Wet Milling of Fe/Al/Al2O3 and Fe2O3/Al/Al2O3 Powder Mixtures

Wet milling of Al₂O₃-aluminide alloy (3A) precursor powders in acetone has been investigated by milling Fe/Al/Al₂O₃ and Fe₂O₃/Al/Al₂O₃ powder mixtures. The influence of the milling process on the physical and chemical properties of the milled powders has been studied. Particle refinement and homogenization were found not to play a dominant role, whereas plastic deformation of the metal particles leads to the formation of dislocations and a highly disarranged polycrystalline structure. Although no chemical reactions among the powder components in Fe₂O₃/Al/Al₂O₃ powder mixtures were observed, the formation of a nanocrystalline, ordered intermetallic FeAl phase in Fe/Al/Al₂O₃ powder mixtures caused by mechanical alloying was detected. Chemical reactions of Fe and Al particle surfaces with the atmosphere and the milling media lead to the formation of highly porous hydroxides on the particle surfaces. Hence the specific surface area of the powders increases, while the powder density decreases during milling. The fraction of Fe oxidized during milling was determined to be 0.13. The fraction of Al oxidized during milling strongly depends on the metal content of the powder mixture. It ranges between 0.4 and 0.8.     

Reaction Sintering of ZnO-AI2O3

The reaction sintering of equimolar mixtures of ZnO and A1₂O₃ powders was investigated as a function of primary processing parameters such as the temperature, heating rate, green density, and particle size. The powder mixtures were prepared by two different methods. In one method, the ZnO and A1₂O₃ powders were ball-milled. In the other method, the ZnO powder was chemically precipitated onto the A1₂O₃ particles dispersed in a solution of zinc chloride. The sintering characteristics of the compacted powders prepared by each method were compared with those for a prereacted, single-phase powder of zinc aluminate, ZnAl₂O₄. The chemical reaction between ZnO and A1₂O₃ occurred prior to densification of the powder compact and was accompanied by fairly large expansion. The mixing procedure had a significant effect on the densification rate during reaction sintering. The densification rate of the compact formed from the ball-milled powder was strongly inhibited compared to that for the single-phase ZnAl₂O₄ powder. However, the densification rate of the compact formed from the chemically precipitated mixture was almost identical to that for the ZnAl₂O₄ powder. The difference in sintering between the ball-milled mixture and the chemically precipitated mixture is interpreted in terms of differences in the microstructural uniformity of the initial powder compacts resulting from the different preparation procedures.     

Effect of Physical Nature of Powders and Firing Atmosphere on ZnAI2O4 Formation

The rate of ZnA1₂O₄ formation for binary powder mixtures of ZnO and α-Al₂O₃ (dense coarse particles and weak agglomerates of fine powder) fired in air or O₂ atmospheres was measured and the microstructures of those systems were observed by scanning electron microscopy. With dispersed dense particles of α-Al₂O₃, the Al₂O₃ surfaces were covered with ZnO and the spinel grew into the particles maintaining essentially a constant reaction interface area. Calculations based on geometric measurements and use of Jander's equation gave a similar high activation energy, 354 kJ/mol, which corresponds to the activation energy of volume diffusion of Zn²⁺ in ZnAl₂O₄. An oxygen atmosphere had no effect. With a matrix of fine α-Al₂O₃ powder and dispersed granules of ZnO, a higher reaction rate occurred because of an increase in reaction interface area due to penetration of the powder compact matrix by ZnO vapor, which was enhanced by an O₂ atmosphere. The reaction layer grew into the alumina matrix adjoining the ZnO granules with a parabolic rate law. Apparent activation energies below ∼200 kJ/mol were calculated.     

Formation of Nanometric TiB2 from TiO2

Titanium diboride can be produced by ball-milling a mixture of TiO₂, B₂O₃, and Mg metal for between 10 and 15 h. The reaction was found to be completed during the milling with no evidence of residual Mg. The unwanted phase, MgO, was readily removed by leaching in acid. The leached powder obtained after 15 h milling had a particle size of <200 nm and was highly faceted. The particle size decreased to ∼50 nm after 100 h milling and seemed to be relatively monodisperse. Scherrer calculation of the crystallite size showed that the product particles were probably single crystal.     

