ChemTexts (2023) 9:4

https://doi.org/10.1007/s40828-022-00176-z

LECTURE TEXT

Chemistry in light‑induced 3D printing

Alejandra Salas1 · Marcileia Zanatta2 · Victor Sans2 · Ignazio Roppolo1

Received: 23 November 2022 / Accepted: 30 December 2022 / Published online: 21 January 2023
© The Author(s) 2023

Abstract
In the last few years, 3D printing has evolved from its original niche applications, such as rapid prototyping and hobbyists,
towards many applications in industry, research and everyday life. This involved an evolution in terms of equipment, software
and, most of all, in materials. Among the different available 3D printing technologies, the light activated ones need particular
attention from a chemical point of view, since those are based on photocurable formulations and in situ rapid solidification
via photopolymerization. In this article, the chemical aspects beyond the preparation of a formulation for light-induced 3D
printing are analyzed and explained, aiming at giving more tools for the development of new photocurable materials that
can be used for the fabrication of innovative 3D printable devices.
Graphical abstract

Keywords 3D printing · Photopolymerization · Additive manufacturing · Vat technologies · Photocurable formulations

* Ignazio Roppolo
[email protected] Introduction
1
Department of Applied Science and Technology, Politecnico
Di Torino, Corso Duca Degli Abruzzi 24, 10129 Turin, Italy Three-dimensional printing (3DP), the common name
2 employed for polymeric additive manufacturing (AM), has
Institute of Advanced Materials (INAM), Univesitat Jaume I,
Avda Sos Baynat S/N, 12071 Castellón, Spain emerged in the last decade as an advanced and versatile

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technology that enables a rapid, personalized and on-demand The major challenge nowadays is the limited availabil-
fabrication of parts and objects. Currently, 3DP is one of the ity of materials specifically designed for 3DP, since their
most promising manufacturing technologies, gaining more development did not keep pace with the evolution of the
importance both in research and in industry [1]. Unlike in techniques [9]. In the last decade, novel materials have
traditional manufacturing processes, using 3DP it is possible been developed for processing via 3D printing and provide
to fabricate almost any arbitrarily complex shapes, with very advanced properties to the final object. The combination of
few limitations. The general concept is a build-up process additive manufacturing and functional properties, such as
which starts from a digital model (computer-aided design stimuli responsiveness, is called 4D printing and is aimed
files or CAD) of the geometry to be fabricated. This file is at integrating specific structures and smart functionalities to
then divided in slices by a dedicated software and sent to enable applications in advanced fields such as medicine and
the 3D printer, which reproduces the object typically in a aerospace [10]. In this context, chemistry is fundamental
layer-by-layer fashion. This computer-aided manufacturing for the evolution of novel materials. Among the different
(CAM) has a high degree of automation and reproducibility, 3DP techniques, light-induced 3DP (alternatively called vat
allowing precise control over the production [2]. polymerization 3D printing, VP 3DP) better matches chemi-
Nowadays, there are several 3D printing technolo- cal background with technological development.
gies available. They are usually classified according to For these reasons, this article is focused on showing the
the raw material employed and/or by the operating prin- chemistry beyond light-induced 3DP, highlighting different
ciples through which the layers are created. According to aspects that are focus of current research, thus giving the
the American Society for Testing and Materials (ASTM), tools for further advancements. First, the 3D printing tech-
there are more than 50 different AM technologies that can niques will be briefly described, focusing on the basis of
be classified into seven different categories: material extru- photopolymerization. Afterwards, the single materials ele-
sion, material jetting, binder jetting, sheet lamination, vat ments will be discussed, with particular focus on the chemi-
photopolymerization, powder bed fusion and direct energy cal aspects.
deposition [3]. These techniques rely on different character-
istics of the printer and fabrication parameters, which influ-
ence the model design and topological optimization, and VAT polymerization
determine the object resolution and production times, with
a different characteristic in terms of the size of the features Vat polymerization (VP) is an AM technology, in which a
at various scales [4]. photopolymerization occurs in a tank of resin, commonly
Being related to virtual models, 3DP enables the on- known as a vat, containing a formulation of monomers,
demand fabrication of customized products in a cost-effec- additives, photoinitiators and fillers, detailed in the follow-
tive manner, especially for limited productions, due to the ing sections [11]. The set-up includes a light source that
ease modification of digital files. The modifications can be photopolymerizes layer by layer a digital 3D design. Com-
then spread virtually, enabling distributed fabrication, sav- pared with other commonly employed AM techniques such
ing on time and transportation costs [5]. In addition to these as Fused Filament Fabrication (FFF), VP can achieve high
advantages, there are environmental benefits such as lower printing resolution and accuracy, faster printing times and
energy consumption for small-batch productions and more has the ability to tailor the formulations and consequently
efficient material use, since waste is extremely limited by the properties of the materials fabricated.
the possibility of reusing almost all the feeding material. VP techniques based on stereolithography (SL) processes
However, drawbacks related to the suitability, toxicity and were first developed in the early 1980s by Hideo Kodama
sustainability of materials still need to be fully addressed [6]. and Charles Hull [12, 13]. SL is based on the focused polym-
On the other hand, 3DP still did not reach its premises. erization of a thin layer of ink inside the vat by means of
To do so, it is necessary to re-think the way products are a laser beam. Afterwards, different related methodologies
designed and manufactured, gathering a controlled spatial were developed, including digital light processing (DLP)
arrangement to achieve hierarchical and intricate architec- [14, 15], micro-stereolithography (µSL) [16], continuous liq-
tures, with graded or multi-material structures [7]. Thus, uid interface production (CLIP) [17, 18], two-photon polym-
more efforts should be devoted to equipment improvement: erization (2PP) [19] and computed axial lithography (CAL)
3DP can be slower compared with conventional processing, [20]. A scheme of these techniques is depicted in Fig. 1.
but it is more versatile and agile since it relies on single- The spatiotemporal-controlled photoactivated polym-
step fabrication of a near-net shape object. This reduces the erization process enables precise over control the localized
number of processing and post-processing steps required to solidification of resin materials, which results in high shape
achieve the final component, leading to a significant reduc- fidelity of the final object compared with the digital model.
tion in the overall operational time [8]. The printing resolution on the XY plane, perpendicular to

