinone
mention that for linear di-functional monomers, the longer and content in their liquid resin (lower storage modulus with higher
softer the chain length, the higher the conversion degree.[57] camphorquinone content, obtained by photo-rheology tests).[62]
Concerning branched multifunctional monomers, the authors Additionally, several articles mention the existence of an
observed a decrease in the conversion degree for highly optimum concentration of photoinitiator. Beyond this opti-
branched monomers. They explained that the branches cause mum, the further addition of photoinitiator does not improve
steric hindrance, reducing the conversion degree.[58] However, the mechanical properties due to increased radical recombina-
no mechanical characterization was performed. tion. This shows a direct link between the photoinitiator content
Finally, Borrello et al. worked on DLP and demonstrated and mechanical properties.[61,63,64] Wang et al. tried to optimize
that according to the monomer/cross-linker ratio, a wide vari- the concentration of the camphorquinone photoinitiator in their
ety of Young’s moduli can be obtained.[25] They performed acrylate-based resin to achieve the best mechanical proper-
tensile tests and observed experimentally that a high quantity ties.[65] They observed that the degree of conversion (obtained
of 1,6-hexanediol diacrylate cross-linker (HDDA) strongly by near-infrared spectroscopy), the mechanical properties (elas-
increased the Young’s modulus. Additionally, the ultimate ten- tic modulus and hardness), as well as the curing depth ­Dp (in
sile strength was also slightly increased. Similarly, Shi et al. Jacobs’ law) were maximized for an optimum photoinitiator

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 Table II.  Main components of a photopolymerization resin.
Resin component Role and definition Examples Structures

Monomer Contains one or several acrylate HDDA, TMPTA, PEGDA,

groups will generate a polymer UDMA, Bis-GMA[13]
composed of repetitive units

Oligomer Small polymer (less than 10 PEGDA (Mw = 200, 500,

1,6-hexanediol-diacrylate (HDDA)
repetitive units) containing one or ­ EAAM[44]
7000 g/mol), P
several acrylate groups. Its longer
chain increases the viscosity of the
formulation
Crosslinker Monomer or oligomer that contain TMPTA or HDDA
multifunctional acrylate and can
crosslink monomers or oligomers
densely

Photoinitiator Chemical compound able to gener- Irgacure 819,[12] TPO,[49] Trimethylolpropane triacrylate (TMPTA)
ate radical species when excited at BAPO,[50] ­DMPA[44]
a specific wavelength
Photoabsorber Dye or photo-absorbing compound Sudan I,[51] III, ­Tinuvin[52]
that consumes radical species and
favors the termination process of
polymerization

Plasticizer and Addi- Long soft polymer chains, often PEGDA,[53] ­TEGMA[54] Poly(ethylene glycol) diacrylate (PEGDA)
tives functionalized with acrylates that
contributes to lowering the viscos-
ity to favor printing

concentration. This was also observed by Musanje et al. who with compressive tests for different exposures and different
shed light on the fact that the excess of photoinitiator (cam- dye concentrations. The authors observed that the higher the
phorquinone) could hamper the hardness.[63] In the same way, light absorber content, the lower the compressive strength,
Steyrer et al. found an optimal concentration by carrying out whatever the exposure time [Fig. 2(a)]. They explained that
DMA and tensile tests to investigate the effect of three different a high amount of absorber hampers light penetration and thus
photoinitiators.[64] decreases polymerization. The bonding between layers is weak-
As a result, these articles agree on the fact that the polym- ened, which results in a lower compressive resistance. Hofstet-
erization kinetics depends on the nature of the photoinitiator. ter et al. presented a method to determine the best amount of
In reviewing the literature, a concentration around 1–3 wt% photoabsorber.[24] However, they did not evaluate the impact
of photoinitiator seems to be optimal in terms of mechanical of the absorber on mechanical properties such as the Young’s
properties. modulus.
As a result, photoabsorbers are mostly used to improve the
Photoabsorber printability and resolution of DLP/LCD printed objects, but
With the increase of photoinitiator concentration, polymeri- tend to decrease the stiffness of materials. Nonetheless, few
zation quickly initiates and there is a risk of an uncontrolled studies compare mechanical properties with and without pho-
reaction. Such an uncontrolled propagation leads to a decrease toabsorbers, and this is area deserves additional research.
in printing resolution. To avoid that, photoabsorbers are intro-
duced in the system, in order to consume some of the radical Plasticizers and additives
species and, thus, to regulate the reaction propagation. Unlike Plasticizers decrease the viscosity of resins to ease the print-
photoinitiators that are consumed during the photopolymeriza- ing (Table II); they can also increase the resolution. However,
tion process, photoabsorbers remain active and undestroyed. they also have a negative impact on the mechanical properties.
Photoabsorbers are often dyes used to increase the printability For example, Yang et al. added a plasticizer (PEG300) to an
and decrease ­Dp in Jacobs’ law,[12,24,52] but it is important to acrylate formulation (based on PEGDA), and compared both
determine their effect on the final properties of the material. the printability and mechanical properties via tensile tests.[53]
Bagheri Saed et al. studied the influence of a photoabsorber The authors observed an increase in strain and a decrease
(an orange dye) on the mechanical compression of their scaf- in ultimate tensile strength with the addition of a plasticizer
fold printed by DLP.[66] They characterized their scaffold [Fig. 2(b)]. Thus, if a small amount of plasticizer is helpful for

