Optimization of the sintering thermal treatment and the ceramic ink used in direct ink writing of α-Al2O3: Characterization and catalytic application

Unlike other engineered ceramic products, alumina (Al₂O₃) displays interesting mechanical and physical properties, which makes it an ideal candidate for a wide range of uses in different fields and in particular for catalytic applications. However, the manufacturing of ceramic components has still a major drawback in production of highly complex three-dimensional (3D) shapes, microfeatures or structures with tailored porosity. Direct Ink Writing (DIW), also known as robocasting, is a material extrusion Additive Manufacturing technology and is one of such versatile methods with unique flexibility in material and geometry. In this work, α-Al₂O₃ ceramic materials were designed and produced by DIW to determine the most suitable sintering treatment and ceramic ink composition to design new components for catalytic applications. Several thermal treatments varying sintering temperature and time were tested previously to the preparation of inks with different ceramic loadings, up to 75 wt%. A systematic study of the DIW specimens sintered at the optimal sintering temperature – time combination, in terms of microstructure (density and porosity) and mechanical properties (hardness and indentation fracture toughness), was performed to determine the optimize ceramic loading. Finally, finite element modeling and catalytic experiments conducted for the optimal ceramic ink showed that 3D printed parts with a rectilinear infill pattern and 40% infill density favored catalytic performance.     

Fabrication of bulk piezoelectric and dielectric BaTiO3 ceramics using paste extrusion 3D printing technique

A simple and facile method was developed to fabricate functional bulk barium titanate (BaTiO₃, BT) ceramics using the paste extrusion 3D printing technique. The BT ceramic is a lead-free ferroelectric material widely used for various applications in sensors, energy storage, and harvesting. There are several traditional methods (eg, tape casting) to process bulk BT ceramics but they have disadvantages such as difficult handing without shape deformation, demolding, complex geometric shapes, expansive molds, etc. In this research, we utilized the paste extrusion 3D printing technique to overcome the traditional issues and developed printable ceramic suspensions containing BT ceramic powder, polyvinylidene fluoride (PVDF), N,N-dimethylformamide (DMF) through simple mixing method and chemical formulation. This PVDF solution erformed multiple roles of binder, plasticizer, and dispersant for excellent manufacturability while providing high volume percent and density of the final bulk ceramic. Based on empirical data, it was found that the maximum binder ratio with good viscosity and retention for desired geometry is 1:8.8, while the maximum BT content is 35.45 vol% (77.01 wt%) in order to achieve maximum density of 3.93 g/cm³ (65.3%) for 3D printed BT ceramic. Among different sintering temperatures, it was observed that the sintered BT ceramic at 1400°C had highest grain growth and tetragonality which affected high performing piezoelectric and dielectric properties, 200 pC/N and 4730 at 10³ Hz respectively. This paste extrusion 3D printing technique and simple synthesis method for ceramic suspensions are expected to enable rapid massive production, customization, design flexibility of the bulk piezoelectric and dielectric devices for next generation technology.     

Direct ink writing of hierarchical porous alumina-stabilized emulsions: Rheology and printability

Bio-inspired multi-scaled (hierarchical) porous structures have remarkable strength and stiffness-to-density properties. Direct ink writing (DIW) or robocasting, an additive manufacturing (or also commonly known as 3D printing) material extrusion technique is able to create near-net-shaped complex geometries. A new approach of combining DIW, colloidal particle-stabilized emulsion paste inks and partial densification to create tailored architectures of hierarchical porosity on three scales has been demonstrated. The printed and sintered ceramic lattice structures possess relatively high overall porosity of 78.7% (on average), comprising mainly (64.7%) open porosity. The effects of formulation (surfactant and oil concentrations, solids particle size, and mixing speed) on rheology and pore size and morphology have been investigated. The rheological properties (storage modulus, yield stress, and recovery of storage modulus) of the emulsions have been found to delineate the samples with good shape retention from those that slump. Additionally, the internal features of the sintered structures have been analyzed via X-ray tomography and scanning electron microscope. The role of emulsion stability on printability and the internal structure of the prints has been investigated.     

Effect of MgO sintering additive on mullite structures manufactured by fused deposition modeling (FDM) technology

An optimized recipe for 3D printing of Mullite-based structures was used to investigate the effect of MgO sintering additive on the processing stages and final ceramic properties. To achieve dense 3:2 mullite, ceramic filaments were prepared based on an alumina powder, a methyl silicone resin, EVA elastomeric binder and MgO powder. Using 1 wt% MgO and a dwell time of 5 h at 1600 °C, a dense mullite structure could be obtained from filaments with a diameter of 1.75 mm. Ceramic structures with and without sintering additive were printed in vertical and horizontal direction, to investigate the effect of printing direction on mechanical strength after sintering. Using four-point bending test, it was demonstrated that by using MgO, the printing orientation did not affect the mechanical strength significantly anymore. The low Weibull modulus could be explained by the closed porosity that emerge during the degassing of the preceramic polymer due to cross-linking.     

