Flexible interconnected ceramic parts 3D printed by two-component material extrusion with water-soluble support structures

Material extrusion (MEX) of complex thermoplastic structures often depends on the reliable printing of a water-soluble support structure. The material of choice is typically polyvinyl alcohol (PVA), which is not used in ceramic MEX printing due to a limited printing compatibility with most ceramic feedstocks (poor layer adhesion). Herein, a new thermoplastic feedstock was developed as temporary support material on the basis of NaCl mixed with a commercial injection molding binder system. The NaCl feedstock is fully compatible for MEX printing with ceramic feedstocks and showed excellent printing properties and high green body strength. The support structure is mostly dissolved in water and the rest can be removed manually or during thermal debinding. The NaCl support material was used to print flexible Al₂O₃ samples with hinges or chainmail samples. This strategy is an attractive way to introduce additional functionality and new applications which were so far inaccessible to technical ceramics.     

Digital light processing additive manufacturing of in situ mullite-zirconia composites

Digital light processing (DLP) can produce small series ceramic parts with complex geometries and tiny structures without the high cost of molds usually associated with traditional ceramic processing. However, the availability of feedstock of different ceramics for the technique is still limited. Mullite-zirconia composites are refractory materials with diverse applications, nevertheless, their 3D printing has never been reported. In this work, alumina and zircon were used as raw materials for additive manufacturing by DLP followed by in situ mullite and zirconia formation. Thus, coarse zircon powder was milled to submicrometric size, alumina-zircon photosensitive slurries were prepared and characterized, parts were manufactured in a commercial DLP 3D printer, debound, and sintered at different temperatures. The printed parts sintered at 1600 °C completed the reaction sintering and reached a flexural strength of 84 ± 13 MPa. The process proved capable of producing detailed parts that would be unfeasible by other manufacturing methods.     

Processing of hydroxyapatite and its composites using ceramic fused filament fabrication (CF3)

In this article, we report the fabrication of hydroxyapatite (HAp) and its composites with 7.75 vol% Si₃N₄ (HAp10SN) using ceramic fused filament fabrication (CF³). Homogeneous feedstock with 40 vol% ceramic powder was prepared and used to extrude filaments for further printing using a desktop printer. Our results showed that the addition of Si₃N₄ to HAp increases the feedstock viscosity. However, the filaments and CF³ parts made using HAp and HAp10SN feedstocks exhibited comparable densities without gross defects. We have obtained relatively smoother CF³ parts with HAp10SN than pure HAp, which is attributed to their high feedstock viscosity and formation of liquid phase during sintering. Sintering at 1250 °C for 4 h in air, after thermal debinding, resulted in a relative density of ~85% with HAp and tricalcium phosphate (TCP) as major constituents. Sintered HAp10SN samples also revealed almost 70% reduction in the grain size and 4-fold increase in the hardness compared to pure HAp. Our results indicate that the CF³ processed HAp10SN samples containing ~15% porosity, Si₃N₄ particles and Si-substituted HAp/TCP have strong potential as bone replacements.     

Binder stabilization and rheology optimization for vat-photopolymerization 3D printing of silica-based ceramic mixtures

Enhancing inlet gas temperature in aero/gas turbines to reduce their carbon-footprint, has led to a strive for better performing inlet cooling mechanism of the turbine blades. The internal cooling of the blades is made by ceramic cores in their casting process, but conventional ceramic molding has long reached its maximum possible geometrical complexity, hence shedding light on 3D printing of these cores. The objective of this study is to develop low-viscous, fully stabilized, commercially viable ink for vat-photopolymerization of silica-based ceramics. This paper investigates the best dispersion type and amount for different formulated monomer mixtures, and explains the best correlation between viscosity, solid loading, binders, dispersants, peeling forces and mechanical properties, and offers an optimized mixture to avoid the common ceramic printing issue, namely crack propagation of cores during sintering. Among five dispersant agents, the SOL20, SOL24 and FA4611 exhibited better performance than other dispersion agents, and the optimum concentration level for each binder and dispersant agent was ensured through sedimentation test. Their dispersion capability and long-term stability were further investigated to designate the best dispersion agent for each binder system. Further verification was made by sedimentation study of the samples at 40 °C for 40 days and reducing the superficial area of the used powder mixture. According to the result of the rheology analysis, the best dispersions were achieved using SOL20 for the loaded binder mixtures of M1 and M4, SOL24 for M3and FA4611 for M2. The instability of M1 and M2 with their respective dispersant agent was coordinated through the thixotropic agent of TX/2, and complete stabilization and near-Newtonian behavior were achieved. However, the research showed that the addition of TX/2 to fully stabilized M4 and M2 suspensions negatively impacts the mixtures’ rheological behavior from near-Newtonian to shear-thickening. In the final stage of this study, peeling forces, sintering and three-point bending tests were conducted to determine the final formulated suspension to print ceramic core components. M4 and SOL20 combination was selected for SiO₂-ZrSiO₄ loading and dispersing, respectively. The impact of solid loading between the range of 58 and 65 vol% on the rheological behavior of the final suspension and the mechanical properties of sintered bodies were investigated to assign an optimum solid rate. The adequate strength on sintered and degree of viscosity for ceramic vat-polymerization processing was achieved at 58 vol%. Lastly, a validation study is conducted by printing a complex ceramic core model by a commercial LCD hobby printer. This validation shows the significance of this study to scale up the manufacturing of complex-shaped ceramic cores and to revolutionize the sector, by printing inexpensive and readily available irregular-shaped (non-atomized) ceramic powder, using the most cost-effective LCD printers (non-specialized expensive ceramic printers).     

