Nanocrystalline metals and ceramics with <100 nm grain sizes and superior properties (e.g., mechanical strength, hardness, fracture toughness and stored dielectric energy) are of great interest. Much has been discussed about achieving nano grains, but little is known about maintaining grain-size uniformity that is critical for material reliability. An especially intriguing question is whether it is possible to achieve a size distribution narrower than what Hillert[1] theoretically predicted for normal grain growth, a possibility suggested, for growth with a higher growth exponent, by the generalized mean-field theory[2] of Lifshitz, Slyozov, Wagner (LSW)[3,4] and Hillert but never realized in practice. We demonstrate that this can be achieved in bulk materials with an appropriately designed two-step sintering route that (a) takes advantage of the large growth exponent in the intermediate sintering stage to form a most uniform microstructure despite porosity remaining, and (b) freezes the grain growth thereon while continuing densification to reach full density. The resultant dense bulk Al2O3 ceramic has an average grain size of 34 nm and a much narrower size distribution than Hillert's prediction. Bulk Al2O3 with a grain-size distribution narrower than the particle-size distribution of starting powders was also demonstrated using this strategy, as were highly uniform bulk engineering metals and ceramics of either high purity and high melting points (Mo and W-Re) or highly complex compositions (core-shell BaTiO3 and 0.87BaTiO3-0.13Bi(Zn2/3(Nb0.85Ta0.15)1/3)O3).
The present work reports the effect of Ta on densification and microstructure evolution during non-isothermal and spark plasma sintering of nanocrystalline W. Nanocrystalline W-5wt.%Ta alloy powder was synthesized using mechanical alloying. The nanocrystalline powder was characterized thoroughly using X-ray diffraction line profile analysis. Furthermore, the shrinkage behavior of nanocrystalline powder was investigated during non-isothermal sintering using dilatometry. Subsequently, the alloy powder was consolidated using spark plasma sintering up to 1600 °C. The role of Ta on stabilizing the …
The present work reports the role of different atomic mobility induced localized pore evolution on densification during spark plasma sintering of nanocrystalline W-Mo alloy powder. The shrinkage (or expansion) behavior of cold compacted milled powders was studied using dilatometry during non-isothermal sintering up to 1600 °C. Subsequently, the milled powders were densified to ~95% relative density using spark plasma sintering up to 1600 °C. The enhanced localized Joule heating due to dynamically evolved porous structure could be attributed for the densification during spark plasma sintering.
The effect of sintering temperatures (Ts) on the structural and magnetic properties of Ni0.6Zn0.4Fe2O4 (NZFO) ferrites synthesized by conventional double sintering method has been reported. The samples are sintered at 1200, 1250 and 1300 °C. The X-ray diffraction (XRD) analysis reveals the formation of a single phase cubic spinel structure of the sample. The magnetic parameters such as saturation magnetization, Ms; coercive field, Hc; remanent magnetization, Mr and Bohr magneton, μB are determined and well compared with reported values. The obtained values are found to be 71.94 emu/gm and 1.2 …
Nanocrystalline bulk materials are desirable for many applications as they combine mechanical strength and specific electronic transport properties. Our bottom up approach starts with tailored nanoparticles. Compaction and thermal treatment are crucial, but usually the final stage sintering is accompanied by rapid grain growth which spoils nanocristallinity. For electrically conducting nanoparticles, field activated sintering techniques overcome this problem. Small grain sizes have been maintained in spite of consolidation. Nevertheless, the underlying principles, which are of high practical i…
A cylindrical sintering method for more realistic grain boundaries in nanocrystalline thin films
Institute of Physics of Materials, The Czech Academy of Sciences（材料物理研究所，捷克科学院）；Central European Institute of Technology, Brno University of Technology（中欧技术研究所，布尔诺理工大学）；Charles University, Faculty of Mathematics and Physics（查理大学，数学与物理学院）
Nanocrystalline metal alloys show great potential as structural materials, but are often only available in small volumes such as thin films or powders. However, recent research has suggested that dopant segregation and grain boundary structural transitions between states known as complexions can dramatically alter grain size stability and potentially enable activated sintering. In this study, we explore strategic consolidation routes for mechanically alloyed Cu-4 at.% Zr powders to capture the effects of amorphous complexion formation on the densification of bulk nanostructured metals. We obse…
Nanostructure and mechanical properties of bulk nanocristalline cubic boron nitride have been studied by transmission electron microscopy, and micro- and nanoindentation. The obtained data on hardness, elastic properties and fracture toughness clearly indicate that nano-cBN belongs to a family of advanced ultra-hard materials.
