1 s2.0 S2214860421004395 Main

Additive Manufacturing 47 (2021) 102279
Contents lists available at ScienceDirect
Additive Manufacturing
journal homepage: www.elsevier.com/locate/addma
Vat photopolymerization of polymers and polymer composites: Processes

and applications
Ans Al Rashid a, *, 1, Waqas Ahmed b, 1, Muhammad Yasir Khalid b, Muammer Koç a
a
Division of Sustainable Development, College of Science and Engineering, Hamad Bin Khalifa University, Qatar Foundation, Doha 34110, Qatar
b
Department of Mechanical Engineering, University of Management and Technology Lahore, Sialkot Campus, 51041, Pakistan
A R T I C L E I N F O A B S T R A C T
Keywords: Synthesis and manufacturing of polymers and their composites have been a topic of interest recently in research
3D Printing and development owing to their wide margin of superiority over traditionally employed industrial materials.
Stereolithography Polymer composites provide a higher strengths, easily customizable product properties, flexible manufacturing
Digital light processing
processes, high resistance to corrosion or erosion, and lower cost. In addition, the additive manufacturing (AM)
Polymer composite
Review
techniques for polymer composites offer numerous benefits, including higher accuracy, lesser cost, and
complexity of fabricated parts. The recent progress in AM processes has paved the way for even a broader range
of design flexibilities and materials selection for several industrial sectors, including mechanical, biomedical,
filtration, and electrical. However, some challenges remain in additive manufacturing for polymer composites.
Vat photopolymerization (VP) processes is an AM technique that provides a benefit of relatively lower cost and
higher resolutions; therefore, a comparative review of VP processes for polymers and polymer composites and
their applications is presented in this study. This study aims to provide researchers with an updated under
standing of the underlying challenges and opportunities. It will also help the reader to systematically reveal the
research problems, gaps and future directions related to polymer composite materials and VP processes.
1. Introduction objects [4]. Material extrusion is a technique that uses a heated nozzle to
melt the filament material, which is deposited through the nozzle in the
Additive manufacturing processes, also called 3D printing (3DP), desired shape [5]. Material jetting uses inkjet technology to print 3D
provide several benefits over conventional manufacturing processes. objects by moving the inkjet head in cartesian coordinates and depos
Above all, the freedom to fabricate complex structures and material iting the liquid photopolymers, which is subsequently cured by an ul
savings have attracted researchers and industries to employ these pro traviolet lamp to create desired physical model [6]. Binder jetting is
cesses [1]. 3D Printing enables the fabrication of lighter, complex, and similar to material jetting, except it uses a binder dispensed to powder
more substantial parts. It uses computer-aided designs to directly de material in a bed to produce a 3D shape [7]. Powder bed fusion is quite
posit the material layer by layer to create a three-dimensional shape. identical to binder jetting, except the layers of powders are fused and
Since its introduction in the early ‘80 s, these processes are under cured using a heat source (such as laser or electron beam) [8]. In the
continuous development and improvement to employ existing and sheet lamination process, thin sheets are fused using an adhesive or heat
newly developed materials [2]. These processes are now being utilized source to produce a 3D physical object [9]. Directed energy deposition
widely in the manufacturing, aerospace, automotive, biomedical, and has multi-nozzles mounted on multi-axis arms to deposit the melted
construction industries [3]. materials on specific surfaces. This process is the same as material
3DP processes are broadly classified into seven main categories: vat extrusion, except it uses multiple nozzles that offer a higher degree of
photopolymerization, material extrusion, powder bed fusion, material freedom [10].
jetting, binder jetting, directed energy deposition, and sheet lamination Vat photopolymerization (VP) is the first-ever introduced 3DP pro
[2]. A vat contains a photopolymer resin cured layer-by-layer using UV cess, which utilizes a light source to perform polymerization reactions in
light or laser in the vat photopolymerization process, resulting in 3D photosensitive materials [11]. These processes are further classified into
* Corresponding author.
E-mail address: anrashid@hbku.edu.qa (A. Al Rashid).
1
First two authors contributed equally in this paper.
https://doi.org/10.1016/j.addma.2021.102279
Received 2 February 2021; Received in revised form 5 July 2021; Accepted 30 August 2021
Available online 11 September 2021
2214-8604/© 2021 The Author(s). Published by Elsevier B.V. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
A. Al Rashid et al. Additive Manufacturing 47 (2021) 102279
several categories depending on the light source and mechanism used polymerization of the resin [11]. The significant difference between
for polymerization. Subsequently, several lab-scale and commercial these two technologies resides in that DLP induces an instantaneous
technologies following the same working principle have been intro entire layer polymerization using digital micro-mirrors devices (DMD)
duced [12]. Several industrial sectors, including mechanical, medical [15,16]. In contrast, in SLA, a single laser point (e.g., layer pixel) is
sciences, electrical/electronics, etc., have adopted these processes to exposed at a time. As a result, DLP offers a higher printing speed than
fabricate functional components. With increasing reported literature on SLA and other technology competitors [6]. The applied light source has
this topic, it is vital to summarize the existing literature for researchers also evolved from standard lamps to light-emitting diode covering, thus,
to grasp compact information quickly, utilize it to identify research a more comprehensive range of wavelengths at a lower cost [17]. The
outlooks, and increase knowledge over materials, processes, and appli hardware setup for DLP offers higher lateral printing resolution. The
cations. This article presents a review on 3DP of photocurable materials, z-resolution is tightly correlated with light penetration and scattering,
process technologies, and their applications. Building upon a compre which can be improved by adding light absorbers and polymerization
hensive review of existing literature, this study aims to provide readers facilitators. DLP achieves a resolution of about 1 µm (while the printing
with different vat photopolymerization process technologies, photoc speed is about 30mm3 s − 1) regardless of the layer’s lateral area and
urable materials used in these technologies, and their applications. Be complexity [18]. The working principles of SLA and DLP technologies
sides, it also provides a comprehensive discussion on topical hindrances are presented in Fig. 1.
related to these materials and processes. Two-photon polymerization (2PP) is another vat
The first section of the paper presents the VP processes reported in photopolymerization-based printing system like SLA and DLP, but it can
the literature for polymers and their applications followed by the dis provide better control and higher print quality [19]. Due to
cussed processes for polymers and polymer composites. Later, other VP single-photon polymerization in SLA, the process occurs on the surface
processes, besides the most used SLA and DLP processes, are also pre of a photosensitive resin that only allows building 3D structures layer by
sented. Finally, a critical analysis of reviewed articles was performed to layer. On the other hand, in 2PP, which uses near-infrared (NIR)
identify challenges related to VP of polymer composites with detailed femtosecond (Fs) laser pulses, the two photons are simultaneously
discussion on future research directions from the gaps identified in the absorbed by the photo-initiator [11]. Allowing them to act as a single
literature. photon to initiate polymerization, enabling direct writing of any desired
3D model into the volume of photosensitive materials transparent in the
2. Vat photopolymerization processes NIR and highly absorptive in the UV spectral range [20].
Volumetric 3D printing directly prints structures in three dimensions
The vat photopolymerization process is an AM technique in which by using a rotating vat and an index-matching resin [21]. Projecting six
photo-sensitive materials are exposed to radiation/light in a controlled distinct images of the object taken from specific angles and continuously
manner to obtain polymerized material layers. Subsequent layers alternating them during rotation allows objects to be built. Contrary to
combine to form a 3D object; however, this process’s application is other methods where the 3D structure is built by 2D layers, the object is
limited to the materials that polymerize on exposure to light [13]. created directly in 3D [14,22].
Photopolymers and resins can be processed using this technology [1]. VP processes provide the highest printing resolution among the
Depending upon the variation in curing source, VP processes can further processes discussed here. Despite having an excellent resolution, several
be classified into; stereolithography (SLA), digital light processing factors affect the properties of 3D-printed parts. The main limitation is
(DLP), two-photon polymerization (2PP), and volumetric 3D printing the printing time; although the technology can quickly produce one
[14]. layer, curing the processed layer takes time. Secondly, the resin needs to
SLA photopolymer resins mainly consist of monomers, oligomers/ be refilled continuously in the resin tank, which adds delays to the
binders, photoinitiators, and some additives. Monomers and oligomers process. Finally, the mechanical properties of the 3D printed parts are
are the main constituents of photopolymer resin, which solidifies due to affected by the degree of polymerization and post-print curing process
crosslinking. Photoinitiators convert into radicals and react with oligo [23].
mers and monomers, providing crosslinking to produce polymer chains
on exposure to curing light. Additives may include nanoparticles or 3. Vat photopolymerization of polymers
pigmentation for improved resin properties or desired coloring [4].
Digital light processing (DLP) also relies on UV light-induced In this section, VP processes for polymers are presented. The main
Fig. 1. Working Principle of (a) SLA and (b) DLP Technologies

Reproduced with Permission from [11].
2
sections are further classified into subsections presenting applications of 19% CV only. The high dispersion and anisotropic behavior were lower
these processes in different industrial sectors. than expected due to the pixilation effect, non-uniform energy dose, and
non-post-curing. Garcia et al. [29] also reported the impact of
3.1. Stereolithography (SLA) post-curing and printing parameters on the mechanical properties of
standard clear resin (from Formlabs) produced via SLA. Post curing time
Stereolithography (SLA) was the first-ever introduced 3DP process significantly affected the specimens’ mechanical properties. The 3D
[24]. In this process, a laser source is utilized to initiate the polymeri printed samples revealed an averaged elastic modulus, UTS, and ulti
zation reaction in photocurable materials. Galvano-scanners control the mate strain of 1.2 GPa, 31 MPa and 34%, respectively, while post curing
laser movement, which helps maintain the printing speed with improved process improved elastic modulus and UTS to 2.9 GPa and 59 MPa,
accuracy. The printing speed is highly correlated to curing depth and respectively.
light penetration due to the nature of the material being used. These The incorporation of additives has proven to improve the curing
parameters can be improved by using light absorbers and polymeriza process and mechanical properties of photosensitive materials. For
tion facilitators. Typically, photopolymer resins consist of acrylate and instance, Alamdari et al. [30] used surface energy reducing agents
are not preferable for biomedical applications due to their cytotoxicity. (SERA) in the liquid bridge micro-stereolithography technique (LBMSL)
However, polylactic acid (PLA) can be used in such applications as process. Specific concentrations of monomers, light absorbers, photo
FDA-approved polymer material. Some researchers have introduced the initiators, and SERA were introduced to photopolymer resin, and the
process variants to improve these materials’ mechanical properties by adhesion force and mechanical properties of resulting materials were
incorporating the metal or ceramic particle suspension in photopolymer investigated. The adhesion force between 3D printed part and the top
resin [25]. More details on the processing of photocurable materials substrate was minimum at 5 wt% concentration of SERA. However, the
through SLA 3DP technology are presented in the following sections. introduction of SERA resulted in a decline in elastic modulus from
540 MPa to 320 MPa for 0–20% SERA concentration.
3.1.1. SLA for mechanical applications Wu et al. [31] investigated the effect of soft-start exposure on the
SLA technology has recently been used to process photosensitive bottom-up ceramic mask projection stereolithography process. It was
materials for mechanical applications. The choice of process parameters observed that different exposure modes displayed different curing fea
and post-curing treatments are crucial in this process and ultimately tures when implemented to the ceramic slurry. When compared, critical
affect the final product. Several researchers reported the effect of pro exposure energy (Ec) of the ceramic slurry was less in soft-start exposure
cess parameters on print quality and mechanical properties of the 3D than in constant exposure keeping the same thickness. The dimensional
printed parts. For instance, Naik et al. [26] investigated the impact of accuracy of soft-start exposure was 25–45% higher than constant
build orientation, layer thickness, strain rate, and size effect on speci exposure. Flexural strength of soft-start exposure was 3%− 5% less after
mens’ mechanical properties manufactured through the SLA technique. sintering than constant exposure, but Weibull moduli were higher in the
Mechanical properties were unaffected when samples were printed in an case of soft-start exposure. Fabrication of sintered samples of soft-start
‘on edge’ configuration. However, 3D printed specimens revealed lower exposure having higher (maximum increase of 47.22%) Weibull
young’s modulus and ultimate strength under a ’flat’ configuration. moduli indicated that soft-start exposure is a more stable curing process
Young’s modulus and tensile strength were improved by 30.15% and [31].
21.22% with an increase in layer thickness from 25 µm to 100 µm; be Wang et al. [32] introduced the AM of ceramic using SLA by using
sides, a 58.69% increase in strain rate was observed. Average tensile preceramic polymers with thiol-ene click chemistry to enhance the
strength and young’s modulus were improved by 45.17% and 47.38%, chemical and mechanical properties of produced polymers. Three pre
respectively, with the rise in strain rate from 0.0033 s− 1 to 0.0131 s− 1 ceramic polymers, polysiloxane SPR212, polycarbosilane SMP10, and
and varying layer thickness 100–25 µm, while average strain was polysilazane Durazane1800, were used to produce ceramic composi
decreased by 35.43%. Tensile strength and fracture strain was observed tions of SiOC, SiC, and SiCN after heat treatment, respectively. The mean
to be independent of specimen size, but lower young’s modulus was reduced modulus and hardness of SiOC were calculated as 106 ± 6 and
observed for larger specimens due to partial curing during the poly 12 ± 1 GPa, respectively. The mechanical testing was performed,
merization process. revealing the compressive strength of 216 MPa, and theoretical density
Likewise, Liu et al. [27] investigated the impact of build orientation was measured to be 97% with minimum pours and defects. Some pre
on mechanical properties of photocurable epoxy resin (NH-09) speci vious works related to different polymers produced from the SLA process
mens produced via SLA. The fabricated samples were 3D printed under for mechanical applications are reported in Table 1.
different build orientations and were analyzed under tensile, compres
sion, and impact loadings. Specimens were made with various config 3.1.2. SLA for biomedical applications
urations, including; on edge, flat, and rotated from 0◦ to 90◦ (to build Additive manufacturing processes, specifically SLA, have been
plate). The samples printed on edge exhibited higher ultimate tensile widely used recently for dentistry applications [34]. AM processes have
strength (UTS) and lower failure strain than flat 3D printed samples and gained attraction due to the freedom to design customized and
revealed a maximum UTS of 37.2 MPa for edge XY. The maximum patient-specific dentures; however, process optimization is vital to
young’s modulus of 908 MPa was achieved when the specimen was achieving desired product performance. Hada et al. [35] fabricated
printed along flat X (at 90◦ ). Impact test was performed on flat (X and Y) dentures base using 3D CAD models through the SLA process. Dentures
and edge (X and Y) specimens and observed that axis X and Y disclosed were produced in three different directions, and the effect of printing
no effect on the impact strength. For more details on build orientations, direction on stress distribution was investigated. Rosette strain gauges
please refer to Liu et al. [27]. Casafont et al. [28] studied the anisotropy were used to measure the stress distribution at four different locations
effect on compression behavior of acrylate resin 3D printed parts using along the dentures’ midline, as shown in Fig. 2 and Fig. 3. Variable load
mask image projection SLA technology in the top-bottom configuration. ranging from 0 N to 200 N was applied at a rate of 20 N/s. From ob
Strain gauges, two-dimensional digital image correlation (2D DIC), tained maximum principal strain and direction, stress distribution was
extensometer, and crosshead displacement methods were adopted to lowest for the dentures 3D printed at 45◦ .
acquire stress-strain data. Specimens were produced under six orienta Due to photopolymer resins’ cytotoxic nature, these materials cannot
tions without a post-curing process. The maximum anisotropic effect be utilized for biomedical applications. Therefore, recent research is
was observed when the extensometer was used for experiments and focused on synthesizing biocompatible and biodegradable materials for
showed 32% percent deviation (PD) and 39% coefficient of variance their utilization in 3DP processes. Chartrain et al. [36], using mask
(CV) , while 2D-DIC and crosshead measurement displayed 15% PD and projection micro-stereolithography, fabricated biocompatible and
3
Table 1
Different Polymers produced via the SLA process for mechanical applications.
Base Material Additives & Reinforcements Highlights Properties improved Ref.
Methacrylate-based photopolymer resin • Photo initiator • layer thickness range 25–100 µm Effect of layer thickness [26]
• Pigments • strain rate range 0.0033 s-1 to 0.0131 s-
1
• Other additives • Increase in tensile strength up to
21.22%
• Increase in young’s modulus up to
30.15%
• Increase in strain rate by 58.69%
Effect of strain rate
• Increase in tensile strength up to