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and post-curing processes are typically applied to remove

non-polymerized resin and to improve the mechanical prop-
erties of the fabricated parts. The post-curing enhances the
long-term structural stability of the printed structure because
it increases the final cross-linking density, thus increasing
the degree of polymerization, since the printing is performed
to reach the gel point without inducing complete conversion
of the resins [23]. SL machines that can be configured for the
building platform to rise (bottom up) or lower (top down)
(Fig. 1a). The light comes from the opposite direction to the
movement of the platform. In the top-down configuration,
the platform and printed part are submerged in the vat during
the printing process. The light source is situated above the
vat and the reaction occurs on the free surface [24]. For each
cured layer, the object descends into the liquid precursor to
coat another fresh uncured layer above it, and this requires
deep tanks and large volumes of resin. In the bottom-up
configuration, the laser beam hits the resin from the bot-
tom of the vat through a transparent window, and the object
remains attached to the platform that rises according to the
Fig. 1  SL-based technologies. a Methodologies to solidify the pho- formation of each layer. This is normally preferred, since
topoloymer resins in laser-based SL and in digital light projection it reduces the volume of resin required, especially to build
technologies. Reprinted from [11]. b Bottom-up versus top–down vat
technologies. Adapted with permission from [52] large parts and it is not dependent on the vat depth, which
limits the size of the printable geometries. In SL, the laser
spot size determines the XY resolution achievable. Classic
the light irradiation, and in the vertical direction parallel to SL technology can achieve ca. 10 µm XY resolution [25].
the irradiation path outlines the minimum volume unit, or In the early 1990s, micro-stereolithography AM (MSL
voxel, that can be resolved. In SL machines, the solidified or µSL) was developed, with the main difference compared
polymer is typically formed by focusing the laser using a with SL in the laser spot size of about 5 µm [16]. Recently,
galvanometric head on a building platform to create the first the use of more precise lasers has allowed the genera-
layer [21]. This polymerized layer remains attached to the tion of structures with submicron features [26]. Digital
building platform. After one layer has been cured, the plat- light processing (DLP) 3D printers direct the light with
form is raised or lowered depending on the printing configu- deformable mirror device (DMD) chips [27, 28]. Here,
ration. The resin optical transparency and therefore the light each micro-mirror on the DMD represents one pixel from
penetration is an important factor to determine the step size, the digital image in the layer to be solidified. Under opti-
which should be sufficient for the entire layer to be cured mized conditions, printing resolutions of 3–5 µm in the
but not too small to avoid a curing depth beyond the desired XY plane can be achieved [29]. For each layer printed, the
layer height, which would lead to over-curing and ultimately entire cross-section of the object is projected, which is sig-
lower the resolution of the printed parts. Layer thickness and nificantly faster than the single-point laser SL technology.
irradiation times are key parameters that need to be carefully Indeed, the photopolymerization of the entire cross-section
selected and optimized. The Z-axis steps should be selected of the object significantly reduce printing times compared
to reach a compromise between high resolution and short with SL techniques, and enables printing of larger areas.
build times. The vertical resolution depends mainly on the Currently, the best commercial DLP-based printers claim
precision of the stepper motor screw of the printer and the resolutions of about 20 µm [30]. Recently, another tech-
mechanical accuracy of its rotation screw that controls the nology has gained enormous commercial interest due to
motion of the building platform [22]. However, other print- its simplicity and low cost, while maintaining resolutions
ing parameters affect the resolution on the Z axis, including close to DLP. They use a light-emitting diode (LED) array,
the power and wavelength of the incident light. The sub- usually at 405 nm, as a light source and a liquid-crystal
sequent layers are polymerized following the same proce- display (LCD) screen to act as a mask that directs the layer
dure until the complete fabrication of the object. It is usual polymerization. These technologies are very affordable
to have longer polymerizations times for the first layers, to and can achieve high resolutions (28 × 28 µm) dictated by
ensure a robust binding to the platform. After the printing is the LCD screen resolution, rapid printing times (1–3 s/
complete, washing with alcohols (e.g. ethanol, isopropanol) layer) and high build volumes [31]. A breakthrough in the

