In situ observation of evolution of internal structure of alumina during sintering by swept-source OCT

In situ observation of sintering of ceramics is important to understand the sintering behavior, including the development of internal structures, and to fabricate ceramics with superior properties. However, there has been no studies thus far on high-speed in situ observation of the internal structure of green and sintered bodies at high temperatures with micrometer-scale resolution. Here, we applied swept-source optical coherence tomography (OCT) to observe the evolution of the internal structure in Al₂O₃ green bodies during sintering. In situ OCT observations revealed that internal structure changes during sintering, such as the development of density distribution and growth of coarser pores. We could also obtain the sintering shrinkage ratio and relative density from the OCT images. The OCT observation of the internal structure during sintering of green bodies with added or stacked granules of different primary particle sizes confirmed that inhomogeneous regions developed as the densification progressed at high temperatures. These results indicate that in situ observation of the sintering behavior of ceramic green bodies using swept-source OCT is a novel technique that facilitates real-time observation of the evolution of the internal structure during sintering.     

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.     

Partial wick-debinding of low-pressure powder injection-moulded ceramic parts

Al₂O₃-based green bodies were shaped using low-pressure injection moulding. The binder content and the binder distribution during the thermal debinding inside a wicking embedment were analyzed. A distinct trailing front, which separates the binder-lean and binder-rich regions, was observed. This kind of binder distribution forms suddenly, after the moulded piece is heated above the melting point of the binder and is then cooled down. Mechanisms that can explain the observations are presented. The non-uniform binder distribution is explained by a capillary extraction of the binder with two different mobilities, which depend on the size of the pores inside the moulded piece. A sudden loss of binder at the beginning of the debinding process is the result of exudation, caused by a large thermal expansion of the binder as it melts. During cooling, the binder solidifies, which significantly affects the binder distribution due to a contraction of the binder.     

Gelation forming of ceramic compacts using agarose

Abstract

The development of a cast forming process for ceramics based on agarose gelation is described and the properties of green and sintered bodies are presented. For this process, a warm alumina slurry containing more than 50 vol.-% solids loading and ～1 wt-% agarose binder (Al₂O₃ basis) is cast into a relatively cold, non-porous mould, resulting in a tough green body formed by gelation (37°C) of the agarose molecules. The green compacts show uniform density distribution, with precise dimensions and very smooth surfaces. After drying, they can be sintered directly without special binder burn out procedures. Complex ceramic parts with thick and thin cross-sections can be formed. The process is illustrated for the preparation of a turbine rotor component.     

Pyrolysis of polyvinyl butyral (PVB) binder in thermoelectric green tapes

The pyrolysis of polyvinyl butyral (PVB) binder and other organic additives in thermoelectric green tapes, are analysed through differential thermal analysis (DTA), thermogravimetric analysis (TGA) and published results of fourier transformer infrared spectroscopy (FTIR). Based on these analyses the optimum balance of binder degradation mechanism, heating rate, burnout temperature and burnout atmosphere were determined. The maximum upper temperature at which pyrolysis can take place in an oxidising atmosphere, was imposed at 450°C, to avoid the risk of oxidising the thermoelectric material above this temperature, which could degrade its thermoelectric properties. Thermoelectric cast green tapes made with PVB formulation were found to leave char residue after pyrolysis at 450°C, estimated to be almost 20% of the total PVB content in the tape. Different pyrolysis atmospheres of air, argon, CO₂ and Ar/H₂O were used to minimise the char content. The best pyrolysis for the PVB was obtained with the use of CO₂ atmosphere at 450°C with a hold-out time of 5 h, which reduced the char residue to only 1%. Even with this small percentage, the char residue was in the form of a very fine black powder (soot) which covered the thermoelectric material powder in the tape, preventing its densification at the later stages of the sintering process. It was therefore concluded that the PVB system was not a suitable binder candidate to be used in the fabrication of thermoelectric generator by the tape casting method.     

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.     

Binder Burnout from Layers of Alumina Ceramics Under Centrifugal Force

The effect of centrifugal force on the delamination of layered green body during binder burnout has been studied in terms of internal gas pressure resulting from gas flow kinetics in porous media. Here, a sheet of nano-particle of γ-alumina was prepared by tape casting using polyvinyl butyral (PVB, binder) and dibutyl phthalate (DBP, plasticizer). Because of the fine pore structure (average pore size of 25 nm), molecular flow kinetics was applied to estimate internal pressure arising from evolved gases. Assuming that delamination is related to internal pressure, the interfacial strength of the layer was estimated. This strength was modified by applying a compressive pressure controlled by a centrifugal force. Because of the increased interfacial strength, delamination was suppressed, even during rapid heating. The compressive pressure required increased proportionally with increasing heating rate, a tendency that agreed with the expectation based on the gas flow kinetics in porous media.     

