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Zirconium diboride (ZrB2) and silicon carbide (SiC) composites have long been of interest since it was observed that ZrB2 improved the thermal shock resistance of SiC. However, processing of these materials can be difficult due to high and different sintering temperatures and differences in the thermodynamic stability of each material. ZrB2–SiC composites have been processed in a variety of ways including hot-pressing, spark-plasma sintering, reactive melt infiltration, pack cementation, chemical vapor deposition, chemical vapor infiltration, stereolithography, direct ink writing, selective laser sintering, electron beam melting, and binder jet additive manufacturing. Each manufacturing method has its own pros and cons. This review serves to summarize more than 60 years of research and provide a coherent resource for the variety of methods and advancements in development of ZrB2–SiC composites.

Digital light processing (DLP) stereolithography was used to prepare layers and samples for dimensional calibration from commercial alumina slurries. Single-layer squares were studied to understand the penetration depth and curing behavior, and samples with varying curing time and intensity were printed and sintered. Fourier-transform infrared spectroscopy (FTIR) of the squares was performed to measure the relative amount of curing based on the change of the bond transparency of the polymer during various printing conditions. X-ray computed tomography (XCT) scans were performed after printing of squares and parts as well as after sintering parts. The morphologies and structures of the squares and parts were studied after printing and after sintering. The dimensions were measured, and the differences before and after sintering are reported for the various printing conditions. The study shows how FTIR can monitor curing of printed parts, and dimensional accuracy of 0.20 mm can be achieved.

In-situ formation of ZrB2–SiC composites was investigated by reactive spark plasma sintering of precursor powders according to the reaction B4C + 2ZrC + 3Si → 3SiC + 2ZrB2. The reaction and process presented here involves a diffusion reaction between B4C and ZrC which facilitates the formation of ZrB2, while liquid phase sintering of silicon facilitates atomic diffusion and combines with free C from the B4C and ZrC reaction to form SiC within minutes of heating and there were some residual unreacted precursor materials. An interpenetrating matrix of ZrB2–SiC was formed that shows increased fracture toughness (6.03 ± 0.45 MPa m1/2) despite relatively low density (95 %).

Traditionally, WC-based composites use Co as the metal binder phase to consolidate using liquid-phase sintering with a small percentage of Co, but a potentially lower cost binder phase can be made with a different approach when using large amount of metal binder phase. FeNi as a metal binder material is much cheaper than Co. WC can be liquid-phase sintered and melt infiltrated with FeNi, but by making FeNi in situ, costs lower even further. Composites of WC-(Fe-Ni) were made by first pressing a mixture of WC and Fe powders and subsequently melt infiltrating Ni in an amount corresponding to less volume than the porosity of the preform to ensure high WC content. The research objective was to make highly dense composites via melt infiltration with a low-cost metal binder phase in situ. This method has the potential to make fully dense composites, rather than hardmetals, with suitable properties at lower costs. The density and hardness are 97.4%TD and 6.72 GPa, respectively.

Additive manufacturing (AM) of tungsten carbide-cobalt (WC-Co) is explored starting with WC preforms shaped with binder jet additive manufacturing (BJAM) followed by melt infiltration of Co. The research objective is to demonstrate the ability to net-shape WC-Co composites through BJAM of a WC preform followed by backfilling with cobalt via pressureless infiltration. This method also has the potential to minimize shrinkage and grain growth compared to other AM techniques. The effects of sintering, Co content, and infiltration time on the net shaping and properties of processed composites are shown. The best shaped material had an average grain size of 5.1 μm, 32 vol.% Co, density of 98.54% theoretical, fracture toughness of 23.2 MPa m1/2, and hardness of 9.0 GPa. Data presented illustrates that the proposed approach results in favorable ceramic-metal (cermet) properties and is viable for fabricating cermets of other material combinations. Successful AM of cermets provides complex geometries, high throughout, and low costs.

