Correlation between densification rate and microstructural evolution for pure alpha alumina

Correlation between microstructural evolution and macroscopic measurements has been investigated on pure alpha alumina under non-isothermal conditions. The densification of different as-received and milled powders of alumina has been monitored during sintering. Densification rate curves as a function of relative density are sensitive to microstructure, such as initial parameters of microstructure (agglomeration, pore size, heterogeneities), and heating schedule (thermal pre-treatment, heating rate). Densification rate curves can be correlated with microstructural evolution during overall sintering and are expected to be a good help to choose raw materials.     

Dimensionless Parameters for Microstructural Pathways in Sintering

Dimensionless parameters have been developed to study microstructural pathways for the sintering of powders. These parameters are designed to facilitate the comparison of microstructural paths for any sintering experiments, independent of the characteristic length scales in the microstructures. Microstructural pathways constructed with the dimensionless parameters are found to be similar for three different alumina ceramics. The systematic differences between the experimental results and the predictions of models based on simplifying geometric assumptions are explained in terms of the packing disruptions in the green microstructures.     

Combined-Stage Sintering Model

By focusing on the similarities between the three stages of sintering, a single equation is derived that quantifies sintering as a continuous process from beginning to end. The microstructure is characterized by two separate parameters representing geometry and scale. The dimensionless geometry parameter, denoted T, comprises five scaling factors that relate specific microstructural featuers (e.g., surface curvature) to the scale (grain diameter). Calculations of T from experimental data show (a) agreement with computer simulations of initial-stage sintering, (b) the effect of surface diffusion on T, and (c) changes in T with microstructural evolution during sintering. Application of the model to the design of firing schedules and the study of microstructural geometry effects on sintering is discussed.     

Progress in SiAlON ceramics

In view of the considerable progress that has been made over the last several years on the fundamental understanding of phase relationships, microstructural design, and tailoring of properties for specific applications of rare-earth doped SiAlONs, a clear review of current understanding of the basic regularities lying behind the processes that take place during sintering of SiAlONs is timely. Alternative secondary phase development, mechanism and full reversibility of the α′ to β′ transformation in relation with the phase assemblage evolution are elucidated. Reaction sintering of multicomponent SiAlONs is considered with regard of wetting behavior of silicate liquid phases formed on heating. Regularities of SiAlON's behavior and stability are tentatively explained in terms of RE element ionic radii and acid/base reaction principle.     

A Screening Design Approach for the Understanding of Spark Plasma Sintering Parameters: A Case of Translucent Polycrystalline Undoped Alumina

An experimental screening design was used to evaluate the effects of spark plasma sintering (SPS) parameters such as heating rate, sintering temperature, dwell duration, and green-shaping processing on the relative density, grain size, and the optical properties of polycrystalline alumina (PCA). It is shown that heating rate and sintering temperature are the most critical factors for the densification of PCA during SPS. Green-shaping processing could prevent grain growth at low SPS sintering temperatures. No predominant SPS parameters are observed on the optical properties. Hence, the optical properties of PCA are controlled by microstructural evolution during the SPS process.     

Multi-Scale Study of Sintering: A Review

An integrated approach, combining the continuum theory of sintering with a kinetic Monte-Carlo (KMC) model-based mesostructure evolution simulation is reviewed. The effective sintering stress and the normalized bulk viscosity are derived from mesoscale simulations. A KMC model is presented to simulate microstructural evolution during sintering of complex microstructures taking into consideration grain growth, pore migration, and densification. The results of these simulations are used to generate sintering stress and normalized bulk viscosity for use in continuum level simulation of sintering. The advantage of these simulations is that they can be employed to generate more accurate constitutive parameters based on most general assumptions regarding mesostructure geometry and transport mechanisms of sintering. These constitutive parameters are used as input data for the continuum simulation of the sintering of powder bilayers. Two types of bilayered structures are considered: layers of the same particle material but with different initial porosity, and layers of two different materials. The simulation results are verified by comparing them with shrinkage and warping during the sintering of bilayer ZnO powder compacts.     