Synthesis and Characterization of MgAl2O4 Spinel Precursor from a Heterogeneous Alkoxide Solution Containing Fine MgO Powder

A precursor was synthesized from a heterogeneous alkoxide solution that contained fine MgO powder, which allowed the preparation of MgAl₂O₄ spinel powder with high sinterability characteristics. The precursor consisted of a mixture of boehmite (AlO(OH)) and a mixed hydroxide (Mg₄Al₂(OH)₁₄· 3H₂O). The spinel phase formed through two steps: (i) decomposition of the mixed hydroxide at low temperature and (ii) solid-state reaction between MgO and γ-Al₂O₃ at higher temperatures. Dense polycrystalline spinel could be obtained from the calcined powders at sintering temperatures as low as 1400°C.     

Preparation of Al2O3–AlN–Ni Composites

A method is proposed to prepare Al₂O₃-AlN-Ni composites. The composites are prepared by sintering Al₂O₃/NiAl powder mixtures at 1600°C in a mixture of nitrogen and carbon monoxide. The presence of NiAl particles raises the green density of Al₂O₃/NiAl powder compacts. During sintering, NiAl reacts with nitrogen to form AlN and Ni inclusions. A volume expansion accompanies the reaction. Because of the high green density and the reaction, the volume shrinkage of the Al₂O₃-AlN-Ni composite decreases with the increase of added NiAl content.     

Grain Growth of ZnO in ZnO-Bl2O3 Ceramics with Ai2O3 Additions

Grain growth of ZnO during liquid-phase sintering of a ZnO-6 wt% Bi₂O₃ ceramic was investigated for A1₂O₃ additions from 0.10 to 0.80 wt%. Sintering in air for 0.5 to 4 h at 900° to 1400°C was studied. The AI₂O₃ reacted with the ZnO to form ZnAl₂O₄ spinel, which reduced the rate of ZnO grain growth. The ZnO grain-growth exponent was determined to be 4 and the activation energy for ZnO grain growth was estimated to be 400 kJ/mol. These values were compared with the activation parameters for ZnO grain growth in other ceramic systems. It was confirmed that the reduced ZnO grain growth was a result of ZnAl₂O₄ spinel particles pinning the ZnO grain boundaries and reducing their mobility, which explained the grain-growth exponent of 4. It was concluded that the 400 kJ/mol activation energy was related to the transport of the ZnAl₂O₄ spinel particles, most probably controlled by the diffusion of O^2- in the ZnAl₂O₄ spinel structure.     

Double Precursor Solution Coating Approach for Low-Temperature Sintering of [Pb(Mg1/3Nb2/3)O3]0.63[PbTiO3]0.37 Solids

Lead-based piezoelectric ceramics typically require sintering temperatures higher than 1000°C at which significant lead loss can occur. Here, we report a double precursor solution coating (PSC) method for fabricating low-temperature sinterable polycrystalline [Pb(Mg_1/3Nb_2/3)O₃]_0.63-[PbTiO₃]_0.37 (PMN–PT) ceramics. In this method, submicrometer crystalline PMN powder was first obtained by dispersing Mg(OH)₂-coated Nb₂O₅ particles in a lead acetate/ethylene glycol solution (first PSC), followed by calcination at 800°C. The crystalline PMN powder was subsequently suspended in a PT precursor solution containing lead acetate and titanium isopropoxide in ethylene glycol to form the PMN–PT precursor powder (second PSC) that could be sintered at a temperature as low as 900°C. The resultant d ₃₃ for samples sintered at 900°, 1000°, and 1100°C for 2 h were 600, 620, and 700 pm/V, respectively, comparable with the known value. We attributed the low sintering temperature to the reactive sintering nature of the present PMN–PT precursor powder. The reaction between the nanosize PT and the submicrometer-size PMN occurred roughly in the same temperature range as the densification, 850°–900°C, thereby significantly accelerating the sintering process. The present PSC technique is very general and should be readily applicable to other multicomponent systems.     

Translucent Sintered MgAl2O4

A translucent polycrystalline MgAl₂O₄ ceramic was prepared from finely divided coprecipitated spinel in which a small amount of CaO added as a sintering aid was uniformly distributed. The CaO promotes densification through the formation of a liquid phase at the sintering temperatures. Depending on the sintering treatment, the relative density of the sintered spinel was 99.7 to ∼100% of theoretical. The in-line optical transmission was > 10% from 0.3 to 6.5 μm. Total transmission in the visible region was between 67 and 78%.     

