Densification mechanisms and microstructural evolution during spark plasma sintering of boron carbide powders

Micron-sized boron carbide (B₄C) powders were subjected to spark plasma sintering (SPS) under temperature ranging from 1700 °C to 2100 °C for a soaking time of 5, 10 and 20 min and their densification kinetics was determined using a creep deformation model. The densification mechanism was interpreted on the basis of the stress exponent n and the apparent activation energy Q_d from Harrenius plots. Results showed that within the temperature range 1700–2000 °C, creep deformation which was controlled by grain-boundary sliding or by interface reaction contributed to the densification mechanism at low effective stress regime (n = 2,Q_d = 459.36 kJ/mol). While at temperature higher than 2000 °C or at high stress regime, the dominant mechanism appears to be the dislocation climb (n = 6.11).     

High field ZnO varistors prepared by spark plasma sintering

Abstract

ZnO varistors with submicrometre and nanoscaled microstructures and enhanced electrical properties were prepared by spark plasma sintering (SPS). The densification, grain size and switch field of the varistors were compared with those of hot pressed material. The switching field increased with decreasing grain size, and very rapidly below 500 nm. Switching fields up to 180 kV cm^?1 were obtained for ceramics with submicrometre grain sizes (380 nm). This is nearly two orders of magnitude higher than those currently reported for commercial ZnO varistors. A nano powder, prepared by high energy milling, was sintered to a high density at much lower temperatures compared with the submicron powders and had a nanoscale grain size (45 nm). The nanoceramic broke down dielectrically under very high fields (>260 kV cm^?1) before a varistive response was apparent.     

Fabrication and thermal conductivity of AlN/BN ceramics by spark plasma sintering

Aluminum nitride/boron nitride (AlN/BN) ceramics with 15–30 vol.% BN as secondary phase were fabricated by spark plasma sintering (SPS), using Yttrium oxide (Y₂O₃) as sintering aid. Effects of Y₂O₃ content and the SPS temperature on the density, phase composition, microstructure and thermal conductivity of the ceramics were investigated. The results revealed that with increasing the amount of starting Y₂O₃ in AlN/BN, Yttrium-contained compounds were significantly removed after SPS process, which caused decreasing of the residual grain boundary phase in the sintered samples. As a result, thermal conductivity of AlN/BN ceramics was remarkably improved. By addition of Y₂O₃ content from 3 wt.% to 8 wt.% into AlN/15 vol.% BN ceramics, the thermal conductivity increased from 110 W/m K to 141 W/m K.     

Reactive sintering cBN-Ti-Al composites by spark plasma sintering

When synthesizing polycrystalline cubic boron nitride (PcBN) at normal pressure, cBN had a trend of hexagonal transformation, which reduces the hardness and strength of PcBN. The cBN-Ti-Al composite was prepared by spark plasma sintering with introducing Ti and Al to absorb hexagonal boron nitride (hBN) transformed from cBN. By the results of X-ray diffraction (XRD), Ti and Al reacted with BN and forming TiN, TiB₂, and AlN, which combined cBN as the binder by chemical bonding. The mechanical properties of the prepared composite increased as the increment of sintering temperature. The threshold temperature for preparing composite without hBN phase was at 1400 °C. The composite with optimal mechanical properties was prepared at 1400 °C, and the relative density, the bending strength, hardness, and fracture toughness were 98.9 ± 0.1%, 390.7 ± 4.4 MPa, 14.1 ± 0.5 GPa, and 7.6 ± 0.1 MPa·m^0.5, respectively.     

Heating mechanism of spark plasma sintering

According to the plasma sintering process and our theoretical calculation, we analyzed the heating mechanism of spark plasma sintering (SPS). It is proposed that the sintering temperature of conductive materials rises faster mainly due to the contribution of the direct current (DC) component in pulse current, current skin effect and eddy current in the mould and blank, Joule's heat generated by eddy current in grains, small heat capacity of the heated system and direct-contact heating. For non-conductive materials, the similar reasons can be found except for the heat effect of eddy current. By analyzing the heating mechanism of SPS, it is concluded that the temperature on the surface of a conductive green body should be higher than that on the inner surface of the die, whereas the opposite case holds for a non-conductive blank, that has already been verified by Nagae et al. [Journal of the Japan Society of Powder and Powder Metallurgy 44 (1997) 945–950] and by Sumi et al. [Journal of the Japan Society of Powder and Powder Metallurgy 45 (1998) 153–157].     

