多孔陶瓷的直写成型工艺研究进展

多孔陶瓷内部含有大量三维孔隙,具有轻质、高强、高比表面积、低导热系数等特性,但是多孔陶瓷的传统制备工艺对结构和性能的可控性较低,很难满足先进能源、航空航天、电子信息等领域的发展对多功能高性能材料的需求。直写成型工艺是一种制造成本低、材料使用性广、技术可拓展性高的3D打印工艺,不仅可以直接制备具有轻量化特点的多孔陶瓷,而且结合其他工艺可以实现多孔陶瓷的层级结构和多功能化,有望实现设计与制造、材料与器件、结构与功能的一体化。介绍了直写成型法3D打印多孔陶瓷的工艺原理,综述了直写成型法直接制备多孔陶瓷、直写成型结合乳液/泡沫法和冷冻干燥法制备层级多孔陶瓷的研究进展。由于工艺柔性高,直写成型法能够与其他方法良好融合,以制备具有特殊结构和性能的多孔材料,尤其是兼顾高强度、高孔隙率和形状可控性的层级多孔陶瓷。最后,总结了目前直写成型工艺制备多孔陶瓷的优势和不足,并对打印材料性能、打印设备和主要应用领域的发展进行了展望。     

Electrophoretic deposition of alumina,yttria, yttrium aluminium garnet and lutetium aluminium garnet

The electrophoretic deposition (EPD) method has been adapted for the deposition of ceramic green bodies from aqueous nanodispersions of alumina, yttria, yttrium aluminium garnet and lutetium aluminium garnet. These materials have been selected, since they are promising candidates for optically transparent ceramics. Films as well as cylindrical bodies have been successfully prepared by application of pulsed direct current (pDC) EPD. To guarantee constant deposition yield during pDC, a variant with variable pulse widths and pulse heights has been developed. The obtained green bodies were studied by surface area analysis, scanning electron microscopy, optical transmittance measurements, determination of pycnometric density and sintering behaviour. The effect of colloid-chemical dispersion properties on green and sintered ceramics is discussed as well. The green ceramics received are nanoporous and dense, providing excellent properties for further processing under mild conditions to optical materials. For comparison, EPD-formed green bodies were either processed directly to ceramic bodies or after additional compacting by hot-pressing in a piston-cylinder apparatus.     

Shape forming of ceramics via gelcasting of aqueous particulate slurries

Gelcasting is a promising technique for shape forming of bulk dense or porous ceramic, metal structures. The process offers a number of advantages over processes such as slip casting, injection molding in forming complex ceramic shapes. It is shown here that the optimization of slurry rheology, choice of mold material, mold design and the drying conditions have a significant role in the overall success of the process. In this process, components of simple or complex shapes can be produced to near net shape by direct casting. If required complex shapes can also be produced by machining the green gelcast bodies. The process of gelcasting also has a lot of potential in forming highly porous ceramic shapes.     

3D printing vertically: Direct ink writing free-standing pillar arrays

Over the last three decades, a variety of additive manufacturing techniques have gradually gained maturity and will potentially play an important role in future manufacturing industries. Among them, direct ink writing has attracted significant attention from both material and tissue engineering areas, where the colloidal ink is extruded and dispensed according to a pre-designed path, usually in the X-Y plane with suitable increments in the Z direction. Undoubtedly, this way of disassembling geometries, simple or complex, can facilitate most of the printing process. However, for one extreme case, i.e. pillar arrays, the size resolution can deviate from both nozzle and design if the common way of slicing and additive manufacturing is used. Therefore, a different printing path is required – directly depositing pillars in a converse gravitational direction. This paper gives multiple examples of printing viscoelastic colloidal ceramic and metal inks uniaxially and periodically into free-standing and height-adjustable pillar arrays. It is expected to inspire the additive manufacturing community that more versatile degrees of freedom and complex printing paths, not confined within only complex shapes, can be achieved by ink-based 3D printing.     

