Freeform Fabrication of Ceramics via Stereolithography

Ceramic green bodies can be created using stereolithography methods where a ceramic suspension consisting of 0.40–0.55 volume fraction ceramic powder is dispersed within an ultraviolet-curable solution. Three ceramic materials were investigated: silica for investment casting purposes, and alumina and silicon nitride for structural parts. After mixing the powders in the curable solution, the ceramic suspension is photocured, layer by layer, fabricating a three-dimensional ceramic green body. Subsequent binder removal results in a sintered ceramic part. Three-dimensional objects have been fabricated from a 0.50 volume fraction silica suspension.     

Aqueous Gelcasting of Fused Silica Using Colloidal Silica Binder

An aqueous‐based gelcasting of fused silica ceramics by using colloidal silica binder was developed. Fused silica slurries having different volume percentage of solid loading from 63 to 74 vol% in colloidal silica were made and the rheological properties were evaluated. It was found that the slurry with 73 vol% of solid loading with viscosity 0.70 Pa.s is suitable for this gelcasting system. The influence of solid loading on physical and mechanical properties of gelcast green and sintered bodies has been studied. The fabricated green body by using colloidal silica binder exhibited a flexural strength of 9 MPa and 88% of theoretical density with 2.2% of drying shrinkage while the sintered sample exhibited flexural strength of 60 MPa and 95% of theoretical density with 4.3% of sintering shrinkage. It was observed that, the nano silica particles from the colloidal silica binder is filling the interstitial positions in the consolidated fused silica green body and enhancing physical and mechanical properties.     

Diglyceryl acrylate as alternative additive dedicated to colloidal shaping of oxide materials – Synthesis,characterization and application in manufacturing of ZTA composites by gelcasting

The paper reports the synthesis of a new compound named diglyceryl acrylate (DGA) and its application in manufacturing of ZTA composites by gelcasting method. The compound can be used as a monomer able to polymerize in suspensions and also as a dispersing agent for fine-crystalline powders. The paper describes the synthesis of DGA, the properties of the monomer, the resulting polymer, ceramic suspensions and sintered bodies. The distribution of zirconia grains in alumina matrix was observed on SEM. Vickers hardness and fracture toughness of ZTA composites have been measured. The research revealed that with the use of DGA it is possible to obtain highly concentrated ceramic suspension (60 vol%) of low viscosity. The positive influence of the new monomer on the properties of ceramic suspensions and sintered bodies is explained on the basis of the analysis of spatial structures of all 8 regioisomers of DGA molecule.     

Effect of Polyethylene Glycol (PEG) Powder on Compressibility and Microstructural Properties of Sintered α-Alumina

This study examines the effect of various contents of polyethylene glycol (PEG) powders on density, compressibility, and microstructural properties of sintered α-alumina samples. Moreover, the effect of compaction pressure on the green density of the compacts is studied by applying different pressures ranging from 400 to 550 MPa. Samples were prepared by mechanical blending of alumina and various amounts of PEG powders in a Turbula mixer. The binder contents vary from 1 wt.% to 4 wt.%. The as-prepared mixture was compacted in a universal machine at room temperature under the pressure of 6 MPa to produce disk-shaped samples in a pre-compaction step. Experimental results revealed that adding various amounts of PEG powders has a detrimental effect on the green density of alumina pellets and decreases the green density from 1.95 to 1.87 g/cm³. The results also show that sintered density of samples increased by increasing the compaction pressure to pressures higher than 400 MPa. It is observed that a sudden increase in green density has been observed between 450 and 550 MPa.     

3D printing of CaO-based ceramic core using nanozirconia suspension as a binder

The 3D printing of a ceramic core with nanoceramic suspension as a binder was performed to investigate a novel method for the fabrication of a complex-shaped ceramic core. Green bodies were printed using CaO powder as a precursor material and nanozirconia-absolute ethyl alcohol solution suspension as a binder. The green bodies were sintered at 1300–1500 °C for 2 h. The effects of binder saturation level on the properties of the sintered bodies were investigated. Increasing the binder saturation level caused decreases in the linear shrinkage of the sintered bodies, but increases in hydration resistance and bending strength. The nanozirconia particles were deposited on the surfaces of the CaO particles and filled the pores of green bodies, and then formed a high melting temperature CaZrO₃ layer with the CaO at the surfaces of the CaO grains, which improved the hydration resistance of the CaO-based ceramic core parts.     