Formation of 0.65 Pb(Mg1/3Nb2/3)O3–0.35 PbTiO3 Using a High-Energy Milling Process

We have investigated the synthesis of lead-magnesium-niobate–lead-titanate perovskite powder using high-energy milling of the constituent oxides. The compositions of the crystalline and amorphous phases as a function of milling time were determined with X-ray powder diffraction using a Rietveld refinement. The perovskite can be formed by two reaction routes. In the initial stage of milling, it is formed directly from the highly activated nano-sized constituent oxides, and after a certain milling time it is mainly formed from a pyrochlore phase. The obtained as-milled powder consists of crystalline perovskite and an amorphous phase that crystallizes into the perovskite after heating at 800°C.     

Zircon Synthesis via Sintering of Milled SiO2 and ZrO2

The formation of zircon (ZrSiO₄) via sintering of milled SiO₂ and ZrO₂ powders was studied, and the effects of slurry vs dry milling, sintering time, and particle size on zircon yield were examined. It was found that very high zircon yields could be obtained via slurry milling, cold pressing, and sintering of the oxide precursors. The controlling factor in determining zircon yield was found to be the particle size of the SiO₂ and ZrO₂ powders. Zircon yield as a function of sintering time was examined, and found to be similar to previous studies in which sol-gel precursors seeded with zircon were used. SEM studies reveal a homogeneous product with particle sizes on the order of 1–5 µm. It was found that complete reaction to zircon can be achieved from a once-through milling, pressing, and sintering process of SiO₂-ZrO₂ powders.     

Formation and Densification Behavior of MgAl2O4 Spinel: The Influence of Processing Parameters

Different types of dense stoichiometric and nonstoichiometric magnesium aluminate (MgAl₂O₄) spinel (MAS) ceramics were prepared following a conventional double-stage firing process using different commercially available alumina and magnesia raw materials. Stoichiometric, magnesia-rich, and alumina-rich spinels were sintered at 1500°–1800°C for 1–2.5 h. The influence of the different processing parameters (average particle size, degree of spinel phase, green density, mass of the powder compact, sintering temperature, holding time at the peak temperature, and starting composition) on the densification behavior of MAS was assessed by measuring the bulk density, apparent porosity, and water absorption capacity, and microstructural observations. Most of the MAS compositions tested exhibited excellent sintering properties.     

A Review on the Sintering and Microstructure Development of Transparent Spinel (MgAl2O4)

A review of the densification mechanisms and the microstructural development for transparent spinel made by free sintering and by hot pressing is given. The paper is divided into two main parts. The first part considers spinel without any sintering additives because there still is some controversy concerning the role of cation stoichiometry on sintering and grain growth. The second part discusses the role of the classic sintering aid, LiF, in processing transparent spinel. LiF is shown to have multiple behaviors: (1) it initially wets spinel and forms a liquid phase at relatively low temperatures, which affects early-stage densification and also grain growth; (2) upon cooling from intermediate temperatures, or even from higher temperatures if microstructure evolution (e.g., formation of closed porosity) prevents volatization, the LiF-containing liquid dewets and resides in isolated pockets; (3) LiF alters the cation stoichiometry, thereby enhancing diffusion via an increase in the concentration of oxygen vacancies; this affects both the densification rate and grain growth; and (4) it reacts with impurities in the system, thereby acting as a cleanser. For the production of transparent spinel, it is critical that LiF or associated reaction products not be retained as a secondary phase.     

Preparation of MgAl2O4 Spinel Powders via Freeze-Drying of Alkoxide Precursors

High-sinterability MgAl₂O₄ powder has been produced from alkoxide precursors via a freeze-drying method. Clear alumina sol and magnesium methoxide were used as starting materials in the process. The spinel powders were characterized by various techniques, such as thermal analysis, X-ray diffraction, scanning electron microscopy, and transmission electron microscopy. The tap density and sinterability of the spinel power are affected by the ball-milling techniques. Highly dense, transparent, polycrystalline MgAl₂O₄ has been obtained from these powders by sintering and hot isostatic pressing. Bimodal grain-size microstructure is observed in a HIPed sample.     

Microstructure and Surface Segregation of 3 mol% Y2O3-Doped ZrO2 Particles

Microstructure of a commercial 3 mol% yttria-doped zirconia nano-particulate powder was observed by transmission electron microscopy, and the distribution of yttrium cation was investigated by energy-dispersive X-ray spectroscopy (EDS) with a probe size less than 1 nm. The cross-sectional high-resolution transmission electron microscopy observations revealed that there are two kinds of particles, consisting of single-phase tetragonal and two phases comprising tetragonal and monoclinic. EDS analysis revealed that yttrium cations segregate to the surface of the tetragonal particle. The origin of tetragonal to monoclinic transformation was considered to be due to external stress during the powder milling process.     