Microstructure and thermal conductivity of fully ceramic microencapsulated fuel fabricated by spark plasma sintering

Fully ceramic microencapsulated pellet (FCM), consisting of tristructural isotropic (TRISO) particles embedded in silicon carbide (SiC) matrix, was fabricated using spark plasma sintering. The parameters affecting the densification of SiC matrix were first investigated, and then FCM pellets were prepared using TRISO particles with/without outer pyrolytic carbon (OPyC) layer. Effects of thermal exposure on the TRISO particles during SPS were evaluated. In addition, the thermal condcutvitities of FCM pellet, as well as the SiC matrix, were measured using laser flash. It was revealed that the TRISO particles with OPyC layers significantly lower the thermal conductivity of FCM pellet. Based on Maxwell‐Eucken model, the predicted effective thermal conductivities of TRISO particles with/without OPyC layers were 14.4 W/m K and 25.2 W/m K, respectively. Finite elements simulation indicated that the SiC layer in TRISO particle plays a dominant role on the thermal conductivity of FCM. The presence of OPyC layers would generate gaps/porous SiC near the interface and resist the heat flows, leading to a lower thermal conductivity of FCM.     

Flash spark plasma sintering of 3YSZ

Flash SPS (FSPS) consolidation of 3YSZ cold pressed pellets was investigated. The results show that FSPS allows ultra-rapid consolidation of 3YSZ samples in 30–90 s under an applied electric field. The DC field induces electrochemical blackening. The partial reduction process starts from the cathode (-) and propagates toward the anode (+). This phenomenon, not previously discussed in FSPS literature, induces the development of internal temperature gradients resulting in a polarity dependent grain size/densification.     

Simple method for the identification of electrical and thermal contact resistances in spark plasma sintering

The electrical and thermal contact resistances are key parameters for obtaining an accurate electro-thermal model of the spark plasma sintering (SPS) process. However, due to the lack of a general expression, these parameters are usually determined empirically. Thus, they are only valid for a specific material and SPS configuration. A simple method based on a limited amount of experiments as well as a new formulation of the electrical and thermal contact resistances are developed. First, the evolution of those resistances is optimized on simple shapes (pellets) experiments. They are then transferred into the electro-thermal simulation of complex shapes configurations, which showed a good agreement between the experimental and computed data.     

Micromechanical properties and microstructure evolution of magnesia partially stabilized zirconia prepared by spark plasma sintering

Magnesia partially stabilized zirconia (Mg-PSZ) is a widely used engineering ceramic owing to its high hardness and exceptional toughness. It is usually processed by conventional firing followed by subeutectoid aging. In this work, Mg-PSZ was prepared by spark plasma sintering (SPS) followed by sequential subeutectoid aging to fine-tune its mechanical properties. Mg-PSZ prepared by SPS with the rapid heating capability presents much smaller grains than conventionally prepared counterparts. After aging, a significant fraction of the matrix cubic phase transforms into tetragonal, orthorhombic, and monoclinic zirconia. Microindentation and in-situ microcompression tests reveal that aging Mg-PSZ for 4 h leads to maximum fracture toughness and fracture strain due to the tetragonal-to-monoclinic transformation toughening. Post compression TEM analyses show dominant monoclinic ZrO₂ decorated by a high density of twin boundaries and stacking faults formed to accommodate the shear deformation. Preparation of Mg-PSZ by SPS offers rapid and effective approaches in finetuning the phases and mechanical properties.     

Carbon nanotube toughened hydroxyapatite by spark plasma sintering: Microstructural evolution and multiscale tribological properties

Carbon nanotube (CNT) reinforced hydroxyapatite (HA) composite synthesized using spark plasma sintering is investigated in this study. Quantitative microstructural analysis suggests that CNTs play a role in grain boundary pinning and are responsible for the improved densification and retention of nanostructure throughout the thickness of the sintered pellet. HA crystal forms coherent interface with the CNT, resulting in a strong interfacial bond. The uniform distribution of 4 wt.% CNTs in the HA matrix, good interfacial bonding and fine HA grain size help to improve the fracture toughness by 92% and elastic modulus by 25% as compared to the HA matrix without CNT. Toughening mechanisms have been explained in terms of interfacial shear strength and pull-out energy of CNT from the HA matrix. CNT plays a major role in improving the wear resistance of HA matrix at both macro- and nano-scale. It is concluded that graphene layer removal from the CNT surface occurs during macro-wear, but not for nano-wear. Thus, the coefficient of friction (CoF) in HA-CNT decreases in macro-wear due to lubrication available through delaminated graphene layers.     

