Extrusion-based additive manufacturing of functionally graded ceramics

The Ceramic On-Demand Extrusion (CODE) process has been recently proposed for additive manufacturing of dense, strong ceramic components via extrusion with uniform layered drying. This study focuses on enabling CODE to fabricate functionally graded ceramics. A controlled volumetric flowrate for each ceramic paste was used to achieve a gradient between alumina and zirconia. A dynamic mixer was built to mix constituent ceramic pastes homogeneously. Functionally graded alumina/zirconia samples were printed, sintered, and tested to examine the capability of CODE in fabricating functionally graded components. The desired and actual material compositions were compared using energy dispersive spectroscopy. Dimensions of sintered samples were evaluated to study the deformation of functionally graded components during drying and sintering. Vickers hardness was also measured at different locations, corresponding to different material compositions. Finally, a case study was conducted to demonstrate the capability of the proposed method to build functionally graded ceramics with complex geometries.     

Additive manufacturing of zirconia parts with organic sacrificial supports

Ceramic On-Demand Extrusion (CODE) process has been recently proposed for additive manufacturing of strong ceramic components via extrusion. This paper focuses on fabricating 3 mol% yttria-stabilized zirconia (3YSZ) components using CODE process, and enabling CODE to produce parts with support structures. A colloidal suspension of 3YSZ was developed and deposited through the main nozzle, and an organic feedstock was developed and deposited by means of another nozzle to fabricate supports. After printing and drying of raw parts, supports were removed by increasing the temperature and parts were then sintered to near theoretical (~99%) density. The maximum overhang angle that could be built with no support was also found out to be approximately 60 degrees. Three organic support materials, that is, polycaprolactone (PCL), silicone, and petrolatum were prepared and tested. PCL and petrolatum were identified as feasible support materials. Specimens were fabricated to validate the efficiency of the support materials and to evaluate CODE's capability for building parts with complex geometry. The microstructures of these parts were also analyzed via scanning electron microscopy.     

Mechanical characterization of parts produced by ceramic on‐demand extrusion process

Ceramic On‐Demand Extrusion (CODE) is an additive manufacturing process recently developed to produce dense three‐dimensional ceramic components. In this paper, the properties of parts produced using this freeform extrusion fabrication process are described. High solids loading (~60 vol%) alumina paste was prepared to fabricate parts and standard test methods were employed to examine their properties including the density, strength, Young's modulus, Weibull modulus, toughness, and hardness. Microstructural evaluation was also performed to measure the grain size and critical flaw size. The results indicate that the properties of parts surpass most other ceramic additive manufacturing processes and match conventional fabrication techniques.     

Flexural strength and Weibull analysis of Y-TZP fabricated by stereolithographic additive manufacturing and subtractive manufacturing

Digital light processing (DLP) is a relatively mature technology of ceramic additive manufacturing and is promising for fabricating zirconia-based dental restorations. It allows for manufacturing ceramic components with nearly unlimited geometries compared to traditional subtractive manufacturing technology. In order to explore its potential for fabricating dental prosthesis and determine its clinical indications, it is essential to investigate its microstructural characteristics and mechanical behavior. In this study, yttria-stabilized tetragonal zirconia polycrystal (Y-TZP) fabricated by stereolithographic additive manufacturing, namely DLP acquired favorable flexural strength close to that of conventional subtractive-manufactured Y-TZP as indicated by uniaxial (three-point bending) and biaxial (ring on ring) tests, though the Weibull modulus of DLP-manufactured zirconia was lower than that of subtractive-manufactured zirconia. The strength predicting approach that uses effective area calculations was found to be applicable for both DLP-manufactured zirconia and subtractive-manufactured zirconia. Though both materials showed similar microstructures considering grain size and phase composition, significant differences in critical defects were observed.     