Highly loaded hydroxyapatite microsphere/ PLA porous scaffolds obtained by fused deposition modelling

The goal of the work was the manufacturing of hydroxyapatite microsphere/polylactic acid (PLA) scaffolds by means of fused deposition modelling (FDM). Micrometer-sized hydroxyapatite spheres synthesized by spray drying (sdHA), were dispersed in PLA by extrusion compounding. Composite filaments were obtained from extrusion which were used in FDM 3D printing for the production of macroporous scaffolds. The sdHA microspheres were used in the composite in order to improve the biomimicry and the bioactivity of the 3D printed scaffold to increase the bone regeneration capacity. Morphological, thermal, physical and mechanical characterizations were performed on the 3D printed composites. Pure PLA scaffolds were 3D printed and used as a reference.Thermal analyses, TGA and DSC evidenced that the glass transition temperature and the degree of crystallinity of PLA were not influenced by the presence of sdHA. Morphological analysis showed a smooth surface of the printed samples when pure PLA was used. A rough surface was found on the PLA/sdHA composites, confirming, the homogeneous dispersion of the ceramic phase in the polymeric matrix. The higher porosity of the composite samples compared to PLA ones, most likely caused a decrease of the mechanical performances of the PLA/sdHA scaffolds. Composite scaffolds displayed stiffness values compatible with that of bone tissue.     

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.     

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 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.     

Nanogrooved carbon microtubes for wet three‐dimensional printing of conductive composite structures

Recent advances in three‐dimensional (3D) printing have enabled the fabrication of interesting structures which are not achievable using traditional fabrication approaches. The 3D printing of carbon microtube composite inks allows fabrication of conductive structures for practical applications in soft robotics and tissue engineering. However, it is challenging to achieve 3D printed structures from solution‐based composite inks, which requires an additional process to solidify the ink. Here, we introduce a wet 3D printing technique which uses a coagulation bath to fabricate carbon microtube composite structures. We show that through a facile nanogrooving approach which introduces cavitation and channels on carbon microtubes, enhanced interfacial interactions with a chitosan polymer matrix are achieved. Consequently, the mechanical properties of the 3D printed composites improve when nanogrooved carbon microtubes are used, compared to untreated microtubes. We show that by carefully controlling the coagulation bath, extrusion pressure, printing distance and printed line distance, we can 3D print composite lattices which are composed of well‐defined and separated printed lines. The conductive composite 3D structures with highly customised design presented in this work provide a suitable platform for applications ranging from soft robotics to smart tissue engineering scaffolds. © 2019 Society of Chemical Industry     

Coating optimization of yield pseudoplastic paste-based stereolithography 3D printing of alumina ceramic core

Yield pseudoplastic paste is prepared for self-supported stereolithography (SLA) 3D printing with critical shear stress of 290.7 Pa and viscosity of 28810 mPa·s under strain rate of 30 s^?1. Simulation analysis of paste coating is carried out based on established constitutive equation. Furthermore, corresponding stress field is analyzed under different layer thicknesses (25–100 μm) and blade speeds (1.5–4.5 mm/s). Then, flexural strength, porosity, surface roughness and microstructure of components, printed with different layer thicknesses and sintered at different temperatures, are systematically investigated. Finally, complex-shaped cores are fabricated with flexural strength of 38.56±1.45 MPa, porosity of 21.57±0.8% and surface roughness of R_a < 3 μm. The optimized parameters include layer thickness of 25–50 μm, blade speed of 3.5 mm/s, and sintering temperature of 1300 ^oC. Moreover, step-like undulating fracture morphology of the core is observed along printing layer, which shows that the coating process has an important influence on the mechanical properties of ceramic parts.     

Fabrication of complex shaped alumina parts by gelcasting on 3D printed moulds

Alumina ceramic components were produced using gelcasting and 3D printing techniques to generate the end product. The 3D printed mould made from (acrylonitrile butadiene styrene) ABS filament provides a convenient demoulding method by dissolution of the mould using acetone as a solvent. This process enables low cost production of complex shaped ceramic components. The effect of the suspension solid loading on the properties and microstructure of complex shaped alumina parts was investigated. The produced ceramic components had densities up to 99.0%, hardness of 18 GPa, flexural strength of 374 MPa and a fracture toughness of 3.8 MPa√m after sintering in air for 3 h, in good agreement with published values.     

