Dispersion and Grinding of Oxide Powders into an Aqueous Slurry

The present paper deals with a comprehensive analysis of the dispersion behavior of oxide powders to determine accurate conditions for mixing and grinding dense slurries without the use of steric dispersing agents. The experimental support of the work was the synthesis of (Zr,Sn)TiO₄ microwave dielectric ceramics by the solid-state reaction of raw materials mixed and ground by attrition milling. Zeta potential measurements were performed on the raw materials versus pH to determine the optimum pH of the slurry, allowing a good dispersion of all the species: the absolute value of the zeta potential of every powder >20 mV, with all potentials having the same sign. During the grinding process, as the surface of the materials increases due to the breakup of the grains, surface reaction occurs with the dispersion liquid, and pH must be continuously adjusted to be maintained at an adequate level. We have correlated these characterizations of the optimal processing conditions with the rheological behavior of the slurries, thus providing an analysis of the flocculated or deflocculated state. When applied to synthesizing (Zr,Sn)TiO₄ microwave dielectric ceramics, these conclusions made it possible to produce reproducible resonators with a k = 37 dielectric constant and characterized by a quality factor, Q × F > 60 000 GHz measured at 3 GHz, the highest value reported for this composition.     

Sol-Gel Coating of Lithium Zinc Ferrite Powders

Lithium zinc ferrite powders of composition Li_0.3Zn_0.4Mn_0.05− Fe_2.25O₄ were prepared by solid—state synthesis. Liquid-phase borosilicate sintering additives were applied to the ferrite particle surfaces at room temperature via a sol—gel coating technique. Calcined and comminuted ferrite powder was dispersed in methanol with predetermined quantities of tetraethyl orthosilicate and triethyl borate. Hydrofluoric acid was used to catalyze the sol—gel reactions. Amorphous coatings of 10 to 20 nm thickness were observed on particle surfaces by TEM. Chemical bonding in the coatings was studied using diffuse reflectance FTIR spectroscopy.     

Systematic Approach for Dispersion of Silicon Nitride Powder in Organic Media: II, Dispersion of the Powder

A novel dispersant—O-(2-aminopropyl)-O'-(2-methoxyethyl)-polypropylene glycol (AMPG)—was developed to disperse submicrometer-sized Si₃N₄ powder in nonaqueous media, based on the surface chemistry of the powder. The dispersing phenomena and mechanisms have been studied systematically, both in model systems (using atomic force microscopy and ellipsometry) and in powder systems (using rheological behavior and adsorption isotherms). The results from the model systems correlated well with those from wet powder systems. It is demonstrated that highly concentrated (with a solids volume fraction of >0.50) and colloidally stable nonaqueous Si₃N₄ suspensions can be realized using AMPG.     

Effect of Polyelectrolyte Dispersants on the Preparation of Silica-Coated Zinc Oxide Particles in Aqueous Media

Sodium silicate was utilized to obtain a SiO₂ coating on ZnO particles to prevent a photocatalytic reaction between ZnO and phenol. During the coating process, pH control is important to avoid dissolution of the ZnO as well as to obtain a good dispersion. Two kinds of polyelectrolyte dispersants were used to control the surface charge of the ZnO particles in aqueous media. As a result, poly(ethylenimine) (PEI) shifted the isoelectric point of ZnO from pH 9 to pH 10, whereas poly(ammonium acrylate) (PAA) made the surface charge of ZnO negative between pH 6 and pH 11. The change in the ZnO surface charge produced by adding polyelectrolyte dispersants makes it possible to obtain uniform silica–coated ZnO particle in aqueous media. UV–irradiation experiments showed that PEI, which can make the surface charge opposite to that of SiO₂, is more effective in obtaining a thick silica coating on ZnO.     