Mechanical and lamination properties of alumina green tapes obtained by aqueous tape-casting

Mechanical characterisation and lamination were carried out on alumina green tapes prepared by aqueous tape casting using two acrylic emulsions having different glass transition temperatures (T_g) as binders. The tensile strength and strain were strongly dependent on the binder nature and content. Namely, the mechanical properties of the green tapes reflected those of the binders at room temperature: the green tapes obtained with the higher T_g binder showed a brittle behaviour, whereas those obtained with the lower T_g binder showed an elastoplastic behaviour. The mechanical properties of the green tapes prepared by mixing the two acrylic binders lies in between, giving the possibility of tailoring the flexibility and strength in the range of the values obtained for pure binders. Lamination gave rise to an increase of both green and sintered densities, compared with monolayer specimens, whatever the composition of the binder system. Such improvements significantly depended on lamination pressure, but were insensitive to lamination temperature for the two temperatures tested higher than the T_g of the two binders. ©     

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.     

Preparation and physical properties of polylactide/cellulose nanowhisker/nanoclay composites

Polylactide (PLA) has been getting lots of interests in step with global concerns on sustainable green technology because it is biodegradable with reasonable mechanical strength and can be processed quite easily. But, to compete with commodity polymers in the market PLA‐based green composites need to have higher mechanical and thermal properties. Therefore, in this study, cellulose nanowhiskers (CNWs) as well as nanoclay were used as nanofillers to improve physical properties of PLA. CNWs were prepared from microcrystalline cellulose (MCC) powder by acid hydrolysis, and confirmed by TEM. To improve interfacial bonding between PLA and CNWs maleic anhydride‐grafted PLA (MAPLA) was prepared and used as a compatibilizer. PLA‐based composites were prepared by melt mixing followed by compression molding. Mechanical properties of the composites were measured by UTM and DMA. The melt mixing conditions were optimized first, and then composition was optimized step by step to obtain a PLA‐based green composite with excellent physical properties. CNWs were much better than MCC powder as reinforcing natural fillers. MAPLA and nanoclay could improve considerably physical properties of the PLA‐based composites. Compared to the PLA/MCC composite the tensile strength of the PLA/CNW/MAPLA/nanoclay composite was almost doubled and the glass transition temperature of the composite was 23°C higher, making the composite possible for commercial applications. POLYM. COMPOS., 2013 © 2013 Society of Plastics Engineers     

Processing and characterization of YSZ‐PSS‐DBS composites

PSS‐PEGL and PSS‐PEGL‐DBS polymeric systems have been used in YSZ slurry formulation. These organic materials with different chemical structure and functional groups had great effect on the ceramic slurry formulation. Physical properties, such as viscosity of slurry, hardness and density for green and sintered bodies, and thermal decomposition, were studied as a function of the binder composition. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 502–509, 1999     

Fabrication and Properties of Tape-Cast Laminated and Functionally Gradient Alumina–Titanium Carbide Materials

A tape-casting process was used to prepare various Al₂O₃–TiC green tapes, from which laminated and functionally gradient Al₂O₃–TiC materials (FGM Al₂O₃–TiC) were produced by cutting, stacking, and laminating the material, removing the binder, and hot-pressing the green bodies. The bending strength of the FGM Al₂O₃–TiC composites was not much less than that of the laminated Al₂O₃–TiC composites. However, the fracture toughness was >50% higher; the fracture toughness of the FGM composite sintered at 1700°C was 9.43 MPa·m^1/2. This increased toughness was attributed to the stress distribution that was caused by variations in the composition of the FGM composite layers. The present results demonstrate that the FGM design is a useful method for modifying the mechanical properties of ceramic composites.     