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。     

Micro powder injection moulding of alumina micro-channel part

A feedstock consisting of submicron alumina powder and a formulated binder, was developed to fabricate alumina micro-channel part by micro powder injection moulding. During small scale-mixing, the mixing torques of feedstocks with four different powder loadings were used to establish a suitable powder loading. The thermal and rheological properties of the selected feedstock were examined and used to establish conditions for large scale mixing, debinding and injection moulding. The micro-channel parts were pressureless sintered at different temperatures. The results showed that the moulded, debound and sintered micro-channel parts had good shape retention. The dimensions of the micro-channel part changed with the different processing steps. High densification of the micro-channel parts was achieved at sintering temperatures of 1350 °C and above. Above 1350 °C, the grain grew significantly with increasing the sintering temperatures and thus it led to a decrease in the microhardness.     

De-Agglomeration Kinetics of Feedstocks with Granule Tetragonal Zirconia Polycrystalline Powder

This study establishes the relationship between homogeneity of tetragonal zirconia polycrystalline (TZP) feedstocks and the kneading time in order to understand the kneading energy adsorption during the de-agglomeration period of pre-existing ceramic granules. Two spray-dried Y-TZP powders with different compress strengths were investigated using torque rheometer and transmission optical microscopy. Several properties, kneading torque ( T ), Casson viscosity (μ), Reynolds number ( Re ), and dispersive index ( D _s) of the feedstocks were introduced, and monitored as a function of kneading time. Optimal processing windows were identified from the dependence of dispersive index with a power number ( N _p). The best shear-kneading procedure was proposed in consideration of best feedstock homogeneity and shortest kneading time. One homogenous feedstock and two comparable cases were prepared for subsequent injection molding, debinding, sintering, and mechanical testing. The fracture strength of sintering parts by a partially homogeneous feedstock can be improved from 520 to 680 MPa by a homogeneous feedstock.     

熔融沉积3D打印机机械结构的设计

3D打印技术作为一种快速成型技术,其采用数字式模型文件作为基础,采取逐层打印的办法将可粘合性的塑料或者粉末金属用以构筑所预想的实体技术.由于3D打印技术可采用的耗材种类不同,故其存在着不同的3D打印技术用于构造不同类型的部件.3D打印耗材常有尼龙玻纤、铝合金、钛合金、石膏、镀金银以及橡胶等材料.为了拓宽3D打印机所使用...     

Interplay of the phase and the chemical composition of the powder feedstock on the properties of porous 8YSZ thermal barrier coatings

Some chemical impurities enhance sintering kinetics of ceramic Thermal Barrier Coatings (TBCs) which can cause their premature failure during operation in gas turbine engine by causing reduction in coating’s strain compliance as well as faster bond-coat oxidation due to increased thermal conductivity. Certain chemical impurities are also believed to suppress resistance to tetragonal to monoclinic phase transformation in 8YSZ, which can also be an important factor regarding TBC’s performance. Most of the impurities and some of the monoclinic phase present in the powder feedstocks can survive into the as-sprayed coating. Therefore, there is a general trend towards OEMs requiring the lowest amounts of chemical impurities and the lowest amounts of monoclinic phase in the powder feedstocks. This paper presents a comprehensive investigation aimed at understanding the role and the relative importance of the chemical and phase purities of the powder feedstock for the properties and performance of thick 8YSZ TBCs.     

