Direct Coagulation Casting of Alumina Suspensions Using Jack Bean as a Urease Source

This paper reports on the use of Jack bean meal as an alternative source of urease for direct coagulation casting (DCC) processes. Al₂O₃ suspensions were prepared to compare the effect of Jack bean meal and pure urease on the hydrolysis of urea, the slurry coagulation rate, and the mechanical properties of consolidated bodies. Results indicate that the Jack bean meal is a promising economic alternative for the consolidation of ceramic parts, mainly because of its lower susceptibility to enzyme deactivation when exposed to room temperature and relatively humid environments.     

Coagulation Method of Aqueous Concentrated Alumina Suspensions by Thermal Decomposition of Hydroxyaluminum Diacetate

Consolidation of aqueous concentrated suspensions was used to shape alumina green bodies because it enabled us to obtain complex-shape components with accurate sizes. A high state of alumina particle dispersion was achieved by using (HO)₂C₆H₂(SO₃Na)₂ (Tiron), which allowed us to obtain stable alumina suspensions at pH 9 with a powder concentration higher than 60 vol%. The addition to the suspension of hydroxyaluminum diacetate, (CH₃CO₂)₂AlOH, which decomposed as the temperature increased, permitted us to coagulate an alumina suspension dispersed with Tiron efficiently. Adsorption measurements, electrokinetic mobility, and the rheological behavior of the suspensions provided useful methods to characterize each processing stage. Dense green bodies with sufficient cohesion could be demolded and dried, demonstrating that the dispersant and the flocculant agent chosen permit one to optimize the direct coagulation casting processing of alumina components.     

In Situ Rheological Investigation of the Coagulation in Aqueous Alumina Suspensions

Electrostatically stabilized alumina suspensions can be destabilized by the enzyme-catalyzed decomposition of urea (direct coagulation casting). Depending on the conditions, this reaction can shift the pH of a suspension to the buffer pH of the reaction products or increase the ionic strength at the buffer pH. The coagulation for both mechanisms was investigated using in situ rheological measurements. Using a vane tool in oscillation mode, the measuring conditions were optimized to find a reasonable method for time-dependent measurements. Constant parameters (stress or strain) proved to be unsuitable, because the linear viscoelastic region shifted considerably during the coagulation. Furthermore, the gel structure produced on coagulation via increase of ionic strength (Δ I ) was very sensitive to the oscillation. Therefore, for long-time experiments, a short continuous measurement with a low strain was followed by amplitude sweeps with increased intervals to determine the linear values of G ' and G ". In this way, the increase of the moduli G ' and G " could be followed for longer times, and it was possible to demonstrate two results. First, the final G ' of the network was about 10 times higher for Δ I -coagulated material than for suspensions coagulated via pH shift (ΔpH). Second, particle rearrangement processes took place in Δ I -coagulated networks even after the chemical changes were finished, whereas ΔpH-coagulated samples were "frozen-in" when approaching the isoelectric point and showed no further physical changes afterward.     

Ink-Jet Printing of Wax-Based Alumina Suspensions

Suspensions of fine alumina powder in a paraffin wax have been successfully formulated with viscosity values sufficiently low to allow ink-jet printing using a commercial printer. A commercial-grade paraffin wax, with stearylamine and a polyester, were used as the dispersant system. Suspensions with powder loadings up to 40 vol% were passed through the ink-jet printer head. Unfired ceramic bodies with a feature size of <100 μm have been successfully fabricated with waxes that had a powder loading of 30 vol%. The influence of suspension fluid properties on the ink-jet printing process has been studied, and the importance of the acoustic resonance within the ink-jet printing apparatus has been demonstrated.     