Novel structure of ceramic tape for multilayer devices

To reduce the content of binders surrounding ceramic powders in a ceramic tape and the residual pore after burnout to a minimum, a ceramic tape with double layers was manufactured. One layer was comprised of only organic binder, which imparted sufficient strength and strong adhesive property to the green tape. The other one was a ceramic layer with a very small amount of binder. The binder content of the slurry for ceramic layer was less than 2 wt%, which could lower the viscosity, make the slurry well dispersed and considerably increase solid loading in the slurry. This higher solid loading led to higher green tape density, higher fired density of the product. The two-layer ceramic tape showed much better qualities than a common (or conventional) green tape especially in microstructure, laminatablilty, and tape density. In the multilayer structure made of the two-layer ceramic tape, the binder layer completely disappeared after binder-burnout and no defects from the two-layer structure were observed.     

Improving the properties of binder jetted ceramics via nanoparticle dispersion infiltration

To improve the dimensional accuracy, surface quality, and mechanical properties of binder jet additive manufactured ceramic parts, in this work, nanozirconia dispersion and binder were used to prepare a jet solution to investigate the effect of nanozirconia content of the jet solution on the properties of zirconia ceramic green and sintered bodies. When the nanozirconia content of the jet solution increased from 0 to 20 wt%, the forming precision of the zirconia ceramic green bodies improved, the surface roughness decreased, and the density increased. After sintering at 1400 °C for 2 h, linear shrinkage along the height, width, and length of the zirconia ceramics decreased by 6.27%, 10.20%, and 5.45%, respectively, while the surface roughness decreased by 42.87%, and the bending strength increased by 145.60%. With increasing nanozirconia content of the jet solution, the spreading and infiltration distance of the jetted solution in the powder layer decreased, the thickness of the deposition layer of nanozirconia on the surface of the zirconia particles in the powder layer increased, and the pore size of the powder layer decreased significantly. This increased the density of the green bodies; thus, improving the sintering properties of the zirconia ceramics.     

Effects of Excess Barium Ions on Aqueous Barium Titanate Tape Properties

The effects of excess free barium ions in aqueous barium titanate slip on the resulting BaTiO₃ tape properties were investigated in terms of the slip behavior, green/sintered tape density and morphology, and dielectric properties. The excess free barium ions expressed by means of the Ba/Ti ratio adversely affected most tape properties. Increase in the slip viscosity, green porosity, and agglomeration along with a decrease in mechanical properties and green/sintered density were found with the increase in the Ba/Ti ratio. However, dielectric permittivity was increased with increase in the Ba/Ti ratio. An effort was made to correlate these phenomena with Ba²⁺ leaching in water for realistic multilayer ceramic capacitor applications.     

3D printing ceramic cores for investment casting of turbine blades,using LCD screen printers: The mixture design and characterisation