大壁厚3D打印SiO2陶瓷快速制备技术研究

选用复合分散剂制备低粘度陶瓷料浆,采用自主研发的陶瓷3D打印机,以DLP(digital light processing)工艺制备出了大壁厚(>3 mm)SiO₂空心内六角陶瓷部件,坯体精度均在50 μm内。分析了3D打印陶瓷素坯在空气气氛和氩气气氛下的热分解过程,研究了气氛对大壁厚(>3 mm)SiO₂陶瓷部件脱脂与烧结的影响。结合扫描电子显微镜(SEM)分析了大壁厚(>3 mm)3D打印SiO₂陶瓷坯体快速脱脂烧结的工艺,氩气气氛有利于大壁厚SiO₂陶瓷快速脱脂烧结。氩气气氛下,控制气流量,进行了大壁厚(>3 mm)SiO₂陶瓷部件的快速制备,脱脂烧结周期大大缩短,为21.8 h,较自国外某公司进口的料浆及其工艺的制备周期(以进口的该公司料浆及工艺制备的相同产品制备周期为283 h)缩短92.3%,较公开报道的3D打印相同工艺制备的SiO₂陶瓷空心叶片制备周期缩短82%以上。     

Yttria stabilized zirconia formed by micro ceramic injection molding: Rheological properties and debinding effects on the sintered part

Micro Ceramic Injection Molding (μCIM) is a near net-shape process to produce smaller and intricate parts at a competitive cost. The application of nano-sized ceramic powder in μCIM has the advantages of fine grain size growth and good surface finish. However, the nano size effect causes agglomeration and low powder loadings, which result in defects during the μCIM process and in the sintered components. This study extensively investigated the debinding and sintering of yttria-stabilized zirconia (YSZ), as well as its rheological properties, using polypropylene (PP) as the primary binder and palm stearin as the secondary binder. 50 nm Yttria stabilized zirconia (YSZ) powders were mixed with palm stearin and PP at a powder loading of 37–43 vol%. The results of rheological studies showed that the feedstock had a dilatant flow characteristic and a viscosity of around 10–40 Pa s. Feedstock with 38 vol% powder loading had the lowest activation energy of 9.48 kJ/mol. The green part of the injected feedstock had flexural strength ranging from 13 to16 MPa, within which the feedstock with 43 vol% powder loading had the highest green density. Solvent debinding was carried out at three temperatures (50, 60, and 70 °C) using heptane. A large porous region was clearly identified at 70 °C compared with 50 °C. A debinding split furnace with argon gas was used to remove PP at 450 °C for 4 h. The debound samples did not shrink when 94%–98% of the binder system was removed. All debound samples sintered at 1350 °C and 41 vol% had the highest mechanical properties with hardness of 900 HV and a flexural strength of 400 MPa.     

Ink-Jet Printing of Wax-Based Alumina Suspensions

Suspensions of fine alumina powder in a paraffin wax have been successfully formulated with viscosity values sufficiently low to allow ink-jet printing using a commercial printer. A commercial-grade paraffin wax, with stearylamine and a polyester, were used as the dispersant system. Suspensions with powder loadings up to 40 vol% were passed through the ink-jet printer head. Unfired ceramic bodies with a feature size of <100 μm have been successfully fabricated with waxes that had a powder loading of 30 vol%. The influence of suspension fluid properties on the ink-jet printing process has been studied, and the importance of the acoustic resonance within the ink-jet printing apparatus has been demonstrated.     

Rheological and thermal debinding behaviors of silicon nitride in powder injection molding

In powder injection molding process, it is important to analyze the rheological and thermal debinding behaviors of feedstock, because they can directly affect the final quality of products. Therefore, for the silicon nitride based feedstocks, the rheological and thermal debinding behaviors were investigated and compared between feedstocks prepared with the combination of two types of powders and sintering aid ratios. At first, the optimal solids loading for each feedstock was determined based on the results of the torque rheometer experiment. The viscosity of the feedstocks was measured using the capillary rheometer, and rheological properties were evaluated with the Power Law-Arrhenius model. Silicon nitride (JPN) feedstock with 5 wt% yttria and 2 wt% alumina (JPN+5Y2A) had the highest moldability index among all feedstocks. The powders with sintering aid ratio of 5 wt% yttria and 2 wt% alumina made the feedstocks have a high moldability index. Thermogravimetric experiment was also performed to analyze the pyrolysis behavior of the feedstocks, and the apparent activation energies for each feedstock were obtained using Kissinger method with the thermogravimetric analysis results. Based on the results, the master decomposition curve (MDC) was developed, and the utility of MDC for optimizing the thermal debinding process was verified.     

