Constrained Densification of Alumina/Zirconia Hybrid Laminates, I: Experimental Observations of Processing Defects

Various forms of damage were observed in pressure-less-sintered Al₂O₃/ZrO₂symmetric laminates and asymmetric laminates (bilayers) fabricated by tape casting and lamination. These defects included channel cracks in the ZrO₂ layers, Al₂O₃ edge-effect cracks parallel to the layers, delamination in the Al₂O₃layers, and debonding between the Al₂O₃and ZrO₂layers. Based on detailed microscopic observations, the defects were attributed to sintering rate and thermal expansion mismatch between the layers. Cracks or cracklike defects were formed in the early stages of densification, and these cracks either opened during sintering or acted as preexisting flaws for thermal expansion mismatch cracks. Consequently, the extent of cracking could be reduced or even eliminated by decreasing mismatch stresses during the sintering and cooling stages. This can be accomplished by reducing the heating and/or cooling rates or by adding Al₂O₃in the ZrO₂layers. The sintering mismatch stresses were estimated from the degree of curling in asymmetric laminates and from layer viscosities that were obtained by cyclic loading dilatometry. The measured curvature was an indication of the mismatch in sintering strain between Al₂O₃and ZrO₂and were consistent with the dilatometric data that were obtained for the component layers.     

Determination of the Mechanical Response of Sintering Compacts by Cyclic Loading Dilatometry

Determination of the mechanical response of a powder compact during densification is critical in analyzing defect formation and macroscopic dimensional changes, particularly in systems where constrained sintering is involved. Cyclic loading dilatometry is proposed as a novel approach in evaluating the mechanical response of the sintering compact, including sintering pressure, elastic modulus, and viscosity. The advantage of this technique is that only one experiment is needed to determine the equilibrium elastic and viscous properties of a sintering material at any temperatures for any given heating schedule, and no interrupted tests are necessary. This methodology is demonstrated for sintering compacts of Al₂O₃, Ce-TZP, and their composite mixture. The loading dilatometric data showed that the compact behaved elastically prior to the onset of sintering and during the very initial stages of sintering, which was followed by a transition leading to a viscous behavior for the latter part of the densification. Application of different load levels, ranging from 0.25 to 1 MPa, showed that the compact viscosity is essentially linear within the applied stress range at temperatures greater than 1100°C.     

Effect of Crystallization on the Stress Required for Constrained Sintering of CaO–B2O3–SiO2 Glass–Ceramics

The effect of crystallization on the stress required for complete constrained sintering of a low-temperature cofirable CaO–B₂O₃–SiO₂ glass–ceramics has been investigated under uniaxial constant and cyclic loading. As the formation of crystalline phase of wollastonite (CaSiO₃) increases, the uniaxial viscosity of the porous glass–ceramics during firing increases. Moreover, the required uniaxial stress to have complete constrained sintering, i.e., zero strain or strain rate at the perpendicular directions, is in the range of 80–180 kPa, which shows no significant dependence on heating rate and firing temperature. The measured data of required stress are close to those calculated using the viscous analogy for the constitutive relationship of a porous sintering compact.     

Sintering Kinetics at Constant Rates of Heating: Effect of Al2O3 on the Initial Sintering Stage of Fine Zirconia Powder

The sinterabilities of fine zirconia powders including 5 mass% Y₂O₃ were investigated, with emphasis on the effect of Al₂O₃ at the initial sintering stage. The shrinkage of powder compact was measured under constant rates of heating (CRH). The powder compact including a small amount of Al₂O₃ increased the densification rate with elevating temperature. The activation energies at the initial stage of sintering were determined by analyzing the densification curves. The activation energy of powder compact including Al₂O₃ was lower than that of a powder compact without Al₂O₃. The diffusion mechanisms at the initial sintering stage were determined using the new analytical equation applied for CRH techniques. This analysis exhibited that Al₂O₃ included in a powder compact changed the diffusion mechanism from grain boundary to volume diffusions (VD). Therefore, it is concluded that the effect of Al₂O₃ enhanced the densification rate because of decrease in the activation energy of VD at the initial sintering stage.     

Liquid-Phase Sintering of MgO–Bi2O3

Liquid-phase sintering of MgO-5 wt% Bi₂O₃ was studied by loading dilatometry. The ratio of the creep viscosity to the densification viscosity (∼1.8) and the sintering stress remained nearly constant in a wide density interval. These results, together with results on several other systems, indicate that the constancy of the sintering stress during densification may be a general phenomenon, regardless of densification mechanism.     

