脉冲电流烧结机理的研究进展

脉冲电流烧结（Ｐｕｌｓｅ ｅｌｅｃｔｒｉｃ ｃｕｒｒｅｎｔ ｓｉｎｔｅｒｉｎｇ,ＰＥＣＳ）是材料科学领域开发出的一种新型快速烧结技术,已广泛应用于金属与合金、结构陶瓷、氧化物超导体、复合材料、热电材料、高分子材料以及功能梯度材料的制备．本文简介脉冲电流烧结特征,结合ＰＥＣＳ烧结条件对铜粉末和氧化铝粉体致密化及显微结构影响的实验证据,就脉冲电流烧结过程和机理进行探讨．     

Densification of pure magnesium by spark plasma sintering-discussion of sintering mechanism

In this study, high-quantity pure magnesium was prepared by SPS, and the sintering densification mechanism was discussed by using numerical simulation and simultaneous experiment. Results show that a layer of dense magnesium oxide was formed at the surface of Mg particles, and the oxide reduction can be observed owing to the effect of oxide film removal in SPS. The high energy pulsed current flows preferentially through particle contact surfaces, which provides the conditions for the generation of micro-arc between particles and the temperature at the particles contact point can be up to 1979 °C. With the low pressure at the initial sintering stage, local high temperature induced by micro-arc makes the melting (even evaporation) appearance. At the same sintering temperature of 570 °C, the obvious difference in bending strength also demonstrates the significance of spark discharge in SPS. The formation process of sintering neck demonstrates that sintering process is the reflection of melting (even evaporation), diffusion and plastic deformation. In order to realize tiny area and high-quality connection between powder particles, an innovative powder sintering technology using high-frequency pulse electric current (High frequency pulse current assisted sintering) is proposed based on the enlightenment of the skin, proximity and arc discharge effect of high-frequency pulse current. This technology is also instructive for other alloys and engineering materials.     

脉冲电流烧结AlOOH的非均匀性

采用相变方法系统研究了脉冲电流烧结AlOOH样品不同截面处相的状态.结果发现（1）样品上表面与下表面具有不同的相,表明样品中温度由高至低逐渐变化,（2）样品上表面较次上表面衍射峰弱.通过微波等离子轰击及热压烧结的实验模拟,发现样品上表面的XRD图与微波等离子轰击同样样品产生的XRD图极为相似.说明上表面的衍射峰与被离子轰击产生晶格缺陷有关.对形成这种上下表面结构不均匀性的原因进行了分析,并给子适当解释.     

Fabrication of Iron-base Alloy by Spark Plasma Sintering

Fe-2Cu-2Ni-lMo-0.8C (wt pct) elemental mixed powders were rapidly sintered within 6 min by spark plasma sintering, and the effects of sintering parameters on the densification degree and performance of the assintered materials were investigated. Results showed that when a proper combination of pulse electric current and constant electric current was employed for sintering, the density and bend strength of the as-sintered material reached the maxima, being 7.61×103 kg/m3 and 1540 MPa, respectively. Its corresponding fracture morphology was characterized as the mix of ductile, intergranular and cleavage fractures.     

用放电等离子技术烧结TiB2陶瓷

利用脉冲大电流快速烧结技术（也称放电等离子烧结SPS技术）研究了TiB2的烧结过程。结果表明：升温速率对烧结样品的相对密度、晶粒尺寸及烧结过程中真空室气压均有重要影响。最佳的升温速率使TiB2烧结晶粒相对最小、烧结体相对密度较高。分析认为，在SPS条件下的快速升温有利于颗粒表面活化，烧结体晶粒尺寸既受控于烧结时间，也受控于晶粒生长活化能。     

闪烧合成高熵氧化物陶瓷(MgCoNiCuZn)O的性能

闪烧技术是一种温度场与电场耦合的烧结技术,具有低温快速传质的特性,在高熵陶瓷的合成上具有显著的优势。本研究通过闪烧法合成了相对致密的高熵氧化物陶瓷(MgCoNiCuZn)O,并与传统烧结试样的性能进行了对比。在室温,电场强度为50 V/cm,电流密度为300 mA/mm²条件下闪烧,物相转变的时间仅为10 s。闪烧试样最高相对密度为94%,比传统烧结试样最高密度提高了22.8%。闪烧试样的最高硬度5.05GPa,比传统烧结试样高3.95 GPa。当频率<2Hz时,闪烧试样的介电常数比传统烧结试样高一个数量级。闪烧试样性能的提高,一方面与临界电场加速传质,提高材料致密度有关;另一方面与临界电场引入额外的缺陷有关。     

