Heterocoagulation moulding of alumina powder suspensions prepared using citrate dispersant

Coagulation characteristics of aqueous alumina suspensions prepared using di-ammonium hydrogen citrate (DHC) dispersant has been studied using MgO coagulating agent for direct coagulation casting (DCC). Mg–citrate complexes formed by the reaction between the DHC and MgO act as dispersant for alumina at pH near its iso-electric point. Setting of the alumina suspensions takes place, at MgO concentrations higher than the equivalent amount required to react with the DHC, by heterocoagulation of the alumina and MgO particles due to their opposite surface charges. The yield strength and Young's modulus of the wet-coagulated alumina bodies increased with aging time due to the hydration of the excess MgO. The minimum time required for mould removal decreases and yield strength and Young's modulus of the wet-coagulated bodies increases with MgO concentration. Alumina green bodies prepared at MgO concentrations in the range of 0.2–0.5 wt% sintered to ～97% theoretical density at 1550 °C and the sintered ceramics showed more or less similar microstructures irrespective of MgO concentrations.     

Direct coagulation casting of YSZ powder suspensions using MgO as coagulating agent

Direct coagulation casting (DCC) of aqueous 8 wt% yttria stabilized zirconia (YSZ) powder suspensions prepared using ammonium poly(acrylate) dispersant has been studied using MgO as coagulating agent. Small amount (<0.1 wt% based on YSZ) of MgO powder dispersed in the YSZ powder suspension at ∼5 °C set the suspension in to stiff wet-coagulated body when exposed to room temperature (30 °C) due to the reaction between ammonium poly(acrylate) and MgO. MgO concentration equivalent to react with dispersant did not coagulate the YSZ powder suspension though it precipitate the whole ammonium poly(acrylate) dispersant as Mg-poly(acrylate). This is because of the ability of the YSZ powder to disperse in water at alkaline pH (∼9.5) without any dispersant by electrostatic mechanism. The YSZ powder suspensions form stiff coagulated bodies at MgO concentration double or more of the equivalent amount required for reacting with the dispersant. Setting of the YSZ powder suspension is due to the heterocoagulation of the YSZ particles and MgO particles added in excess of the equivalent amount to react with the dispersant, having opposite surface charges. The wet-coagulated body showed relatively high compressive yield strength (155 kPa) and Young’s modulus (3.1 MPa). The green bodies prepared by humidity controlled drying of the wet-coagulated bodies sintered to >98% TD at 1550 °C.     

Rapid and uniform in-situ solidification of alumina suspension via a non-contamination DCC-HVCI method using MgO sintering additive as coagulating agent

A novel rapid, uniform and non-contamination in-situ solidification method for alumina suspension by DCC-HVCI method using MgO sintering additive as coagulating agent was reported. MgO was used to release Mg²⁺ in suspensions via reaction with acetic acid generated from glycerol diacetate (GDA) at elevated temperature as well as to improve density and suppress grain growth of alumina ceramics during sintering. Influence of adding 0.7 wt% MgO with 2.0 vol% GDA in alumina suspension on coagulation process and properties of green bodies and sintered samples were investigated. It was indicated that the controlled coagulation of the suspension could be achieved after treating at 70 °C for 10 min. Homogeneous composition distribution of Mg element in EDS result indicated the uniform solidification of suspensions. Compressive strength of wet-coagulated bodies is 2.09±0.25 MPa. Dense alumina ceramics with relative density of 99.2% and flexural strength of 354±16 MPa sintered at 1650 °C for 4 h present homogeneous microstructure. The result indicated that the novel DCC-HVCI method via a sintering additive reaction with no contamination, short coagulation time and uniform in-situ solidification is a promising colloidal forming method for preparing high-performance ceramic components with complex shape.     