Rapid Rate Sintering of Nanocrystalline ZrO2−3 mol% Y2O3

Conventional ramp-and-hold sintering with a wide range of heating rates was conducted on submicrometer and nanocrystalline ZrO₂–3 mol% Y₂O₃ powder compacts. Although rapid heating rates have been reported to produce high density/fine grain size products for many submicrometer and smaller starting powders, the application of this technique to ZrO₂–3 mol% Y₂O₃ produced mixed results. In the case of submicrometer ZrO₂–3 mol% Y₂O₃, neither densification nor grain growth was affected by the heating rate used. In the case of nanocrystalline ZrO₂–3 mol% Y₂O₃, fast heating rates severely retarded densiflcation and had a minimal effect on grain growth. The large adverse effect of fast heating rates on the densification of the nanocrystalline powder was traced to a thermal gradient/differential densification effect. Microstructural evidence suggests that the rate of densification greatly exceeded the rate of heat transfer in this material; consequently, the sample interior was not able to densify before being geometrically constrained by a fully dense shell which formed at the sample exterior. This finding implies that rapid rate sintering will meet severe practical constraints in the manufacture of bulk nanocrystalline ZrO₂–3 mol% Y₂O₃ specimens.     

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 Rigid Inclusions on the Densification and Constitutive Parameters of Liquid-Phase-Sintered YBa2Cu3O6+x Powder Compacts

The presence of rigid inclusions in a powder compact leads to a reduction in the densification rate of the compact and may also lead to processing defects. In this paper, the densification rate and the constitutive parameters of both homogeneous YBa₂Cu₃O_{6+ x} and composite powder compacts (YBa₂Cu₃O_{6+ x} powder with 10 vol% dense inclusions of YBa₂Cu₃O_{6+ x} ) are reported. A small amount of liquid phase, which formed during sintering, was present in the samples. However, even with the presence of a liquid phase, the addition of inclusions still reduces the densification rate of the composite and increases its viscosity. The results have been compared with a published analysis of the problem using measured values of the constitutive parameters. Both the viscosity and viscous Poisson's ratio of the porous body have been measured.     

Rapid Densification and Deformation of Li-Doped Sialon Ceramics

Two lithium-doped sialon ceramics were densified and superplastically deformed by spark plasma sintering (SPS). Rapid densification with linear shrinkage rates of approximately 5 × 10⁻³ s⁻¹ were observed for samples heated at a rate of 100°C/min up to ∼1400°C under a uniaxial pressure of 40 MPa. Isothermal deformation by SPS-preprepared, fully densified ceramics performed at T ≥ 1450°C yielded strain rates in the order of 10⁻² s⁻². It is suggested that a high heating rate promotes material transport via formation of a nonequilibrated oxygen-rich liquid of low viscosity. This finding most likely holds true for other liquid-phase sintered ceramics as well and has implications for cost-effective manufacturing of ceramic components.     

Formation of a High-Temperature Liquid Phase During the Sintering of PbFe2/3W1/3O3

A high-temperature liquid phase (rather than a low-temperature liquid phase at 690°C as reported recently) has been demonstrated to form at 860°C on heating and to solidify at 840°C on cooling in PbFe_2/3O₃. This liquid phase not only promotes densification, but also induces the formation of rounded PbFe_2/3W_1/3O₃ grains during sintering at 870°C. Through slow cooling at a rate of 25°C/h after sintering, platelike grains, designated G phase, are found to form in a thin surface layer of specimens. This formation of platelike G phase is considered to be related to the solidification and recrystallization of the liquid phase exuded from the interior. The amount of the G phase on the surfaces decreases with the increase of cooling rates, indicating that fast cooling will lead the liquid phase to be solidified in the bulk of specimens. These results reveal that the microstructure of PbFe_2/3W_1/3O₃ is greatly affected by the high-temperature liquid phase; additionally, the slow cooling treatment seems to be a direct and effective method for removing the residual liquid phase from PbFe_2/3W_1/3O₃.     

