陶瓷部件3D 打印技术的研究进展

近年来,三维连续网络结构的陶瓷／金属复合材料由于兼具陶瓷材料的耐磨、高强、高硬、抗氧化、耐蚀及钢铁材料的导热性及良好的韧性受到人们的广泛关注。三维连续网络结构的陶瓷／金属复合材料的陶瓷结构的构建是制备复合材料的难题。3D打印技术突破了传统的加工模式,不依赖复杂模具和机械加工,并可根据材料不同的性能要求,开发出不同结构的陶瓷骨架,这将使陶瓷／金属复合材料领域发生巨大变化。本文介绍了陶瓷3D 打印技术的原理、分类、工艺特点及研究进展,并对3D打印技术未来的发展方向进行了展望。     

基于浆料形态的陶瓷3D打印技术的浆料体系研究进展

3D打印技术因其操作简单便捷、成型快速灵活、可制备复杂结构的器件等优点,在精密陶瓷零件制造方面具有广泛应用。本文根据3D打印陶瓷的材料形态综述不同3D打印技术在陶瓷制备方面的特点,重点介绍了陶瓷3D打印成型技术中直写式3D打印、光固化3D打印、喷墨3D打印等技术所涉及的粘结剂、分散剂等组分的应用及作用机理,并对水基和非水基两种类型的添加剂组分进行总结和探讨,以期为3D打印技术制备高性能陶瓷样件提供参考。     

Processing and 3D printing of SiCN polymer-derived ceramics

Preceramic polymer resins are attractive for the 3D printing of net-shaped ceramic components. Recently various processes have been demonstrated for 3D printing of polymer-derived ceramics (PDCs). Ultimately in these processes, the process outcomes strongly depend on the process parameters. In particular, for PDCs the ceramic density, and ceramic yield are affected by the catalyst concentration and cross-linking duration. Here, we use thermal analysis and FTIR to quantify the interrelation of the process parameters on the process outcome for polysilazanes and demonstrate 3D printing of PDC components based on the best-identified process parameters. The results of this work can be used as guidelines for future additive manufacturing of PDCs.     

A review of 3D printed porous ceramics

Three-dimensional (3D) printing of ceramics has gained widespread attentions in recent years. Many excellent reviews have reported the printing of ceramics. However, most of them focus on printing of dense ceramics or general ceramic aspects, there is no systematical review about 3D printing of porous ceramics. In this review paper, the 3D printing technologies for fabricating of porous ceramic parts are introduced, including binder jetting, selective laser sintering, direct ink writing, stereolithography, laminated object manufacturing, and indirect 3D printing processes. The techniques to fabricate hierarchical porous ceramics by integrating 3D printing with one or more conventional porous ceramics fabrication approaches are reviewed. The main properties of porous ceramics such as pore size, porosity, and compressive strength are discussed. The emerging applications of 3D printed porous ceramics are presented with a focus on the booming application in bone tissue engineering. Finally, summary and a perspective on the future research directions for 3D printed porous ceramics are provided.     

Additive manufacturing of ceramics: Advances,challenges, and outlook

Additive manufacturing (AM) of ceramics is relatively more challenging with respect to polymers and metals, owing to their high melting temperatures and inherent brittleness. Thus, this review aims to provide a comprehensive survey of recent AM technologies successfully employed to produce net shape ceramic components. In recent years, several techniques have been developed and the latest progress in this field are highlighted, as well as the current challenges in the complex shaped ceramic parts production via AM technologies. The state of the art concerning the various 3D printing processes applied to the fabrication of ceramic components is discussed with, for each method, the presentation of its advantages, disadvantages, and possible applications. The potential of AM for producing complex shape ceramic components and the challenges to overcome are discussed as well.     

Digital light processing-stereolithography three-dimensional printing of yttria-stabilized zirconia

Digital light processing (DLP)-stereolithography three-dimensional (3D) printing is a well known technique for fabricating components with complex geometries. However, the application of DLP 3D printing to functional ceramics such as 8 mol% yttria-stabilized zirconia (8YSZ), which is one of the most extensively used electrolyte materials for solid oxide fuel cells, is still a great challenge. Therefore, the fabrication of fully 8YSZ monoliths via DLP 3D printing was attempted herein, including the preparation of UV-curable ceramic suspensions, shaping of green bodies, and debinding and sintering. The results show that intact green bodies printed using a 30 vol% 8YSZ-photosensitive resin suspension with 0.1 wt% oleic acid as the dispersant under the optimized printing conditions was sufficiently dense without connected pores after vacuum debinding and sintering in air. The successful fabrication of 8YSZ monoliths with design flexibility via 3D printing provides a simple method for preparing functional ceramic components and may expand the application of 3D printing technology to the energy field.     

