Influence of Atmosphere on the Final-Stage Sintering Kinetics of Ultra-High-Purity Alumina

The influence of sintering atmosphere on the final-stage sintering of ultra-high-purity alumina has been investigated. Model final-stage microstructures were tailored via a latex sphere impregnation and burnout technique. Critical experiments have been conducted to quantitatively examine the influence of the oxygen partial pressure on the final-stage sintering kinetics. Samples were sintered at 1850°C in either dry hydrogen ( P o₂∼ 3 × 10⁻¹⁷ atm) or wet hydrogen P o₂∼ 5 × 10⁻¹⁰ to 2 × 10⁻¹¹ atm), and their microstructures were characterized as a function of sintering time, Sintering in dry hydrogen decreased the susceptibility of the final-stage microstructure to pore/boundary breakaway. In the kinetic analysis, the variation in the number of pores per grain, N _g, was taken into account. It was found that in both atmospheres, the densification rate was controlled by grain boundary diffusion, and that sintering in dry hydrogen increased the densification rate by a factor of 2.25. In addition, it was determined that the grain growth rate in both atmospheres was controlled by the rate of surface diffusion of matter around the pores and that sintering in dry hydrogen enhanced the grain growth rate by a factor of 5.6. The overall effect of the dry hydrogen atmosphere was that it enhanced the coarsening rate relative to the densification rate by a factor of 2.5, and consequently shifted the grain size-density trajectory to much lower densities for a given grain size.     

Plastic Deformation of Hydroxyapatites and Its Application to Joining

A plastic deformation process was demonstrated to self-join hydroxyapatite (HA), fabricating pore-free joints at 1275°C at a strain rate of 10⁻⁵ s⁻¹. To determine optimum joining conditions, high-temperature compressive deformation of HA was investigated for strain rates between 5 × 10⁻⁶ and 10⁻⁴ s⁻¹ at temperatures 1175–1275°C. X-ray diffraction revealed primarily the HA phase with the presence of tri- and tetra-calcium phosphate phases. Steady-state flow stresses were 0.6–45 MPa and increased with increasing strain rates. Stress exponents of ≈1 indicated a viscous diffusion-controlled deformation mechanism with an activation energy of ≈354±36 kJ/mol. Absence of cavitation and grain shape changes was consistent with grain boundary sliding.     

Correlation Between the Microstructure and the Electrical Properties of ZrTiO4 Ceramics

A series of ZrTiO₄ (ZT) ceramics were prepared by sintering ball-milled precursor powders. Ceramics with homogenously dispersed micropores containing both low-temperature (ordered) and high-temperature (disordered) ZrTiO₄ phases were achieved by sintering at 1400°C. The porosity and the morphology were modified by changing the sintering time. The impedance spectra followed the observed changes in the ceramics' microstructure. The grain boundaries' shape, rather than the grain size, has the major influence on the conductivity. The lowest value for electrical conductivity, 8.1 × 10⁻¹⁰ (Ω·m)⁻¹, was obtained in the ceramics sintered at 1400°C for 4 h. This confirms the blocking effect of the imperfect grain boundaries; i.e., the defects of the grain boundaries, which were formed during the grain growth, were followed by an almost complete loss of pores.     

Effect of Dynamic Microstructural Change on Deformation Behavior in Liquid-Phase-Sintered Silicon Carbide with Al2O3–Y2O3–CaO Additions

Nanocrystalline β-SiC with additions of 7 wt% Al₂O₃, 2 wt% Y₂O₃, and 1 wt% CaO was subjected to tensile deformation to study its microstructural behavior under the dynamic process. The liquid-phase-sintered body had a relative density of >97% and an average grain size of 170 nm. Tension tests were conducted at initial strain rates ranging from 2 × 10⁻⁵ to 5 × 10⁻⁴ s⁻¹, in the temperature range 1973–2023 K, in both argon and N₂ atmospheres. Although grain-boundary liquids formed by the additions vaporized concurrently with the decomposition of SiC and extensive grain growth, the maximum tensile elongation of 48% was achieved in argon. Annealing experiments under the same conditions revealed that vaporization and grain growth were both dependent on experimental time. Therefore, high strain rates suffered less from the hardening effect when cavitation damage was more severe. Testing in an N₂ atmosphere brought about crystallization of the grain-boundary phase and prevented severe vaporization; however, fracture occurred at only 8% elongation. Grain-boundary sliding was still the dominant mechanism for deformation.     