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 Prospective

the printability, it also lowers the mechanical strength, and this between layers.[71,72] Finally, the degree of oxygen inhibition
must be considered in the design of the formulation. is dependent of the resin formulation itself.[73]
Oezkan et al. investigated the effect of the content of HDDA
as a diluent on the tensile properties of their LCD-printed Curing temperature
objects.[48] As the viscosity is a key parameter for the print- The curing temperature is a very important parameter insofar
ability of resins, some diluents are added, such as TEGMA, as it directly influences the resin viscosity. The temperature is
to significantly increase printability.[54] However, Lin et al. driven by the illumination system of the process (e.g., diode,
observed an increase in shrinkage with the diluent content.[54] laser, LED) and by the polymerization itself, which is exother-
Shrinkage is the reduction of volume occupied by the resin mic. A few studies indicate that increasing the temperature can
during the polymerization process. Excessive shrinkage can make printing easier and increase the conversion rate. How-
cause the delamination of different printed layers. Further- ever, the consequences on the mechanical properties are not
more, according to Yang et al. diluents like water can induce a well known.
decrease in hardness.[53] According to Lu et al., using low temperatures might be
Thus, the use of plasticizers is interesting for highly vis- interesting to reduce polymer shrinkage.[74] Scherzer et al. com-
cous resins. However, improvements in the printability must pared an epoxy-acrylate and a trifunctional acrylate photopoly-
be balanced against decreases in the Young’s modulus due to merization at different temperatures from ambient to 90°C.[75]
plasticization. They observed an important increase in the acrylate conversion
rate (obtained by real-time ATR-FTIR) with temperature.[60]
Sekmen et al. also made this observation in their DLP study.[76]
Effect of printing parameters This result is attributed to a decrease in viscosity, which allows
Printing atmosphere: oxygen inhibition the faster diffusion of species in the medium.[75] Moreover, the
As explained by Yamada and Goto: “Oxygen inhibition causes authors proved that increasing the temperature decreases the
numerous undesirable effects on free radically cured products, amount of dissolved oxygen in the resin. Therefore, a high cur-
including slow polymerization rate, long induction periods, low ing temperature favors the initiation of the reaction. However,
reaction conversion and tacky surface properties”.[68] There- the authors did not link these results to mechanical properties.
fore, when it comes to acrylate photopolymerization, the con- Steyrer et al. investigated the effect of curing temperature from
sumption of radicals by oxygen can drastically influence the 23 to 70°C for DLP photopolymerization of acrylate resins.[39]
final material. They also concluded that the differences obtained were linked
More precisely, an excess of oxygen leads to the incomplete to the decrease in viscosity. The authors demonstrated the
polymerization of acrylate systems. Indeed, oxygen consumes decrease of E ­ c in Jacobs’ law when increasing the temperature:
the radicals and hinders the radical polymerization. Resulting the polymerization could start at lower exposure.[39]
materials are tacky and not completely polymerized [Fig. 2(c) As a result, increasing temperature permits not only a reduc-
under oxygen]. Even when the exposition time is increased, tion in the printing time but also an increase in conversion
the problem persists. rate. ­Tg is also increased, but the precise mechanisms are still
On the other hand, a lack of oxygen leads to very strong not perfectly understood.[38,77] The increase of the curing tem-
and uncontrolled polymerization at the bottom of the vat. It perature might improve the mechanical properties such as the
can also lead to delamination between layers and difficulties in Young’s modulus, but no clear demonstration has been made
detaching the object. Deng et al. worked illustrated this in their yet. More work is needed to confirm these trends and elucidate
DLP study by purging the resin of oxygen with argon, which the mechanisms.
led to uncontrolled curing due to total absence of inhibition
[Fig. 2(c)]. To avoid these consequences, some solutions were Exposure time
found by manufacturers. Most often, the bottom of the vat is The exposure time and light power are of the utmost impor-
permeable to oxygen. This limits the polymerization of the part tance because they determine the conversion degree. Aznarte
at the bottom of the vat. Thus, the force needed to lift-off the et al. observed a decrease of the elastic modulus with lower
piece at the end of a layer printing is reduced. However, for exposure times for DLP printed samples.[78] The authors ration-
LCD printers, where the vat is in direct contact with the screen, alized the result by the curing degree of the resin: lower curing
this solution is not applicable. Another possibility is the addi- time results in lower material stiffness, due to a lower conver-
tion of a rake that mixes the resin between each layer. Finally, sion of acrylate groups.
there is the tilt solution, which displaces the object laterally On the contrary, for longer exposures, layers are exposed to
before uplifting the plate, limiting the suction forces.[69,70] a higher amount of light energy, thus, the conversion is higher
As a result, the amount of oxygen in the resin must be con- and the interlayer zone is reinforced. This generates better
trolled because it has direct consequences on the printability adhesion between the layers and a higher Young’s modulus (or
and on the interlayer adhesion. The presence of a dead zone stiffness). Bagheri Saed et al. also observed an increase in com-
or permanent liquid interface is favorable for good adhesion pressive strength with increasing exposure time for DLP.[66]
Similarly, Pyo et al. observed an increase in the stiffness of