45.17%
• Increase in tensile strength up to
47.38%
• Decrease in average strain up to
35.43%
bi- and trifunctional acrylates • Al2O3 powder • layer thickness 50 µm • Dimensional accuracy of 25–45% [31]
• Exposure 12.78, 16.74, and 19.38 mJ/ • Increase in Weibull moduli of
cm2 47.22%
• Exposure time 1–5 s
photopolymerizable resin • 3DMix ZrO2 • thickness between 200 and 250 µm • Fracture resistance through non- [33]
• surface roughness between 0.17 and aging process 634.52 N
0.18 µm • Maximum achieved flexural
strength 320.32 ± 40.55 MPa
Formlabs standard clear resin • methacrylic acid esters • Printing resolution 140 µm Effect of non-post cure [29]
• photo initiator • layer thickness, 25, 50, and 100 µm
• post curing time 0, 60 and 120 min • Maximum achieved elastic
• Part rotation (spin) about X and Y modulus 1.2 GPa
• Part orientation about X, Y, and Z • Maximum achieved UTS 31 MPa
• Part position BackLeft, Middle, Front • Maximum achieved ultimate
Right strain 34%
Effect of post cure
• Maximum achieved elastic

modulus 2.9 GPa
• Maximum achieved UTS 59 MPa
• Maximum achieved ultimate

strain 14%
preceramic polymers: • Photo initiator: phenylbis (2,4,6-tri- • wavelengths below 450 nm • mean reduced modulus [32]
methylbenzoyl) phosphine oxide • layer thickness 100 µm 106 ± 6 GPa
• liquid methylvinylhydrogen (BAPOs) • post cure time 30 min • hardness 12 ± 1 GPa
polysiloxane (polyramic SPR-212) • Photo absorber: Sudan Orange G • pyrolyzed temperature 1100 ◦ C • compressive strength 216 MPa
• Allylhydrydopolycarbosilane • theoretical density 97%
(StarPCS™ SMP10) • free radical scavenger: hydroquinone
epoxy based photocurable resin NH-09 • Nil • build orientation: flatX, flatY, edgeX, • Maximum achieved young’s [27]
edgeY, flatX specimens (from 0◦ − 90◦ ), modulus for flatX at (90◦ ),
flatXY, and edgeXY 908 MPa
• laser wavelength 355-nm • Maximum achieved impact
• critical exposure of 10 mJ/cm2 strength on edgeX, 22.8KJ/m2
• penetration depth 110 µm • Maximum achieved compressive
strength at flatX0◦ , 25.9 MPa
Acrylate photoactive resin • Nil • Printing directions: (X, Y, Z, XY, XZ and • Decrease in percent deviation [28]
YZ) (PD) up to 68%
• pixel resolution 62.5 µm • Decrease in coefficient of variance
• layer thickness of 75 µm up to (CV) 105%
• Elastic modulus ratios (Ei/Ej)
range 0.81–0.97
Monomers: • Photoinitiator: 2,2-dimethoxy-2-phe • Laser wavelength 365 nm • maximum achieved elastic [30]
• isobornyl acrylate (IBXA), nylacetophenone (1 wt%) • light irradiance of ~9.6 mW/ cm2 modulus 540 MPa
• 1,6-hexanediol diacrylate (HDDA), • Light absorber: Tinuvin 327™ • exposure time 6 s
• bisphenol-A-ethoxylate (4) diacrylate (0.15 wt%) • layer thickness 10 µm
(BEDA) • Surface reducing agent: BYK-UV 3500 • optimum SERA concentration 5 wt%
• weight ratio 4.5:4.5:1 by wt% (0–20%)
biodegradable tissues with improved printability, low cytotoxicity, and transition temperature was also favorable for PTEGA-DMA applications
adequate cell adhesion, shown in Fig. 4. Using this process feature size of in tissue engineering.
50 µm was achieved. PTEGA-GMA (‘Poly (tri (ethylene glycol) adipate) Silbert et al. [37] synthesized bio-based methacrylate and acrylate
dimethacrylate’) polyester was used with mouse preosteoblasts resins from epoxidized sucrose soyate (ESS) for the SLA process. Three
(‘MC3T3-E1’) to introduce biocompatibility and adhesion properties. resins were prepared from ESS: AESS (acrylated ESS), DMESS (di-me
0.05 wt% of avobenzone was also added to reduce the penetration depth thacrylated ESS), MBSS (methacrylated butylated ESS). Tensile, flex
and achieve thin layers (<50 µm). The dynamic mechanical analysis ural, rheological, and thermomechanical properties of these resins were
revealed the storage modulus of 11.3 ± 3.5 MPa at 37 ◦ C. Glass also compared with three commercially available SLA resins (‘Peopoly
4
Fig. 2. Four rosette strain gauges mounted on the oral surface of each denture: above the labial frenum (A), at the incisive papilla (B), at the endpoint of the denture
(D), and at the mid-point of the B and D (C). Positions of loading points by three stainless less-steel balls assuming bilateral balanced occlusion [35].
(Image reproduced with permission).
different types and shapes of membranes through very controlled and

precise methods [38]. Additive manufacturing has major advantages
over conventional methods, such as controlling the pores, thickness,
surface roughness, and density of membranes [39]. Ray et al. [39]
proposed using solvent-based slurry stereolithography technique to
fabricate the membranes for the filtration process. This research aimed
to observe the roughness, thickness, porosity, and pore sizes of mem
branes fabricated through SLA. For that purpose, two different slurry
compositions (S1 and S2) were prepared. S1 was consist of 23% vol of
0.3–0.4 µm alumina particles along with 13% vol of 40–50 µm alumina
and S2 was consist of equal vol of 0.3–0.4 µm and 40–50 µm alumina
along with other slurry components. After sintering and debinding of
green parts, densities of S1 and S2 based parts were measured to be 3.8
and 3.68 g/cm3. After post-curing, S1 and S2 based parts showed 3.7%
and 6.8% pores as S2 consisted of a large portion of aluminium grains.
SEM imaging was performed, which showed that both membraned
possessed a thickness of about 225–230 µm. S1 based membrane showed
pores with a range of 7.9–9.8 nm, while slurry 2 based membrane
showed 13.7–8.2 nm pores. The surface roughness of S1 based and S2
based membranes was 0.17 and 0.18 µm, respectively. The topology of
both membranes seemed to be smooth as compared to conventional
techniques. Also, the contact angle of the membrane does not depend on
Fig. 3. Measuring the stress distribution on the 3D printed dentures by
the gran size as it does not change with size variation. This study is
applying the load on the molar parts. The applied load was ranging from 0 N to
useful for ultrafiltration. Fig. 5 presents SEM analysis of porous ceramic
20 N, at the rate of 20 N/s on a universal testing machine [35].
membrane fabricated by 3D printing technique.
3.1.4. SLA for electrical applications