Superplastic Alumina Ceramics with Grain Growth Inhibitors

Superplastic deformation of alumina ceramics was studied at 1400° to 1450°C and at a strain rate of 4 × 10⁻⁵ to 5 × 10⁻⁴ s⁻¹. MgO and ZrO₂ were introduced to suppress dynamic grain growth. The latter was especially effective; grain growth was minimal in 10-vol%-ZrO₂-containing material. Both materials were superplastically stretched under biaxial tension to 100% engineering strain with good surface finishing, demonstrating the feasibility of superplastic forming for alumina ceramics.     

Experimental Assessment of Plasticity of Nanocrystalline 1.7 mol% Yttria Tetragonal Zirconia Polycrystals

High temperature mechanical behavior of nanocrystalline 1.7 mol% (3 wt%) yttria tetragonal zirconia polycrystals (nc-YTZP) was characterized by compression creep tests. The hot isostatically pressed nc-YTZP with mean grain size of 120 nm was subjected to grain growth to obtain grain sizes in the range of 120–310 nm. Direct measurements of the creep parameters were performed in the temperature range 1150°–1300°C and stress range 5–400 MPa. The strain rates at 1150°C ranged between 2 × 10⁻⁷ and 9 × 10⁻⁵ s⁻¹ when increasing the stress from 15 to 400 MPa. Values of the stress exponent, n =2.0±0.3, and the activation energy, Q =630±40 kJ/mol, were obtained for all test conditions. A value of the grain size exponent, p =1.5±0.3, was obtained at 1150°C in the stress range studied. Detailed microstructural observations revealed the absence of glassy phase at the grain boundaries. The creep parameters were compared with those from the literature, and the results were discussed in terms of the model recently developed by the authors, with a reasonable agreement.     

Intergranular Fracture of Lithium Fluoride–22% Calcium Fluoride Hypereutectic Salt at 800 K

Constant-velocity compression tests were conducted at 800 K on as-cast LiF-22 mol% CaF₂ hypereutectic salt with engineering strain rates varying between 1.8 × 10⁻⁶ and 2.3 × 10⁻¹ s⁻¹. Considerable stain hardening was observed during the initial stages of deformation, and the true stress-strain curves exhibited maxima. Plots of the true strain rate against the flow stress at the proportional limit and the peak stress exhibited a power-law relation with stress exponents of 7.7. Microstructural examination of the deformed specimens showed extensive grain-boundary cracking and cavitation. These results suggest that grain-boundary cracking and interfacial sliding is important for cavity nucleation at the grain boundaries and at the LiF-CaF₂ interfaces, and cavity growth and interlinkage, which appear to depend on the morphological differences between different grain boundaries, occur through the preferential failure of the weaker LiF phase.     

Superplastic Deformation in Fine-Grained YBa2Cu3O7−x

The superplastic behavior of YBa₂Cu₃O_{7− x} ceramic superconductors was studied. Large compressive deformation over 100% strain was measured in the temperature range of 775°–875°C, with a strain rate of 1 × 10⁻⁵ to 1 × 10⁻³/s, and a grain size of 0.5–1.4 μm. The nature of the deformation was investigated in terms of three deformation parameters: the stress exponent ( n ), the grain size exponent ( p ), and the activation energy ( Q ). The measured values of these parameters were n = 2 ± 0.3, p = 2.7 ± 0.7, and Q = 745 ± 100 kJ/mol. With the aid of the deformation map, the deformation mechanism was identified as grain boundary sliding accommodated by grain boundary diffusion. The conclusion is consistent with the microstructural observations made by SEM and TEM: the invariance of equiaxed grain shape, the absence of significant dislocation activity, no grain boundary second phases, and no significant texture development.     