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 Figure 2.  (a) Compressive strength of the scaffolds for different absorbers versus the exposure time, from Bagheri Saed et al. reproduced
with ­authorization[66] (b) Effect of a plasticizer (PEG300) on the mechanical properties, from Yang et al. reproduced with a
­ uthorization[53] (c)
Results of the different structures printed in different atmospheres, from Deng et al. reproduced with a ­ uthorization[67]

their Digital micromirror device (DMD)-printed green chem- samples.[82] Nevertheless, anisotropy is reduced with higher
istry-derived polyurethane with longer light exposures.[79] Yang layer thickness.
et al. investigated the effect of the exposure time of acrylate Concerning the sample size, most studies focus on the
resin in DLP on the printability and the hardness.[53] Concern- printer resolution, which reaches about 100 µm for the best
ing the mechanical properties, a strong increase in hardness performances.[67,71] However, very few works focused on the
was observed, which went from 0 to 107.2 N as the exposure size effect of bigger parts for DLP and LCD printing. Štaffová
was varied from 2 to 8 s. In the same way, Yao et al. generated et al. worked on DLP and studied the evolution of the network
microneedles for medical applications through DLP polymeri- density obtained via DMA, depending on the sample thick-
zation and evaluated the effect of exposure time on the mechan- ness. They observed that “the deformation, glass transition
ical performance in compression.[80] They observed an increase temperature, molecular weight between entanglements and
in stiffness with the increase of exposure time, but a decrease network density” were unchanged with the different sample
in the resolution. thicknesses.[40] However, no study observed the influence of
Thus, if the exposure time increases, the conversion degree the layer area on the mechanical properties.
and the stiffness increase, but the resolution decreases. High
exposures also increase the force needed to raise the object
from the vat, which might cause delamination issues. As a Layer orientation
result, compromises must be achieved between accurate print- The layer-by-layer printing process generates anisotropy in
ing and good mechanical properties, insofar as an excess of the material and influences the stiffness as well as the frac-
exposure time leads to very long processes and over-cured scaf- ture resistance. Steyrer et al. investigated the effect of orienta-
folds. It is also important to note that “dark polymerization” tion on the stiffness, measured by DMA and tensile testing for
exists, and that the reaction continues even after turning off DLP printed samples.[39] They observed that the green parts
the UV light.[22] presented different behaviors depending on the printing direc-
tion. This was also observed by Keβler et al.[81] Aznarte et al.
Layer thickness and sample size observed that specimens printed by DLP in the Z direction (per-
Small layer thicknesses generate more cohesion and thus pendicular to the tensile test direction) presented a lower tensile
increase material stiffness. Indeed, Yang et al. mentioned that modulus and a lower ultimate tensile stress ­value[78] [Fig. 3(a)].
“reduced layer height was beneficial to printing accuracy but This is due to the anisotropy generated by the process as well as
adverse to printing efficiency” due to the increase in printing the orientation of the tensile test itself. However, unexpectedly,
time when using small layers.[53] However, they did not study the specimen printed in X and Y directions (both parallel to the
the consequences on mechanical properties. However, as men- tensile test direction) presented different moduli, stresses and
tioned by Keβler et al., small layer thicknesses increase the strains, although there should be theoretically no difference (the
risk of printing error or void inclusion insofar as voids tend to layer is always printed in the XY plan). As a result, this might
appear in the interlayer area.[81] come from the printing parameters, an influence which is not
According to Kowalska, high layer thickness are det- fully understood yet. Thus, the orientation of layers during the
rimental because they increase polymer stress shrinkage printing process affects the Young’s modulus. Studies agree on
during polymerization. [15] This is in agreement with the the fact that higher moduli seem to be obtained when layers are
results obtained by Wu et al. who observed higher distortion oriented in the same direction as the tensile test.
stress and higher bending curvatures for high layer height