Weakly Flocculated Aqueous Alumina Suspensions Prepared by the Addition of Mg(II) Ions

Well-dispersed aqueous alumina suspensions were prepared at an inherent pH via the addition of an anionic dispersant. With the addition of an appropriate amount of magnesium acetate to such a suspension, the surface charge of the particles was neutralized, which was reflected in the destabilization of the slurry. Because of the formation of coordinative bonds between the Mg ion and the two dissociated carboxylic groups of the dispersant, a thin neutral layer was formed on the surface of the particles, which established a nontouching particle network and resulted in a weakly flocculated suspension.     

Effect of Particle Volume Fraction on the Gelation Behavior of the Temperature Induced Forming (TIF) Aqueous Alumina Suspensions

Stable aqueous Al₂O₃ suspensions that can be flocculated by increasing temperature were prepared using tri-ammonium citrate and poly(acrylic acid) (PAA). Effects of particle volume fraction on the rheological properties of Al₂O₃ suspensions were investigated. The modified Dougherty–Krieger equations were used to describe the volume fraction dependence of relative viscosity for both the PAA-addition and PAA-free suspensions. An equation using percolation model was proposed to analyze the temperature and volume fraction dependence of the relative viscosity of the suspensions. The calculated results were in good agreement with the experimental data.     

Colloidal Filtration and (Simultaneous) Sedimentation of Alumina and Silica Suspensions: Influence of Aggregates

Colloidal filtration and (simultaneous) sedimentation is studied for suspensions of alumina particles and monodisperse silica spheres. A comparison is made between stable suspensions and systems which are aggregated due to salt addition (silica) or absence of a deflocculant (alumina). From separate sedimentation experiments we conclude that the stable silica settles as an ordered particle array, that the unstable silica sediments as separate aggregates, and that aggregated aluina behaves as a densifying network. The filtration results show that settling of aggregates during filtration changes the filtration kinetics in accordance with our model for simultaneous filtration and sedimentation. Further, aggregates in suspension are shown to have little influence on the silica compact microstructure, whereas they clearly increase porosity and permeability of the alumina compact. We also find that for all suspensions porosities of compacts prepared by sedimentation are clearly larger then porosities of filter compacts.     

Hierarchically Structured Materials by Anodic Coagulation Casting of Fibrinogenic Alumina Suspensions

Anodic coagulation casting of fibrinogenic ceramic suspensions is a novel processing technology, which is based on the electrically induced transformation of the water soluble fibrinogen into the insoluble fibrin. Contrary to the direct coagulation casting (DCC) technology, green formation does not depend on a pH‐shift and as the fibrin coagulate forms on an anode, it can be combined with the electrophoretic deposition (EPD) technology. In this study, the conversion of fibrinogen into fibrin is activated via electron transfer processes at an electrode material and is combined with the green formation of alumina by embedding the ceramic particles in the protein matrix. The focus of this work was to establish a technology to shape thin hierarchically structured ceramic films and thick porous materials with a distinct pore structure. Film thickness and porosity were controlled by the applied voltage and the processing‐time. The range of the established green bodies included two‐dimensional and simple three‐dimensional shapes including multilayered deposition and fiber coatings. Overall the process of anodic coagulation casting can be reported to be successful for all established ceramic shapes except multilayers, where delamination was observed. The deposited alumina ceramics were characterized using light microscopy, scanning electron microscopy (SEM), atomic force microscopy (AFM), and synchrotron micro computed tomography (μCT), while the coagulation mechanism was studied using high‐performance liquid chromatography (HPLC).     

Additive Manufacturing of Dense Ceramic Parts via Direct Ink Writing of Aqueous Alumina Suspensions

Additive manufacturing of near‐net‐shaped dense ceramic components has been established via room‐temperature direct writing of highly loaded aqueous alumina suspensions in a layer‐by‐layer fashion. The effect of alumina solid loading on rheology, specimen uniformity, density, microstructure, and mechanical properties was studied. All suspensions contained a polymer binder (~5 vol.%), dispersant, and 51–58 vol.% alumina powder. Rheological measurements indicated all suspensions to be yield‐pseuodoplastic, and both yield stress and viscosity were found to increase with increasing alumina solid loading. Shear rates ranging from 19.5 to 24.2/s, corresponding to viscosities of 9.8 to 17.2 Pa·s, for the 53–56 vol.% alumina suspensions were found to produce the best results for the 1.25‐mm tip employed during writing. All parts were sintered to >98% of true density, with grain sizes ranging from 3.2 to 3.7 μm. The average flexure strength, which ranged from 134 to 157 MPa, was not influenced by the alumina solid loading.     

