Aqueous and Nonaqueous Colloidal Processing of Difficult‐to‐Densify Ceramics: Suspension Rheology and Particle Packing

Aqueous and nonaqueous colloidal processing of zirconium diboride (ZrB₂) and boron carbide (B₄C) has been investigated. The aqueous and nonaqueous ZrB₂ and B₄C suspension formulations have been optimized. The suspensions were cast into green bodies using slip casting. The correlation between the state of dispersion with the rheological properties of the suspensions and the resulting packing density was observed in both aqueous and nonaqueous processing. The attractive interactions between powder particles in water were difficult to overcome with electrical double layer or electrosteric repulsion. Reasonably low viscosity aqueous ZrB₂ suspensions up to 45 vol% solids could be prepared. It was not possible to produce low viscosity (viscosity below 1 Pa·s at shear rate of 100 s^?1) aqueous B₄C suspensions with solid content above 30 vol%. Slip casting of the weakly aggregated ZrB₂ suspensions resulted in low packing densities (~55% relative density) of the green bodies. On the other hand, dispersion of powder particles in nonaqueous media (cyclohexane and dodecane) enabled suspensions with lower viscosities and a higher maximum solid concentration (up to 50 vol%) to be prepared. The well‐dispersed nonaqueous suspensions promoted an efficient particle packing, resulting in higher green densities (64% and 62% relative density for ZrB₂ and B₄C, respectively) compared to aqueous processing. The significantly high green densities are promising to allow densification of the materials at lower sintering temperature.     

Suppressed Reactivity of AlN Powder in Water at 5°C

The hydrolysis behavior of AlN powder suspensions (5–25 wt%) at 5°C has been investigated to explore the impact of low temperatures on the hydrolysis behavior. Throughout the 312‐h long experiment, the pH value of the suspensions was below 9, where the hydrolysis remained in the induction period and was eventually suppressed due to the formation of a few‐nanometers‐thick film of amorphous aluminum hydroxide gel around the AlN particles, acting as a passivation layer. Moreover, the aqueous part of the suspension possessed a remarkably high value of dissolved [Al(III)]_aq, being an order of magnitude higher at a given pH value than the aqueous AlCl₃ solution.     

Fabrication and Thermal Properties of Polyimide/Ba0.77Sr0.23TiO3 Nanocomposites

Polyimides (PIs) are considered to be one of the most important engineering materials. The nano-particle of barium strontium titanate (BST) with formulation of Ba_0.77Sr_0.23TiO₃ was synthesized by the sol-gel method. In this process, different contents of BST suspensions in polyamic acid (PAA) solution were imidized by heat treatment to form PI/BST nanocomposites. Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), simultaneous thermal analysis (STA), scanning electron microscope (SEM), and transmission electron microscopy (TEM) were used to characterize the structure and properties of the obtained nanocomposites. It was found that the BST nanoparticles sized 32–40 nm were dispersed homogeneously in the polyimide matrix without aggregation. The ζ potential of PI/BST 33 vol.% was decreased in contrast with that of the pure polyimide. The coefficient of thermal expansion (CTE) of PI/BST 33 vol.% was measured between 36°C and 600°C. CTEs comparison showed about 80% decrease in the CTE value of the nanocomposite in respect to the pure polyimide in a wider temperature range.     

Influence of solid loading on densification behavior,micromorphology and dielectric properties of Ba0.67Sr0.33TiO3 ceramics fabricated by a novel DCC-HVCI method

Ba_0.67Sr_0.33TiO₃ (BST) ceramics with highly improved dielectric performance were fabricated by a novel direct coagulation casting via high valence counter ions (DCC-HVCI) method. The influence of solid loading on densification behavior, micromorphology, and dielectric performance of the samples was investigated. With the increase of solid loading from 40 to 50 vol%, the maximum densification rate of BST ceramics increased from 0.090 to 0.122 s⁻¹, and the densification temperature decreased from 1424 to 1343 °C, which indicated that high solid loading could promote the densification behavior of samples during sintering. BST ceramics fabricated by the DCC-HVCI method showed uniform grain size and microstructure, which was beneficial for the dielectric properties of BST ceramics. Samples obtained from 45 vol% suspensions possessed the lowest dielectric permittivity (ε_r ≈ 2801), and the dielectric loss (tanδ≈0.0262) was about 1/10 of that of dry-pressed samples (tanδ≈0.301), which could be attributed to the composition homogenization.     