Fractography of zirconia-specimens made using additive manufacturing (LCM) technology

A relatively new method to manufacture complex ceramic prototypes and components is additive manufacturing (AM). With the LCM (Lithography-based Ceramic Manufacturing)-technology the green body is manufactured layer-by-layer using selective curing of light-sensitive ceramic slurry by a mask exposure process. After curing by blue light the component is removed from the building platform and the green body is sintered to a ceramic component.The aim of this work is to investigate the influence of processing and layer architecture on the mechanical properties of an Yttria-stabilized zirconia ceramic. Strength tests were performed by uniaxial bending tests and by biaxial Ball-on-three Balls (B3B) tests. To identify typical fracture initiating flaws a systematic fractographic investigation was performed on different batches of Ball-on-three Balls-test and bending test specimens, respectively.Through additional investigations it was found that hardness and fracture toughness were independent on the layer architecture. But an extensive fractographic analysis showed that the strength was limited by flaws, which were introduced by processing and handling. If these flaws can be avoided by optimisation of the process the strength should be equal to that of conventional processed ceramics.     

Additive manufacturing and mechanical characterization of high density fully stabilized zirconia

Mechanical properties of additively manufactured 8 mol% yttria-stabilized zirconia (8YSZ) parts were extensively studied for the first time. A novel freeform extrusion fabrication process, called Ceramic On-Demand Extrusion (CODE), was employed to deposit an aqueous viscous suspension (~50 vol% solids loading) of fully stabilized zirconia powder in a layer-by-layer fashion. Each layer was exposed to infrared radiation after deposition to attain partial solidification due to drying. Before exposure, the layer was surrounded by oil to preclude non-uniform evaporation, which could cause warpage and crack formation. After the fabrication process was completed, the parts were humid-dried in an environmental chamber and densified by sintering under atmospheric pressure. Standard test methods were employed to examine the properties of sintered parts including density, Vickers hardness, fracture toughness, Young's modulus, and flexural strength. Microstructural evaluation was also performed to observe the microstructural morphology and measure grain size. The results indicate that the properties of 8YSZ parts produced by the CODE process match those obtained by conventional fabrication techniques.     

Robocasting of dense 8Y zirconia parts: Rheology,printing, and mechanical properties

Advanced ceramics with complex geometry have become indispensable in engineering applications. Due to limitations of traditional ceramic fabrication processes, additive manufacturing represents a revolution for shaping and consolidation because of its unique capabilities for increasing shape complexity and reducing waste material. Among the additive manufacturing techniques, robocasting is often considered to yield fine and dense ceramic structures with geometrically complex morphology and high strength. Within this context, it is the objective to attain dense 8 mol% yttria-stabilized zirconia (8Y-ZrO₂) by evaluating the influence of solid loading and filament orientation on the physical and mechanical properties of sintered parts. In doing so, a printable ink was developed using an inverse-thermoresponsive hydrogel. Results revealed that ceramic charges of 67.5 and 70 wt% achieved the best balance regarding density, hardness, and compression strength. Furthermore, rectilinear geometry with a filament orientation at 45º displayed higher mechanical response than 0/90º and cylindrical ones.     

Thermoplastic 3D Printing—An Additive Manufacturing Method for Producing Dense Ceramics

In our new approach—thermoplastic 3D printing—a high‐filled ceramic suspension based on thermoplastic binder systems is used to produce dense ceramic components by additive manufacturing. Alumina (67 vol%) and zirconia (45 vol%) suspensions were prepared by ball milling at a temperature of about 100°C to adjust a low viscosity. After the preparation the suspension solidified at cooling. For the sintered samples (alumina at 1600°C, zirconia at 1500°C), a density of about 99% and higher was obtained. FESEM studies of the samples' cross section showed a homogenous microstructure and a very good bond between the single printed layers.     

