Fabrication of silicon nitride nanoceramics—Powder preparation and sintering: A review

Fine-grained silicon nitride ceramics were investigated mainly for their high-strain-rate plasticity. The preparation and densification of fine silicon nitride powder were reviewed. Commercial sub-micrometer powder was used as raw powder in the “as-received” state and then used after being ground and undergoing classification operation. Chemical vapor deposition and plasma processes were used for fabricating nanopowder because a further reduction in grain size caused by grinding had limitations. More recently, nanopowder has also been obtained by high-energy milling. This process in principle is the same as conventional planetary milling. For densification, primarily hot pressing was performed, although a similar process known as spark plasma sintering (SPS) has also recently been used. One of the advantages of SPS is its high heating rate. The high heating rate is advantageous because it reduces sintering time, achieving densification without grain growth. We prepared silicon nitride nanopowder by high-energy milling and then obtained nanoceramics by densifying the nanopowder by SPS.     

Thermal and mechanical properties of uranium nitride prepared by SPS technique

Nitride fuel is a promising nuclear fuel in fast breeder reactor (FBR) or accelerator-driven subcritical reactor (ADSR) system. In this study, high-density UN pellets were prepared by Spark plasma sintering (SPS) technique. The sample density strongly depended on the sintering temperature and pressure, and the pellets with 90% of theoretical density were easily obtained with low sintering temperature and short sintering time without any milling process. The grain size and pore size were much smaller compared with those for samples prepared by conventional sintering process. Despite of the small grain size, the thermal conductivity remains the high value. The SPS process permits easy densification of nitrides without any deterioration of thermal and mechanical properties, considered to be suitable as a preparation method of nitride fuels.     

Superfast densification of nanocrystalline oxide powders by spark plasma sintering

Spark plasma sintering (SPS) is a newly discovered old technique which recently has been used for superfast densification of ceramic powders. Simultaneous application of pulsed high dc current densities and load is the necessary condition for rapid and full densification of ceramic powders by SPS. Commercial nanocrystalline magnesium oxide (nc-MgO) and yttrium aluminum garnet (nc-YAG) powders were densified to optical transparency using spark plasma sintering at distinctly different homologous temperatures (0.3 T _m for nc-MgO and 0.7 T _m for nc-YAG). The observed microstructure, density and grain size evolutions versus the SPS temperature were analyzed. The enhanced densification of the nc-MgO powder at the present SPS conditions was related to plastic deformation followed by diffusion processes. Densification of nc-YAG powder was described by the formation of viscous layer at the particle surfaces and corresponding densification by grain rotation and diffusion through the liquid phase. Densification by normal grain growth takes place at higher relative densities, regardless of the material.     

Spark plasma sintering synthesis of intermetallic T2 in the Mo–Si–B system

Mo₅SiB₂ (T2) was synthesized by sparking plasma sintering (SPS) under different heating rates and sintering temperatures. The powder mixture with a T2 composition (Mo–12.5Si–25B (at.%)) failed to produce the T2 single-phase alloy due to the volatilization of Si during SPS process. Extra 0.5 at.% Si added to this mixture offset the volatilization loss. It has been found that heating of the mixture at low heating rates favored the formation of binary phases in the solid state at medium temperatures. In this work, the T2 alloy with a fine-grained microstructure was obtained via a liquid–solid reaction when the mixture was heated fleetly to the temperatures above the silicon melting point at the rapid heating rate of 200 °C/min. The sintering temperature at 1500 °C for T2 synthesis is beneficial to enhance further densification, as well as to avoid abnormal grain growth at higher temperatures.     

Spark plasma sintering on nanometer scale WC–Co powder

Nanometer scale WC–11Co powder was sintered by spark plasma sintering (SPS) process in order to improve the properties of the cemented carbides. Properties such as density and hardness were measured. The microstructures of sintered WC–11Co cemented carbides were observed. The grain size of WC in alloys was also obtained. The results showed that spark plasma sintering could lower the sintering temperature, increased the density and circumscribed the growth of grain size of WC. Besides, the hardness of the sintered cemented alloys that was dependent on the grain size and densification could also be improved by SPS. SPS was an effective method to get WC–11Co cemented carbides with fine grain size and good properties.     

