陶瓷材料闪烧制备技术研究进展

陶瓷材料制备过程中,常规烧结需要很高的烧结温度以及较长的保温时间,实现材料致密化不仅能量消耗较大,效率低下,且长时间高温烧结也会带来晶粒长大问题,影响材料性能。近年来,一种名为"闪烧"的新型烧结技术被广泛报道,该技术不仅烧结温度低,保温时间短,且制备的陶瓷材料具有更加优异的微观形貌,引起了学术界的普遍关注。本文归纳了闪烧技术的研究进展,分别对闪烧技术的实验装置、技术参数、制备材料种类以及闪烧技术目前提出的机理进行介绍,分析了闪烧技术当前存在的问题并展望其前景,以期为继续发掘闪烧技术优势、扩展闪烧技术应用领域提供参考。     

氧化铝陶瓷闪烧工艺的研究进展

氧化铝陶瓷具有硬度高、耐磨性能好、耐高温和优良的化学稳定性等特质特性。烧结是实现氧化铝陶瓷上述应用和特质特性的关键技术,常压烧结是氧化铝陶瓷的传统烧结工艺,但其缺点也越来越明显,如烧结温度高、烧结时间长、致密度低、晶粒异向生长或异常长大、显微组织粗化和力学性能降低等,严重阻碍了其进一步的发展。因此,从材料性能、环境及经济等方面考虑,降低氧化铝陶瓷烧结温度、缩短烧结时间、提高致密性、保持或提高性能成为亟须解决的课题。近年来,相继提出了热压烧结、热等静压烧结、微波烧结、微波等离子烧结、放电等离子烧结和闪烧等烧结工艺来解决上述问题。其中闪烧工艺具有烧结温度低、烧结时间短、晶粒细小甚至纳米化的微观组织等优势,是一种使氧化铝陶瓷致密化的非常有前途的烧结工艺。因此,闪烧工艺有望解决氧化铝陶瓷材料传统烧结工艺中存在的问题。本文综述了氧化铝陶瓷闪烧工艺自2010年报道以来的相关实验和理论研究进展,包括闪烧工艺的原理、实验平台的搭建、工艺参数对氧化铝陶瓷显微结构和性能的影响。阐述了闪烧工艺的烧结机理,当前存在的主要难点和挑战,并对闪烧工艺前景进行了展望。     

加压辅助闪烧工艺制备四方相氧化锆

研究了加压辅助闪烧烧结工艺参数(温度、电压、电流、压力)对钇稳氧化锆致密度、微观组织结构和成分组成的影响,该工艺在热压烧结基础上叠加闪烧效应,利用高电场强度使高温导电氧化锆瞬间发生密实化烧结。结果表明:钇稳氧化锆的闪烧临界温度为880℃,在相同的电场强度条件下,闪烧临界温度处烧结可获得最大的闪烧收缩量。氧化锆在临界烧结温度下瞬时放电快速烧结符合焦耳热效应和接触点局部热效应,临界闪烧温度的高峰值功率闪烧易导致样品的组织结构和成分变化,峰值功率应进行控制,即电流强度应低于3 A。     

四方相氧化锆分步加压辅助闪烧烧结制备及性能

开发了一种四方相氧化锆陶瓷材料的二次分步加压辅助闪烧烧结工艺,该工艺对加压辅助闪烧工艺进行了优化,消除了临界闪烧温度下高功率闪烧导致的微观组织结构劣化现象。结果表明:多次分步加压辅助闪烧工艺保留了闪烧方法低温、瞬时烧结的优点,规避了复杂生坯压制工序和贵金属电极高昂成本,钇稳氧化锆可通过多次闪烧获得致密化,该工艺烧结温度低于1 050℃,烧结时间小于200 s,制备的四方氧化锆陶瓷材料的密度达到90%以上。     

四方相氧化锆分步加压辅助闪烧烧结制备及性能EI北大核心CSCD

开发了一种四方相氧化锆陶瓷材料的二次分步加压辅助闪烧烧结工艺,该工艺对加压辅助闪烧工艺进行了优化,消除了临界闪烧温度下高功率闪烧导致的微观组织结构劣化现象.结果表明:多次分步加压辅助闪烧工艺保留了闪烧方法低温、瞬时烧结的优点,规避了复杂生坯压制工序和贵金属电极高昂成本,钇稳氧化锆可通过多次闪烧获得致密化,该工艺烧结温度低于1050℃,烧结时间小于200 s,制备的四方氧化锆陶瓷材料的密度达到90%以上.     