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field was reported in 2015, when the continuous liquid Principle of photopolymerization
interface production (CLIP) was reported [32]. Here, a and influence of light absorbers
thin interfacial layer of oxygen is created at the bottom of
the vat through an oxygen-permeable window. The oxygen Photopolymerization is a polymerization method that basi-
acts as a polymerization inhibitor in the window surface, cally employs the energy provided by photons (i.e. light) to
allowing a continuous interface for polymerization, very initiate the reaction. Different from other polymerization
near the bottom window. This results in a ‘layer-less’ print- methods, photopolymerization can occur only by polyad-
ing and therefore considerably increases the printing speed dition, with the continuous reaction of propagating species
(500 mm/h). An added advantage of this technology is that (radical of cation) with unreacted monomers. This reaction
the parts fabricated are considerably more isotropic than brings about the formation of polymer chains and, conse-
other SL techniques due to the layer-less nature. Recently, quently, polymeric materials [34].
the group of Prof. Mirkin reported a breakthrough that A photopolymerization reaction is typically divided into
permits the area of printing and the speed to be increased, three steps:
branded high-area rapid printing (HARP) [32]. A flow of
a thin layer of fluorinated oil employed in the base of the • Initiation, i.e. the step in which light generates the
printing bed avoids the adhesion of the materials to the active species;
base and facilitates the continuous cooling in the printing • Propagation, i.e. the step in which photogenerated spe-
front. This helps dissipate the heat generated during the cies react with monomers, leading to an increase in
polymerization. This technique allows to fabricate multi- molecular weight and the formation of the polymeric
ple materials beyond photopolymers, including elastomers, chains or networks;
ceramics and thermoplastics. • Termination, i.e. the step in which the polymerization
Other niche applications have also been developed, reaction ends, for multiple reasons [35].
namely two-photon polymerization (2PP) and computed
axial lithography (CAL). The main feature of 2PP is that Thus, the first necessary step to induce photopolym-
the process is activated by the simultaneous absorption of erization is the generation of reactive species, which is
two photons generated by a pulse of a pico- or femtolaser induced by the light. This can happen only employing
pulse [33]. The absorption happens in the more energetic chemical compounds, called photoinitiators, which are
part of the laser spot, which starts the free-radical polym- able to absorb the light radiation and consequently gener-
erization, resulting in structures in the range of 100 nm. ate the initiating species. This can occur by direct genera-
[15, 33] Despite the impressive resolutions achievable, tion of the reactive species (Norrish I photoinitiators) or
2PP suffers from important drawbacks for industrial imple- aided by a co-initiator (Norrish II photoinitiators). The
mentation including the high cost of the equipment, the photochemical mechanisms beyond these two types of
limited building volume (< 1 mm in height) and the low photoinitiators have already been explored[36, 37], but
printing velocity, typically in the range of 0.5–1 mm/s. for the sake of clarity they are summarized here. In Nor-
Computed axial lithography (CAL) was developed at Law- rish I photoinitiators, the absorbed light excites the mol-
rence Livermore National Laboratory and is a volumetric ecule to a triplet state, which then decays to a singlet state,
3D printing technique, in contrast to traditional ‘layer- with consequent cleavage of a σ-bond and generation of
by-layer’ approach. CAL employs computed tomography two radicals, able to initiate the polymerization reaction.
(CT) images to generate a hologram within a controlled Differently, in Norrish II photoinititiators, the excited
photopolymer volume. This hologram is generated by the molecule abstracts an H atom from a donating co-initiator
simultaneous projection of several 2D images while the (usually amines), decaying to equilibrium state, whereas
vat tank rotates continuously. The images combine through the co-initiator can now start the polymerization. In any
the liquid resin from different angles, resulting in a three- case, independently from the path, the initiation mecha-
dimensional hologram with enough energy to photopo- nism can be shown as follows (Eq. 1):
lymerize a volume of resin. The key parameters of CAL
h𝜐
techniques are the angular velocity and the resins’ viscos- PI → R. Ri = Φi Iz 𝜀[PI] (1)
ity. The speed of rotation has an impact on the printed
features, if it is too fast and viscosity must be enough to where Ri is the initiation rate, Φi is the initiation quantum
prevent a relative the relative shift of the 3D printed model yield, ε is the molar extinction coefficient at a given wave-
and the rest of the liquid resin. CAL present some inter- length, [PI] the molar concentration of the photoinitiator and
esting features, including high production speed, since it Iz is the incident photonic flux. This coefficient is related to
works volumetrically and has high surface definition. the incident radiation Io (i.e. the radiation at the surface)
through the equation (Eq. 2)

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IZ = Io 10−A (2) polymers, which are generally soluble in their monomers,