This article focuses on binder-jetting technologies in additive manufacturing (AM) that produce metal artifacts either directly or indirectly. The intent is to focus on the most strategic and widespread uses of the binder jetting technology and review some of the challenges and opportunities for that technology. The discussion includes a historical overview and covers the major steps involved and the advantages of using the binder jetting process. The major steps of the process covered include printing, curing, de-powdering, and sintering.

This work investigates the feasibility of a binderless, extrusion-based additive manufacturing approach to fabricate alumina ( A l 2 O 3 ) parts from nanopowder. Traditional manufacture of ceramics with subtractive methods is limited due to their inherent hardness and brittleness, inevitably leading to ceramic parts with less-than-optimal geometries for the specific application. With an additive manufacturing approach, ceramic parts with complex 3D geometries, including overhangs or hollow enclosures, become possible. These complex ceramic parts are highly valuable in heat exchanger, condenser, biomedical implant, chemical reactant vessel, and electrical isolation applications. This research employed direct coagulation of alumina nanopowder slurries with the polyvalent salt tri-ammonium citrate providing the solidification mechanism in an extrusion-based printing process. The viscosity of the slurries was adjusted from ∼35 Pa-s to ∼1000 Pa-s by adjusting pH from ∼9 to ∼4, resulting in a paste that is suitable for extrusion, which retains near-net geometry. It was shown that the direct coagulation approach can be used to create a suspension with tuneable flow characteristics and coagulation rate, and a mechanism describing the process was proposed. The direct coagulation printing (DCP) method is described in detail, including how slurry is extruded, solidified, and printed in complex geometries, and sintered to full density. Parts were printed with a sintered resolution of 450 μm and green densities as high as 65%. After sintering at 1550 °C for up to 2 h, parts were shown to be fully dense (>97%) with an average grain size of ∼2 μm. Mechanical properties were characterized with a comparison to different materials and methods from literature, showing hardness and flexural modulus up to ∼1800 HV and 400 GPa, respectively.

As a non-beam-based additive manufacturing (AM) method, binder jet 3D printing (BJ3DP) is a process in which a liquid binder is jetted on layers of powdered materials, selectively joined, and then followed by densification process. Among AM technologies, binder jetting holds distinctive promise because of the possibility of rapid production of complex structures to achieve isotropic properties in the 3D printed samples. By taking advantage of traditional powder metallurgy, BJ3DP machines can produce prototypes in which material properties and surface finish are similar to those attained with traditional powder metallurgy. Various powdered materials have been 3D printed, but a typical challenge during BJ3DP is developing printing and post-processing methods that maximize part performance. Therefore, a detailed review of the physical processes during 3D printing and the fundamental science of densification after sintering and post–heat treatment steps are provided to understand the microstructural evolution and properties of binder jetted parts. Furthermore, to determine the effects of the binder jetting process on metallurgical properties, the role of powder characteristics (e.g., morphology, mean size, distribution), printing process parameters (e.g., layer thickness, print orientation, binder saturation, print speed, drying time), sintering (e.g., temperature, holding time), and post-processing are discussed. With the development of AM technologies and the need for post-processing in 3D printed parts, understanding the microstructural evolution during densification is necessary and here, processing steps are explained. Finally, opportunities for future advancement are addressed.