Novel Coagulation Method for Direct Coagulation Casting of Aqueous Alumina Slurries Prepared Using a Poly(Acrylate) Dispersant

Coagulation of concentrated aqueous alumina slurries prepared using an ammonium poly(acrylate) dispersant by MgO has been studied for direct coagulation casting (DCC). A small amount of MgO (0.2 wt% of alumina) increased the viscosity of the concentrated alumina slurry with time and finally transformed it into a stiff gel. The mechanism of coagulation is proposed such that the time-delayed in situ generation of Mg²⁺ ions from the sparingly soluble MgO forms Mg–poly(acrylate) with the unadsorbed ammonium poly(acrylate) molecules in solution that shift the poly(acrylate) adsorption equilibrium toward the left by depleting the poly(acrylate) molecules adsorbed on the alumina particle surface. This leads to insufficient dispersant coverage on the particle surface and coagulation of the slurry. DCC using MgO is possible only if the slurry is prepared at a dispersant concentration higher than that required for optimum dispersion as the slurries prepared at the optimum dispersant concentration underwent premature coagulation. The gelation time could be tailored within 20 min to a few hours by maintaining the temperature in the range of 70°–30°C. The wet coagulated bodies prepared from 50 vol% alumina slurry showed a compressive strength of nearly 0.05 MPa.     

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.     

Effect of Concentration of Ammonium Poly(acrylate) Dispersant and MgO on Coagulation Characteristics of Aqueous Alumina Direct Coagulation Casting Slurries

Coagulation of aqueous alumina slurries prepared using various concentrations (0.43–1.04 wt% based on alumina) of ammonium poly(acrylate) dispersant by MgO has been studied for direct coagulation casting (DCC) of alumina. The slurries prepared at dispersant concentration below 0.84 wt% are not suitable for DCC at room temperature (∼30 ° C) as they undergo premature coagulation. Mixing the slurry with MgO at a low temperature of nearly 5 ° C slows down the reactions leading to coagulation and keeps the slurry viscosity low for a sufficient period of time. Coagulation of slurries prepared at a dispersant concentration of 0.92 wt% and above at room temperature requires MgO concentrations much higher than the equivalent amount required for reaction with the dispersant. This anomalous behavior at higher dispersant concentration is explained such that the Mg-poly(acrylate) formed by the reaction between ammonium poly(acrylate) and MgO formed a sheath over the remaining MgO particles and prevented them from further dissolution at room temperature. Faster coagulation could be achieved by heating the slurries after casting in closed molds. The Mg-poly(acrylate) acts as a binder and stabilizes the coagulated bodies as their strength and stability against oscillatory stresses increase with an increase in dispersant concentration.     

Direct coagulation casting of yttria-stabilized zirconia using magnesium citrate and glycerol diacetate

Direct coagulation casting via controlled release of high valance counter ions (DCC-HVCI) has been reported in recent years. In this paper, concentrated yttria-stabilized zirconia (YSZ) suspensions were coagulated using DCC-HVCI method with magnesium citrate as coagulating agent assisted by pH shift in the presence of glycerol diacetate. The effect of ammonium polyacrylate (PAA-NH₄) on the dispersibility of YSZ powder was investigated. The influence of concentrations of glycerol diacetate and magnesium citrate on pH and viscosities of YSZ suspensions was studied. The results indicate that concentrated YSZ suspensions can be coagulated by adding 2 vol% glycerol diacetate and magnesium citrate above 0.5 wt% at room temperature for 2–5 h. The compressive strength of coagulated wet samples is above 2.0 MPa. YSZ ceramics sintered at 1450 °C show homogeneous microstructures with relative densities of 98.9–99.2%. Flexural strength of YSZ ceramics is 869±84 MPa.     

Gelcasting of alumina suspensions containing nanoparticles with glycerol monoacrylate

An acrylic monomer of low toxicity containing two hydroxyl groups has been synthesized and used for gelcasting in water. The results have been compared to those achieved with the use of a commercially available monomer (2-hydroxyethyl acrylate). Due to the chemical structure of the synthesized monomer, no addition of the crosslinking agent was necessary for gelation and similar results in terms of rheology of suspensions, density and microstructure of the bodies were obtained with respect to those obtained with the commercial monomer. However, higher time for gelation was observed.Two alumina powders with very different particle sizes were used in this study: a commercial submicron-sized powder (d₅₀ = 0.35 μm) and a nanometer-sized alumina obtained by freeze-drying from aluminum sulphate solutions. The rheological behavior of concentrated suspensions was studied in order to establish their stability and to analyse the effect of the different monomers used in the process. Once the suspensions were optimized, the influence of the size of the powder on the gelation process was studied. The sintered density of submicrometer-sized alumina was higher (99%) than that measured when the bimodal suspension was used due to the difficulty to obtain highly concentrated suspensions from nanometric powder.     