( )
disabling the possibility of obtaining solid objects. Most of
where A (the absorbance) is defined by the Lambert Beer the ‘standard’ commercial resins for VP 3D printing have
law (Eq. 3) these characteristics since the priorities were rapid print-
ing and extreme precision. Nowadays, many resins with
A = εzc (3) different characteristics are developed for light-induced 3D
where c is the concentration of the absorbing species, that printing, with different mechanical and physico-chemical
in the present case is the concentration of the photoinitiator. properties (discussed below).
Consequently, the initiation rate (i.e. the efficiency of polym- Finally, termination of the polymerization occurs when
erization starting) is related to both the chemical character- two growing polymeric chains react, following this mecha-
istics of the photoinitiator (via Φi) and the light intensity. nism (Eq. 5)
On the other hand, it also emerges that given a certain light
source (i.e. fixed Io), increasing the photoinitiator concentra-
P. + P. → PolymerRt = kt [P. ]2 (5)
tion [PI], the penetration length of the light (z) decreases. In where Rt is the rate of termination and kt is the kinetics con-
VP 3D printing, where Z steps are fixed by the operator (i.e. stant of the reaction. By combining these relations, the rate
slicing), this is of particular importance, since the control of polymerization can be expressed as (Eq. 6)
of the penetration allows both an efficient adhesion of the
different layers and a more precise printing, avoiding uncon- kp [ ]0.5
trolled polymerization beyond the desired voxel.
Rp = Ri [M] (6)
kt0.5
The second step of photopolymerization, propagation,
starts when an initiating species ­R. reacts with a monomer This equation was demonstrated to be particularly valid
(M), thus generating a propagating reactive group which, for mono-functional monomers. When termination occurs
interacting with other monomers, leads to the growing poly- mainly for kinetics effect, related to the decrease of the
meric chain (P). This process is described by the following mobility of the species in the polymeric network, which
equation (Eq. 4) but is typical for 3D photopolymerization, a modification of
M
this kinetics equation is necessary, as demonstrated in
R. + M → RM . → P. Rp = kp [P. ][M](4) (4) the literature [34]. Notably, the polymerization kinetics
is proportional to the first power of the concentration of
where Rp is the rate of polymerization and kp is the constant monomers and to the square root of light intensity. Thus,
of chain propagation. the quantum yield of the polymerization ΦP results (Eq. 7)
In most cases, in photopolymerization this polyaddition
propagating reaction is a chain-grow mechanism, typical RP
ΦP = (7)
of unsaturated bonds (vinyl, acrylate, methacrylate, etc.) Iz
or rings (epoxy, etc.). An alternative to this mechanism
is step-growth polymerization, which is typical of thiol- which clearly decreases increasing light intensity. In addi-
ene/-yne photopolymerization reactions; the kinetics of tion, Eq. 5 shows that the termination rate is proportional
this polymerization mechanism is out of the scope of to the power of two to the concentration of the propagating
this article, but it can be found described in detail in the macro-molecular species (P.), which depends on the concen-
literature [38]. The extent of the propagation step deter- tration of the initiating species. Consequently, it is necessary
mines the molecular wight, which in turn determines many to limit the photoinitiator concentration, since on one side it
parameters such as the gel-point, and the mechanical and speeds up polymerization but on the other side, if in excess,
physiochemical properties of the polymer. The relation- leads to high termination [41].
ships between these properties have been reported in the While in many applications of photopolymerization it
literature [39, 40], but it is worthy to mention some aspects is ‘simply’ necessary to have a fast and effective polym-
directly related to light-induced 3D printing. Fast kinetics erization, in 3D printing it is also necessary to have spatial
and rapid gelling of the formulation imply a shorter irra- control over the polymerization, to obtain precise struc-
diation time, which is preferred to decrease printing times tures [42, 43].
and to increase precision, since after gelling, propagating In most cases, the resolution is empirically obtained by
species hardly proceed. For that reason, in light-induced adjusting the quantity and type of the photoinitiator and
3D printing, multifunctional monomers are employed, the printing parameters, such as layer exposure time and
which generates highly cross-linked polymers with rapid light intensity. In addition, other important parameters that
gelification and (theoretically) infinite molecular weight. affect the rate of polymerization are the monomer reactiv-
Furthermore, mono-funtional monomers lead to linear ity and the temperature.

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Two strategies can be applied to increase precision in polymerization rate but efficiently end propagation, con-
3D printing. The first one involves the use of dyes and fining polymerization in the irradiated area and increasing
photoabsorbers, i.e. molecules able to absorb the light in resolution.
the same spectral range of photoinitiators, but without gen-
erating reactive species. In this case, the absorbance of a
formulation (Af) can be described as (Eq. 8) 3D printable formulations
∑
Af = z 𝜀i ci (8) A common photocurable formulation, suitable for all the
above-mentioned 3D printing technologies, is composed
where Af at a given wavelength with a given optical path of at least two components: monomers/oligomers and
length (z) is simply the sum of the contributions of the con- photoinitiator(s) (PI) [49, 50]. Independently of the tech-
centration ( ci ) of every absorbing species i multiplied for nology or polymerization mechanism, resins could also con-
the corresponding coefficient of its molar extinction ( 𝜀i ). tain other ingredients that can enhance their printability or
Dyes, competing with the photoinitiator in photon absorp- provide specific properties, such as radical scavengers, dyes
tion, increase the absorbance and, in turn, decrease the rate and fillers or additives.
of initiation (Eq. 1) with obvious consequences on the pho- As mentioned in the previous sections, the VP process
topolymerization mechanism. In this context, the dyes in VP starts with a patterned exposure to light that activates the PI,
3D printing allow a finer control on the XY plane, decreas- which absorbs the incident radiation and generates reactive
ing propagation out of the pixel of irradiation [44]. species, usually radicals, encouraging the conversion of the
Furthermore, the following equation must be taken into liquid monomers into a cured covalent network [51]. This
consideration (Eq. 9) PI must be compatible with the corresponding light source,
(
EMAX
) commonly UV or visible light, the latter being much safer
Cd = Dp ln (9) and compatible with cell-laden water-based inks [52, 53].
Ec
On the other hand, photocurable species, such as monomers
where the Cd is the curing depth, Dp the light penetration or oligomers have single or multiple active groups, as side or
depth, EMAX the energy dosage per units of area and Ec is the chain-ends, that enable their association into a cross-linked
‘critical’ energy to activate the reaction. Dp is empirically network predominantly on the irradiated regions [54]. There-
defined as (Eq. 10) fore, for an accurate 3D printable formulation, there should
be tuning between the composition and the properties, which
1 in turn define the curing kinetics and penetration depth.
Dp = (10)
2.3𝜀[PI] These, combined with adequate printing parameters such
So, inversely proportional to ε and to the concentra- as light intensity and time exposure, allows an optimized
tion of photoinitiator, it thus emerges that the presence VP regarding the curing speed, precision and mechanical
of dyes increases the coefficient of molar extinction and integrity.
decreases the curing depth. In this respect, dyes allow the In all these light-based technologies, the polymerized
precise control of C d which, in principle, should be as object has continuous contact with the liquid resin, therefore
close as possible to the Z step of the 3D printing process. it must not be soluble in the ink during the printing. This
[42, 45, 46] condition is achieved by supplying enough energy to reach
The second approach involves the use of scavengers, the material’s gel point [55]. In the next sections, the chem-
in particular radical scavengers. These chemical com- istry of the main components of a 3D printable formulation
pounds are able to trap radicals, thereby stabilizing them. will be introduced.
It emerges that in a radical photoinduced process, radical
scavengers may react both with initiating species (Eq. 1) Monomers
and with propagating species (Eq. 4), inducing termina-
tion (Eq. 5). If on the one hand radical scavengers reduce Free-radical polymerizable resins are frequently based on
the speed of the 3D printing process by decreasing the the highly reactive (meth) acrylate functionalities [56].
rate of the polymerization, which in turn implies longer These groups are employed as building blocks to develop
irradiation times per layer, on the other hand they can bigger molecules due to their high reactivity upon light irra-
interact with growing macro-molecules, that are generated diation, well-established mechanisms and commercial avail-
in the irradiated voxels and then propagate out of those, ability [57]. A few examples of the most common monomers
stopping the polymerization [47, 48]. A balanced intro- and oligomers according to their nature are shown in Fig. 2.
duction of radical scavengers can thus slightly affect the Other functionalities can also be used, such as polyester,
vinyl, vinyl ether, thio-ene/yne and even cationic-based