Manufacture of a non-stoichiometric LSM cathode SOFC material by aqueous tape casting

This work deals with the manufacture of non-stoichiometric strontium-doped lanthanum manganite (LSM) as a cathode material by aqueous colloidal processing. This requires some knowledge of the processability and sinterability of this material. The stability of aqueous suspensions of a fine non-stoichiometric LSM powder was studied by measuring the zeta potential as a function of pH and deflocculant content. Concentrated suspensions were prepared to solids loadings as high as 50 vol.%. The best dispersing conditions and the influence of binders and tape casting performance were determined by means of rheological measurements. LSM cathode tapes were characterized in the green state and after sintering at 1500 °C/2 h, leading to high density compacts. Maximum sintering rate is achieved at 1350 °C. Once the sintering behavior is known a porous material can be easily designed using a sintering temperature compatible with the other components of the semi-cell.     

Effect of molecular weight of an anionic dispersant on the properties of BaTi4O9 slurries

The colloidal stability of BaTi₄O₉ (BT₄) aqueous suspensions with poly(acrylamide‐co‐4‐carboxylamino‐4‐oxo‐2‐butenate) (PAC) of different molecular weights at pH 9 has been investigated by means of zeta potential, adsorption, sedimentation, and particle size measurements. The results indicate that PAC could improve the dispersion of the particles from agglomeration. The resulting suspensions became more stabilized, and contained powder with smaller particle size. Consequently, the compacts with PAC exhibited better properties in terms of density and dielectric constant than those without any polymer present. The performance of PAC increased with decreasing polymer molecular weight. Clearly, PAC1 (M_w = 1.8 × 10⁴) was most effective in dispersing the BT₄ particles, and stabilizing the ceramic suspensions. This is attributed to the highest adsorption of this polymer onto BT₄ powder, and causes strongest electrostatic repulsions among solid particles. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Aqueous slip casting and hydrolysis assisted solidification of MgAl2O4 spinel ceramics

Abstract

Abstract

This paper reports on synthesis of MgAl₂O₄ spinel (MAS) powders with six different chemical compositions and the consolidation of the synthesised MAS powders following an aqueous slip casting and hydrolysis assisted solidification (HAS) routes. The synthesised MAS powders were surface passivated against hydrolysis before being dispersed in distilled water to obtain suspensions with 41–45?vol.‐% solid loading using suitable dispersing agents. In the case of the HAS process, the consolidation of suspensions was achieved in non‐porous moulds under ambient conditions by the incorporation of AlN equivalent to 1–5?wt‐%Al₂O₃ into the suspension. The stoichiometric MAS powder consolidated by slip casting and dry pressing routes was sintered along with those consolidated by HAS route at 1550–1650°C for 1?h. Various characterisation techniques were utilised to evaluate the effect of composition and consolidation technique on slurry characteristics and sintered properties of MAS ceramics.     

Evaluation of the phase stability,and mechanical and thermal properties of Ba(Sr1/3Ta2/3)O3 as a potential ceramic material for thermal barrier coatings

Ba(Sr_1/3Ta_2/3)O₃ (BST) ceramic was synthesized by a solid-state reaction method. The phase stability, microstructural evolution, and mechanical and thermal properties of the BST ceramic were investigated and characterized to evaluate the potential application of BST as a top coating material for thermal barrier coatings (TBCs). The results show that BST can maintain a stable hexagonal perovskite structure up to 1600 °C. Anisotropic growth of the grains above 1400 °C was observed. Its low elastic modulus and high fracture toughness suggest a high damage tolerance for the BST ceramic. In addition, the moderate coefficient of thermal expansion and superior heat insulation capability of the BST ceramic provide this ceramic the potential to serve as a top coating material of TBCs at higher temperature.     

