Two-photon excitation provides a means of activating chemical or physical processes with high spatial resolution in three dimensions and has made possible the development of three-dimensional fluorescence imaging, optical data storage, and lithographic microfabrication. These applications take advantage of the fact that the two-photon absorption probability depends quadratically on intensity, so under tight-focusing conditions, the absorption is confined at the focus to a volume of order λ3 (where λ is the laser wavelength). Any subsequent process, such as fluorescence or a photoinduced chemical reaction, is also localized in this small volume. Although three-dimensional data storage and microfabrication have been illustrated using two-photon-initiated polymerization of resins incorporating conventional ultraviolet-absorbing initiators, such photopolymer systems exhibit low photosensitivity as the initiators have small two-photon absorption cross-sections (δ). Consequently, this approach requires high laser power, and its widespread use remains impractical. Here we report on a class of π;-conjugated compounds that exhibit large δ (as high as 1, 250 × 10−50 cm4 s per photon) and enhanced two-photon sensitivity relative to ultraviolet initiators. Two-photon excitable resins based on these new initiators have been developed and used to demonstrate a scheme for three-dimensional data storage which permits fluorescent and refractive read-out, and the fabrication of three-dimensional micro-optical and micromechanical structures, including photonic-bandgap-type structures.

Two-photon polymerization initiators for three-dimensional optical data storage and microfabrication

Additive manufacturing (AM), also known as three-dimensional (3D) printing, has boomed over the last 30 years, and its use has accelerated during the last 5 years AM is a materials-oriented manufacturing technology, and printing resolution versus printing scalability/speed trade-off exists among various types of materials, including polymers, metals, ceramics, glasses, and composite materials Four-dimensional (4D) printing, together with versatile transformation systems, drives researchers to achieve and utilize high dimensional AM Multiple perspectives of the AM of structural materials have been raised and illustrated in this review, including multi-material AM (MMa-AM), multi-modulus AM (MMo-AM), multi-scale AM (MSc-AM), multi-system AM (MSy-AM), multi-dimensional AM (MD-AM), and multi-function AM (MF-AM) The rapid and tremendous development of AM materials and methods offers great potential for structural applications, such as in the aerospace field, the biomedical field, electronic devices, nuclear industry, flexible and wearable devices, soft sensors, actuators, and robotics, jewelry and art decorations, land transportation, underwater devices, and porous structures

Additive manufacturing of structural materials

Additive manufacturing (AM) has gained significant attention due to its ability to drive technological development as a sustainable, flexible, and customizable manufacturing scheme. Among the various AM techniques, direct ink writing (DIW) has emerged as the most versatile 3D printing technique for the broadest range of materials. DIW allows printing of practically any material, as long as the precursor ink can be engineered to demonstrate appropriate rheological behavior. This technique acts as a unique pathway to introduce design freedom, multifunctionality, and stability simultaneously into its printed structures. Here, a comprehensive review of DIW of complex 3D structures from various materials, including polymers, ceramics, glass, cement, graphene, metals, and their combinations through multimaterial printing is presented. The review begins with an overview of the fundamentals of ink rheology, followed by an in‐depth discussion of the various methods to tailor the ink for DIW of different classes of materials. Then, the diverse applications of DIW ranging from electronics to food to biomedical industries are discussed. Finally, the current challenges and limitations of this technique are highlighted, followed by its prospects as a guideline toward possible futuristic innovations.

Direct Ink Writing: A 3D Printing Technology for Diverse Materials

Additive Manufacturing of Piezoelectric Materials

Preparation of high solid loading and low viscosity ceramic slurries for photopolymerization-based 3D printing

Along with extensive research on the three-dimensional (3D) printing of polymers and metals, 3D printing of ceramics is now the latest trend to come under the spotlight. The ability to fabricate ceramic components of arbitrarily complex shapes has been extremely challenging without 3D printing. This review focuses on the latest advances in the 3D printing of ceramics and presents the historical origins and evolution of each related technique. The main technical aspects, including feedstock properties, process control, post-treatments and energy source–material interactions, are also discussed. The technical challenges and advice about how to address these are presented. Comparisons are made between the techniques to facilitate the selection of the best ones in practical use. In addition, representative applications of the 3D printing of various types of ceramics are surveyed. Future directions are pointed out on the advancement on materials and forming mechanism for the fabrication of high-performance ceramic components.