Lattice-structured SiC ceramics obtained via 3D printing,gel casting,and gaseous silicon infiltration sintering

In view of technical difficulties in preparing ceramics with complex shapes, gel casting combined with 3D printing was here adopted to prepare silicon carbide ceramic green body, and gaseous silicon infiltration sintering was used to prepare 3D lattice-structured ceramics. The preparation of the slurry, gel curing, and ceramic molding was investigated. Results demonstrate that the ratio of components affects the fluidity and stability of slurry. However, when volume fraction of the solid phase of the slurry reaches 56%, the viscosity of slurry is only 300 mPa s, and drying shrinkage rate of green body is 6.6%; these characteristics make slurry suitable for 3D complex model injection molding. Furthermore, both the temperature and the initiator affect gel curing speed. As the temperature and initiator content increase, the induction and gel time are rapidly shortened. When demolding at 300 °C and when gaseous silicon infiltration sintering is carried out at 1550 °C, a 3D lattice-structured ceramic with relative density of 87% and average compressive strength of 433 MPa can be obtained.     

First printing of continuous fibers into ceramics

This article reports a novel method for three-dimensional (3D) printing of continuous fibers into ceramics to improve the mechanical properties of printed ceramics, which is difficult in other 3D printing technologies. The ceramics were derived by pyrolysis of thermoplastic ceramic precursor feedstocks, which were prepared by two methods. One is homogeneously mixing thermoplastic resins and ceramic precursors. The feedstocks prepared by this method exhibit good thermoplastic properties and can be extruded into filaments. Ceramics were obtained by heating the feedstocks to 1100°C in argon atmosphere. The ceramics were amorphous and remained stable during 1100-1300°C; at 1400°C they decomposed into β–SiC with simultaneous volatile gas generation. Above 1400°C, their quality decreased significantly due to cracking of ceramic skeletons. The other method is directly heating, extruding and printing the ceramic precursor. The precursors showed good printability and complex ceramic structures were printed with continuous carbon fibers inside. The continuous carbon fibers improved the flexural strength of pyrolytic ceramics, which is about 7.6 times better than that of the ceramics without fibers. The novel method unravels the potential of 3D printing of continuous fibers into ceramics with complex lightweight structures to improve the strength.     

Direct ink writing of aluminum-phosphate-bonded Al2O3 ceramic with ultra-low dimensional shrinkage

Three-dimensional (3D) printing of ceramics has attracted increasing attention in various fields. However, the pyrolysis of organic components used for binding or polymerization in 3D printing commonly causes a large shrinkage (up to 30 %–40 %), high porosity, and cracking or deformation, severely limiting practical applications. In this study, 3D printing of Al₂O₃ ceramic architectures with ultra-low shrinkage is realized by introducing inorganic binder aluminum dihydrogen phosphate (Al(H₂PO₄)₃, AP) as a ceramic precursor. Compared to organic binders, the inorganic AP binder can undergo crystallization conversion, which reduces mass loss during sintering at high temperatures, resulting in low shrinkage. Moreover, AP can be used as a rheological modifier to regulate the printability of the ceramic ink for direct ink writing of Al₂O₃ ceramic architectures, such as wood-piled scaffolds, honeycomb structures, and tubes with high fidelity. The resultant Al₂O₃ structural ceramics sintered at 1250 °C exhibit good mechanical performance and structural integrity. Most importantly, the linear shrinkage of the printed ceramics is less than 5 %, which is several times lower than that of ceramics with organic binders. This study provides a viable strategy for fabricating high-performance ceramic architectures with good dimensional fidelity for practical applications.     

A review: 3D printing of microwave absorption ceramics

Along with extensive research on the 3D printing and microwave absorption ceramics, 3D printing technology provides a great possibility for microwave absorption ceramics with arbitrary shapes in a faster, cheaper and more flexible way. This review focuses on the latest evolution in the raw materials, the structure design and the advanced additive manufacturing technologies of 3D printing microwave absorption ceramics. Firstly, the representative raw materials are divided into three categories, including ceramic powder, cermet powder and precursor resin. In addition, additives give rise to improvement of microwave absorption properties of ceramics. Secondly, based on two attenuation theories, structure design makes further efforts to enhance the microwave absorption performance of ceramics. Finally, comparisons are made between diversified manufacturing technologies to facilitate the selection of the best ones for different application in practical use. This study presents a summary of research that has been conducted to produce microwave absorption ceramics by additive manufacturing.     

