Synthesis of Magnesium Aluminate Spinel Platelets from α-Alumina Platelet and Magnesium Sulfate Precursors

Spinel platelets were formed from a powder mixture of 3–5 μm wide and 0.2–0.5 μm thick α-Al₂O₃ and 1–8 μm (average 3 μm) MgSO₄ heated 2 h at 1200°C. The hexagonal platelet shape of the original α-Al₂O₃ platelet was maintained in the spinel, although their size was slightly increased and their surface roughened. When a mixture of α-Al₂O₃ platelets and MgO powder was heated 3 h at 1400°C, the spinel formed lost the platelet morphology of the alumina.     

Mechanism of Material Removal from Silicon Carbide by Carbon Dioxide Laser Heating

The mechanism of material removal from SiC by CO₂ laser heating was studied using sintered and single-crystal α-SiC. Removal rate and width of the groove showed maxima when plotted as a function of translation speeds. Groove depth decreased as the translation speed of samples increased. Similar results were obtained if argon or air was used as gas assist, which indicated that the material removal mechanism is induced dissociation of SiC. Microstructure of the material deposited in and outside of the groove was studied by SEM. At low scanning speeds, columnar grains 10 to 50 μm long appeared. As the scanning speed increased, columnar grains became smaller and finally only irregular polycrystalline particles were observed. By using Raman spectroscopy, Auger analysis, and X-ray diffraction, phases inside and outside the groove were identified as Si, β-SiC, C, and SiO₂. Columnar grains were identified as β-SiC covered with thin layers of C, Si, and SiO₂. Slow scanning speeds enhanced the growth of β-SiC. At slow scanning speed, free silicon was always found in the grooves of lased single crystals but not in the grooves of lased sintered SiC. It can be concluded that the mechanism of material removal from silicon carbide by CO₂ laser heating is a vaporization process, and material found in the groove and on the surface near the groove is formed by condensation from the vapor.     

Toughened Oxide Composites Based on Porous Alumina-Platelet Interphases

A novel mechanism for debonding at a weak interphase in an all-oxide composite is introduced. This methodology involves the use of alumina platelets that have a diameter of 10–15 or 5–10 μm and a thickness of 1 μm. The platelets induce constrained sintering of the ceramic powder, which results in permanent porosity. For room-temperature properties, only minor additions (0–3 vol%) of matrix powder yield sufficiently weak debonding interphases. The platelets lie in random, three-dimensional orientations and provide a debonding mechanism that is independent of temperature, in chemically compatible matrixes. Laminated composites with two types of matrixes—mullite and alumina—have been fabricated with modified fibrous monoliths of alumina in a triple-layer "core/interphase/matrix" arrangement. In the laminated systems, the intimate mixing of strong versus tough microstructures has been tailored by alternating various matrix:interphase thickness ratios. Preliminary load–displacement curves clearly demonstrate characteristics of "graceful failure" and notable improvements in the work of fracture. Scanning electron microscopic observation of the crack paths confirms the viability of platelets for producing permanently porous, debondable interphases at elevated temperatures in air.     

Kinetics of Phase Change in Explosively Shock-Treated Alumina

The effect of shock treatment on the kinetics of transformation of transition-phase alumina has been examined. Alumina powder, consisting of spherical particles produced by melting and quenching, was shock-treated at 13- to 26-GPa maximum pressure and subsequently heat-treated at 1000° and 1050°C for various times. At 1050°C, the transformation of unshocked powder was typical of other aluminas with an incubation period of 60 min before significant conversion occurred. In contrast, in the shock-treated material, no incubation period was observed and the α-phase content increased exponentially with time. The growth kinetics of the shocked powder corresponded to a linear growth process with an activation energy of 482 kJ/mol. TEM examination revealed α-phase morphologies consistent with linear growth.     