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Fig. 2  Chemical structure of commercially available polymers and monomers for application in 3D printing

systems (combining free radical systems) [58–61]. The acrylates are characterized instead by lower shrinkage and
selection of suitable monomers or oligomers for VP is based adequate kinetics. [30, 63–66]
on the application and processing technology to be used. Other monomers with a wide range of functional groups
The main criteria for their selection are functionality have been reported, including (meth)acrylamides, which
(mono-, di- or poly-), viscosity, reaction kinetics, hydropho- are compatible with different AM technologies (Fig. 3b).
bicity/hydrophilicity, shrinkage, costs, shelf life, volatility, The reactivity of these moieties decreases together with the
toxicity and the final mechanical and functional character- inductive effect, this way, the methyl-functionalized mol-
istics of the product [54]. However, commercially available ecules also have a lower tendency to homopolymerization.
resins are based on the optimum criteria for printing accord- Therefore, reactivity can be modulated by electron acceptor
ing to the chosen technology, but their formulation tends to groups that impart stability to intermediate radical species
be a selection of multifunctional monomers that are usually [67]. Furthermore, molecules with a polymerizable double
not explained in detail. bond, such as methacryloyl groups can be used on the back-
For the selection of monomers in a photocurable formula- bone of an unreactive species, by esterification of hydroxy or
tion, it is necessary to know that the reactive groups mainly amino groups to provide photoreactivity [68]. This method
control the kinetics, while the backbone mainly influences enables the functionalization of natural (e.g. gelatin, chi-
the physicochemical and mechanical properties (strength, tosan or cellulose) and synthetic polymers [23].
brittleness and hydrophilicity) of the polymer [62]. On the other hand, reactivity also depends on the num-
The preference for acrylates is due to their fast reactiv- ber of present functionalities in the reactive species. As
ity related to their chain growth-polymerization mechanism multiple functionalities lead to an auto-acceleration in the
(Fig. 3a) and oxygen inhibition, that allows good adhesion early phases of the propagation, a higher viscosity and a
between printing layers[54]. However, they tend to shrink denser and stiffer network, which would mean a consid-
when cured, leading to poor resolution, internal stress or erable amount of unreacted double bonds [52]. Monomer
even damage to printed objects. Meanwhile, methacrylate molecular weight has a great impact on this phenomenon,
monomers reduce the shrinkage problem but with a slower as low-molecular-weight species have lower viscosities
curing rate. Aromatic or high-molecular-weight (meth) and increased mobility while higher-molecular-weight

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Fig. 3  Schematic representation of photopolymerization mechanisms. a Chain growth and b examples of reactions of various reactive species. c
Step-growth polymerization mechanisms, d examples for various reactive species. Reprinted with permission from [52]