We present atomistic simulations for the mechanical response of ultra nanocrystalline diamond, a polycrystalline form of diamond with grain diameters of the order of a few nm. We consider fully three-dimensional model structures, having several grains of random sizes and orientations, and employ state-of-the-art Monte Carlo simulations. We calculate structural properties, elastic constants and the hardness of the material; our results compare well with experimental observations for this material. Moreover, we verify that this material becomes softer at small grain sizes, in analogy to the obse…
Ultra-nanocrystalline diamond is a polycrystalline material, having crystalline diamond grains of sizes in the nanometer regime. We study the structure and mechanical properties of this material as a function of the average grain size, employing atomistic simulations. From the calculated elastic constants and the estimated hardness, we observe softening of the material as the size of its grains decreases. We attribute the observed softening to the enhanced fraction of interfacial atoms as the average grain size becomes smaller. We provide a fitting formula for the scaling of the cohesive energ…
Nanocrystalline alloys (nanoalloys) are prone to grain growth. It is known that grain boundary segregation and precipitation can stabilize nanoalloys, but the stabilization becomes less effective at high temperatures and adding grain growth inhibitors often reduces sinterability. Herein, we have simultaneously achieved improved sinterability and exceptional high-temperature stability for a class of MoNbTaTiW-based refractory high-entropy nanoalloys (RHENs). Bulk pellets of RHENs were fabricated through planetary ball milling and spark plasma sintering, achieving 93-96% relative densities with …
The paper describes the capability of magnetic softening of a coarse grained bulk material by a severe deformation technique. Connecting the microstructure with magnetic properties, the coercive field decreases dramatically for grains smaller than the magnetic exchange length. This makes the investigation of soft magnetic properties of severely drawn pearlitic wires very interesting. With the help of the starting two phase microstructure, it is possible to substantially refine the material, which allows the investigation of magnetic properties for nanocrystalline bulk material. Compared to the…
A new flash (ultra-rapid) spark plasma sintering method applicable to various materials systems, regardless of their electrical resistivity, is developed. A number of powders ranging from metals to electrically insulative ceramics have been successfully densified resulting in homogeneous microstructures within sintering times of 8-35 s. A finite element simulation reveals that the developed method, providing an extraordinary fast and homogeneous heating concentrated in the sample's volume and punches, is applicable to all the different samples tested. The utilized uniquely controllable flash p…
New approach for obtaining ceramic NASICON (Na$_3$Zr$_2$ (SiO$_4$)$_2$PO$_4$) films sintered in situ by a sol-gel method, using spray deposition and Near-Infra Red Sintering
Thermal conductivity of nanocrystalline and ultra-nanocrystalline films is analyzed with effective medium theory (EMT) models. The existing EMT models use the spherical inclusion approximation. Although this approximation works quite well it is inconsistent, mostly with respect to the maximal packing of 74{\%}, which may be unrealistic for polycrystalline films. To check the consistency of these models we devise an EMT model with arbitrarily shaped inclusions. We pick the EMT model with cubic inclusions and we compare its results with the results of the EMT model with spherical inclusions. It …
The perovskite (1-x)YMnO$_3$-xBiFeO$_3$ binary system is very promising because of its multiferroic end members. Nanocrystalline phases have been recently obtained by mechanosynthesis across the system, and the perovskite structural evolution has been described. Two continuous solid solutions with orthorhombic Pnma and rhombohedral R3c symmetries were found, which coexist within a broad compositional interval of 0.5 < x < 0.9. This might be a polar-nonpolar morphotropic phase boundary region, at which strong phase-change magnetoelectric responses can be expected. A major issue is phase decompo…
Effect of interfacial Fe3O4 nanoparticles on the microstructure and mechanical properties of textured alumina densified by ultrafast high-temperature sintering
The fabrication of various suspended microstructures made from ultra-nanocrystalline diamond was performed without sacrificial layer. Arrays of bridges and cantilevers of various dimensions were successfully fabricated by a well-controlled process. Mechanical characterizations and finite element calculations allowed us to estimate both the Young's modulus as well as the residual stress built in the ultra-nanocrystalline diamond film.