Two-step pressure sintering of transparent lutetium oxide by spark plasma sintering

Transparent lutetium oxide (Lu₂O₃) body was prepared by spark plasma sintering using a two-step pressure profile combined with a low heating rate. The effects of pre-load pressures from 10 to 100 MPa and heating rates from 0.03 to 1.67 K s⁻¹ on the microstructures and optical properties were investigated. With increasing pre-load pressures from 10 to 100 MPa, the grains became smaller with a narrower distribution, whereas the transmittance showed maxima at 30 MPa. The average grain size slightly increased from 0.67 to 0.86 μm as the heating rate increased from 0.03 to 1.67 K s⁻¹, while the transmittance decreased. Transmittances of 60% at 550 nm and 79% at 2000 nm were obtained under a pre-load pressure of 30 MPa at a heating rate of 0.17 K s⁻¹.     

Consolidation by spark plasma sintering of polyimide and polyetheretherketone

This article presents two high‐temperature thermoplastic powders which were sintered by spark plasma sintering in order to get homogeneous mechanical properties. Dense polyimide (PI) and polyetheretherketone (PEEK) specimens were obtained at temperatures as low as 320°C for PI and 200°C for PEEK, respectively. Relative densities higher than 99% were reached for both materials. In order to characterize their properties, in situ measurements with compression and hardness tests were carried out on sintered samples. This method allowed to obtain polymeric materials with improved mechanical properties. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40783.     

The thermal stability and consolidation of perovskite variant Cs2SnCl6 using spark plasma sintering

Defect perovskites, a category of air and moisture stable perovskite molecular salts, have gained attention for photovoltaics in the search of alternatives to the organic lead‐based photovoltaics which show exceptional photovoltaic performance but suffer significant environmental instability and toxicity of Pb. Defect perovskites also have exceptional structural flexibility and diverse crystal chemistry, and thus, display potentials as host phases for incorporating high amounts of halides such as iodine and chorine. In this study, pure Cs₂SnCl₆, a lead‐free defect perovskite variant, was synthesized through a solution‐based route that produced particles ranging from 200 to 500 nm. The thermal stability of the as‐synthesized Cs₂SnCl₆ powders was investigated using thermogravimetric analysis (TGA), demonstrating stability up to 615°C, above which a phase decomposition occurs leading to the loss of constituent component of SnCl₄. Consolidation of Cs₂SnCl₆ into dense pellets (≥94% theoretical density) was achieved via spark plasma sintering (SPS) at a low sintering temperature of 350°C. X‐ray diffraction confirms no phase decomposition in the SPS‐densified perovskite pellets as a result of rapid consolidation of the SPS sintering at a short duration and lower temperature, and the TGA analysis suggest a comparable thermal stability up to 627°C for the densified pellet, slightly better than the as‐synthesized powders. The thermal diffusivity of Cs₂SnCl₆ at room temperature was determined as 0.388 mm²·s^?1 by laser flash measurement. This work further discussed the potential applications of the SPS‐densified Cs₂SnCl₆ beyond perovskite photovoltaics, introducing potential nuclear separations and waste forms for chlorine.     

Rapid formation of α-sialon during spark plasma sintering: Its origin and implications

α-Sialons with varied chemical compositions and starting precursors were sintered in spark plasma sintering (SPS) furnace to verify the influence of electrical conduction, mechanical pressure and heat transfer efficiency. The internal temperature that the sample was exposed to and its evolution during the heating were experimentally estimated and discussed. XRD and SEM grain size analysis were carried out to evaluate the phase and microstructure evolution. Mechanical pressure was eliminated to create a free sintering condition under SPS. By free sintering and surrounding the sample with graphite wool the heat transfer was sufficiently retarded and a usual slow reaction was demonstrated. It is verified that the efficiency of heat transfer is more influential in the enhancement of α-sialon formation and grain growth by SPS than the efficiency of electric conduction.     

Enhanced particle rearrangement during liquid phase spark plasma sintering of silicon nitride-based ceramics

Densification evolution has been analysed in liquid phase assisted spark plasma sintering (SPS) of silicon nitride (Si₃N₄)-based materials. Monolithic ceramics with variable amounts of Al₂O₃/Y₂O₃ sintering additives, and carbon nanotubes (CNTs) containing Si₃N₄ composites have been considered. The shrinkage behaviour of SPSed monolithic Si₃N₄ showed a noticeable enhancement of the particle rearrangement stage, exhibiting a complete wetting of the grain boundary phase even for the lowest additive content (1.70 vol.%), unlike the corresponding hot pressed (HPed) material. An improvement of the liquid phase wetting by the presence of electromechanical forces is proposed to explain the enhanced densification occurring in the particle rearrangement stage of the SPS process. Furthermore, the addition of CNTs seems to increase the efficiency of this mechanism, decreasing the particle rearrangement temperature.     