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 Prospective

This anisotropy is also observed in compression tests. For Other printing parameters
example, Wang et al. used DLP printing and demonstrated the As showed in the review by Al Rashid et al. dedicated to com-
existence of different behaviors of polyurethane acrylate resins posites, the main parameters investigated for increasing the
in response to compression and tensile tests, depending on the Young’s modulus, tensile strength, flexural strength, hardness
orientation of the load.[83] Indeed, they observed that compres- and compressive strength have been the layer thickness, the
sion of the samples led to less anisotropy. exposure time, the concentration of acrylate oligomer and the
On the contrary, in fracture studies, higher resistance is light intensity.[86] However, other printing parameters remain
observed when the layers are perpendicular to the fracture unexplored such as the effect of the retracting speed. Indeed,
stress. Štaffová et al. studied via DLP the effect of the ori- after the printing of each layer, the plate on which the object
entation of the layer on the fracture resistance of samples is fixed goes up to allow the printing of the next layer. To our
[Fig. 3(b)].[40] They observed important differences in the current knowledge, the speed at which the plate moves is not
fracture resistance. With a stress applied in the Z direction, studied in the literature although it generates a lot of stress on
specimens printed with layers in the X direction presented the the resin. Its local viscosity might be changed depending on the
highest resistance to failure (layers perpendicular to the fracture applied speed, which might result in different layer thicknesses
stress) while samples with layers in the Z direction were less for different rising speeds. Additionally, printing parameters
resistant. This might be due to weak interlayer bonding, which such as the local heating of the screen and the pixel resolution
favors fracture propagation along the interlayer zone. The crack are rarely studied. Zinelis et al. printed the same resin with
must go through every layer to break the whole material, which different 3D printers (LCD and DLP) and observed significant
requires much more energy than the propagation along a weak dispersions in some mechanical measurements (hardness and
interface [Fig. 3(c)]. Moreover, Keβler et al. observed by SEM indentation modulus for example).[85] This emphasizes the
microscopy fracture specimens printed by DLP in the Z direc- importance of device-specific parameters.
tion and noted the presence of voids between two consecutive As a result, the printing parameters are still not completely
layers [Fig. 3(d)]. These voids might behave as weak points mastered due to their high number and the intrinsic correlations
initiating fracture. The authors supposed these voids might between them. This is also because they are not always acces-
be reduced by a better atmosphere and humidity control.[84] sible to users. The exploration of the various printing param-
Wang et al. analyzed the fracture morphology of the samples eters is intrinsically made difficult by the printers themselves
submitted to parallel and vertical tension as well as the crack because not all parameters can be modified. As presented in
formation of samples submitted to compression (both verti- Table III, many parameters have been investigated, but the cor-
cally and horizontally).[83] The authors observed flatter tensile responding chemical characterization is often missing to fully
fracture morphology for samples submitted to vertical tension understand the changes at the molecular or mesoscopic scale.
(perpendicular to the layers) while samples submitted to hori- Additionally, another processing step: the post-treatment, also
zontal tension presented rougher crack surface. Thus, fracture strongly determines the mechanical properties.
resistance is highly anisotropic. However, fracture toughness is
only defined for isotropic materials, i.e., materials that present
the same properties in all directions. It is not the case here due Effect of post‑processing
to the anisotropy of the printing process (layer-by-layer). Wang Layer-by-layer printing generates a raw printed object called
et al. showed that the orientation has an influence on fracture the “green part”. This green part is always subjected to post-
resistance, but it might not be accurate enough to employ the treatments including washing steps and insolation with UV
term fracture toughness as defined by linear elastic fracture light to achieve total polymer ­conversion[87] (Table IV).
mechanics.
As a result, layer orientation drives the mechanical proper- Washing steps
ties and the anisotropy of the final material. Process parameters Printing is followed by a washing step (mostly with isopropanol
are still not well understood and the differences in directions for acrylates) to eliminate the residual uncured monomers from
might come from the process itself. Furthermore, little attention the object surface. This washing step seems to influence the
is given to process defects like voids and inclusions that might mechanical performance; to some extent, it depends on the sol-
induce interlayer weakness. vent. This was observed by Bardelcik et al., who printed poly-
It is important to state that few studies include statistical methyl methacrylate (PMMA) resin with SLA. They observed
analysis although many exploit the tensile test (Table III). This variations in Young’s modulus with the solvents used (e.g., iso-
highly empirical method must be accompanied by statistical propanol, detergent, hydrogen peroxide).[88] They observed an
studies. In addition, repeatability studies concerning the print- increase of the strain of the samples loaded via tensile test due
ing are required to better understand the disparity and defects to the plasticization induced by the solvent washing. Jang et al.
of the printed materials. investigated the effect of washing conditions on the flexural
strength and conversion degree of objects printed by DLP.[89]
No significant difference in surface roughness for the different