Consolidation Behavior of High-Performance Ceramic Suspensions

Colloidal processing has been shown to produce low defect and uniform ceramic microstructures from submicrometer ceramic powders. These concepts were applied to colloidal pressing to determine critical design relationships for uniaxial consolidation of dense and uniform green bodies from colloidal suspensions. Carefully controlled constant rate of strain consolidation experiments were carried out using alumina in water. The compression index decreased from 0.143 for a poorly dispersed alumina system to 0.077 for a well-dispersed alumina suspension compression curve, indicating that the well-dispersed system is stiffer in consolidation. The compression curves showed that, as the degree of dispersion decreases, increased consolidation stresses are required to achieve a given particle packing density. The compression index increased with increasing strain rate for well-dispersed alumina suspensions. Permeability through the sample ranged from 3 × 10^–8 to 4 × 10⁻⁷ cm/s, decreasing with decreasing void ratio during consolidation. Well-dispersed samples gave lower permeabilities than did poorly dispersed samples over a given consolidation increment. Coefficients of consolidation were nonconstant over the experimental effective stress range, invalidating the general solution to the linear consolidation equation. An approximate incremental solution was applied which indicated rapid pressing cycles are possible by starting with a suspension having a high solids concentration. Application of this consolidation data to nonlinear consolidation models is recommended for more exact prediction of consolidation time.     

Compaction and Sintering Behavior of Bimodal Alumina Powder Suspensions by Pressure Filtration

The compaction behavior of fine alumina powders with different particle sizes or bimodal particle-size distributions that are undergoing pressure filtration was investigated. Three alumina powders—average particle sizes of 0.2—0.86 μm—were compacted to a solids fraction of 62—65 vol% from suspensions at pH 3, which was the pH level at which the suspensions showed their lowest viscosity. When the powders of different average sizes were mixed, the suspensions showed better flowability, and the lowest viscosity was obtained when the fraction of fines was ∼30 vol% and pH = 3. The mixed-sized powder suspensions were compacted to higher density than the suspensions of unmixed fine or coarse powders, and the maximum density was obtained for mixed suspensions that had the lowest viscosity, despite the different particle-size ratio. Maximum densities of 72.5% and 75.0% were attained when the size ratios were 2 and 5, respectively. The compacts that were pressure-filtered from mixed suspensions exhibited a single-peaked pore-size distribution and a homogeneous microstructure, whereas the pore-size distributions of dry-pressed compacts were double-peaked. The sintering behavior of the compacts that were pressure-filtrated from bimodal powders exhibited significantly better sinterability and much-less linear shrinkage than the coarser powders and the dry-pressed powder compacts.     

Direct Coagulation Casting of Alumina Suspension from Calcium Citrate Assisted by pH Shift

Direct coagulation casting of alumina suspension via controlled release of high valence counter ions (DCC–HVCI) using calcium citrate as coagulating agent was reported. Hydrolysis of glycerol diacetate shifts the pH of suspension to weakly acidic region which helps to decompose calcium citrate and release calcium ions. The effect of concentration of glycerol diacetate and calcium citrate on the pH and viscosity of alumina suspension was investigated at 25°C and 60°C, respectively. The pH of suspensions with glycerol diacetate and calcium citrate decreases to 8.6 and 7.5 treated at 25°C and 60°C, respectively. It is indicated that high viscosity is achieved by adding 2 vol% glycerol diacetate and 0.5 wt% calcium citrate which is enough to coagulate the suspension. Green body with compressive strength of 1.0 MPa is obtained by treating the alumina suspension with 2 vol% glycerol diacetate and 0.5 wt% calcium citrate at 60°C for 1 h. The alumina ceramics sintered at 1550°C have homogeneous microstructure with relative density above 99.0%.     