Laser additive manufacturing and homogeneous densification of complicated shape SiC ceramic parts

To improve the density of SiC ceramic components with complicated shape built by laser sintering (LS), cold isostatic pressing (CIP) and reaction sintering (RS) were incorporated into the process. In the process of LS/CIP/RS, Phenol formaldehyde resin (PF)-SiC composite powder was prepared by mechanical mixing and cold coating methods, with an optimized content of PF at 18?wt%. For the purpose of obtaining improved density of the sintered body after final reaction sintering, carbon black was added into the initial mixed powder. The material preparation, LS forming and densification steps were optimized throughout the whole fabrication process. The final sintered SiC bodies with the bending strength of 292 ~ 348?MPa and the density of 2.94–2.98?g?cm^{? 3} were prepared using the PF coated SiC-C composite powder and the LS / CIP / RS process. The study further showed a positive and practical approach to fabricate SiC ceramic parts with complicated shape using additive manufacturing technology.     

Effect of nano-TiO2 on properties of 3 mol% yttria-stabilized zirconia ceramic via layered extrusion forming

Layered extrusion forming (LEF), as an additive manufacturing technology, can freely form ceramic components. In this paper, 3 mol% yttria-stabilized zirconia (3YSZ) ceramic powder, nano-TiO₂ dispersion solution and methylcellulose were used as raw materials to prepare water-based ceramic slurry with 84 wt.% solid content. The ceramic green body was then prepared by the LEF technology, following by drying, degreasing and sintering to obtain ceramic components. The effects of addition amount of nano-TiO₂ dispersion solution and sintering temperature on properties of the 3YSZ ceramic were investigated. The optimal comprehensive performance of the 3YSZ ceramic was obtained when the content of nano-TiO₂ dispersion solution was 4.35 wt.% and sintering temperature was 1550 ℃, and the bending strength, linear shrinkage, apparent density were 328 ± 5 MPa, 18.31 %, 5.9 g/cm³, respectively. Moreover, the mechanisms of performance improvement were investigated. Finally, 3YSZ ceramic components with complex structure were fabricated by using the optimal process scheme.     

Effect of powder treatment on injection moulded zirconia ceramics

Agglomerated fine zirconia powder was exposed to dry and wet ball milling and to wet mixing. The subject of study was the effect of powder treatment on the disintegration of agglomerated particles, on the rheological properties of thermoplastic ceramic mixtures, and on the properties of sintered yttria-stabilized tetragonal zirconia polytrystalline ceramics (Y-TZP). Test specimens in the shape of bars and discs were produced by injection moulding of ceramic mixtures containing 52.5 and 49 vol% of powder. The powder treatment was found to yield improved rheological properties of ceramic mixtures and improved mechanical properties of sintered specimens in the case of 52.5 vol% of powder in the ceramic mixture. However, the same or even better mechanical properties of sintered components were found when the loading of ceramic mixture was reduced to 49 vol% of powder and non-treated powder was used.     

Accurate printing of a zirconia molar crown bridge using three-part auxiliary supports and ceramic mask projection stereolithography

Zirconia ceramic is a widely used material for dental restoration. Stabilized zirconia all-ceramic teeth have excellent mechanical properties, biocompatibility, and aesthetic properties. At present, the CAD/CAM technique for zirconia all-ceramic dental prosthesis leads to low material efficiency and high tool wear. Although restorations fabricated using additive manufacturing are gaining attention, it is still very challenging to obtain accurate shapes and proper mechanical properties in zirconia restorations. In this investigation, a type of three-part auxiliary support was adopted and added to the occlusal surface to fabricate a typical molar crown bridge. A ceramic solid content of 40 vol% acrylic-based slurry was prepared, and a molar crown bridge was fabricated using mask projection stereolithography. The experimental results showed that the average dimensional error of the printed green body was ±150 μm. The density of the sintered ceramic parts was 6.026 g/cm³, and the three-point bending strength was 541 ± 160 MPa, which is higher than that of human dentin (160 MPa), but lower than that of CAD/CAM zirconia (900–1200 MPa). Although the proposed process still needs to be optimized to improve the mechanical properties and reliability of the crown bridge, the mask projection process combined with the adopted three-part auxiliary supports are capable of individualized manufacturing of complex zirconia crown bridges.     