3D printing of ceramics: A review

Lightweight and high-strength polymer-derived SiOC ceramics with varied lattice structures have been successfully produced using different polysiloxanes as preceramic polymers (PCPs) via photopolym...

https://www.tandfonline.com/doi/pdf/10.1080/17452759.2019.1710919

Additive manufacturing of lightweight and high-strength polymer-derived SiOC ceramics

Inkjet printing is a promising alternative for the fabrication of thin film components for solid oxide fuel cells (SOFCs) due to its contactless, mask free, and controllable printing process. In order to obtain satisfying electrolyte thin layer structures in anode-supported SOFCs, the preparation of suitable electrolyte ceramic inks is a key. At present, such a kind of 8 mol% Y2O3-stabilized ZrO2 (8YSZ) electrolyte ceramic ink with long-term stability and high solid loading (> 15 wt%) seems rare for precise inkjet printing, and a number of characterization and performance aspects of the inks, such as homogeneity, viscosity, and printability, should be studied. In this study, 8YSZ ceramic inks of varied compositions were developed for inkjet printing of SOFC ceramic electrolyte layers. The dispersing effect of two types of dispersants, i.e., polyacrylic acid ammonium (PAANH4) and polyacrylic acid (PAA), were compared. The results show that ultrasonic dispersion treatment can help effectively disperse the ceramic particles in the inks. PAANH4 has a better dispersion effect for the inks developed in this study. The inks show excellent printable performance in the actual printing process. The stability of the ink can be maintained for a storage period of over 30 days with the help of initial ultrasonic dispersion. Finally, micron-size thin 8YSZ electrolyte films were successfully fabricated through inkjet printing and sintering, based on the as-developed high solid loading 8YSZ inks (20 wt%). The films show fully dense and intact structural morphology and smooth interfacial bonding, offering an improved structural quality of electrolyte for enhanced SOFC performance.

/pdf/additive-manufacturing-of-thin-electrolyte-layers-via-inkjet-2rdd74nd0e.pdf

Additive manufacturing of thin electrolyte layers via inkjet printing of highly-stable ceramic inks

Previous research often failed to prepared polymer-derived SiOC ceramic components with dense and thick monoliths/skeletons based on additive manufacturing processes, due to the porosities and cracks generated during the pyrolysis process. Herein, we report a simple solution which combines the introduction of phenolic resin (PR) as an additive and the use of controlled strategy of pyrolysis, for the vat photopolymerization additively manufactured SiOC ceramics. As a result, crack-free dense monolith and lattice skeleton structural polymer-derived SiOC ceramics are successfully prepared despite the low ceramic yield of 19.3 wt% and large linear shrinkage of 50% generated after pyrolysis. The prepared dense monoliths possess a thickness of over 5 mm and the lattices show attainable maximum dense skeletons thickness of ~2 mm. The maximum dense thickness of the samples after pyrolysis is over 7 times that of other samples prepared based on additive manufacturing reported in the literature. As an indicator of dimensional retention, the specific dense thickness to ceramic yield ratio (T/Y) is deduced, resulting maximum values of 101.9 µm/(wt%) for lattice skeletons and 254.7 µm/(wt%) for monoliths. The former is even larger than that for dense monolith SiOC structures prepared by other conventional gel casting and isostatic pressing techniques with much higher ceramic yields of > 80 wt%, and is about 6.1 times the largest T/Y ratio (=16.7 µm/(wt%)) achievable in the AM-based works reported in the literature. This shows predominance of the current work over other types of polymer-derived ceramic structures prepared by additive manufacturing and even conventional methods. The lattice structures’ apparent density and specific strength reached 0.55 g/cm 3 and 6.6 × 10 4 N∙m/kg, respectively. The mechanical performance surpasses other structural polymer-derived ceramic structures with similar apparent density reported in the literature. Through the advanced characterization and analysis of material phase and morphology evolution during the pyrolysis process, the mechanism of defect-free densification is revealed. That is, the introduction of PR enables a highly smooth gas-releasing process due to the generation of ordered gas-releasing channels in the sample bodies during the pyrolysis process. As a result, the generation of cracks and defects was successfully prevented. Moreover, due to the high carbon residue of the PR, the samples containing 15 wt% PR in the preceramic state still possessed amorphous SiOC ceramics after pyrolysis at 1400 ℃, while 0 wt% PR samples showed SiC crystallization. Compared with similar materials reported, the ceramics prepared in this study exhibit enhanced structural and mechanical performance. The strategy investigated in the study can be a viable route for the additive manufacturing of high-performance crack-free and thick monolith and lattice skeleton SiOC ceramic structures based on vat photopolymerization. 

Ziyong Li

Papers

3D printing of ceramics: A review

Additive manufacturing of lightweight and high-strength polymer-derived SiOC ceramics

Additive manufacturing of thin electrolyte layers via inkjet printing of highly-stable ceramic inks

3D printing of crack-free dense polymer-derived ceramic monoliths and lattice skeletons with improved thickness and mechanical performance

Characterisation of indentation microstructures for porous SOFC cathodes