Rheology in the technology of ceramics and refractories. 8. Disperse systems with composite flow

In contrast to classical types of disperse systems with thixotropic and dilatant flow actual dispersions are often characterized by more complex rheological properties. The present paper is devoted to disperse systems with thixotropic-dilatant, dilatant-thixotropic, and thixotropic-dilatant-thixotropic types of flow. The microrheological classification suggested by Dintenfass is considered in comparison with the rheological classifications of thixotropic-dilatant, dilatant-thixotropic, and thixotropic-dilatant-thixotropic disperse systems suggested by the author. The effect of the main factors determining the considered anomalies in the behavior of the systems is considered for some ceramic suspensions.     

Effects of dispersant concentration and pH on properties of lead zirconate titanate aqueous suspension

Lead zirconate titanate (PZT) aqueous suspensions were prepared at 60 wt.% solids loading using a commercial ammonium polyacrylate (APA) dispersant. Effects of the dispersant concentration on rheological behavior, dispersion and stability of PZT aqueous suspensions were investigated by means of zeta potential, viscosity and sedimentation height measurements. The results showed that, under suitable conditions, APA dispersant promoted particle dispersion and stabilization in PZT aqueous suspensions. For 60 wt.% solids loading suspensions, the dispersant concentration yielding the lowest viscosity was 0.5 wt.% based on PZT powder dried weight basis. Effects of pH on particle dispersion in the suspensions prepared with APA were studied by laser light scattering technique and scanning electron microscopy. The results showed an improvement in particle dispersion for the alkaline condition, which led to relatively low viscosity and highly stable suspension. Possible particle stabilization mechanisms at various pHs were discussed based on dissociation of the dispersant in water, polymer conformation and adsorption behavior of the dispersant on the particle surface.     

Effect of Powder Surface Chemistry on the Stability of Concentrated Aqueous Dispersions of Alumina

The surface chemistry differences between two alumina powders is shown to have a significant effect on the properties of concentrated aqueous dispersions of the powders. The initial dispersion pH and magnitude and sign of the initial mobility of the particles (determined by acoustophoresis) are different for the two powders because of differences in surface impurity contents. As a result, the two powders require different amounts of dispersant to achieve stability in dispersions near their isoelectric points. The surface chemistry differences between these two aluminas illustrate the importance of examining ceramic dispersion properties at the concentrations used in processing the material.     

Aqueous Processing of Titanium Carbide Green Sheets

TiC sheets were prepared by an aqueous tape-casting process. The zeta potential measurement showed that the isoelectric point for TiC powders in the absence of dispersant had a pH value of ∼3.3. According to the surface properties of TiC powders, a cationic polymer PEI was selected as dispersant. In the presence of dispersant, the isoelectric point increased to a pH value of ∼10.4. The slip stability was determined by visual observation of the fluidity of the slip as well as the settling of the powders. Results showed that the amount of dispersant required to achieve a minimum of viscosity for 50 vol% suspensions was equal to 1.2 wt%. In the absence and presence of dispersant, stable slips could be obtained in the pH ranges 7–9 and 11–12, respectively. The rheological measurements showed that with PEI as dispersant, TiC suspensions exhibited a small time dependent behavior. With polyvinyl alcohol as binder and glycerol as plasticizer, suspensions showed a thixotropic feature. As-cast tapes were dried in air at room temperature. The results showed that it was possible to fabricate homogeneous green tapes with smooth surfaces from these suspensions.     

Influence of pH and Ionic Impurities on the Adsorption of Poly(acrylic) Dispersant onto a Zinc Oxide Surface

We have studied the properties of aqueous suspensions of ZnO powders with different purities. Our results suggest that powder purity determines the amount of dispersant necessary to form a stable aqueous suspension as well as the maximum adsorption capacity of the dispersant: the higher the positive surface charge of the as-received ZnO powders, the higher the amount of dispersant adsorbed onto the metal oxide surface. The surface charge of the ZnO particles in suspension is affected by the concentration of zinc as well as sulfate ions, which are the major impurities in the supernatant. The pH of the aqueous ZnO suspensions increases with increasing concentration of poly(acrylic) dispersant until the maximum adsorption capacity is attained. Further additions of dispersant do not increase the pH because of a buffer formation with impurity ions.     

Electrophoretic Deposition Behavior of Aqueous Nanosized Zinc Oxide Suspensions

The rheological behavior and electrophoretic deposition (EPD) of ZnO nanopowder (nano-ZnO) in aqueous media have been described. A cationic polyelectrolyte (polyethylenimine, PEI) was used to disperse and modify the surfaces of the ZnO nanoparticles. The rheological properties of the ZnO aqueous suspension were investigated by measuring the viscosity versus the pH and amount of dispersant. The EPD processing was conducted via cathodic electrodeposition, using stable suspensions with low viscosity, and the depositional behavior was investigated. Bubble-free nano-ZnO deposits with uniform microstructures were successfully obtained, which was an indication of good sintering behavior.     