Moai Blue’, ‘Ebecryl 220’ and ‘Ebecryl 1290’). The specimens were
The scope of electrically conductive materials has widened their
printed at different orientations (0◦ and 90◦ ). MBSS showed relatively
applications in various fields, such as in engineering, to make trans
high tensile strength than DMESS and AESS. DMESS achieved the
ducers, sensors, and actuators [40]. Due to their high demand for elec
highest young’s modulus out of all ESS formulated resins and was
trical simulations to modulate biological processes, its applications in
comparable to Moai Blue, Ebecryl 220, and Ebecryl 1290 in 90◦ orien
medical fields are growing [41]. The most commonly used piezoelectric
tation. MBSS showed the highest flexural strength among other acrylate
materials are composed of lead zirconate titanate (PZT) due to their high
groups. The flexural moduli of DMESS and MBSS were about 1000 MPa,
piezoelectric constant (d33 >300 pC/ N) but owing to the high toxicity
while AESS revealed a significantly low flexural modulus of about
ingredient (lead) present in them, researchers started using lead-free
200–250 MPa in either orientation. Some previous works related to
piezoelectric materials such as Potassium-Sodium Niobate (KNN) and
different polymers produced from the SLA process for biomedical ap
Barium Titanate (BaTiO3) [40]. Wang et al. [40] proposed a method to
plications are reported in Table 2.
produce high-performance piezoelectric nano-ceramic material using
stereolithography having low viscosity and high solid loading suspen
3.1.3. SLA for filtration applications
sions. BaTiO3 powders were used as ceramic fillers with particle size
Fabrication of filtration membranes and separation membranes
500 nm and a low specific area of 2.3 m2/g. 40% vol of BaTiO3 was used
using additive manufacturing techniques has introduced a new area of
in suspension mixture along with HDDA, polyethylene glycol, and
research these days as it has enabled researchers to fabricate and design
5
Fig. 4. Image and SEM micrographs of PTEGA-DMA scaffolds and Hokie bird fabricated using MPμSL. a,b,c) image consist of 2 wt% DMPA and 0.05 wt% avo
benzone. d) was printed using 2 wt% DMPA [36].
(Images reproduced with permission).
Table 2
Different Polymers produced via the SLA process for biomedical applications.
Base Material Additives & Reinforcement Highlights Properties improved Ref.
Methacrylate-based photopolymer • Diphenyl (2,4,6- • layer thickness 100 µm • Achieved lowest stress distribution at 45◦ [35]
resin trimethylbenzoyl) phosphine • printing direction: 0◦ , 45◦ ,
oxide and 90◦
• laser wavelength 405 nm
• x-y resolution 150 µm
Poly(tri(ethylene glycol)adipate) • Photoinitiator (2 wt% DMPA) • ultraviolet LED light source • Maximum storage modulus 11.3 ± 3.5 MPa [36]
dimethacrylate (PTEGA-DMA) • Avobenzone (0.05 wt%) wavelength 365 nm • Achieved glass transition temperature (Tg) 3.6 ◦ C
• MC3T3-E1 mouse preosteoblasts • light intensity 5.0 mJ/cm2 ± 3.6 ◦ C
• layer thickness 50 µm
epoxidized sucrose soyate (ESS) • Photoinitiator: Irgacure TPO-L • layer height 100 µm • Maximum achieved Flexural modulus ~1000 MPa [37]
(1.18%) • print speed 85 mm/s • Highest achieved glass transition temperature
• Diluent: bisphenol A ethoxylate • laser 150 mW 69.2 ◦ C (for MBSS (methacrylated butylated ESS)
diacrylate (49.41%) • light wavelength 405 nm
• Monomer: Hexanediol diacrylate • printing orientation 0◦ and
(7.41%) 90◦
diphenyl (2, 4, 6-trimethylbenzoyl) phosphine oxide, a photo initiator. BaTiO3 with 232 mPa⋅s at 46.5 s − 1 shear rate. XRD results showed that
Dispersant (1.0 wt% BYK) was used in suspension due to the resulting the ceramic sample consists of only tetragonal phase BaTiO3 (ICCD-PDF
minimum suspension viscosity and minimum particle size distribution of #05–0626), which is suitable for piezoelectric applications. The
428 nm. The viscosity of 45% volume suspension was measured at dielectric constant εr of ceramic was measured from 2762 to 2620 with a
46.5 s − 1 shear rate, 357 mPa.s, less than the critical value of frequency range of 1 kHz–1 MHz, and dielectric loss remained lower
self-leveling (3000 mPa.s). Shear-thinning rate of suspension was than 0.02. Bulk density was measured to be 5.69 g/cm3, which resulted
observed when suspension consisted of 40% vol of solid loading of in 95% of empirical density value. The piezoelectric constant was
6
Fig. 5. SEM micrographs of a porous ceramic membrane made through stereolithography process [39].
measured to be (d33 =163 pC/N), which is sufficient for use in thus provides better print quality and accuracy. DLP offers a higher
ultra-capacitors and transducers [40]. Fig. 6 presents a general sche printing speed than all AM technologies, including SLA. This technology
matic diagram of the SLA technique and solidification process of ce uses digital micro-mirrors devices (DMD) to fully cure the resin layer at a
ramics. Fig. 7 shows the graph of viscosities of suspensions with different time that is controlled by numerically controlled slicing data. For
solids loading at shear rate. Whereas Fig. 8 presents different 3D instance, the mirrors that control the orientation of light pixels will be
structures SLA printed by 40 vol% BaTiO3 suspensions. oriented to reflect the incident light accordingly. Mirrors corresponding
to dark pixels will be oriented to avoid the incident light.
Thus, light reflected by DMD mirrors is exposed towards the resin,
3.2. Digital light processing (DLP) which is then illuminated and polymerized. The light energy source is
usually an arc lamp with a liquid crystal display panel, providing a more
Digital light processing (DLP) is quite similar to stereolithography comprehensive wavelength range at an economical cost. Similar to
(SLA), except the difference is that SLA uses laser beam technology to stereolithography, DLP also offers a wide range of materials which
completely cure the layers by point-to-point tracing the geometry and
Fig. 6. Process diagram of (a) Stereolithography technique and (b) solidification process of ceramics [40].
7
Fig. 7. The graph shows resin’s volume fraction and viscosity using different solid loadings at a 46.5 s − 1 shear rate [40].
Fig. 8. Shows the 3D printed structures printed through the Stereolithography process using 40 vol% BaTiO3 suspensions [40].
includes pure polymers (e.g., poly (lactic acid) (PLA) and poly-ε-cap in this study, and mechanical properties were observed. As the layer
rolactone (PCL)) and composites which contains ceramic and metallic thickness decreased from 50 µm to 10 µm, an increase in mechanical
particles. High lateral penetration is controlled by digital micro-mirrors behavior was observed. The same behavior was seen as the exposure
devices (DMD). The light penetration and scattering are directly linked time increased from 1.6 s to 2 s. Under the optimized conditions, elastic
with z-resolution, which can be avoided by introducing polymerization modulus, UTS, and ultimate strain increased up to 214% (from 0.39 GPa
facilitators and light absorbers. DLP has achieved a resolution of about to 1.3 GPa), 301% (7.9–34 MPa) 347%.
1 µm at a printing speed of about 30 mm3 s − 1, disregarding the Aznarte et al. [43] proposed a similar approach to measure the effect
complexity and lateral area of layers. Similar to SLA, DLP also requires of different printing parameters on the anisotropic tensile strengths of
the support structures for complex and intricate geometries taking into parts produced by the DLP process. PR-48 type of resin was used during
account the post-processing steps for part finishing. experimentation. Printing parameters under observation were layer
thickness, part orientation, and exposure time. Different mechanical
3.2.1. DLP for mechanical applications tests such as tensile test, Ultimate stress, and ultimate strain test were
Parts fabrication through digital light processing (DLP) is a growing performed simultaneously and measured the corresponding mechanical
demand of design and manufacturing industries due to its fast-printing properties. Average elastic modulus and maximum stress were achieved
speed and high resolution. But printing parameters are the most to be 0.749 GPa and 21.7 MPa, respectively. Decreasing thickness and
important one that significantly impacts the printing accuracy and me increasing exposure time improved these properties. The effect of y-axis
chanical properties of printed 3D objects. Garcia et al. [42] reported the orientation also enhanced the elastic modulus ultimate stress. Ultimate
effect of printing parameters on the mechanical properties such as strain test was then performed, resulting in an average of 5.8% having a
elastic modulus, UTS, and ultimate strain using the standard deviation of ± 1.87%. The minimum strain was observed at
vat-photopolymerization (DLP) process. All the specimens were printed minimum layer thickness, minimum exposure time, and z-axis orienta
using PR-48, Autodesk Standard Clear Resin. Printing parameters, such tion. Also, printing time was observed, linking it with tensile strength.
as layer thickness, exposure time, and part orientation were considered All tests were performed having the printing time range of 17–111 min
8
and observed that the best tensile strength was achieved at lower build while the specimen printed at 200klx displayed the storage modulus of
time. 934 MPa at 31 ◦ C. A series of octet truss structures were manufactured
Valentinčič et al. [44] enhanced the dimensional accuracy of printed to measure their mechanical properties by varying intensities in
parts made of Deep Black (Fun To Do, Netherlands) and minimized the different proportions. Octet truss fabricated using 200klx intensity,
production via digital light processing (DLP). The authors addressed displayed the highest elastic modulus, offset compressive yield strength,
three main challenges in achieving the desired resolution and accuracy: compressive strength, and stain-to-break of 63.29 MPa, 1.98 MPa,
uneven illumination of DLP projector, the direction of illumination, and 2.88 MPa, and 0.097 mm/mm, respectively. Fig. 9 shows elastic
optical process parameters such as exposure time, layer thickness, and modulus (black) and offset (0.2%) compressive yield strength (red) with
time-span between two consecutive exposures. Uneven illumination of changing light intensity.
DLP projector was reduced by implementing mask, but exposure time Thrasher et al. [50] developed a series of photo resins to manufacture
and manufacturing time were increased along with light intensity tensile specimens via the white light projection DLP process by changing
reduction. Better accuracy was achieved when photopolymerization was the chemical formulations. The photo resins used in this study include
performed using the constrained surface (bottom-up) method. PDMSDMAA, SilOHfle, ThrashOHfle, and HydrOHflex with different
Taguchi-based surface response methodology was adopted to optimize additives. The photo resin PDMSDMAA displayed the maximum elon
the input parameters that were exposure time 16.5 s, layer thickness gation of 472% under tensile strain and the shore A hardness of
0.06 mm, the time between two consecutive exposures 4 s. The devia 13.7–33.3. Monzón et al. [51] investigated the impact of printing di
tion of actual dimensions from nominal was reduced to 30 µm in the rection, post-curing, and anisotropic behavior on mechanical properties
x-direction, 10 µm in the y-direction, and 80 µm in the z-direction. of parts fabricated via the DLP process. Three polymers (castable blend,
Patel et al. [45] studied the elastic and mechanical properties of industrial blend, and VisiJet® FTX Green) were used in this study, and
highly stretchable and UV curable elastomers (SUV) using SUV elas the samples were fabricated using three methods such as casting,
tomer polymer resin via the DLP technique. Epoxy aliphatic acrylate manual layer by layer (MLL), and ProJet™ 1200 (DLP) printer. It was
(EAA) and aliphatic urethane diacrylate (AUD) were added to resin with observed that the tensile modulus of VisiJet® FTX Green-based samples
different compositions of EAA-AUD ranging from 5:5–0:10 to check the was improved by 40% when a sample was produced in horizontal
mechanical properties. It was observed that by increasing the AUD orientation without supports using ProJet™ 1200 (DLP) process. After
concentration from 5:5–0:10, young’s modulus increased from post-curing of parts fabricated through ProJet™ 1200 (DLP), the ulti
0.58 MPa to 4.21 MPa and displayed elongation from 240% to 1100%, mate flexural strength was increased to 41% (for horizontally printed
almost five times greater than commercial UV elastomers. Also, the samples) and 77% (for vertically printed samples). Fig. 10 demonstrates
toughness increased from 1 × 106 to 50 × 106 Jm− 3 as the ratio the effect of anisotropy on photopolymer parts made by digital light
increased from 5:5–0:10. processing.
Lee et al. [46] proposed achieving low viscosity of photocurable Keshavarzan et al. [52] investigated the response of shape memory
ceramic slurries at high loading via the DLP process to avoid the slurry polymeric cellular lattice structures such as Rhombic, Body-Centered
from clogging in the pores without affecting polymerization behavior. Cubic (BCC), and cylindrical bulk samples manufactured via DLP.
The homogeneous mixture of hexanediol diacrylate (HDDA) monomer Samples consisted of 3DM-LED.W photopolymer resin. Different prop
and camphor (diluent) was prepared with different % content and erties such as energy absorption, energy recovery, deformation of
observed that when camphor was added to HDDA monomer in an structures, strain rates, cyclic behavior, and strain recovery were
amount ranging from 0 wt% to 40 wt%, a significant reduction in vis investigated. The effect of temperature on shape memory polymers
cosity was observed from 10.4 ± 0.2 mPa⋅s to 2.17 ± 0.3 mPa⋅s. So the (SMP) was also under investigation at cold (below Tg), warm (at Tg), and
mixture, having 40% vol of camphor, was used. As the ceramic material, hot (above Tg) temperature ranges. With an increase in applied strain
the effect of calcium phosphate (CaP) loading was observed by varying it rate, strength and residual strain in both structures (BCC and Rhombic)
from 35 vol% to 48 vol% which showed increasing viscosity behavior increased due to materials’ viscoelastic property. Also, both structures
from 66 ± 5.0 mPa⋅s to 157 ± 3.0 mPa⋅s and decreasing shrinkage from revealed the same strain recovery rate when a specific strain rate was
28.3 ± 0.69% to 20.1 ± 0.61%, so CaP with 48% loading was used as applied. However, rhombic structure exhibited higher strength and
optimal concentration. Mechanical properties of parts were measured, stiffness than BCC, so absorption energy and recovery energy was higher
and the flexural strength of 87 ± 2.8 MPa was achieved with overall for rhombic structure.
50.6% part porosity. Overall, part porosity also affected the mechanical He et al. [53] synthesized a liquid photosensitive silicon EPS-acrylic
properties. Decreasing the porosity from 69.4 ± 0.66 vol% to polymer (EPS resin, SH-023–7) to fabricate a SiOC lattice using the DLP
50.6 ± 0.24 vol%, the comprehensive strength and modulus were
increased from 10.2 ± 2.47 MPa to 23.8 ± 2.45 MPa and from
210 ± 5.2 MPa to 276 ± 20.7 MPa, respectively.
Lovo et al. [47] characterized the commercially available resins for
the DLP process. The authors prepared five different commercial pho
tocurable acrylic-based resins using acrylic monomers, oligomers, pho
toinitiators, and inorganic additives to observe their mechanical
properties and inorganic compositions. The resin 1 (LS600), among the
five resins, achieved the highest 53 MPa of tensile strength, 110 MPa of
compression strength, 79 MPa of flexural strength, and 82.3 Shore D
hardness. These properties are comparable to the polymers that are used
in the injection molding process and have better performance than
conventional polymers [48]. Peterson et al. [49] studied the cross-linked
density of diacrylate-based G+ Yellow photo resin, and mechanical
properties varied by varying the light intensity using the DLP process.
Light intensity range was set as 50 klx to 200 klx to study its effect on
mechanical properties such as Elastic modulus and offset compressive
yield strength of cylindrical specimens. There was a significant increase Fig. 9. The graph between Elastic modulus (black) and offset (at 0.2%)
in mechanical properties with increased intensity from 50 klx to 200 klx. compressive yield strength (red) with changing light intensity [49].
Specimens printed at 50 klx showed a storage modulus of 548 MPa, (Image reproduced with permission).
9
Fig. 10. Anisotropic behavior of photopolymer samples made by DLP Process [51].
technique. Non-photosensitive hydroxyl silicone oil (HPMS) was added that were 34.67%, 52.20%, and 66.37%, respectively. UTS was
to the resin to make channels for the by-product gas release. Pyrolysis maximum in Z orientation and minimum in X orientation, 0.49 MPa and
was performed, which produced micro-sized channels (around 1 µm) for 0.23 MPa, respectively. The measured error in dimensional accuracy
gases to release due to the addition of HPMS. Compressive strength and was about 1.3%, and the average shrinkage rate was 0.3%.
elastic modulus of printed SiOC ceramics were determined with and Wu et al. [55] proposed a method for four-dimensional printing
without HPMS, and observed compressive strength increased to using shape memory polymers (SMPs) through the DLP process.
3.45 MPa at 1000 ◦ C when 20%wt HPMS was used compared to SiOC Acrylate-based photosensitive resins were used with other additives;
ceramic (0%wt HPMS) having compressive strength 2.07 MPa at tert-Butyl acrylate (monomer), 1, 6-hexanediol diacrylate (HDDA) as a
1000 ◦ C. crosslinker, and 2, 4, 6-trimethyl-benzoyl diphenylphosphine oxide
Kim et al. [54] investigated the dimensional accuracy, isotropic (photoinitiator). The effect of HDDA on mechanical properties and
mechanical behavior, and post-cure shrinkage of methacrylated poly shape memory effect (SME) was observed. 10%wt concentration of
dimethylsiloxane (PDMS) using digital light processing (DLP). Me HDDA bore 16 consecutive cycles with a 100% shape recovery rate after
chanical properties of printed samples were observed at three different 14 cycles, while 20%wt HDDA resulted in a shape fixity ratio of 96%.
orientations (X, Y, Z). Specimens printed in the Y direction displayed the The concentration of HDDA also affected the glass transition tempera
highest elastic modulus of 0.96 MPa compared to X and Z, where ture (Tg) , increased by 10% (48.3 ◦ C) with increasing HDDA concen
modulus was 0.78 MPa and 0.87 MPa, respectively. While the maximum tration. Maximum Tg was achieved at 50%wt concentration (76.3.◦ C).
elongation was observed in the Z direction, followed by Y and X axes Storage modulus increased from 927 MPa to 1.48 × 103 MPa as the
Fig. 11. Single material structure and two-material structures printed using 3DM-ABS alone or 3DM-ABS and VeroBlack. [56].
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concentration increased from 10%wt to 50%wt. bone-shaped specimen, and ultimate tensile strength, young’s modulus,
Kowsari et al. [56] fabricated a multi-material parts having high and elongation at break were observed. Ultimate tensile strength and
resolution and high efficiency using DLP. Five resins were used for this young’s modulus were slightly greater in UV postcured (1.5 MPa and
study: 3DM-ABS, VeroClear, VeroWhite, TangoPlus, and VeroBlack. A 0.70 MPa) than in without postcured samples (1.4 MPa and 0.66 MPa);
multi-material specimen consisting of VeroBlack and Tangoplus frac however, elongation was the same. These values showed great differ
tured away from the interface because of a strongly bonded ence with 10:1 PDMS (Sylgard 184) samples having ultimate tensile
multi-material layer. But the young’s modulus of all three specimens strength, young’s modulus, and elongation at break of 1.32 MPa,
(VeroBlack, Tangoplus, and half-half composites made of VeroBlack, 5.13 MPa, and 93%, respectively.
Tangoplus) was very low, i.e., 129.9 MPa, 0.4 MPa, and 1.1 MPa. These Xue et al. [62] used electrospray photolithographic patterning (EPP)
values were lower than provided by manufacturers. Fig. 11 shows single process to produce a 3D multi-layered porous microstructure by inte
and two-material structures fabricated using 3DM-ABS alone or grating the electrospray (ES) and DLP without using the mask. In this
3DM-ABS and VeroBlack. method, monodisperse microparticles were produced by ES, and then
Wang et al. [57] used polymer-derived silicon-nitride ceramic to DLP exposure was used to form the desired pattern after depositing the
fabricate cuboid, complex honeycomb structure, and lattice structure microparticles on the substrate. S1813 photoresist particulates were
via the DLP process. Polysilazane (PSZ) was used as a preceramic used along with 184 PDMS pre-polymer. The molded poly
polymer and acrylic resin as a binder at 2:1. Photoinitiator (TPO) with a dimethylsiloxane (PDMS) samples were printed, and the mechanical
weightage of 3 wt% was mixed with resin and PSZ. Si3N4 ceramic properties were observed. The young’s modulus and hardness of 3D
cuboid, honeycomb, and lattice were prepared with a layer thickness of green parts were 8.19 MPa, and 2.81 MPa, respectively.
25 µm and an exposure time of 15 s using 3D printing. Compression Cheng et al. [63] developed a yellow-resistant photosensitive resin
experiments were performed on printed samples. The compressive digital light processing process. Polyurethane acrylate (PUA) was syn
strength of 2D-structured Si3N4 ceramic honeycomb and 3D-structured thesized, and 3DP-PUH2 resin was prepared with optimal ratios of
Si3N4 ceramic lattice were 65.5 MPa and 5.12 MPa, respectively. PUH2/TPO/RYOJI-292/ dye/nanosilica (i.e., 100/5/0.4/0.01/0.1).
Moreover, the elastic modulus of the structures were 768.5 MPa, and Mechanical testing was performed to measure the tensile strength of
2.1 MPa, respectively. samples printed with different content of PUA (50–90%). It was
Kuang et al. [58] proposed a grayscale digital light processing observed that the highest strength was achieved at 70% of PUA. Simi
technique (g-DLP) to fabricate highly functionally graded materials larly, the effect of PUA:BPA2 on tensile strength was measured, which
using grayscale light. Complex 2D/3D lattices were fabricated using showed the highest strength at 3:2.
g-DLP, and different physical properties were observed. The resin was Zhang et al. [64] developed ZrO2 based 3D printed ceramic structure
prepared by using different additives such as bisphenol A ethoxylate by reinforcing the 3Y-TZP via the DLP process. The impact of 3Y-TZP
diacrylate (BPADA), glycidyl methacrylate (GMA), and n-butyl acrylate concentration (0, 5, 7.5, and 10 vol%) on the linear density, mechani
(BA) with a weight ratio of 69:23:8, along with 0.7 wt% photoinitiators cal properties, linear shrinkage, and microstructure were investigated.
(Irgacure819), 0.07 wt% photo-absorber (Sudan I), and 7 wt% of poly Monoclinic ZrO2 (m-ZrO2) with solid loading of 50 vol% was used as
(propylene glycol) bis(2-aminopropyl ether) (D230). Uniaxial tension raw material powder with strengthening additive 3Y-TZP. 1,6-Hex
tests were performed to evaluate the mechanical properties. It was anedioldiacrylate (HDDA) and 1,1,1-Trimethylolpropane triacrylate
observed that as the grayscale concentration (G%) decreased from 93% (TMPTA) were used as monomers, along with Diphenyl (2, 4, 6-tri-
to 0%, the young’s modulus was increased from 1.4 MPa to 1.2 GPa. methyl benzoyl) phosphine oxide (TPO) photoinitiator, KOS110,
Schmidt et al. [59] used preceramic polysiloxane to add active dispersant, and MgO as a sintering additive. A flexible strength test was
alumina fillers and fabricated complex mullite structures through digital performed, and it was observed that ZrO2 ceramic powders with 7.5%
light processing. Different porous ceramic components were fabricated, vol 3Y-TZP showed the highest flexural strength of 306.53 MPa with less
and their properties were compared to the parts with stochastic porosity. than 20% linear shrinkage and 96.40% relative density.
Mechanical testing was performed and it was observed that the printed Lin et al. [65] investigated dense aluminum nitride ceramics using
ceramic parts exhibited a compressive strength of 1.8 ± 0.3 MPa with the DLP process and observed the mechanical properties, cure width,
total porosity of 90 vol%. Dou et al. [60] fabricated green structures of cure depth, and rheological behavior. Ceramic powder AlN was used
lunar regolith using digital light processing (DLP) and studied the effect along with Y2O3 at 5 wt%. The resin consisted of ethoxylated pentaer
of temperature and atmosphere on the mechanical properties, chemical ythritol tetraacrylate (PPTTA), 1,6-hexanediol diacrylate (HDDA),
composition, and microstructure. The ceramic slurry was prepared by di-functional aliphatic urethane acrylate (U600), octanol, and
adding Lunar regolith simulant CLRS-2 with the photocurable acrylic poly-ethylene glycol. Phenylbis (2,4,6-trimethyl benzoyl) phosphine
resin in 45 vol% (70 wt%). Parts were printed with a layer thickness of oxide was used as a photoinitiator. A comparison was performed be
50 µm and then sintered at two different atmospheres: in air and Ar tween unmodified AlN powder and modified AlN powder. Stearic acid
atmosphere. Sintering was done at two temperatures, 1100 ◦ C, and (SA) and oleic acid (OA) were used to modify AlN powder in different
1150 ◦ C. It was observed that maximum compressive strength, flexural concentrations (0.3, 0.5, 1.0, 2.0, and 3.0 wt%). OA-modified AlN
strength, and hardness were achieved by sintering green parts at powder showed better properties than SA-modified AlN powder with the
1150 ◦ C in the air that were 312.2 MPa, 74.1 MPa, and 822HV, flexural strength and hardness of sintered specimens of 398 MPa and
respectively. These values were 5.66, 3.09, and 33.41 times higher than 10.47 GPa, respectively, with a sintered density of 99%.
parts sintered at 1150 ◦ C in Ar atmosphere. Wang et al. [66] fabricated molds for aluminium casting using
Gonzalez et al. [61] fabricated micro-fluidic devices such as 3D partially stabilized zirconia (PSZ) via the DLP process. The ceramic
printed microfluidic chips using DLP through Polydimethylsiloxane. suspension consisted of ceramic powder with multifunctional acrylate
Acrylate-polydimethylsiloxane (PDMS) was used as a photopolymer monomers, photoinitiator (Irgacure 819 with 2 wt% of the resin), and
along with 0.6 wt% to the TRAD oligomer and 0.6 wt% of BAPO-Si as a amine (dispersant 3 wt% of the ceramic powder). The parts with layer
photoinitiator. 0.1 wt% of the Methacrylate group (DR1-MA) was used thickness and exposure time 25 µm and 3 s were sintered at 14800 C.
as a dyeing agent with a small amount of methyl methacrylate (MMA) Mechanical testing was performed using a three-point bending method,
for dispersion of the dye. The fabricated specimens were observed for and the flexural strength and Young’s modulus were measured. It was
storage modulus (G’) and loss (G’’) modulus versus irradiation time. found that flexural strength and young’s modulus of sintered parts were
Before light illumination, loss modulus was higher than storage higher, 803.7 MPa and 203.4 GPa, than green parts with 41.5 MPa and
modulus, but G’ crossed the G’’ curve and showed the elastic response as 3.1 GPa, respectively.
the illumination started. Tensile testing was also performed on the dog Shen et al. [67] studied the effect of exposure time and angle of
11
printing on the flexural strength and curing behavior of fabricated parts elongation, and crease recovery at optimum printing conditions such as
by the DLP process. In this study, three mol% yttrium-stabilized zirconia curing time, layer thickness, and photopolymer concentration. Firstly,
(3Y-TZP) suspension was used with a solid loading of 50% vol. The effect the effect of photopolymer resin was observed by changing concentra
of exposure time (2 s,3 s,4 s, 5 s,14 s) on curing depth was observed, and tion (10%, 20%, 30%, and 40% (v/v)) and maximum tensile strength
it was observed that curing thickness increased with an increase in elongation at break was observed at 10%v/v. Secondly, the effect of
exposure time with a minimum thickness of 30 µm at 1 s. The maximum curing time was observed at 8, 10, 12,14, 16,18, and 20 s), optimal
thickness of 120 µm at 11 s remained the same up to 13 s after debinding tensile strength and elongation at break were achieved at 14 s. Thirdly,
up to 500 ◦ C, and sintering up to 1550 ◦ C. The effect of exposure time on the effect of layer thickness (50, 100, and 200 mm) on tensile strength
flexural strength was observed that maximum strength was 580 MPa at and elongation at break was observed and the optimal strength was
13 s with a Weibull modulus of 8.84. Minimum flexural strength was achieved at 100micro meters. Results were compared with properties of
371 MPa at 6 s with a Weibull modulus of 3.68. Similarly, parts were parts printed by FDM and good resolution, surface morphology, and
printed at different angles ranging from (0–90◦ ), and the effect of strength were observed.
printing angle on flexural strength was analyzed. Maximum strength Chen et al. [70] fabricated cordierite ceramic parts using the DLP
was observed when the angle was 0 ◦ which was 506 MPa, and the process to study printed specimens’ mechanical properties and micro
lowest strength was 142 MPa at 45 ◦ . Fig. 12 shows flexural strength structures. Three different slurries were prepared by Cordierite having
data and the corresponding Weibull moduli of the sintered bending particle size (D50 =7.41 µm, 3 µm and 0.35 µm) with 40 vol% solid
samples fabricated under different exposure times. loading. Three factors were studied, such as (layer thickness, exposure
Ji et al. [68] investigated photocuring elastomers by DLP process time, and particle size) to observe their impact on mechanical properties
having excellent mechanical strength and resilience. In this work, and microstructures of printed specimens. Repeated experiments were
modified polyethylene glycol (Acryl@PEG) such as (PEG800, PEG4000, performed with a layer thickness (25 µm, 50 µm, and 100 µm) and
PEG10000, and PEG20000) were tested with diluent 2-hydroxyethyl exposure time (2 s, 3 s, and 4 s). Parts were 3D printed in rectangular
methacrylate (HEMA) in different ratios to study the mechanical shape and then processed through debinding and sintering. It was found
strength and resilience of printed parts of different shapes. Acryl@ that, with an increase in exposure time and particle size, the curing
PEG10000 and Acryl@PEG20000 showed a residual strain of 158.3% depth and penetration depth increased, respectively. So, optimal pa
under 200% strain and 232.8% under 300% strain which showed poor rameters corresponde3d to layer thickness of 50 µm, exposure time
resilience. On the other hand, Acryl@PEG4000 showed the tensile of 3 s, and particle size of 0.35 µm. With increased particle size from
strength of 17.2 MPa and residual strain of 19.0% under 150% strain, 0.35 µm to 7.41 µm, elastic modulus decreased from 90 GPa to 7 GPa;
therefore, Acryl@PEG4000 was selected for preparing photocuring ink. hardness decreased from 6 GPa to 0.2 GPa and compressive strength
Photocuring ink consisted of Acryl@PEG4000 (having 33 wt% 1122TF) decreased from 46.3 MPa to 29.8 MPa, respectively. The effect of par
for improved resilience, HEMA, 3% photoinitiator Irgacure 819%, and ticle size on other factors (layer thickness and exposure time) was also
0.05% polymerization inhibitor Orasol dye. Tunable mechanical prop dominant. So particle size 3 µm were selected for sample preparation.
erties were obtained by varying the ratio of Acryl@PEG4000 and HEMA. Li et al. [71] fabricated a ceramic shell made of calcined kaolin
With increasing HEMA content, tensile strength was enhanced from 4.2 (Al2O3.2SiO2) suspension with a solid loading of 45 vol% for precision
to 20.3 MPa, having an optimal elongation at break of 245.0% with the casting using the DLP process. Polyethylene glycol diacrylate, 3, 3-dime
ratio of 1:1. Similarly, the elastic modulus was increased to 4.2 MPa, thylacrylic acid, and 2,4,6-trimethyl benzoyl- diphenyl phosphate oxide
28.3 MPa, and 333.4 MPa for 1:0, 1:1, and 1:3, respectively. Hence, were used as the monomer, crosslinker, and a photoinitiator, at a ratio of
Acryl@PEG4000 and HEMA 1:1 provided high tensile strength of 45: 45: 8: 2, respectively. The suspension exhibited shear-thinning fluid
14.1 MPa with an elongation of 245%. behavior. After 3D printing with layer thickness of 95 micrometers,
Kim et al. [69] developed fabrics using the DLP process using poly green parts were processed through debinding and then sintered at
urethane acrylate photopolymer, and measured the tensile strength, 1200 ◦ C, which removed all the cracks and voids and increased the
Fig. 12. Flexural strength (σ‾) and Weibull moduli (m) of 3D printed sintered bending samples fabricated under different exposure times [67].
12
density from 1.14 g/cm3 to 2.08 g/cm3 with porosity of 24.5%. Trans compressive and flexural strength of 12.6 ± 1.6 MPa and
verse rupture strength of sintered parts was 9.98 MPa, similar to tradi 4.8 ± 0.9 MPa, respectively. Fig. 13 shows the plot for the average
tional ceramic shells prepared by the dip-coating method. mechanical properties of all of the polymer resin formulations, deter
Cao et al. [72] fabricated complex shapes made of flex activated mined from the uniaxial extension of dogbone-shaped test specimens for
mechanophore to investigate nondestructive assessment of mechano each formulation. Some previous works related to different polymers
chemical reactivity via DLP-AM. The photo resin consisted of 2-hydrox produced from the DLP process for mechanical applications are reported
yethyl acrylate (HEA), Irgacure 819 as photoinitiator, in Table 3.
oxanorbornadiene-dimethacrylate (OND-DMA), and Nile Red as a light
absorber, at 98.52 wt%, 0.49 wt%, 0.99 wt%, and 0.01 wt%, respec 3.2.2. DLP for biomedical applications
tively. To measure the elongation at break, tensile testing was performed Osman et al. [80] 3D printed the zirconia implant using the DLP
on dog bone-shaped specimens and strain of 156–188% was observed in process and studied the mechanical properties, surface topology, and
curing time of 5–11 s dimensional accuracy of printed parts. Yttria tetragonal stabilized zir
Duan et al. [73] performed 3D printing using AlN ceramics via the conia (TZ-3Y-E) was mixed into the photocurable resin to form a ceramic
DLP process and measured the mechanical properties and thermal slurry. The parts (zirconia implant and disc) were printed with a layer
conductivities. The suspension was prepared by adding AlN powder and thickness of 30 µm and then debinding was performed to remove the
Y2O3 powder in photosensitive resin with a mass ratio of 95:5 and solid extra resin. After that, sintering was performed at 1500 ◦ C to obtain
loading of 55%vol. Specimens were printed with a layer thickness of density up to 99.9%. Biaxial flexure strength test was performed on
25 µm. The green bodies were processed through debinding at 500 ◦ C, printed discs at three build angles of (0◦ ,45◦ , and 90◦ ) and it was
and then sintering was performed at 1780 ◦ C, 1800 ◦ C, 1825 ◦ C, observed that the maximum flexural strength was achieved at 0◦ angle
1830 ◦ C, 1835 ◦ C, 1840 ◦ C, and 1845 ◦ C. It was observed that as the with a value of 943.26 MPa and Weibull modulus of 7.03 compared to
sintering temperature increased from 1780 ◦ C to 1845 ◦ C, the porosity specimens printed at 45◦ and 90◦ , which was 822.3 MPa and 834.4 MPa,
decreased from 20% to 4% and, density and thermal conductivity respectively. All these specimens had strength comparable to the
increased from 2.67 to 3.20 g/cm3 and 82 W/(m⋅K) to 155 W/(m⋅K), strength of milled zirconia (800–1000 MPa).
respectively. Mechanical testing was performed and flexural strength Maturi et al. [81] developed a novel bio-based resin to improve
was measured, increasing from 139 MPa to 265 MPa with increasing mechanical resistance, better rigid structure, and lower fragility using
sintering temperature from 1780 ◦ C to 1845 ◦ C, respectively. the DLP process. The resin mixture consisted of poly(1,
Shen et al. [74] 3D printed ceramic cellular materials using triply 3-propanediol-co-glyceryl) itaconate-co-vanillate (PPGIV), bis
periodic minimal surface architectures (TPMSs) via the DLP process and (2-(methacryloyloxyethyl) itaconate (BHI), tris(2-(methacryloylox
studied their mechanical properties. Zirconia was used as raw material yethyl) citrate (THC), initiators, terminator, and dyes in concentrations
and was mixed with photosiensitive resin with solid loading of 50% vol. of 48.5%, 24%, 24%, 1.5 wt%, 2.0 wt%, and 0.01 wt%, respectively.
Four ceramic cellular structures p-cell, gyroid, IWP and s14 were The resin contained 96.6% of bio-based contents. Tensile testing and
fabricated with layer thickness of 50 µm and then sintered at 1550 C. flexural testing of printed parts was performed on dog-bone shaped and
Elastic modulus and compressive strength were measured which rectangular bar specimen, respectively. Tensile modulus, ultimate ten
concluded, that s14 structure showed the highest compressive strength sile strength, and elongation at break were achieved to be 61 MPa,
and elastic modulus of 105 MPa and at structural density of 30.5%, 5.4MPa, and 18%. Flexural modulus and maximum flexural strengths
while on the other hand gyroid structure showed low compressive were 350 MPa and 12.6 MPa, respectively.
strength of 5.6 MPa at density of 6.7%. Highest elastic modulus was Kim et al. [18] proposed a printing bioink via DLP, which possessed
5352.7 MPa for IWP and lowest was 194MPa for P-cell. The order of biocompatibility, printability, biometric properties, and enough me
compressive strength of four structures are as follows: chanical properties to be used in tissue engineering. The bioink was
s14 > IWP>gyroid>p-cell. All TPMS structures could sustain >2% produced with the help of silk fibroin, using glycidyl methacrylate
strain without failure. (GMA) through the methacrylation process, named SF-based bioink
Steyrer et al. [75] used Methacrylate resins to fabricate 3D printed (Sil-MA). The mechanical properties were tested using 10%, 20%, and
parts using Visible Light Photoinitiator via DLP process and studied the 30% of Sil-MA hydrogel, and it was observed that compressive elastic
effect of photoinitiator (Ivocerin, BAPO, and TPO-L) and post-processing modulus increased with increasing the concentration of Sil-MA hydro
on the mechanical properties. Parts were printed with The cubiflow gel. Compressive stress increased to 2.6-fold after every 10% increment
photopolymer resin, having 50 µm-thick layers and an exposure time of of Sil-MA hydrogel. It was observed that 910 KPa of compressive stress
the 40 s. It was observed that sintered parts containing TPO-L showed achieved using 30% Sil-MA hydrogel and compressive strain increased
the best mechanical properties, such as maximum yield strength 41 MPa to 80%. As long as the Sil-MA concentration increased, the value of
and 112 C glass transition temperature at a 1.18 wt% concentration. All tensile strength and breaking elongation increased (124% at 30%
sintered parts, made of different photoinitiators, showed the elongation Sil-MA). Tensile elastic modulus was also enhanced by increasing the
at a break ranging 80–100%. concentration of Sil-MA hydrogel that was 14.5kPa at 30% Sil-MA. It
Liu et al. [76] proved the feasibility of using lunar regolith to was noted that the tensile strength and breaking elongation of 30%
fabricate different functional and architectural structures using the vat Sil-MA was 1.5 times and 1.6 times greater than 20% Sil-MA hydrogel.
photopolymerization process and observed their mechanical properties. So, 30% Sil-MA hydrogel can be used in tissue engineering. Fig. 14 and
The slurry consisted of 100 g lunar regolith simulant CLRS-2, 500 g Fig. 15 show printed products of ear and brain mimicked shape and
zirconium oxide, 150 g isopropanol (IPA) with high density poly Trachea, heart, lung, and vessel mimicked shape.
ethylene (HDPE) grinded into fine powder. The resin and ground pow Chen et al. [82] synthesized three PCL-based polyurethane acrylates
der was mixed with a ratio of 55–45 vol%. The samples were printed such as m-PUA530, m-PUA800, and m-PUA1000 and formulated twelve
with different layer thicknesses (25 µm, 50 µm, 100 µm) at different further resins from them by altering the ratio of poly (ethylene glycol)
exposure times (30 s, 60 s, 150 s), respectively. After sintering, diacrylate (PEGDA), and propylene glycol (PPG) for DLP 3DP process.
compressive and flexural strength was measured. It was noted that both Compressive tests and hardness measurements were made on parts
compressive and flexural strength increased with decreasing layer printed by using twelve resins. The compressive strength of pure
thickness. Maximum compressive and flexural strength was achieved at PUA530, PUA800, and PUA1000 was 256.52 MPa, 186.38 MPa and
25 µm, which was 428.1 ± 39.7 MPa and 129.5 ± 13.6 MPa, respec 127.66 MPa, and compressive modulus was 34.43 MPa, 19.82 MPa, and
tively, which is 1.25 and 2.16 times greater than samples at 100 µm. 16.29 MPa. It was observed that as the concentration of PPG in resins
These strengths were significantly higher than the cement having was increased, both compressive strength and modulus decreased. The
13
Fig. 13. Elastic Modulus or Ultimate tensile stress and strain with EGPEA formulation fraction, obtained from performing the uniaxial extension test on dogbone-
shaped test specimens for each formulation [12].
compressive strength of twelve resins was 6.8–23.4 MPa, while the Fig. 16 shows a printed scaffold with a feature size of 500 µm after
compressive modulus was 5.4–18.3 MPa. On the other hand, viscosities cleaning and post-printing UV curing.
of twelve resins were decreased by ten times compared to pure PUA Schmidt et al. [85] converted the glass-filled photosensitive resin
resins, which make them suitable candidates for tissue engineering. into a bioactive glass-ceramic scaffold using DLP to check its possibility
González et al. [83] studied the effect of suitable materials and and biocompatibility in tissue engineering. The glass used in this
post-curing protocols on the biocompatibility of materials with A549 experiment was wollastonite-diopside, having ~52 mol% wollastonite
cancer cell lines, using the DLP process. Three monomers such as (CaO⋅SiO2) and 48 mol% diopsides (CaO⋅MgO⋅2SiO2) and was added to
polyethylene glycol diacrylate (PEGDA), 1,6-hexanediol diacrylate acrylated polymer resin (tri-propylene glycol diacrylate) resin. No
(HDDA), and bisphenol A ethoxylate diacrylate (BEDA), were used along photoinitiator and photo absorber were used in this experiment. 63%wt
with photoinitiators, phosphine oxide-based compound (BAPO). 96- and of resin was used along with 41%vol of glass. Heat treatment at 1100 ◦ C
24-wells-like parts were fabricated for testing purposes. DMA was per was performed, which resulted in wollastonite-diopside biocompatible
formed to test the storage modulus as a function of time. It was observed glass-ceramic with cubic kelvin cell structures. Total porosity achieved
that as the lamp switch is set to ON after 60 s, there was a sudden in was 83 vol% with the mechanical strength of 3.2 MPa, which is quite
crease in storage modulus, and maximum storage modulus was observed compatible with human trabecular bone with mechanical strength and
in the case of BEDA + 1 wt% BAPO, around 106 GPa. porosity of (2–12 MPa) and (75–95 vol%). Around 25% homogeneous
Paredes et al. [84] fabricated bioactive ceramic scaffolds using DLP linear shrinkage was observed. Fig. 17 shows SEM images of samples
to determine the effect of pores and strut size on the manufacturability with a Kelvin cell architecture.
and mechanical performance. The ceramic resin was prepared by adding Xue et al. [86] fabricated a Cell-Seeding Hydrogel Scaffold with
β-tricalcium phosphate (β-TCP) powders in acrylic resin. The porous regionally varied stiffness using DLP and observed the effect of exposure
scaffold was prepared with cubical shape external dimensions. Opti time, without changing the geometry structure, on the mechanical
mized pore and strut size selected was sp=sS= 400 µm (because of its properties of the scaffold. Poly- (ethylene glycol) diacrylate (PEGDA)
high compressive strength) with powder concentration of 50 wt% with was used as resin, and lithium phenyl- 2,4,6-trimethylbenzoyiposphi
optimized exposure time and layer thickness of 0.3 s and 25 µm, nate (LAP) was used as a photoinitiator. Mechanical tests were per
respectively. The uniaxial compressive test was performed in formed on printed pillars made of PEGDA, and stress-strain curves were
sp=sS= 500 µm, perpendicular and parallel to printing direction to obtained at three different exposure times (3.1, 3.5, and 3.9 s). it was
measure the compressive strength (22 ± 4 MPa) in a parallel configu observed that ultimate stress increased by increasing exposure time, but
ration and 12 ± 3 MPa in case of perpendicular configuration. Both ultimate strain decreased with increasing exposure time. Elastic moduli
strengths were within the range of cancellous bone strength values. calculated at 3.1, 3.5, and 3.9 s were 2950, 3140, and 3410 kPa.
14
Table 3
Different Polymers produced via the DLP process for mechanical applications.
PR-48, Autodesk Standard Clear • Nil • Light wavelength 405 nm • Increase in elastic modulus up to 214% [42]
Resin • Resolution 50 µm • Increase in ultimate tensile strength up to
• Layer thickness 10 µm, 301%
25 µm, 50 µm • Increase in ultimate strain up to 347%
• Exposure time 1.6 s,
1.8 s, 2 s
PR-48, Autodesk Standard Clear • Nil • Resolution in X and Y axis • Maximum achieved elastic modulus [43]
Resin 50 µm 0.749 ± 0.196 GPa
• Resolution in Z axis • Maximum achieved ultimate stress
10 µm 21.7 ± 6.5 MPa
• Light wavelength 405 nm
• Exposure time 1.6 s, • Maximum achieved ultimate strain
1.8 s, 2 s 5.8 ± 1.87%
• Layer thickness 10 µm,
25 µm, 50 µm
SUV elastomer polymer resin • Photoinitiator: trimethyl benzoyl diphenyl • light range 400–800 nm • Increase in young’s modulus up to 625% [45]
phosphine oxide (2%) • layer thickness 100 µm (0.58–4.21 MPa)
• Monomer: epoxy aliphatic acrylate (EAA) • exposure time 10 s • Increase in elongation up to 358%
• Crosslinker: aliphatic urethane diacrylate (AUD)
• isobornyl acrylate (33 wt%) • Increase in toughness from
1 × 106–50 × 106 Jm-3
calcium phosphate (CaP) • camphor • Exposure time 18 s • flexural strength 87 ± 2.8 MPa [46]
• Layer thickness 200 µm • reduction in viscosity 2.17 ± 0.3 mPa⋅s
• decrease in shrinkage up to 20.1 ± 0.61%
• relative density up to 97.1 ± 0.02%
• increase in compressive strength up to
233%
• increase in elastic modulus up to 131%
commercial photocurable acrylic- • acrylic monomers • wavelength 405 nm LED • Maximum achieved tensile strength [47]
based resins • oligomers light source 53 MPa
• photoinitiators • Layer thickness 50 µm • Maximum achieved compressive strength
• inorganic additives • Resolution in X and Y axis 110 MPa
62.5 µm • Maximum achieved flexural strength
• Resolution in Z axis 79 MPa
12.5 µm • Maximum achieved hardness 82.3 Shore D
Ebecryl 8413 (Allnex) • Monomers: cyclic trimethylo-propane for- mal • Light wavelength 405 nm • Maximum achieved tensile strength [48]
acrylate and 2-(((butylamino)carbonyl)oxy) • light intensity(3.68 mW/ 10 MPa
ethyl acrylate cm2) • Maximum achieved elastic modulus
• Photoinitiator: phosphine oxide (TPO) • layer thickness 100 µm 10 MPa
• Maximum achieved elongation 365%
photoresin G+ Yellow • Nil • layer height 0.1 mm • Maximum achieved elastic modulus [49]
• exposure time 12 s 63.29 MPa
• bottom exposure time • Maximum achieved offset compressive
12 s strength 1.98 MPa
• lift speed, 60 mm/min • Maximum achieved compressive strength
• z retract speed, 100 mm/ 2.88 MPa
min • Maximum achieved strain-to-break
• slide tilt value 0 0.097 mm/mm
• intensity range between
50 klx to 200klx
Bis(propylacrylamide)poly • Photoinitiator: Irgacure 819 (0.25 wt%) • Light intensity 80 klx • Maximum achieved elongation 472% [50]
(dimethylsiloxane) • layer cure times 6 − 24 s
• toluene (5%)
VisiJet® FTX Green Monomers: • layer thickness, 0.03 mm • Increase in tensile modulus up to 40% [51]
• Triethylenglycol diacrylate • speed of vertical build, • Increase in ultimate flexural strength from
• Tricyclodecane dimethanol diacrylate 14 mm/h 41% to 77%
Photoinitiator: • average irradiance time • Maximum achieved elastic modulus
• Phenyl oxide bis (2,4,6-trimethylbenzoyl) per layer, 8.3 s 1073 MPa
phosphine • wavelength, 315–400 nm
epoxy silicone resin (EPS resin, SH- • Catalyst: triethylamine • Wavelength 405 nm • Maximum achieved compressive strength [53]
023–7 • Moderator: p-Methoxyphenol (MEHQ) • layer thickness: 50 µm 3.45 MPa
(0–30 wt%) • Additive: Hydroxyl silicone oil (HPMS) • exposure time: 4 s per
• Photoinitiator: ethyl phenyl (2,4,6- layer
trimethylbenzoyl) phosphonate (TPOL) (1 wt%) • UV light energy intensity:
• Absorber: Sudan III (0.01 wt%) 3.2 mW/cm2
methacrylated PDMS-macromer • photoinitiator:2,4,6-Trimethylbenzoyldi- • X-Y resolution 50 µm • Maximum achieved elastic modulus in Y [54]
Phenylphosphinate (TPO-L) • Layer thickness 25 µm direction 0.96 MPa
• exposure time 10 s • Maximum achieved elongation in Z
• power density 100 W/m2 direction 66.37%
• power level 52% • Maximum achieved UTS in Z direction
• Peeling speed 0.49 MPa
0.0625 mm/s
acrylate-based photosensitive resins • photoinitiator: 2, 4, 6-trimethylbenzoyldiphenyl • power density is • Maximum Tg achieved at 50%wt [55]
phosphine oxide (TPO) 1250–1450 μW/cm2 concentration 76.3 ◦ C
(continued on next page)
15
Table 3 (continued )
• monomer: tert-Butyl acrylate (tBA) • UV light wavelength • Increase in storage modulus up to 59%
• Crosslinker: 1, 6-hexanediol diacrylate (HDDA) 405 nm
• exposure time 30 s
acrylic based photocurable resin • multi-walled carbon nanotubes (MWCNTs) • layer thickness 19.05 ųm • Increase in ultimate tensile strength up to [77]
(Are3d-dlp405) • exposure time 40 s 21%
• 0.3 wt% loading of • Increase in young’s modulus up to 45%
MWCNT • Decrease in elongation at break up to 10%
3DM-ABS, VeroClear, VeroWhite, • Nil • pixel size 15 ųm • Maximum achieved young’s modulus by [56]
TangoPlus and VeroBlack • Light wavelength 405 nm VeroBlack, Tangoplus and their composite,
• Layer thickness 25 ųm 129.9 MPa, 0.4 MPa, and 1.1 MPa
• high-speed translational
stages 400 mm/s
Urethane acrylate resinEbecryl 8232 • Fe3O4 nanofillers • layer thickness 20 µm • Glass transition temperature Tg − 10.7 C [78]
(Eb) • exposure time 20 s • Maximum elastic modulus 7 MPa
• intensity 10 mW/cm2
• UV post-curing for
10 min
Tangoplus FLX 930(photo absorber • Photo absorber: Rhodamine B (Acros Organics) • Bottom-up DLP 3D • Maximum achieved elongation at break [79]
and the resin as 3:1000) printer 170%–220%
• Resolution 50 µm • Increase in Maximum achieved ultimate
• Layer thickness 87.5 µm strain up to 246%
• ultraviolet (UV) light
source wavelength
385 nm
• light intensity 60% of the
brightness
Polysilazane (PSZ) • Binder: Commercial acrylic resin (Formlabs Inc, • 3D printer resolution: • Maximum achieved compressive strength [57]
USA) 25–50 µm 65.5 MPa and 5.12 MPa
• Photoinitiator: 2, 4, 6-trimethylbenzoyldiphenyl • layer thickness 25 µm • Maximum achieved elastic modulus
phosphine oxide (3 wt%) • exposure time 15 s 768.5 MPa, and 2.1 MPa
• Initiaitor: Sinopharm Chemical Reagent • wavelength 405 nm • Linear shrinkage 27.63%
• pyrolysis temperature • Relative density 88.43%
1200, 1400, and 1600 ◦ C
bisphenol A ethoxylate diacrylate • Photoinitiator: Irgacure 819 (0.7 wt%) • exposure time 20 s • Increase in young’s modulus from 1.4 MPa [58]
(BPADA) • Photo-absorber: Sudan I (0.07 wt%) • layer thickness 60 µm to 1.2 GPa
• poly(propylene glycol) bis(2-aminopropyl • light resource • Glass transition temperature Tg range from
ether) (7 wt%) wavelength (385 nm) 14◦ to 68◦ C
• glycidyl methacrylate (23 wt%)
• n-butyl acrylate (8 wt%)
CLRS-2, photocurable resins • zirconium oxide (500 g) • layer thickness (25 µm, • Maximum achieved compressive strength [76]
• isopropanol (150 g) 50 µm, 100 µm) (25 µm) 428.1 ± 39.7 MPa (25%
• high density polyethylene (HDPE) • exposure time of (30 s, enhancement)
60 s, 150 s) • Maximum achieved flexural strength
• Ultraviolet light source (25 µm) 129.5 ± 13.6 MPa (116%
with peak wavelength improvement)
405 nm
• sintering temperature
1150 ◦ C
highly acrylated, liquid • dispersing agent: (0.24 wt% phosphoric acid • wavelength • Maximum achieved compressive strength [59]
photocurable polysiloxane polyester) (455–465 nm) 1.8 ± 0.3 MPa
• Photoinitiator: (Lithoz GmbH, Austria) (0.2 wt • layer thickness 25 µm • Total porosity 90 vol%
%) • exposure time 6 s
• Photoabsorber: azo dye (0.06 wt%) • UV lamp (Intensity
~20 mW/cm2)
• Sintering temperature
range 1200–1400 ◦ C
Commercial photocurable acrylic • lunar regolith simulant CLRS-2 (70 wt%) solid • layer thickness 50 µm • Maximum achieved compressive strength [60]
resin (material details were loading • Sintering temperatures 312.2 MPa
confidential) was 1100 ◦ C and 1150 ◦ C • Maximum achieved flexural strength
74.1 MPa
• Maximum achieved hardness 822HV
acrylate-polydimethylsiloxane • Oligomer: TRAD (0.6 wt%) • light intensity 10 mW/ • Maximum ultimate tensile strength [61]
(PDMS) • Photoinitiator: BAPO-Si (0.6 wt%) cm2 1.5 MPa
• dyeing agent: Methacrylate group (DR1-MA) • UV light wavelength • Maximum achieved young’s modulus
(0.1 wt%) 405 nm 0.70 MPa
Sylgard 184 polydimethylsiloxane • S1813 particles • UV dose 495 J cm-2 • Maximum achieved young’s modulus [62]
(PDMS) pre-polymer • Layer thickness 8.19 MPa
28 ± 3 µm • Maximum achieved hardness 2.81 MPa
Monoclinic ZrO2 (m-ZrO2) with • 3Y-TZP (7.5% vol) • UV light (Wavelength: • Maximum achieved flexural strength [64]
solid loading of 50 vol% • Monomers:1,6Hexanedioldiac ylate and 1,1,1- 405 nm) 306.53 MPa
Trimethylol propane triacrylate • Intensity: 6000 μw/cm2 • Linear shrinkage < 20%
• Photoinitiator: TPO • Exposure time: 5 s • Relative density 96.40%
16
• Dispersant: KOS110 • Layer thickness 50 µm