Roles of polymeric dispersant charge density on lead zirconate titanate aqueous processing

Poly(acrylic acid) (PAA) and poly(acrylic acid-co-maleic acid) (PACM) were used as dispersants in preparation of lead zirconate titanate (PZT) aqueous suspensions. The effects of dispersant structure on particle stabilization were investigated through properties of the suspensions. Viscosity and sedimentation height measurements showed that addition of the dispersants improved particle stabilization. The dispersant concentrations to obtain the lowest viscosity were 0.4 wt% for PAA and 0.2 wt% for PACM based on powder dried weight basis. Furthermore, effects of pH were studied on the suspensions prepared with 0.2 wt% dispersants. Viscosity and sedimentation behaviors indicated the improvements of particle dispersion and suspension stability with an increasing pH. Particle dispersion revealed by laser light scattering and scanning electron microscopy supported an improvement of particle dispersion at alkaline pHs. Detailed analysis of these data indicated that the PACM exhibited higher dispersant efficiency for PZT aqueous suspension in all conditions. The results were discussed based on the concentrations of anionic –COO^? groups at various pHs and charge density along polymeric backbone of the dispersants.     

Direct coagulation casting of silicon nitride suspension via a dispersant reaction method

A direct coagulation casting method for silicon nitride suspension via dispersant reaction was reported. Tetramethylammonium hydroxide (TMAOH) was used as dispersant to prepare silicon nitride suspension with high solid loading and low viscosity. Influences of TMAOH and pH value on the dispersion of silicon nitride powder were investigated. Glycerol diacetate (GDA) was used to coagulate the silicon nitride suspension. Influences of the concentration of glycerol diacetate on the viscosity and pH value of the suspension were investigated. It was indicated that high viscosity sufficient to coagulate the suspension was achieved by adding 1.0–2.0 vol% glycerol diacetate at 40–70 °C. The coagulation mechanism was proposed that the silicon nitride suspension was destabilized by dispersant reacting with acetic acid which was hydrolyzed from glycerol diacetate at elevated temperature. Coagulated samples could be demolded without deformation by treating 50 vol% silicon nitride suspensions with 0.2 wt% tetramethylammonium hydroxide and 1.0–2.0 vol% glycerol diacetate at different temperatures. Dense silicon nitride ceramics with relative density above 98.8% had been prepared by this method using glycerol diacetate as coagulating agent sintered by different methods.     

Fabrication of porous fibrous alumina ceramics by direct coagulation casting combined with 3D printing

A novel forming method for preparing porous alumina ceramics using alumina fibers as raw materials by direct coagulation casting (DCC) combined with 3D printing was proposed. Porous fibrous alumina ceramics were fabricated through temperature induced coagulation of aqueous-based DCC process using sodium tripolyphosphate (STPP) as dispersant and adding K₂SO₄ as removable sintering additives. The sacrificial coated sand molds was fabricated by 3D printing technology, followed by the infiltration of silica sol solution for the subsequent suspension casting. Stable alumina suspension of 40 vol% solid loading was obtained by adding 2.0 wt% STPP and 40 wt% K₂SO₄. The controlled coagulation of the suspension could be realized after heating at 90 °C for about 35 min. The ceramic sample sintered at 1450 °C for 2 h showed the highest compressive strength of 24.33 MPa with porosity of 57.38%. All samples sintered at 1300–1450 °C had uniform pore size distributions with average pore size of 7.2 µm, which indicated the good structure stability when sintered at high temperature.     