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 ­ uthorization[78] (b) samples printed in
Figure 3.  (a) Scheme of the 3 orientations tested in tensile test Aznarte et al., reproduced with a
X, Y and Z direction and SEM images of these samples, taken from Štaffová et al. reproduced with a ­ uthorization[40] (c) Scheme of the
best orientations to optimize fracture resistance or Young’s modulus, (d) SEM picture of horizontal parallel printing and fracture initia-
tion at the surface of voids, arrows indicate the propagation, which was initiated at the void positions, by Keβler et al. reproduced with
­authorization[81]

conditions was observed, whereas a significant difference in the post-curing temperature, the post-curing duration and even
conversion degrees was obtained (via FTIR measurements). the post-curing methods, drastically affects the final properties
The authors explained that inefficient washings might result in (Table IV).
over-curing during post-treatment while highly washed samples Štaffová et al. observed via SEM analysis that a 30-min post-
present suspended solid particles that could be responsible for treatment with UV further polymerized the interlayer zones
the roughness. In the same way, Lambart et al. investigated the [Fig. 3(b)].[40] The post-treatment resulted in an increase in
flexural strength in three point bending tests of dental acrylate- failure temperature, ­Tg and storage modulus obtained via DMA
based resins printed in DLP submitted to different washing measurements. Similarly, Steyrer et al. observed that the UV
treatments and report similar observations.[90] post-treatment applied to their DLP samples and observed that
Concerning fracture resistance, Hargreaves mentioned the the Young’s modulus and tensile strength of the green samples
ability of solvents like ethanol or soap solutions to initiate were significantly increased after the post-treatment.[39] The
cracks in PMMA with more damage than water.[93] Indeed, increase of modulus after UV post-treatment is due to the den-
according to Štaffová et al., isopropanol washing can lead to sification of the polymer network as observed by an increase
the initiation of cracks in their DLP printed material.[40] in the material rigidity. The increase of post-treatment time
As a result, the washing steps generate swelling and weaken increases the network density and ­Tg in the same way, tending
the inter-layer zones, decreasing the ultimate tensile strength to an asymptotic limit. Thus, UV post-treatment increases the
and Young’s modulus (Table IV). There is still a lack of knowl- Young’s modulus, double bond conversion, and ­Tg.
edge on the washing of DLP and LCD printed objects: what is But a major problem with post-curing, whatever the 3D
the best washing protocol for each resin? Is it preferable to use printing method, is the distortion of the objects, as described
one long wash or several shorter washes per sample? by Wu et al..[82] The authors analyzed the shape of the samples
during UV exposure (post-treatment) with a camera to estimate
Post‑curing the curvature. They tried to link it to the post-treatment process
Post-curing consists of insolating and exposing to UV-light and other printing parameters. They observed a UV-induced
the freshly printed samples, also called green parts. During bending (a final distortion) amplified for low thicknesses.[41]
this crucial step, the polymerization continues, redefining the Nevertheless, uncertainties and disagreements remain concern-
mechanical properties. However, the amount of light received, ing the post-curing kinetics. Besides, one legitimate question

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 Table III.  Outline of experimental works linking printing parameters to mechanical properties.
Main idea Type of Resin chemistry PI content Jacobs law Printing Chemical Mechanical Mechanical Microscopy? Main conclu-
printer parameters parameters analysis properties tests sion
investigated

Scherzer There is a No printer Tripropyl- 1 wt% N.I Atmosphere/ Real-time N.I N.I N.I The induc-
et al.[60] temperature ene glycol oxygen ATR-FTIR, tion period
depend- diacrylate inhibition UV–visible decreases
ence on the (TPGDA) with tem-
solubility and bisphe- perature (due
of oxygen nol A epoxy to lower
in acrylate diacrylate— Oxygen
resin photoinitia- solubility)
tors Irgacure
819 Darocur
1173
Deng et al.[67] Rapid print- DLP ACMO N.M N.I Atmosphere/ FTIR- Melt Young modu- Tensile test N.I Absence of
ing of (4-acryloyl- oxygen and dissolu- lus oxygen leads
thermoplas- morpholine) inhibition tion tests to uncon-
tic polymer monomer, trolled curing
is pos- Sudan III while too
sible when as photo- high oxygen
controlling absorber, content
2 competing Irgacure 819 leads to low
processes: as photoini- printability
polymeriza- tiator accuracy
tion and
polymer
dissolution
Scherzer Understand No printer Tripropyl- 0,1 and 1 N.I Curing tem- Real-time N.I N.I N.I A high curing
et al.[75] how tem- ene glycol wt% perature ATR-FTIR, temperature
perature diacrylate viscosim- favors the ini-
influences (TPGDA) and etry, DSC, tiation of the
the photopo- a bisphenol GA reaction and
lymerization A epoxy the degree of
kinetics of diacrylate conversion,
diacrylate oligomer mostly due to
(BA-EpAc), the viscosity
different pho- reduction
toinitiators
investigated

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367
 Table III.  (continued)

368   
Main idea Type of Resin chemistry PI content Jacobs law Printing Chemical Mechanical Mechanical Microscopy? Main conclu-
printer parameters parameters analysis properties tests sion
investigated