Direct Laser Sintering of Al2O3–SiO2 Dental Ceramic Components by Layer-Wise Slurry Deposition

This publication presents a solid freeform fabrication technique for ceramics in the alumina–silica system by layering binder-free, high-loaded ceramic slurries, followed by selective laser sintering. The low melting silica phase and the reaction sintering between silica and alumina favor the rapid prototyping of pure ceramic parts. On the basis of electroacoustic and viscosity measurements, stable slurries from Al₂O₃/SiO₂ powder mixtures and water with a high fluidity have been prepared for the layer deposition with a doctor blade like in tape casting. Layers with a thickness of about 100 μm were processed. It was found in laser parameter studies that ceramic parts can only be obtained using special alumina contents and laser parameters. But the biphasic approach may allow greater flexibility in the processing regime than is afforded by the use of just one material. The microstructure of these parts depends mainly on the temperature gradient induced by the laser absorption and thermal conduction. The wet shaping facilitates laser-sintered parts with a relatively high density, which could be increased by a thermal post-treatment.     

Preparation of alumina/polystyrene core-shell composite powder via phase inversion process for indirect selective laser sintering applications

Indirect selective laser sintering (SLS) is one of the promising additive manufacturing (AM) methods that can process conventionally difficult or even impossible materials such as ceramics. In this work, an innovative phase inversion technique is used to fabricate spherical alumina particles coated with a thin layer of polystyrene (PS). Then, indirect SLS is used to fabricate green parts from the 6 wt% PS coated alumina particles via a Nd:YAG laser. The assessed SLS process parameters were the scan speed, laser power, scan spacing, pulse frequency, and pulse width. The characterization of the AL₂O₃/PS core-shell composite particles was described using techniques including SEM (for morphology), FT-IR (for chemical bonding at the interfaces), TGA (for mass loss), and DSC (for glass transition temperature, T_g). 3D green parts were then fabricated using proper process parameters as a proof of the feasibility of using SLS technique for AL₂O₃/PS core-shell composite powder. The results showed that using a Nd:YAG laser with less absorption by alumina and PS provides greater penetration through a powder bed. In addition, the possibility of sound connections among particles in every direction was observed due to the uniformity of the coating process in spite of a minimal amount of binder. In addition, green part density measurements show high values compared to previously reported results.     

Preparation of Highly Dense PZN–PZT Thick Films by the Aerosol Deposition Method Using Excess-PbO Powder

Lead zinc niobate–lead zirconate titanate thick films with a thickness of 50–100 μm were deposited on silicon and alumina substrates using the aerosol deposition method. The effects of excess lead oxide (PbO) on stress relaxation during postannealing were studied. Excess PbO content was varied from 0 to 5 mol%. The as-deposited film had a fairly dense microstructure with nanosized grains. The films deposited on silicon were annealed at temperatures of 700°C, and the films deposited on sapphire were annealed at 900°C in an electrical furnace. The annealed film was detached and cracks were generated due to the high residual compressive stress and thermal stress induced by thermal expansion coefficient mismatch. However, the film deposited using powder containing 2% of excess PbO showed no cracking or detachment from the substrate after the postannealing process. The PbO evaporation at elevated temperature during the postannealing process seemed to have reduced the residual compressive stress. The remanent polarization and relative dielectric constant of the 50 μm thick films annealed at 900°C were 43.1 μC/cm² and 1400, respectively, which were comparable with the values of a bulk specimen prepared by a powder sintering process.     

Novel fabrication route for porous silicon carbide ceramics through the combination of in situ polymerization and reaction bonding techniques

For the first time, an in situ polymerization technique was applied to produce mullite‐bonded porous SiC ceramics via a reaction bonding technique. In this study, SiC microsized particles and alumina nanopowders were successfully coated by polyethylene (PE), which was synthesized from the particle surface in a slurry phase reactor with a Ziegler–Natta catalyst system. The thermal studies of the resulting samples were performed with differential scanning calorimetry and thermogravimetric analysis. The morphology analysis obtained by transmission electron microscopy and scanning electron microscopy (SEM) confirmed that PE was successfully grafted onto the particle surface. Furthermore, the obtained porous ceramics were characterized in terms of their morphologies, phase composition, open porosity, pore size distribution, and mechanical strength. SEM observations and mercury porosimtery analysis revealed that the quality of the dispersion of nanosized alumina powder into the microsized SiC particles was strongly enhanced when the particles were coated by polymers with in situ polymerization. This resulted in a higher strength and porosity of the formed ceramic porous materials with respect to the traditional process. In addition, the X‐ray diffraction results reveal that the amount of mullite as the binder increased significantly for the samples fabricated by this novel method. The effects of the sintering temperature, forming pressure, and polymer content on the physical and mechanical properties of the final porous ceramic were also evaluated in this study. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40425.     