• Sinitering additive: MgO
Ceramic powders (AlN and Y2O3) • Photoinitiator: Phe- nylbis (2,4,6- • UV light (Wavelength: • Maximum achieved flexural strength [65]
trimethylbenzoyl) phosphine oxide 405 nm) 398 MPa
• ethoxylated pentaerythritol tetraacrylate • exposure energy 105 mJ/ • Maximum achieved hardness 10.47 GPa
• 1,6-hexanediol diacrylate cm2 • Sintered density 99%
• di-functional aliphatic urethane acrylate
• octanol
• polyethylene glycol
multifunctional acrylate monomers • Partially stabilized zirconia (PSZ) • Layer thickness 25 µm • Maximum achieved flexural strength [66]
• Photoinitiator: Irgacure 819 having 2 wt% of the • Exposure time 3 s 803.7 MPa
resin • Sintering temperature • Maximum achieved young’s modulus
• Dispersant: amine (3 wt% of the ceramic 1480 ◦ C 203.4 GPa
powder) • Light intensity 90 mW/
cm2
• wavelength LED light
405 nm
3 mol% yttrium-stabilized zirconia • Nil • Sintering temperature • Maximum achieved flexural strength [67]
(3Y-TZP) suspension 1550 ◦ C 580 MPa, at 13 s
• exposure time (2 s,3 s,4 s, • Maximum achieved flexural strength
5 s, … 14 s) 506 MPa, at 0 ◦
• layer thickness
30–120 µm
• wavelength of the UV
light 405 nm
polyethylene glycolAcryl@PEG4000 • Diluent: 2-hydroxyethyl methacrylate (HEMA) • Layer thickness 108.2 µm • Maximum achieved tensile strength [68]
(having 33 wt% 1122TF) • Photoinitiator: Irgacure 819 (3%) 17.2 MPa
• polymerization inhibitor Orasol dye (0.05%) • Maximum achieved residual strain 19.0%
• Acryl@PEG4000 under 150% strain
• Optimal elongation at break 245.0%
• Maximum achieved elastic modulus
333.4 MPa
• Excellent resilience (recover to 90.85%
after 30 min under the 200% strain)
polyurethane acrylate photopolymer • acrylate oligomer (10%, 20%, 30%, and 40% (v/ • Exposure time (8, 10, • Maximum tensile strength at optimal [69]
v)) 12,14, 16,18, and 20 s) concentrations and process parameters
• Optimal exposure time • Maximum elongation at optimal
14 s concentrations and process parameters
• Layer thickness (50, 100,
and 200 mm)
• Optimal layer thickness
100 mm
• Optimal concentration of
acrylate oligomer 10%v/
v
• UV light-emitting diode
(LED) (405 nm)
Cordierite powder (40% of slurry • Diluent/monomer TMPTA (80% of premix • particle size • maximum achieved elastic modulus [70]
volume) volume) (D50 =7.41 µm, 3 µm 90 GPa
• Diluent/monomer HDDA (20% of premix and 0.35 µm) • maximum achieved hardness 6 GPa
volume) • Layer thickness (25, 50, • maximum achieved compressive strength
• Surfactant KH-570 (2% of slurry weight) and 200 µm) 46.3 MPa
• Dispersant disperbyk-111 (5% of slurry weight) • exposure time (2 s, 3 s,
• Photoinitiator TPO (2% of premix weight) and 4 s)
• optimum layer thickness
50 µm
• optimum exposure
time= 3 s
• optimum particle
0.35 µm
Shrinkagecalcined kaolin • Monomer: Polyethylene glycol diacrylate (45% • layer thickness 95 µm • Maximum achieved transverse rupture [71]
powdersolid loading of 45 vol% vol) • sintering temperature strength 9.98 MPa
• Crosslinker: 3, 3-dimethylacrylic acid (8%vol) 1200 ◦ C • Maximum achieved porosity 24.5%
• Photoinitiator: 2,4,6-trimethylbenzoyl-
diphenyl phosphate oxide (2%vol)
2-hydroxyethyl acrylate (HEA) • Photoinitiator: Irgacure 819 (0.49 wt%) • curing time 5–11 s • Maximum achieved strain range [72]
(98.52 wt%) • light absorbers: oxanorbornadiene- 156–188%
dimethacrylate (OND-DMA, 0.99 wt%), and Nile
Red (0.01 wt%)
Photosensitive resin • AlN and Y2O3 powder having mass ratio of 95:5 • sinterimg temperature • Increase in flexural strength up to 90% [73]
and solid loading of 55%vol from 1780 ◦ C to 1845 ◦ C • Maximum achieved bending strength
• debinding temperature 265 ± 20 MPa
500 ◦ C • Total porosity 4%
• layer thickness of 25 µm • Maximum achieved thermal conductivity
155 W/(m⋅K)
17
photosiensitive resin • Zirconia (solid loading of 50% vol) • layer thickness 50 µm • Maximum achieved compressive strength [74]
• sintering temperature 105 MPa
1550 C • Maximum achieved elastic modulus
5352.7 MPa (for IWP)
Methacrylate Resins • Photoinitiators: (Ivocerin, BAPO, and TPO-L) • layer thickness 50 µm • maximum achieved yield strength 41 MPa [75]
• exposure time 40 s (for TPO-L at 1.18 wt% concentration)
• light wavelength 405 nm
Fig. 14. The compressed and released photographs of Ear and brain, fabricated with the DLP printing technique [18].
Octahedral type scaffold was printed using 20% PEGDA and stress-strain indicating good fluidity. The authors also observed that loss modulus
curve showed that ultimate stress at 3.1, 3.5, and 3.9 s were 6.7 kPa, 7.9 was higher than storage modulus with respect to strain at 30%wt HA.
kPa, and 11.5 kPa, respectively, while the elastic moduli were 17.8, Axial compression test was performed on the 3D printed scaffold and it
22.4, and 30.1 kPa. So, 60% of the increase in elastic modulus was was observed that the maximum compression of 12.8 MPa was achieved
achieved in scaffolds by varying the exposure time, which is in the range in the vertical direction compared to the horizontal direction where
of modulus of muscle (8–17 kPa) and collagen (25–40 kPa). It was noted strength was 6.3 MPa. The average strength remained above 10 MPa
that no fracture was observed until compression strain reached up to and below 10 MPa with an average value of 11.8 MPa and 5.1 MPa, for
25% by compression testing. vertical and horizontal direction, respectively.
Krkobabić et al. [87] investigated the effect of poly(ethylene glycol) Liu et al. [89] investigated a method to fabricate the hydroxyapatite
400 (PEG 400), sodium chloride (NaCl), and mannitol, that act as hy (HA) porous bone scaffold using digital light processing. A slurry was
drophilic excipients to enhance the drug release rate of tablets produced prepared using photopolymer and micron HA powder with 45% solid
by the digital light processing process. Polyethylene glycol diacrylate content with suitable viscosity. Different parameters were adjusted to an
(PEGDA) was taken as a photopolymer, and diphenyl (2,4,6-trimethyl optimized condition, such as delamination thickness 100 µm, exposure
benzoyl) phosphine oxide (DPPO) was used as a photoinitiator in the intensity 10,000 μW/cm2, and exposure time of 4 s. Mechanical testing
reaction mixture. The concentration of photopolymers and excipients was performed and it was noted that the compressive strength and
were varied and its effect was investigated on mechanical properties, compressive modulus of HA porous bone scaffold were 15.25 MPa and
dissolution rate, and internal structures. Tensile testing was performed, 0.97 GPa, respectively, with 49.8% porosity. The bending strength of
and it was observed that the prints that contained a higher amount of the sintered sample was observed to be 41.3 MPa, which shows that HA
PEGDA showed higher tensile strength, while as the amount of PEG 400 porous scaffolds have good biocompatibility and can be used in human
increased, tensile strength decreased. So maximum tensile strength was bone repair.
observed for F0 and N0 (both have 0% PEG 400). Formulations F0-F3 Feng et al. [90] studied the AM of hydroxyapatite (HA) bioceramic
and M0-M15 were acceptable because tensile strength was higher than scaffolds using DLP and investigated the dispersion, mechanical prop
1.7 MPa, which is necessary for tablets. In addition, the addition of erties, biocompatibility, and sintering. In this study, HA was used as raw
mannitol, NaCl/ water, and PEG 400 increased the drug dissolution rate. powder. Three different monomers resins, 1,6-hexanediol diacrylate
Zeng et al. [88] fabricated a 3D Hydroxyapatite (HA) scaffold with (HDDA, 2-hydroxyethyl methacrylate (HEMA), and trimethylolpropane
good mechanical and biocompatibile properties using the DLP process. triacrylate (TMPTA), were used in a ratio of 6:3:1. Diphenyl (2,4,6-tri
The liquid photopolymer used in this experiment was DSM’s SomosÒ methylbenzoyl), phosphine oxide (TPO), and Solsperse 17,000 were
WaterShed XC 11122, and different concentrations of HA powder (10, used as photoinitiators and dispersants. The effect of dispersant dosage
20, 30, 40, 45 wt%) were used to form different slurries. It was observed (1 wt%, 2 wt%, and 3 wt%), solid loading (40 vol%, 45 vol%, and
that the slurry, which with 30%wt of HA powder, showed good fluidity 50 vol%), and sintering temperature (1200, 1250, and 1300 ℃) on
and hence further used for experiments. The storage modulus and loss mechanical properties was observed. Because of low viscosity, high
modulus of 30%wt HA slurry was observed concerning time and it was compression strength, and flexural strength of (161.9 and 27.8 MPa,
noted that the loss modulus was much higher than the storage modulus, respectively), an optimum value of dispersant was set to 2 wt%. The
18
Fig. 15. CAD models of Trachea, heart, lung, and vessel with printed samples using Digital Light Processing technique [18].
maximum flexural strength and compression strength of 12.9 MPa and