monomers can reduce shrinkage but restrict mobility and In Fig. 3d, the possible polymerization mechanisms in the
viscosity, requiring a diluent. Also, as mentioned, the back- presence of thiols are shown.
bone influences the mechanical stress and properties of the These photoinduced reactions follow an orthogonal click
final polymer. The propagation has diffusion-controlled chemistry because each available thiol group reacts only
kinetics, where limited mobility of the macro-radical chain once with one alkene double bond, producing homogene-
ends produces a heterogeneous network with highly and ous networks with consistent bulk and local properties [73].
loosely cross-linked regions [69]. This selectivity can be exploited by performing the reaction
For more niche applications, thiol-ene/-yne systems and in an off-stoichiometric ratio to control the reaction’s conver-
epoxy are also used in VP, known for their reduced shrink- sion and still have residual functionalities from the excess
age, lower stress and higher conversion compared with component and perform post-printing functionalization [38].
acrylate [60, 66, 70]. C–S–C bonds in thiol-enes implies However, the kinetics are dependent on the alkene’s reactiv-
low mechanical properties, but this can be overcome by ity, which increases as the double bond’s electron density
adding allyl ethers to the mixtures. [66] Furthermore, an increases, with norbornene showing the highest reactivity
increase in the glass transition temperature of the polymers among -ene monomers because of the inherent ring strain
can be obtained by replacing alkene with an alkyne in the [70]. The stability of the intermediate carbon-centred radi-
mixtures with thiols monomers, because of the increase of cals and steric hindrance also influences the reactivity, where
cross-linking density in the network [30]. Thiol-ene polym- terminal -ene groups are usually more reactive.
erization follows a step-growth pathway, as depicted in Regular network formation can be achieved by using
Fig. 3c, requiring a PI instead of a chemical catalyst [52, multifunctional thiolated cross-linkers with more than two
71]. The advantages of thiol-ene networks include their high moieties, that can undergo reversible disulfide bond forma-
rate of reaction and conversion under ambient conditions, tion as a side reaction when in excess, providing a dynamic
with reduced shrinkage due to the delay in the gel point and behaviour [74]. As mentioned, thiol-ene can be less brittle
mechanical stress, as well as their lower susceptibility to than (meth)acrylate networks, leading to soft materials and
oxygen inhibition compared with the first mechanism [72]. low operational temperatures. Their rigidity can be increased

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by exploiting the hydrogen bonding between urethane chains more energetic light sources, are more compatible with SLA,
end-capped with norbornene as -ene building blocks [63]. which uses more light sources at 355 nm. [89]
Finally, epoxy can be cured by cationic-induced mecha- Many photoinitiators belong to Norrish I class. Benzyl
nisms. In this case, the PI generates a cationic active cen- ketals are efficient PIs based on the formation of a methyl
tre after UV light irradiation, which in turns initiates the and benzoyl radical, examples such as 2-hydroxy-2methyl-
photopolymerization of epoxy or vinyl ether monomers 1-phenyl-propane-1-one (Irgacure 1173) and 2,2-dimethoxy-
[75]. Cationic photopolymerization is slower than radical 2-phenylacetophenone (DMPA, Irgacure 651) are used in
polymerization, but offers some advantages such as reduced SLA due to their light absorbance on the UV range. [90]
shrinkage and residual stresses, which enhances the mechan- One of the most common benzyl ketals, 2-hydroxy-4’-(2-
ical properties of the components.[76] hydroxyethoxy)-2-methylpropiophenone (Irgacure 2959) has
a hydrophilic nature due to its hydroethoxy group and does
not produce harmful by-products, making it compatible with
Photoinitiators cells [91].
Instead, phosphine oxide PIs present lower energy levels
A photoinitiation system converts absorbed light into the in their excited states because of the proximity of the phos-
reactive species to initiate polymerization, as explained pre- phorous atom to the carbonyl group, absorbing wavelengths
viously. The PIs can be either radical or cationic, accord- around 400 nm, preferable on DLP [92, 93]. Acyl phosphine
ing to the initiating reactive species that they generate. [62] oxides, such as diphenyl(2,4,6-trimethylbenzoyl)phosphine
The absorption wavelength of the selected PI must match oxide (MAPO or TPO) and bis(2,4,6-trimethylbenzoyl)phe-
the emission of the 3D printer used, to have efficient ini- nylphosphine oxide (Irgacure 819, BAPO) provide photo-
tiation [81]. On the market, many photoinitiators are avail- sensitivity in the wavelengths 380–450 nm, and generate
able, which, according to their photochemical properties, radicals under visible light irradiation [94–96].
are activated at different wavelengths, both in the UV, vis- As introduced in the previous section, Norrish II pho-
ible and near-infrared light (NIR) ranges (Fig. 4). [82–87]. toinitiators can also be employed. Norrish type II PIs dif-
Most of the radical PIs absorb light in the UV and visible fer from type I PIs in a bimolecular process. They pro-
range, which is compatible with all VP techniques, in par- duce free radicals through direct hydrogen abstraction or
ticular for DLP, that often exploits light emitting at 405 nm. electron transfer once it reaches the excited triplet states
[88] On the other hand, cationic photoinitiators, which need under light exposure in the presence of a co-initiator

Fig. 4  PI absorption. Chemical structures and maximum absorption wavelength of the recalled PIs used for 3D photopolymerization. Some of
these PIs have multiple absorption peaks

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4 Page 10 of 16 ChemTexts (2023) 9:4