Direct ink writing of hierarchical porous ultra-high temperature ceramics (ZrB2)

An approach to producing hierarchical multi-scale porous ultra-high temperature ceramics (zirconium diboride, ZrB₂) using 3D printing has been developed. Porous ceramic filaments can be 3D printed via Direct Ink Writing (DIW) (paste extrusion). Millimeter scale porosity is created by the 3D printed scaffold filaments. We introduce 20-micron-scale porosity into the scaffold filaments with the addition of oil to produce capillary suspension paste inks. Micron-scale porosity is also developed by partial sintering of the ceramic. The rheological (flow) properties of the capillary suspension paste inks suitable for printing by extrusion through the needle of the 3D printer have been characterized. The samples are strengthened by partial sintering at high temperatures. Complex-shaped components can be printed and sintered into crack-free components, but distortion during drying and sintering lead to poor shape and tolerance control. X-ray tomography is used to characterize the internal structure of the printed components. Printed test bars measured in 4-point bend testing exhibit high strength to density ratio. Such materials potentially have applications as insulation near very high-temperature surfaces in aerospace applications.     

Stereolithography 3D printing of SiC ceramic with potential for lightweight optical mirror

Silicon carbide (SiC) ceramic is the most prospective candidate material for space-based lightweight optical mirror. Stereolithography 3D printing has been reported to fabricate many kinds of ceramics, showing great potential for fabricating lightweight SiC ceramic optical mirror. In this paper, SiC ceramic was fabricated using stereolithography 3D printing combined with polymer burn-out, pre-sintering, and precursor infiltration and pyrolysis (PIP). The relative density, flexural strength, and microstructure during each step were investigated. The as-prepared lightweight SiC ceramic optical mirror exhibited high accuracy and high quality. Finally, it was proved that stereolithography 3D printing has a great potential for lightweight SiC ceramic optical mirror fabrication.     

陶瓷增材制造(3D打印)技术研究进展

高性能陶瓷是现代技术发展和应用不可或缺的关键材料。常规的陶瓷制造技术难以满足对个性化、精细化、轻量化和复杂化的高端产品快速制造的需求。新兴的增材制造技术(3D打印)在高性能陶瓷的成型制造领域具有巨大的发展潜力,有望突破传统陶瓷加工和生产的技术瓶颈,为陶瓷关键零部件的应用开辟新的途径。本文针对陶瓷材料及其快速成型和后处理工艺,重点阐述了三维打印技术、光固化成型技术、选择性激光烧结技术等主流陶瓷增材制造技术的研究现状,并指出了目前存在的问题及发展趋势。     

Cf/SiC复合材料的原料高效改性及其3D打印制备研究进展

选用3D打印制备的碳纤维增强碳化硅陶瓷基（Cf/SiC）复合材料被广泛应用在航空航天、国防军事等重大领域。碳纤维（Cf）作为陶瓷基复合材料的主要候选增强体之一,由于表面惰性的存在,为了提高其与碳化硅（SiC）陶瓷基体的粘附性,对原料Cf的表面改性工作是十分必要的。粉末原料的高效改性制备是3D打印成型陶瓷的重要途径。本文综述了近年来国内外针对Cf改性的各种方法及特点,对Cf/SiC复合材料的3D打印成型及其高效制备方法进行归纳总结。     

3D打印成型陶瓷零件坯体及其致密化技术

3D打印技术在陶瓷零件成型方面具有较大应用潜力,被认为是近净尺寸成型高性能复杂结构陶瓷零件的一种新途径。本文比较了陶瓷零件或其坯体的激光选区熔化、薄材叠加制造、熔融沉积造型、光固化、三维打印和激光选区烧结等不同3D打印工艺及其致密化手段的优势和不足,认为较低的相对密度和强度是阻碍3D打印陶瓷零件实现产品应用的主要障碍。本团队近年来采用造粒混合法制备出具有良好流动性的3D打印复合陶瓷粉体,再通过激光选区烧结(SLS)和冷等静压(CIP)技术分别进行坯体成型及均匀致密化处理,制备出了高性能、复杂结构的Al_2O_3致密陶瓷零件。本文回顾了这些工作,并补充介绍了溶解沉淀和溶剂蒸发这两种制备复合陶瓷粉体的新方法,利用SLS/CIP复合工艺进一步制造了ZrO_2、SiC、高白土等其它材质的复杂陶瓷零件,为3D打印陶瓷用于航空航天、医疗、艺术等领域奠定了基础。     

3D打印氧化硅陶瓷的制备及性能研究

随着陶瓷3D打印技术的发展,3D打印高性能陶瓷越来越受关注,在航空航天领域得到快速应用.通过研究分散剂、浆料pH、氧化硅粉体粒径和固相含量对浆料粘度和流动性的影响,可制备出粘度低、固相含量高、流动性好的陶瓷浆料.测试了不同固相含量对SiO2陶瓷的弯曲强度、烧成收缩率、气孔率和致密度的影响.结果表明:在68vol%的固相含量条件下,烧结后SiO2陶瓷的致密度达到74.32%,烧成收缩率为0.95%.     

