The effect of polyvinyl alcohol as a binder and stearic acid as an internal lubricant in the formation, and subsequent sintering of spray-dried alumina

The production of ceramic components using fewer processing steps on a shorter timescale is very important when considering the industrial and economic aspects of the manufacture of these materials in bulk. Spray-dried granules are expected to give compacts with fewer defects due to their low shear strength compared to conventional powders. Several extent studies show results for product of high relative densities (∼50% at 10 MPa), however, this study arrives at a process for making ceramic components with comparable density (48-49%) at 10 MPa), using less processing time and fewer processing steps which becomes extremely important when one considers the industrial aspects such as bulk production and manufacturing cost. In the present investigation, 35 vol% alumina slurries with 0.5% weight dispersant (ammonium polyacrylate) have been synthesized with different contents of binder (PVA) and lubricant (stearic acid). It is found that variations in the amounts of these additives plays a significant role in the formation of spray-dried granules, as well as the subsequent consolidation and densification of the compacts made using the granule particles. There is support for adopting the concept of a ‘compact process’.     

Preparation of coatings on alumina ceramic for wettability

To improve the wetting ability between ceramic and metal, titanium and copper coatings on alumina ceramics were prepared by infiltration of molten salt and electroless plating, respectively. A Ti/Cu bi-layer was also obtained by combining the two methods. The preparation process was optimized. The phase composition of the coatings was analyzed by X-ray diffraction (XRD). And the wettability of the titanium coating was investigated. The results showed that the copper droplet was easily spread on the surface of titanium coated alumina. The titanium coated alumina was well composited with high chromium white cast iron and the interface between ceramic and metal was well combined.     

Castable matrix,additives and their role on hydraulic binder hydration

The influence of alumina-based castable matrices, dispersants and Li₂CO₃ on the hydration process of different hydraulic binders was evaluated. The experiments were followed by temperature measurements with the time, the oscillatory rheometry technique and the normal force during the penetration of a blade through the material’s surface. By doing these tests, the chemical features of binder hydration, working and demolding time of suspensions could be assessed. The experiments have shown that the alumina-based matrix presented an accelerating effect which is related to its sodium content. Citric acid and ammonium citrate were the dispersants with the highest delaying effect and could be effectively associated with the accelerator (Li₂CO₃) in order to adjust the setting time of the suspensions. Nonetheless, their accelerating and retarding effect varied according to the hydraulic binder.     

The role of zircon particle size distribution, surface area and contamination on the properties of silica-zircon ceramic materials

Zircon is used as an additive to silica ceramics for use in investment casting to improve their high temperature properties. However, little is known about the mechanisms by which this occurs. To investigate the effect of zircon addition to a silica ceramic a number of silica-zircon formulations were created utilising three different batches of zircon with different particle size distributions (PSDs), surface areas and contaminant inclusions. The contaminant inclusion of the zircon, present in the zircon from the ball-milling stage of manufacture, appeared to have a large effect on the room temperature flexural strength, high temperature flexural strength and high temperature creep properties. It is also suggested that any increase in post-fired cristobalite content and any change to crystal growth morphology was due to the inherent contaminant inclusions and not because of the zircon itself. Hence, use of silica-zircon materials in ceramics for investment casting should account for variation in the contaminant inclusion of the zircon in order to maintain the specific material properties required.     

Influence of magnesia on sintering stress of alumina

The sintering stress and the densification of MgO-doped Al₂O₃ were measured with a self-loading apparatus and a thermomechanical analyzer, respectively. The densification started at 950 °C and finished at about 1450 °C. The measured surface tensions were 0.7–0.8 N m⁻¹ in the intermediate sintering stage but drastically decreased to 0.2 N m⁻¹ in the final stage of sintering.     