Heterogeneity of grain refinement and texture formation during pulsed electric current sintering of conductive powder: A case study in copper powder

The heterogeneity of grain refinement and texture formation in conductive copper powder during pulsed electric current sintering have been investigated by means of microstructural analysis of the particle-contacting zone of the samples sintered with micron-sized powders. The particle-contacting region was indicated to experience a higher level of grain refinement than the particle center due to the inhomogeneous temperature distribution among the particle when pulsed electric current passed through. Meanwhile, two main textures of Cube (1?0?0)[0?0?1] texture and Goss (1?1?0)[0?0?1] texture were directly detected in the sintered Cu samples by a combination of electron backscatter diffraction and X-ray diffraction. Based on the experimental results, a feasible mechanism for the formation of texture during the pulsed electric current sintering has been proposed by considering the applied uniaxial pressure and pulsed electric current as well as the rearrangement of grains. In addition, the effects of heterogeneous grain refinement and texture formation on the tensile properties of the sintered Cu samples were also discussed based on the tensile properties and fractographic. These results would contribute to the basic understanding of the sintering mechanisms in pulsed electric current sintering process.     

Pulse electric current sintering of hydroxyapatite/β-tricalcium phosphate composites

Hydroxyapatite (HA)/β-tricalcium phosphate (β-TCP) composites attract attentions as bone implant materials. As one of the fabrication method of HA/β-TCP is mixing of HA and β-TCP powder in advance of sintering. This method enables to control the ratio of content of β-TCP easier. However, it is difficult to obtain dense composites. In this study, we focused on pulse electric current sintering (PECS) to obtain dense HA/β-TCP composites. The sinterability is evaluated with relative density and grain size measurements. Composition of sintered body was also characterized by X-ray diffraction. In comparison with pressureless sintering, PECS increased relative density of the composites without grain growth. In HA/β-TCP sintered by PECS, the phase transformation from β-TCP to α-TCP was promoted. This is due to higher thermal energy by spark discharge during PECS. On the other hand, sintering additives (MgO) inhibited phase transformation. It was suggested that sinterability of HA/β-TCP composites was improved by PECS.     

Thermo-mechanical stability of porous alumina: effect of sintering parameters

Recently, we proposed a two-step heating schedule involving pulse electric current sintering (PECS), a kind of pressure assisted vacuum sintering, and subsequent post-heat treatment in air to fabricate porous alumina support, using commercially available alumina and carbon powders [J. Mater. Res. 18 (2003) 751]. During pressure assisted vacuum sintering, Al₂O₃–C system of low porosity was obtained and in second stage, i.e. during post-heat treatment in air, carbon particles present in the Al₂O₃–C system burnt out to form highly porous Al₂O₃ support. Following our previous brief study, the effects of sintering parameters such as temperature, pressure, and heating rate on the properties of the porous alumina were investigated. The porosity varied between 28 and 38% depending on the sintering parameters. As desired, the pore size distribution did not change with post-heat treatment temperature and hence the mechanical properties as well. It was concurred from this present study that the sintering parameters of PECS greatly influenced pore characteristics and other properties of porous compacts. We admit that the initial composition ratio of powder mixture (Al₂O₃:C) also plays important role on properties such as porosity, pore size, etc. which is beyond the scope of this present study.     

