3D printing of complex shaped alumina parts

Alpha-alumina powder was mixed with methyl cellulose as a binder with concentration as low as 0.25% by weight in an aquoes medium and kneaded in a high shear mixer to obtain a printable paste. The paste was subjected to rheological measurements and exhibited a shear rate exponent of 0.54 signifying the shear thinning behavior. The paste was used for printing parts with various shapes according to CAD model by employing a ram type 3D printer. Printed parts were dried and the green density was determined. Further, the parts were also subjected to X-ray radiography in order to evaluate the possible occurrence of printing defects. The samples were sintered under pressureless condition at 1650?°C in a muffle furnace and Hot Isostsically Pressed (HIP) at 1350?°C and a pressure of 1650?bar using a vacuum encapsulated SS CAN. Hot Isostatic pressing resulted in a higher density of 3.94?g/cc in comparison to 3.88?g/cc obtained under pressureless conditions and also shown superior mechanical properties. HIPing of 3D printed samples not only resulted in possible healing of printing defects as reavealed by X-ray radiography but also enhanced the diffusion at low temperature of 1350?°C leading to finer grain sizes as complemented by the microstructure.     

Silica strengthened alumina ceramic cores prepared by 3D printing

Ceramic cores based on alumina and silica are important in the manufacturing of hollow blades. However, obtaining good properties and precision is still challenging. In this research, alumina-based ceramics cores were obtained by 3D printing technology, and the effects of silica contents on the mechanical properties of the as-obtained alumina ceramic cores were evaluated. The results showed significant improvements in flexural strengths of the ceramics from 13.3 MPa to 46.3 MPa at silica contents from 0 wt% to 30 wt% due to formation of mullite phase (Al₆Si₂O₁₃). By contrast, the flexural strengths declined as silica content further increased due to the generation of massive liquid phase. Also, porous structures and cracks were observed by scanning electron microscopy due to the removal of cured photosensitive resin and the mullitization reaction between alumina and silica, respectively. The manufacturing process of hollow blades required ceramic cores with flexural strengths greater than 20 MPa to resist the strike of metal liquid, as well as open porosity above 20 % to provide space for alkali liquor to dissolve the ceramic cores. As a result, 10 wt% silica was determined as the optimal value to yield ceramics with improved properties in terms of flexural strength (35.6 MPa) and open porosity (47.5 %), thereby satisfy the application requirement for the fabrication of ceramic cores.     

Inkjet printing ceramics: From drops to solid

Inkjet printing is a powerful microfabrication tool that has been applied to the manufacture of ceramic components. To successfully fabricate ceramic objects a number of conditions must be satisfied concerning fluid properties and drop placement accuracy. It has been proposed that fluids are printable within the bounds 1 < Z < 10 (where Z is the inverse of the Ohnesorge number) and these limits are shown to be consistent with ceramic suspensions delivered by piezoelectric drop-on-demand inkjet printers. The physical processes that occur during drop impact and spreading are reviewed and these are shown to define the minimum feature size attainable for a given printed drop diameter. Finally the defects that can occur during the drying of printed drops are reviewed (coffee staining) and mechanisms and methodologies to reduce this phenomenon are discussed.     

Nanomechanical properties of zirconia- yttria and alumina zirconia- yttria biomedical ceramics,subjected to low temperature aging

Samples of ZTA composites {80 wt%Al₂O₃+20 wt%TZ-3Y}, ATZ composites {20 wt%Al₂O₃+80 wt%TZ-3Y}, tetragonal polycrystalline zirconia (3Y-TZP), and cubic stabilized zirconia (8Y-CSZ) were prepared to study the nanomechanical properties by nanoindentation before and after low temperature aging or degradation. Moreover, structural properties and crystalline present phases were evaluated by X-Ray Diffraction (XRD) and Electron Diffraction Patterns from transmission electron microscopy (TEM). The 8Y-CSZ ceramic showed the best mechanical behavior among all the analyzed materials (ZTA, ATZ and 3Y-TZP), the 8Y-CSZ sample did not showed any phases transformations when subjected to low temperature degradation (LTD). Absolute nanohardness, Young's modulus and fracture toughness after the LTD were carried out in different samples, the obtained results, in a decreasing order were: 8Y-CSZ>ZTA>3Y-TZP>ATZ, 8Y-CSZ>3Y-TZP>ZTA>ATZ and 8Y-CSZ>3Y-TZP>ATZ>ZTA, respectively. The 8Y-CSZ ceramic, did not showed any variations in nanomechanical properties due to the absence of anisotropic behavior, manifesting high hardness, elastic modulus and relative values of fracture toughness. Perhaps this material could be candidate for biomedical applications.     