Influence of Grain Growth on Dielectric Properties of Nb-Doped BaTiO3

Effects of grain size and grain growth in Nb-doped BaTiO₃ on temperature and frequency dependencies of the dielectric constant were investigated. When 0.65 μm powder is sintered to an average grain size of 1 μm, two dielectric constant peaks indicate the presence of Nb-free BaTiO₃ and of Nb-containing material. Single peaks are observed above room temperature after additional grain growth or when 0.07 μm powder is sintered to an average grain size of 1 μm. The Curie point of pure BaTiO₃ with 1 μm grains is 4 to 6°C lower than that of material with grains >10 μm. Thermodynamically, this behavior is accounted for by a phase inversion stress ∼ the room-temperature stress.     

Ambient-Temperature Mechanical Response of Alumina–Fluoromica Laminates

Flexural delamination experiments were used to evaluate the mechanical performance of thermochemically stable alumina–fluoromica laminates. Hot-pressed, precracked laminate specimens, in which two MgAl₂O₄-spinel-coated alumina substrates were separated by a thin layer of fluorophlogopite (KMg₃(AlSi₃)O₁₀F₂), were tested in fourpoint flexure at room temperature. Two types of mechanical response were observed: steady-state delamination and brittle failure. Microstructural analysis showed that the delamination response was associated with fine (≤5 μm) grains of the mica; the brittle response occurred when the mica interphase consisted of large (>30 μm) grains that bridged the interphase. The steady-state strain-energy release rate ( G _ss) measured on the graceful, delaminating beams was 9.1 ± 0.4 Jm^–2 for randomly oriented ∼ 5–μm grains but only 2.8 ± 0.2 Jm^–2 for ∼1–μm grains that were aligned with easy-cleavage planes parallel to the laminate interfaces. The results suggested that debonding of the specimens occurred via cleavage of the mica grains. Observation of delamination cracks confirmed this point: propagation occurred within the fluoromica interphase rather than along the spinel/alumina or spinel/fluorophlogopite interfaces. The mechanical feasibility of laminate specimens without the protective spinel coating on the substrate containing the notch was also tested to address an issue related to the preparation of alumina fiber/mica interphase/alumina matrix composites. The delamination response again occurred for the case of a fine-grained mica interphase.     

Making Nanostructured Ceramics from Micrometer-Sized Powders via Grain Refinement During SPS Sintering

In this paper, we have demonstrated that dense bulk nanostructured ceramics can be synthesized from micrometer-sized powders by using an electrical field-activated sintering process. A dense Pb(Mg_1/3Nb_2/3)O₃-PbTiO₃ ceramic with grain sizes of 20–100 nm was obtained from the starting powder of 1 to 10 μm. Structural and property analysis confirmed that the entire specimen is composed of nano-sized grains. The significant microstructural refining is attributed to a pulsed electric field-induced thermo-mechanical fatigue process, which in situ "shattered" the large particles into nano-sized grains during sintering. An advantage of this technique over the previous ones is that it avoids the usage of ultrafine nanometer-sized powders, which are difficult to process and mass produce in an economic and consistent way. In principle, the process demonstrated here can be applied to other material systems.     

Densification Behaviors of Fine-Alumina and Coarse-Alumina Compacts during Liquid-Phase Sintering with the Addition of Talc

The densification behavior of fine alumina (mean particle size of ∼0.31 μm) and coarse alumina (mean particle size of ∼4.49 μm) during liquid-phase sintering with additions of talc have been studied, as well as the microstructural evolution. Small amounts (0, 5, and 10 wt%) of talc were added to the fine alumina and coarse alumina, which were sintered at various temperatures for 2 h. When 5 wt% of talc was added to the coarse alumina, densification proceeded rapidly above the liquid-formation temperature in alumina–talc compacts, because of the promotion of a rearrangement process of the solid grains by the liquid phase. The addition of 10 wt% of talc greatly accelerated densification by increasing the volume fraction of liquid. On the other hand, in the fine alumina, which has a higher activity and a greater driving force for sintering, appreciable densification started below the liquid-formation temperature, which prevented further densification after liquid formation. Moreover, the densification was suppressed as the talc content increased. The rigid skeleton of solid grains that was formed by densification below the liquid-formation temperature is believed to have suppressed the rearrangement process of the solid grains, and further densification of the compacts was retarded, even after the formation of a liquid phase above the liquid-formation temperature.     