The primary objective of this study is to demonstrate the possibility of developing silica, alumina, and zircon-based photocurable ceramic suspensions that can be used for visible light photopolymerization (> 450 nm) and to optimise the binder formulations for the purpose of LCD-based ceramic 3D printing applications. Reference ceramic components for this work are ceramic cores employed in the investment casting of high-pressure turbine blades and vanes. Arguably, one of the most critical steps in photoinduced ceramic 3D printing is developing suitable ceramic suspensions, having high ceramic loading, low viscosity, and short curing times. Ceramic suspensions with four different novel binder formulations and commercial ceramic powders used in core manufacturing (SiO₂, Al₂O₃ and ZrSiO₄) were investigated to achieve the best trade-off between: (1) their curing performance (cure depth and curing speed), (2) rheological properties of the binder mixtures at the solid loadings of 60 vol.% for SiO₂, 55 vol.% for ZrSiO₄, and 45 vol.% for Al₂O₃; and (3) the green body mechanical properties of the mixtures after printing. The effect of ceramic particles on the selected binders was examined individually, and the correlation between cure depth (C_d), volumetric loading, and curing speed are evaluated. The results show all binders designed in this study provide an adequate cure depth, even at high ceramic loadings. When the curing behaviour of all unloaded binder mixtures from the previous study [1] compared with the 10 vol.% SiO₂ loaded mixtures, the cure depth of all formulated binder mixtures increased 50–55 % and the curing thickness of 60 vol.% SiO₂ loaded suspensions were still slightly higher than their unloaded counterparts. The rheology outcomes indicate that lower viscosity binders always result in lower viscosity of the ceramic loaded inks, even without taking the effect of dispersants into account. Besides, the addition of N-Vinyl-2-Pyrrolidone (NVP) monofunctional monomer to the binder mixtures significantly reduces the viscosity and changes the normally linear relationship of the mix viscosity and its silica loading content. Among the binder formulations loaded with 60 vol.% of SiO₂, the formulation providing the lowest viscosity and highest mechanical property consists of 5 wt.% of NVP, 45 wt.% of HDDA and 50 wt.% of Photocentric 34 resin. Although this binder mixture showed the highest green flexural strength when loaded by 55 vol.% ZrSiO₄, all other mixtures loaded with zircon flour also demonstrated a near-fluid behaviour, below 200 s^?1. In Al₂O₃ loaded mixtures, the HDDA di-functional binder formulations present lowest viscosity and the di- and multifunctional monomer blends (HDDA-Photocentric27) showed the highest mechanical properties when used in a 50/50 ratio. This work summarises the best binder choices for silica, alumina and zircon based ceramic suspensions used in core printing for investment casting applications through LCD screen printing.     

Binder jetting yttria stabilised zirconia ceramic with inorganic colloid as a binder

ABSTRACT

The new inorganic colloid is a particle-free decomposable binder that can solve the nozzle clogging problem and precipitate zirconia particle upon heating. The inorganic colloidal binder can be used as a binder precursor to replace commonly used PVP binder in printing ZrO₂ ceramics parts using binder-jet technology. Green bodies were printed using inorganic colloid binders with different saturation level and PVP binder separately, then cured and sintered. The effects of binder saturation level and sintered temperature on the properties of the green and sintered bodies were investigated. After being deposited into the powder bed interstices and cured, the inorganic colloidal binder containing zirconium basic carbonate decomposes and forms ZrO₂ ceramic particles that are filled the interstices and sintered to provide bonding strength to the printed parts. Samples with inorganic colloidal binder eventually perform better surface quality and denser sintered body than polymer binder when using same saturation ratio.     

Effect of the addition of silica sol on layered extrusion forming of Al2O3-based cores

Layered extrusion forming of ceramic cores with a nanoceramic suspension as a binder was conducted to explore a novel method to produce complex-shaped ceramic cores. Green bodies were prepared using Al₂O₃ particles as precursor materials and silica sol combined with aqueous polyvinyl alcohol solution as a binder. Increasing the silica sol content increased the viscosity of the slurry, enhanced the green bending strength, and decreased the green linear shrinkage. The green microstructure showed the nanosized silica particles were deposited on the surface of the Al₂O₃ particles and among the pores formed by Al₂O₃ particles irregular packing. In addition, increasing the silica sol content increased the bending strength, however, decreased linear shrinkage and open porosity of the sintered bodies. During sintering, the nanosized silica particles converted to the melting phase and reacted with Al₂O₃ and the microstructure of sintered bodies indicated the existence of sintering neck with silica sol addition.     