Direct-ink writing 3D printed energy storage devices: From material selectivity,design and optimization strategies to diverse applications

Additive manufacturing, also known as three-dimensional (3D) printing technology, has recently emerged as a promising fabrication technology for a variety of applications with diverse complex architectures, as it allows for simple printing of desired pattern, fast prototyping, reduced fabrication process and low cost. As an important type of 3D printing technology, direct ink writing (DIW) endows the electrochemical energy storage devices (EESDs) with excellent electrochemical performance with high areal energy density and excellent rate capability owing to enhanced ion/electron transportation and surface kinetics induced by the designed patterns and device architecture. In view of the current infancy and urgency, as well as the lack of in-depth discussion, we critically overview the DIW 3D printing technology for EESDs devices in terms of materials selectivity principle for ink formulation and rheology, technical challenges (design principles and optimization strategies) and various EESDs applications in a comprehensive yet concise fashion. In this review, firstly, we introduce the typical features of DIW 3D printing technology. Subsequently, we discuss the design and optimization strategies towards several key parameters of DIW, including printable ink formulation, printing process and post treatment, device configuration and electrode pattern, porosity and tortuosity, as well as the package. Thereafter, we summarize the advances and recent progress of various EESDs devices fabricated by DIW technology, including conventional lithium/sodium ion batteries, newly emerged lithium sulfur/selenide/oxygen batteries, lithium/sodium-metal batteries, Ni-Fe batteries, zinc-air batteries, zinc ion batteries and supercapacitors, with a detailed analysis of rational design mechanism of each EESD. At last, the remaining challenges and research orientations in this booming field are proposed to motivate the future research and development of 3D printed EESDs.     

Hierarchically porous ceramics via direct writing of preceramic polymer-triblock copolymer inks

Hierarchically porous ceramics possess tailored porosity across multiple length scales, giving rise to materials with low density, high specific properties, and multifunctionality. Here, we report a method that combines self-assembly and 3D printing to create ceramic architectures with hierarchical porosity spanning from the nano- to microscale. To programmably define their microscale porosity, an additive manufacturing method, known as direct ink writing, is used to create 3D lattices composed of cylindrical struts. Nanoscale porosity is generated within each strut by block copolymer templating followed by photopolymerization and pyrolysis in a non-oxidative environment, which transforms the preceramic polymer, polycarbosilane, into silicon oxycarbide with a “nanocoral” morphology. The resulting hierarchically porous ceramic lattices exhibit excellent mechanical energy absorption (0.31 MJ/m³), comparable to metal alloy foams. They also possess an order of magnitude lower thermal conductivity (0.087–0.16 W/m⋅K) compared to bulk preceramic polymer-derived ceramics. Prior to pyrolysis, the printed architectures can be manipulated to produce more complex shapes, including lattices with twisted, helical, and overhang features as well as repeated folding to create an origami airplane. By combining self- and directed assembly, our approach opens new avenues for creating hierarchically porous ceramics.     

A New 3D Printing Strategy by Harnessing Deformation,Instability, and Fracture of Viscoelastic Inks

Direct ink writing (DIW) has demonstrated great potential as a multimaterial multifunctional fabrication method in areas as diverse as electronics, structural materials, tissue engineering, and soft robotics. During DIW, viscoelastic inks are extruded out of a 3D printer's nozzle as printed fibers, which are deposited into patterns when the nozzle moves. Hence, the resolution of printed fibers is commonly limited by the nozzle's diameter, and the printed pattern is limited by the motion paths. These limits have severely hampered innovations and applications of DIW 3D printing. Here, a new strategy to exceed the limits of DIW 3D printing by harnessing deformation, instability, and fracture of viscoelastic inks is reported. It is shown that a single nozzle can print fibers with resolution much finer than the nozzle diameter by stretching the extruded ink, and print various thickened or curved patterns with straight nozzle motions by accumulating the ink. A quantitative phase diagram is constructed to rationally select parameters for the new strategy. Further, applications including structures with tunable stiffening, 3D structures with gradient and programmable swelling properties, all printed with a single nozzle are demonstrated. The current work demonstrates that the mechanics of inks plays a critical role in developing 3D printing technology.     

