Photopolymerization in 3D Printing
20 Feb 2019-Vol. 1, Iss: 4, pp 593-611
TL;DR: The field of 3D printing is continuing its rapid development in both academic and industrial research environments as mentioned in this paper, which offers flexibility over the final properties of the 3D printed materials (such as optical, chemical and mechanical properties) using versatile polymer chemistry.
Abstract: The field of 3D printing is continuing its rapid development in both academic and industrial research environments. The development of 3D printing technologies has opened new implementations in rapid prototyping, tooling, dentistry, microfluidics, biomedical devices, tissue engineering, drug delivery, etc. Among different 3D printing techniques, photopolymerization-based process (such as stereolithography and digital light processing) offers flexibility over the final properties of the 3D printed materials (such as optical, chemical, and mechanical properties) using versatile polymer chemistry. The strategy behind the 3D photopolymerization is based on using monomers/oligomers in liquid state (in the presence of photoinitiators) that can be photopolymerized (via radical or cationic mechanism) upon exposure to light source of different wavelengths (depending on the photoinitiator system). An overview of recent evolutions in the field of photopolymerization-based 3D printing and highlights of novel 3D print...
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TL;DR: In this article, three photopolymerization technologies, namely, stereolithography (SLA), digital light processing (DLP), and continuous digital light process (CDLP), are reviewed.
Abstract: Additive manufacturing (3D printing) has significantly changed the prototyping process in terms of technology, construction, materials, and their multiphysical properties. Among the most popular 3D printing techniques is vat photopolymerization, in which ultraviolet (UV) light is deployed to form chains between molecules of liquid light-curable resin, crosslink them, and as a result, solidify the resin. In this manuscript, three photopolymerization technologies, namely, stereolithography (SLA), digital light processing (DLP), and continuous digital light processing (CDLP), are reviewed. Additionally, the after-cured mechanical properties of light-curable resin materials are listed, along with a number of case studies showing their applications in practice. The manuscript aims at providing an overview and future trend of the photopolymerization technology to inspire the readers to engage in further research in this field, especially regarding developing new materials and mathematical models for microrods and bionic structures.
191 citations
04 Jun 2020
TL;DR: This review paper summarizes a few typical applications of P μSL including mechanical metamaterials, optical components, 4D printing, bioinspired materials and biomedical applications, and offers perspectives on the directions of the further development of PμSL based 3D printing technology.
Abstract: Projection Micro Stereolithography (PμSL) is a high-resolution (up to 0.6 μm) 3D printing technology based on area projection triggered photopolymerization, and capable of fabricating complex 3D architectures covering multiple scales and with multiple materials. This paper reviews the recent development of the PμSL based 3D printing technologies, together with the related applications. It introduces the working principle, the commercialized products, and the recent multiscale, multimaterial printing capability of PμSL as well as some functional photopolymers that are suitable to PμSL. This review paper also summarizes a few typical applications of PμSL including mechanical metamaterials, optical components, 4D printing, bioinspired materials and biomedical applications, and offers perspectives on the directions of the further development of PμSL based 3D printing technology.
174 citations
Cites background from "Photopolymerization in 3D Printing"
...The photopolymerization is a free radical based polymerization, and includes four main steps: radical generation, initiation, propagation, and termination [62, 63]....
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TL;DR: In this work, crosslinking methods used in 3D bioprinting studies are reviewed, parameters that affect bioink chemistry are discussed, and the potential toward improving crossl linking outcomes and construct performance is highlighted.
Abstract: Three-dimensional (3D) bioprinting has recently advanced as an important tool to produce viable constructs that can be used for regenerative purposes or as tissue models. To develop biomimetic and sustainable 3D constructs, several important processing aspects need to be considered, among which crosslinking is most important for achieving desirable biomechanical stability of printed structures, which is reflected in subsequent behavior and use of these constructs. In this work, crosslinking methods used in 3D bioprinting studies are reviewed, parameters that affect bioink chemistry are discussed, and the potential toward improving crosslinking outcomes and construct performance is highlighted. Furthermore, current challenges and future prospects are discussed. Due to the direct connection between crosslinking methods and properties of 3D bioprinted structures, this Review can provide a basis for developing necessary modifications to the design and manufacturing process of advanced tissue-like constructs in future.