Spark plasma sintering of silicon nitride using nanocomposite particles

The spark plasma sintering (SPS) of silicon nitride (Si₃N₄) was investigated using nanocomposite particles composed of submicron-size α-Si₃N₄ and nano-size sintering aids of 5 wt% Y₂O₃ and 2 wt% MgO prepared through a mechanical treatment. As a result of the SPS, Si₃N₄ ceramics with a higher density were obtained using the nanocomposite particles compared with a powder mixture prepared using conventional wet ball-milling. The shrinkage curve of the powder compact prepared using the mechanical treatment was also different from that prepared using the ball-milling, because the formation of the secondary phase identified by the X-ray diffraction (XRD) method and liquid phase was influenced by the presence of the sintering aids in the powder compact. Scanning electron microscopy (SEM) observations showed that elongated grain structure in the Si₃N₄ ceramics with the nanocomposite particles was more developed than that using the powder mixture and ball-milling because of the enhancement of the densification and α-β phase transformation. The fracture toughness was improved by the development of the microstructure using the nanocomposite particles as the raw material. Consequently, it was shown that the powder design of the Si₃N₄ and sintering aids is important to fabricate denser Si₃N₄ ceramics with better mechanical properties using SPS.     

Mo-8wt%Cu纳米复合粉末的制备和烧结

采用机械合金化法制备出Mo-8wt%Cu超细复合粉末,并对由该复合粉末所制得的压坯进行了液相烧结,利用SEM、XRD等分析手段对复合粉末的特性和烧结体的组织进行了表征和观察,实验结果表明,该方法制备的Mo-8wt%Cu超细复合粉末颗粒细小,平均粒径在300nm左右,高能球磨后的复合粉末由Mo-Cu过饱和固溶体相和Cu相组成,而且两相的晶粒度达到纳米级,其中Mo-Cu过饱和固溶体相的晶粒约为106nm,复合粉末具有很高的烧结特性,经高温烧结后合金致密度达到98.5%以上,而且金相组织分布均匀。     

Gas pressure sintering of silicon nitride — current status

Gas pressure sintering of silicon nitride is now common for obtaining a dense as well as tough product. A review of earlier works has revealed that there are still controversies in prediction of mechanism of the sintering process. Analysis of the kinetics of the process obtained by integration of a dilatometer inside the furnace has been presented. The mechanism of sintering silicon nitride powder compacts in presence of hyperbaric nitrogen atmosphere has been discussed. It has been observed that intermediate stage densification kinetics is very much susceptible to sintering atmosphere and time of pressurisation. The microstructure of the final product has been found to be dependent primarily on the method of incorporation of additive in the starting silicon nitride powders.     

Microstructure and mechanical properties of biocompatible high density Ti–6Al–4V/W produced by high frequency induction heating sintering

High frequency induction heating sintering method is used for sintering of the metal and ceramics powder. This technique has been used to produce high density compacts, containing as small grains as possible of powders. The alloy of Ti–6Al–4V was modified by addition of 2.5, 5, and 10 wt.% tungsten through powder metallurgy. Ti–6Al–4V/W was prepared by high-energy mechanical milling. The use of the high frequency induction heating sintering technique allows sintering to nearly full density at comparatively low temperatures and short holding times, and therefore suppressing grain growth. Different process parameters such as sintering temperature, and applied pressure have been investigated. The obtained compacts are characterized with respect to their densities, grain morphologies and pore distributions as well as hardness. Ti–6Al–4V/W powder precursors have been successfully compacted and consolidated to densities exceeding 98.8%. The maximum compressive strengths were obtained at sintering temperature 1000 °C for the samples containing 5% W, and at 1100 °C for the samples with 10% W. Maximum hardness was obtained 45 HRC at 1100 °C for 10% W.     

Microstructure and properties of spark plasma sintered AlN ceramics

Spark plasma sintering (SPS) is a newly developed technique that enables poorly sinterable aluminum nitride (AlN) powder to be fully densified. It is addressed that pure AlN sintered by SPS has relatively low thermal conductivity. In this work, SPS of AlN ceramic was carried out with Y₂O₃, Sm₂O₃ and Li₂O as sintering aids. Effects of additives on AlN densification, microstructure and properties were investigated. Addition of sintering aids accelerated the densification, lowered AlN sintering temperature and was advantageous to improve properties of AlN ceramic. Thermal conductivity and strength were found to be greatly improved with the present of Sm₂O₃ as sintering additive, with a thermal conductivity value about 131 Wm⁻¹K⁻¹ and bending strength about 330 MPa for the 2 wt% Sm₂O₃-doped AlN sample SPS at 1,780 °C for 5 min. XRD measurement revealed that additives had no obvious effect on the AlN lattice parameters. Observation by SEM showed that AlN ceramics prepared by SPS method manifested quite homogeneous microstructure. However, AlN grain sizes and shapes, location of secondary phases varied with the additives. The thermal conductivity of AlN ceramics was mainly affected by the additives through their effects on the growth of AlN grain and the location of liquid phases.     