水披覆转印的研究进展

水披覆转印工艺包括水转印膜的制作、水转印和后处理3个部分,主要材料有载体薄膜、印刷油墨、油墨活化剂及底漆与面漆,其印刷方式一般采用传统的凹版印刷。水披覆转印的载体薄膜一般为水溶性PVA薄膜,油墨通常为溶剂型油墨,活化剂主要是以芳香烃为主的有机混合溶剂。以水性油墨替代溶剂型油墨、无毒活化剂替代有毒或微毒活化剂、彩色喷墨印刷方式替代传统的凹版印刷方式等绿色环保、生产效率高的水披覆转印技术是今后水转印技术的研究方向与重点。     

氧化铝陶瓷局部活化及选择性化学镀铜的研究

为解决陶瓷表面局部化学镀存在的问题,研制了一种针对氧化铝陶瓷局部化学镀铜前处理用的活化胶,其由具有活化能力的银盐(或钯盐)和粘稠的复合物有机载体组成.将活化胶印于氧化铝陶瓷表面,经500℃高温烧结形成局部活化层后,可直接置于化学镀液中进行镀铜处理,得到与印刷图形一致的局部镀铜层.利用电化学工作站测定样品在化学镀铜溶液中电位随时间的变化情况,考察不同活化条件对Cu2+还原的催化活性,利用SEM/EDS进行表面形貌及成分分析,确定了活化胶中银盐和钯盐的适宜浓度.结果表明,该两种活化胶应用于氧化铝陶瓷表面化学镀铜的活化工艺,可实现敏化活化的一步化,使陶瓷表面局部化学镀工艺流程简化,成本降低,具有较高的实用价值.     

3D打印陶瓷材料研究进展

作为新一代成型技术,3D打印技术具有操作简单、成型速度快、精度高等优点,而采用3D打印技术制备出的多功能化陶瓷零件,在建筑、工业、医学、航天航空等领域将会得到广泛的应用,其发展前景十分广阔。主要介绍了3D打印陶瓷方面的成型技术和材料,回顾了3D打印陶瓷的发展及国内外产业状况,并对可应用于3D陶瓷的打印技术和打印材料进行了展望。     

The effect of polysiloxane on the properties of Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-NbC composite material produced by pyrolysis process

Recently, studies have been developed in order to obtain Al₂O₃-NbC composite materials. The reinforced materials have shown good potential to be used as cutting tool materials at high-speed cutting and high temperature as a substitute to WC-Co material. The main disadvantage to produce these alumina-reinforced materials is the necessity to use pressure assisted sintering or high sintering temperatures to produce dense bodies. Manufacturing of composite ceramic materials derived from polymer reactive filler has been intensively investigated. Polymer pyrolysis is a relatively new and very promising method for obtaining ceramic material in complex shapes and lower sintering temperatures. This work investigated a ceramic composite matrix based in SiC_xO_y and Al₂O₃ and reinforced with NbC obtained by means of the active fillers pyrolysis process. The results obtained in this work demonstrate that using a mixture of polysiloxanes produces a composite material with better properties when compared to others polymer materials.     

3D打印氧化铝陶瓷的气氛脱脂热处理工艺研究

脱脂热处理工艺对于3D打印陶瓷的成形质量具有重要的影响。目前光固化3D打印制备得到的氧化铝生坯经过在空气中的脱脂热处理工艺后烧结最终得到的氧化铝陶瓷存在的微观裂纹等缺陷, 将导致其力学性能较差。本工作研究了基于数字光处理(Digital light processing, DLP)技术的氧化铝陶瓷打印热处理工艺, 将3D打印制备得到的氧化铝陶瓷生坯分别在空气与氩气中脱脂后比较其宏观形貌, 发现在空气下脱脂的氧化铝生坯存在微观裂纹。再将脱脂后的生坯在空气下烧结得到氧化铝陶瓷, 并对其微观形貌和宏观性能进行表征, 发现在氩气下脱脂的氧化铝陶瓷平均晶粒尺寸要比直接在空气中脱脂得到的氧化铝陶瓷平均晶粒尺寸大, 而且晶粒结构致密, 无明显气孔和杂相, 而且具有更高的抗压强度。这说明在氩气中脱脂后烧结得到的氧化铝陶瓷性能更好。在氩气中脱脂的氧化铝致密度最高可达到96.72%, 抗压强度可达到761.7 MPa, 相比于只在空气中脱脂的氧化铝陶瓷性能得到显著提升。     