陶瓷材料闪烧技术研究进展EI北大核心CSCD

总结了闪烧研究中所涉及的实验内容(包括平台、制度和材料体系等)和烧结机理(包括焦耳热效应、快速升温致密化、接触点局部热效应和缺陷作用理论等),比较了闪烧和传统烧结制得材料的微观形貌和力学性能,展望了闪烧技术的发展趋势和方向。结果表明:闪烧技术可广泛应用于离子导体、绝缘体、半导体和类金属导电陶瓷等多种陶瓷材料的制备中,闪烧制备的陶瓷材料较传统烧结具有更精细的微观形貌和更优异的力学性能。     

陶瓷材料闪烧技术研究进展

总结了闪烧研究中所涉及的实验内容(包括平台、制度和材料体系等)和烧结机理(包括焦耳热效应、快速升温致密化、接触点局部热效应和缺陷作用理论等),比较了闪烧和传统烧结制得材料的微观形貌和力学性能,展望了闪烧技术的发展趋势和方向。结果表明:闪烧技术可广泛应用于离子导体、绝缘体、半导体和类金属导电陶瓷等多种陶瓷材料的制备中,闪烧制备的陶瓷材料较传统烧结具有更精细的微观形貌和更优异的力学性能。     

超低温烧结微波介质陶瓷制备工艺的研究进展

传统方法制备微波介质陶瓷通常需要1 000℃以上高温，不仅工艺周期长、能量消耗高，而且难以实现多种材料体系的集成共烧。如今，无线通讯技术的不断革新和蓬勃发展对微波器件小型化、集成化提出了更高要求，低温共烧陶瓷/超低温共烧陶瓷技术被开发和广泛应用。研究烧结温度更低、烧结效率更高，且微波介电性能优异的节能环保型绿色制备工艺，已经成为全球范围内研究热点之一。液相烧结、热压烧结、微波烧结、放电等离子体烧结、闪烧等烧结工艺的提出促进了低温烧结微波介质陶瓷的发展。最近，又出现了一种新的超低温烧结工艺—冷烧结技术。冷烧结具有极低的烧结温度(一般≤300℃)、可在短时间内实现陶瓷高致密化，且在物相稳定性、复合共烧以及晶界控制等方面有着优势，为超低温烧结工艺以及微波介质材料体系的开发提供了新的契机。     

基于冷烧结技术的微波介质陶瓷研究进展

微波介质陶瓷作为介质材料被广泛应用于物联网、工业互联网、5G通信、全球卫星通信系统的无源器件中。从微波介质陶瓷的研究背景出发,介绍了冷烧结的致密机理和工艺参数,总结了冷烧结微波介质陶瓷的主要材料体系和器件,指出了冷烧结微波介质陶瓷的主要问题和发展前景。冷烧结技术具有烧结温度低(<300℃)、可共烧异质材料、烧结前后晶粒尺寸差异小、制备工艺简单、节能环保等多种优点,在多层共烧陶瓷和微波系统集成方面具有潜在应用。     

固相法烧结温度对钛酸钡陶瓷介电性能的影响

研究了固相法烧结温度对钛酸钡陶瓷介电性能的影响.采用固相法在不同温度下烧结钛酸钡陶瓷.结果表明,不同烧结温度对钛酸钡陶瓷晶体结构、微观形貌、介电常数、介电损耗、居里温度等都会产生不同的作用效果.钛酸钡陶瓷只有在最佳烧结温度附近才具有最好的结构和性能,烧结温度过低会使烧结过程不充分,引起过多的点缺陷;而过高的烧结温度也会由于过烧现象的存在而使晶粒与晶界间相互作用出现异常,两种情况都会导致钛酸钡陶瓷介电性能的劣化.     

