S The need for fully dense material with well-engineered microstructures has led to the promising emergence of innovative sintering technologies among which the Spark Plasma Sintering (SPS) is one of the most favorite. Unlike the conventional sintering processes, SPS takes advantage of a current flow passing through the sintering die and metallic powders by which fast densification with minimal grain growth and enhanced physicomechanical properties can be obtained. Albeit there is a growing interest in the exploitation of SPS in producing sufficiently consolidated metallic parts, no analytical review has been released over the effects of SPS parameters on the densification behavior, microstructure evolution, and resultant physicomechanical properties of metallic parts and their alloys. In the present review, recent developments and ongoing challenges in modeling the SPS of metallic systems are thoroughly explored. Then, the effects of main SPS parameters including sintering temperature, dwell time, heating rate, and pressure on the microstructure and physicomechanical properties of metals and alloys are comprehensively investigated. These properties are categorized into two groups: (i) physical properties including relative density, electrical and thermal conductivities; (ii) mechanical properties with a systematic focus on hardness, elastic modulus, and tensile, compressive, and bending strengths. In each section, the general trends along which SPS parameters grow to affect each corresponding property are comprehensively discussed. Additionally, various microstructural phenomena being more likely to occur at the given metallic systems are fully addressed. The present work seeks to elaborate on the aforementioned issues and provide an overview of the unresolved challenges and proposed solutions to them.

Nanostructured iron-oxide based materials with tailored mechanical and magnetic behavior are produced in bulk form. By applying ultra-fast heating routines via spark plasma sintering (SPS) to supercrystalline pellets, materials with an enhanced combination of elastic modulus, hardness and saturation magnetization are achieved. Supercrystallinity – namely the arrangement of the constituent nanoparticles into periodic structures – is achieved through self-assembly of the organically-functionalized iron oxide nanoparticles. The optimization of the following SPS regime allows the control of organics' removal, necking, iron oxide phase transformations and nano-grain size retention, and thus the fine-tuning of both mechanical properties and magnetic response, up until the production of bulk mm-size superparamagnetic materials.

Supercrystalline nanocomposite materials with micromechanical properties approaching those of nacre or similar structural biomaterials can be produced by self-assembly of organically modified nanoparticles, and further strengthened by crosslinking. The strengthening of these nanocomposites is controlled via thermal treatment, which promotes the formation of covalent bonds between interdigitated ligands on the nanoparticles’ surface. In this work it is shown how the extent of the mechanical properties’ enhancement can be controlled by the solvent used during the self-assembly step. We find that the resulting mechanical properties correlate with the Hansen solubility parameters of the solvents and ligands used for the supercrystal assembly: hardness and elastic modulus decrease as the Hansen solubility parameter of the solvent approaches the Hansen solubility parameter of the ligands that stabilize the nanoparticles. Moreover, it is shown that self-assembled supercrystals that are subsequently uniaxially pressed can deform up to 6 %. The extent of this deformation is also closely related to the solvent used during the self-assembly step. These results indicate that the conformation and arrangement of the organic ligands on the nanoparticle surface not only control the self-assembly itself, but also influence the mechanical properties of the resulting supercrystalline material. The Hansen solubility parameter may therefore serve as tool to predict what solvents and ligands should be used to obtain supercrystalline materials with good mechanical properties.

Biomaterials often display outstanding combinations of mechanical properties thanks to their hierarchical structuring, which occurs through a dynamically and biologically controlled growth and self-assembly of their main constituents, typically mineral and protein. However, it is still challenging to obtain this ordered multiscale structural organization in synthetic 3D-nanocomposite materials. Herein, we report a new bottom-up approach for the synthesis of macroscale hierarchical nanocomposite materials in a single step. By controlling the content of organic phase during the self-assembly of monodisperse organically-modified nanoparticles (iron oxide with oleyl phosphate), either purely supercrystalline or hierarchically structured supercrystalline nanocomposite materials are obtained. Beyond a critical concentration of organic phase, a hierarchical material is consistently formed. In such a hierarchical material, individual organically-modified ceramic nanoparticles (Level 0) self-assemble into supercrystals in face-centered cubic superlattices (Level 1), which in turn form granules of up to hundreds of micrometers (Level 2). These micrometric granules are the constituents of the final mm-sized material. This approach demonstrates that the local concentration of organic phase and nano-building blocks during self-assembly controls the final material’s microstructure, and thus enables the fine-tuning of inorganic-organic nanocomposites’ mechanical behavior, paving the way towards the design of novel high-performance structural materials.

Supercrystalline nanocomposites deform plastically like atomic crystals, even after a boost in strength, and feature compaction.