Novel coalescence-driven grain-growth mechanism during annealing/spark plasma sintering of NiO nanocrystals

A novel oriented attachment growth mechanism of nanograins has been suggested for spark plasma sintering and annealing of NiO nanopowder. A hierarchical microstructure built by cube-shaped nanograins was observed during pressure-less spark plasma sintering at temperatures above 1000 °C and when the powders were annealed in ambient atmosphere at and above 700 °C. Irrespective of the processing method used, a rotation assisted grain attachment of irregularly shaped nanocrystals results in such a microstructure with parallel epitaxy, twinning or line defects at the grain interface. The unique microstructural features and the governing factors for the attachment process have been discussed.     

Fabrication of transparent SiO2 glass by pressureless sintering and spark plasma sintering

Transparent SiO₂ bodies were prepared by pressureless sintering (PLS) and spark plasma sintering (SPS). The effects of sintering and annealing temperature on the transmittance of the SiO₂ bodies were investigated. The SiO₂ bodies sintered by SPS and PLS at 1073–1573 K were amorphous. With increasing the sintering temperature to 1673 K, the SiO₂ bodies sintered by PLS were crystallized while those sintered by SPS were still amorphous. The relative density of the SiO₂ bodies sintered by SPS was 98.5% at 1373 K and 100% at 1573 K, whereas that sintered by PLS was 92.6% at 1373 K and 98.9% at 1573 K. The transmittance was 91.0% and 81.5% at a wavelength (λ) of 2 μm for the SiO₂ sintered bodies by SPS and PLS, respectively. In the ultraviolet range, the transmittance of the SiO₂ bodies sintered by SPS at 1573 K was about 40% at λ = 200 nm and increased to 75% after annealing at 1073 K for 1 h, which was about three times of the transmittance of the SiO₂ bodies sintered by PLS (24.8%).     

BiFeO3 ceramics synthesized by spark plasma sintering

Phase-pure BiFeO₃ particles were synthesized by an improved solid state technique. High density BiFeO₃ ceramics were prepared using these particles by spark plasma sintering (SPS). The dielectric permittivity and loss of SPS samples were measured as functions of sintering temperature, frequency, and annealing conditions. Dielectric spectra of the ceramics annealed at 650 °C were characterized in a broad range of temperature (300–725 K) and frequency (100 Hz to 20 MHz). Two kinds of dielectric relaxation following the Arrhenius law were detected in low and high temperature ranges, respectively. The low temperature dielectric relaxation could be almost completely removed by annealing in vacuum and it should be assigned to be a valence fluctuation of Fe ions, while the high temperature dielectric relaxation was proposed to stem from the short-range motion of oxygen vacancies.     

High strength porous alumina by spark plasma sintering

High strength porous alumina was fabricated by spark plasma sintering (SPS) at temperatures between 1000 and 1200 °C with nanocrystalline Al(OH)₃ as the starting powder without any seeds, dopants or inclusions. Decomposition of the Al(OH)₃ produced a series of transitional alumina phases depending on sintering temperature and pressure and finally the stable α-alumina phase was obtained. A network of continuous pores with unimodal pore size distribution was estimated by mercury porosimetry and BET surface area measurements, with the porosity ranging between 20% and 60% based on sintering conditions. Predominance of fine grains and extensive necking between them led to better strength in the sintered samples. The bending strength of the sintered compacts rapidly increased with sintering temperature while retaining reasonable porosity suitable for practical applications. The results clearly indicate that in situ phase formation of α-Al₂O₃ and θ-Al₂O₃ provides strength and porosity, respectively. Phase transformation, pore morphology and microstructure evolution were also studied.     

Two-step sintering assisted consolidation of bulk titania nano-ceramics by spark plasma sintering

This work investigates the feasibility to the fabrication of high density of nano-grained titanium dioxide ceramics by two-step sintering process under spark plasma conditions. First step is carried out by fast-heating-rate sintering in order to obtain an initial high density and a second step is held at a lower temperature by isothermal sintering aiming to increase the density without obvious grain growth. Experiments are conducted to determine the appropriate temperatures for each step. The temperature range between 840 and 850 °C is effective for the first step sintering (T₁) due to its highest densification rate. The isothermal sintering is then carried out at 810–830 °C (T₂) for various hours in order to avoid the abnormal grain growth and improve the density at the same time. TiO₂ bulk ceramics with nano-sized grain were fabricated successfully by combination of spark plasma sintering (SPS) with the two step sintering method (TSS). Titanium dioxide nano-ceramics with >95% theoretical density could be obtained with T₁ and T₂ taken as 850 °C and 830 °C, respectively. The relative grain growth quotient D/D_o for the used starting powder was almost ～1. Further XRD investigations indicated no obvious anatase–rutile transition was found in the prepared nano-crystalline ceramics.