Ultrafast laser 3D lithography based on non-linear light–matter interactions, widely known as multi-photon lithography (MPL), offers unrivaled precision rapid prototyping and flexible additive manufacturing options. 3D printing equipment based on MPL is already commercially available, yet there is still no comprehensive understanding of factors determining spatial resolution, accuracy, fabrication throughput, repeatability, and standardized metrology methods for the accurate characterization of the produced 3D objects and their functionalities. The photoexcitation mechanisms, spatial-control or photo-modified volumes, and the variety of processable materials are topics actively investigated. The complexity of the research field is underlined by a limited understanding and fragmented knowledge of light-excitation and material response. Research to date has only provided case-specific findings on photoexcitation, chemical modification, and material characterization of the experimental data. In this review, we aim to provide a consistent and comprehensive summary of the existing literature on photopolymerization mechanisms under highly confined spatial and temporal conditions, where, besides the excitation and cross-linking, parameters such as diffusion, temperature accumulation, and the finite amount of monomer molecules start to become of critical importance. Key parameters such as photoexcitation, polymerization kinetics, and the properties of the additively manufactured materials at the nanoscale in 3D are examined, whereas, the perspectives for future research and as well as emerging applications are outlined.
In this study, acrylated epoxidized soybean oil (AESO) and mixtures of AESO and vanillin dimethacrylate (VDM) or vanillin diacrylate (VDA) were investigated as photosensitive resins for optical 3D printing without any photoinitiator and solvent. The study of photocross-linking kinetics by real-time photorheometry revealed the higher rate of photocross-linking of pure AESO than that of AESO with VDM or VDA. Through the higher yield of the insoluble fraction, better thermal and mechanical properties were obtained for the pure AESO polymer. Here, for the first time, we validate that pure AESO and mixtures of AESO and VDM can be used for 3D microstructuring by employing direct laser writing lithography technique. The smallest achieved spatial features are 1 µm with a throughput in 6900 voxels per second is obtained. The plant-derived resins were laser polymerized using ultrashort pulses by multiphoton absorption and avalanche induced cross-linking without the usage of any photoinitiator. This advances the light-based additive manufacturing towards the 3D processing of pure cross-linkable renewable materials.
Materials obtained from renewable sources are emerging to replace the starting materials of petroleumderived plastics. They offer easy processing, fulfill technological, functional and durability requirements at the same time ensuring increased bio-compatibility, recycling, and eventually lower cost. On the other hand, optical 3D printing (O3DP) is a rapid prototyping tool (and an additive manufacturing technique) being developed as a choice for efficient and low waste production method, yet currently associated with mainly petroleum-derived resins. Here we employ a single bio-based resin derived from soy beans, suitable for O3DP in the scales from nano-to macro-dimensions, which can be processed even without the addition of photoinitiator. The approach is validated using both state-of-the art laser nanolithography setup as well as a widespread table-top 3D printer-sub-micrometer accuracy 3D objects are fabricated reproducibly. Additionally, chess-like figures are made in an industrial line commercially delivering small batch production services. Such concept is believed to make a breakthrough in rapid prototyping by switching the focus of O3DP to bio-based resins instead of being restricted to conventional petroleum-derived photopolymers. Bio-based polymers are emerging as replacement for petroleum-derived polymers. The growth of the production and market is 2.05 Mtons of bio-plastics 1 and 700 bilion Euros in Europe only 2. The main advantages of bio-based plastic products compared to the conventional plastics are the preservation of fossil resources by using bio-mass which is a renewable resource and provision of the unique potential of carbon neutrality, as well as bio-degradability of the certain types of bio-plastics which offers additional means of recovery at the end of a product's life 3. The spectrum of bio-based plastics usage varies from nanocomposites 4-8 and films 9-11 to adsorbents 12-14. Vegetable oils are potential starting materials for the preparation of polymers due to their ready availability, inherent bio-degradability, negligible toxicity, and existence of modifiable functional groups 15. Nowadays there are a lot of scientific research dedicated to the light induced polymerization. As there exist diverse technical implementations of this technology, it is known in many names: lithography (stereolithography, digital light processing (DLP)/projection lithography), direct laser writing (DLW) or alternatively laser direct writing (LDW), two-photon polymerization (2PP), nonlinear lithography (NLL), multi-photon lithography (MPL), etc. However, this additive manufacturing process simply can be called by one common name: optical 3D printing (O3DP) as it is based on photons. This rapid prototyping tool is being developed as a choice for efficient and low waste production tool, yet currently associated with mainly petroleum-derived resins 16-19. On the other hand, O3DP in combination with post-processing (thermal-treatment) allows fabrication of free-form structures which can serve as 3D templates f...
Although the topic of tooth fractures has been extensively analyzed in the dental literature, there is still insufficient information about the potential effect of enamel microcracks (EMCs) on the underlying tooth structures. For a precise examination of the extent of the damage to the tooth structure in the area of EMCs, it is necessary to carry out their volumetric [(three-dimensional (3D)] evaluation. The aim of this study was to validate an X-ray micro-computed tomography ($$\mu $$ μ CT) as a technique suitable for 3D non-destructive visualization and qualitative analysis of teeth EMCs of different severity. Extracted human maxillary premolars were examined using a $$\mu $$ μ CT instrument ZEISS Xradia 520 Versa. In order to separate crack, dentin, and enamel volumes a Deep Learning (DL) algorithm, part of the Dragonfly’s segmentation toolkit, was utilized. For segmentation needs we implemented Dragonfly’s pre-built UNet neural network. The scanning technique which was used made it possible to recognize and detect not only EMCs that are visible on the outer surface but also those that are buried deep inside the tooth. The 3D visualization, combined with DL assisted segmentation, enabled the evaluation of the dynamics of an EMC and precise examination of its position with respect to the dentin-enamel junction.
Grid polarisers 3D-printed out of commercial acrilic resin were tested for the polariser function and showed spectral regions where the dichroic ratio and implying importance of molecular and/or stress induced anisotropy. Metal-coated 3D-printed THz optical elements can find a range of applications in intensity and polarization control of IR-THz beams. The used 3D printing method allows for fabrication of an arbitrary high aspect ratio grid polarisers. Polarization analysis of synchrotron THz radiation was carried out with a standard stretched polyethylene polariser and revealed that the linearly polarized (horizontal) component contributes up to 22% ± 5% to the circular polarized synchrotron emission extracted by a gold-coated mirror with a horizontal slit inserted near the bending magnet edge. Comparison with theoretical predictions shows a qualitative match with dominance of the edge radiation.
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