Steyrer Hot VS room DLP Bisphenol- N.M Ec ≈ 10 mJ/ Curing Rheometer, Tg, E, tensile DMA SEM obser- Increasing the
et al.[39] temperature A-dimeth- cm2 and Dp tempera- ATR-FTIR stress vations temperature
printing of acrylate-based ≈ 70–80 µm ture/layer spectros- decreases
a dimeth- resin, BAPO orientation copy Ec. Lower
acrylate photoinitia- mechanical
tor and light properties for
absorber layers ori-
UV-1995 ented in the
(photoab- Z direction
sorber) (anisotropy)
Štaffová Improvement DLP Commercial 6 wt% Ec = 3,3— Post-curing/ HDT, photo- Tg, E, rubber DMA SEM obser- Post-curing
et al.[40] of printing, acrylate trans- 5,7 mJ/ layer orien- DSC, modulus, vations time and
post- parent clear cm2 and tation strain, print orienta-
printing and resin, TPO Dp = 187 to hardness, tion affect

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thermome- photoinitiator 360 µm network mechanical
chanical density properties.
properties of Possible
photopol- uncured
merization regions in the
resins layer bound-
ary
Chan Kim Uv-curing Multi-Jet Commercial 2 wt% N.I Curing tem- ATR-FTIR Tg Differential N.I Possible
et al.[38] kinetics and UV-curable perature (for conver- scanning description
performance 3D printing sion rate) photo- of the Tg
of curable resin (VeroW- calorimetry depending on
materials hitePlus (DPC) and UV curing.
RGD 835), DSC Increased
photoinitiator, curing
diphenyl- temperature
2,4,6-trimeth- increases the
ylbenzoyl conversion
phosphine degree
oxide
 Table III.  (continued)
Main idea Type of Resin chemistry PI content Jacobs law Printing Chemical Mechanical Mechanical Microscopy? Main conclu-
printer parameters parameters analysis properties tests sion
investigated

Yang et al.[53] Printability DLP PEGDA, 1 wt% N.I Exposure N.I Young modu- Tensile test, N.I Decreasing
of DLP PEG300 as time/layer lus, stress, compres- layer height
structures: a plasticizer, thickness strain, hard- sion test, increases
Influence of DPPO as a ness hardness printing accu-
a plasticizer photoinitia- test racy. Increas-
on the print- tor, tartrazine, ing expo-
ability and methylene sure time
mechanical blue and coc- increases
properties cine as photo- hardness
absorbers
Pyo et al.[79] 3D printing DMD Diurethanes 2% (w/v) N.I Exposure FT-IR, UV– N.I N.I N.I Increase of
of green functional- time visible, material
aliphatic ized with DSC stiffness with
polyure- methacrylate, the increase
thanes photoini- of exposure
tiator lithium time
phenyl-2,4,6-
trimethylben-
zoylphosphi-
nate (LAP)
Aznarte Anisotropic DLP Commercial N.M N.I Exposure N.I Elastic modu- Tensile test N.I Small layer
et al.[78] tensile con- standard clear time/layer lus, ultimate (n = 6) thickness and
sideration of resin (PR-48) thickness/ stress, long expo-
DLP printed orientation ultimate sure times
materials strain increase elas-
tic modulus,
and ultimate
stress. Higher
mechanical
properties
in the X/Y
direction

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369
 Table III.  (continued)

370   
Main idea Type of Resin chemistry PI content Jacobs law Printing Chemical Mechanical Mechanical Microscopy? Main conclu-
printer parameters parameters analysis properties tests sion
investigated

Park et al.[26] Thermome- SLA Formlabs clear N.M N.I Layer ATR-FTIR Tg, E DMA Optical Decreas-
chanical resin thickness/ (for conver- microscopy ing layer
properties printing sion rate) thickness
of stereo- orientation increases
lithgraphy Tg. No
printed parts significant
difference in
parallel or
perpendicular
orientation
for SLA
Wu et al.[82] Mechanics DLP PEGDA, Irga- 0,69 wt% N.I Layer thick- ATR-FTIR N.I N.I N.I Higher stress
of shape cure 819 and ness (for conver- and higher
distortion Sudan I as sion rate) bending

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of DLP photoabsorber curvatures
structures for high layer
during post- thickness
curing— samples
modelling
Keβler Influence of DLP Methacrylate 1–5 wt% N.I Layer orien- N.I Flexural Three-point SEM obser- Higher
et al.[81] printing based com- tation strength bending vations mechanical
direction on mercial dental and flexural tests properties in
the flexural resins modulus, the X direc-
strength and Weibull tion: layers
modulus of parameters play the role
3D-printed of "crack
materials arrester".
Voids in the
interlayer
zone are
weak points
inducing
fracture
 Table III.  (continued)
Main idea Type of Resin chemistry PI content Jacobs law Printing Chemical Mechanical Mechanical Microscopy? Main conclu-
printer parameters parameters analysis properties tests sion
investigated