Coagulation of mixed organic systems and alumina particles for paste production

Pastes of alumina with plastic properties were prepared by direct coagulation casting (DCC) of concentrated suspensions (≥50 vol%). Two polyelectrolytes were used to produce mixed systems of organic and mineral particles. An anionic polymer, bearing both sulfonate and carboxylate functions, was used to disperse efficiently alumina powder in water. A cationic polymer, the chitosan (CT), which complexes with the anionic one was added into the stable suspension to form an organic network dispersed into the ceramic matrix. The sequence of addition of the chitosan in the suspension appears to be a significant parameter in order to optimise the suspension formulation. After in situ coagulation, cylinders were extruded.     

Preparation of silicon carbide ceramics using chemical treated powder by DCC via dispersant reaction and liquid phase sintering

Dense silicon carbide ceramics using chemical treated powder by DCC via dispersant reaction method and liquid phase sintering was reported. Ammonium peroxydisulfate ((NH₄)₂S₂O₈) and ammonium carbonate ((NH₄)₂CO₃) were used as acid and base solutions to treat the silicon carbide powder, respectively. Influence of silicon carbide powder with chemical treatment on the preparation of silicon carbide suspension was studied. It was indicated that 50 vol% and 52 vol% silicon carbide suspensions with viscosities of 0.71 Pa s and 0.80 Pa s could be prepared using acid and base treated powders. Influence of silicon carbide powder with chemical treatment on the coagulation process and properties of green bodies and sintered ceramics were studied. It was indicated that silicon carbide green bodies with compressive strength of 1.13 MPa could be prepared using base treated powder. Dense silicon carbide ceramics with relative density above 99.3% and flexural strength of 697 ± 30 MPa had been prepared by DCC via dispersant reaction and liquid phase sintering using Al₂O₃ and Y₂O₃ as additives at 1950 °C for 2 h.     

Effect of milling time and pH on the dispersibility of lead zirconate titanate in aqueous media for inkjet printing

Micrometre-sized Pb(Zr_0.53Ti_0.47)O₃ (PZT) powder was dispersed in water, stabilized with the ammonium polyacrylate (PAANH₄) and milled to reduce the particle size. The influence of the pH, the amount of PAANH₄, and the milling time on the zeta potential, the PZT particle size and the particle size distribution was studied. The agglomeration took place regardless the milling time at pH 3. The suspension, containing 5 vol.% of PZT and 5 wt.% of PAANH₄, milled at pH 10 for 240 min, was stable and contained particles with a narrow, log-normal particle size distribution with the median size of 160 nm. The dissociated carboxyl groups from the PAANH₄ interacted with the PZT particles as evidenced by Fourier transform infrared spectroscopy and electrosterically stabilized the particles in water at pH 10. The PZT particle size and the stability of the suspension fitted the requirements for the ink, suitable for ink-jet printing.     

Rheological characteristics of alumina platelet–Hydroxyapatite composite suspensions

The rheological behaviour of aqueous suspensions of alumina platelet–hydroxyapatite mixtures for slip casting was investigated. The stabilisation of the suspensions requires the use of a dispersing agent and the breakdown of powder agglomerates. The addition of alumina platelets to the HAP powder does not modify significantly the behaviour of the suspensions which remains always quasi-Newtonian. Nevertheless, this behaviour becomes shear-thinning at low shear rates for high alumina contents when platelets of small size are used. The viscosity increases at low shear rates with the increase of small platelets content. These modifications are assumed to result from orientation phenomena of alumina disks under shear stress in the direction of flowing. The disk-shaped morphology of alumina is detrimental to the preparation of high density green composites. Suspensions containing between 50 and 70 wt% of powder are castable but the best rearrangement of solid particles during the casting process is reached for suspensions containing 65 wt% of powder.     