Sinter-Forging of Nanocrystalline Zirconia: I, Experimental

Nanocrystalline (15 nm) yttria (3 mol%)-stabilized zirconia (3Y-TZP) was sinter-forged under conditions of varying temperature (1050–1200°C), plastic strain rate (5 × 10⁻⁵ to 2 × 10⁻³s⁻¹), and green density (33–48%), using constant-crosshead-speed tests, constant-load (i.e., load-and-hold) tests, and constant-loading-rate tests. The densification and pore size evolution results indicate that plastic strain is largely responsible for elimination of large pores, while diffusional mechanisms control the elimination of small pores. Grain growth during sinter-forging is observed to be dependent solely on porosity during intermediate-stage sintering. Once the powder compact enters final-stage sintering, however, both static (time- and temperature-dependent) and dynamic (plastic-strain-dependent) grain growth take place, greatly accelerating the overall rate of grain growth. The use of fast strain rates to impose plastic strain before the onset of dynamic grain growth is proposed as a method of preserving small grain sizes during sinter-forging.     

Effect of Cobalt(II) Oxide and Manganese(IV) Oxide on Sintering of Tin(IV) Oxide

Additions of 0. 5 to 2. 0 mol% of CoO or MnO₂ onto SnO₂ promote densification of this oxide up to 99% of theoretical density. The temperature of the maximum shrinkage rate ( T_M ) and the relative density in the maximum densification rate (p*) during constant sintering heating rate depend on the dopant concentration. Thus, dopant concentration controls the densifying and nondensifying mechanisms during sintering. The densification of SnO₂ witih addition of CoO or MnO₂ is explained in terms of the creation of oxygen vacancies.     

Nickel–Boron Nanolayer-Coated Boron Carbide Pressureless Sintering

Sintering of pure B₄C and Ni₂B nanolayer-coated B₄C was studied from 1300° to 1600°C, with the holding time at the peak temperatures being 2 or 10 h. Compacts were made by uniaxial die compaction and combustion-driven compaction. Pure B₄C sample shows less sintering at all conditions. Ni₂B-coated B₄C sample shows more extensive densification, neck formation, and grain shape accommodation. The combustion driven compaction process accelerates sintering by offering higher green density to start with. The Ni₂B species on the B₄C particle surfaces melts into a nickel–boron-containing liquid phase during heating, remains as liquid during sintering, and then transforms into Ni₄B₃ and NiB during cooling. High-resolution composition analysis shows that there is no nickel diffusion into bulk B₄C during the sintering process. However, there is boron diffusion into the Ni₂B coating layer. Carbon diffusion cannot be directly measured but is believed to be a simultaneous process as boron diffusion. A multievent sintering process has been proposed to explain the observations.     

Viscous Flow as the Driving Force for the Densification of Low-Temperature Co-Fired Ceramics

Filled glass–ceramic composites, like low-temperature co-fired ceramics (LTCC), must densify at temperatures <900°C. The densification mechanism of LTCC is often described by liquid-phase sintering. The results of this paper clearly show that densification of ceramic-filled glass–composites with a glass content above 60 wt% can be attributed to viscous sintering, which is decisively controlled by the viscosity of the glass during the heat treatment. This is demonstrated by the experimental determination of the viscosity of a MgO–Al₂O₃–B₂O₃–SiO₂ glass dependent on temperature, by investigation of the wetting behavior of the glass on the ceramic filler mullite, and of the microstructural development. It was found that the glass does not wet the filler material in a temperature range up to 1000°C. Therefore, liquid-phase sintering can be excluded. Independent of any wetting effect and therefore in the absence of capillary forces, densification starts at a temperature of 750°C, which corresponds to a viscosity of 10^9.5 dPa·s. This densification can be attributed to viscous flow of the glass matrix composite.     

Effects of Porosity on the Threshold Strength of Laminar Ceramics

Ceramic laminates exhibiting a threshold strength have been fabricated by dip-coating thick tape-cast Al₂O₃ layers into slurries containing mixtures of Al₂O₃ and either unstabilized zirconia (MZ-ZrO₂) or mullite to produce thin compressive layers via both a molar volume change and a differential thermal contraction. Porosity was introduced into the thin compressive layers by adding rice starch to the dip-coating slurries, which decomposed during densification of the laminate. As the volume fraction of porosity is increased, the residual compressive stress (σ_C), as measured by piezospectroscopy, is reduced and approaches zero at approximately 0.65 volume fraction of porosity. The elastic modulus mismatch ( E ₁/ E ₂) between the thin and thick laminate layers accounted for approximately one-half of the threshold strength for volume fractions of porosity ≤ 0.30 ( E ₁/ E ₂<0.4). Above 0.40 volume fraction of porosity, the strength significantly increased as did the scatter in strength values, and it was observed that the highly porous layers completely arrested crack extension; these materials no longer exhibited a threshold strength. For these laminates, failure occurred by the independent, sequential failure of one layer after another, followed by catastrophic failure due to delamination.     

