Electric field effects during spark plasma sintering of ceramic nanoparticles

The effects of the applied electric field during the spark plasma sintering of ceramic nanoparticles were examined at various stages of the process. It was assumed that local intensification of the electric field arises due to the nanoscale structural features. Enhanced surface conductivity is expected in the nanoparticles during the heating, which otherwise are electrically non-conducting as a bulk. Percolation of the electric current at “optimal” electrical conductivity is obtained by fractal dimension. The defective nanoparticle surfaces experience charging–discharge cycles which lead to local breakdown and to plasma formation due to the ionized surface molecules. High local temperatures which evolved in a nonlinear fashion at the particle surfaces lead to enhanced sintering and densification kinetics, consistent with the flash sintering phenomenon. The contribution of the pondermotive force to the enhancement of the diffusion kinetics is discussed. Temperature windows for enhanced densification kinetics via plastic deformation or plasma-assisted processes are estimated for MgO, Al₂O₃, and YAG.     

Transparent polycrystalline ruby ceramic by spark plasma sintering

Fine-grained and transparent polycrystalline ruby ceramics (Cr₂O₃-doped Al₂O₃) were successfully prepared by spark plasma sintering (SPS). The effect of Cr₂O₃ concentration on the grain size, hardness, fracture toughness and thermal conductivity of ruby ceramics was investigated systematically. For 0.05 wt.% Cr₂O₃, high in-line transmittance of 85% at 2000 nm can be reached, further increase of Cr₂O₃ concentration leads to the decrease in transmittance. High hardness of 23.95-25.05 GPa can be achieved due to the fine grain size in all ruby ceramics. The fracture toughness of 1.9-2.29 MPa m^1/2 indicates that no improvement in fracture toughness over pure Al₂O₃ can be obtained by Cr₂O₃ doping in these submicron grained ruby ceramics. High thermal conductivity of 28-29.8 W/(m K) at room temperature, close to that of single crystal sapphire, can be achieved. The change in grain size for different Cr₂O₃ concentrations is the major reason for the change in mechanical and thermal properties, but not for the change in optical properties.     

Grain growth during spark plasma and flash sintering of ceramic nanoparticles: a review

Spark plasma and flash sintering process characteristics together with their corresponding sintering and densification mechanisms and field effects were briefly reviewed. The enhanced and inhibited grain growth obtained using these field-assisted densification techniques were reported for different ceramic nanoparticle systems and related to their respective densification mechanisms. When the densification is aided by plastic deformation, the kinetics of grain growth depends on the particles’ rotation/sliding rate and is controlled by lattice and pipe diffusion. When the densification is aided by spark, plasma, and the particles’ surface softening, grain growth kinetics is controlled by viscous diffusion and interface reactions. Grain growth in both cases is hierarchical by grain rotation, grain cluster formation and sliding, as long as the plastic deformation proceeds or as long as plasma exists. Densification by diffusion in a solid state via defects leads to normal grain growth, which takes over at the final stage of sintering. Various field effects, as well as the effect of external pressure on the grain growth behaviour were also addressed.     

Temperature and stress fields evolution during spark plasma sintering processes

Numerical modelling of Spark Plasma Sintering (SPS) processes is essential to evaluate temperature and stress distributions that can result in sample inhomogeneities. Most of the available literature, however, produced analysis in static conditions. In this work, we focused our attention on the time evolution of current density, temperature and stress distribution during a SPS process using a new approach that includes a PID control in the algorithm, allowing a realistic simulation of experiments performed using a temperature controller. Controlled temperature experiments have been simulated and discussed, with special interest focused on the time evolution of the process. The results showed that stress gradients inside the samples (~40%) are much greater than the temperature gradients (~2%), suggesting that heterogeneities in the microstructure can also be caused by the stress gradient. During the evolution of the process, a peak in stresses is experienced by the alumina sample at the beginning of the cooling stage, caused by differences in contraction between the sample and the die. It has been proved that, using a controlled cooling stage, these peaks in the stresses can be easily eliminated.     

Tough yttria-stabilized zirconia ceramic by low-temperature spark plasma sintering of long-term stored nanopowders

Weakly agglomerated 1.75 and 3 mol% yttria stabilized zirconia nanopowders were used in this study after six years of storage in vacuum-processed plastic containers. The proper storage conditions of the Y-TZP nanopowders avoided the hard agglomeration. Untreated and bead-milled nanopowders were used to obtain dense ceramics by slip casting and subsequent low-temperature sintering. Fully dense nanostructured 1.75Y-TZP and 3Y-YZP ceramics with and without doping of 1 wt% Al2O3 were produced by an optimized spark plasma sintering (SPS) technique at the temperatures of 1050-1150 degrees C at a pressure of 100 MPa. The SPS has revealed the clear advantage of consolidation of the weakly agglomerated nanopowders without preliminary deagglomeration. The Vickers hardness of both the low-temperature and spark plasma sintered samples was found to lie in the range of 10.98-13.71 GPa. A maximum fracture toughness of 15.7 MPa m(1/2) (average 14.23 MPa m(1/2)) was achieved by SPS of the 1.75Y-TZP ceramic doped with 1 wt% Al2O3 whereas the toughness of the 3Y-TZP ceramics with and without alumina doping was found to vary between 3.55 and 5.5 MPa m(1/2).     