聚乙二醇对聚乳酸/淀粉纳米晶复合材料性能的影响

以聚乳酸（PLA）和淀粉纳米晶（SNC）为主要原料,聚乙二醇（PEG）为增塑剂,采用溶剂蒸发法制备PLA/SNC和PLA/SNC/PEG复合材料,通过差示扫描量热仪（DSC）、热台偏光显微镜（PLM）、X射线衍射仪（XRD）、扫描电子显微镜（SEM）等研究了PEG对复合材料结晶行为、力学性能及界面相容性的影响。结果表明,PEG能够与SNC协同促进PLA结晶,使PLA/SNC/PEG复合材料的结晶速率明显提高;PEG的添加未改变PLA/SNC复合材料的结晶结构;随着PEG含量的增加,PLA/4%（质量分数,下同）SNC复合材料的拉伸强度先升高后下降,断裂伸长率不断提高;当PEG含量为2%时,PLA/4%SNC/2%PEG复合材料的力学性能最佳,拉伸强度为47.86 MPa,断裂伸长率为10.20%,PLA与SNC间界面相容性得到改善。     

Strength of Green Ceramics with Low Binder Content

Acrylic-based polymers are common binders that impart high green strength (>2 MPa) at low concentrations (<5.0 vol%). Strength at low binder concentrations may be determined by chemical bonding at the ceramic–polymer interface. We have studied the binding mechanisms as a function of ceramic surface chemistry using a cross-linkable binder, which is based on a soluble poly(acrylic acid) (PAA, MW = 60 000) and glycerol. The cross-linked PAA binder system has been integrated into a solid freeform fabrication process, which provides a means of fabricating very reproducible green bodies, including SiO₂, TiO₂, Al₂O₃, multicomponent oxides, and non-oxides, with uniform density and composition. The ceramic parts contain only 2.5 vol% binder (solids basis), which increases the strength of the ceramic systems by at least a factor of 8 while the strength of Al₂O₃ components increases by a factor of ∼24 (0.3 to 7.6 MPa). Addition of the binder improves the toughness of the ceramic bodies by an order of magnitude with SiO₂ representing the largest relative increase (2.8 × 10⁻³ to 4.4 × 10⁻² MPa·m^1/2). The mechanical properties are dictated by two binding mechanisms: binder adsorption and mechanical interlocking. High green strengths result from adsorption of the binder onto the ceramic surface whereas toughness is enhanced by poor adhesion of the binder to the ceramic surface.     

Modeling Density Contributions in Preceramic Polymer/Ceramic Powder Systems

A model is presented that examines the mixing of ceramic powders with preceramic polymer binders that are converted to ceramic material on pyrolysis. Such polymer/powder systems, which have applications in the compaction of both SiC and Si₃N₄ powders, can be effective in increasing the green density of die-pressed bodies. This model examines the relative importance of various physical parameters of the components of the system in maximizing the green density of the resulting pyrolyzed body .     

In-situ investigation on crack-initiation and deformation of Al2O3 green bodies during dewaxing process by combined OCT-TG-FTIR and TMA

The dewaxing process is used to remove an organic binder from the ceramic green bodies before sintering, which occasionally generates cracks. The crack formation behavior depends on various factors including softening and decomposition of the organic binder, generation of gases, and strength degradation of the green body thereby. Herein, this correlation was investigated to elucidate the crack formation behavior during the dewaxing process using two types of Al₂O₃ green bodies; one is added with polyvinyl butyral (PVB) and stearic acid (SA) and the other is with paraffin. The internal structures of Al₂O₃ green bodies during dewaxing were observed using optical coherence tomography (OCT), and the generated gases were analyzed simultaneously using a thermogravimetric (TG) analyzer and Fourier transform infrared (FTIR) spectroscopy (TG-FTIR). The mechanical properties of the green bodies were investigated at RT–600 °C using a thermomechanical analyzer (TMA). The weight change occurred in both the green bodies with formation of gases depending on the type of the binder. In the OCT studies, cracks were observed with substantial deformation in the PVB/SA-added green body during the dewaxing, whereas no cracks were seen in the paraffin-added one. The TMA investigation showed that the paraffin-added sample possessed higher strength and better structural stability than the PVB/SA-added one throughout the dewaxing, leading to the crack-free green body of the former. Therefore, the crack-initiation and deformation behaviors of the green bodies were significantly affected by the type of the binder used. The combination of the in-situ observations using the combined OCT-TG-FTIR system and the mechanical properties measurement using TMA was found to be effective in verifying the structural stability of the green bodies during the dewaxing.