Fabrication of alumina ceramics with functional gradient structures by digital light processing 3D printing technology

Alumina ceramics with different unit numbers and gradient modes were prepared by digital light processing (DLP) 3D printing technology. The side length of each functional gradient structure was 10 mm, the porosity ratio was controlled to 70%, and the number of units were (1 × 1 × 1 unit) and (2 × 2 × 2 unit) respectively. The different gradient modes were named FCC, GFCC-1, GFCC-2 and GFCC-3. SEM, XRD, and other characterization methods proved that these gradient structures of alumina ceramics had only α-Al2O3 phase and good surface morphology. The mechanical properties and energy absorption properties of alumina ceramics with different functional gradient structures were studied by compression test. The results show that the gradient structure with 1 × 1 × 1 unit has better mechanical properties and energy absorption properties when the number of units is different. When the number of units is the same, GFCC-2 and GFCC-3 gradient structures have better compressive performance and energy absorption potential than FCC structures. The GFCC-2 gradient structure with 1 × 1 × 1 unit has a maximum compressive strength of 19.62 MPa and a maximum energy absorption value of 2.72 × 105 J/m3. The good performance of such functional gradient structures can provide new ideas for the design of lightweight and compressive energy absorption structures in the future.     

Assembling unidirectionally frozen alumina/camphene bodies for aligned porous alumina ceramics with larger dimensions

This paper proposes a novel way of producing aligned porous alumina ceramics with larger dimensions by assembling unidirectionally frozen alumina/camphene bodies, particularly those containing polystyrene (PS) polymer as the binder. The compressive strength of the samples sintered at 1450 °C for 3 h increased remarkably from 2 ± 0.1 to 16 ± 2 MPa with increasing PS content from 5 to 20 vol.% due to the prevention of cracks generally caused by drying shrinkage. In addition, frozen samples with a PS content of 20 vol.% could be assembled into larger dimensions without difficulty. The height of the assembled sample produced with a lamination number of 5 could be increased to ∼24 mm without a severe decrease in compressive strength (16 ± 3 MPa at a porosity of ∼79 vol.%) due to the maintenance of an aligned porous structure with good interfacial bonding between the laminations.     

Inkjet printing of 3D metal–insulator–metal crossovers

The inkjet deposition of a single functional material on a substrate is well developed, however, little attention has been paid to the sequential printing of different functional elements to generate complex 3D structures. The successful all additive manufacture of electronics circuits requires the printing of features such as crossovers and interconnections, the passive elements in electronics where metal–insulator–metal must be sequentially deposited with retained function. We describe the inkjet printing of both a commercial silver nanoparticle metal and a cationic/thermally cured epoxy insulator, SU8, and discuss the role of print strategy and surface treatment on retaining functionality. The issues to be addressed in the successful all inkjet printing of such features are discussed.     

Porosity features and gas permeability analysis of bi-modal porous alumina and mullite for filtration applications

Bimodal porous structures were prepared by combining conventional sacrificial template and partial sintering methods. These porous structures were analysed by comparing pore characteristics and gas permeation properties of alumina/mullite specimens sintered at different temperatures. The pore characteristics were investigated by SEM, mercury porosimetry, and capillary flow porosimetry. A bimodal pore structure was observed. One type of pore was induced by starch, which acted as a sacrificial template. The other pore type was due to partial sintering. The pores produced by starch were between 2 and 10 µm whereas those produced by partial sintering exhibited pore size of 0.1–0.5 µm. The effects of sintering temperature on porosity, gas permeability, and mullite phase formation were studied. The formation of the mullite phase was confirmed by XRD. Compressive strengths of 37.9 MPa and 12.4 MPa with porosities of 65.3% and 70% were achieved in alumina and mullite specimens sintered at 1600 °C.     

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.     