DLP 3D printing porous β-tricalcium phosphate scaffold by the use of acrylate/ceramic composite slurry

Digital light processing (DLP) 3D printing has been utilized to fabricate controlled porous β-tricalcium phosphate (β-TCP) scaffolds, which promote cell adhesion and angiogenesis during bone regeneration. However, the current limitation of DLP 3D printing for the fabrication of β-TCP scaffold is how to prepare a low viscosity ceramic slurry and remove the toxicity of residual non-polymerized slurry. The present study has developed a low viscosity ceramic slurry system by mixing β-TCP with photosensitive acrylate resin, and the viscosity of slurry is about 3 Pa s and the solid content of β-TCP can be as high as 60 wt%. After optimizing the ratio of slurry, printing, degreasing and sintering processes, the maximum compressive strength of the DLP printed scaffolds reaches up to 9.89 MPa, while the porosity keeps ca. 40%. According to the proliferation of cells, it confirms the preserved biocompatibility of DLP-fabricated β-TCP scaffolds. These porous scaffolds made by DLP 3D printing technology is of great significance for bone regeneration, and will also help to expand the application of DLP technology in biomedical field.     

3D printing of honeycomb Si3N4 ceramic

In this paper, a honeycomb Si₃N₄ ceramic was fabricated by 3D printing with a well-preserved structure. The effects of Si₃N₄ content on the rheological properties of Si₃N₄/sol–silica ink and the printing resolution of products were investigated. The microstructure, phase composition, liner shrinkage rate, and fracture behavior of printed samples before and after sintering were systematically characterized in detail. The results showed that the modified inks had the optimized rheological properties, and the stress–shear rate curves corresponding to each slurry could be well described by Bingham and Herschel–Bulkley fluid models. The corresponding slump rates of the printed samples with different Si₃N₄ to sol–silica mass ratios were all lower than 4%, and the linear shrinkage rate of all of the samples after sintering was below 20%. The fracture behavior under compressive loading of the honeycomb Si₃N₄ ceramics tended to be non-catastrophic fractures both before and after sintering. The compressive strengths of all of the printed samples decreased with the increase of the Si₃N₄ content, and the highest compressive strength of the honeycomb ceramics could reach 131.2 MPa after sintering at 1600°C, which was about 366.9% higher than that of the samples in green state prior to the sintering.     

Fabrication of Ti3SiC2-based pastes for screen printing on paper-derived Al2O3 substrates

This paper describes the development and fabrication of pastes suitable for screen printing process using Ti₃SiC₂ as the ceramic filler and ethyl cellulose as the binder. With the aim of obtaining high quality screen printed films, the influence of different amounts of Ti₃SiC₂ filler (20–40?vol%) and binder (0–5?vol%) on the rheological properties of the pastes was investigated. Samples with higher viscosity, such as pastes containing 30?vol% and 40?vol% Ti₃SiC₂ filler, regardless of the amount of ethyl cellulose, showed a higher printing quality compared to the samples with other compositions. The different paste compositions were screen printed onto paper-derived Al₂O₃ substrates containing 28.6 ± 4.8% open porosity and sintered for 1?h under an argon atmosphere at 1600?°C. X-ray diffraction (XRD) measurements and scanning electron microscopy (SEM) analysis showed that the sintered films contained TiC as a primary phase and Ti₃SiC₂ as a secondary phase. The partial decomposition of Ti₃SiC₂ after sintering can be attributed to residual carbon from the organic additives, which decreases the thermal stability of this material.     

Fabrication of piezoelectric nano-ceramics via stereolithography of low viscous and non-aqueous suspensions

A high-performance piezoelectric nano-ceramic was fabricated through stereolithography of low viscosity and high solid loading ceramic/polymer composite suspensions. Through the proper fitting calculation of experimental data, the maximum theoretical solid loading, rheological and curing behaviors of the suspension system were evaluated and lucubrated. The suspensions with a 40 vol% solid loading of the BaTiO₃ nanoparticles displayed shear thinning behavior and a relatively low viscosity of 232 mPa·s at 46.5 s⁻¹ shear rate. After post-process, the 3D printed ceramic specimens showed a nanometer-level grain size with a density of 5.69 g/cm³, which corresponds to about 95% of the theoretical density. The printed ceramics exhibit a piezoelectric constant of 163 pC/N and relative permittivity of 2762 respectively. The results achieved in this research indicate that the stereolithography process is a promising 3D printing technology to fabricate piezoelectric materials with complex geometries and exquisite features for the applications of ceramic components.     