SPS制备AlN/BN复相陶瓷及其性能优化

采用放电等离子烧结技术(SPS),在1750～1850℃烧结制备出兼顾高热导率和优良可加工性能的AlN/BN复相陶瓷.结果表明,通过调节添加剂Y2O3的加入量,能够显著抑制BN对材料热传导性能的劣化作用,BN含量为25%(体积分数)时,热导率仍能达到120W/(m·K),与AlN单相陶瓷相比仅下降18.9%.在SPS制备条件下,添加不同量的Y2O3导致不同组成的Al-Y-O晶界相,随着Y2O3的增加,晶界相在烧结过程中大量挥发,致使Al-Y-O残留量减少,优化了材料的显微组织,有效地提高热传导性能.     

放电等离子烧结技术的原理及应用

放电等离子烧结(SPS)是一种用于材料烧结致密化的新技术,为深入研究和探讨其技术优势,介绍了SPS的基本原理和系统的组成,讨论了SPS技术在纳米材料的制备、梯度功能材料的烧结和高致密度、细晶粒陶瓷制备等方面的应用,并对其研究和应用前景予以展望。     

Low-temperature spark plasma sintering of NiO nanoparticles

NiO nanoparticles of 20 nm in diameter were spark plasma sintered between 400 °C and 600 °C for 5 and 10 min durations. Application of 100 MPa pressure from room temperature resulted in densities between 75% and 92%. The final grain size was between 26 nm and 68 nm. Lower densities were recorded when 100 MPa was applied at the SPS temperature. Two shrinkage rate maxima of ∼3.4 × 10⁻³ s⁻¹ and ∼2 × 10⁻³ s⁻¹ were observed around 390 ± 10 °C and at the SPS temperature. The two shrinkage rate maxima were related to densification by particle sliding followed by diffusional grain boundary sliding during the heating. The strong effects of the surface and interfacial processes which are active during the SPS were highlighted.     

Comparisons of grain size-density trajectory during spark plasma sintering and hot-pressing of zirconia

Spark plasma sintering (SPS) and hot-pressing (HP) of a granulated stabilized zirconia powder have been investigated for a fixed macroscopic compaction pressure of 100 MPa and a fixed heating rate (25 °C/min for HP, 50 °C/min for SPS). The “relative density/grain size” trajectories have been established for both sintering methods.HP is shown to be similar to SPS for the manufacturing of polycrystalline TZ3Y materials with a final grain size well below the micrometer. Independently of the sintering technology employed, it is interesting to note that three kinds of microstructures are obtained depending on the experimental parameters: porous materials (opened porosity, relative density between 61 and 90%) with a nanometer grain size (around 75-80 nm), dense materials (closed porosity, relative density between 90 and 98%) with a nanometer grain size (around 75-80 nm), fully dense material with a submicron grain size (around 160 nm using SPS and around 105 nm using HP).     

Pore evolution model of ceramic membrane during constrained sintering

Pore size has been found to strongly depend on the sintering program in the preparation of porous ceramic membranes. In this paper, a model was developed to predict the variation in pore size and porosity of membranes during the sintering process. A comparison of shrinkage characteristics was made between the sintering processes of supported membranes and unsupported membranes. For supported membranes, the effect of restriction coming from a rigid substrate on the sintering behavior has been taken into account in the calculation. It is predicted that the pore size increases in supported membranes and decreases in unsupported membranes as the sintering temperature is increased. Calculations also showed that the loss of porosity in the supported membranes was less than that in the unsupported membranes. In order to verify reliability of this model, unsupported and supported membranes were prepared with α-Al₂O₃ powders at the sintering temperatures ranging from 1125 °C to 1325 °C. The pore size and porosity were measured by gas permeation technique and Archimedes’s method. The experimental results for the unsupported and supported α-Al₂O₃ membranes showed a good agreement with those calculated from the model. Therefore, this model provides an effective tool in predicting the porosity and the pore size of ceramic membranes at the different sintering temperatures.     

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.     

放电等离子烧结(SPS)YAG陶瓷的初步研究

研究了采用放电等离子烧结(Spark Plasma Sintering SPS),利用高纯的氧化钇和氧化铝,在1500～1700℃,真空度优于10Pa,反应快速合成YAG陶瓷,但试样的致密度不高,而低气孔率是制备透明陶瓷的关键,实验表明,TEOS的掺加和粉料粒度的减小对烧结试样致密度的提高有一定的作用.     