Freeze Casting of Aqueous Alumina Slurries with Glycerol

Freeze-drying concepts were utilized in the shape forming of alumina parts by pressureless slip molding using aqueous slurries. A water solidification modifier, glycerol, was utilized to eliminate the defects associated with the expansion and ceramic particle rejection of water during freezing. Castable alumina slurries with solids loading up to 60 vol% were prepared and characterized using viscosity and zeta-potential measurements with and without glycerol additions. Frozen parts were dried under vacuum by sublimation of ice to obtain net-shape green bodies. The combined effects of high-solids-loading slurries, >57.5 vol%, and glycerol additions were essential for freeze casting to achieve highly dense alumina bodies with a uniform microstructure.     

碳酸钙悬浮液混凝处理后的流变性

应用LVDV-Ⅲ+型可编程流变仪测定了微米级碳酸钙悬浮液混凝处理后的流变特性,考察因素包括悬浮液固相质量浓度、pH值、混凝剂种类及添加量、搅拌速度.结果表明,混聚后碳酸钙悬浮液在测定范围内流变曲线符合Herschel-Bulkley模型.表观粘度随颗粒浓度的增大而增大,其中屈服应力随体系浓度的增大而增大,刚性系数随体系...     

Gelling of Alumina Suspensions Using Alginic Acid Salt and Hydroxyaluminum Diacetate

This paper proposes a novel direct casting method of alumina suspensions using alginic acid salt and the coagulation agent hydroxyaluminum diacetate (HADA). These two compounds allowed the consolidation of alumina suspensions through a simultaneous time-delayed physical and chemical gelation process. The physical gel was formed by the gradual release of aluminum and acetate ions from the HADA in water, while the chemical gel originated from the cross-linking of alginate molecules by the polyvalent aluminum ions. Wet alumina green bodies displayed enhanced mechanical properties with the addition of minimal contents of organic material (<0.1 wt%).     

Electrochemical Aspects of Electroosmotic Dewatering of Clay Suspensions

An attempt is made to elucidate the electrochemical aspects of the electroosmotic dewatering (EOD) of clays as reported in some recent work, especially that on interrupted DC power electroosmotic dewatering published by Rabie, Mujumdar and Weber (2). These authors showed that the dewatering by EOD stops after the DC power has been on for several minutes or hours; on interruption of their power and on short-circuiting of the electrodes, conditions can be created again for some further dewatering by DC power EOD. This discovery, of Rabie et al. is interpreted as a fuel cell effect and it is shown that it affords clues to several other electrochemical strategies for the possible enhancement of the efficiency of the EOD by DC power.

Further, the open circuit potentials observed by Rabie et al. (2) on the interruption of DC power are given an electrochemical interpretation which leads to quantitative estimates in agreement with the experimental values.     

Electrochemical Aspects of Electroosmotic Dewatering of Clay Suspensions

ABSTRACT

An attempt is made to elucidate the electrochemical aspects of the electroosmotic dewatering (EOD) of clays as reported in some recent work, especially that on interrupted DC power electroosmotic dewatering published by Rabie, Mujumdar and Weber (2). These authors showed that the dewatering by EOD stops after the DC power has been on for several minutes or hours; on interruption of their power and on short-circuiting of the electrodes, conditions can be created again for some further dewatering by DC power EOD. This discovery, of Rabie et al. is interpreted as a fuel cell effect and it is shown that it affords clues to several other electrochemical strategies for the possible enhancement of the efficiency of the EOD by DC power.