LAS glass–ceramic scaffolds by three-dimensional printing

Highly porous (>60% open porosity) glass–ceramic scaffolds with remarkable mechanical properties (compression strength of ～15 MPa) were produced by indirect 3D printing. Precursor glass powders were printed into 3D ordered structures and then heat treated to sinter and develop crystalline phases. The final glass–ceramic contained a β-spodumene solid solution together with a secondary phase of lithium disilicate.The precision of the printed geometry and the density of the struts in the scaffold depended on several processing parameters (e.g. powder size and flowability, layer thickness) and were improved by increasing the binder saturation and drying time. Two types of powders with different particle size distribution (PSD) and flowability were used. Powders with a larger PSD, could be processed within a wider range of printing parameters due to their good flowability; however, the printing precision and the struts density were lower compared to the scaffolds printed using the powder in a smaller average PSD.     

3D printing boehmite gel foams into lightweight porous ceramics with hierarchical pore structure

We herein report a novel hierarchically porous ceramic foams derived from boehmite gel foams, which possess both high porosity and superior strength. The gel foams show excellent printability due to its predominant stability, high yield stress and storage modulus, which endows such foam material ideal ink for 3D printing lightweight and complex-shape materials via direct ink writing approach. The 3D printed ceramic foams possess programmable architecture assembled by porous filaments, uniform macro-pores with tunable size in the range of 4∼70 μm, as well as nanoscale pores in cell wall, after sintering at relatively low temperature of 1200–1300 °C. In this way, ceramic foams with high strength were achieved, attributed to the tiny grains, large amount of grain boundaries, uniform pores and hierarchical pore structure. Notably, the foams sintered below 1200 °C have significant advantage on specific surface area, which could reach up to 300-400 m²/g.     

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.     

Suture Fiber Reinforcement of a 3D Printed Gelatin Scaffold for Its Potential Application in Soft Tissue Engineering

Gelatin has excellent biological properties, but its poor physical properties are a major obstacle to its use as a biomaterial ink. These disadvantages not only worsen the printability of gelatin biomaterial ink, but also reduce the dimensional stability of its 3D scaffolds and limit its application in the tissue engineering field. Herein, biodegradable suture fibers were added into a gelatin biomaterial ink to improve the printability, mechanical strength, and dimensional stability of the 3D printed scaffolds. The suture fiber reinforced gelatin 3D scaffolds were fabricated using the thermo-responsive properties of gelatin under optimized 3D printing conditions (−10 °C cryogenic plate, 40–80 kPa pneumatic pressure, and 9 mm/s printing speed), and were crosslinked using EDC/NHS to maintain their 3D structures. Scanning electron microscopy images revealed that the morphologies of the 3D printed scaffolds maintained their 3D structure after crosslinking. The addition of 0.5% (w/v) of suture fibers increased the printing accuracy of the 3D printed scaffolds to 97%. The suture fibers also increased the mechanical strength of the 3D printed scaffolds by up to 6-fold, and the degradation rate could be controlled by the suture fiber content. In in vitro cell studies, DNA assay results showed that human dermal fibroblasts’ proliferation rate of a 3D printed scaffold containing 0.5% suture fiber was 10% higher than that of a 3D printed scaffold without suture fibers after 14 days of culture. Interestingly, the supplement of suture fibers into gelatin biomaterial ink was able to minimize the cell-mediated contraction of the cell cultured 3D scaffolds over the cell culture period. These results show that advanced biomaterial inks can be developed by supplementing biodegradable fibers to improve the poor physical properties of natural polymer-based biomaterial inks.     

High-performance and high-precision Al2O3 architectures enabled by high-solid-loading,graphene-containing slurries for top-down DLP 3D printing

To date, obtaining the high-solid-loading Al₂O₃ slurry and overcoming the trade-off between high solid loading and printing accuracy and strength of printed green bodies to achieve high-performance and precision Al₂O₃ ceramic parts by DLP 3D printing remain challenging. In this study, an Al₂O₃ slurry with high solid loading of 60 vol% was developed through dispersant optimisation for top-down DLP 3D printing. Graphene was innovatively introduced during slurry fabrication to decouple the printing accuracy and strength of green bodies from such high solid loading. Simultaneously, graphene addition could considerably reduce slurry fluidity, thereby facilitating its coordination with top-down DLP. With 0.07 wt% graphene addition, the dimension deviations of printed green bodies improved from 90 to 880 µm to ≤ 70 µm, and the bending strength increased by 17.75%. High-performance and precise Al₂O₃ ceramic components with low sintering shrinkages were prepared. The density and microhardness were 99.7% and 18.61 GPa, respectively.