Geometry and Electrical Properties of Grain Boundaries in Manganese Zinc Ferrite Ceramics

For large-grained manganese zinc (MnZn) ferrite ceramics, grain misorientation determined by electron backscatter diffractions and grain-boundary resistance measured using microcontact impedance spectroscopy have been correlated. The degree of oxidation of grain boundaries and, hence, the barrier height depends on the overall grain-boundary network as well as on the individual boundary structure; therefore, a statistical analysis has been performed based on several hundreds of local measurements. When the boundaries are divided into low- and high-resistance groups, statistically significant differences in rotation axis and angle distributions are found. The misorientation distribution of the low-resistance boundary group is suggested to reflect the low-energy configurations of boundary planes in MnZn ferrites.     

Dispersion of aluminum‐doped zinc oxide nanopowder in non‐aqueous suspensions

This study proposes appropriate dispersants for dispersing aluminum‐doped zinc oxide (AZO) nanopowder in the commonly used organic solvent‐dimethylacetamide (DMAC). The dispersion efficiencies and stabilization mechanisms of four DMAC‐soluble dispersants, poly(acrylic acid) (PAA), polyethyleneimine (PEI), poly(vinyl alcohol) (PVA), and poly(vinyl pyrrolidone) (PVP), are compared. The non‐polyelectrolyte‐based PVA and PVP surprisingly exhibit greater efficiency than the polyelectrolyte‐based PAA and PEI. This is because the nano AZO is soft‐agglomerated in DMAC and easily de‐agglomerated by the application of ultrasonic power; therefore, the increased viscosity contributed from additions of PVA and PVP efficiently prevent reagglomeration and sedimentation of the nanopowder. This stabilization mechanism is evidenced by an experimental analysis of zeta potentials and rheology and also by theoretical calculations based on Stokes’ law.     

Dispersing Behavior of Hydroxyapatite Powders Produced by Wet-Chemical Synthesis

Three hydroxyapatite powders with different surface properties were produced by wet-chemical synthesis and characterized. The electrokinetic properties of powders dispersed in water were investigated by electroacoustic spectroscopy measurements. The different surface reactivity (pH_iep and ζ potential versus pH curves) was related to the interplay of dissolution and adsorption of Ca²⁺ ions. With a view toward the preparation of porous bodies by sponge impregnation, the behavior of powder suspensions was studied. Four deflocculants were tested, and the optimum dispersing conditions for each powder were found. Anionic polyelectrolytes resulted in the best effective dispersing agent, with different optimum amounts added to the suspensions.     

Double Injection Synthesis and Dispersion of Submicrometer Barium Titanyl Oxalate Tetrahydrate

A modified Clabaugh method has been used to produce a well-dispersed barium titanyl oxalate tetrahydrate (BTO) powder with a particle size of less than 0.2 μm. Production of the BTO powder is based on a double injection system, with reactants rapidly mixed using pressurized gas. The mixture resulting from the double injection of the reactants was subsequently quenched into a solution containing polyethyleneimine as a dispersant. The resulting dispersed BTO powder forms a suspension that is stable against coarsening or aggregation for greater than 1400 h. The dispersed BTO powder was also shown to produce BaTiO₃ with a particle size of 0.25 μm or less after calcination.     

Influence of Impurities on Dispersion Properties of Bayer Alumina

Among the different impurities contained in Bayer alumina (Ca, Fe, Na, Si, Mg), calcium was found to greatly influence the dispersion of alumina particles in water. Up to 90% of calcium is dissolved at acidic pH, whereas calcium remains on the alumina surface in the basic pH range and screens the negative Al–O⁻ charges. The presence of calcium, through reducing repulsive interactions between particles, has a negative effect on the dispersion of alumina. The adsorption of the Na⁺ salt of poly(acrylic acid) (PAA-Na) is strongly influenced by Ca²⁺/PAA-Na interactions in suspension with an increase of the maximum adsorbed amount of PAA-Na in the presence of calcium. The amount of PAA-Na needed to reach a high electrostatic repulsion and a minimum of viscosity is 2 times higher in the presence of 400 pm calcium than for a low calcium content (∼80 ppm). Finally, with an appropriate amount of PAA-Na, a similar state of dispersion can be reached with or without the presence of calcium.     

