Effect of MgO Solute on Microstructure Development in Al2O3

The effect of MgO as a solid-solution additive in the sintering of Al₂O₃ was studied. The separate effects of the additive on densification and grain growth were assessed. Magnesia was found to increase the densification rate during sintering by a factor of 3 through a raising of the diffusion rate. The grain-size dependence of the densification rate indicated control primarily by grain-boundary diffusion. Magnesia also increased the grain growth rate during sintering by a factor of 2.5. The dependence of the grain growth rate on density and grain size suggested a mechanism of surface-diffusion-controlled pore drag. It was argued, therefore, that MgO enhanced grain growth by raising the surface diffusion coefficient. The effect of MgO on the densification rate/grain growth rate ratio was, therefore, found to be minimal and, consequently, MgO did not have a significant effect on the grain size/density trajectory during sintering. The role of MgO in the sintering of alumina was attributed mainly to its ability to lower the grain-boundary mobility.     

An Experimental Measurement of Effective Diffusion Distance for the Sintering of Ceramics

The traditional models of sintering predict a pronounced dependence of densification rate on the scale of the microstructure as measured by the grain size. This study evaluates the grain size exponent for densification during isothermal sintering of an aggregated nanocrystalline zirconia powder, and for a submicrometer alumina powder. The results gave grain size exponents that are much higher than those anticipated for the expected sintering mechanisms. Furthermore, microstructural analysis showed that this overestimate of the exponent could be due to the spatial heterogeneity in the microstructure on the scale of the diffusion distance. To assess this issue, pore boundary tessellation was used to determine a new measurement of effective diffusion distance that takes into account the local spatial arrangement of pores. This measurement gives exponents much closer to those expected for the sintering of tetragonal zirconia by volume diffusion, and for the sintering of the alumina by grain-boundary diffusion.     

Effect of Yttrium and Lanthanum on the Final-Stage Sintering Behavior of Ultrahigh-Purity Alumina

Final-stage sintering has been investigated in ultrahigh-purity Al₂O₃ and Al₂O₃that has been doped individually with 1000 ppm of yttrium and 1000 ppm of lanthanum. In the undoped and doped materials, the dominant densification mechanism is consistent with grain-boundary diffusion. Doping with yttrium and lanthanum decreases the densification rate by a factor of ˜11 and 21, respectively. It is postulated that these large rare-earth cations, which segregate strongly to the grain boundaries in Al₂O₃, block the diffusion of ions along grain boundaries, leading to reduced grain-boundary diffusivity and decreased densification rate. In addition, doping with yttrium and lanthanum decreases grain growth during sintering. In the undoped Al₂O₃, surface-diffusion-controlled pore drag governs grain growth; in the doped materials, no grain-growth mechanism could be unambiguously identified. Overall, yttrium and lanthanum decreases the coarsening rate, relative to the densification rate, and, hence, shifted the grain-size-density trajectory to higher density for a given grain size. It is believed that the effect of the additives is linked strongly to their segregation to the Al₂O₃grain boundaries.     

Effect of Pore Distribution on Microstructure Development: III, Model Experiments

Model experiments have been conducted on a series of alumina samples in which the microstructures have been tailored to conform to the classical configuratins depicted in the models of final-stage sintering. Simultaneous measurements of sintered density, grain size, pore number density, and pore size distribution were made as a function of sintering time at constant temperature (1850°C). The data supported a model of grain-boundary-diffusion-controlled densification and surface-diffusion-controlled grain growth. An atom flux equation for grain-boundary diffusion transport was deduced from the data. The kinetics analysis highlights the importance of incorporating the number of pores per grain as an independent variable in mechanistic studies of final-stage sintering. The number of pores per unit volume was identified as a critical factor influencing densification kinetics. The effect of pore distribution on microstructure development was simulated for comparison with the data obtained from the model experiments.     

Sintering of Ultrafine Silicon Powder

The sintering behavior of compacts of ultrafine silicon powder (0.02 to 0.1 μm particle size) was investigated. Two sintering modes occur: normal sintering associated with densification and subnormal sintering without densification. The micro-structure developed in normal sintering has a fine grain size (0.05 to 0.3 μm) and fine porosity; the grains contain stacking faults and twins. The microstructure developed in subnormal sintering exhibits larger grains (∼1 μm in size) and coarse pores. Green densities >42% of theoretical and temperatures >1100°C are required for densification. Densification follows an exponential time and temperature dependence with an activation energy of 470 kJ/mol, indicating bulk diffusion as the transport mechanism. Grain-boundary diffusion is thought to be inhibited by grain-boundary oxide films. The carbon phase-separates into discrete amorphous regions and is thought to have little effect on sintering behavior.     