150 citations
TL;DR: Improved tissue adhesion of the bioinspired MN allows for more stable and robust performance for drug delivery, biofluid collection, and biosensing.
143 citations
TL;DR: An overview of the vat polymerization techniques, their unique applications in the fields of drug delivery and medical device fabrication, material examples and the advantages they provide within healthcare, is provided.
136 citations
References
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TL;DR: In this paper, commercial photoinitiators and monomers/oligomers applicable for 3D printing are presented, and newly developed photo-initiator and monomer-based materials with various properties and the application in 3D bio-printing are also demonstrated.
221 citations
TL;DR: An optical approach is used to guide custom formulation of resins to minimize the cross sectional size of fabricated flow channels as exemplars of such voids and lays the foundation for 3D printing of <100 μm microfluidic features.
Abstract: Microfluidics imposes different requirements on 3D printing compared to many applications because the critical features for microfluidics consist of internal microvoids. Resins for general 3D printing applications, however, are not necessarily formulated to meet the requirements of microfluidics and minimize the size of fabricated voids. In this paper we use an optical approach to guide custom formulation of resins to minimize the cross sectional size of fabricated flow channels as exemplars of such voids. We focus on stereolithgraphy (SL) 3D printing with Digital Light Processing (DLP) based on a micromirror array and use a commercially available 3D printer. We develop a mathematical model for the optical dose delivered through the thickness of a 3D printed part, including the effect of voids. We find that there is a fundamental trade-off between the homogeneity of the optical dose within individual layers and how far the critical dose penetrates into a flow channel during fabrication. We also experimentally investigate the practical limits of flow channel miniaturization given the optical properties of a resin and find that the minimum flow channel height is ~3.5-5.5ha where ha is the optical penetration depth of the resin, and that the minimum width is 4 pixels in the build plane. We also show that the ratio of the build layer thickness to ha should be in the range 0.3-1.0 to obtain the minimum flow channel height for a given resin. The minimum flow channel size that we demonstrate for a custom resin is 60 μm × 108 μm for a 10 μm build layer thickness. This work lays the foundation for 3D printing of <100 μm microfluidic features.
221 citations
TL;DR: Oscillatory shear data indicated the CNC-PEG nanocomposite Hydrogels were more viscous than the neat PEG hydrogels and were efficient at energy dissipation due to the reversible interactions between CNC and PEG polymer chains.
Abstract: The preparation and mechanical properties of elastomeric nanocomposite hydrogels consisting of cellulose nanocrystals (CNCs) and poly(ethylene glycol) (PEG) are reported. The aqueous nanocomposite CNC/PEG precursor solutions covalently cross-linked through a one-stage photocross-linking process. The mechanical properties of nanocomposite hydrogels, including Young's modulus (E), fracture stress (σ), and fracture strain (e), were measured as a function of CNC volume fraction (φCNC, 0.2-1.8%, v/v) within polymeric matrix. It was found that the homogeneously dispersed nanocomposite hydrogels can be prepared with φCNC being less than 1.5%, whereas the heterogeneous nanocomposite hydrogels were obtained with φCNC being higher than 1.5%. The nanocomposite hydrogels exhibited higher strengths and flexibilities when compared with neat PEG hydrogels, where the modulus, fracture stress, and fracture strain enhanced by a factor of 3.48, 5, and 3.28, respectively, over the matrix material alone at 1.2% v/v CNC loading. Oscillatory shear data indicated the CNC-PEG nanocomposite hydrogels were more viscous than the neat PEG hydrogels and were efficient at energy dissipation due to the reversible interactions between CNC and PEG polymer chains. It was proposed that the strong gel viscoelastic behavior and the mechanical reinforcement were related to "filler network", where the temporary interactions between CNC and PEG interfered with the covalent cross-links of PEG.