Optimization of binder removal for ceramic microfabrication via polymer co-extrusion

The objective of this study is to assess the feasibility of solvent extraction (SE) for partial binder removal in the context of polymer co-extrusion with a thermoplastic binder component. Polymer co-extrusion is able to produce multilayered, functionally graded and/or textured structures in an efficient manufacturing process, but requires a polymer binder system with suitable flow characteristics. Traditionally, the binder is removed by thermal debinding (TD), which, however, is prone to form cracks or blisters, both of which are attributed to a lack of initial pore space that allows pyrolysis products to escape. The primary focus of this work is to demonstrate that a binder system with a high soluble binder content is suitable for conventional polymer co-extrusion and to document that a two-step binder removal process involving both SE and TD eliminates debinding defects. The overall fabrication process is documented for the extrusion of solid ceramic rods and co-extrusion of tubes, where alumina powder was batched with polyethylene butyl acrylate (PEBA) as backbone polymer and polyethylene glycol (PEG) as water soluble binder. SE for specimen with varying PEBA:PEG ratios was tested in water at three different temperatures for various times. The 1:1 mixture showed a PEG removal up to 80 wt.% of the original PEG content after 6 h extraction; after subsequent thermal debinding, rods and tubes sintered successfully without defects, demonstrating the viability of the process.     

Influence of corrosion and mechanical loads on advanced ceramic components

Advanced oxide ceramics are prospective materials for severe application conditions, including corrosion, particularly, in oxygen-rich environments, combined with the action of mechanical loads. The corrosion behavior and mechanical strength decrease of oxide ceramics, such as high alumina, alumina–mullite and zirconia-based ceramics, were studied in water steam supercritical conditions (elevated temperatures and pressures). The strength decrease under the action of the studied aggressive environment is mostly dealt with the glassy phase dissolution and intergranular corrosion for alumina–mullite and high alumina ceramics, while degradation of zirconia-based ceramics is also dealt with the phase transformation. The influence of structure defects related to processing of the ceramics on corrosion is considered.     

Joining of alumina with a porous alumina interlayer

In the joining of structural ceramics, a porous interlayer is generally believed to deteriorate the mechanical properties of the joint. This paper, however, shows that a porous interlayer can sustain high adhesion strength when cavities or interfacial cracks are eliminated. The characteristic of the new slurry approach, described in this work, is that a pure alumina slurry interlayer is dried between two adjoining dense alumina plates and sintered with a negligible external pressure to form the porous interlayer. The effect of slurry concentration was studied to optimize the microstructure of interlayer. By controlling the interlayer microstructure and nature of the flaws, it was possible to fabricate high-strength bonds. The new slurry approach opens up the possibility of pure diffusion bonding which requires neither high pressure during heat treatments nor flat surfaces.     

Stability of alumina suspensions in the presence of Tiron

The stability of alumina suspensions in the presence of Tiron was studied and discussed in the light of surface properties of alumina powder used, ionization chemistry of Tiron, and sedimentation behavior of the suspensions. The point of zero charge of alumina with and without addition of Tiron was determined using a batch equilibration method. The sedimentation of the suspensions was evaluated via screen sedimentation tests as a function of pH and Tiron concentration. The dissociation constant, pK_a1, of the hydroxyl groups of the Tiron molecule was determined by potentiometric titration carried out in water and KNO₃ as a background electrolyte. Tiron was shown to adsorb specifically onto the alumina surface in the examined pH range 4–10, but impart stability to the suspensions only at pH ≥ 6.     

Reaction sintering of colloidal processed mixtures of sub-micrometric alumina and nano-titania

The fabrication of composites formed by alumina grains (95 vol%) in the micrometer size range and aluminium titanate nanoparticles (5 vol%) by reaction sintering of alumina (Al₂O₃) and titania (TiO₂) is investigated. The green bodies were constituted by mixtures of sub-micrometric alumina and nano-titania obtained from freeze-drying homogeneous water based suspensions, and pressing the powders. The optimization of the colloidal processing variables was performed using the viscosity of the suspensions as control parameter. Different one step and two step sintering schedules using as maximum dwell temperatures 1300 and 1400 °C were established from dynamic sintering experiments. Specimens cooled at 5 °C/min as well as quenched specimens were prepared and characterized in terms of crystalline phases, by X-ray diffraction, and microstructure by scanning electron microscopy of fracture surfaces.Even though homogeneous final materials were obtained in all cases, full reaction was obtained only in materials treated at 1400 °C. The microstructure of the composites obtained by quenching was formed by an alumina matrix with bimodal grain size distribution and submicrometric aluminium titanate grains located inside the largest alumina grains and at triple points. However a cooling rate of 5 °C/min led to significant decomposition of aluminium titanate. This fact is attributed to the small size of the particles and the effect of the alumina surrounding matrix.     