Temperature gradient and microstructure evolution in AC flash sintering of 3 mol% yttria-stabilized zirconia

Systematic statistical analysis of the microstructural changes in 3?mol% yttria-stabilized zirconia was performed after flash sintering by alternating current (AC). The micrographs in the gauge section of the specimen were identical to those from DC flash sintered samples while no evident electrode effect was present for AC flash sintered samples. However, finite element modeling revealed a temperature gradient from the surface to the volume of the sintered body. Microstructure gradients, across the width of gauge section, were revealed for the AC flash sintered sample. Classical grain growth models due to Joule heating were insufficient in justifying the microstructural evolution under the simulated temperature distribution. Bimodal grain diameter distributions in flash sintered samples were observed. Therefore, it is proposed that faster grain growth mechanisms activated on a fraction of the grains by electric field/current occurred during flash sintering, and is responsible for the instantaneous grain growth.     

Fabrication of Ni-P alloy closed cellular solid containing polymer by the pulse current hot pressing technique

Phenol resin sphere particles covered with nickel-phosphorus alloy were used for fabricating a metallic cellular solid with a fine structure by using the pulse current hot pressing (PCHP), which is also called spark-plasma-sintering (SPS) technique. During the sintering process, strong electric current pulses were applied on the particles in a die. The particles in the die were sintered in a shorter time and at lower temperature than that of normal sintering methods. The polymer materials inside the cells seem to remain partly after the sintering process. The mechanical properties of the cellular materials containing phenol resins were measured. The influence of the PCHP process on the mechanical properties of the specimens was examined.     

氧化物陶瓷闪烧机理及其应用研究进展

闪烧是近些年广受关注的一种电场辅助烧结技术。本文介绍了闪烧的起源与发展, 并对闪烧的基本特征进行了分析。在闪烧孕育与引发过程的研究方面, 发现了孕育阶段的非线性电导特征和电化学黑化现象, 提出了氧空位主导的缺陷机制; 在闪烧阶段的快速致密化研究方面, 提出了电场作用导致的缺陷产生和运动会在粉体颗粒间产生库仑力, 有利于烧结前期的致密化过程, 同时发现闪烧致密化过程中还伴随着金属阳离子的快速运动; 在闪烧阶段的晶粒生长和微结构演变方面, 发现了试样温度沿电流方向呈非对称分布, 试样中间位置的晶界迁移率明显提高, 提出电化学缺陷对微观结构有重大影响。基于上述研究成果, 本团队利用电场作用下出现的低温快速传质现象, 发展了陶瓷闪焊技术, 实现了同种陶瓷/陶瓷、陶瓷/金属, 甚至异种陶瓷/陶瓷之间的快速连接; 发展了陶瓷闪烧合成技术, 不仅实现了典型氧化物陶瓷的快速合成, 而且实现了高熵陶瓷和具有共晶形貌的氧化物陶瓷的快速合成; 发展了氧化物陶瓷的电塑性成形技术, 初步实现了氧化锆陶瓷低温低应力下的快速拉伸和弯曲变形。本文最后总结了闪烧机理研究面临的挑战, 并从焦耳热效应和非焦耳热效应两方面展望了闪烧的发展方向, 期望对闪烧技术在国内的发展有所裨益。     

高体积分数的 SiCp/Al复合材料的 SPS致密化机理研究

运用放电等离子烧结（SPS）技术制备出体积分数达60％，致密度达99％的SiCp／Al复合材料．从烧结工艺的控制及电场的影响两方面对SPS烧结SiC，／Al复合材料的机理进行了研究，认为SPS烧结SiCp／Al复合材料的致密化过程主要依靠烧结温度、压力及升温速率的合理搭配，使Al熔融粘结SiC颗粒，而又不溢出模具；烧结过程中未发现明显的放电现象，可能由于电场太弱不足以引发放电．     

脉冲电流辅助烧结和真空热压烧结对NiAl-Al_2O_3微观组织和力学性能的影响

通过机械合金化合成了NiAl-Al2O3复合材料粉末,并分别采用脉冲电流辅助烧结(PCAS)和真空热压烧结(HPS)制备了NiAl-Al2O3复合材料。测试了两组材料的力学性能,并从烧结机理的角度分析了烧结方法对材料微观组织和力学性能的影响。结果表明:与HPS方法相比,通过PCAS方法制备的材料致密度更高,晶粒更为细小,且Al2O3颗粒明显球化。相较于HPS方法制备的材料,PCAS方法制备的材料在室温下和高温下都表现出更高的屈服强度,并且其断裂韧性增高,室温压缩变形量明显增大。     