The influence of ZrO2 additive on sintering and microstructure of lithium and lithium-titanium-zinc ferrites

The effect of ZrO₂ addition (0–3?wt%) on sintering and microstructure of lithium and lithium-titanium-zinc ferrites was studied. The Vickers hardness and dc electrical resistivity were investigated and discussed in correlation with the structural properties. Ferrite powders with the chemical compositions of LiFe₅O₈ and Li_0.65Fe_1.6Ti_0.5Zn_0.2Mn_0.05O₄ were prepared by the conventional ceramic technique. The synthesized ferrites were doped with various amount of ZrO₂ and then were sintered at 1050?°C for 2?h. Dilatometric studies showed that the zirconia addition affects the densification process of ferrite ceramics so that the shrinkage rate of pressed ferrite powders during their heating decreased with an increase in ZrO₂ content. The bulk density of the sintered ferrites varied slightly as the concentration of the additive was increased from 0 to 2?wt%, while the density of ferrite doped with 3?wt% ZrO₂ significantly decreased. X-ray diffraction and scanning electron microscopy analyses showed that the lattice parameter of ferrites increases and their average grain size decreases as the additive content grows. It was established that small amounts of ZrO₂ additive (up to 2?wt%) improve significantly the hardness and the electrical resistivity of ferrites.     

Polymer-derived silicon nitride ceramics by digital light processing based additive manufacturing

In this work, silicon nitride ceramic components with simple cuboid and complex honeycomb and lattice structures from preceramic polymers were fabricated by using digital light processing (DLP) based additive manufacturing and pyrolysis. The photosensitive precursor for DLP based additive manufacturing was prepared by mixing high ceramic yield polysilazane with commercial acrylic resin and photoinitiator. The material formulation and the structure of the green body were characterized by using FTIR. Si₃N₄ ceramic cuboid, 2D-structured Si₃N₄ ceramic honeycomb, and 2D-structured Si₃N₄ ceramic lattice with high precision were fabricated. The DLP-prepared specimens were pyrolyzed at different temperatures, and the crystalline phases after pyrolysis were analyzed by using XRD. The optimal pyrolysis temperature was found to be 1400°C.microstructures were characterized by using SEM. The compressive behavior of the complex-shaped Si₃N₄ ceramic structures was measured and discussed in detail.     

High-performance zirconia ceramic additively manufactured via NanoParticle Jetting

Additive manufacturing has received tremendous attention in the manufacturing and materials industry in the past three decades. Zirconia-based advanced ceramics have been the subject of substantial interest related to structural and functional ceramics. NanoParticle Jetting (NPJ), a novel material jetting process for selectively depositing nanoparticles, is capable of fabricating dense zirconia components with a highlydetailed surface, precisely controllable shrinkage, and remarkable mechanical properties. The use of NPJ greatly improves the 3D printing process and increases the printing accuracy. An investigation into the performance of NPJ-printed ceramic components evaluated the physical and mechanical properties and microstructure. The experimental results suggested that the NPJ-fabricated ZrO₂ cuboids exhibited a high relative density of 99.5%, a glossy surface with minimum roughness of 0.33 μm, a general linear shrinkage factor of 17.47%, acceptable hardness of 12.43 ± 0.09 GPa, outstanding fracture toughness of 7.52 ± 0.34 MPa m^1/2, comparable flexural strength of 699 ± 104 MPa, dense grain distribution of the microstructure, and representative features of the fracture. Subsequently, the exclusive printing scheme that achieved these favorable properties was analyzed. The innovative NanoParticle Jetting? system was shown to have significant potential for additive manufacturing.     