We employ magnetic small-angle neutron scattering to investigate the magnetic interactions in $(Fe_{0.7}Ni_{0.3})_{86}B_{14}$ alloy, a HiB-NANOPERM-type soft magnetic nanocrystalline material, which exhibits an ultrafine microstructure with an average grain size below 10 nm. The neutron data reveal a significant spin-misalignment scattering, which is mainly related to the jump of the longitudinal magnetization at internal particle-matrix interfaces. The field dependence of the neutron data can be well described by the micromagnetic small-angle neutron scattering theory. In particular, the theo…
Ultra-high-temperature ceramics (UHTCs) are candidate structural materials for applications that require resiliency to extreme temperature (>2000°C), high mechanical loads, or aggressive oxidizing environments. Processing UHTC transition metal carbides as standalone materials using additive manufacturing (AM) methods has not been fully realized due to their extremely slow atomic diffusivities that impede sintering and large volume changes during indirect AM that can induce defect structures. In this work, a two-step, reactive AM approach was studied for the formation of the ultra-high temperat…
Grain Growth Kinetics in (Cr,Mo,Ta,V,W)C1-δ High-Entropy Carbide Ceramics
Missouri University of Science and Technology（密苏里科技大学）；Pennsylvania State University（宾夕法尼亚州立大学）；Duke University（杜克大学）；University of California, Irvine（加州大学尔湾分校）
A theoretical model for understanding the formation of interfacial thin films is presented, which combines density functional theory calculations for interface energies with thermodynamic modeling techniques for multicomponent bulk systems. The theory is applied to thin film formation in VC-doped WC-Co cemented carbides. It is predicted that ultrathin VC films may exist in WC/Co interfaces at the high temperature sintering conditions where most of the WC grain growth occurs, which provides an explanation of the grain growth inhibiting effect of VC additions in the WC-Co system.
Ultra-high-temperature ceramics (UHTCs) are optimal structural materials for applications that require extreme temperature resilience, resistance to chemically aggressive environments, wear, and mechanical stress. Processing UHTCs with laser-based additive manufacturing (AM) has not been fully realized due to a variety of obstacles. In this work, selective laser reaction sintering (SLRS) techniques were investigated for the production of near net-shape UHTC ceramics such as HfC, ZrC, TiC, HfN, ZrN, and TiN. Group IV transition metal and metal oxide precursor materials were chemically converted…
A combined theoretical/numerical/experimental program is outlined for extending the ILG approach to consider time lags, stochasticity and multiphysics couplings. Through this extension it is possible to discuss the interplay between deformation internal lengths (ILs) and ILs induced by thermal, diffusion or electric field gradients. Size-dependent multiphysics stability diagrams are obtained, and size-dependent serrated stress-strain curves are interpreted through combined gradient-stochastic models. When differential equations are not available for describing material behavior, a Tsallis non-…
Titanium diboride (TiB2) is a low-density refractory material belonging to the family of ultra-high temperature ceramics (UHTCs). This paper reports on the production and microstructural and optical characterization of nearly fully dense TiB2, with particular interest to its potential utilization as novel thermal solar absorber. Monolithic bulk samples are produced starting from elemental reactants by a two-step method consisting of the Self-propagating High-temperature Synthesis (SHS) followed by the Spark Plasma Sintering (SPS) of the resulting powders. The surface of obtained samples has-be…
Texture in dense or porous ceramics can enhance their functional and structural properties. Current methods for texturation employ anisotropic particles as starting powders and processes that drive their orientation into specific directions. Using ultra-low magnetic fields combined with slip casting, it is possible to purposely orient magnetically responsive particles in any direction. When those particles are suspended with nanoparticles, templated grain growth occurs during sintering to yield a textured ceramic. Yet, the final grains are usually micrometric, leading weak mechanical propertie…
The creep mechanism in the compression testing of the tungsten carbide with different grain sizes has been studied. The WC samples with high density (96.1-99.2%) were obtained by SPS from nano-, submicron, and micron-grade WC powders. The samples had a coarse-grained (CG) surface layers of ~0.3 mm in thickness and ultrafine-grained (UFG) central parts consisting of WC with a small fraction of W2C. The creep tests were conducted in two regimes: (Mode #1) holding at different temperatures (1300-1375C) at 70 MPa; (Mode #2) tests at different stresses (50, 70, 90 MPa) at 1325C. Tests in Mode #1 we…