Superplasticity of Liquid-Phase-Sintered β-SiC with Al2O3–Y2O3–AlN Additions in an N2 Atmosphere

Compression and tension tests were performed on liquid-phase-sintered β-SiC fabricated by hot-pressing, using ultrafine powders, at 1973–2048 K in an N₂ atmosphere. Amorphous phases were observed at the grain boundaries and at multigrain junctions in the as-sintered material. Strain hardening was observed under all experimental conditions. Stress exponents in the compression test were 1.7–2.1 in the temperature range 1973–2023 K. A maximum tensile elongation of 170% was achieved at the initial strain rate of 2 × 10⁻⁵ s⁻¹ at 2048 K.     

Microstructural and Thermoelectric Characteristics of Zinc Oxide-Based Thermoelectric Materials Fabricated Using a Spark Plasma Sintering Process

M-doped zinc oxide (ZnO) (M=Al and/or Ni) thermoelectric materials were fully densified at a temperature lower than 1000°C using a spark plasma sintering technique and their microstructural evolution and thermoelectric characteristics were investigated. The addition of Al₂O₃ reduced the surface evaporation of pure ZnO and suppressed grain growth by the formation of a secondary phase. The addition of NiO promoted the formation of a solid solution with the ZnO crystal structure and caused severe grain growth. The co-addition of Al₂O₃ and NiO produced a homogeneous microstructure with a good grain boundary distribution. The microstructural characteristics induced by the co-addition of Al₂O₃ and NiO have a major role in increasing the electrical conductivity and decreasing the thermal conductivity, resulting from an increase in carrier concentration and the phonon scattering effect, respectively, and therefore improving the thermoelectric properties. The ZnO specimen, which was sintered at 1000°C with the co-addition of Al₂O₃ and NiO, exhibited a ZT value of 0.6 × 10⁻³ K⁻¹, electrical conductivity of 1.7 × 10⁻⁴Ω⁻¹·m⁻¹, the thermal conductivity of 5.16 W·(m·K)⁻¹, and Seebeck coefficient of −425.4 μV/K at 900°C. The ZT value obtained respects the 30% increase compared with the previously reported value, 0.4 × 10⁻³ K⁻¹, in the literature.     

Sintering of Zinc Sulfide

The mechanisms of the sintering of ZnS were determined by measurement of the rate of growth of the necks between polycrystalline spheres. In vacuum (10⁻⁶ mm Hg) at temperatures higher than 600° C the mechanism of sintering is that of volume diffusion with coefficient D_v, = 1.06 × 10⁻² exp (-26,400/RT); below 600°C surface diffusion predominates, with coefficient D₃, = 9.14 × 10_-3 exp (-5700/RT). In Zn vapor (10⁻² mm Hg) between 550° and 650°C the predominating mechanism of sintering is surf ace diffusion, D₃, = 7.06 × 10⁻² exp (-8600/RT). It has been found that in an argon atmosphere the diffusion coefficient is much lower.     

Effect of Oxygen Partial Pressure During Liquid-Phase Sintering on the Dielectric Properties of 0.9MgTiO3–0.1CaTiO3

Microstructural evolution and microwave dielectric properties of liquid-phase-sintered 0.9MgTiO₃–0.1CaTiO₃ dielectric ceramic material have been investigated as a function of oxygen partial pressure (     ) during sintering. Sintering in a weakly reducing atmosphere (     =10⁻¹⁴ atm) generally increased the density, permittivity, quality factor ( Q × f ), and the temperature coefficient of resonance frequency (τ_f), but further reducing atmosphere down to     of 10⁻¹⁴ atm generally decreased Q × f and τ_f. When the 5 wt% lithium borosilicate glass-added specimen was sintered at 950°C and     =10⁻¹⁴ atm, it demonstrated a permittivity of 18.8, Q × f of 19 000 GHz, and τ_f of 10 × 10⁻⁶ K⁻¹.     