Effect of dispersant on the rheological properties and slip casting of concentrated sialon precursor suspensions

The ability of Hypermer KD1 to disperse high solids loading reaction sialon suspensions for slip casting has been characterised. It has been found to be a very effective dispersant in organic media of 60-vol.% MEK and 40-vol.% Ethanol, yielding fluid and highly homogeneous suspensions. The effects of added amounts of KD1 have been observed through adsorption data, sedimentation tests and rheology measurements. KD1 imparts low viscosity and stability to the suspension. It has been found that 3-wt.% addition of KD1, based on the weight of reaction sialon powders, results in a very stable and high flowable suspension with near Newtonian flow behavior. Less amounts of dispersant lead to unstable suspensions with obvious shear thinning flow behaviors, while adding excessive dispersant leads to high viscosities, especially at high solids loading. Measuring the pore size distribution of green bodies from different suspensions has proved the effects of dispersant amounts on dispersing the slurries and on slip casting performance.     

氧化铁-水悬浮液的流变性研究

应用DV-Ⅲ+型可编程流变仪测定了三氧化二铁-水悬浮液的流变特性。考察因素包括颗粒浓度、pH值以及分散剂用量。结果表明,悬浮液在测定范围内表现出宾汉流体的特征。表观粘度随颗粒浓度的增大显著增加,其模型可用本文提出的三阶多项式模型表示。悬浮液的表观粘度受pH值的影响,pH在等电点处时,溶液的流动性最差;pH低于等电点时的粘度比pH高于等电点时要明显降低。这些现象可用颗粒的空间结构化理论及凝聚原理予以解释。改善悬浮液流动性的分散剂添加量存在最佳点。     

Dispersion and Rheology of Aqueous Suspensions of Nanosized BaTiO3

The zeta potential and the rheological behavior of aqueous suspensions of a commercial nanosized BaTiO₃ powder were studied. The influence of the volume fraction of solids, the kind and concentration of dispersant, the homogenization technique, and times were investigated. Because the as-received powder contained ∼5 wt% organics, the powder was calcined to 350°C/0.5 h. After calcination, a good dispersion was achieved for suspensions with up to 80 wt% solids using a polyacrylic-based dispersant combined with tetramethylammonium hydroxide and 10 min of ultrasound. Green bodies obtained by slip casting had relatively low densities (2.6 g/cm³, 43% TD), but homogeneous, agglomerate-free microstructures.     

Preparation of concentrated barium titanate suspensions incorporating nano-sized powders

In order to reduce agglomeration and overcome the low packing density issues of working with nano-sized powders, a colloidal processing route has been chosen in this study. Commercial BaTiO₃ (BT) powders with a particle size in the range of 50 nm have been dispersed in the aqueous media. Rheological properties have been analyzed on suspensions with different solids loading, dispersant concentration, and pH conditions. Optimum dispersing conditions were obtained for suspensions prepared at basic pH (pH 10) with 0.646 wt% ammonium poly (acrylic acid) (NH₄PAA) as a dispersant. Suspensions have been centrifugally cast to obtain the green body, and the sintering conditions have been investigated by examining the phase evolution, microstructures and electrical properties of the sintered samples through XRD, SEM and dielectric measurements, respectively. The results show that for a 45 vol% suspension sintered at 1325 °C, the density of bulk ceramic can reach 5.85 g/cm³, nearly 97.0% of the theoretical density.     

Beta-phosphate tricalcium colloidal processing

Beta Tricalcium phosphate (β-TCP) is an important ceramic material for biomedical applications and can help the regeneration of bone. In this work, it was studied the rheological behaviour of β-TCP suspensions, using the slip casting forming method, in order to adjust the necessary conditions for future use as bone graft. The characterization of the material powder was performed by the analysis of the specific surface area, the particle shape, the morphological aspect, the particle size distribution and the Zeta potential in water media. The suspensions studied were produced with distilled water, using sodium silicate as dispersant, and homogenized in ball mill for times up to 24 h. The rheological measurements were performed using a rotational rheometer. Products generated with 2.0 wt% of sodium silicate, with the addition of 0.5 wt% carboxymethyl cellulose and homogenized in ball mill during 24 h after sintering had porosity that can be adequate for a future use as biomaterial.     