Yong-Hong Mechanicals PolyJet Acrylic mono- N.M N.I Layer orien- DSC, DPC Tg, Elastic Tensile test Optical "The ani-
et al.[77] properties mer/Isobornyl tation modulus, (n = 8) microscopy sotropic
of curable acrylate/ ultimate properties are
resins Phenol, stress, ulti- clearly seen
4,4’-(1-meth- mate strain, in tensile
ylethylidene) tensile toughness
bis-, polymer toughness and elonga-
with (chlo- tion at break
romethyl) with respect
oxirane, to a printing
2-propenoate/ direction,
Diphe- while it is
nyl-2,4,6- not seen in
trimeth- their Young’s
ylbenzoyl modulus
phosphine and tensile
oxide strength" for
this PolyJet
study
Zinelis Comparative DLP and Commercial N.M N.I Difference N.I Martens- Hardness N.I Different
et al.[85] analysis of LCD resin used between Hardness, testing mechanical
different in dentistry LCD and indentation- machine properties
3D printers (Tera Harz DLP modulus due to differ-
resulting TC- 85DAW, and elastic- ent irradiance
mechanical Graphy, index conditions
properties Seoul, Korea) but also to
parameters
such as the
resolution
or the layer
thickness

NI not investigated, NM not mentioned.

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371
 Table IV.  Outline of experimental works linking post-treatment parameters to mechanical properties.

372   
Ref Main idea Type of printer Washing treatment Post-curing method Mechanical properties Mechanical tests Main conclusion

Štaffová et al.[40] Improvement of print- DLP Isopropanol for less Prusa CW1 curing 10 E, Tg, G’ DMA, HDT, tensile Ispropanol wahsing
ing, post-printing and than 15 s mW ­cm−2 at 35 °C test increases defects,
thermomechanical delamination and
properties of pho- swelling. Post-curing
topolymerization
resins
Bardelcik et al.[88] Influence of wash- DLP Isopropyl Alcohol N.I E, tensile strength, ten- Tensile test Washing treatments
ing treatment on (IP) (60 and 90%), sile strain (at break) consequences depend
mechanical proper- Hydrogen Peroxide on the solvent nature.
ties of 3D printed (HP) (2,5 and 5%), Risk of swelling and
PMMA Detergent (D)— increase in strain with
10 min at ambient prolonged washings
temperature
Jang et al.[89] Effect of the washing DLP Isopropyl alcohol N.I Roughness, contact Optical profiler, The degree of conver-
treatment on the frac- (IPA) for 5 s, 1 min angle, flexural contact angle device, sion increased with the
ture strength and the or 10 min, tripropyl- strength three-point flexural increase of washing

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conversion degree ene glycol monome- fracture test time. Residual mono-
thyl ether (TPM) for mers do not affect
10 min flexural strength in a
significant way
Lambart et al.[90] Effect of the wash- DLP IPA, ethanol (EtOH), Light-curing unit Roughness, flexural Three point bending Flexural strength
ing treatment on EASY 3D Cleaner (Otoflash G171) with strength test significant differences
the roughness and (EYC), Yellow 2 × 2000 flashes (λ depending on the
flexural strength Magic7 (YM7), and from 280 to 700 nm) solvent. No significant
RESINAWAY (RAY) under a nitrogen difference in rough-
atmosphere ness
Zguris et al.[91] Influence of UV-curing SLA N.I UV light at 365, 385 Young modulus, ulti- Tensile test Reaching full post-
on mechanical prop- and 405 nm at 25 °C, mate tensile strength curing increases the
erties of stereolithog- 44 °C and 60 °C Young modulus and
raphy parts tensile strength (high
temperature and long
exposures) at the best
wavelength
Mendes Felipe et al.[92] Evaluation of post- SLA 2-propanol in two suc- Post-curing with- Tg, E’, E" DSC, TGA, DMTA Complete cure achieved
curing process on the cessive 15 min baths out any source of (Dynamic mechani- in 30 h without and
thermomechanical light and with the cal thermal analysis) with UV-light. Post-
properties of SLA exposure to an UV curing process influ-
resin light at 371 nm ences curing degree
wavelength and and thus mechanical
2.0–2.5mWcm − 2 for properties
5 min, 30 min, and 2,
5, 15, 20, 24 and 30 h
 Table IV.  (continued)
Ref Main idea Type of printer Washing treatment Post-curing method Mechanical properties Mechanical tests Main conclusion
[77]
Yong-Hong et al. Mechanicals properties PolyJet N.M UV and electron beam Tg, Tensile strength, DSC, DPC, tensile test Electron beam treatment
of curable resins are compared Young’s modulus, increases mechanical
elongation at break, properties and erases
isotropy the size dependent and
anisotropic behaviors
Keβler et al.[81] Influence of print- DLP Rinsing with 96% Postcured for 2 × 2,000 Flexural strength and Three-point bending Thermocycling aging
ing direction on the ethanol flashes under a nitro- flexural modulus, tests decreases failure prob-
flexural strength gen atmosphere and Weibull parameters ability (Weibull plots)
and modulus of thermocycling aging
3D-printed materials for some samples
Wu et al.[82] Mechanics of shape DLP N.M UV post-curing for curvature / distortion modelization of cur- Distortion results in z
distortion of DLP different times vature gradient of conversion
structures during degree generated dur-
post-curing—model- ing the postcuring
ling
Salmoria et al.[87] Evaluation of post- SLA N.M 1 h in a UV chamber Tg, shrinkage, shore Dilatometer, DSC, Defects appear in
curing sterolithogra- (300 W), or 4 min in hardness hardness machine the structure due to
phy parameters a Toshiba microwave uncured resin trapped
oven (700 W), or in the cured network.
under isothermal Thermal post-cured
treatment at 125 °C leads to better perfor-
for 30 min in a con- mances
ventional oven
Steyrer et al.[39] Hot VS room tem- DLP N.M UV flood curing for Tg, E, tensile strength DMA The UV post-curing
perature printing of a 2 × 300 s at 100% leads to similar
dimethacrylate intensity properties even if the
two materials were
not cured at the same
temperature