12.5 MPa were achieved at 50% solid loading. Setting solid loading to
50%, optimum compression strength and flexural strength were ach
ieved at 1250 ℃ sintering temperature, 16.9 MPa, and 18.3 MPa.
Kim et al. [91] proposed to fabricate zirconia prostheses having high
mechanical strength and translucency for their use in dental applications
by the DLP process. Zirconia powder, Yttria-stabilized zirconia (Zpex4)
was used along with 1,6-hexanediol diacrylate (HDDA) monomer and
decalin diluent to form 4Y-PSZ slurry. Three slurries were prepared with
different solid loadings (40 vol%, 45 vol%, and 50 vol%). To achieve
high densification, a slurry with 50% solid loading was selected for 3D
printing. Mechanical testing was performed to determine the flexural
strength (831 ± 74 MPa) after sintering at 1500 ◦ C for 2 h. and high
optical transmittance of 30 ( ± 1.2) % achieved, which makes it a good
candidate for dental applications.
Mao et al. [92] fabricated the microtissues of the liver using the DLP
process. The cell-laden bioink was prepared by combining liver decel
Fig. 16. Printed scaffold with features size of 500 µm after cleaning and post- lularized extracellular matrix (dECM), which was produced by decel
printing UV curing [84]. lularization of porcine liver tissues and then was added to the
(Image reproduced with permission). methacrylated gelatin (GelMA) with a photoinitiator, lithium phenyl-2,
4,6-trimethyl-benzoyl phosphinate (LAP), producing GelMA/dECM
cell-laden bioink. The solution consisted of concentration of 10% (w/v)
GelMA and 0.5% (w/v) LAP. Before 3D printing, human-induced
19
Fig. 17. SEM images of samples with a Kelvin cell architecture: as printed (A, B); sintered at 1100 ◦ C (C, D) [85].
hepatocytes (hiHep cells) were deposited on ink, and the inner gear-like dye. Parts were printed with a layer thickness of 50 µm. The effect of
structure was printed. To observe the mechanical properties, rectan exposure time and dye concentration on the compressive strength was
gular shape specimens were fabricated, and compressive modulus and observed and concluded that compressive strength increased by
young’s modulus were measured. These mechanical properties were increasing exposure time from the 30–70 s and decreasing dye concen
compared between the native liver, GelMA, and GelMA+dECM speci tration from 0.075 wt% to 0.025 wt% and observed maximum strength
mens and it was found that pure GelMA and GelMA+dECM had the same of 2.2 MPa at 70 s exposure time and dye concentration 0.5 wt%.
modulus and young’s modulus. The compressive modulus of both Fer et al. [95] developed Poly(propylene fumarate) Oligomers to 3D
GelMA and GelMA+dECM was higher than native liver, but young’s print specimens using the DLP process and recorded their viscosity,
modulus of both materials was less than the native liver’s modulus. mechanical properties, and printing characteristics. Poly(propylene
Wei et al. [93] fabricated high-performance Osteoinductive Calcium fumarate) (PPF) was used as resin, diethyl fumarate (DEF) as a diluent,
Phosphate (CaP) ceramics using the DLP process to enhance the me phenyl bis(2,4,6-trimethyl benzoyl)phosphine oxide (BAPO), Irgacure
chanical properties, bioactivity, and better potential for bone repairing as photoinitiators, and radical scavenger oxybenzone (HMB). Three
applications. Raw material consisted of CaP powder, 1,6-Hexanediol resin solutions were prepared by changing the ratios of PPF:DEF with
diacrylate (monomer), Phenyl bis(2,4,6-trimethyl benzoyl)-phosphine molecular mass 1.1, 1.7, and 2.0 kDa. Dog-bone specimens were printed
oxide (photoinitiator), and different surfactants (stearic acid, oleic acid, at layer thickness and exposure time of 50 µm and 120 s to observe the
sebacic acid, and mono alcohol ethoxylate phosphate (MAEP)) with mechanical properties such as tensile strength, elastic modulus, and
different concentrations (1.0%, 2.0%, 3.0%, 4.0%, 5.0%, and 6.0%). It elongation at break at three different molecular masses 1.1, 1.7, and
was observed that mono alcohol ethoxylate phosphate (MAEP) showed 2.0 kDa. It was observed that tensile strength decreased and elongation
the lowest viscosity with a concentration of 5.0% compared to other at break increased by increasing the molecular mass. All the parts
surfactants and thus used for further study. Next, MAEP-modified CaP printed at 1.1, 1.7 and 2.0 kDa showed strength above 15 MPa with
powders were used with a different solid loading of (50, 55, 60, 63 wt%) strain range 15%− 25%, comparable with the range of human trabec
were prepared to get optimal loading which was 60 wt%. The parts were ular bone (2 and 45 MPa). Elastic modulus was 199 MPa, 178 MPa, and
3D printed with a layer thickness (50 µm), exposure time 8 s, and 185 MPa at 1.1, 1.7, and 2.0 kDa, respectively.
different porosities of (67%, 70%, and 74%), which after sintering, were Elsayed et al. [96] developed bioactive glass-ceramic scaffolds for
reduced to 64.5%, 67.3%, and 72.6%. The mechanical tests were per tissue engineering using glass powders and reactive silicone binder via
formed and measured the compressive strength of parts and the porosity the DLP process. Non-photocurable liquid silicone (H62C) was used in
decreased from 72.6% to 64.5% and the compressive strength increased this study with commercial acrylate resin, which acted as a preceramic
from 3.60 to 9.03 MPa. polymer binder. The obtained solution was mixed with silica-defective
Bagheri Saed et al. [94] fabricated a porous scaffold using the DLP glass WB-15 with 59 wt% solid loading and parts printed with layer
process using optimized process parameters. Poly L-lactic acid (PLLA) thickness 50 µm and exposure time 5 s resulting in the ceramic scaffold.
was used as resin which was prepared by adding (Zn(CH₃CO₂)₂⋅2 H₂O) to A compressive strength test was performed and observed the strength
L-lactic acid monomers, forming oligomers and then adding Methacrylic 3.7 MPa with total porosity 76%, which comes within the range of
anhydride to the oligomer, finally resulted in PLLA. Resin for 3D reference value (2–12 MPa) of human trabecular bone. Previous works
printing was formulated by 56 wt% functionalized PLLA, 20 wt% related to different polymers produced from the DLP process for
TMPTMA, as crosslinker, 20 wt% N-methyl pyrrolidone (NMP), as a biomedical applications are reported in Table 4.
non-reactive diluent, and 4 wt% photoinitiator TPO along with orange
20
Table 4
Different Polymers produced via the DLP process for biomedical applications.
Yttria tetragonal stabilized zirconia • Pigment • layer thickness 30 µm • Maximum achieved flexural [80]
(Y-TZP) • Al2O3 (≤ 0.1–0.4 wt%) • sintering temperature 1500 ◦ C strength 943.26 MPa at 0 ◦
• SiO2 (≤ 0.02 wt%) • Maximum achieved characteristic
• Fe2O3 (≤ 0.01 wt%) strength 1006.6 MPa
• Obtained density 99.9%
• Na2O (≤0.06 wt%)
poly(1,3-propanediyl-co-glyceryl) • bis(2-(methacryloyloxyethyl) itaconate (BHI) • x–y nominal printing resolution • Maximum achieved tensile [81]
itaconate-co-vanillate (PPGIV) (24%) of 50 µm strength 5.4 MPa
• tris(2-(methacryloyloxyethyl) citrate (THC) • tuneable z resolution up to • Maximum achieved tensile
(240025) (24%) 20 µm modulus 61 MPa
• initiators (1.5 wt%) • exposure time range 3–5 s • Maximum achieved elongation at
• terminator (2.0 wt%) break 18%
• dyes (0.01 wt%) • Maximum achieved flexural
modulus 350 MPa
• Maximum achieved flexural
strength 12.6 MPa
glycidyl methacrylate (GMA) • Photoinitiator: LAP (0.2% w/v) • Wavelength 365 nm • Maximum achieved compressive [18]
• light intensity of 3.5 mWcm-2 stress 910 KPa
• exposure time 3 s • Increase in compressive strain up
• thickness 2 mm to 80%
• optimum Sil-MA hydrogel con • Increase in breaking elongation up
centration 30% to 124%
• Increased stiffness > 4 kPa
Monomers: • Photoinitiator: phosphine oxide-based compound • LED light source wavelength • Maximum achieved storage [83]
• Polyethylene glycol diacrylate (BAPO) (405 nm) modulus around 106 GPa
• 1,6-hexanediol diacrylate • XY pixel resolution 50 µm
• bisphenol A ethoxylate diacrylate • light intensity of 20 mW/cm2
PCL-based polyurethane acrylates • polyethylene glycol (600) diacrylate (PEG600DA) • layer thickness 50 µm Mechanical properties of pure [82]
m-PUA530, m-PUA800 and m- • polypropylene glycol (PPG, Mn 450) • exposure time 4 s resins m-PUA530, m-PUA800 and
PUA1000 • 3% w/w diphenyl (2,4,6-trimethylbenzoyl) • base layer curing time 5 s m-PUA1000
phosphine oxide (TPO) • Wavelength 405 nm
• Maximum achieved compressive
strength of 256.52 MPa,
186.38 MPa and 127.66 MPa
modulus 34.43 MPa, 19.82 MPa
and 16.29 MPa
Mechanical properties of resins
with addition of additives
• Maximum compressive strength