Spark plasma sintering and thermoelectric evaluation of nanocrystalline magnesium silicide (Mg2Si)

Recently magnesium silicide (Mg₂Si) has received great interest from thermoelectric (TE) society because of its non-toxicity, environmental friendliness, comparatively high abundance, and low production material cost as compared to other TE systems. It also exhibited promising transport properties, including high electrical conductivity and low thermal conductivity, which improved the overall TE performance (ZT). In this work, Mg₂Si powder was obtained through high energy ball milling under inert atmosphere, starting from commercial magnesium silicide pieces (99.99 %, Alfa Aesar). To maintain fine microstructure of the powder, spark plasma sintering (SPS) process has been used for consolidation. The Mg₂Si powder was filled in a graphite die to perform SPS and the influence of process parameters as temperature, heating rate, holding time and applied pressure on the microstructure, and densification of compacts were studied in detail. The aim of this study is to optimize SPS consolidation parameters for Mg₂Si powder to achieve high density of compacts while maintaining the nanostructure. X-Ray diffraction (XRD) was utilized to investigate the crystalline phase of compacted samples and scanning and transmission electron microscopy (SEM & TEM) coupled with Energy-Dispersive X-ray Analysis (EDX) was used to evaluate the detailed microstructural and chemical composition, respectively. All sintered samples showed compaction density up to 98 %. Temperature dependent TE characteristics of SPS compacted Mg₂Si as thermal conductivity, electrical resistivity, and Seebeck coefficient were measured over the temperature range of RT 600 °C for samples processed at 750 °C, reaching a final ZT of 0.14 at 600 °C.     

Effect of Ni powder characteristics on the consolidation of ultrafine TiMoCN cermets by means of SPS and HIP technologies

Fully dense titanium carbonitride cermets have been consolidated from Ti(C,N)–Ni–Mo₂C–TiAl₃ powder mixtures either by spark plasma sintering or hot isostatic pressing techniques. Carbonyl Ni powders enhance the densification of the cermets produced by SPS (spark plasma sintering), a phenomenon likely related to a more efficient dissolution of Mo₂C additions and the possible precipitation of α″ phase. Both SPS and HIP (hot isostatic pressing) processes lead to materials with a bimodal Ti(C,N) grain size distribution containing a considerable fraction of nanometric grains. Unlike SPS, HIP induces significant graphite precipitation which could be explained by the destabilization of the carbonitride phase under high isostatic pressures at high temperature. Optimized compositions processed by SPS exhibit a combination of hardness and toughness close to the range covered by ultrafine WC–Co hardmetals of similar binder contents.     

Effect of temperature-related factors on densification,microstructure and mechanical properties of powder metallurgy TiAl-based alloys

In the present work, the influence of temperature-related factors, including sintering temperature, heating step and temperature-control mode, on the densification, microstructure and mechanical properties of Ti-46.5Al-2.15Cr-1.90Nb-(B, Y, Mo) alloys prepared by SPS has been investigated and discussed in detail. The results obviously indicate that the sintering temperature plays a key role on densification and phase transition, when compared with the heating step and temperature-control mode. Based on the experimental results and theoretical analysis, the densification process and microstructural evolution of TiAl-based alloys during sintering are studied. Moreover, the mechanical properties of the sintered alloys are determined by the combined effects of the densification and microstructure. The obtained results will help to optimize the microstructure and properties for this kind of intermetallic alloys through controlling sintering parameters during powder metallurgy process.     

Moving finite-element mesh model for aiding spark plasma sintering in current control mode of pure ultrafine WC powder

The intricate bulk and contact multiphysics of spark plasma sintering (SPS) together with the involved non-linear materials’ response make the process optimization very difficult both experimentally and computationally. The present work proposes an integrated experimental/numerical methodology, which simultaneously permits the developed SPS model to be reliably tested against experiments and to self-consistently estimate the overall set of unknown SPS contact resistances. Unique features of the proposed methodology are: (a) simulations and experiments are conducted in current control mode (SPS-CCm); (b) the SPS model couples electrothermal and displacement fields; (c) the contact multiphysics at the sliding punch/die interface is modeled during powder sintering using a moving mesh/moving boundary technique; (d) calibration and validation procedures employ both graphite compact and conductive WC powder samples. The unknown contact resistances are estimated iteratively by minimizing the deviation between predictions and on-line measurements (i.e., voltage, die surface temperature, and punch displacement) for three imposed currents (i.e., 1,900, 2,100, 2,700 A) and 20 MPa applied pressure. An excellent agreement is found between model predictions and measurements. The results show that the SPS bulk and contact multiphysics can be accurately reproduced during densification of ultrafine binderless WC powder. The results can be used to benchmark contact resistances in SPS systems applicable to graphite and conductive (WC) powder samples. The SPS bulk and contact multiphysics phenomena arising during sintering of ultrafine binderless WC powders are finally discussed. A direct correlation between sintering microstructure, sintering temperature, and heating rate is established. The developed self-consistent SPS model can be effective used as an aiding tool to design optimum SPS experiments, predict sintering microstructure, or benchmark SPS system hardware or performances.     