Reliability studies of gelcast fused silica between organic and inorganic binder systems

Fused silica ceramics was prepared by using conventional organic binder, mathacrylamide‐N,N′‐methylenebisacrylamide (MAM‐MBAM) system by gelcasting process. Mechanical properties of green bodies were studied as a function of solid loading varying from 60 to 72 vol%. After evaluating the green body mechanical properties, the samples were densified at different sintering temperature from 1200 to 1450°C with definite intervals of 50°C and subjected to flexural strength analysis. Variation in flexural strength with sintering temperature was observed and correlated with the quantity of devitrification of fused silica during sintering. Quantification of devitrified cristobalite was carried out by using 20 wt% rutile (TiO₂) as an internal standard by X‐ray diffraction. It was found that, as the cristobalite content increased, flexural strength decreased. Reliability studies were carried out for the samples having maximum flexural strength with and without crystalline content. Reliability studies have shown that for this organic binder system the sample sintered at 1300°C is crystalline free and most reliable product. The mechanical properties and reliability of this product processed with organic binder are compared with inorganic binder system. Results indicate that the sample fabricated using inorganic binder system is exhibiting high Weibull modulus and thus better reliability.     

Tape casting of aqueous Al2O3 slurries

The well-dispersed aqueous Al₂O₃ slurries suitable for tape casting were prepared, the effects of the concentration of dispersant, of the pH value, of solid content etc. on the properties of slurries were investigated, and the results indicated that the rheological of slurries was effected greatly by pH value and organic additives. After cutting, laminating and binder removal, the laminated Al₂O₃ green bodies were sintered by hot-press in a vacuum furnace. SEM micrographs showed that the microstructure of the aqueous green-body and samples were different from that of non-aqueous, and the mechanical properties of aqueous Al₂O₃ samples were much high than that of non-aqueous Al₂O₃.     

The influence of physicochemical properties of ZSM-5 on catalytic dewaxing

A decrease in the crystallite size increases the activity as well as the selectivity and reduces the deactivation of ZSM-5 zeolites in the dewaxing of petroleum fractions. Isomorphous replacement of Al³⁺ by Fe³⁺ reduces the dewaxing activity but enhances the yield of dewaxed oil and gasoline at the expense of C₁-C₄ gases. Within limits, the Si/Al ratio does not affect the performance of ZSM-5 zeolite in the hydrodewaxing process.     

Investigation of preparation and properties of Ti3SiC2/Al2O3 multilayered composites

Ti₃SiC₂/Al₂O₃ multilayered composites were prepared by the combination of tape casting and hot pressing sintering. The slurry was produced by adjusting the amounts of each organic material, including triethyl phosphate (TEP) as a dispersion, polyvinyl butyrate (PVB) as a binder, dioctyl phthalate (DOP) as a plasticizer, and anhydrous ethanol as an organic solvent. When TEP content was 3 wt.%, PVB content was 4.5 wt.%, R-value (DOP/PVB) was 1.4, and solid content was 38 wt.%; the cast film with a smooth surface, good flexibility, and uniform thickness was obtained after defoaming, tape casting, and drying. Three samples were prepared, namely, S1–S3. The S1 was monolithic Ti₃SiC₂/Al₂O₃ (mass ratio is 1:1) composites. S2 and S3 were Ti₃SiC₂/Al₂O₃ multilayered composites, which matrix layers were Ti₃SiC₂/Al₂O₃ composites (mass ratio is 1:1) and Al₂O₃, respectively, and their interface layer was Ti₃SiC₂. S1–S3 were also sintered at 1550°C. The bending strength of multilayered materials were lower than that of monolithic material, but the fracture toughness of multilayered materials significantly increased. Due to the introduction of Ti₃SiC₂ interface layer, the friction coefficient and wear rate of Ti₃SiC₂/Al₂O₃ multilayered composites were reduced by 30.7% and 33.8%, respectively, compared with monolithic material.     

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.     

Organic Distributions in Dried Alumina Green Tape

Distributions of organic binder (poly(vinyl butyral) (PVB)) and plasticizer (dibutyl phthalate (DBP)) in alumina green tape dried at different temperatures are studied. More PVB and DBP are observed on the bottom (Mylar side) than on the top surface (air side) of the green tape. Inside the green tape, however, PVB distribution, which remains relatively unchanged with drying temperature in the range of 30°–80°C, increases with distance from the bottom to the top. In contrast, the DBP concentration remains relatively unchanged with the depth of green tape when the drying temperature is <50°C. At 80°C, however, a significant drop in DBP concentration near the top surface of green tape is found. Mathematical analysis using the finite difference method is completed to describe the PVB distribution in alumina green tape, and the results show reasonable agreement with experimental observations.     