MgO calcination for easy direct coagulation casting of aqueous alumina slurries

The reactivity of MgO with ammonium poly(acrylate) and diammonium hydrogen citrate dispersants was decreased by high-temperature calcination which enabled easy preparation of direct coagulation casting slurries without cooling. The decrease in reactivity of MgO with an increase of calcination temperature (30–1200?°C) was due to the decrease of surface area (52.7–0.7?m²/g) as a result of an increase of average particle size (285–2075?nm) as well as a change of particle morphology from flaky to near spherical. The MgO calcined at a temperature of 1000?°C and above provided sufficient time for mixing with aqueous alumina slurries by ball milling at room temperature (~30?°C) without producing an adverse increase in viscosity before casting. The setting time of 55?vol% alumina slurries was in the ranges of 260–1070 and 10–50?min at room temperature and at 70?°C, respectively, at MgO concentrations in the range of 0.1123–1.2?wt%. The faster setting at 70?°C was due to a combination of faster dispersant-MgO reaction, faster hydration of MgO and high valance counter ion effect.     

Colloidal processing and partial sintering of high-performance porous zirconia nanoceramics with hierarchical heterogeneities

High-performance, porous, Y-TZP nanoceramics with hierarchical heterogeneities originating from uniform, intra- and inter-particle packing were prepared by colloidal processing and partial sintering of a mesoporous powder. The powder consisted of 100–150-nanometer-sized secondary particles initially composed of smaller, loosely aggregated, primary, nanoscale crystallites. Green bodies were prepared by centrifugal slip casting of weakly flocculated suspensions. During the initial stage of sintering, necking between the secondary particles was accompanied by intra-particle pore coalescence, while the pores originating from the secondary particle packing remained intact. Such microstructures with porosity levels between 46 and 18.3% and pore areas between 18 and 4 m²/g led to attractive properties, i.e., much reduced thermal conductivities of 0.63–1.88 W m^?1 K^?1, high bending strengths of 70–540 MPa and lowered elastic moduli of 32–156 GPa, making them potentially ideal as thermal insulators and/or load-bearing porous biomaterials owing to the possibility of further impregnation with bioactive ingredients.     

Molten salt synthesis of PZT powder for direct write inks

The preparation of lead zirconate titanate (PZT) powder by molten salt synthesis (MSS) is described and a mechanism proposed. The effect of process parameters, such as reaction time and temperature and heating rate, on particle size and shape was investigated. A reaction mechanism for the synthesis of PZT by molten salt method is proposed, where dissolved Pb initially reacts with insoluble TiO₂ to form intermediate PbTiO₃. Subsequently Zr diffuses into and reacts with PbTiO₃ to form PZT. Spherical particles, ～340 nm in size, were obtained, using a NaCl/KCl salt, by heating the starting materials at 850 °C for 60 min, with a ramp rate of 3.3 °C min^?1.     

A PCE-based rheology modifier allows machining of solid cast green bodies of alumina

The performance of a poly(carboxylate ether) (PCE)-based superplasticizer to enable the machining of green bodies that are solid cast from suspensions of alumina was investigated. An alumina loading of 35 vol% in the presence of 1.25 wt% superplasticizer was established to be suitable for lathing and removal of significant amount of material through drilling. A reduction of 77% in the diameter of green bodies that corresponds to a 59% reduction in volume was achieved. The lathed green bodies exhibited smooth terraces without visible cracks. All of the green bodies were sintered without a polymer burnout step.     

Characterization of porous alumina bodies fabricated by high-temperature evaporation of boric acid with sodium impurity

For steel-making refractories, porous alumina bodies fabricated by the evaporation of chemical impurities at high temperatures was studied. Boron hydroxide and sodium carbonate were added in different proportions as impurities into the starting aluminum hydroxide powder compacts, which were heated at various temperatures for 1 h to form porous alumina bodies. During heating, the borate compounds that reacted with sodium seems to be formed in the liquid phase, so that all alumina particles were able to grow into platelets. Although the sodium inside the compacts was completely evaporated by 1400 °C, the boron melt was maintained above 1400 °C. Hence, alumina platelets grew with a card-house structure, which preserved the high porosity of the alumina body. After heating at 1600 °C for 1 h, the remaining boron oxide was completely evaporated and sintering between the alumina particles began to decrease the porosity. The compressive strength and porosity of the alumina bodies obtained by heating at 1700 °C for 1 h were 0.8 MPa and 64%, respectively. It is expected that the resulting porous alumina bodies can be used as castable porous clinkers.