Flash sintering behaviour of 8YSZ-NiO composites

Flash sintering is an electric field/current assisted sintering technique, which is reported to lower the furnace temperature and to reduce sintering time significantly. In this work, we have studied the processing of 8YSZ/NiO composites by flash sintering, for the first time. Two composites, with different amount of NiO (one below the percolation limit and another one above it) were processed in two different sintering atmospheres. Constant heating rate experiments were performed to know the minimum furnace temperature required to flash sinter the samples for a given applied electric field. Subsequently, isothermal flash sintering experiments were performed at different current densities. The flash onset temperature of the composites was lower in the reducing atmosphere compared to in air. The power dissipated in stage III of the flash was strongly influenced by the composite composition and the sintering atmosphere. The extent of densification in the composites was controlled by the current density. The composites were densified up to a relative density of ～90% in 30 s when flash sintered in air. In reducing atmosphere, there was in-situ reduction of NiO to Ni. As a result, for composites containing NiO above the percolation limit, the current preferentially flew through the in-situ formed metallic phase and there was no densification in the composite in reducing atmosphere. Phase and microstructure evolution in the composites was studied through XRD, SEM and EDS. With proper control of the electrical parameters (electric field and current density), composites with controlled porosity can be processed through flash sintering which may have applications for solid oxide fuel cells.     

Tailoring the microstructure by a proper electric current control in flash sintering: The case of barium titanate

Flash sintering is arousing growing interest because high-density ceramics can be obtained at lower temperatures and shorter dwell times than conventional sintering. However, not only temperature and dwell times should be controlled during flash sintering but also parameters such as the electric field and electric current should be considered. Controlling all the parameters during the processing allows comprehensive control of the microstructure and, consequently, functional properties can be improved. In this work, it is evidenced that an exhaustive control of the flash electric current is a crucial factor for tailoring the microstructure of BaTiO₃ ceramics. The results reveal that the most suitable way to control the sintering process is by using non-linear current profiles because better densification and improved grain growth is achieved. Although the results focus on BaTiO₃, this work offers a new pathway to tailor the microstructure of flash sintered ceramics, which may be extended to other materials.     

Sintering behavior of 8YSZ-Ni cermet: Comparison between conventional,FST/SPS,and flash sintering

Cermets are ceramic metal composites. The metallic phase in the cermet typically undergoes oxidation during sintering in air. Electric field-assisted sintering processes such as field-assisted sintering technology/spark plasma sintering (FAST/SPS) and flash involves very high heating rates, short processing time and low processing temperature. The main aim of this work was to see if field-assisted sintering techniques can prevent the oxidation of the metallic phase in the cermet. Sintering behavior of 8YSZ-5 wt.% Ni cermet was studied by three different techniques namely; conventional sintering, FAST/SPS and flash sintering. Phases and microstructure were analyzed through X-ray diffraction and scanning electron microscopy, respectively. Temperature and time required for sintering the samples via FAST/SPS and flash sintering was significantly lower than that during conventional sintering. In addition, we found limited grain growth during FAST/SPS and flash sintering. During conventional sintering in reducing atmosphere (Ar and vacuum), Ni particles retained their elemental state, however the extent of densification was poor in the cermet. FAST/SPS in argon and vacuum resulted in almost complete densification (relative density > 97%) and Ni particles were retained in their elemental state in the cermet. During flash sintering in air, the samples sintered to a high densification (relative density ∼98%), however, Ni particles were completely oxidized.     

Influence of geometry on thermal gradients and hotspot formation during flash sintering

Hotspot or preferential current path formation is a major problem halting the advance of flash sintering as an industry applicable densification method. In-situ infrared thermal imaging shows significant dependence of the surface temperature distribution on the sample geometry, causing significant changes in the onset parameters, the course of the flash event and sample quality. Current-ramped flash sintering is compared to conventional flash sintering experiments and reveals an effective reduction in temperature differences. The role of the setup design on the thermal losses and the gradients is highlighted.     