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.     

Structural and dielectric properties of B2O3/Li2O-added Ba0.6Sr0.4TiO3 multilayer ceramics for tunable devices

B₂O₃ and Li₂O (B/L)-added Ba_0.6Sr_0.4TiO₃ (BST) ceramics sintered at 940 °C exhibited a dense microstructure with large grains. The amount of B/L additive was 4.5 wt% with a B/L ratio of 1.5:1. The B/L-related liquid phase assisted the densification of the BST ceramics. This BST ceramic displayed a large dielectric constant (ε_r) of 2834 with a low dielectric loss (tan δ) of 0.21% at 1.0 MHz. It also displayed a large tunability (28.2% at 10 kV/cm) and a high figure of merit (FOM) of 134. BST thick-films were synthesized using the tape casting method. The thick-film densified at 940 °C exhibited a large tunability of 18.7% at 10.0 kV/cm and an FOM of 208; these are higher than the values reported in the literature. Multilayer ceramics (MLCs) consisting of five layers of 40-μm-thick BST thick-films and Ag electrodes were also fabricated at 940 °C. No diffusion occurred between the Ag electrode and BST thick-film. A large tunability of 67.6% at 52 kV/cm with a high FOM of 294 was obtained from this MLC. This verified that the B/L-added BST ceramic is effective for application in tunable multilayer devices.     

Gelcasting of concentrated aqueous silicon carbide suspension

Gelcasting of high concentrated aqueous silicon carbide suspension with 50 vol.% solids loading is discussed in this paper. It is found that SiC powder is suitable for being suspended in basic solution, provided that a proper pH value is chosen for it. The rheological property of SiC suspension is also affected by solids loading. When SiC slurry is cast at 70°C, reaction between free Si on the surface of SiC powder and an organic base used as dispersant gives out H₂ gas, which produces pores in green bodies. However, by vacuum pumping and controlling pH value of the suspensions, complicated shapes of uniform SiC green bodies without pores are prepared.     

Low-temperature sintering and electrical properties of Ba0.68Sr0.32TiO3 thick films

Ba_0.68Sr_0.32TiO₃ (BST) thick films were prepared by screen printing on a flexible fluorophlogopite substrate. In order to realise the co-firing of the BST film with a silver electrode at a lower temperature, the BST precursor was used as a solvent for the screen-printing slurry and the cold sintering technique was used to pretreat the film. The sintering temperature of BST thick films prepared by conventional sintering process was higher than 1200 °C. When sintered at 950 °C, the thick films exhibited a high porosity. The density of the thick films was significantly improved after pretreatment with the cold sintering process (CSP). After the cold-sintered thick films were sintered at 950 °C for 30 min and then fired with a silver electrode, the samples exhibited a relative dielectric constant of 773 (at 25 °C and 10 kHz), a dielectric loss of 0.025, a remanent polarization of 5.3 μC/cm², and a coercive field strength of 38.1 kV/cm. Therefore, the low-temperature co-firing of BST thick films with a silver electrode was successfully realised.     

Transient liquid-phase assisted spark-plasma sintering and dry sliding wear of B4C ceramics fabricated from B4C nanopowders