Analyses of Young's modulus and thermal expansion coefficient of sintered porous alumina compacts

This paper reports the derivation of Young's modulus (E) and thermal expansion coefficient (TEC, β) for a sintered porous structure with open pores. The theoretical E is affected by the number of grains and the grain boundary area in sintered ceramics. The measured E–porosity relationship for porous alumina compacts were compared with the theoretical E values that were derived for the present open-pore structure and also for the dispersed (closed)-pore structure treated previously. With decreasing porosity (50% → 10%), the scattered E values showed a gradually increasing tendency, which were located between two theoretical curves for the open-pore structure. The sudden increase of E values in the porosity range from 10% to 0% was well explained by the theoretical dependence of E on porosity for the open- or closed-pore structure. The β values for the porous alumina structures were independent of porosity and close to the β values reported for fully dense alumina compacts. This result was in accordance with the theoretical β–porosity relationships for the open-pore and closed-pore structures.     

Inkjet printing of photocatalytically active TiO2 thin films from water based precursor solutions

In this work, aqueous chemical solution deposition route suited for inkjet printing is used for the synthesis of photocatalytically active TiO₂ coatings. Environmentally friendly precursor solutions with electromagnetic ink-jet printing, allows cheap and simple processing of TiO₂ films on glass. The hydrolysis reaction of water sensitive titanium alkoxide (Ti-alkoxide) precursor is controlled by adding complexing agents as citric acid and triethanolamine prior to water addition, and aqueous stable solutions are achieved. The pH of the solutions is brought to neutral to guarantee flexible processing, avoid damage to substrates and equipment. Solution parameters are adapted to obtain optimal gelation conditions and good jettability. The influence of processing parameters on the phase formation and surface morphology is studied by thermogravimetric analysis and differential thermal analysis (TGA/DTA), X-ray diffraction (XRD), scanning electron microscopy (SEM) and atomic force microscopy (AFM). The photocatalytic activity of the films is evaluated by the degradation of methyl orange.     

Influence of preparation method and alumina content on crystallization and morphology of porous yttria stabilized zirconia

Influence of addition of alumina and preparation methods (sol-gel synthesis and mechanochemical preparation) on crystallization and morphology of yttria stabilised zirconia was examined. Presence of alumina was found to delay crystallization of zirconia, the effect being more pronounced at higher alumina content. The two oxides form easily distinguished separate phases. Milling lowers the crystallization temperatures of the sol-gel derived powders since nuclei are formed during the milling and smaller particle size allows easier removal of residual organic components. The milling results in crystallization of some monoclinic zirconia, both in sol-gel derived powders and in case of mechanochemical processing. There are no significant differences between the preparation methods in pore size and relative density of sintered tablets: powders obtained by mechanochemical processing and milled sol-gel derived powders both give tablets with homogeneous morphology. The advantage of sol-gel process is preparation of pure tetragonal zirconia phase without traces of monoclinic phase.     

Fracture and mechanical properties of lightweight alumina ceramics prepared by fused filament fabrication

Fused filament fabrication (FFF), as one of the additive manufacturing technology, provides cost-effective and relatively fast preparation of 3D objects of desired dimensions and design. In this work, a composite filament containing 50 vol. % of sub-micron alumina powder was successfully used for the manufacturing of samples with prismatic design. The influence of the layer thickness (0.1–0.3 mm) on the final bulk density and mechanical properties were investigated. Sintering at 1600 °C for 1 h results in relative densities ranging from 80 to 89 % and the flexural strength reached 200–300 MPa depending on the layer thickness used for the printing.     

Novel freeze-casting fabrication of aligned lamellar porous alumina with a centrosymmetric structure

A novel freeze-casting method is used to fabricate aligned lamellar porous alumina with a centrosymmetric structure from aqueous alumina slurries. Two cold fronts oriented perpendicularly to each other, originating from the bottom and side of the cylindrical copper mold, induce the growth of ice crystals in specific directions along the radius of the cylindrical mold. Lamellar channels of porous alumina are arranged centrosymmetrically along the radial axis. The pore distribution of the currently prepared porous ceramics is more regular when compared with that of porous ceramics prepared by conventional freeze casting. This affords porous ceramics with improved mechanical properties and stability. The current method addresses the issue of partial failure as induced by the randomly distributed channels in lamellar porous ceramics.     