range 6.8–23.4 MPa

modulus 5.4–18.3 MPa
acrylic resin (FTD Standard Blend • Commercial powders β-TCP (particle size 2.36 µm) • layer thickness 25 µm • Maximum achieved compressive [84]
3D Printing resin, Fun To Do, • exposure time 0.3 s strength 22 ± 4 MPa
Alkmaar, The Netherland) • Pigment: (Poinsettia, Squires Kitchen) • wavelength range of
400–500 nm
acrylated polymer resin (tri- • Glass: wollastonite-diopside having ~52 mol% • exposure time 1.5 s • Total achieved porosity 83% vol [85]
propylene glycol diacrylate) resin wollastonite (CaO⋅SiO2) and 48 mol% diopside • sintering temperature 1100 ◦ C • Maximum achieved mechanical
(CaO⋅MgO⋅2SiO2) • Layer thickness 100 ųm strength 3.2 MPa
• Maximum observed linear
shrinkage 25%
poly- (ethylene glycol) diacrylate • Photoinitiator: lithium phenyl- 2,4,6-trimethylben • exposure times (3.1, 3.5, and • Maximum achieved elastic [86]
(PEGDA) zoyiposphinate (LAP) 3.9 s) modulus at different times
• ultraviolet (UV) light source 2950kPa, 3140kPa, and 3410 kPa
wavelength 405 nm • Maximum achieved ultimate
• Layer thickness 50 µm stress at different times 6.7 kPa,
• Printing resolution 7.9 kPa, and 11.5 kPa
characterized 10 µm.
• Maximum achieved compression
strain 25%
polyethylene glycol diacrylate • Photoinitiator: diphenyl (2,4,6-trimethylbenzoyl) • layer thickness 0.1 mm • Maximum achieved tensile [87]
(PEGDA) phosphine oxide (DPPO) • exposure time 100 s strength > 1.7 MPa
• poly(ethylene glycol) 400 (PEG 400) • blank time 1.5 s
• sodium chloride (NaCl) • settle time 1.5 s
• mannitol
DSM’s SomosÒ WaterShed XC • Hydroxyapatite powder (10, 20, 30, 40, 45 wt%) • Optimum concentration of HA • Maximum achieved compressive [88]
11122 powder 30%wt strength 12.8 MPa
• layer height 0.05 mm
21
• print speed 20 mm/s

hydroxyapatite (HA) • Dispersant: liquid sodium polyacrylate • Layer thickness 100 µm • maximum achieved compressive [89]
• exposure intensity 10000 μW/ strength 15.25 MPa
cm2 • maximum achieved compressive
• exposure time 4 s modulus 0.97 GPa
• maximum achieved bending
strength 41.3 MPa
• total porosity 49.8%
Zirconia powder, Yttria-stabilized • Monomer: 1,6-hexanediol diacrylate (HDDA) • UV power ~16 mW • Maximum achieved flexural [91]
zirconia (Zpex4) • Diluent: decalin • peak wavelength ~405 nm strength 831 ± 74 MPa
• Dispersant: DISPERBYK180 • exposure time range • high optical transmittance of 30
• Photoinitiator: TPO (2 s − 30 s) ( ± 1.2) %
• relative density 99.4%
CaP powder • Monomer: 1,6-Hexanediol diacrylate • layer thickness 50 µm • Increase in compressive strength [93]
• Photoinitiator: Phenyl bis(2,4,6-trimethylbenzoyl)- • exposure time 8 s up to 151%
phosphine oxide • exposure intensity (10.14 mW/ • Reduction in porosity up to 12%
• Surfactants: stearic acid, oleic acid, sebacic acid, cm2
and monoalcohol ethoxylate phosphate (MAEP) • optimum susfactant MEAP
(concentration 5.0% and 60 wt
%. solid loading)
Poly L-lactic acid (PLLA) having • crosslinker: 20 wt% TMPTMA • layer thickness 50 µm • Maximum achieved compressive [94]
56 wt% • non-reactive diluent: 20 wt% N-methyl pyrrolidone • exposure time range 30–70 s strength 2.2 MPa
(NMP) • light intensity 0.8 mJ/cm2
• photoinitiator: TPO (4 wt%) • optimum dye concentration
• orange dye 0.025 wt%
• optimum exposure time 70 s
acrylate resin (in form of oligomeric • Non-photocurable liquid silicone (H62C) (59 wt% • layer thickness 50 µm • Maximum achieved compressive [96]
precursors, RF Resin – HT) solid loading) • exposure time 5 s strength 3.7 MPa,
• Total porosity 76%
hydroxyapatite (HA) Monomer resins • sintering temperatureS (1200, • Maximum achieved compression [90]
• 1,6-hexanediol diacrylate (HDDA 1250, and 1300 ℃) strength 16.9 MPa
• 2-hydroxyethyl methacrylate (HEMA) • Optimum concentration of • Maximum achieved flexural
• trimethylolpropane triacrylate (TMPTA) dispersant 2 wt% strength 18.3 MPa
Photoinitiator: • Optimum solid loading 50 wt% • Shrinkage rate 15.3%
• diphenyl (2,4,6-trimethylbenzoyl) phosphine • Optimum sinitering
oxide (TPO) temperature 1250 ℃
dispersant: • Wavelength 405 nm
• Solsperse 17000 • intensity 8000 μW/cm2
Poly (propylene fumarate) (PPF) • Diluent: iethyl fumarate (DEF) • layer thickness 50 µm • maximum achieved elastic [95]
• Photoinitiators: phenylbis (2,4,6-trimethylbenzoyl) • exposure time 120 s modulus 199 MPa at 2.0 kDa
phosphine oxide (BAPO) and Irgacure • maximum achieved strain range
• radical scavenger: oxybenzone (HMB) 15%–25%
3.2.3. DLP for electrical applications obtained. The maximum ultimate strain obtained was 0.9 against the
Ge et al. [79] fabricated a soft pneumatic actuator using the DLP corresponding stress of 0.26 MPa.
process to obtain high-precision parts. The resin used in this study was Ji et al. [97] fabricated the multi-material magnetic driving soft
Tangoplus FLX 930 (having the elongation at break, of 170–220%), actuator using the DLP process. Different magnetic and non-magnetic
which acts as photocurable elastomer with photo absorber Rhodamine B resins were used with different content of Fe3O4 nanoparticles, and
(Acros Organics) with a mass ratio of 3:1000. Mechanical testing was observed the mechanical properties and printed morphologies for resins.
performed using a uniaxial tensile test, and a stress-strain curve was Different specimens were fabricated with different Fe3O4 contents, and
Fig. 18. a) Schematic diagram of the magnetic driving gripper. b) Illustration of the 3D printed magnetic gripper fabricated through the DLP process and performing
the tasks of grabbing and transporting a cotton ball controlled by a magnet [97].
22
maximum elastic modulus was observed at 0.5% Fe3O4. The tensile

strength of flexible resin without Fe3O4 NPs was 1.4 MPa at a strain of
≈ 30%, which was lower than the strength at 0.25, 0.5, and 0.75 wt% of
Fe3O4 NPs in resins. Fig. 18 shows the schematic illustration of the
magnetic driving gripper set-up and demonstration of the 3D printed
gripper achieving the task of grabbing and transporting a cotton ball
controlled by a magnet.
4. Vat photopolymerization of polymer composites
Polymer composites possess exceptional mechanical properties, and