Recent advances in 3D printing of porous ceramics: A review

3D printing, alongside the rapidly advancing field of porous ceramics, is quickly expanding the horizon of what is going to be possible in the future. In this paper, 3D printing technology is evaluated for its compatibility with porous ceramic materials, due to its competitive process in terms of speed and specific tooling, especially for good quality fabrication. The paper reviews the capabilities of these new technology techniques for the fabrication of porous ceramic. The basic technology is the 3D printing techniques, which are used to fabricate porous green ceramic parts that are later sintered. Different ceramic materials are evaluated and the classification of different powders according to their 3D printing quality as well as material aspects is examined. The evaluation of 3D printing process in terms of the powders’ physical properties such as particle size, flowability and wettability is also discussed. The relationship between the different 3D printing parameters and the final printing outcome are assessed.     

石墨烯/陶瓷复合材料制备工艺研究进展

制备工艺是调控石墨烯/陶瓷复合材料结构、优化其力学和热电等性能的关键.重点综述了石墨烯/陶瓷复合材料的粉末压坯烧结工艺和3D打印工艺及其研究进展.粉末压坯烧结工艺包括无压烧结、热压烧结、放电等离子烧结、微波烧结和高频感应加热烧结等,具有工艺简单、材料性能好、制备参数易控制等优点,是石墨烯/陶瓷复合材料的主要制备工艺,用于制备致密的块体复合材料;主要3D打印工艺有直写成形、激光选区烧结、喷墨打印和立体光固化等,具有结构和形状可控的特点,是目前石墨烯/陶瓷复合材料的研究热点,用于成形复杂形状和特定性能的复合材料器件.另外,还简要介绍了原位生成法、碳热还原法等利用特定物理化学反应制备石墨烯/陶瓷复合材料的制备工艺,并综述了石墨烯在复合材料中的分散工艺.     

水解反应诱导凝胶化工艺成型碳化硅陶瓷

发现静电稳定的碳化硅浆料在碳化硅粉体表面的无定形氧化硅层的影响下,可以象氧化硅溶胶一样发生溶胶－凝胶转变,并将这一发现用于碳化硅陶瓷的成型．通过预先加入的酯或内酯的水解反应,把浆料的ｐＨ值从碱性区降至有利于凝胶的中性区,体系发生固化． 利用小幅震荡剪切技术对影响固化过程的各种因素进行研究表明,固化速度及固化强度不仅依赖于体系最终的ｐＨ值,还取决于体系最初的ｐＨ值以及ｐＨ值变化的速度．这些影响因素说明,体系的固化不是一个简单的凝聚的过程,而是一个凝胶的过程,浆料的固化是碳化硅颗粒间形成Ｓｉ－Ｏ－Ｓｉ键的结果．     

基于光敏浆料的直写精细无模三维成型

配制了一种具有光敏特性的陶瓷浆料, 并用此浆料通过直写精细无模三维成型技术制备了线条直径为300μm的BaTiO3陶瓷基木堆结构. 系统地讨论了光敏浆料的配制方法、浆料直写无模成型的工作原理以及采用的烧结工艺. 制备过程中不同阶段的研究表明, 光敏浆料中的BaTiO₃纳米颗粒在烧结前未发生团聚, 从而保证挤压成型顺利进行; 烧结后样品成瓷效果好, 各向收缩均匀, 整体无变形、开裂. 该技术具有成型速度快、制造周期短、可用材料范围广等特点.     