A new process aid for melt compounding of PVC with ethylene copolymer resins

Ethylene copolymer resin (ECR) modifiers are solid, high molecular weight, permanent plasticizers for PVC. During the melt compounding step, the low melting ECR (m.p. ～50°C) melts first forming a relatively low viscosity phase in which the higher melting (Tg ～80°C) and more viscous PVC powder grains (～150 μm in diameter) are suspended. Under these conditions, it is sometimes difficult to get enough shear energy into the system to break down, or flux, all of the PVC grains into unagglomerated primary particles (～1 μm diameter). The remaining grains appear as gel-like heterogeneities, in the final blend, that can produce rough, pimpled extrudates with reduced physical properties. This paper describes the use of a new experimental process aid that significantly improves homogenization, during the melt compounding process, leading to improved product quality and/or production rates.     

Synthesis of High Aspect Ratio Platelet SrTiO3

A method for synthesis of high aspect ratio platelet seeds by growth of SrTiO₃ on Sr₃Ti₂O₇ core particles is reported. The aim of this study was to identify and control the morphology and size of SrTiO₃ particles via molten salt synthesis. Platelet and tabular morphologies with rectangular faces were obtained using rutile and anatase, respectively. Platelet SrTiO₃ particles with an edge length of 10–40 μm and a thickness of 1–4 μm were obtained. High aspect ratios (edge length to thickness) of 7–10 were measured for platelet particles as opposed to lower aspect ratios of 2–4 for tabular particles. Highly anisotropic platelets are suitable template candidates to achieve textured ceramics.     

Low-Temperature Sintering of Seeded Sol—Gel-Derived, ZrO2-Toughened Al2O3 Composites

Seeding a mixture of boehmite (AIOOH) and colloidal ZrO₂ with α-alumina particles and sintering at 1400°C for 100 min results in 98% density. The low sintering temperature, relative to conventional powder processing, is a result of the small alumina particle size (∼0.3 μm) obtained during the θ-to α-alumina transformation, homogeneous mixing, and the uniform structure of the sol-gel system. Complete retention of pure ZrO₂ in the tetragonal phase was obtained to 14 vol% ZTA because of the low-temperature sintering. The critical grain size for tetragonal ZrO₂ was determined to be ∼0.4 μm for the 14 vol% ZrO₂—Al₂O₃ composite. From these results it is proposed that seeded boehmite gels offer significant advantages for process control and alumina matrix composite fabrication.     

Sintering of Mixtures of Seeded Boehmite and Ultrafine α-Alumina

α-Alumina was fabricated by dry pressing mixtures of seeded boehmite and fine α-alumina (i.e., 0.2 and 0.3 μm diameter) to reduce the large shrinkage of boehmite-derived α-alumina. The maximum green density was obtained with mixtures containing ∼70%α-alumina for both alumina powders. The ∼15% linear shrinkage and microstructures of these samples were comparable to 100% alumina powder samples. Samples with 0.2 μm alumina sintered to densities >95% at 1300°C whereas 1400°C was needed for samples with 0.3 μm alumina. These results indicate that boehmite can be used as a substitute for relatively expensive ultrafine α-alumina powders.     

Formation and Densification Behavior of Magnesium Aluminate Spinel: The Influence of CaO and Moisture in the Precursors