Quantitative Analysis of Zinc Vaporization from Manganese Zinc Ferrites

Zinc vaporization of Mn-Zn ferrites was quantitatively characterized in terms of oxygen partial pressure P _O2, temperature, grain size and sample geometry. The amount of zinc loss was measured as a function of time at various temperatures by a thermogravimetric method. The weight loss due to irreversible zinc vaporization showed a linear behavior with time and increased exponentially with temperature. The observed weight loss due to zinc evaporation at 1100°C was small, whereas a significant weight change was detected at 1200°C. The weight loss was even greater in a reducing atmosphere ( P _O2= 5 × 10⁻⁵). Below 1300°C, the diffusion of elemental zinc was sufficiently fast to compensate the zinc loss at the interface region, resulting in a linear dependence on time. At temperatures ≥1400°C, the weight change no longer followed the linear dependence and showed a rather parabolic behavior with a concave upward slope. The core shape and the gas flow around ferrite cores were important factors that affected the rate of zinc vaporization, but not the grain size.     

Dispersion and Slip Casting of Hydroxyapatite

The dispersibility in deionized water of hydroxyapatite (HA) synthesized by a high-temperature (1000°C) solid-state reaction between tricalcium phosphate and calcium hydroxide was investigated as a function of the pH of the medium and the quantity of two dispersing agents (A = inorganic, B = organic) added to the slips. Although pH modification had a negligible effect on dispersibility, both of the dispersing agents produced a good dispersion at considerably higher concentrations (>2 wt% of HA). At optimum amounts (2–4 wt%) of the dispersing agents, the slips showed near-Newtonian flow behavior up to 45 wt% solids loading and non-Newtonian behavior at >50 wt%. By the optimal addition of dispersing agents and conditioning by ball milling, 60–67 wt% (32–39 vol%) solids-loaded HA slips could be cast into plaster molds to produce 50%–58% dense green bodies, which, in turn, sintered to 90%–94% density in the temperature range 1300°–1400°C. The sintered HA exhibited a three-point flexural strength of 40–60 MPa and a homogeneous microstructure, with interspersed microporosities.     

Processing and Characterization of Hexagonal Ferrite Thin Films from Organometallic Compounds

Thin films of BaFe₁₂O₁₉ were deposited on resistor-grade alumina by a chemical solution processing method involving the hydrolysis of a barium alkoxide and iron carboxylate. Conversion of the deposited organometallic precursor to an amorphous oxide was accomplished by a thermal decomposition/oxidation at 370°C. Subsequent development of the M-type hexagonal structure was accomplished with postannealing in air at temperatures in excess of 600°C. All films were characterized by scanning electron microscopy, X-ray diffraction, and magnetic measurements.     

Electrical Properties and Phase Stability of a Zinc Ferrite

The electrical conductivity and theromoelectric power of a zinc ferrite of nominal composition 0.46ZnO·0.54Fe₂O₃ were examined as a function of oxygen partial pressure under equilibrium conditions at elevated temperatures. The isothermal variations of both transport properties were found to be closely correlated with P _O2-induced phase transitions from wustite to ferrite spinel to hematite with successively increasing P _O2's. The region of thermodynamic stability of each phase was determined from either of the two property isotherms. Within the single-phase field of the spinel ferrite, both properties are P _O2 dependent. Applying the small polaron hopping model to these results, the P _O2 and temperature dependencies of the octahedral ferrous and ferric ion concentrations were extracted and interpreted in terms of the buffering capability of the nominal A-site cation and the variability of the partial molar enthalpy of oxygen with the progress of the oxidation reaction of Fe²⁺ to Fe³⁺.     

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.     