Surface Diffusivity under High-Pressure Gas

The sintering behavior of TiO₂ under high-pressure gas (100 MPa) was studied with respect to densification rate, decreasing rate of specific surface area, and narrowing rate of pore size distribution. At the low sintering temperature (800°C) used in this study, the densification rate under high- pressure gas was similar to that under low (i.e., 1 atm) pressure. The specific surface area decreased and the pore size distribution narrowed at a faster rate under high- pressure gas than under low-pressure gas. These results imply that high-pressure gas enhances surface diffusion.     

Constrained Sintering of Silver Circuit Paste

Densification kinetics and stress development during constrained sintering of a silver film on a rigid silicon substrate have been studied. Compared with free sintering, the sintering of constrained silver film exhibits a much lower densification and slower densification kinetics. The densification-controlled mechanism changes from fast grain-boundary diffusion kinetics for free sintering to slow lattice diffusion kinetics for constrained sintering. The in-plane tensile stress developed during constrained sintering of silver film, measured using a noncontact laser-scanning optical system, increases rapidly to a maximum level of 1.0–1.5 MPa initially, gradually decreases, and then becomes constant at 0.8–1.0 MPa. The maximum stress observed increases with increasing sintering temperature as a result of the faster densification rate. It is believed that the retardation of densification kinetics of constrained silver film is caused by a change in densification mechanism and the existence of in-plane tensile stress.     

Theory of the Dependence of Densification on Grain Growth During Intermediate-Stage Sintering

A semiempirical model for intermediate-stage sintering is developed based on simultaneously occurring volume and grain-boundary diffusion mechanisms of mass transport and explicitly incorporating the effects of grain growth. The sintering equation derived depends strongly on the reduction of pore number density associated with grain growth and is independent of the mechanism of grain growth. The time and temperature dependencies of densification predicted by the equation, which are tested using data for metal and ceramic powders, agree well with observations. The data indicate that grain-boundary diffusion contributes negligibly to densification.     

Sintering and densification of nanocrystalline ceramic oxide powders: a review

Abstract

Observation of the unconventional properties and material behaviour expected in the nanometre grain size range necessitates the fabrication of fully dense bulk nanostructured ceramics. This is achieved by the application of ceramic nanoparticles and suitable densification conditions, both for the green and sintered compacts. Various sintering and densification strategies were adopted, including pressureless sintering, hot pressing, hot isostatic pressing, microwave sintering, sinter forging, and spark plasma sintering. The theoretical aspects and characteristics of these processing techniques, in conjunction with densification mechanisms in the nanocrystalline oxides, were discussed. Spherical nanoparticles with narrow size distribution are crucial to obtain homogeneous density and low pore-to-particle-size ratio in the green compacts, and to preserve the nanograin size at full densification. High applied pressure is beneficial via the densification mechanisms of nanoparticle rearrangement and sliding, plastic deformation, and pore shrinkage. Low temperature mass transport by surface diffusion during the spark plasma sintering of nanoparticles can lead to rapid densification kinetics with negligible grain growth.     

Sintering Effects on the Porous Characteristics of Functionally Gradient Ceramic Membrane Structures

A method to drain cast porous ceramics has been conceived and established, where samples were shown to have a functionally gradient cross-section with a continuously increasing mean particle size between the two principal surfaces.Ceramic discs approximately 45 mm in diameter, and 3.3 mm thick were cast by sedimentation. These green bodies were dried prior to sintering. Maximum sintering temperature and the length of the sintering soak time were varied for samples made from suspensions of both 5 and 10 volume percent solids. Mercury porosimetry was used to obtain the porosity and pore size distribution in each sample. Additionally, a number of atomic force microscopy (AFM) measurements were made on some samples in order to correlate bulk porous properties with those on the outside surfaces.The results showed that as the sintering temperature increased, the densification of the bodies proceeded more rapidly. In general, the longer the sintering soak time, the denser the samples became as well. For the samples prepared at the lower temperatures however, the porosity showed less of a soak time dependence. The green body had a clustered and asymmetric microstructure, which contributed to differing degrees of localized densification and coarsening effects depending on the sintering temperature. Densification effects were more pronounced with the samples made from the more concentrated suspenisions.There was an inverse correlation between the bulk and surface pore dimensions, attributable to the different size scales of particles in the two regions. The much finer surface layer particles were able to undergo some amount of densification while surface diffusion sintering mechanisms were primarily at work elsewhere in the structure.     