217 citations
TL;DR: The results of this study revealed that the successive transfer model instead of the cooperative sensitization model can be applied to explain the UC behaviors of the beta-NaYF4:Yb,Tm nanocrystals.
Abstract: Monodisperse β-NaYF4 : Yb,Tm nanocrystals with controlled size (25–150 nm), shape (sphere, hexagonal prism, and hexagonal plate), and composition (Yb: 20–40%, Tm: 0.2–5%) were synthesized from the thermolysis of metal trifluoroacetates in hot surfactant solutions. The upconversion (UC) of near-infrared light (980 nm) to ultra-violet (360 nm), blue (450 and 475 nm), red (650 and 695 nm) and infrared (800 nm) light in the β-NaYF4 : Yb,Tm nanocrystals has been studied by UC spectroscopy. Both the total intensity of UC emissions and the relative intensities of emissions at different wavelengths have shown a strong dependence on different particle sizes and different Tm3+ and Yb3+ concentrations. As a result, different overall output colors of UC emissions can be achieved by altering sizes and Yb3+/Tm3+ doping concentrations of the β-NaYF4 : Yb,Tm nanocrystals. The intensity-power curves of a series of samples have proved that emissions at 360 and 450 nm can be ascribed to four-photon process (1D2 to 3H6 and 1D2 to 3H4, respectively), while emissions at 475 and 650 nm are three-photon processes (1G4 to 3H6 and 1G4 to 3H4, respectively) and emissions at 695 and 800 nm are two-photon ones (3F2 to 3H6 and 3F4 to 3H6, respectively). A UC saturation effect would occur under a certain excitation intensity of the 980 nm CW diode laser for the as-obtained β-NaYF4 : Yb,Tm nanocrystals, leading to the decrease of the slopes of the I–P curves. The results of our study also revealed that the successive transfer model instead of the cooperative sensitization model can be applied to explain the UC behaviors of the β-NaYF4 : Yb,Tm nanocrystals. Further, an unexpected stronger emissions of four-photon process at 360 and 450 nm for ∼50 nm β-NaYF4 : Yb,Tm nanocrystals than those for the bigger (∼150 nm) nanocrystals was observed and explained in terms of the effects of crystallite size, surface-to-volume ratio and homogeneity of the doping cations.
214 citations
TL;DR: In this article, the 2PA properties of common, commercially available photoinitiators typically utilized in conventional radiation curing science and technologies, and often used in 2PA-based polymerizations were investigated.
Abstract: Recent interests in and applications of two-photon absorption (2PA) induced photopolymerization have afforded advanced opportunities to perform three-dimensionally resolved polymerization, resulting in intricate microfabrication and imaging. Many of the reported 2PA-induced polymerizations make use of commercially available photoinitiators, and a key parameter to consider is the two-photon absorption cross-section (δ) of the initiator. To date, there has been no comprehensive investigation of two-photon absorptivity of commercial photoinitiators, though a few studies presenting novel photoinitiators for two-photon polymerization have appeared. Herein, we report the 2PA properties of common, commercially available photoinitiators typically utilized in conventional radiation curing science and technologies, and often used in 2PA-based polymerizations. Z-scan and white-light continuum (WLC) pump–probe techniques were utilized to obtain two-photon absorption cross-sections ( δ). The results for most compounds were found to yield good agreement between the two methods. Most of the photoinitiators studied possess low δ, except Irgacure OXE01, indicating a need for the development of new photoinitiators with improved properties optimized for 2PA applications. A compound prepared in our laboratories exhibits high 2PA and was useful as a two-photon free-radical photoinitiator. © 2004 Elsevier B.V. All rights reserved.
210 citations