Strain-Rate-Dependent Transformation Behavior of a 9 mol% Ce-TZP Ceramic

The strain rate dependence of the stress-induced t–m transformation behavior of a Ce-TZP ceramic with a grain size of 1.1 μm has been investigated both in four-point bend and Charpy impact tests. The crosshead speed was varied from 8.3 × 10⁻⁸ m/s to 8.3 × 10⁻³ m/s in the four-point bend tests. In the impact tests, the striking velocity was 2.5 m/s. Double notches ( a/w = 0.5) were made on one side of the specimen to measure the stress-induced t–m transformation zone size at the nonpropagated notch tip. It was found that a transition of the transformation zone size with crosshead speed occurred at about 10⁻⁶ to 10⁻⁵ m/s. Above this critical speed, the transformation zone was at least an order of magnitude larger in size. This new strain-rate-dependent transformation behavior has not been previously reported.     

Mechanical and Fretting Wear Behavior of Novel (W,Ti)C–Co cermets

In an effort to refine the composition and properties of existing hard metals, (W,Ti)C–20 wt% Co cermets have been developed. The present research reports the mechanical and tribological properties of these novel materials. Single-step as well as two-stage and three-stage sintering experiments were conducted on the cermets, processed from the (W,Ti)C solid solution powders. For property comparison, premixed WC/TiC powders were used to fabricate a reference (W,Ti)C–20 wt% Co cermet material. Higher sintered density (9.57 g/cm³) as well as better elastic modulus (467 GPa) and hardness (∼17 GPa) were obtained after three-stage sintering of solid solution powders. In order to evaluate the tribological properties, the fretting wear experiments (mode I, linear relative tangential displacement) were performed against bearing steel for varying normal load in the range of 2–10 N. The experimental results reveal that the steady-state coefficient of friction (COF) varies between 0.50 and 0.65, and a lower COF is recorded at 10 N load for cermets processed from solid solution powders. Under varying tribological conditions, the cermets sintered from solid solution powders exhibit low wear depth (∼1–4 μm) and lower wear rate (7 × 10⁻⁷–18 × 10⁻⁷ mm³·(N·m)⁻¹ when compared with cermet prepared from the premixed WC/TiC starting powders (wear rate ∼14 × 10⁻⁷–22 × 10⁻⁷ mm³·(N·m)⁻¹). The wear rate data are critically evaluated based on the phenomenological models. Broadly, abrasive wear is the dominant wear mechanism, and limited contribution from localized spalling of tribolayer and tribochemical wear was also observed.     

Vapor Pressure of Barium and Copper Components in YBa2Cu3O7−x Superconductor Ceramics

Purified air is passed over a specimen of YBa₂Cu₃O_{7– x} at 890°C; the vaporized substances are condensed in a pure alumina tube, then subjected to inductively controlled plasma analysis. Vapor pressure values of 2.5 × 10⁻⁵ Pa for BaO( g ), 1.2 × 10⁻⁴ Pa for Cu( g ), and 2.2 × 10⁻⁵ Pa for CuO( g ) are obtained under 2.1 × 10⁴ Pa (0.21 bar) of oxygen pressure. No Y vapor is detected at this temperature.     

Piezoelectric Properties of PZT-Based Ceramic with Highly Aligned Pores

Porous lead zirconate titanate–lead zinc niobate (PZT–PZN) piezoelectric ceramics with a high degree of pore alignment were fabricated using directional freeze casting of a ceramic/camphene slurry. Well-aligned pores were formed as the replica of the camphene dendrites that grew in a preferential orientation, while a high porosity of 90% was achieved by employing a low initial solid loading of 5 vol%. As the orientation angle of the pores to the poling direction was decreased, the hydrostatic piezoelectric properties, such as hydrostatic piezoelectric strain coefficient ( d _h), the hydrostatic piezoelectric voltage coefficient ( g _h), and the hydrostatic figure of merit, increased significantly. The sample containing pores aligned parallel to the poling direction showed an extremely high HFOM of 161019 × 10⁻¹⁵ Pa⁻¹, which was ∼1300 times higher than that (124 × 10⁻¹⁵ Pa⁻¹) of the dense sample, owing to the presence of aligned pores.     