(COI) or synergist [97] (Eq. 2). For instance, the most Dyes in VP
common photosensitizers are camphorquinone (CQ) and
benzophenone (BP), and isopropyltyhioxanthone (ITX) In 3DP technologies, the fundamental roles of the dye are
and COI are usually tertiary amines, that produce stable printability and resolution. Generally, dyes are used as addi-
radicals [98]. Considering chemical stability and blocking tives for controlling the polymerization, fundamental for
effects, type II PIs possess more advantages for initiating high-fidelity printing and for avoiding a loss of features and
polymerization, but as drawbacks, these systems suffer precision by attenuating light absorption. However, their use
from poor water solubility, low reactivity, a tendency for results in an undesired final colour or, in some cases, are
discolouration and the inclusion of volatile and odorous applied only for aesthetic aspects [44].
amines [99, 100]. Dyes are typically UV and visible light absorbers (e.g.
Additionally, Eosin Y can be considered a cytocompat- azobenzenes, benzotriazoles families). These additives can
ible [101] visible-light type II PI. This is a xanthene dye be dispersed in the liquid formulation or covalently linked
used for histological staining, absorbing light from 490 to the monomer/polymer chains. [9, 105] The most common
to 650 nm, requiring both a tertiary amine as COI and dyes are listed in Table1.
a nitrogen-containing monomer (1-vinyl-2 pyrrolidinone The selection of the correct dye must be done consid-
NVP) to react [161]. ering the absorption spectrum of the used photoinitiator
Besides Norrish-type reactions, PIs for redox reactions and the dye, and the emission wavelength of the printing
are also reported, where Eosin Y has been used with- machine. Commonly, the photoinitiators absorb in a simi-
out the need for a COI [100]. The excited PI oxidizes lar working range to the 3D printing machines, e.g. around
phenolic tyramine groups into tyrosyl radicals, which 355 nm for some SL lasers, to 385/405 for common DLP.
form dityrosine bonds from nearby tyrosine groups and For this reason, in general the dyes also absorb in the UV
are cross-linked in a tyramine network [102]. Moreover, range or at wavelengths below 500 nm. [18] Sudan I is prob-
organometallic complexes are included in this category, ably the most common photoabsorber, and its use has been
as tris(2,2’-bipyridyl)-ruthenium(II) chloride hexahydrate thoroughly investigated to limit the curing depth and obtain
([Ru(II)(bpy)3]Cl2). It has strong visible light absorption, better Z-resolution [45, 111, 116].
relatively long-lived excited states and suitable redox
potentials [103]. Ru(II) complexes are water soluble
and in joining with a persulphate can accept electrons Fillers
when Ru is photoexcited to a triple state [104]. Once the
Ru(III) is formed, the persulphate dissociates into sul- The addition of fillers is the most common strategy to
phate radicals that follow the free-radical or thiol-ene overcome polymeric materials limitations, to introduce
chain polymerization. controlled anisotropy or obtain specific properties such as
Regarding the cationic process, the most commonly electrical or thermal conductivity, luminescence, stiffness,
used PIs are diazonium salts, diaryliodonium salts as the electromagnetic shielding or antibacterial properties. In
Bis-(4-t-butylphenyl)-iodonium hexafluorophosphate addition, fillers can reduce the shrinkage and consequently
(Speedcure 938) [77], triarylsulfonium salts, alkylsulfo- result in better accuracy. [118–124] The main function of the
nium salts, iron arene salt, sulfonyloxyketone and triar- fillers can be observed in Fig. 5.
ylsiloxane. While the monomers suitable for this mecha- The use of carbon materials (e.g. graphene, nanotubes),
nism are mainly epoxy, vinyl ethers, lactones, acetals, ceramic and metal powders, and glassy and fibrous materials
cyclic ethers, etc. (e.g. cellulose) as fillers reinforce the structure and improve
The activation of the onium salts involves the photo- mechanical properties. Meanwhile, to improve thermal,
excitation and decay of the resulting excited singlet state, chemical and UV resistance, the most common fillers are
with both heterolytic and homolytic cleavages [78]. The minerals (e.g. titanium) and bio-fillers (e.g. coffee grounds,
generated cationic radicals are aryl and aryliodine cati- wood flour) [125].
ons generated during photolysis that further react with In some cases, the filler content can be higher than the
the components on the formulations, mainly monomers, main matrix material turns out to be the principal compo-
to give Brønsted acids which are the predominant initia- nent. The selection of the filler should be done taking into
tors [50, 79, 80]. The strength of this acid is the key to account that the composite resin must be stable during the
determining whether and how the polymerization pro- process. This means a stable and homogeneous suspension
ceeds. If the acid is not strong enough, the paired anion that does not suffer with sedimentation, agglomeration or
has a strong nucleophilicity and is easily combined with collateral reactions. [122, 126] Additionally, the fillers can-
the carbon cationic centre to prevent polymerization not present excessive absorption that compromises the trans-
proceeding. parency of the blend or generates scattering phenomena.

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ChemTexts (2023) 9:4 Page 11 of 16 4

Table 1  List of most common dyes used in VP 3D printing

Dye names and structure λmax (nm) Concentration reported in literature and a­ pplicationa

Avobenzone; butylmethoxy-dibenzoyl-methane 357 0.38 wt% in PEGDA; biomedical applications [106]

1% in PEGDA; microfluidics channels [107]

2-nitrophenyl phenyl sulfide (NPS) 360 2 wt% in PEGDA [106]; microfluidics channels [107] and
microchannels [108]

Tinuvin 327; 2-(2′-Hydroxy-3′,5′-di-tert-butyl-phenyl)-5- 365 0–0.15 wt % in IBXA HDDA /BEDA mixture; 3D microstruc-
chlorobenzo-triazole tures [109]

Benetex OB; 375; 0.25% in PEGDA; microfluidics channels [107]