石膏的直写成型：可打印石膏浆料的研制

石膏是雕像、建筑和铸造模具(合金和陶瓷)的常用材料。采用直写成型(Direct Ink Writing, DIW)打印石膏可避免其他3D打印技术(如Binder Jetting, PBBJ等)中存在水化反应不充分等问题, 获得高强度3D打印石膏。为了延缓水化反应获得充足的打印操作时间, 本研究通过添加缓凝剂和增稠剂, 研制了一种适用于直写成型的石膏浆料, 并打印了多种石膏三维结构(如蜘蛛网和木材堆积结构等)。结果表明, 质量分数为0.6%柠檬酸(Citric Acid, CA)的缓凝效果最好, 极大地减少了石膏流动性的经时损失。质量分数为0.3%羟丙基甲基纤维素(Hydroxypropyl Methylcellulose, HPMC)的增稠效果最好, 使石膏浆料具有良好的打印性能。CA的选择性吸附使得石膏晶体定向生长, 延长水化反应时间, 但一定程度降低石膏强度。HPMC加速石膏浆料中絮凝结构形成, 导致其粘度和剪切弹性模量升高。直写成型3D石膏件的抗压强度约为20 MPa, 远高于PBBJ等方法制备的石膏件的抗压强度。     

Transparent Polycrystalline Alumina Ceramic with Sub‐Micrometre Microstructure by Means of Electrophoretic Deposition

The optical quality attainable in coarse‐grained polycrystalline alumina is severely limited by grain‐boundary scattering, which is inherent to non‐cubic materials. The optical properties of sub‐micrometre polycrystalline alumina are of growing interest triggered by the fact that a decrease in the grain sizes of the final sintered material yields an improvement in the optical quality while the scattering mechanism changes as the grain size becomes comparable with the wavelength of light. To achieve transparent alumina ceramics with a fine‐grained microstructure, however, porosity and other defects must be avoided. This necessitates the optimization of processing and sintering procedures. Electrophoretic deposition (EPD) is a colloidal process in which ceramic bodies are directly shaped from a stable suspension by application of an electric field. Electrophoretic deposition enables the formation of homogeneous, uniform green microstructures with high density, which can be sintered to transparency. It is a simple and precise technique to synthesize not only monoliths, but also composites with complex geometries [1]. Alumina green bodies were deposited from stabilized aqueous suspensions with and without doping. Green alumina compacts were evaluated based on their pore size distribution and density. Densification behaviour was characterized by dilatometric studies conducted at constant heating rate. Samples were sintered at different temperatures with subsequent post‐densification by hot isostatic pressing. Transparency was evaluated by means of spectroscopic measurements. The measured in‐line transmission of the samples at 645 nm was more than 50 % and that is 58 % of the value of sapphire. The influence of dopings on transparency was investigated. The mechanical properties of the samples were tested.     

含硅材料凝胶注模成型中的放气反应对生坯显微结构的影响

原位凝固胶态成型工艺,譬如凝胶注模成型,是目前能制备形状复杂,均匀性好和可靠性高的陶瓷材料的理想成型工艺。含硅的陶瓷粉料,包括硅,碳化硅在氮化硅粉料,适于在碱性水溶液中分散。然而,硅粉及含在碳化硅和氮化硅粉料中的游离硅易于发生水解。放出氢气,在胶态成型的坯体中产生显气孔,特别在碱性溶液中如此。氮化硅本身在水溶液中具有化学不稳定性,易于在碱笥条件下水解或与其他化学物质反应放出气体,同样可能在坯体中产生气泡。确定凝胶注模成型坯体中产生显气孔的真正原因,采用恰当的解决方案,可制备无显气孔的坯体。     

水基注凝成型技术的研究进展

注凝成型是一种近净尺寸陶瓷成型技术,为制备高性能复杂形状的陶瓷制品提供了一条有效的技术途径.对陶瓷水基注凝成型技术中的悬浮体的制备、凝胶体系的选择、悬浮体的真空处理和固化、坯体和烧结体的性能特点等方面的研究进行了综述,并简要介绍了该技术的国内外应用情况,同时展望了该技术的发展趋势.