Residual stresses in alumina–zirconia laminates

Significant residual stresses can arise in hybrid ceramic laminates during the densification and cooling processing cycles. The densification stresses in alumina–zirconia laminates were calculated assuming the layers to be linear viscous with data obtained by cyclic loading dilatometry. These stresses placed the zirconia layers in biaxial tension and even at 1 MPa or less, they were sufficient to cause a type of linear cavitation damage. The methodology was also applied to asymmetric laminates, successfully predicting their observed curling behaviour. Thermal expansion mismatch stresses arise during cooling, again placing the zirconia layers in residual biaxial tension and leading to the formation of transverse (channelling) cracks. The stresses were calculated using both elastic and viscoelastic formulations and were confirmed with indentation measurements. Additions of alumina to the zirconia layers were effective in reducing both sources of residual stress and allowed crack formation during processing to be avoided. Residual stresses were also shown to improve mechanical performance.     

Very Rapid Densification of Nanometer Silicon Carbide Powder by Pulse Electric Current Sintering

Rapid densification of a nanometer SiC powder doped with 2.04 wt% Al₄C₃ and 0.4 wt% B₄C was conducted by using a nonconventional sintering technique called pulse electric current sintering (PECS). In all experiments, the sintering temperature and applied pressure were kept to be 1600^oC and 47 MPa, respectively, while heating rates varied between 100^oC/min and 400^oC/min and the holding time was either 2 or 5 min. All of the specimens which were PECS-sintered under various conditions reached near-theoretical density. The microstructures of the rapidly densified SiC ceramics consisted of large elongated grains, and the grain size increased with the increase of heating rate. Polytype transformation of SiC occurred during the PECS process, where faster heating favored the formation of 6H polytype while slower heating favored 4H polytype.     

Processing of Tape–Cast Laminates Prepared from Fine Alumina/Zirconia Powders

This paper addresses the effect of thermocompression pressure, shear deformation of green laminates, and postsinter HIPing on the microstructural homogeneity of cast tapes and laminates prepared from fine Al₂O₃, and Al₂O₃/ ZrO₂, powders. Green density increases with increasing thermo–compression pressure. Sintered densities, however, depend more on the macroscopic uniformity in the green tapes. When density gradients develop within the individual green tapes (because of improper drying), sintering is constrained in two dimensions and densities remain low. Postsinter HIPing does not significantly increase the sintered densities because of the retention of open porosity within the individual tape–cast layers. The use of a revised thermocompression process involving shear deformation results in higher sintered densities and complete densification after HIPing. Sintered densities increase with the degree of shear strain during green–state deformation processing. Thus, green-state deformation can improve homogeneity in laminates. A further variation of the shear deformation process has also been developed that allows the formation of complex shapes from tape–cast laminates in the green state, while retaining layer integrity.     

Densification of Nanocrystalline Yttria by Low Temperature Spark Plasma Sintering

We investigated the densification of undoped, nanocrystalline yttria (Y₂O₃) powder by spark plasma sintering (SPS) at sintering temperatures between 650°C and 1050°C at a heating rate of 10°C/min and an applied stress of 83 MPa. In spite of the low sinterability of the undoped Y₂O₃, a remarkable densification of the powder started at about 600°C, and a theoretical density of more than 97% was achieved at a sintering temperature of 850°C with a grain size of about 500 nm. The low temperature SPS is effective for fabricating dense Y₂O₃ polycrystals.     

Sintering of Nanophase γ-Al2O3 Powder

The sintering of ultrafine γ-Al₂O₃ powder (particle size ∼10–20 nm) prepared by an inert gas condensation technique was investigated in air at a constant heating rate of 10°C/min. Qualitatively, the kinetics followed those of transition aluminas prepared by other methods. Measurable shrinkage commenced at ∼ 1000°C and showed a region of rapid sintering between ∼1125° and 1175°C followed by a transition to a much reduced sintering rate at higher temperatures. Starting from an initial density of ∼0.60 relative to the theoretical value, the powder compact reached a relative density of 0.82 after sintering to 1350°C. Compared to compacts prepared from the as-received powder, dispersion of the powder in water prior to compaction produced a drastic change in the microstructural evolution and a significant reduction in the densification rate during sintering. The incorporation of a step involving the rapid heating of the loose powder to ∼1300°C prior to compaction (which resulted in the transformation to α-Al₂O₃) provided a method for significantly increasing the density during sintering.