Rheology of aqueous mullite-starch suspensions

One of the forming methods developed for the manufacture of porous materials by direct consolidation, in which a ceramic suspension consolidates into non-porous molds (e.g. metal molds) by thermogelation of an organic agent, uses starch as both consolidator/binder of the ceramic suspension and pore former at high temperature. Changes in the rheological behavior of the aqueous suspensions are produced by starch gelatinization thermal process. This process as well as the presence of both the ceramic particles and added processing additives, influences the kinetics of green ceramic body formation and its microstructural features.In this work, the thermogelling behavior of mullite aqueous suspensions (40 vol.%; 0.45 wt.% of a polyacrylic polyelectrolyte as dispersant) containing 10 vol.% of different native starches (potato, cassava, and corn) was studied by dynamic rheology in order to determine the experimental conditions that must be used for forming mullite green bodies by thermal consolidation. Viscoelastic properties (G′ and G″) as a function of temperature (30-95 °C) and deformation (0.1-625.0% at 40 °C) were determined by temperature sweep tests and dynamic strain sweep tests, respectively. From these tests, and considering previous results of the rheological behavior of starch suspensions, we analyzed the influence of ceramic particles on the starch gelatinization process and the strength of the developed gels. On the other hand, shear flow properties of aqueous mullite-starch suspensions were also analyzed to obtain information on the rheological behavior of the suspensions at room temperature.     

Study of alumina ceramic parts fabricated via DLP stereolithography using powders with different sizes and morphologies

Selecting suitable ceramic powders for the preparation of UV-curable ceramic suspensions, which are well suited for printing processes and production of high-performance ceramic components, is a crucial factor in the practical industrial application of digital light processing (DLP) stereolithography. Therefore, this study aims to provide a comprehensive evaluation of alumina ceramic parts fabricated via DLP stereolithography using a variety of alumina powders with varying sizes and morphologies. Experiments were conducted to examine the rheological response, recoating performance, and curing behavior of UV-curable alumina suspensions. Additionally, the thermal decomposition behavior of three-dimensional (3D)-printed green-bodies, as well as the physical and mechanical properties of 3D-printed sintered alumina components were thoroughly investigated. The best physical and mechanical performances were achieved by printing 55 vol% suspensions prepared using near-spherical AA04 alumina powders (median diameter .4 μm). This study elucidates the effects of ceramic particle size and morphology on the entire technological process of DLP-based ceramic stereolithography, thereby establishing the guidelines for the fabrication of high-performance 3D-printed ceramic objects in industrial and engineering production by selecting appropriate ceramic powders.     

Effect of Acid Cleaning and Calcination on Rheological Properties of Concentrated Aqueous Suspensions of Silicon Nitride Powder

The powder characteristics of two types of Si₃N₄ (referred to as FD1 and FD2), as well as the rheological properties of their aqueous suspensions, were studied in this paper. There are distinctive differences in size distribution, soluble counterions, and surface groups. Highly concentrated aqueous slurries could not be prepared from these two as-received powders. Acid cleaning and calcination improved the solids loading of their aqueous slurries, but the improvement varied with the powder. For the as-received FD1 powder, poor dispersibility was caused by high-valence counterions, which can be eliminated through acid-cleaning. However, for the as-received FD2 powder, it was the surface group of amine structures and carbon-hydrogen bonding that limited the dispersibility. The calcination of FD2 can remove the amine structure and carbon-hydrogen bonding and improve the slurry's rheological properties almost perfectly. For acid-cleaned and calcined FD1, and calcined FD2, the solids loading of their aqueous suspensions reached 50 vol% with a viscosity below 300 mPa·s.     

Rheological properties of aqueous α A12O3 suspensions: Influence of dispersant concentration

The effects of concentration of polyacrylic acid as a dispersant on rheological properties of aqueous alumina suspensions have been investigated under steady and oscillatory shear conditions. At solid volume fractions between 0.45 and 0.6, a high degree of particle stabilization is achieved when 0.2 wt% of polyacrylic acid is added. At lower dispersant concentrations, suspensions exhibit pronounced irreversible thixotropic behaviour, whereas at higher dispersant concentrations, time dependent effects on the flow properties are not detectable. When the saturation adsorption limit of the polyelectrolyte on Al₂O₃ is reached, further addition of the dispersant appreciably changes the flow behaviour, as well as the viscoelastic response of investigated suspensions. The data under steady shear are described by application of the generalized Casson model, and for the analysis of viscoelastic data the generalized Maxwell model is used.     

Dispersion and rheological properties of concentrated silicon aqueous suspension

This work focuses on the optimization of the rheological properties of silicon suspensions by changing the concentration of a dispersant and the pH value of the dispersing medium. The zeta potential and rheological properties of silicon suspensions as a function of tetramethyl ammonium hydroxide (TMAH) concentration were carried out. The results show that the isoelectric point of the silicon particles was at pH 1.6. A silicon suspension with 46 vol.% particles displayed a minimum viscosity at pH 9.6. The results also show that TMAH is an efficient dispersant by enhancing the absolute value of the zeta potential of silicon particles. The optimum dosage of the dispersant was 0.4 wt.% of silicon particles.     