Synthesis, Characterization, and Processing of Cordierite-Glass Particles Modified by Coating with an Alumina Precursor

The surfaces of cordierite and glass particles were modified by coating them with an alumina precursor using a precipitation process in the presence of urea. Scanning electron microscopy (SEM), high-resolution transmission electron microscopy, X-ray diffraction, electrophoresis, and rheological measurements were used to characterize the coated powders. SEM and transmission electron microscopy morphologies of the coated powders revealed that amorphous and homogeneous coatings have been formed around the particles. The morphology of the coated powders showed a coiled wormlike surface. The coating Al₂O₃ layer dominated the surface properties of the coated glass and cordierite powders. The influence of the coating layer on the processing ability of cordierite-based glass-ceramics substrates by tape casting was studied in aqueous media. It could be concluded that the coating of the powders facilitates the processing and yields green and sintered tapes with denser, more homogeneous microstructures compared with the uncoated powders.     

Preparation of Hydroxyapatite Lathlike Particles Using High-Speed Dispersing Equipment

Hydroxyapatite lathlike monocrystalline particles were prepared using high-energy dispersing equipment in combination with a pH shock-wave method. The Ca/P atomic ratios were very close to theoretical, and the acidic group content was very small. The particles were nonporous, with anisotropic crystal growth and average grain size ∼140–1300 nm in length, ∼20–100 nm in width, and ∼10–40 nm in thickness. The high-speed dispersing equipment created the proper hydrodynamic conditions for lathlike particle growth in the [001] direction. The hydroxyapatite particles formed aggregates of 1–5 μm average diameter.     

Influence of a Dispersion of Aluminum Titanate Particles of Controlled Size on the Thermal Shock Resistance of Alumina

The possibility of developing fine-grained (∼0.5–3 μm) and dense (≥0.98ρ_th) alumina (90 vol%)–aluminum titanate (10 vol%) composites with improved thermal shock resistance and maintained strength is investigated. One alumina material and one composite with similar microstructures (porosity and grain-size distribution) were fabricated to investigate the effect of Al₂TiO₅ on thermal shock behavior. The size of the Al₂TiO₅ particles was kept under 2.2 μm to avoid spontaneous microcracking. The mechanical and thermal properties of the materials involved in their response to thermal shock and the results for the evolution of indentation cracks of equal initial crack length with increasing Δ T in samples quenched in glycerine are described. The combination of thermal and mechanical properties—thermal conductivity, thermal expansion coefficient, Young's modulus, and toughness—improve the thermal shock resistance of the alumina–aluminum titanate composite in terms of critical temperature increment (>30%). The suitable structural properties of alumina—hardness and strength—are maintained.     

Dispersion and densification of nano Si–(Al)–C powder with amorphous/nanocrystalline bimodal microstructure

The dispersion behavior and densification of nano Si–(Al)–C powder with amorphous/nanocrystalline bimodal microstructure were investigated. The Si–C powders synthesized by a mechanical alloying (MA) process had a near‐spherical shape with an average particle size of 170 nm. A solid loading of 62 vol% was achieved using polyethyleneimine (PEI) as a dispersant. The optimum dispersant amount was 1 wt% based on zeta potential, sedimentation, and viscosity analysis data. The high zeta potential value (73 mV) compared with that of the commercially available SiC (65 mV) was caused by modified surface properties and consequent promotion of the cationic dispersant adsorption. A Si–Al–C slurry containing 6.5 wt% of sintering additives with a solid loading of 60 vol% was also prepared. The relative density of the dried Si–Al–C slurry was 63.3% without additional compaction, which could be densified at 1650°C at a pressure of 20 MPa using a spark plasma sintering furnace.     

Interaction between Dissolved Ba2+ and PAA-NH4 Dispersant in Aqueous Barium Titanate Suspensions

The interaction between dissolved Ba²⁺ and dissociated ammonium salt of poly(acrylic acid) (PAA-NH₄) in aqueous suspension has been studied. The dissolved Ba²⁺ causes flocculation of dissociated PAA-NH₄, thus degrading its dispersing effectiveness in aqueous BaTiO₃ suspensions. The concentration of PAA-NH₄ required to stabilize aqueous BaTiO₃ suspension increases with increasing Ba²⁺ concentration at a given pH. A stability map, which is determined by a rheological study, is constructed to describe the amount of PAA-NH₄ required to have well-dispersed aqueous BaTiO₃ suspensions as a function of Ba²⁺ concentrations at different pH values.