Sintered silicon nitride/nano-silicon carbide materials based on preceramic polymers and ceramic powder

A flexible method is presented, which enables the fabrication of porous as well as dense Si₃N₄/nano-SiC components by using Si₃N₄ powder and a preceramic polymer (polycarbosilazane) as alternative ceramic forming binder. The SiCN polymer benefits consolidation as well as shaping of the green body and partially fills the interstices between the Si₃N₄ particles. Cross-linking of the precursor at 300 °C increases the mechanical stability of the green bodies and facilitates near net shape machining. At first, pyrolysis leads to porous ceramic bodies. Finally, subsequent gas pressure sintering results in dense Si₃N₄/nano-SiC ceramics. Due to the high ceramic yield of the polycarbosilazane binder, the shrinkage during sintering is significantly reduced from 20 to 15 lin.%. Investigations of the sintered ceramics reveal, that the microstructure of the Si₃N₄ ceramic contains approx. 6 vol.% nano-scaled SiC segregations, which are located both at the grain boundaries and as inclusions in the Si₃N₄ grains.     

Determination of rapid heating cycles for binder removal from open pore green ceramic components

Abstract

Rapid heating cycles have been determined for the thermal removal of binder from open pore green ceramic components. The samples are multilayer green bodies with barium titanate as the dielectric, and the binder consists of poly(vinyl butyral) and dioctyl phthalate. The kinetics of binder decomposition, the gas permeability of the green body and the conditions at failure of the green body were determined from a combination of experiments and modelling. These results were then used with an algorithm based on variational calculus to develop successful rapid heating cycles without causing failure of the component.     

New route for processing of multilayer Al2O3-Co3O4 materials through gelcasting

Multilayer dense ceramic materials composed of Al₂O₃ and Al₂O₃-Co₃O₄ layers have been obtained by gelcasting. The key stage in the process was the optimization of the polymerization idle time in order to ensure strong adhesion between layers without cracks and delamination in a green state and after sintering. The significant advantage of this method is occurence of strong connections between consituent layers due to the slight migration of the slurry to the gelled bottom part of the sample, what is not obseved in techniques based on lamination processes. The multilayer samples were composed of two Al₂O₃ layers and two Al₂O₃-Co₃O₄ layers arranged alternately. The rheological characterization of the slurries was done. The properties of the sintered multilayer bodies were examined in comparison to the single-layer alumina samples. Observations in SEM and ligth miscroscope were performed. The presence of the transition layer in the sintered bodies was observed.     

New laser machining technology of Al2O3 ceramic with complex shape

A new method was developed for the fabrication of complex-shaped Al₂O₃ ceramic parts by combining laser machining and gelcasting technique. The unwanted ceramic powders parts were selectively removed by laser machining specified by a computer program, and the gelcast Al₂O₃ green bodies were machined to a designed shape by a CO₂ laser at a wavelength of 10.6 μm. The influences of solid loading, laser output power, scanning speed and nitrogen purge on the machining of green Al₂O₃ ceramic bodies were studied. The experimental parameters were optimized, the green Al₂O₃ bodies with solid loading of 40 vol% or below were easier to be machined, while the green bodies with solid loading of 45 vol% or above were hard to be further machined due to the surface sintering. Better machining quality and deeper machining depth could be obtained when the laser power is 30 W. The green Al₂O₃ bodies with complex shape were obtained by the laser machining.     

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.     

Microstructure evolution during reactive sintering of Y3Al5O12:Nd3+ transparent ceramics: Influence of green body annealing

The effect of green bodies’ mesostructure on the porosity, optical properties and laser performance of reactive sintered Y₃Al₅O₁₂:Nd³⁺ transparent ceramics was studied. Only minor changes in microstructure were revealed for green bodies without annealing and those annealed at 600, 800, 1000 °C, while average pore size increases to 140 nm for sample annealed at 1200 °C. Y₃Al₅O₁₂:Nd³⁺ ceramics sintered at 1750 °C for 10 hours possess significant differences in the final porosity, optical and laser characteristics. Despite all green bodies exhibit a similar phase evolution and sintering behavior on heating, the differences appear in the final stage, when the latest percentage of porosity is removed. The green bodies annealed at 600 °C have an optimal mesostructure from the standpoint of uniform densification. Y₃Al₅O₁₂:Nd³⁺ ceramics prepared using these green bodies exhibit porosity ≤0.001 vol% and yield efficient laser emission at 1.06 μm with slope efficiency as high as 67% in quasi-continuous pumping at 807 nm.     

Producing Large Complex‐Shaped Ceramic Particle Stabilized Foams

Highly porous ceramic foams can be produced by combining particle stabilized foams and gelcasting concepts. Sulfonate‐type surfactants are selected to weakly hydrophobize the alumina surface and stabilize air bubbles in suspensions containing gelcasting additives, polyvinyl alcohol (PVA), and 2,5‐dimethoxy‐2,5‐dihydrofurane (DHF). The aim of this work was to prepare large complex‐shaped ceramic foam objects with homogeneous microstructure and high porosity. A key to avoiding drying cracks is to strengthen the wet green body via gelcasting. The influence of the amount of gelcasting additives on the mechanical strength of the ceramic foam green bodies is investigated as well as the effect of using cross‐linking agent versus the addition of just a binder. The presence of a cross‐linked polymeric network within the green body increases its mechanical strength and minimizes crack formation during drying.