Rheology of Concentrated Suspensions Containing Weakly Attractive Alumina Nanoparticles

The use of nanoparticles for the fabrication of new functional ceramics and composites often requires the preparation of concentrated fluid suspensions. However, suspensions containing nanoparticles are limited in solids content because of the excluded volume formed by the dispersant adlayer around the particles. We investigated the effect of the adlayer thickness on the rheological behavior of suspensions containing model alumina nanoparticles, using dispersant molecules with deliberately tailored chain length. The apparent viscosity and yield stress of the particle suspensions were markedly decreased by increasing the dispersant length, mainly due to a reduction of the attractive forces among particles. Fluid suspensions with solids content up to 35 vol% were prepared in toluene using a dispersant length of 2.5 nm. Our experimental results and viscosity predictions based on a hard sphere model indicate that fluid suspensions with up to 43 vol% of 65 nm alumina particles could be prepared using an optimum dispersant length of about 3.6 nm.     

Rheological Characterization and Coagulation Casting of Al2O3–Nano Zirconia Suspensions

The rheological behavior of electrosterically dispersed aqueous suspensions composed of submicrometer alumina and nano zirconia particles in different ratios and solids contents (from 34 to 40 vol%) has been studied during in situ coagulation casting. Glucono-δ-lactone was used as the coagulant to achieve destabilization of the ceramic suspensions by acidifying the suspension so that the pH became close to the isoelectric point for both powders. The effects of the lactone content (from 0.5 to 6.7 wt%) and the solids loading on the rheological parameters (dynamic and static measurements) during the coagulation process were studied. Dynamic measurements showed an increasing elastic modulus, G', with time and lactone content (viz. 180 and 340 kPa for 6.7 wt% lactone addition after 40 and 60 min, respectively, and 57.3 kPa for 0.5 wt% lactone after 60 min), suggesting the formation of stronger green bodies at higher additions and longer times. The conditions were optimized to yield homogeneous green samples with a uniform nanozirconia distribution and densities between 58% and 60% of the theoretical. These were subsequently sintered to yield composites with a final density up to 97%.     

Fabrication of doped β-tricalcium phosphate bioceramics by Direct Ink Writing for bone repair applications

β-tricalcium phosphate (β-TCP, β-Ca₃(PO₄)₂) is one of the most attractive biomaterials for bone regeneration and β-TCP macroporous scaffolds are very promising for both cell proliferation and mechanical support. The Additive Manufacturing (AM) process called Direct Ink Writing (DIW), based on the extrusion of a concentrated ceramic slurry, is particularly adapted to resolve the main drawbacks associated with conventional shaping of ceramic scaffolds. In this work, co-doped β-TCP powders were synthetized and used to print macroporous scaffolds by DIW. Doped β-TCP powders have been proved to exhibit higher thermal stability, densification and mechanical properties compared to undoped β-TCP. Two co-doped compositions were produced via the aqueous precipitation technique combining magnesium, strontium, silver and copper cations: Mg-Sr (2.0–2.0 mol%) and Mg-Sr-Ag-Cu (2.0–2.0–0.1–0.1 mol%). DIW slurries were optimized with undoped and co-doped β-TCP with the use of a dispersant and a carboxymethylcellulose and polyethyleneimine mixture to obtain aqueous slurries filled with 42 vol% of powder. Complete rheological characterizations were realized to assess the suitability of the β-TCP slurries for the DIW process (shear-thinning and thixotropic behaviour). The whole processing chain including printing, osmotic drying (PEG 10000) and sintering (1100 °C, 3 h) was optimized to successfully print co-doped β-TCP macroporous scaffolds. Characterizations after sintering showed a reduction of macropores and microcracks using co-doped β-TCP powders as well as improved compressive strengths and densities compared to undoped β-TCP. A significant enhancement of compressive strength values was obtained compared to literature data.     

Triggering the aqueous interparticle association of γ‒Al2O3 hierarchical assemblies using divalent cations and cellulose nanofibers

Understanding aqueous dispersion, rheological properties and colloidal stabilisation mechanisms of hierarchically assembled ceramic powders is important for progress in the fields of catalysis, separation and/or adsorption. The present study was designed to evaluate the rheological and sedimentation behaviour of highly loaded aqueous suspensions (up to φ_A = 0.126) containing AlN-powder-hydrolysis-derived, micron-sized, mesoporous, gamma alumina (MA) particulates with a high surface area (～180 m²/g) dispersed with sodium polyacrylate (NaPAA). The as-prepared suspensions were prone to sedimentation and segregation. However, when divalent cations (Mg²⁺, Ca²⁺) or cellulose nanofibers were added, the formation of interparticle association networks in the aqueous suspensions containing MA particles was triggered, facilitating their long-term resistance to sedimentation lasting more than 12 weeks.