Laser stereolithography of ZrO2 toughened Al2O3

Ceramic laser stereolithography is a manufacturing process suitable candidate for the production of complex shape technical ceramics. The green ceramic is produced layer by layer through laser polymerisation of UV curable ceramic suspensions. A number of critical issues deserve attention: high solid loading and low viscosity of the suspensions, high UV reactivity, prevention of interlayer delamination in the green and in the sintered body, good mechanical performance. In this work, ZrO₂-reinforced Al₂O₃ components have been obtained from an acrylic modified zircon loaded with alumina powders. The zircon compound is effective as organic photoactivated resin and allows the dispersion of a high volume fraction of Al₂O₃ powder (up to 50 vol.%) while keeping viscosity at reasonable low values. The zircon compound also represents a liquid ceramic precursor that converts to oxide after burning out of the binder. Thank to the good dispersion of the alumina powder in the zircon acrylate, a uniform dispersion of ZrO₂ submicron particles is obtained after pyrolysis. These are located at the grain boundaries between alumina grains. Formation of both monoclinic and tetragonal ZrO₂ occurs as evidenced by XRD. No delamination occurs in bending tests as evidenced by SEM fractography, satisfactory modulus and strength values were concurrently found.     

Preparation and characterization of mullite whisker reinforced ceramics made from coal fly ash

Ceramics with mullite whiskers were prepared from coal fly ash and Al₂O₃ raw materials, with AlF₃ used as an additive. The phase structures and microstructures of the ceramics were identified via X-ray diffraction and scanning electron microscopy, respectively. The results show that pickling of coal fly ash is an effective method for enhancing the flexural strength of ceramics. Sintering temperature and AlF₃ addition were also key factors influencing the creation of ideal ceramics. The ceramic made from pickled coal fly ash, 6?wt% AlF₃, and sintered at 1200?°C, exhibited the highest flexural strength of 59.1?MPa, and had a bulk density of 1.32?g/cm³ and porosity of 26.8%. The results show that ceramic materials made under these conditions are ideal candidates for manufacturing ceramic proppants for the exploitation of unconventional oil and gas resources.     

Laser stereolithography of ZrO2 toughened Al2O3

Ceramic laser stereolithography is a manufacturing process suitable candidate for the production of complex shape technical ceramics. The green ceramic is produced layer by layer through laser polymerisation of UV curable ceramic suspensions. A number of critical issues deserve attention: high solid loading and low viscosity of the suspensions, high UV reactivity, prevention of interlayer delamination in the green and in the sintered body, good mechanical performance. In this work, ZrO₂ reinforced Al₂O₃ components have been obtained from an acrylic modified zircon loaded with alumina powders. The zircon compound is effective as organic photoactivated resin and allows the dispersion of a high volume fraction of Al₂O₃ powder (up to 50 vol.%) while keeping viscosity at reasonable low values. The zircon compound also represents a liquid ceramic precursor that converts to oxide after burning out of the binder. Thanks to the good dispersion of the alumina powder in the zircon acrylate, a uniform dispersion of ZrO₂ submicron particles is obtained after pyrolysis. These are located at the grain boundaries between alumina grains. Formation of both monoclinic and tetragonal ZrO₂ occurs as evidenced by XRD. No delamination occurs in bending tests as evidenced by SEM fractography, satisfactory modulus and strength values were concurrently found.     

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.     

Effects of added aluminum chromium slag on the structure and mechanical properties of colored zirconia ceramics

Colored zirconia ceramic samples were prepared via pressureless sintering with yttria-stabilized zirconia as a raw material and aluminum chromium slag (ACS) as an additive. Then, the effects of added ACS (0-15.0 wt%) on the microstructure, phase composition, and mechanical properties of the ceramic were investigated. The addition of ACS changed the apparent color of zirconia ceramics from white to pink, and the color deepened as the ACS content increased. In addition, more pores appeared in the sintered ceramic substrate as the content of ACS increased, and the relative density of samples declined from 97.7% to 91.1% with an increase in ACS content. However, the microhardness and bending strength each reached their maximum values (1887.2 HV and 433.5 MPa, respectively) when the content of ACS was 5.0 wt%. Fracture surface analysis of the samples showed that intergranular fractures were the main features of sintered samples with no added ACS, whereas numerous transgranular fractures occurred in sintered samples to which ACS had been added. The XRD results revealed that the prepared mainly composite ceramics were composed of t-ZrO₂, m-ZrO₂, and chromium-corundum, and the content of the t-ZrO₂ gradually increased as the ACS content increased.