Synthesis of Celsian (BaAl2Si2O8) from Solid Ba-Al-Al2O3-SiO2 Precursors: I, XRD and SEM/EDX Analyses of Phase Evolution

An intimate Ba-Al-Al₂O₃-SiO₂ powder mixture, produced by high-energy milling, was pressed to 3 mm thick cylinders (10 mm diameter) and hexagonal plates (6 mm edge-to-edge width). Heat treatments conducted from 300° to 1650°C in pure oxygen or air were used to transform these solid-metal/oxide precursors into BaAl₂Si₂O₈. Barium oxidation was completed, and a binary silicate compound, Ba₂SiO₄, had formed within 24 h at 300°C. After 72 h at 650°C, aluminum oxidation was completed, and an appreciable amount of BaAl₂O₄ had formed. Diffraction peaks consistent with hexagonal BaAl₂Si₂O₈, BaAl₂O₄, β-BaSiO₃, and possibly β-BaSi₂O₅ were detected after 24 h at 900°C. Diffraction peaks for BaAl₂O₄ and BaAl₂Si₂O₈ were observed after 35 h at 1200°C, although SEM analyses also revealed fine silicate particles. Further reaction of this silicate with BaAl₂O₄ at 1350° to 1650°C yielded a mixture of hexagonal and monoclinic BaAl₂Si₂O₈. The observed reaction path was compared to prior work with other inorganic precursors to BaAl₂Si₂O₈.     

Fabrication of High-Density Homogeneous ThO2-UO2 Fuel Pellets

Thorium oxide and uranium oxide pellet fuel development activities leading to a process fohd fabrication of high density, homogeneous fuel pellets are described. Conventional dry ball-milling was used to comminute commercially available powders. After separate milling, these ThO₂-UO₂mixtures were co-milled, pressed, and sintered to 95 % of theoretical density with a homogeneous distribution of the components. An intimate mix of highly active powders promotes solid solution formation and yields high density pellets.     

Sintering Kinetics of a MgAl2O4 Spinel Doped with LiF

The sintering kinetics of a pure magnesium aluminate spinel, MgAl₂O₄, and that doped with LiF were determined through the use of the master sintering curve technique developed by Su and Johnson. ²⁰ Powders with 0%, 0.5%, and 1.0% by mass LiF were densified in a vacuum hot press under a range of unaxial pressures. After the sintering mechanisms in each temperature and pressure regime were determined, an optimized vacuum hot-pressing schedule was formulated for spinel powders doped with 1.0% by mass of LiF. In addition to forming a transient liquid phase, the presence of LiF leads to the formation of oxygen vacancies that promote late-stage sintering in MgAl₂O₄.     

Mechanical Activation of Heterogeneous Sol–Gel Precursors for Synthesis of MgAl2O4 Spinel

MgAl₂O₄ spinel precursor was prepared using a heterogeneous sol–gel process. The effect of high-energy milling on the precursor decomposition and spinel formation was investigated. The milling decreased the Al(OH)₃ dehydroxylation temperature from 190° to about 130°C. The activation energy for spinel formation decreased from 688 kJ/mol for the as-prepared precursors to 468 kJ/mol for the precursors milled for 5 h. Milling of the precursor lowered the incipient temperature of spinel formation from 900° to 800°C, and the temperature of complete MgAl₂O₄ spinel formation from >1280° to ∼900°C.     

Fabrication of a Nano-Si3N4/Nano-C Composite by High-Energy Ball Milling and Spark Plasma Sintering

A nano-Si₃N₄/5 wt% nano-C composite was successfully fabricated for the first time via high-energy ball milling, followed by spark plasma sintering. The milling promoted the amorphization of the starting powders; most of the carbon particles were transformed into nano-size and embedded in the amorphous phase. This, combined with a low sintering temperature and a rapid densification rate, prevented the reactions between carbon and the other starting powders, leading to a uniform nano/nano-composite microstructure. Nano-sized carbon grains with an average diameter of about 10 nm were homogeneously dispersed in nano-sized (about 70 nm) Si₃N₄ grain boundaries. The hardness of the obtained nano-ceramics is comparable with that of conventional Si₃N₄, whereas Young's modulus is significantly decreased.