Creep study on alumina and alumina/SWCNT nanocomposites

Alumina and alumina/SWCNT nanocomposites have been sintered by spark plasma sintering, obtaining relative densities higher than 99%. Microstuctural characterization revealed a grain microstructure in the submicron range, where alumina/SWCNT nanocomposites exhibited a good CNTs dispersion thought the ceramic matrix. Creep experiments performed in both materials showed a similar mechanical behavior, where the addition of CNTs seems to have a negligible effect on the strain rate, in contrast to results reported by other authors. Grain boundary sliding accommodated by lattice diffusion has been identified as the high temperature deformation mechanisms in both samples, alumina and alumina/SWCNT nanocomposites. We have discussed about the role of CNTs influence on the plasticity of these composites.     

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.     

Mechanical properties of thermally sprayed porous alumina coating by Vickers and Knoop indentation

Depending on the thermal spraying conditions, coatings obtained can present different defects, like pores, cracks and/or unmelted particles, and different surface roughnesses, that can affect the determination of the hardness and elastic modulus. The present work investigates the mechanical properties, determined by means of Knoop and Vickers indentations, of a plasma as-sprayed alumina coating, obtained with a nano-agglomerated powder sprayed using a PTF4 torch, in order to highlight how the surface defects interfere into the indentation process. As a main result, Knoop indentation compared to Vickers one gives less dispersive results (15% and 33%, respectively), that are, in addition, more representative of the coating properties. The mean values obtained are 110 ± 40 GPa for the elastic modulus and 1.75 ± 0.42 GPa for the hardness. In addition, and for the two indenter types used, multicyclic indentation has been performed because it allows a more appropriate characterization of such heterogeneous coatings due to the representation of the mechanical properties as a function of the indentation load and/or the penetration depth, leading to more reliable results according to the depth-variability of the coating microstructure.     

Effect of starch addition on microstructure and properties of highly porous alumina ceramics

Porous alumina ceramics with ultra-high porosity were prepared through combining the gel-casting process with the pore-forming agent technique. Porosity and pore size distribution of the sintered bulks were evaluated with and without adding starch, respectively. In particular, the influences of starch addition on the properties, including thermal conductivity and compressive strength were studied. It was found that the incorporation of starch increased the nominal solid loading in the suspension and subsequently promoted the particle packing efficiency. The porosity is raised with increasing starch content from 0 to 30 vol%, which brings the decrease in thermal conductivity, whereas the compressive strength isn't seriously degraded. The further higher starch addition (40 vol%), however, would deteriorate the performance of the alumina porous ceramics. It is believed that the appropriate starch amount (lower than 30 vol%), working as a pore-forming agent, suppresses the driving force of densification without affecting the connections of neighboring grains while excessive starch amount would lead to the collapse of the porous structure.     

Effect of particle size on mechanical properties of alumina ceramic processed by photosensitive binder jetting with powder spattering technique

As an Additive Manufacturing technique, Binder Jetting enables the fabrication of customized and complex ceramic parts. However, the insufficiency of powder packing in green parts restricts the final products’ densifications and strengths. To form a layer of ceramic green parts, Photosensitive Binder Jetting with powder spattering technique provides entrapment of ceramic powder by printing of photo-curable resin and recoating by releasing the powder through a vibrating mesh. This recoating technique enables the processing of fine alumina powders, the average particle sizes of which are 3 μm, 1.65 μm, and their mixtures. Apparent densities, porosities, mechanical properties, and microstructures of the sintered parts were investigated. The alumina sample with the apparent density of 3.70 g/cm³, the compressive strength of 94.87 MPa, the biaxial strength of 50.06 MPa, and the porosity of 41.01 % was attained by the mixture with 70:30 wt.% of the 3 μm and 1.65 μm powders respectively.     

Inkjet Printing of Aqueous Photoluminescent CdSe/CdS Nanorods on Solid Substrates

In order to deposit colloidal nanocrystals on different substrates, a large variety of methodologies have been developed, such as dipcoating, spin coating, or spray coating. The deposition of CdSe/CdS core‐shell nanorods (NRs) with a conventional office printer onto conducting tin‐doped indium oxide glass surfaces is presented. This involves the preparation of water‐based inks containing the NRs. To improve the connection between the CdSe/CdS NRs and the underlying substrates, the glass surfaces were modified by means of silanes. Homogeneous films were obtained by consecutively printing several layers of CdSe/CdS NRs.