Sintering forces acting among particles during sintering by grain-boundary/surface diffusion

The microstructural evolution during sintering involves the formation and pinch-off of pore channels. The sintering of 3 particles in 3 dimensions is a simple model for studying the pinch-off of a pore channel. We simulate the solid-state sintering of 3 particles by using Brakke's Surface Evolver program, which incorporates coupled grain-boundary diffusion and surface diffusion. The pinch-off of pore channel divides the sintering process into 2 stages; the initial stage and the later stage. The contact area has a noncircular shape bounded by both surface triple junction and triple junction in the later stage. A general method is presented to determine the sintering force acting on the noncircular contact. The mechanical approach of densification, where the relative motion of particles is driven by both sintering force and applied force, is applicable not only for the initial stage, but also for the later stage.     

Effect of Shear Stress on Sintering

The effect of small uniaxial stresses on the sintering of CdO powder compacts was studied using a loading dilatometer. Compacts of two different green densities were sintered at 1123 K and subjected to stresses between 0 and 0.25 MPa. Densification and creep occur simultaneously, and the effects of these two processes can be separated. Between relative densities of 0.5 and 0.9, the dependence of the uniaxial creep rate on density can be described in terms of a stress intensification factor which depends exponentially on the porosity but is independent of the grain size. Comparison of the densification and creep rates permits definition of the sintering stress, which is found to decrease with increasing density, and verification of the Zener relation. The stress and grain size dependence of the creep rate, and the grain size dependence of the densification rate, support grain-boundary diffusion as the rate-controlling step in both processes.     

Effects of ceramic types on evolution of micrometer-sized features during sintering

In this work, ZnO and ZrO₂ ridges with 2 μm size are created based on a centrifuge-aided micromolding approach and then sintered with different time. Characterization of feature morphology, fidelity, grain size, relative density, and linear shrinkage has been conducted. The densification mechanisms for both ZnO and ZrO₂ are controlled by grain-boundary diffusion, but their grain growth mechanisms are dominated by gas diffusion and surface diffusion respectively. The sintering behavior for the bulk can be described with a N_g/N_b factor at 36, while for the features, a smaller N_g/N_b factor (15 for ZnO and 8 for ZrO₂) is needed. Attributed to their sintering mechanism difference, the grains in the ZnO features have a faster growth rate than those in the bulk, while the grains in the ZrO₂ features have a similar growth rate to those in the bulk. ZnO has a much faster grain growth behavior, leading to ridge fidelity loss and severe ridge destruction, while ZrO₂ has a much slower grain growth rate, resulting in high ridge fidelity and strong resistance to ridge destruction.     

Fabrication of YAG transparent ceramics by two-step sintering

Yttrium aluminum garnet (YAG) nanopowders with mean particle size of about 50 nm synthesized by a modified co-precipitation method were used to sinter bulk YAG ceramic by two-step sintering method. Full densification was achieved by heating the sample up to 1800 °C followed by holding at 1550 °C for 10 h. Transparent YAG ceramics were obtained by suppressing grain-boundary migration while promoting grain-boundary diffusion during the two-step sintering process. The microstructure of the YAG ceramic is homogeneous without abnormal grain growth and the transmittance of the sintered sample is 43%.     

Densification and Grain Growth of Al2O3 Nanoceramics During Pressureless Sintering

α - Al₂O₃ nanopowders with mean particle sizes of 10, 15, 48, and 80 nm synthesized by the doped α-Al₂O₃ seed polyacrylamide gel method were used to sinter bulk Al₂O₃ nanoceramics. The relative density of the Al₂O₃ nanoceramics increases with increasing compaction pressure on the green compacts and decreasing mean particle size of the starting α-Al₂O₃ nanopowders. The densification and fast grain growth of the Al₂O₃ nanoceramics occur in different temperature ranges. The Al₂O₃ nanoceramics with an average grain size of 70 nm and a relative density of 95% were obtained by a two-step sintering method. The densification and the suppression of the grain growth are achieved by exploiting the difference in kinetics between grain-boundary diffusion and grain-boundary migration. The densification was realized by the slower grain-boundary diffusion without promoting grain growth in second-step sintering.     