W-ZrC composites were successfully prepared by reactive melt infiltration (RMI) of stoichiometric and excess amounts of Zr2Cu into sintered and un-sintered WC preforms made from binder jet 3D printing. The focus of this work was to study the conversion of reactant powders and liquid infiltrant with varying preform density and infiltrant amount by controlling the processing time to reach high conversion yield while understanding the phase composition, microstructure, and hardness. To investigate the effect of time, the reactive melt infiltration was conducted at 1400 °C for 2, 4 and 8 h in a furnace with 96% Ar - 4% H2 gas atmosphere. The increase in reaction time from 2 to 8 h increased the W and W2C phase contents and decreased the ZrC phase content when using sintered WC preforms. Samples prepared from un-sintered WC preforms exhibited improved reactive melt infiltration compared to sintered samples, and there was no detectable W2C phase and nearly full consumption of WC. Similar to sintered WC samples, the content of W and ZrC phases increased with the increase in time from 2 to 8 h. The interfaces and phases at reaction interfaces were investigated using electron diffraction analysis and S/TEM-EDS to understand material stability; the phases were identified and consistent with XRD analysis. Additionally, there was no Cu present at the interfaces. Increasing the amount of infiltrant led to better reactive melt infiltration. In general, the hardness increased with reaction time and the highest Vickers hardness was found in the W-ZrC sample formed from sintered WC reacted with excess Zr2Cu. This research addresses the critical comparison of sintering and RMI time and shows that by using un-sintered samples for 8 h we are able to achieve W-ZrC composites with fewer undesired phases.

High-density WC-FeNi ceramic-metal (cermet) composites were fabricated using liquid-phase spark plasma sintering/field-assisted sintering technology (SPS/FAST) with in-situ formation of metal binder phase. The precursor materials were micron-sized powders of WC, Fe, Ni, and C. A low melting point from a eutectic reaction of the powders enabled the in-situ formation of FeNi alloy and facilitates liquid-phase sintering of the WC. The carbon powder was added to stabilize the formation of the binder phase. Electron backscatter diffraction (EBSD) was performed to measure grain size and orientation. The composite exhibited a 99% theoretical density and a microstructure consisting of rounded and contiguous WC grains. The average grain size is 10.5 μm. The composite has a maximum hardness of 16.1 GPa. This research provides a fast and cost-effective approach to fabricate hard metals.

High silicon (Si) electrical steel has the potential for efficient use in applications such as electrical motors and generators with cost-effective in processing, but it is difficult to manufacture. Increasing the Si content beyond 3 wt.% improves magnetic and electrical properties, with 6.5 wt.% being achievable. The main goal of this research is to design, develop, and implement a scalable additive manufacturing process to fabricate Fe with 6.5 wt.% Si (Fe–6Si) steel with high magnetic permeability, high electrical resistivity, low coercivity, and low residual induction that other methods cannot achieve because of manufacturing limitations. Binder jet additive manufacturing was used to deposit near net shape components that were subsequently sintered via solid-state sintering to achieve near full densification. Here, it is shown that the use of solid-state sintering mitigates cracking since no rapid solidification occurs unlike fusion-based additive technologies. The Fe–6Si samples demonstrated an ultimate tensile strength of 434 MPa, electrical resistivity of 98 μΩ cm, and saturation magnetization of 1.83 T with low coercivity and high permeability. The results strongly supports to replace the only available 0.1 mm thick chemical vapor deposition (CVD) produced Si steel using the cost effective AM method with good mechanical and magnetic properties for motor applications., Electromagnetism, Soft magnetic alloy, Fe–6Si, Binder jet additive manufacturing, DC and AC magnetic properties, Stators

Functionally graded material (FGM) in terms of grain size gradation is fabricated from ZnO with a combination of modified Spark Plasma Sintering (SPS) graphite tooling, water sintering enhancements through transient liquid phase surface transport, and strategic SPS mechanical loading. The grain size gradation of the ZnO FGM spans from 180 nm grains to 1.2 micrometers in a fully dense material. This is the first semiconductor or ceramic to be graded microstructurally to this extent. Predictions of the microstructure with a Master Sintering Curve (MSC) approach were done with a series of isothermal experiments on two different FGM conditions revealing a slight offset due to a constrained mechanism. The mechanical properties were tested with Vickers micro hardness across the sample, showing a gradient in hardness from 2.6 GPa to 4.2 GPa. In addition, the thermoelectric properties of the FGM were measured and show a zT of 2 × 10−5 at 100 °C compared to uniform small- and large-grained samples of 1 × 10−6. This is an order of magnitude difference making a new path for improvements of bulk thermoelectric material.