Fabrication of alumina parts by electrophoretic deposition from ethanol and aqueous suspensions

This paper discusses the effect of the properties of alumina suspensions in ethanol and in water, on green and sintered ceramic parts formed by electrophoretic deposition. The results of the study demonstrate that a small amount of water present in ethanol suspensions as a hidden additive due to the hygroscopicity of alumina powder and ethanol can detrimentally affect the behaviour of the suspension, thus lowering the reliability of the process. Electrophoretic deposition from aqueous suspensions appears to be advantageous over ethanol, from a reliability standpoint, and due to higher achievable green and sintered densities of the deposits and higher deposition rates. Dolapix CE64 appears to be superior surfactant in water as it results in deposits with the lowest green and sintered porosities.     

A new direct coagulation casting process for alumina slurries prepared using poly(acrylate) dispersant

Direct coagulation casting (DCC) of concentrated aqueous alumina slurries prepared using ammonium poly(acrylate) dispersant has been studied using MgO as coagulating agent. Addition of small amounts of MgO increased the viscosity of the concentrated alumina slurries with time and finally transformed it in to a stiff gel. Sufficient working time for degassing and casting could be achieved by cooling the slurries to a temperature of ∼5 °C after proper homogenization after the addition of MgO. The DCC slip with alumina loading in the range of 50–55 vol% showed relatively low viscosity (0.12–0.36 Pa s at shear rate of 93 s⁻¹) and yield stress (1.96–10.56 Pa) values. The wet coagulated bodies prepared from slurries of alumina loading in the range of 50–55 vol% had enough compressive strength (45–211 kPa) for handling during mould removal and further drying. The coagulated bodies prepared from slurries of alumina loading in the range of 50–55 vol% showed linear shrinkage in the range of 4.8–2.3 during drying and 17.1–16.2 during sintering respectively. Near-net-shape alumina components with density >98% TD could be prepared by the DCC process.     

OH and COOH functionalized single walled carbon nanotubes-reinforced alumina ceramic nanocomposites

Alumina ceramics reinforced with 1 wt.% single-walled carbon nanotube (SWCNT) were fabricated via spark plasma sintering (SPS) of composite powders containing carboxyl (COOH) or hydroxyl (OH) group functionalized single-walled carbon nanotubes. The samples were SPS’ed at 1600 °C under 50 MPa pressure for holding time of 5 min and at a heating rate of 4 °C/s. The effects of CNT addition having different surface functional groups on microstructure, conductivity, density and hardness were reported. It was shown that nanotube addition decreased the grain sizeof alumina from 3.17 μm to 2.11 μm for COOH-SWCNT reinforcement and to 2.28 μm for COOH-SWCNT reinforcement. The hardness values of the composites are similar for all samples but there is 4.5 and 7.5 times increase in electrical conductivity with respect to monolithic alumina for COOH-SWCNT and OH-SWCNT, respectively. It was also shown by TEM and FEG SEM observations that transgranular fracture behaviour of alumina was changed to mostly intergranular fracture mode by the addition of both types of CNTs which may be due to location of CNTs along the grain boundaries. A significant grain size reduction in alumina is considered toresult fromthe suppressing effect of CNTs during sintering.     

Effect of freeze-drying treatment on the optical properties of SPS-sintered alumina

This study looks at the influence of alumina powder processing on the preparation of transparent alumina by Spark Plasma Sintering (SPS). Zeta potential measurements were carried out on alumina suspensions in order to determine the best dispersion conditions. Stable slurries were submitted to a spray freeze drying process and their sintering behavior was compared with the corresponding non spray freeze dried powders. Transparent alumina samples were successfully prepared from alumina powders by Spark Plasma Sintering. An optical model considering pore and grain size distributions has been developed to obtain information about porosity in dense materials. It was found that the final density and, accordingly, the optical properties were improved when spray freeze dried starting powder was used.     