their design flexibility in any shape makes them ideal materials for
several engineering applications [98]. The main challenge faced in the
production of polymer composites is maintaining the exact ratio of
reinforcement and matrix, control of fiber direction, and cost [99–101].
A broad scope of manufacturing strategies for composites are utilized;
material lay-up, compression molding technique, resin transfer molding
technique, and filament winding. These techniques employed two-stage
processes first is a material layup, and the second is consolidation or
curing. Usually, in the second stage, constrain should be applied over the Fig. 19. Mechanical Properties of SLA Resin Reinforced with annealed
TiO2 [105].
whole part surface region for uniform pressure distribution, which re
quires costly hardware and expands fabricating costs. Polymer com
posite produced from the 3D printing process possesses further reaction initiated by laser in SLA [107]. Tensile tests were performed on
enhanced properties compared to conventional techniques [102,103]. 3D printed composite specimens. The elastic modulus of 1% AgMAcr
This section provides discussions on polymer composites produced samples was 153 MPa, and tensile strength for AgAcr 2% specimens was
through the SLA process. 5 MPa, therefore improved compared to elastic modulus and tensile
strength of 68 MPa and 3.4 MPa, respectively, for unfilled resins. With
4.1. Polymer composites printing through SLA process the increased concentration of AgNPs, rigidity and strength also
improved, but elongation at break was decreased to 2.4% from 6.1% for
4.1.1. SLA for mechanical applications plain resin. Fig. 20 shows a stress-strain diagram for Ag-filled and un
Mummareddy et al. [104] investigated the fracture properties of filled samples.
ceramic-metal composites produced through Stereolithography. Zhang et al. [108] proposed using softwood kraft lignin in methac
Aluminum and alumina were used as metallic ingredients, and silica was rylate resin for improved mechanical properties. The resin was rein
used as a ceramic material. Interpenetrating metal-ceramic composite forced with a varying content of lignin, ranging from 0.2 to 1.0 wt%. The
(IPC) was manufactured via stereolithography following two stages. The mechanical behavior was observed under tensile loading for post-cured
first stage was curing and sintering of silica used as precursor, and the and uncured samples at different lignin reinforcement. An improved
second stage was metal infiltration. During the curing of printed part, tensile strength (49.9 MPa) was observed for post-cured samples at
1%–3% shrinkage was observed, and the sintering process also resulted 0.4 wt% lignin content than uncured ones (30.7 MPa). A decline in
in some shrinkage due to binder evaporation. After the curing process, tensile strength and young’s modulus was observed for uncured sam
30 µm thick and 1 mm lengthy cracks were observed reduced in size to ples, while post-cured samples revealed the optimum strength at 0.4 wt
30%, and 66% disappear after sintering. After the transformation pro % of reinforcement. Briefly, 46–64% and 13–37% improvement in
cess, the density gained was 3.30 g/cm3, which was 0.66 g/cm3, more tensile strength and young modulus were achieved for post-cured
significant than the IPC produced by binder jetting. This metal-ceramic specimens. However, reinforcing particles restricted the cross-linking
composite displayed compressive and flexural strength of 97 and network of polymer chains, as gel content decreased from
92 MPa that was two times greater than in green and sintered state. And ~98–46.23 wt%. Stress-strain behavior and the effect of lignin content
compressive strength was 2.6 times higher than composite produced by on tensile strength and young’s modulus are reported in Fig. 21 and
binder jetting. Resulted metal-ceramic composite achieved greater Fig. 22.
hardness than observed in sintered part. CTE of the transformed part was Invernizzi et al. [109] proposed to achieve the better mechanical
observed to be 11.02 × 10-6 K-1 that was lower than the CTE of the properties of 3D printed specimens fabricated using
sintered part that is 24 × 10-6 K-1, and two times lower than aluminum cationic/free-radical photopolymer blend via visible light stereo
alloy. lithography process. Photopolymer mixture (ENP) and nanocomposite
Mubarak et al. [105] used annealed anatase titanium dioxide TiO2 in resin (ENPS) based parts specimens were printed and compared the
acrylic-urethane resin to enhance the mechanical of 3D manufactured mechanical properties with commercially available resin (DL260) based
parts produced by SLA. TiO2 reinforcement annealed at different tem parts. The photopolymer mixture (ENP) was prepared by adding two
peratures (400ᴼC to 1000ᴼC) exhibited remarkable mechanical proper epoxies (3,4-epoxycyclohexylmethyl 3,4-epoxy cyclohexane carbox
ties enhancement, as shown in Fig. 19. Among the samples tested, the ylate (ECC)) and a tetrafunctional acrylate (pentaerythritol tetraacrylate
highest tensile strength of 47.43 MPa and elastic modulus of 2.261 GPa (PETA)) along with additives such as bis (4-methyl phenyl) iodonium
was achieved for TiO2 annealed at 800ᴼC, which showed 103% and 32% hexafluorophosphate (PI), and isopropyl thioxanthone, a photosensi
improvement compared to neat stereolithography resin (SLR). tizer. The nanocomposite resin (ENPS) was then manufactured by add
Taormina et al. [106] developed advanced resins for in-situ gener ing silica-reinforced cycloaliphatic epoxy resin (Nano pox A611, with
ation of silver nanoparticles (AgNPs) upon polymerization reaction the composition of 60 wt% of ECC and 40 wt% of silica nanoparticles) to
process. Fig. 20 shows stress-strain diagram for Ag-filled and unfilled ENP. The mechanical properties of the photopolymer mixture (ENP) and
samples. Two different salts, such as silver acrylate (AgAcr) and silver nanocomposite resin (ENPS) were compared with commercial resin
methacrylate (AgMAcr), were synthesized and used in different con DL260, and observed that ENPS showed the young’s modulus of
centrations (0.5% AgAcr, 1% AgAcr, 2% AgAcr, and 1% AgMAcr) as 3.76 GPa compared to ENP and DL260 whose modulus was 2.88 GPa
filler materials, which converted into silver nanoparticles by reduction and 2.24 GPa, respectively. In other words, ENPS showed 31% and 68%
23
Fig. 20. Stress vs strain curves for Ag-filled and unfilled 3D printed samples [107].
Fig. 21. Stress vs. Strain Behavior for Lignin Reinforced Resin Composites [108].
improved young’s modulus than ENP and commercial resin DL260, modulus of 656.5 MPa and 536.7 MPa NdFeB and SrFeO filler com
respectively. Tensile strength was then measured, and ENPS showed posites, respectively. A summary of previous works related to the
tensile strength of 43.8 MPa compared to ENP and DL260 whose polymer composites produced from SLA process for mechanical appli
strength was 29.5 MPa and 29.6 MPa, respectively. But elongation at cations is reported in Table 5.
break of ENPS was less than DL260 and greater than ENP, as given
1.51%, 1.26%, and 1.70%, respectively.
Nagarajan et al. [110] introduced magnetic particles to urethane 4.2. Polymer composites printing through DLP process
acrylate resin to produce photopolymer composites for improved me
chanical properties. Strontium ferrite (SrFeO) and neodymium iron 4.2.1. DLP for mechanical applications
Structures et al. [111] fabricated a nanocomposite by introducing
boron (NdFeB) powders were added to resin with 10 wt% and 25 wt%
graphene as a reinforcing agent to improve the fracture toughness of
individual loadings. Two different commercial additives (Disparlon
net-shaped structures. They examined the effect of graphene on vis
6900–20X and BYK7410ET) were utilized for stable dispersion. Me
cosity, wettability, mechanical, and thermomechanical properties of
chanical testing was performed on composites with 10 wt% of magnetic
resin using the DLP process. The resin consisted of Polylactic acid
particles, as resins with higher magnetic particle loadings were not
–polyurethane oligomer (PLA–PUA) (oligomer), Triethylene glycol
fabricated successfully. Tensile testing revealed tensile strength of
dimethacrylate (TEGDMA) (reactive diluent), and phenyl bis (2,4,
28.1 MPa and 22 MPa, yield point at 10.1 MPa and 8.2 MPa, the elastic
6-trimethyl benzoyl)-phosphine oxide (initiator) in 58:39:3 ratio. A
24
Fig. 22. (a) Effect of Lignin Concentration on Tensile Strength (b) Effect of Lignin Concentration on Young’s Modulus [108].
Table 5
Previous work on polymer composites produced via the SLA process for Mechanical Applications.
Silica • Aluminum and alumina • Layer thickness 50 µm • Compressive strength 97 MPa (200% [104]
• Laser wavelength 405 nm increase)
• Flexural strength 92 MPa (200%
increase)
• Density 3.30 g/cm3
• Crack’s reduction (66%)
acrylic-urethane resin • Anatase TiO2 nanoparticles • Laser wavelength 405 nm • Increase in tensile strength up to 103% [105]
• Laser intensity 155 mW/ • Increase in elastic modulus up to 32%
cm2
• Optimum annealing
temperature 800 C
(Ebecryl 7100) and • situ generate silver nanoparticles (AgNPs) • layer thickness 50 µm • Increase in elastic modulus up to 125% [107]
pentaerythritoltriacrylate (PETIA) • Decrease in ultimate strain up to 154%
• Increase in tensile strength up to 47%
• Increase in glass transition
temperature up to 10.5 C
methacrylate resin (RS-F2- GPCL-04) • Softwood kraft lignin • Layer thickness 100 µm • Increase in tensile strength up to [108]
• UV laser wavelength 46 − 64%
405 nm • Increase in young’s modulus up to
• Photocure light intensity 13 − 37%
280 ± 16 μW/cm2
acrylic photocurable resin • silver nanoparticles (AgNPs) such as AgAce, • layer thickness 50 µm • Increase in young’s modulus up to [106]
AgAcr, AgMAcr 135%
• Increase in ultimate tensile strength up
to 1470%
• Decrease in elongation at break up to
154%
cationic/free-radical resin • silica nanoparticles • Light wavelength 405 nm • Increase in young’s modulus up to [109]
• layer thickness between 50 30.5%
and 25 µm • Increase in ultimate tensile strength up
to 48%
• Increase in elongation at break up to
19%
PR-48 (urethane acrylate) resin • strontium ferrite powder (SrFeO) and • printing resolution in X and • Maximum Tensile strength of NdFeB [110]
neodymium iron boron powder (NdFeB) Y axes 50 µm filler composite 28.1 MPa
• printing resolution in Z axis • Maximum Tensile strength of SrFeO
10 and 100 µm filler composite 22 MPa
• average light power • Maximum young’s modulus of NdFeB
intensity 18.5 mW/cm2 filler composite 656.5 MPa
• Maximum young’s modulus of SrFeO
filler composite 536.7 MPa
• Maximum yield point of NdFeB filler
composite 10.1 MPa
• Maximum yield point of SrFeO filler
composite 8.2 MPa
25
measured and optimized amount of graphene powder 0.5 wt% was while the strength of composite increased and achieved a maximum
added to the resin. It was observed that, with the addition of 0.5 wt% value of 65.8 ± 25.9 MPa at 3 C min-1. Similarly, the maximum elastic
◦
-1,
powder, the flexural modulus increased from 2.68 GPa (for neat resin) to modulus was at 3 C min which was almost 45 GPa for composite.
◦
3.06 GPa (for graphene reinforced resin), with 14% improvement and Cortés et al. [114] developed a carbon nanotube (CNT) reinforced
4% improvement in flexural strength as compared to neat resin. The composites via DLP process to observe the mechanical and strain sensing
28% improvement in fracture toughness was also observed as compared capabilities by changing the CNT concentration and post heat treatment
to neat resin. impacts. CNT was used in different concentrations (0.030, 0.050, 0.075,
Zhao et al. [112] proposed the list of photosensitive resins suitable 0.100, and 0.150 wt%) in acrylate-based UV-curable resin. Samples
for manufacturing silicon elastomers using the DLP process. Several were prepared with different CNT concentrations and with post heat
resins were prepared by changing the content of thiol content of treatment and pre-heat treatment. Mechanical testing was performed
mercaptan-functionalized polysiloxane (MPS), vinyl-terminated poly- and observed that samples with post-cure heat treatment showed higher
(dimethyl siloxane) (VPS), silica filler, and silicone elastomers. Me young’s modulus and three-point bending strength than non-post cure.
chanical tensile testing was performed on the dumbbell-shaped speci It was also observed that the highest values were achieved at a CNT
mens and measured their tensile strength and elongation at break. It was content of 0.050%wt in the case of both (pre-heat treatment and post
noted that photo resin H-PSi-20 achieved the ultimate elongation at a heat treatment).
break of 1400%. As silica content (for H-series) increased from 0% to Li et al. [115] developed SiBCN/Si3N4w based composites through
20%, elongation and tensile strength increased from 0.30 MPa to preceramic polymer using the DLP process. They observed the effect of
2.59 MPa, and 311.4 1403.2%, respectively. Fig. 23 illustrates the whiskers on the mechanical properties, mass loss, linear shrinkage, and
working principle of DLP printing used in this study. microstructures. In this work, preceramic used was Polyborosilazane
Xiao et al. [113] developed a method of 3D printing of SiCN ceramic (PBSZ) and trimethylolpropane triacrylate (TMPTA) as monomer and
matrix composites derived from preceramic polysilazane (PSZ) using the IRGACURE 819 the photoinitiator. To reduce the linear shrinkage and
DLP technique. Preceramic polymer resin was consisting of two mono mass loss after pyrolysis, Si3N4 was used as a whisker and was added in
mers, pentaerythritol triacrylate (PETA) and hexanediol diacrylate 60 wt% of polymer weight which is the optimum value. The slurry was
(HDDA), in a 1:1 ratio along with 3 wt% photo initiator 819 (Heowns). consist of PBSZ and Si3N4 in 5:3 ratio. Parts were 3D printed with 50 mm
To prevent the cracks and voids after pyrolysis, nanofillers SiO2 (20 wt% and sintered at different temperatures of 900 oC, 1200 oC, or 1400 oC.
of polymer) and SiC nanofibers (1 wt%) were added to PSZ. Different Mechanical testing was performed, and it was observed that composite
shapes were printed with DLP and then pyrolyzed at 1300 ◦ C in a ni sintered at 1200 oC showed the maximum flexural strength of 183 MPa
trogen gas environment, resulted in SiCN ceramics samples. It was as compared to the reported value of 57.3 MPa. Hardness and young’s
observed that SiCN/SiO2/SiCf composites’ mechanical properties were moduli were 54.1 GPa and 3.4 GPa for composite1200 that were greater
significantly enhanced compared to SiCN synthesized samples. A com than reference SiBCN ceramic (without Si3N4 whisker), which were
parison was performed between SiCN/SiO2/SiCf composites samples, 7.8 GPa and 54.7 GPa, respectively.
and SiCN synthesized samples by drawing a graph between flexural Zheng et al. [116] fabricated 3D printed parts using Al2O3–ZrO2
strength and elastic modulus vs. heating rate. It was noted that the composite and enhanced the density, bending strength, and fracture
flexural strength of SiCN decreased with an increase in heating rate toughness via the DLP process. The resin consisted of zirconia three mol
Fig. 23. (a) Description of Digital Light Processing method (b, c) Picture of the cat printed through DLP process using polymer resin L-0. (d, e) Pictures of the square-
shaped and dumbbell-shaped specimens, printed through DLP process using photopolymer resin H- Psi-20. (f, g)pictures of honeycomb-shaped samples printed
through DLP process using photopolymer L-0 [112].
26
% yttria with alumina powder in the ratio of 3:1 and prepared ZTA glycerol with 1,3-diglycerolate diacrylate (DiGlyDA), which acts as a
composite powder. 1, 6-hexanediol diacrylate (HDDA), polyethylene photo-initiator. 1-phenyl azo-2-naphthol (Sudan I) was also used as a
glycol (400), diacrylate (PEG(400)DA were added to resin along with photo-absorber. Cellulose Nanocrystals (CNC) in different concentra
BYK dispersant and Diphenyl (2, 4, 6-trimethyl benzoyl) phosphine tions (0.2, 0.5, 1, 2, and 5 wt%) were added to the resulting mixture and
oxide (TPO) photoinitiator. Parts were printed with ZTA composite studied its effect on mechanical and thermal properties. The effect of
powders (Al2O3–ZrO2) and compared its properties with Al2O3 printed layer thickness on thermo-mechanical properties was also observed.
parts. After printing, green parts of both (Al2O3 +ZrO2 and Al2O3) Mechanical testing was performed on dog bone-shaped specimens in
were processed through debinding at 600 ◦ C and after that sintered at uniaxial tensile mode and noted that young’s modulus and UTS were
different temperatures (1500 ◦ C, 1550 ◦ C, 1600 ◦ C, and 1650 ◦ C), to increased as the concentration of CNC was increased. Young’s modulus
check the optimum sintering temperature. Relative density, hardness, was increased from 52.8 ± 1.4 MPa to 133.0 ± 4.0 MPa as the concen
bending strength, and fracture toughness, was checked at different tration increased from 0%wt to 5%wt. The peak value of UTS was
temperatures, and optimum parameters were observed at the tempera observed at 1%wt of CNC, which is 7.6 ± 0.3 MPa. Dynamic mechanical
ture of 1600 ◦ C that is 99.2%, 99.4%; 17.43 GPa, 17.40 GPa; analysis (DMA) was performed, and glassy storage modulus, rubbery
398.8 MPa, 516.7 MPa; 6.25 MPa m1/2, 7.76 MPa m1/2; respectively. storage modulus, and tan d of the composite were also observed,
A summary of previous works related to the polymer composites pro increasing with CNC concentration. Glass transition temperature
duced from the DLP process for mechanical applications is reported in remained constant throughout concentration. Effect of layer thickness
Table 6. on young’s modulus was noted and observed that E increased from
54.4 ± 7.5 MPa to 80.7 ± 3.7 MPa as the thickness decreased from
4.2.2. DLP for biomedical applications 300 µm to 25 µm. A similar trend was observed for UTS and elongation
Goldberg et al. [117] investigated the impact of Co additive on the at break. Fig. 7 shows 3D structures of disk structure, an octet-truss
mechanical, sintering, and cytocompatibility of 3Y-TZP-5Al2O3 ce lattice structure, and an ear model printed through the DLP printer.
ramics using the DLP process. Ceramics powder was synthesized using Fig. 24.
three mol% yttria-tetragonal zirconia polycrystal with five wt% Al2O3 Lee et al. [119] investigated the effect of gelatin on the dimensional
through precipitation method. Four compositions were made from I to stability of silk fibroin composite hydrogel structures produced by DLP.
IV having Co concentration 0%, 0.33%, 1% and 3% mol%. 0.33 mol% Silk fibroin (SF)-based composite ink was developed for 3D printing, and
Co increased the mechanical properties and decreased the sintering to reduce the shrinkage of SF composite hydrogel in phosphate-buffered
temperature. Bending strength of 720 MPa was achieved in composition saline solution, gelatin was added in different concentrations. Different
II at a sintering temperature of 1450 degrees Celsius. The lowest bending samples were prepared with different concentrations of SF and gelatin.
strength was achieved to be 290 MPa at 1350 degrees Celsius in Cylindrical samples were prepared for compression testing at 20%
composition I. Microhardness of up to 11.06 GPa was observed after strain. It was observed that as the gelatin content increased, the me
sintering at 1450 degrees Celsius by addition of Co, having fine grains. chanical properties such as compressive modulus also increased. After
Li et al. [118] fabricated cellulose nanocrystal-based composites printing, pure hydrogel had a compressive strength of less than 0.5kPa,
using the DLP process and studied the mechanical and thermal proper and after the addition of gelatin in the composite hydrogel, it increased
ties. The resin used was poly (ethylene glycol) diacrylate (PEGDA) to 1.1kPa. After storing hydrogel in PBS for 72 h at 370 C increased the
Table 6
Previous work on polymer composites produced via DLP process for mechanical applications.
UV-curable PLA–PUA resin • graphene powder • Light wavelength 405 nm • Increase in flexural modulus up to 14% [111]
• Increase in flexural strength up to 4%
• Increased in fracture toughness up to 28%
Poly((mercaptopropyl)methyl • Photo initiator: phenyl bis (2,4,6- • UV light wavelength 405 nm • Increase in elongation up to 350% [112]
siloxane) (MPS) trimethylbenzoyl) phosphine oxide (PI 819) • layer thickness 100 µm • Increase in tensile strength up to 763%
• reinforcing fillers: Precipitated silica and • Maximum achieved elongation at break of
fumed silica 1400%
• vinyl-terminated poly- (dimethylsiloxane)
(VPS)
• silica filler
• silicone elastomers
preceramic polysilazane (PSZ • nanofillers SiO2 and SiC nanofibers • printing resolution 40 µm • Increase in flexural strength up to 179% [113]
• layer thickness 100 µm • maximum elastic modulus 45 GPa
• pyrolysed temperature
1300 ◦ C
• Light wavelength 405 nm
• Optimum ramping rate
3 ◦ C min-1
High Temp Resin V1 • multi-walled carbon nanotubes (MWCNTs) • layer thickness 30 µm • increase in young’s modulus and three point [114]
• exposure time 5.12 s bending strength with CNT reinforcement
• optimum concentration of
MWCNTs 0.050%wt
Polyborosilazane (PBSZ) • Si3N4 whisker • light wavelength 405 nm • increase in flexural strength up to 219% [115]
• UV dose 528 mW S cm-2 • maximum young’s modulus 54.1 GPa
• layer thickness of 50 mm • Maximum hardness 3.4 GPa
• optimum sintering
temperature 1200 ◦ C
Alumina (Al2O3) • Zirconia (ZrO2) • light wavelength 405 nm • Maximum achieved hardness up to 17.43 GPa [116]
• Sintering temperature • Increase in bending strength up to 29%
1600 ◦ C • Increase in fracture toughness up to 24%
• Debinding temperature • Maximum achieved relative density 99.4%
600 ◦ C
27
Fig. 24. A) Solid circular cylinder with and without the addition of CNC concentration, B) An octet-truss lattice structure with and without addition of CNC
composition, and C) the model of human Ear printed through DLP process [118].
compressive strength up to 65 kPa compared to pure SF hydrogel. β-TCP/PCL composites were then compared with the β-TCP scaffold. It
Elsayed et al. [120] developed a new bioceramic by adding calci was observed that increasing the infiltration time, residual strength,
te/acrylate blends in the photocurable resin and then phosphatizing it to compressive strength, toughness, and strain energy density increased.
convert it into a ceramic composite using the DLP process. Tripropylene The maximum compressive strength achieved was 40 MPa at 60 min,
glycol diacrylate was used as a photocurable resin in which calcium four times greater than the bare β-TCP scaffold at 0 min. Toughness was
carbonate (CaCO3) was added, having a particle size of < 10 µm and measured at the strain at the maximum compressive strength (Gmax), at
solid loading of 50 wt%. Three different structures (cubic, kelvin, and 10% strain (G0.1), and 20% strain (G0.2), and observed the increase
diamond cells) were 3D printed with layer thickness and exposure time from 8 to 50. Also, infiltered samples retained their shape even after
of 50 µm and 6 s, respectively. A compressive test was performed on the 20% strain. A summary of previous works related to the polymer com
cubic structure before and after the pyrolysis at 500 ◦ C, for one hour in a posites produced from the DLP process for biomedical applications is
nitrogen gas environment. It was observed that compressive strength reported in Table 3. Table 7.
increased from 0.6 MPa to 1.4 MPa, before and after phosphatization,
respectively, while the porosity almost remains constant, which was 4.2.3. DLP for electric applications
81% and 80%. Mu et al. [77] investigated a method to produce electrically
Aghdam et al. [121] investigated a novel conductive objects made of nanocomposite polymers to optimize their
Bio-Photopolymer-SWCNT-Ceramic printed by DLP technique for or conductivity, mechanical properties, and printability using DLP. The
thopedic applications. The purpose of the study was to fabricate spongy resin used in this experiment was acrylic-based photocurable resin
bone tissues with controlled porosity matching with bone tissues and (Are3d-dlp405) with multi-walled carbon nanotubes (MWCNTs) as filler
high compressive strength. The resin consisted of polymers, material. It was observed that 0.3 wt% MWCNTs concentration opti
single-walled carbon nanotube (SWCNT) as a reinforcing agent, and mized the conductivity of composite resin (maximum electrical con
hydroxyapatite (HA). Polymer-hydroxyapatite scaffolds were prepared ductivity of 0.027 S/m) with optimized printing parameters such as
with the same porosity as the bone tissues. SWCNT increased the me 19.05 ųm layer thickness and 40 s exposure time. Mechanical testing
chanical properties from 25 MPa to 36 MPa, having a porosity of 55%. was done on dog bone specimens and noted that UTS and young’s
Wu et al. [122] fabricated β-Tricalcium phosphate (β-TCP)/ԑ-poly modulus of MWCNTs filled composite increased by 21% and 45%,
caprolactone composite scaffolds with highly controllable gradient respectively, compared with pristine resins, with a 10% reduction in
structure using the DLP process. Two monomers were hexamethylene elongation at break. Fig. 25 shows images of printed spring as a
diacrylate and trimethylolpropane triacrylate with a ratio of 1:1 along stretchable circuit. Whereas Fig. 26 explains the conductivity as a
with a light absorber and photoinitiator. Composite scaffolds were function of MWCNT loading.
developed in two steps: first, 3D printing of β-TCP scaffold having Lantean et al. [78] investigated the 3D printing of magneto respon
porosity 41.7% and solid loading of 40 vol%. Second, immersion of sive polymer materials and observed the mechanical and magnetic
β-TCP scaffold into melted ԑ-polycaprolactone (PCL) for different infil properties using DLP. The resin used in this experiment was Ebecryl
tration time span such as (10 min, 20 min, 30 min, 40 min, 50 min, and 8232 (100 Eb) and butyl acrylate (BA) as a reactive diluent. Fe3O4
60 min). Mechanical properties and gradient structural properties of nanofillers were used in different concentrations to study the magnetic
28
Table 7
Previous works on polymer composites produced via the DLP process for biomedical applications.
3Y-TZP-5Al2O3 • Co • Layer thickness 35 µm • Increase in Bending strength up to 140% [117]