3D printed ceramic phosphor and the photoluminescence property under blue laser excitation

An Al₂O₃/YAG: Ce³⁺ ceramic phosphor was fabricated for high-flux laser lighting using the digital lighting process (DLP)-based 3D printing method for the first time. The photocurable ceramic suspension for 3D printing was prepared by blending well-treated Al₂O₃/YAG: Ce³⁺ composite powders with photosensitive resin monomers and photo-initiators. The printing parameters, debinding and sintering processes were designed delicately to fabricated the dense sub-millimeter-sized cylinder ceramic with high dimensional accuracy. The ceramic showed excellent luminescence property under blue laser excitation with a threshold of 20.7 W/mm², higher than that prepared via dry-pressing followed by vacuum sintering. The luminescence properties and the microstructures of both ceramics were further comparatively investigated to find the possible interpretations for improvement of laser flux for the 3D-printed ceramic. The present work indicated that the new developed 3D printing method was promising for preparing luminescent ceramics for high-flux laser lighting in a rapid, effective, low-cost and precision-controlled manner.     

Fused deposition fabrication of high-quality zirconia ceramics using granular feedstock

Benefiting from the mature technology of ceramic injection molding, Fused deposition modeling based on highly-filled ceramic-polymer granular feedstocks has been showing great potential and advantage for fabricating 3D ceramics. Herein, 3D zirconia ceramics using granular feedstock were fabricated, and typical morphology, surface quality, and effect of the thermal accumulation on 3D structure were clarified. Typical morphology of printing steps on the surface were quantitatively characterized, and determined by the surface curvature and layer height of the printed structure. Aligned triangular pores were confirmed at the junction of the deposited filaments with elliptical cross-section morphology. Simple square plates with different size were used to illustrate the influence of thermal accumulation on the morphology of 3D structure. Small printing size increased the thermal accumulation during deposition, resulting in decreased printing quality caused by the secondary over-melting of former deposited layers. Except for the pores at the junctions, dense zirconia ceramics with uniform structure and smooth surface could be achieved. A low-cost and high-quality route for the preparation of 3D ceramics was demonstrated via FDM of highly-filled granular feedstocks.     

Enhanced mechanical properties of 3D printed alumina ceramics by using sintering aids

Stereolithography based 3D printing provides an efficient pathway to fabricate alumina ceramics, and the exploration on the mechanical properties of 3D printed alumina ceramics is crucial to the development of 3D printing ceramic technology. However, alumina ceramics are difficult to sinter due to their high melting point. In this work, alumina ceramics were prepared via stereolithography based 3D printing technology, and the improvement in the mechanical properties was investigated based on the content, the type and the particle size of sintering aids (TiO₂, CaCO₃, and MgO). The flexural strength of the sintered ceramics increased greatly (from 139.2 MPa to 216.7 MPa) with the increase in TiO₂ content (from 0.5 wt% to 1.5 wt%), while significant anisotropy in mechanical properties (216.7 MPa in X-Z plane and 121.0 MPa in X–Y plane) was observed for the ceramics with the addition of 1.5 wt TiO₂. The shrinkage and flexural strength of the ceramics decreased with the increase in CaCO₃ content due to the formation of elongated grains, which led to the formation of large-sized residual pores in the ceramics. The addition of MgO help decrease the anisotropic differences in shrinkage and flexural strength of the sintered ceramics due to the formation of regularly shaped grains. This work provides guidance on the adjustment in flexural strength, shrinkage, and anisotropic behavior of 3D printed alumina ceramics, and provides new methods for the fabrication of 3D printed alumina ceramics with superior mechanical properties.     

Transparent alumina ceramics fabricated by 3D printing and vacuum sintering

Transparent alumina ceramics were fabricated using an extrusion-based 3D printer and post-processing steps including debinding, vacuum sintering, and polishing. Printable slurry recipes and 3D printing parameters were optimized to fabricate quality green bodies of varying shapes and sizes. Two-step vacuum sintering profiles were found to increase density while reducing grain size and thus improving the transparency of the sintered alumina ceramics over single-step sintering profiles. The 3D printed and two-step vacuum sintered alumina ceramics achieved greater than 99 % relative density and total transmittance values of about 70 % at 800 nm and above, which was comparable to that of conventional CIP processed alumina ceramics. This demonstrates the capability of 3D printing to compete with conventional transparent ceramic forming methods along with the additional benefit of freedom of design and production of complex shapes.