With the motivation of developing B₄C composites with superior wear resistance for tribological applications, an ultrafine-grained (～200?300 nm) B₄C composite was fabricated, characterized microstructurally, and tested mechanically and tribologically. First, a well-dispersed powder mixture of B₄C nanopowders (～40 nm) with coarse Ti-Al powders (～38 μm) as transient liquid-phase sintering additives was environmentally-friendly prepared by aqueous colloidal processing, optimized by measurements of the zeta potential of dilute suspensions and rheological studies of concentrated suspensions. Second, the powder mixture obtained by freeze-drying was densified by spark-plasma sintering (SPS), identifying the optimal SPS temperature (1850°C) by measurements of density, hardness, and toughness. Third, the dry sliding-wear behaviour of the optimal superhard B₄C composite (～31.5 GPa) was investigated by pin-on-disk tests and observations of the worn surface, determining its specific wear rate (～4.4·10^?8 mm³/(N·m)) as well as wear mode (two-body abrasion) and mechanism (plastic deformation). And lastly, the wear behaviour of the ultrafine-grained B₄C composite was compared with that of a reference fine-grained (～0.7?0.9 μm) B₄C composite, finding that both have the same mode and mechanism of wear but with the former being more resistant than the latter (～2.3·10⁷ vs 1.9·10⁷ (N·m)/mm³). Implications for the fabrication of B₄C tribocomponents with greater superior wear resistance are discussed.     

Gelation of water-based PZT slurries in the presence of ammonium polyacrylate using agarose

Gel casting is a suitable near net shape-forming technique based on the solidification of aqueous suspensions for the production of green parts with interesting economic and environmental benefits. In the present work, PZT-5 suspensions in aqueous media were successfully prepared using ammonium polyacrylate (PAA-NH₄) as the dispersing agent. The gelation of the 46–48 vol.% PZT suspensions in aqueous media based on agarose was studied by measuring the height of the samples before and after demoulding. The study found that the suitable amount condition for development of the green parts made was achieved at 0.082–0.19 wt.% agarose (based on dry solid). The density of the green body produced at the optimum content of agarose was determined. A very uniform part with green density of 52% and 55% before and after drying, respectively, was developed. Small shrinkage was measured after drying and heat treating at 550 °C. Sintered samples at 1250 and 1285 °C showed a theoretical density of 99% with an even smaller shrinkage of 16.2%. The dielectric constant and longitudinal piezoelectric charge coefficients, d₃₃, of the selected samples were 2550 and 680 pC/N, respectively.     

Coal liquefaction by colloidal iron sulphide catalyst

Taiheiyo coal, which was treated with an aqueous solution of dodecyltrimethylammonium chloride, adsorbed colloidal iron sulphide prepared from FeS0₄ · 7H₂O and Na₂S · 9H₂O in aqueous media. The adsorbed colloidal iron sulphide was much more effective as a catalyst for the liquefaction of the coal itself than the usual powder-type iron sulphide. Thus in differential thermal analysis under hydrogen, the coal with 0.35wt% adsorbed colloidal iron sulphide gave an exothermic peak at 401 °C, which was ≈20 °C lower than when using the powder-type iron sulphide. The coal was smoothly hydrogenated at 450 °C to give a yield of ≈60% liquid products.     

Preparation and characterization of crystalline Ba0.5Sr0.5TiO3 thin films on FTO transparent electrodes

To achieve an economic advantage, nanocrystalline Ba_0.5Sr_0.5TiO₃ (BST) thin films were prepared on FTO-coated glass substrates using an aqueous sol–gel process. The crystal structures and chemical states of the obtained thin films were characterized by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The XRD patterns confirmed the perovskite structure of the BST samples, while XPS analysis demonstrated that Ba element was in its single oxidation state in the film with annealing temperature of 600 °C. In contrast, Ba was present in a mixed oxidation state upon increasing the annealing temperature. It was found that the BST thin film prepared at a relatively low annealing temperature of 600 °C exhibited optimal crystallinity and superior dielectric properties, along with excellent optical transparency. More specifically, this film exhibited a dielectric tunability of 44.81% (1.33 MV/cm), a figure of merit of 56.01, and an average transmittance of 87.2% in the visible region.     