On the modeling of the co2‐catalyzed sintering of calcium oxide

A comprehensive mathematical model for the CO₂‐catalyzed sintering of CaO is proposed. It takes into account the mechanisms of surface diffusion and grain boundary diffusion, catalyzed by CO₂ chemisorption and dissolution, respectively. In addition, the model proposed here considers the change in pore size distribution during sintering, grain growth, and the densification by lattice diffusion, which is the intrinsic sintering mechanism of the CaO. Model predictions are validated using experimental data on the sintering of two CaO samples, one of them derived from pure CaCO₃ and the other from limestone. It is found that impurities in limestone‐derived CaO do not significantly affect the CO₂ dissolution or chemisorption processes; however, they strongly increase the rate of sintering by lattice diffusion. It is also established that low temperatures and CO₂ partial pressures promote the coarsening by surface diffusion, whereas high temperatures and CO₂ partial pressures favor densification. © 2017 American Institute of Chemical Engineers AIChE J, 63: 3286–3296, 2017     

Sintering of Covalent Solids

The sintering behavior of primarily covalently bonded β-SiC, Si, and Si₃N₄ was studied using surface area and densification measurements as well as observations of microstructures developed during firing. The existence of highly dense, microscopic regions and large (≥100°) dihedral angles in fired compacts of β-SiC and Si which experience little macroscopic densification suggests that macroscopic densification is not intrinsically limited by the effects of surface energy. The mechanism proposed to explain the microstructure that develops in unsinterable covalent solids which do not undergo a phase change is based on the existence of a high ratio of surface and/or vapor-phase matter transport-to-volume and/or grain-boundary transport. The addition of boron to both β-SiC- and Si-containing carbon retards surface and/or vapor-phase transport and grain growth at lower temperatures, which results in enhanced densification at high temperatures. Macroscopic densification of β-SiC and α-Si₃N₄ can also be retarded by the formation of a continuous network of high-aspect-ratio grains of the polymorphic form that rigidities the sintering body. Finally, the sintering of pure Si depends sensitively on particle size in the submicron range. Nearly theoretical density is achieved in Si powder of ∼0.06-μm size. This result suggests that other pure covalently bonded solids can also be sintered to high density without applied pressure.     

Computer Simulation of Final-Stage Sintering: I, Model Kinetics, and Microstructure

A Monte Carlo model for simulating final-stage sintering has been developed. This model incorporates realistic microstructural features (grains and pores), variable surface difusivity, grain-boundary diffusivity, and grain-boundary mobility. A preliminary study of a periodic array of pores has shown that the simulation procedure accurately reproduces theoretically predicted sintering kinetics under the restricted set of assumptions. Studies on more realistic final-stage sintering microstructure show that the evolution observed in the simulation closely resembles microstructures of real sintered materials over a wide range of diffusivity, initial porosity, and initial pore sizes. Pore shrinkage, grain growth, pore breakaway, and reattachment have all been observed. The porosity decreases monotonically with sintering time and scales with the initial porosity and diffusivity along the grain boundary. Deviations from equilibrium pore shapes under slow surface diffusion or fast grain-boundary diffusion conditions yield slower than expected sintering rates.     

Novel model for the sintering of ceramics with bimodal pore size distributions: Application to the sintering of lime

A mathematical model for the sintering of ceramics with bimodal pore size distributions at intermediate and final stages is developed. It considers the simultaneous effects of coarsening by surface diffusion, and densification by grain boundary diffusion and lattice diffusion. This model involves population balances for the pores in different zones determined by each porosimetry peak, and is able to predict the evolution of pore size distribution function, surface area, and porosity over time. The model is experimentally validated for the sintering of lime and it is reliable in predicting the so called “initial induction period” in sintering, which is due to a decrease in intra‐aggregate porosity offset by an increase inter‐aggregate porosity. In addition, a novel methodology for determination of mechanisms based on the analysis of the pore size distribution function is proposed, and with this, it was demonstrated that lattice diffusion is the controlling mechanism in the CaO sintering. © 2016 American Institute of Chemical Engineers AIChE J, 63: 893–902, 2017