Fabrication of yttria-stabilized-zirconia coatings using electrophoretic deposition: Effects of agglomerate size distribution on particle packing

Yttria-stabilized-zirconia (YSZ) particles with various size distributions have been electrophoretically deposited (EPD) on Fecralloy substrate to investigate the particle size effect on EPD coatings. The deposition rates, as-deposited particle packing densities, green densities and sintered (for 2 h at 1250 °C in air) coating hardnesses are dependent on particle size. The particle packing arrangement in EPD coatings can be affected by further electric field densification (EFD) of the as-deposited coating in which the wet EPD coating is immersed in pure solvent (acetylacetone) with the application of a constant electric field. The effect of EFD was found to be most effective on small particles (<0.5 μm) when they are co-deposited with large particles (>1 μm). The improvements are reflected in increased mechanical hardness of sintered coatings.     

Synthesis of alumina nanofibers by a mercury-mediated method

Alumina nanofibers were successfully synthesized in mercury media at room temperature. Structure and morphology of the nanofibers were characterized by TEM, EDX, FESEM, XRD, TG, DTA and N₂ adsorption–desorption. The results show that the as-grown alumina nanofibers are amorphous, and have diameters of 5–15 nm and lengths up to several micrometers. After calcinated at 850 °C for 2 h, the amorphous alumina nanofibers convert to γ-Al₂O₃ nanofibers. The mechanism for the growth of alumina nanofibers was discussed and a model representing the growth process was presented. During the process, mercury will be produced by metathesis reaction of HgCl₂ and Al, Al atoms continuously dissolve into mercury and diffuse to amalgam/air interface, and then Al atoms react with oxygen and water in air, finally alumina nanofibers can be formed.     

Effects of particulate metallic phase on microstructure and mechanical properties of carbide reinforced alumina ceramic tool materials

Alumina-based composite ceramic tool materials reinforced with carbide particles were fabricated by the hot-pressing technology. Choice of metallic phase added into the present composite ceramic was based on the distribution of residual stress in the composite. The effects of metallic phase on microstructure and mechanical properties of composites were investigated. The metallic phase could dramatically improve room temperature mechanical properties by refining microstructure, filling pores and enhancing interfacial bonding strength. However, it also led to sharp strength degradation at high temperature because the metallic phase was easier to be oxidized and get soft at high temperature in air. The effects of metallic phase on strengthening and toughening were discussed. The improved fracture toughness of composite with metallic phase was attributed to the lower residual tensile stress in the matrix and the interaction of more effective energy consuming mechanisms, such as crack bridged by particle, crack deflection and intragranular grain failure.     

Hydration of CAC cement in a castable refractory matrix containing processing additives

A growing demand for refractory castables with a particular behavior has been inducing a continuous technological evolution, where one of the most important aspects, is an in-depth knowledge of hydraulic binders. These materials greatly influence the rheological properties and mechanical strength evolution of castables, defining their workability range and demolding time, respectively. The hydration process of hydraulic binders is influenced by the presence of matrix and additives (dispersants and accelerators), which affect the setting and demolding time of shaped bodies. In this work, the influence of these variables on the hydration process of calcium aluminate cement was studied by means of temperature measurements, oscillatory rheometry and normal force measurement. These techniques were able to evaluate the setting behavior of different binders, either in plain water or in matrix-representative suspensions. In both cases, the dispersants presented a retarding effect on the hydration process, which was more significant for citric acid and diammonium citrate. The combination of these additives with an accelerator (Li₂CO₃) was shown to be an efficient tool to control the setting time of castables.     

Calcination and associated structural modifications in boehmite and their influence on high temperature densification of alumina

A systematic study is reported on the calcination of boehmite and its associated structural changes, and their effect on densification features. Boehmite precursor gels have been calcined in the temperature range 250-1200 °C. The associated structural changes are identified by FTIR and XRD. The specific surface area measurements indicated a relatively high value of 169 m²/g for boehmite calcined at 400 °C; this value reduced to 4 m²/g on calcination at 1200 °C. In the temperature range 400-1000 °C, the coordination of aluminium changes from a quasioctahedral to a tetrahedral nature, which reverts to octahedral at 1200 °C. The precursor containing γ-alumina gives a 92.1% theoretical density, on sintering at 1500 °C due to the highly unstable quasioctahedral coordination. Boehmite precursors calcined at 400 °C and 1000 °C produced a density of 88.2% and 96.9%, respectively, in the sintered compact at 1500 °C. Boehmite calcined to α-alumina (1200 °C) possesses an octahedral structure having a density of 97.6% at 1500 °C.