Different grades of stoichiometric and non-stoichiometric dense magnesium aluminate spinel (MgAl₂O₄) grains were prepared by a conventional double-stage firing process using two types of alumina and four types of magnesia raw materials. The MgAl₂O₄ spinel formation was found to be highly influenced by CaO and moisture present in the precursor oxides as confirmed by thermogravimetry (TG), differential thermal analysis (DTA), and X-ray diffraction (XRD) techniques. The Fourier transform-infrared spectroscopy (FTIR) study of the precursor oxides revealed the presence of moisture. Influence of alumina and magnesia composition on the densification behavior of MgAl₂O₄ spinels was assessed by characterizing bulk density (BD), apparent porosity (AP), water absorption (WA) capacity, and the microstructures of the stoichiometric, the magnesia-rich, and the alumina-rich spinels sintered at 1650°C for 1 h. Sintering studies indicate that to obtain dense stoichiometric spinel grains with >3.35 g/mL BD, <2.0% AP, and <0.5% WA, the spinel powder should possess a median particle size of <2 μm, CaO content of >0.9%, compact (green) density of >1.95 g/mL, and spinel content of >90%. Among various spinels synthesized, the magnesia-rich spinels exhibited superior properties in terms of high BD, low percentage of AP, and low WA capacity, whereas alumina-rich spinels showed inferior properties. Stoichiometric spinels exhibited an average grain size of 10 μm whereas alumina-rich spinels with 90% alumina had an average grain size of 20 μm. The increase in holding time at higher temperatures enhanced the sintering properties of the spinels, particularly the magnesia-rich spinels. Further, raw mixtures having >0.9% CaO exhibited better sintered properties as compared with others.     

Ultra-fast,selective, non-melting,laser sintering of alumina with anisotropic and size-suppressed grains

In this paper, we report an ultra-fast sintering phenomenon of alumina achieved by the scanning laser irradiation method. Using CO₂ laser irradiation, we found that micrometer-sized alumina powder (d₅₀ = 1.2 µm) can be sintered close to full density within a few tens of seconds. The microstructure of laser-sintered alumina was different from that of the furnace-sintered alumina. The relative density and grain size of the laser-sintered alumina gradually decreased from the center of the laser beam to the edge. Anisotropy of the grain size was measured along and perpendicular to the scanning direction. This anisotropy decreased as the scanning speed decreased from 0.1 mm/s to 0.01 mm/s. The sintering master curve of grain size versus relative density, which reflects the sintering mechanism, was found to be affected by the laser scanning speed. When the laser scanning speed was 0.1 mm/s, grain size suppression was found for the almost fully dense alumina. However, at lower scanning speed (e.g., 0.01 mm/s), there was significant grain growth in the regions where the relative density was greater than 90%. These results clearly indicate that alumina can be sintered, in the solid-state, to a high density in a short time using scanning laser and the microstructure is different from the furnace-sintered alumina.     

Preparation and Characterization of Zirconium Carbide Coating on Coated Fuel Particles

Compact and uniform zirconium carbide (ZrC) coatings have been successfully deposited on coated fuel particles using a ZrCl₄+H₂+Ar+C₃H₆ gas mixture. Zirconium tetrachloride (ZrCl₄) powder feeder was especially designed and manufactured to control accurately the flow rate of ZrCl₄ and produce ZrC on an industrial scale. The coating has a large density (6.57 g/cm³), a thickness of 35 μm, a stoichiometry close to Zr/C=1, and a clear interface between the coating and substrate. The coating exhibits an fcc -ZrC phase with a grain size of 11.18 nm and a (111) texture coefficient of 0.57, which corresponds to a polycrystalline microstructure of randomly oriented ZrC grains. The preparation apparatus, processing conditions, properties, microstructures, and morphologies of the ZrC coating are investigated systematically.     

Synthesis and mechanical properties of mullite ceramics with coal gangue and wastes refractory as raw materials

With coal gangue and high alumina refractory solid wastes as raw materials, needle-like mullite powder, with an average diameter of about 1 μm, was synthesized at 1300°C by using the conventional solid-state reaction method. Mullite ceramics were derived from the inexpensive needle-like powder. Phase composition was examined by using X-ray diffraction (XRD), while morphologies of the ceramics were observed by using scanning electron microscopy. The content and distribution of elements in the sintered samples were characterized with energy dispersive spectrometer and X-ray fluorescence spectroscopy. Mechanical properties of the mullite ceramics were studied by using the three-point bending method. The aspect ratio of the needle-like mullite particles was up to 6. The mullite sample sintered at 1500°C for 3 hours had a density of 2.515 g·cm⁻³, which was slightly lower than the theoretical density. Maximum fracture toughness and bending strength of the mullite ceramics were 1.82 MPa·m^1/2 and 71.76 MPa, respectively. This study realizes the resource utilization of gangue and high alumina refractory solid wastes, and the prepared mullite ceramics have good application prospect.