Preparation of nanostructured TiO2 ceramics by spark plasma sintering

The effect of spark plasma sintering (SPS) on the densification of TiO₂ ceramics was investigated using a nanocrystalline TiO₂ powder. A fully-dense TiO₂ specimen with an average grain size of ∼200 nm was obtained by SPS at 700 °C for 1 h. In contrast, a theoretical density specimen could only be obtained using conventional sintering above 900 °C for 1 h with an average grain size of 1-2 μm.     

Sintering mechanism of large-scale ultrafine-grained copper prepared by SPS method

Spark Plasma Sintering (SPS), as a novel sintering technique, is used for preparing large-scale ultrafine-grained copper. According to the evolution of the microstructure, the sintering process is divided into four stages: activation and refining of the powder, formation and growth of the sintering neck, rapid densification and plastic deformation densification. Only when the above mentioned sintering stages proceed in turn and are all fully completed, the high quality bulk compact can be obtained. For the fine copper powder, the optimized sintering parameters are selected as follows: sintering temperature of 750 °C, initial pressure of 1 MPa, holding pressure of 50 MPa, heating rate of 80 °C/min, and holding time of 6 min. Both the tensile strength and the elongation of the ultrafine-grained copper are all improved due to the fine crystal and the submicron twins.     

Effect of preliminary high-energy ball milling on the structural-phase state and microhardness of Ni3Al samples obtained by spark plasma sintering

The study of the influence of the duration of preliminary high-energy ball milling on the features of the structural-phase state and the level of microhardness of consolidated Ni₃Al samples obtained by the method of spark plasma sintering has been carried out. It was found that the inhomogeneous state of the precursor from the 3Ni-Al powder mixture in the case of preliminary ball milling of a short duration (1 min) is a cause of the formation of an inhomogeneous structural-phase state of the consolidated Ni₃Al sample. An increase in the duration of high-energy ball milling provides a homogeneous phase composition, promotes the refinement of the grain structure and an increase in the microhardness values of the obtained Ni₃Al samples. The main factors determining the processes of structural-phase transformation during the formation of Ni₃Al under the conditions of spark plasma sintering, depending on the preliminary high-energy ball milling, are revealed. It is shown that grain boundary strengthening is the one of the effective mechanisms for increasing the strength of the material under study.     

Rapid densification and reaction sequences in self-reinforced Y-α-SiAlON ceramics with barium aluminosilicate as an additive

Y-α-SiAlON (Y_1/3Si₁₀Al₂ON₁₅) ceramics with 5 wt.%BaAl₂Si₂O₈ (BAS) as an additive were synthesized by spark plasma sintering (SPS). The kinetic of densification, phase transformation sequences and grain growth during sintering process were investigated. Full densification could be achieved by 1600 °C without holding and using a heating rate of 100 °C min⁻¹, but the transformation from α-Si₃N₄ to α-SiAlON is not completed simultaneously with the densification process. The equilibrium phase assemblage could be reached after SPS at 1800 °C for 5 min and the resultant material possesses self-reinforced microstructure with high hardness of 19.2 GPa and fracture toughness of 6.8 MPa m^1/2. The complete crystallization of BAS is beneficial to the high temperature mechanical properties. The obtained could maintain the room strength up to 1300 °C.     

放电等离子烧结Ti-Al系金属间化合物

用机械合金化法(MA)制备了Ti-45% Al纳米晶合金粉末,并对其进行放电等离子烧结(SPS),烧结时间仅为5min.用D-maxIIA型X射线衍射仪、JEM-2000EX型透射电子显微镜对粉末和烧结块体的微观组织及机械性能进行了研究.研究表明:Ti和Al的粉末随着球磨时间的延长,粉末有明显的细化趋势,球磨5h即有非晶产生,球磨20h后得到接近完全非晶相;采用SPS烧结技术,在1200℃下能够制备出较高硬度的TiAl金属间化合物块体材料.     

Densification mechanisms of spark plasma sintering: multi-step pressure dilatometry

The effects of electrical current and mechanical pressure on the densification of spherical copper powder during spark plasma sintering (SPS) are examined. A novel multi-step pressure dilatometry method is introduced to compare the constitutive behavior of the copper powder under nearly equivalent current-insulated and current-assisted SPS process conditions. The strain rate sensitivity agrees with that predicted for a dislocation climb-controlled creep densification mechanism for both processing setups. Accelerated densification rate leading to a higher final relative density is observed for the current-assisted SPS.