2,2’-(2,5-thiophenediyl)bis(5-tert-butylbenzoxazole) 435

Sudan I; solvent yellow 14; solvent orange R 418; ~ 4 wt% in PEGDA; improved printing resolution [110]
476 0.1–0.5 wt% in commercial elastomer; TangoPlus, miniaturized
soft robotics [111]
~0.014 wt% in PEGDMA; antimicrobial hydrogel scaffolds
[112]
0–0.25 wt % in acrylate/allyl/ thiol mixture; uniformity study
[45]
Methyl red; acid red 2 410; 0.05 wt% in bio-based acrylate monomer; high printing resolu-
520 (pH < 4.4) tion [113]
0.2 wt% in starch; hydrogels [114]
0.1 wt% in phosphorescent bio-based resin [115]

Reactive orange 16; remazol; 388; 0.063–0.25 wt.% in PEGDA/AETAC mixture; monolithic ion
Brilliant orange 3R 494 absorbers [116]
0.2 wt% in PEGDA; precise conductive structures [93]
0.2 wt% in BEDA; microcantilever [94]

Brilliant green; diamond green; 650; 0.2 wt% in PEGDA/CNC; hydrogel [117]
Emerald green; ethyl green 440

a
Proportional to the monomer

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4 Page 12 of 16 ChemTexts (2023) 9:4

Fig. 5  Different functions of fillers in polymeric mixtures. Reprinted from [125]

Based on the composition, fillers can be divided into techniques allow local control of chemical–physical prop-
organic and inorganic types. The organic types are rep- erties since it is possible to tune the ink properties. In this
resented by natural polymers (e.g. cellulose), generally context, the chemistry beyond the development of photo-
with an intrinsic fibrillar structure [127] and synthetic curable formulation is much more complicated than in the
polymers (polyamide or polyester). Inorganic compounds development of 3D printable materials suitable for other
include oxides and hydroxides (Al(OH)3, Mg(OH)2, ­TiO2, technologies, and it needs to be fully understood.
­Fe3O4), salts (­ CaCO3, ­BaSO4), metals and silicates [125]. For the scope of this article, the chemistry beyond light-
induced 3D printing is presented, describing the roles and
Radical scavengers effects of the various ingredients necessary to develop 3D
printable formulations. Furthermore, how these interact
A radical scavenger is a chemical substance added to a with each other and how the user can alter the formula-
polymer mixture to remove or de-activate impurities and tion to obtain high printability and the desired properties
undesired reaction products. The polymeric radical scaven- are described. The tools here provided offer a plethora of
gers are desired as easily separable antioxidants or as films strategies that can be implemented and exploited in differ-
having antioxidation activity. For instance, to improve the ent areas. For instance, for a chemist who would like to test
storage stability of a rubber formulation, a radical scavenger newly synthesized photocompounds in 3D printable mate-
can be applied to reduce premature cross-linking reactions rials, replacing photoinitiating systems, it is important to
under dark conditions. [128] Tocopherol and naringenin are know that photoactivicty is not the only requirement, but it
other free-radical scavengers that act as antioxidants or syn- must also go with control of the extent of polymerization.
thetic catalytic scavengers. Alternatively, an engineer who wants to implement device
properties by altering local functionalities, and thus chang-
ing the monomers, must be aware that not all the monomers
Conclusions can efficiently co-polymerize in different layers due to dif-
ferences in the reactivity of surface energy. In both cases, it
Three-dimensional printing plays an important role in is necessary to have a deep understanding of 3D printing,
research, industry and daily life. Among the various 3D from a general perspective, which goes from chemistry to
printing technologies, light-based 3D methods (SL, DLP, device properties, as described here.
CLIP, etc.) represent an intriguing option because they can
Acknowledgements M.Z. and V.S. thank the funding received from
combine fast printing times with high complexity and supe- the European Union’s Horizon 2020 research and innovation pro-
rior precision of the printed objects. Furthermore, these gramme under the Marie Skłodowska-Curie Individual Fellowships

13
ChemTexts (2023) 9:4 Page 13 of 16 4

(GA no. 101026335). V.S. thanks Generalitat Valenciana (CIDEGENT 11. Pagac M, Hajnys J, Ma Q-P, Jancar L, Jansa J, Stefek P et al
2018/036) and UJI (B-2020-44) for funding. (2021) A review of vat photopolymerization technology: mate-
rials, applications, challenges, and future trends of 3d printing.
Author contributions All the authors wrote and reviewed the Polymers 13(4):598
manuscript. 12. Kodama H (1981) Automatic method for fabricating a three-
dimensional plastic model with photo-hardening polymer. Rev
Funding Open access funding provided by Politecnico di Torino within Sci Instrum 52(11):1770–1773. https://​doi.​org/​10.​1063/1.​11364​
the CRUI-CARE Agreement. 92
13. Hull CW (1985) Apparatus for production of three-dimensional
Data availability The authors confirm that the data supporting this objects by stereolithography. United States
study are available within the article or by request to the authors. 14. Stansbury JW, Idacavage MJ (2016) 3D printing with polymers:
challenges among expanding options and opportunities. Dent
Declarations Mater 32(1):54–64. https://d​ oi.o​ rg/1​ 0.1​ 016/j.d​ ental.2​ 015.0​ 9.0​ 18
15. Oesterreicher A, Wiener J, Roth M, Moser A, Gmeiner R, Edler
Conflicts of interest There are no conflicts to declare. M et al (2016) Tough and degradable photopolymers derived
from alkyne monomers for 3D printing of biomedical materials.
Open Access This article is licensed under a Creative Commons Attri- Polym Chem 7(32):5169–5180. https://​doi.​org/​10.​1039/​C6PY0​
bution 4.0 International License, which permits use, sharing, adapta- 1132B
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