Superplastic Deformation of Zinc Sulfide Near Its Transformation Temperature [1020°]

Polycrystalline ZnS was deformed in compression to large strains (up to 100%), near its α⇄β transformation temperature (1020°), at strain rates that ranged from 10⁻⁵ to 3 × 10⁻³ s⁻¹. The flow stress showed a minimum near 1020°. The strain rate sensitivity and the grain size dependence of the flow stress suggest a superplastic mechanism of deformation. There was some evidence of dynamic recrystallization and stress-induced β (fcc) to α (hcp) phase transformation. The polycrystals had a tendency to form in tergranular cavities at the higher temperatures and at faster strain rates.     

Sinter-Forging of Nanocrystalline Zirconia: II, Simulation

A quantitative computer simulation of densification, pore-size evolution, and grain growth during sinter-forging has been developed and applied to the sinter-forging of nanocrystalline yttria (30 mol%)-stabilized zirconia (3Y-TZP) at 1050° and 1100°C. Densification is simulated as a superposition of stress-assisted and plastic-strain-controlled pore-shrinkage mechanisms. Grain growth is simulated as a pore-controlled process during intermediate-stage densification and as a combination of normal (static) grain growth and dynamic grain growth during final-stage densification. The densification portion of the model offers very good agreement with the experiment under a wide variety of imposed forging conditions, despite the absence of adjustable variables. Grain-growth predictions qualitatively illustrate a key feature in the sinter-forging of 3Y-TZP: i.e., the minimization of grain size, as a function of density, under forging conditions that promote high strain rates. This particular effect seems to be due to the quick elimination of large pores by plastic strain while small pores (which shrink by diffusion) are still available to control grain growth.     

Characterization of Material for Low-Temperature Sintered Multilayer Ceramic Substrates

The sintering temperature of multilayer ceramic substrates must decrease to 1000° or below to avoid melting the conductors (Pd-Ag, Au, or Cu) during sintering. In this study, SiO₂, CaO, B₂O₃, and MgO were used as additives to Al₂O₃ to decrease the firing temperature by liquid-phase sintering. Compositions with 18.0 and 22.5 wt% B₂O₃ were sintered at around 1000° in an air atmosphere to yield dense ceramics with good properties: relative dielectric contant between 6 to 7 (1 MHz), tan δ≤× 3 × 10⁻⁴ (1 MHz), insulating resistivity > 10¹⁴ω cm, coefficient of thermal expansion ∼ 7.0 × 10⁻⁶/°, and thermal conductivity ∼ 4.1 W/(m · K).     

Properties of Highly Porous Hydroxyapatite Obtained by the Gelcasting of Foams

Open-cell hydroxyapatite (HA) foams, produced through the novel technique of gelcasting foams with relative porosities ranging from 0.72 to 0.90, were characterized for pore-size distribution, surface area, permeability, compressive strength, elastic modulus, and microstructural features. The porous structure, which is composed of an array of spherical cells interconnected through windows, had a mode pore diameter in the range 17–122 μm, as demonstrated by mercury porosimetry. The BET specific surface area increased from 1.5 to 3.8 m²/g as the sample porosity increased. The compressive strength and elastic modulus were in the range 1.6–5.8 MPa and 3.6–21.0 GPa, respectively. The permeability constants, k ₁ (Darcian) and k ₂ (non-Darcian), were strongly dependent on porosity fraction and varied widely, from 1.22 × 10⁻¹¹ to 4.31 × 10⁻¹⁰ m² and from 1.75 × 10⁻⁶ to 8.06 × 10⁻⁵ m, respectively. This combination of properties make the HA foams suitable for a variety of potential applications in the biomedical field, preferentially nonloading, including materials for bone repair, carriers for controlled drug-delivery systems, and matrixes for tissue engineering.