Further, the open circuit potentials observed by Rabie et al. (2) on the interruption of DC power are given an electrochemical interpretation which leads to quantitative estimates in agreement with the experimental values.     

Effect of Silica Nanoparticle Size on the Stability of Alumina/Silica Suspensions

The influence of the addition of silica particles (5, 15, 25, and 300 nm) on the zeta potential and viscosity of aqueous alumina slurries (250 nm particles) was investigated in a pH range where the surface charge was positive for alumina and negative for silica. For slurries formulated with the smaller silica particles, the isoelectric point shifted from pH 9.0 to pH ∼3 (depending on the particle size of the silica) with increasing volume fraction of silica particles. At pH 9, the original isoelectric point for the alumina alone, these mixed slurries had a shear-rate-independent, low viscosity (Newtonian behavior). Both of these results show that the smaller (≤25 nm) silica particles adsorb to the surface of alumina. The fraction of silica adsorbed to the alumina surface was dependent on the size of the silica particles, and was consistent with surface coverage calculations based on the effect of surface curvature on the limits of dense random parking. The larger silica particles (300 nm) could not physically cover the surface of the alumina particles, and simply formed a mixed, attractive particle network that exhibited a much higher viscosity with non-Newtonian (viz., shear rate thinning) behavior.     

Effect of Oligosaccharide Alcohol Addition to Alumina Slurry and Translucent Alumina Produced by Slip Casting

A slurry used to produce dense green compacts by slip casting should exhibit low viscosity, high solids content, and good dispersion. Slurries with good characteristics were produced in the present study by adding oligosaccharide alcohol to an Al₂O₃ slurry with an NH₄⁺ salt of poly(methacrylic acid) (NH₄⁺-PMA). The role of NH₄⁺-PMA and oligosaccharide alcohol in the Al₂O₃ slurry was examined by DTA, ζ-potential measurement, high-pressure liquid chromatography, and viscometry. The viscosity of the slurry with NH₄⁺-PMA and oligosaccharide alcohol was lower than that of the slurry with NH₄⁺-PMA at a high solids content. Oligosaccharide alcohol did not interact with the Al₂O₃ surface. However, the Al₂O₃ slurry with NH₄⁺-PMA was influenced by the addition of oligosaccharide alcohol. We found that the dispersibility of the slurry was greatly improved by adding oligosaccharide alcohol. The transmittance of the Al₂O₃ ceramics produced by slip casting using the slurry with both NH₄⁺-PMA and oligosaccharide alcohol was higher than that of ceramics produced by slip casting using the slurry with NH₄⁺-PMA alone. The increased optical property resulted from low viscosity, which was attributed to the addition of oligosaccharide alcohol, at a high solids content.     

Gel Casting of Alumina using Boehmite as a Binder

The process for alumina gel casting was developed using an inorganic binder The monohydroxy aluminium oxide (boehmite, AlOOH) was incorporated with ultrafine alumina of particles (0·5 μm) and the slurry rheology was studied and presented. The effect of boehmite in slurry viscosity was observed with respect to different amounts of boehmite and time. The alumina 54 vol% slurry with 10 wt% boehmite showed the viscosity of 880 mPa s at 93 s⁻¹. An external coagulating agent, HMTA, was incorporated with alumina–boehmite slurry and the effective change in slurry viscosity with respect to concentration and time was studied. The addition of HMTA results in faster gelation and the optimum concentration was determined as 0·21 mol L⁻¹. The alumina gelcast body was dried under humidity conditions at 40°C, RH 70%. The defect free dried green body was obtained and the total linear drying shrinkage was calculated as 3·2% and the green density observed was 59·3% of theoretical value. The sintered density of 98% (TD) was achieved at 1450°C in 2 h. The mechanical hardness of sintered alumina measured as 2286 kg mm⁻². The sintered ceramic showed an extremely fine grained microstructure with an average grain size <2 μm. The boehmite acts as an excellent binder and sintering aid for alumina ceramics.