Chemical Absorption of Carbon Dioxide into Aqueous Colloidal Silica Solution with Diethanolamine

Abstract

The chemical absorption rate (R_A) of CO₂ was measured into the aqueous nanometer sized colloidal silica solution of 0–31 wt% and diethanoleamine of 0–2 kmol/m³ in the flat‐stirred vessel with the impeller size of 0.034 m and its agitation speed of 50 rev/min at 25°C and 0.101 MPa, and compared with the values estimated from the model based on the film theory accompanied by chemical reaction. The value of the volumetric liquid‐side mass transfer coefficient (k_La) of CO₂, which was used to estimate the value of R_A, was obtained by the empirical correlation formula presenting the relationship between k_La and the rheological behavior of the aqueous colloidal silica solution. The value of R_A in the aqueous colloidal silica solution was decreased by the reduction of k_La due to the elasticity of the solution.     

Dispersion of nanoscale BaTiO3 suspensions by a combination of chemical and mechanical grinding/mixing processes

The colloidal stability of aqueous nanometer‐ and micrometer‐scale barium titanate (BaTiO₃) utilizing poly (methacrylic acid) (PMAA‐Na) and polyacrylamide/(α‐N,N‐dimethyl‐N‐acryloyloxyethyl)ammonium ethanate (PDAAE) was investigated. In addition to chemical dispersants, the effects of mechanical milling using either conventional ball milling or nanogrinding/‐mixing on the dispersion of BaTiO₃ suspensions were also studied. Characterization of the particle size distribution (d₅₀), viscosity, and morphology of BaTiO₃ particles in the suspensions revealed that a sole chemical dispersant or mechanical milling was insufficient to achieve nanometer‐scale dispersion. The best dispersion results were obtained with a combination of PMAA‐Na dispersant and nanogrinding/‐mixing, which could provide sufficient electronic repulsive force and shear force to disperse the 80‐nm BaTiO₃ powders uniformly in the aqueous suspension. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Controlling colloidal processing of (K,Na)NbO3-based materials in aqueous medium

K_0.5Na_0.5NbO₃-based materials are serious candidates to replace lead-based piezoceramics since they show excellent electrical and piezoelectric properties. The tape casting technique can be used to obtain highly textured KNN-based ceramics; however, despite industrial and environmental advantages of water-based processing, there are not reports about the control of colloidal processing conditions to obtain optimized K_0.5Na_0.5NbO₃-based slurries in aqueous medium. This paper reports a procedure for controlling colloidal stability and rheological behavior of aqueous (K_0.5Na_0.5)_0.97Li_0.03Nb_0.8Ta_0.2O₃ suspensions. Zeta potential and cationic solubility measurements as a function of pH showed that pH 8.5 is adequate for concentrated suspensions, while flow curves analysis allowed optimizing processing parameters, such as, powder content, amount of deflocculant and binder, and sonication time. Optimized colloidal suspensions were prepared and used to obtain high quality tapes. Processed ceramics from these stacked tapes show equivalent properties to those processed directly from powders, which demonstrates the effectiveness of the colloidal route reported here.     

Achieving fabrication of highly transparent Y2O3 ceramics via air pre-sintering by deionization treatment of suspension

An easy albeit quite effective deionization suspension treatment was adopted to alleviate the detrimental effects related to the hydrolysis of Y₂O₃ in an aqueous medium. Fabrication of highly transparent Y₂O₃ ceramics with a fine grain size via air pre-sintering and post–hot isostatic pressing (HIP) treatment without using any sintering additive was achieved using the treated suspensions. The hydrolysis issue of Y₂O₃ powder in an aqueous medium was effectively alleviated by using deionization treatment, and a well-dispersed suspension with a low concentration of dissolved Y³⁺ species was obtained. The dispersed suspensions were consolidated by the centrifugal casting method, and the green bodies derived from the suspension of 35.0 vol% solid loading showed an improved homogeneity with a relative density of 52.1%. Fully dense Y₂O₃ transparent ceramic with high transparency was obtained by pre-sintering consolidated green compacts at a low temperature of 1400°C for 16 h in air followed by a post-HIP treatment at 1550°C for 2 h under 200 MPa pressure. The sample had a fine average grain size of 690 nm. The in-line transmittance of the sample reached 83.3% and 81.8% at 1100 nm and 800 nm, respectively, very close to the theoretical values of Y₂O₃.