Development of a processing map for safe flash sintering of gadolinium-doped ceria

Flash sintering was discovered in 2010, where a dog-bone-shaped zirconia sample was sintered at a furnace temperature of 850°C in <5 s by applying electric fields of ~100 V cm⁻¹ directly to the specimen. Since its discovery, it has been successfully applied to several if not all oxides and even ceramics of complex compositions. Among several processing parameters in flash sintering, the electrical parameters, i.e., electric field and electric current, were found to influence the onset temperature for flash and the degree of densification respectively. In this work, we have systematically investigated the influence of the electrical parameters on the onset temperature, densification behavior, and microstructure of the flash sintered samples. In particular, we focus on the development of a processing map that delineates the safe and fail regions for flash sintering over a wide range of applied current densities and electric fields. As a proof of concept, gadolinium-doped ceria (GDC) is shown as an example for developing of such a processing map for flash sintering, which can also be transferred to different materials systems. Localization of current coupled with hot spot formation and crack formation is identified as two distinct failure modes in flash sintering. The grain size distribution across the current localized and nominal regions of the specimen was analyzed. The specimens show exaggerated grain growth near the positive electrode (anode). The region adjacent to the negative electrodes (cathode) showed retarded densification with large concentration of isolated pores. The electrical conductivity of the flash sintered and conventional sintered samples shows identical electrical conductivity. This quantitative analysis indicates that similar sintering quality of the GDC can be achieved by flash sintering at temperature as low as 680°C.     

Porcelain stoneware consolidation by flash sintering

Porcelain stoneware was consolidated by flash sintering under DC polarization using current densities in the range 4‐20 mA/mm². The results show the applicability of this innovative sintering technology to a material whose densification occurs by vitrification, thus allowing to extend the possible application field of flash sintering to traditional ceramics. Using appropriate current density, the flash‐ sintered samples are dense, homogeneous, and well‐vitrified. XRD and microstructural analysis points out the formation of primary mullite while secondary mullite is only sporadically observed. In addition, comparison between flash sintering and fast firing shows that the densification obtained in the selected ceramic system via the former route cannot be reproduced just by a rapid heating process.     

Effect of thermal insulation on microstructural homogeneity and onset temperature of flash sintered materials

The present work aimed to reduce the microstructure heterogeneity inherent to flash sintering by using alumina blankets as a thermal insulator around ZnO cylindrical samples during the sintering process, under different electric field conditions. Thermal insulation significantly reduced the flash onset temperature and the grain size heterogeneity. For higher electric fields, a temperature reduction as high as 480 °C was observed, which also led to lower densification. These findings were discussed in terms of changes in the heat loss dynamics coupled with the adsorbed water retention, both promoted by the applied thermal insulation. A model to estimate the temperature at stage III of flash sintering was proposed. The final temperature reached with thermal insulation did not differ significantly from the ones without it. Thus, thermal insulation could represent an alternative route to flash sinter materials with lower furnace temperatures with energy savings up to 78 % and a more homogeneous microstructure.     

Preliminary investigation of hydroxyapatite microstructures prepared by flash sintering

Flash sintering is a novel and emerging route for sintering ceramics within a few seconds, even under pressure-less conditions. In the current study, hydroxyapatite (HA) was fully densified by flash sintering at a furnace temperature of 1020°C. Flash sintering with constant electric fields of 750 and 1000?V?cm^?1 reduced the grain growth rate significantly compared to that sintered in the absence of an electric field at 1400°C. The microstructure of HA consolidated by flash sintering was compared with that of the without electric field sintered samples. The flash-sintered samples showed smaller grains (160?～?320?nm) than the without electric field sintered samples (～15?µm). The samples with a higher applied electric field showed slightly better densification than those with the lower field by flash sintering. Overall, the electric flash reduces the sintering temperature effectively and decreases the holding time to densify highly insulating ceramics, such as HA.     

Flash sintering of tricalcium phosphate (TCP) bioceramics

Tricalcium phosphate (β-TCP) bioceramic was consolidated by flash sintering in the present work.TCP powders were synthesized by solid-state route, starting from calcium carbonate and ammonium phosphate, and shaped into cylindrical pellets of different height by uniaxial pressing. Sintering was performed within an on purpose modified dilatometer working under constant heating rate and monitoring shrinkage and electrical parameters (current and field), simultaneously.The obtained TCP bodies exhibit well densified microstructure, maintaining the β-TCP composition.A power balance model, based on a thermal runaway mechanism and considering the contribution of the contact resistance on the voltage actually applied on TCP material, is shown to successfully predict the flash phenomenon.The achieved results, although preliminary, show the possibility to employ flash sintering to obtained dense β-TCP products at lower furnace temperature and in shorter time with respect to the conventional process, avoiding the undesirable expansion related to the β–α transition.