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373
 Table V.  Final table of the consequences of resin and printing parameters on mechanical properties.
Parameter Mechanical consequences Reference

Increase the ratio of rigid monomer/oligomer Modulus increase by a factor 8, Tensile strength increase by Pooput et al.[49]
a factor 5, Hardness increase by a factor 3 (for the specific for-
mulations compared)
Possible increase of Young’s modulus by a factor 3 Chen et al.[55]
Increase of Tg (of 50°C) Zhu et al.[27]
Addition of an acrylate cross-linker Can increase the Young’s modulus from 1 to 30 MPa Borrello et al.[25]
Can increase the Tg up to 56% Shi et al.[59]
Increase of the methacrylation degree Increase of the Young’s modulus from 0,7 to 4 MPa when the Field et al.[12]
methacrylation degree doubled from 40 to 80%
Increase of functionality (from -di, to -tri acrylates Tensile strength increase of 20 MPa and Young’s modulus increase Miao et al.[56]
by a factor 5 (for the specific di and tri acrylate used)
Photoinitiator Existence of an optimum amount of photoinitiator that maximizes Lima et al.[61]
flexural modulus and Young’s modulus (photoinitiator depend-
ant)
Existence of an optimum amount of photoinitiator that maximizes Musanje et al.[63]
hardness
Nature and concentration of photoinitiator influences yield strength. Steyrer et al.[64]
Maximum yield strength obtained for 1.18 wt % TPO-L
Photoabsorber Decrease in compression strength (2.2 MPa to 0.1 MPa with a dye Bagheri Saed et al.[66]
concentration from 0.025 to 0.075 wt%)
Plasticizers Decrease in tensile strength from 7.0 to 5.5 MPa as PEG300 con- Yang et al.[53]
tent increased from 10 to 40%
Printing atmosphere Mostly studies on the resin reactivity—lack of mechanical charac- Scherzer et al.[60]
terizations
Printing T°C Increase of Young’s modulus and Tg with high curing temperature Steyrer et al.[39]
(70°C instead of 20°C)
Layer thickness Small layers increase Young’s modulus (increase layers from 10 Park et al.[26]
to 50 µm decreased Young’s modulus from 1000 to 600 MPa)
Small layers increase Young’s modulus (increase layers from 50 Aznarte et al.[78]
to 200 µm decreased Young’s modulus from 900 to 300 MPa)
Layer orientation X direction presents higher failure resistance (when stress perpen- Štaffová et al.[40]
dicular to layers)
Z direction presents lower Young’s modulus and tensile strength Aznarte et al.[78]
(when stress perpendicular to layers)
Washing step Decrease of Young’s modulus (from 800 MPa to about 500 MPa Bardelcik et al.[88]
and 400 MPa for some solvent)
Decrease of flexural strength for some solvent Lambart et al.[90]
UV Post-treatment Increase of Young’s modulus, tensile strength (factor 2) and Tg Steyrer et al.[39]
with post-treatment

concerns the post-treatment of porous and cellular materials of with many distinct parameters (summarized Table V). From
precise architecture: which one should be chosen? Should it be a chemistry viewpoint, the components of the resin control
adapted to the density? Is there a gradient of polymerization both the reactivity and the final properties such as the stiffness.
from the surface to the core of post-treated objects? The amount and nature of photoinitiator or monomer used can
As explained by Jang et al., research concerning the influence drastically change the resin properties, and thus the properties
of the post-treatment is very scarce whereas numerous studies of the printed material. Besides, not only the resin but also
focus on improving the printing resolution.[89] However, the the numerous parameters (atmosphere, temperature, exposure
post-treatment drives the mechanical properties (Table IV) and time, layer thickness and orientation….) of the layer-by-layer
should be further studied especially with DLP/LCD technology. printing have to be considered. Indeed, they strongly influence
both printability and the final mechanical stiffness. Finally, the
post-treatment plays an important role in the determination of
Summary and perspectives final mechanical properties and should be further studied.
This review revealed the numerous challenges in DLP and LCD Therefore, while many advances in understanding the links
3D printing. While literature is still scarce for LCD printing, between the resin materials and the final mechanical proper-
DLP studies reveal that this new process is quite complex, ties of 3D printed objects have been achieved, many questions

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 Prospective

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