Additive manufacturing (AM) alias 3D printing translates computer-aided design (CAD) virtual 3D models into physical objects. By digital slicing of CAD, 3D scan, or tomography data, AM builds objects layer by layer without the need for molds or machining. AM enables decentralized fabrication of customized objects on demand by exploiting digital information storage and retrieval via the Internet. The ongoing transition from rapid prototyping to rapid manufacturing prompts new challenges for mechanical engineers and materials scientists alike. Because polymers are by far the most utilized class of materials for AM, this Review focuses on polymer processing and the development of polymers and advanced polymer systems specifically for AM. AM techniques covered include vat photopolymerization (stereolithography), powder bed fusion (SLS), material and binder jetting (inkjet and aerosol 3D printing), sheet lamination (LOM), extrusion (FDM, 3D dispensing, 3D fiber deposition, and 3D plotting), and 3D bioprinting....

Polymers for 3D Printing and Customized Additive Manufacturing

Leu-M

This paper reviews the crystal chemistry, synthesis, densification, microstructure, mechanical properties, and oxidation behavior of zirconium diboride (ZrB2) and hafnium diboride (HfB2) ceramics. The refractory diborides exhibit partial or complete solid solution with other transition metal diborides, which allows compositional tailoring of properties such as thermal expansion coefficient and hardness. Carbothermal reduction is the typical synthesis route, but reactive processes, solution methods, and pre-ceramic polymers can also be used. Typically, diborides are densified by hot pressing, but recently solid state and liquid phase sintering routes have been developed. Fine-grained ZrB2 and HfB2 have strengths of a few hundred MPa, which can increase to over 1 GPa with the addition of SiC. Pure diborides exhibit parabolic oxidation kinetics at temperatures below 1100°C, but B2O3 volatility leads to rapid, linear oxidation kinetics above that temperature. The addition of silica scale formers such as SiC or MoSi2 improves the oxidation behavior above 1100°C. Based on their unique combination of properties, ZrB2 and HfB2 ceramics are candidates for use in the extreme environments associated with hypersonic flight, atmospheric re-entry, and rocket propulsion.

Refractory Diborides of Zirconium and Hafnium

Macroporous ceramics with pore sizes from 400 nm to 4 mm and porosity within the range 20%–97% have been produced for a number of well-established and emerging applications, such as molten metal filtration, catalysis, refractory insulation, and hot gas filtration. These applications take advantage of the unique properties achieved through the incorporation of macropores into solid ceramics. In this article, we review the main processing routes that can be used for the fabrication of macroporous ceramics with tailored microstructure and chemical composition. Emphasis is given to versatile and simple approaches that allow one to control the microstructural features that ultimately determine the properties of the macroporous material. Replica, sacrificial template, and direct foaming techniques are described and compared in terms of microstructures and mechanical properties that can be achieved. Finally, directions to future investigations on the processing of macroporous ceramics are proposed.

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Processing Routes to Macroporous Ceramics: A Review

The notion of mimicking natural structures in the synthesis of new structural materials has generated enormous interest but has yielded few practical advances. Natural composites achieve strength and toughness through complex hierarchical designs extremely difficult to replicate synthetically. Here we emulate Nature's toughening mechanisms through the combination of two ordinary compounds, aluminum oxide and polymethylmethacrylate, into ice-templated structures whose toughness can be over 300 times (in energy terms) that of their constituents. The final product is a bulk hybrid ceramic material whose high yield strength and fracture toughness ({approx}200 MPa and {approx}30 MPa{radical}m) provide specific properties comparable to aluminum alloys. These model materials can be used to identify the key microstructural features that should guide the synthesis of bio-inspired ceramic-based composites with unique strength and toughness.

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Tough, bio-inspired hybrid materials.

Porous ceramics are now expected to be used for a wide variety of industrial applications from filtration, absorption, catalysts and catalyst supports to lightweight structural components. During the last decade, tremendous efforts have been devoted for the researches on innovative processing technologies of porous ceramics, resulting in better control of the porous structures and substantial improvements of the properties. This article intends to review these recent progresses of porous ceramics. Because of a vast amount of research works reported in this field these days, the review mainly focuses on macro-porous ceramics whose pore size is larger than 50 nm. Followed by giving a general classification of porous ceramics, a number of innovative processing routes developed for critical control of pores are described, along with some important properties. The processes are divided into four categories including (i) partial sintering, (ii) sacrificial fugitives, (iii) replica templates and (iv) dir...

Macro-porous ceramics: processing and properties

Porous ceramics with complex pore structure were synthesized by a freeze-dry process. Freezing-in of a water-based ceramics slurry was done while controlling the growth direction of the ice. Sublimation marks of the ice were generated by drying under reduced pressure. Porous ceramics having a complex pore structure were obtained by sintering the green body: aligned macroscopic open pores contained micropores in their internal walls. The pore structure was substantially affected by the starting slurry concentration and sintering temperature. The pore formation mechanism is discussed in relation to these effects.

Synthesis of Porous Ceramics with Complex Pore Structure by Freeze‐Dry Processing

Crack-tip bridging by particles is considered to be one of the primary strengthening mechanisms of ceramic nanocomposites. Small, brittle particulate inclusions have been shown to cause crack-tip bridging at short distances behind the crack tip. This mechanism leads to modest toughness but a very steep R-curve, and it is the latter that produces the very high fracture strength of the ceramic nanocomposite. Localized high residual stress around the particles (particularly in the case of silicon carbide-alumina material) causes the strengthening mechanism to operate effectively, even at a small volume fraction of 5%. The present study predicts the magnitude of the toughness increase and the extent of R-curve behavior for the nanocomposite.

Strengthening and Toughening Mechanisms of Ceramic Nanocomposites

Vertically aligned ZnO nanotubes were prepared by etching ZnO rod arrays in aqueous solution, which were previously developed by chemical bath deposition method. The morphological, structural, photoluminescence, as well as photocatalytic properties of the ZnO nanotubes were examined with respect to the pH values of chemical bath solution. The morphology of the products was found to be sensitive to the pH values and chemical bath temperatures. The nanotubes synthesized at a low pH value (5.82) exhibited a strong UV emission and a weak defect-related visible emission. The highest photocatalytic efficiency was also observed at pH = 5.82. The possible mechanism for the difference of photocatalytic efficiency was discussed.

Formation and photocatalytic application of ZnO nanotubes using aqueous solution.

Porous silicon nitride with macroscopically aligned channels was synthesized using a freeze-drying process. Freezing of a water-based slurry of silicon nitride was done while unidirectionally controlling the growth direction of the ice. Pores were generated subsequently by sublimation of the columnar ice during freeze-drying. By sintering this green body, a porous silicon nitride with high porosity (over 50%) was obtained and its porosity was controllable by the slurry concentration. The porous Si 3 N 4 had a unique microstructure, where macroscopically aligned open pores contained fibrous grains protruding from the internal walls of the Si 3 N 4 matrix. It is hypothesized that vapor/solid phase reactions were important to the formation mechanism of the fibrous grains.

Tatsuki Ohji

Papers

Macro-porous ceramics: processing and properties

Synthesis of Porous Ceramics with Complex Pore Structure by Freeze‐Dry Processing

Strengthening and Toughening Mechanisms of Ceramic Nanocomposites

Formation and photocatalytic application of ZnO nanotubes using aqueous solution.

Synthesis of Porous Silicon Nitride with Unidirectionally Aligned Channels Using Freeze-Drying Process