脉冲电流对45钢损伤的恢复作用

研究了脉冲电流对４５钢淬火裂纹的修复作用。结果表明,脉冲电流显著提高有裂纹的马氏体材料的强度和塑性,但硬度降低不多,脉冲电流处理后,裂纹周围的组织发生了显著变化。对裂纹钝化有利,探讨了裂纹在脉冲电流作用下的愈合效应,说明电流,热效应及热压应力可能是诱发该效应的主要因素。     

A methodology to investigate the intrinsic effect of the pulsed electric current during the spark plasma sintering of electrically conductive powders

Abstract

A novel methodology is proposed for investigating the effect of the pulsed electric current during the spark plasma sintering (SPS) of electrically conductive powders without potential misinterpretation of experimental results. First, ensemble configurations (geometry, size and material of the powder sample, die, plunger and spacers) are identified where the electric current is forced to flow only through either the sample or the die, so that the sample is heated either through the Joule effect or by thermal conduction, respectively. These ensemble configurations are selected using a recently proposed mathematical model of an SPS apparatus, which, once suitably modified, makes it possible to carry out detailed electrical and thermal analysis. Next, SPS experiments are conducted using the ensemble configurations theoretically identified. Using aluminum powders as a case study, we find that the temporal profiles of sample shrinkage, which indicate densification behavior, as well as the final density of the sample are clearly different when the electric current flows only through the sample or through the die containing it, whereas the temperature cycle and mechanical load are the same in both cases.     

La2NiMnO6双钙钛矿陶瓷的等离子活化烧结

针对常压烧结La₂NiMnO₆ (简称LNMO)双钙钛矿陶瓷存在的烧结温度高、致密度低、工艺周期长等问题, 采用等离子活化烧结技术(Plasma Activated Sintering, 简称PAS)制备LNMO陶瓷, 主要研究了烧结工艺(温度、压力) 对其物相结构、显微形貌、致密度和介电性能的影响, 以期得到物相单一、结构致密、性能良好的LNMO双钙钛矿陶瓷。利用X射线衍射仪、阿基米德排水法、扫描电子显微镜、阻抗分析仪等手段, 系统测试表征了LNMO陶瓷的结构与性能。结果表明: 升高烧结温度有利于改善LNMO陶瓷的结晶性并增大晶粒尺寸, 但过高温度会导致杂相生成; 增大烧结压力对物相无明显影响, 但在一定程度上提升了致密度。确定了较适宜的PAS条件为: 烧结温度975~1000 ℃、烧结压力80 MPa, 在此条件下烧结得到的LNMO陶瓷为单一的正交结构, 致密度为92%, 具有较大的介电常数(~10 ⁶)。与常压烧结相比, 等离子活化技术集等离子体活化、压力、电阻加热为一体, 可在更低温度(降低400~500 ℃)和更短时间(缩短2~20 h)内获得较为致密的LNMO陶瓷。     

The effect of electric field and pressure on the synthesis and consolidation of materials: A review of the spark plasma sintering method

The use of electric current to activate the consolidation and reaction-sintering of materials is reviewed with special emphasis of the spark plasma sintering method. The method has been used extensively over the past decade with results showing clear benefits over conventional methods. The review critically examines the important features of this method and their individual roles in the observed enhancement of the consolidation process and the properties of the resulting materials.     

A Quantitative Study on Temperature Dependent of Outgrowth in Bi-2223 Tapes

Outgrowths of Bi-system superconducting multifilament tapes were known as an imperfect that could increase ac-current loss. To approach this problem sintering temperature dependent of outgrowth was studied and experimental results were reported in this text. Tapes in the experiments were sheathed with pure silver and silver alloys and carefully treated. Critical current I _c of the sintered tapes was measured at 77 K. Compound phases in tapes were determined by analysis of X-ray powder diffraction. Outgrowths of the tapes were observed and studied by Scanning Electron Microscope. Experimental results showed that outgrowths changed when sintering temperatures increased. It was found that the best sintering temperature for Ag sheathed tape was 840°C, and that for Ag/Mg and Ag/Sb sheathed tapes was lower than 835°C.