Impact of powder morphology on quality of low-pressure injection moulded reaction-bonded net shape oxide ceramics

Low-pressure injection moulding is a very efficient process for net shape manufacturing of ceramic micro parts. In order to obtain sintered ceramic specimens without shape distortion or damages, density gradients in the green bodies have to be avoided. Especially feedstocks with a solid loading near the critical powder volume content often tend to segregate the binder while flowing. However, the value of critical powder content can be significantly influenced by particle size, particle size distribution and particle morphology. This paper compares two powder mixtures of identical chemical compositions with different specific surfaces and morphology and evaluates their workability for low-pressure injection moulding. The aim of this paper is to identify the influence of morphology on feedstock rheology as well as on accuracy, mechanical properties and microstructure of net shape manufactured reaction-bonded zircon ceramics.     

3D printing of high solid loading zirconia feedstock via screw-based material extrusion

Zirconia ceramic (3Y-TZP) feedstocks with solid loadings from 50 vol% to 68 vol%, in a 60:40 paraffin wax to LDPE ratio binder system, were prepared and printed using a screw-based material extrusion printer. A two-step debinding process involving solvent debinding (cyclohexane + ethanol) and thermal debinding (140 °C–600 °C at 0.2 °C/min) followed by sintering at 1500 °C for 2 h was employed. Tests performed include TGA, density test, Vickers hardness and fracture toughness, XRD, and SEM. The TGA result showed two significant drops in weight starting at 180 °C and 380 °C, which corresponds to the decomposition of paraffin wax and LDPE, respectively. A minimum of 40 wt% of soluble binder was removed from the green sample after solvent immersion for 3 h at 40 °C for solid loadings ≥55 vol%. High solid loading feedstocks produced samples with comparable density, Vickers hardness and fracture toughness, which are 97.5%, ∼12.3 GPa, and ∼5.5 MPa m^1/2, respectively; while XRD and SEM shows no adverse tetragonal to monoclinic phase transformation and grain growth, respectively. This study demonstrates that 3D printing of granular 3Y-TZP ceramic feedstock via screw-based material extrusion technique is feasible even with high solid loadings, which is usually difficult to fabricate into flexible filaments and print due to high viscosity.     

Low-pressure injection molding of magnesium aluminate nanoparticles: Rheological behavior and flexural properties of sintered component

This research aims to investigate the density and flexural strength of nanostructured spinel parts fabricated using the low-pressure injection molding (LPIM) method. For this purpose, firstly, the effect of the amount of binder was tested on the rheology behavior of the feedstocks containing spinel nanopowder for producing ceramic parts using the LPIM method. The rheometric analysis indicated that the feedstocks containing 80 wt% powder and 20 wt% binders showed shear-thinning fluid behavior and were chosen as the optimal low-viscosity feedstocks for the LPIM process. After binder removal from LPIMed part, secondly, the effect of sintering temperature was examined on the relative density and flexural strength of the spinel parts. The results indicated that by increasing sintering temperature from 1550 °C to 1700 °C, the size of pores was reduced and grain size was increased from 2 μm to 6 μm. Furthermore, the flexural strength of the parts sintered at 1700 °C was 10 MPa greater than that of the sample sintered at 1650 °C.     

Fabrication of 8-YSZ thin-wall tubes by powder extrusion moulding for SOFC electrolytes

In this work the processing steps for producing YSZ thin tubes by means of powder extrusion moulding (PEM) technique are investigated. Different feedstocks were prepared from a commercial YSZ powder and a multicomponent thermoplastic binder system based in polypropylene and paraffin wax. The surface coating of YSZ powder with stearic acid in a high-performance dispersing instrument reduces the viscosity of the feedstock one order of magnitude respect to a feedstock with a same composition and un-coated powder. This fact allows increasing the solid loading up to 58 vol.% to obtain sintering tubes with densities higher than 97% and with wall thickness lower than 200 μm.     

Injection molding of ceramic cutting tools for wood-based materials

In this study a mutable mold for ceramic cutting tools with inserts of different cutting angles and two different injection positions was designed. Three alumina-based ceramic feedstocks with different types and amount of second phases were developed. A mold filling study was carried out for both sprue positions in order to prove the molding behavior of the feedstock and the functionality of the mold. Debindering and sintering of molded green parts was arranged for each composition, respectively. Mechanical properties, microstructure and achieved cutting edge sharpness of produced tools were investigated. Results show that the mold design and injection molding process play a key role in order to manufacture cutting tools of best possible sharpness enabling a wood machining process. Feedstocks exhibit a good mold filling behavior resulting in comparatively sharp cutting edges of ≈10 μm after sintering. Mechanical properties show high potential for application of wood machining cutting tools.