• Exposure time 180 s • Micro hardness 11.06 GPa
• Optimum sintering
temperature 1400 C
• Optimum Co
concentration 0.33 mol%
poly (ethylene glycol) • Cellulose Nanocrystals (CNC) • layer thickness 100 µm • Increase in young’s modulus based on CNC [118]
diacrylate (PEGDA) glycerol • projector intensity was concentration from 0%wt to 5%wt, up to 151%
18 mW/cm2 • Increase in young’s modulus based on layer
• exposure time 4 s thickness from 300 µm to 25 µm, up to 48%
• optimum concentration of
CNC 1%wt
silk fibroin (SF)-based ink • Gelatin • wavelengths range • Maximum achieved compressive strength 65 kPa [119]
300–800 nm
Tripropylene glycol diacrylate • calcium carbonate (CaCO3) • layer thickness 50 µm • increase in compressive strength up to 133% [120]
• exposure time 6 s • decrease in porosity up to 1%
• pyrolysis temperature
500 ◦ C
• Light wavelength range
400–500 nm
Bio-Photopolymer • Single walled carbon nanotube (SWCNT) • Not mentioned • Increase in mechanical properties up to 44% [121]
• Maximum porosity 55%
β-tricalcium phosphate (β-TCP) • ԑ-polycaprolactone (PCL) • visible light radiation • Maximum achieved compressive strength 40 MPa [122]
• Monomers: hexamethylene diacrylate and (405 nm)
trimethylol-propane triacrylate
• Light absorber
• photoinitiator
Fig. 25. A stretchable conductive spring, printed through Digital Light Processing process and act as a circuit: (a) photographs of strecchable spring in stretched (II)
and compressed (I) form. (b) Variation in resistance of spring circuit during five stretching/releasing cycles [77].
effect. Magnetic properties were evaluated from the stress-strain curve mechanical properties by just changing the ratio of monomer and
by doing mechanical testing and took 100 Eb specimens as reference. As cross-linker. Ethylene glycol phenyl ether acrylate (EGPEA) (as mono
BA concentration increased 0–50 wt%, in 100 Eb and 50Eb50BA, the mer) based resin was introduced in this study. The cross-linker and
elastic modulus decreased from 7 MPa to 4.5 MPa. In the case of photoinitiator used was 1,6-hexanediol diacrylate and
nanocomposites (Fe3O4), the same trend was observed. So, the 2-Benzyl-2-(dimethylamino)− 4′ -morpholino-butyrophenone, respec
maximum magnetic response was observed when the Fe3O4 concentra tively. Polymer resins, consisting of different ratios of monomer and
tion was 6 wt% while considering both mechanical and magnetic crosslinker, ranging from 1:0–1:1 was prepared and cast in dog
properties. Some previous works related to polymer composites pro bone-shaped. In addition to this, three samples with the same geometry
duced from the DLP process for electrical applications are reported in were 3D printed with ratios (1:0.05, 1:0.4, 1:1), and uniaxial tensile
Table 8. testing was performed on all sample specimens. It was observed that the
elastic modulus increased as the cross-linker increased from 0.6 MPa,
5. Other VP processes having ratios 1:0–31 MPa having a ratio of 1:0.75. Similarly, the ulti
mate tensile stress was increased to 2.741 MPa from 0.424 MPa. But the
Borrello et al. [12] proposed a mechanically tunable acrylate resin ultimate strain decreased as the ratio of cross-linker increased. The max
that can be used in both processes SLA and DLP to get a range of stain was observed at a 1:0 ratio, which was 0.746. Printed specimens
29
Fig. 26. (a) The effect of conductivity upon the introduction of MWCNT loading. (b) The effect of MWCNT concentration on the viscosity and three different RMPs.
(c) SEM image of printed MWCNT nanocomposites with 0.3 wt% MWCNT loading. (d) The graph between current and voltage across 0.3 wt% MWCNT printed
nanocomposite resistor [77].
also displayed the same trend as aforementioned. was 0.735 µm. During fabrication, a layer resolution of 20 µm was
Ribó et al. [123] optimized the self-peeling vat for the vat photo achieved.
polymerization process. They addressed the challenge of part deforma Asif et al. [125] investigated the effect of ultrasonic waves on carbon
tion during lifting the printed part from the bottom-up VP process due to fiber-reinforced composite materials in the vat photopolymerization
normal adhesive forces between part and vat by introducing flexible process. The impact of fiber concentration and its alignment on tensile
Fluorinated Ethylene Propylene (FEP) membrane between them. But strength was determined. (0.5%, 1%, 2%, and 4% w/v) fiber concen
this membrane generated a creeping defect that affected the repeat tration was used, and it was observed that 1% concentration in
ability of microfeatures and the endurance of the membrane. To solve single-layered specimen showed a higher tensile strength gain of
this problem, two vat designs were suggested, round and rectangular 2.78 MPa. Two transducers with two opposite glass reflectors were used
vat. They were designed on SolidWorks and were gone through the FEA in a chamber to make the fiber alignments parallel and perpendicular to
process. Round design suffered higher stress of 2.88 MPa at 2.5 N than planes parallel to transducers. Then two-layered specimens having 0–0◦
rectangular design with 0.43 MPa stress at the same force. And and 0–90◦ fiber alignments were considered for tensile strength test and
maximum membrane displacement was 3.99 mm at 2.5 N for round observed that 0–0◦ showed a higher tensile strength of 2.95 ± 0.12 MPa,
design and 0.5 mm was for rectangular design. So maximum resolution which was greater than in case of 0–90◦ which was 2.36 ± 0.14 MPa.
and reduction in adhesive forces were produced by using a rectangular Hence fiber reinforcement improved the mechanical properties.
vat design. Sirrine et al. [126] demonstrated the synthesis, processing, and
Wang et al. [124] produced zirconia ceramic parts using 3 S tech characteristics of polymers having low viscosity using the vat photo
nology. 24.70% shrinkage was observed between green and sintered polymerization process to lower modulus and high molecular weight
parts, having a mean density of 99.45% with a measured standard de (MW) precursor. Two photopolymers were synthesized,
viation of density was 0.35%. A three-point bending test was performed acrylamide-terminated poly (dimethylsiloxane) (PDMS-AA) and
on five samples. The average flexural strength was 731.11 MPa. No thiol-terminated poly (dimethylsiloxane) (PDMS- SH). Different com
cracks were observed, and the structure was dense. Roughness was positions were prepared using PDMS-AA and PDMS- SH. A combination
measured by using a 3D microscopic process, and the average Ra value of relatively low MW dithiol (PDMS1.2k- SH) and a relatively high MW
30
Table 8
Polymer composites produced via the DLP process for electrical applications.
Base Material Reinforcements Highlights Properties improved Ref.
acrylic based photocurable resin (Are3d- • multi-walled carbon nanotubes • layer thickness 19.05 ųm • Increase in ultimate tensile strength up to [77]
dlp405) (MWCNTs) • exposure time 40 s 21%
• 0.3 wt% loading of • Increase in young’s modulus up to 45%
MWCNT • Decrease in elongation at break up to 10%
Urethane acrylate resin • Fe3O4 nanofillers • layer thickness 20 µm • Glass transition temperature Tg − 10.7 C [78]
Ebecryl 8232 (Eb) • exposure time 20 s • Maximum elastic modulus 7 MPa
• UV post-curing for 10 min
diacrylamide (PDMS5.5k-AA) was used in VPP, and a gel fraction of with ε ´ (photopolymer) = 2.67 ± 0.02. also noted that storage modulus
above 90% was observed. It was observed that PDMS5.5k-AA alone, G´was increased by increasing TO. Storage modulus G´of 10% w/v TO
without PDMS-SH photocured and produced part having stress at break was higher than 20% w/v of CCT composite. Storage modulus G´also
of 0.65 ± 0.15 MPa and a strain at break of 58 ± 14. As the quantity of increased by increasing the frequency.
PDMS1.2k-SH enhanced, the stress at break started to decrease, and Sirrine et al. [130] reported the vat photopolymerization of two fully
strain at break started to increase. It was observed that when the con amorphous poly (dimethylsiloxane) (PDMS) terpolymers containing two
centration of PDMS5.5k-AA and PDMS1.2k-SH was used as 0.75:1.0, the repeating units, either diphenylsiloxy (DiPhS) or diethylsiloxy (DiEtS),
tensile strain increased two times 123% as compared when along with MeViS, chain-end vinyl silyl-functional groups, and
PDMS5.5k-AA was lonely used. thiol-functional polydimethylsiloxane (SH). Prepared sample resins
Peer et al. [127] proposed cyclopolymerizable monomers (CPMs) were PDMS7.0k-DiPh (DiPhS), and PDMS7.5k- DiEt (DiEtS). Dynamic
having low viscosity, high volatility, enhanced reactivity, and double mechanical analysis (DMA) and differential scanning calorimeter were
bond conversions in hot lithography. In this study, the most famous and performed to measure different properties. The shear storage modulus
common reactive diluent was isobornyl methacrylate (IBMA). Synthesis (G′ ) of DiPhS + SH system was observed as a function of irradiation time
of CPMs (CPM1 − CPM3) was done, but the most promising was CPM3. at different photoinitiater (DMPA) concentrations that increased with
Resin Bomar XR-741MS was also synthesized. Different resins were increasing concentration. Ratio G′ /G′′ achieved maximum value at
prepared by mixing with different concentrations of Bomar, IBMA, and higher DMPA concentration. The minimum value of DMPA that mini
CPMs, but CPM3 showed the most promising properties. CPM3 was mized the modulus crossover G′ /G′′ and maximized the Rpmax was 0.5 w
thermally stable up to ~130 ◦ C, so it was suitable for hot lithography at %. Thermomechanical response of photocured DiPhS + SH and DiEtS
<70 ◦ C. CPM3 displayed the optimum behavior with methacrylate and + SH was observed as a temperature at 1 Hz frequency and noted that
showed high photoreactivity than IBMA. PolyBomar/CPM3_50 achieved storage modulus (E′ ) dropped with increasing temperature DiPhS + SH
the gel fraction of ~92% and showed a viscosity of 2.5 Pa s at 70 ◦ C. and DiEtS + SH systems displayed tan δ peaks at − 113 and − 118 C,
◦
When tensile testing was performed, it displayed increased tensile respectively.

strength with slightly reduced elongation at break. So the CPM3 was Redmann et al. [131] performed an experimental study to optimize
suitable for working in Hot Lithography (~50 − 150 ◦ C). the thermal post-curing time of epoxy resin without affecting the me
Steyrer et al. [128] observed the effect of temperature on the prop chanical properties and glass transition temperature, using digital light
erties of polymer resin. Ethoxylated (2) bisphenol-A-dimethacry-late synthesis (DLS), i.e., Continuous Liquid Interface Production (CLIP). The
(SR348L) was used as photopolymer resin, and phenyl bis(2,4, epoxy resin used was EPX 82. Different heating rates of 0.5, 1, 2, 3, 4,
6-trimethyl benzoyl) phosphine oxide (BAPO) was used as the photo and 5 K/min were applied at a temperature range of 0–330 C on sam
◦
initiator. Tests were performed to observe the influence of printing ples after printing and observed that mechanical properties change at
temperature on double-bond conversion, tensile properties, and dy different curing cycles. Graphs between temperature and storage
namic mechanical analysis (DMA). Experiments were performed at two modulus and loss modulus were drawn at different maximum conver
temperatures 23 ◦ C and 70 ◦ C. It was observed that the viscosity sion rates (MCR) and maximum heating rate (MHR) and noted that the
decreased from 1.73 Pa.s at 23 ◦ C to 0.036 Pa.s at 70 ◦ C, and curing fastest of this cycle was MCR 0.6 / MHR 5.0, having a total curing time of
depth increased. In addition, critical energy (EC) was minimized from 202 min at a glass transition temperature (Tg) of 154 ◦ C. which is similar
16 mJ cm–2 (23 ◦ C) to 9.8 mJcm-2 (70 ◦ C), but the slope (DP) of the to original cycle having MCR and MHR of 0.6%/min and 1 K/min at
working curve did not change. The double bond conversion increased total curing time of 750 min, respectively. So 73% of total curing time
from 43.9% and 64.9% for green parts but remained almost the same for was reduced without affecting the mechanical properties, as the UTS of
post cured parts (89.3% and 90.6%). The storage modulus and Tg were an original cycle and MCR0.6/MHR5.0 cycle samples is 81.33 MPa and
increased for green parts but remained the same for post-cured parts. 81.51 MPa Tg of 154 ◦ C, respectively.
Tensile strength was increased at elevated temperature for green parts, Weems et al. [132] performed a study on myrcene, a biosourec
and the strain was reduced. Moreover, printing time was reduced from material, using free-radical and anionic polymerization techniques to
the 50–30 s observe their molecular structural, physical, and mechanical properties
Malas et al. [129] proposed to fabricate high permittivity resin for the vat photopolymerization process. β-Myrcene was used as a
composite for the vat photopolymerization process and studied its monomer in this study. Mechanical testing was performed on dog bone
morphology, thermal, mechanical, and dielectric properties. Photo specimens, and DMA was performed on the rectangular sample as per
polymer used was visible light photo-reactive polymer, and the disper standards. Polymyrcene was synthesized using Free-radical and anionic
sant used was DISPERBYK-2055, and fillers were titanium dioxide (TiO2, polymerization techniques. β-Myrcene exhibited lower storage moduli
TO) and calcium copper titanate CaCu3Ti4O12 (CCT) in different con while Polymyrcene showed relatively better storage moduli within the
centrations of 5, 10, 20% w/v. XRD analysis displayed the tetragonal same time. Tensile testing of polymyrcene was conducted, and it was
structure of TO and body-centered cubic perovskite structure of CCT. observed that linear polymyrcene (without cross-linking) showed elastic
Dielectric permittivity of composites increased by increasing the filler behavior and failure strain up to 280% while UTS of 0.4 MPa. Myrcene
content and reached up to ε ´(TO) = 3.88 ± 0.02 and ε ´(CCT) (crosslinked with PETMP) showed strain failure of ~80% and UTS of
= 3.5 ± 0.02 at 20% w/v of TO and CCT, respectively in comparison 2.3 MPa, while printed polymyrcene displayed strain of 120% and UTS
31
of ~2.6 MPa that was greater than myrcene monomer networks. AM processes are relatively new-found than conventional
manufacturing; therefore, several research areas are still active and
6. Conclusion and future perspective under-explored. However, considering the current progress in material
science and evolution of AM processes for nanocomposites, these
VP processes provide several benefits over conventional and other methods and materials are expected to emerge as widely adopted in
AM processes because of their high precision, high resolution, fast several industries.
printing speed, cost-effectiveness, and complex interior & exterior
product designs. But researchers face some challenges that need to be
overcome and hence, are part of future work. Upon in-depth literature Declaration of Competing Interest
review, the following concluding remarks are made that summarize the
research area regarding the SLA and DLP additive manufacturing The authors declare that they have no known competing financial
process: interests or personal relationships that could have appeared to influence
the work reported in this paper.
• Novel Materials: Materials portfolio for digital light processing and
stereolithography needs to keep growing and expanding. A few Acknowledgement
photopolymers such as Methacrylate and acrylic-based photo
polymer resins are currently used with sufficient mechanical strength Authors would like to acknowledge Qatar National Research Fund
and can be used in different mechanical, industrial, and medical (QNRF) for its support through grant (NPRP13S-0126-200172) that
applications. Considering the mechanical properties, reliability, and made this work possible partially. Open Access funding provided by the
biocompatibility, much different photopolymer resins need to be Qatar National Library (QNL).
explored to open the doors towards discovering stronger, light
weight, and durable products. Efforts should be made towards the
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Additive Manufacturing 47 (2021) 102279

Contents lists available at ScienceDirect

Vat photopolymerization of polymers and polymer composites: Processes

Fig. 1. Working Principle of (a) SLA and (b) DLP Technologies

• Increase in tensile strength up to

• Maximum achieved elastic

• Maximum achieved ultimate

different types and shapes of membranes through very controlled and

3.1.4. SLA for electrical applications

• Dispersant: KOS110 • Layer thickness 50 µm

maximum flexural strength and compression strength of 12.9 MPa and

• Maximum compressive strength

• Maximum achieved compressive

• print speed 20 mm/s

maximum elastic modulus was observed at 0.5% Fe3O4. The tensile

4. Vat photopolymerization of polymer composites

Polymer composites possess exceptional mechanical properties, and

3Y-TZP-5Al2O3 • Co • Layer thickness 35 µm • Increase in Bending strength up to 140% [117]

When tensile testing was performed, it displayed increased tensile respectively.

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