Effect of particle size on densification of pure magnesium during spark plasma sintering

The effect of particles size ranges (<38 μm, 75–150 μm, 270–550 μm) of atomized magnesium powders on densification mechanisms during spark plasma sintering (SPS) process was investigated. The intrinsic driving force, local pressure and current of Mg powders with different particle sizes were analyzed by theoretical calculation. The results obviously indicate that the densification of pure magnesium can be improved by the reduction of particle size, suggesting the intrinsic driving force, local pressure and current intensity are enhanced significantly by a decrease in the particle size at the same sintering conditions, which can promote shrinkage of pores, formation of the sintering neck and mass transportation in the SPS process. Not only that, rapid densification is also interpreted in term of mechanical movement of particles, Joule heating effect and plastic deformation. However, the mechanical movement of the large particles is higher than that of small particles due to high punch displacement, and plastic deformation, detected by scanning electron microscopy, plays a main role in densification for large particles in the case during the sintering. Joule heating effect is the key factor for densification of small Mg particles, and high densification degree can be obtained by sintering small particles.     

复相铁氧体材料的的放电等离子体烧结合成

采用化学共沉淀法制备了名义组成为xFe+BaFe12O19(0≤x≤1,△x=0.2)的共沉淀前驱体,研究了该前驱体在放电等离子体烧结条件下形成复相铁氧体材料的结晶行为和烧结体的磁性能.结果表明,所有烧结体中均没有Fe2O3中间相形成,x=0时烧结体为单相M型钡铁氧体(BaM),0相似文献   

Pressure-less spark plasma sintering effect on non-conventional necking process during the initial stage of sintering of copper and alumina

In the present study, we focus on the characterization of the necking mechanisms during the early stages of pressure-less spark plasma sintering (PL-SPS) compared to conventional sintering (CS) of two different types of powdered materials (Cu and α-Al₂O₃). SEM observations of the evolution of particle morphology and necks from the as-received powders to sintered ones show the nature of the neck between particles which were either in contact or not. For alumina, no particular necking process (melt or viscous bridge) was observed regardless of the sintering conditions (PL-SPS and CS), even for a very high heating rate 455 °C/min. For copper, this neck morphology is unequivocally not typical of conventional ones, thus, suggesting mass transport by an ejection mechanism. This particular morphology was seen occasionally. In comparison, the conventionally sintered Cu particles presented a smoother surface, with conventional curved necks suggesting the contribution of surface diffusion mechanisms. Based on partial pressure calculations, a direct thermal effect might not explain the observed non-conventional neck for copper. On the other hand, local field enhancement effect and local favourable thermal breakdown voltage conditions are described and discussed in order to support the experimental results.     

Optimization of spark plasma sintering parameters for NiTiCu shape memory alloys

Nanostructured nickel titanium copper-shape memory alloys (NiTiCu-SMAs) were fabricated using spark plasma sintering (SPS) by varying the significant process parameters. The NiTiCu elements with different particle size were consolidated in a temperature range of 700–900°C and pressure from 20 to 40 MPa with 5 min of soaking time. The sintered products were subjected to mechanical analysis such as density and microhardness. Genetic algorithm (GA) and particle swarm optimization (PSO) techniques were used with integrated artificial neural network (ANN) to optimize the SPS process parameters to obtain better mechanical characteristics. The results indicate that the density and microhardness can be enhanced by the reduction of particle size and increase in pressure and temperature. A maximum density of 6.21 g/cc and Vickers hardness of 766 Hv were obtained the optimal for process parameters of temperature, pressure, and particle size of ~ 800°C, ~ 26 MPa and ~ 6 µm, respectively, in case of NiTiCu nanostructured SMAs.     

Mechanochemical synthesis and spark plasma sintering of hafnium carbonitride ceramics

Submicron powder of non-stoichiometric hafnium carbonitrides (HC_0.5N_0.2) was fabricated by the mechanochemical synthesis method. It was shown that during the first milling stages, primarily reaction between hafnium and carbon took place. The nitridation occurred later when fresh metal surfaces started to form through defragmentation of the brittle layer of a carbon-solid solution. The synthesized powder was consolidated by spark plasma sintering approach to producing dense bulk hafnium carbonitride ceramics. Hardness and fracture toughness measured on consolidated samples were 20.8 ± 1 GPa и 3.5 ± 0.2 MPa?m^1/2, respectively. The obtained results were compared with previously reported data.     

Mechanical alloying and spark plasma sintering of CoCrFeNiMnAl high-entropy alloy

An equiatomic CoCrFeNiMnAl high-entropy alloy was synthesized by mechanical alloying, and alloying behaviors, microstructure and annealing behaviors were investigated. It was found that a solid solution with refined microstructure of 20 nm in grain size could be obtained after 30 h milling. As-milled powder transformed into a face-centered cubic phase above 500 °C. The as-milled powder was subsequently consolidated by spark plasma sintering at 800 °C, BCC phase and FCC phase coexisted in the consolidated HEA, which had excellent properties in Vickers hardness of 662 HV and compressive strength of 2142 MPa.