Microstructural Evolution During Sintering with Control of the Interface Structure

This paper reports recent theoretical perspectives and experimental results on microstructural evolution during sintering in terms of the interface structure, which is either rough (atomically disordered) or faceted (atomically ordered). The paper presents theoretical predictions and calculations of grain growth during liquid-phase sintering based on crystal growth theories. It is shown that various types of grain growth behavior, which may be normal, abnormal, or stagnant, can appear as a result of the coupling effects of the maximum driving force for growth and the critical driving force for appreciable growth. The predictions are also shown to be valid in the case of solid-state sintering. A number of experimental observations showing the effect of some critical processing parameters have been found to be in excellent agreement with the predictions. Principles of microstructure development (grain growth control) during sintering are suggested. In addition, the effect of the interface structure on densification is briefly described and discussed.     

Simulating Microstructural Evolution and Electrical Transport in Ceramic Gas Sensors

An integrated computational approach to microstructural evolution and electrical transport in ceramic gas sensors has been proposed. First, the particle-flow model and the continuum-phase-field method are used to describe the microstructural development during the sintering of a prototype two-dimensional film. Then, the conductivity of the sintering samples is calculated concurrently as the microstructure evolves, using both resistor lattice models and effective medium theory for electrical transport in porous aggregates of lightly sintered particles. This approach, when combined with the modeling of resistivity at the grain–grain contacts as a function of neck geometry, ambient gas concentration and temperature, could facilitate the development and optimization of novel microstructures for advanced ceramic gas sensors.     

Effect of Phase Structure on Sintering Behavior of Zirconia Nanopowders

Zirconia nanopowder compacts with comparable particle sizes and pore size distributions but different phase structures were prepared. The sintering behavior of monoclinic, tetragonal, and cubic zirconia nanopowders was directly compared. The densification and microstructural changes during sintering were investigated. The tetragonal and cubic nanopowders showed similar sintering behavior whereas the monoclinic nanopowder exhibited a more difficult densification and coarser microstructure compared with tetragonal and cubic powders. The differences in the densification of zirconia nanopowders resulted from significant differences in the microstructure evolution during sintering. The microstructural changes in nanopowder compacts during sintering were described and a correlation between microstructural changes and interfacial energies associated with different crystal structures was discussed.     

Microstructure Refinement of Sintered Alumina by a Two-Step Sintering Technique

For a few oxide ceramics, the use of an initial precoarsening step prior to densification (referred to as two-step sintering) has been observed to produce an improvement in the microstructural homogeneity during subsequent sintering. In the present work, the effect of a precoarsening step (50 h at 800°C) on the subsequent densification and microstructural evolution of high-quality alumina (Al2O3) powder compacts during constant-heating-rate sintering (4°C/min to 1450°C) was characterized in detail. The data were compared with those for similar compacts that were sintered conventionally (without the heat treatment step) and used to explore the mechanism of microstructural improvement during two-step sintering. After the precoarsening step, the average pore size was larger, but the distribution in pore sizes was narrower, than those for similar compacts that were sintered conventionally to 800°C. In subsequent sintering, the microstructure of the precoarsened compact evolved in a more homogeneous manner and, at the same density, the amount of closed porosity was lower for the compacts that were sintered by the two-step technique, in comparison to the conventional heating schedule. Furthermore, a measurably higher final density, a smaller average grain size, and a narrower distribution in grain sizes were achieved with the two-step technique. The microstructural refinement that was produced by the two-step sintering technique is explained in terms of a reduction in the effects of differential densification and the resulting delay of the pore channel pinch-off to higher density.     

Microstructural evolution during fabrication of alumina via laser stereolithography technique

Application of additive manufacturing (AM) technology in production of ceramic parts is considered as a state-of-the-art technique which has been recently introduced to industry. In the current study the imperative microstructural characteristics of the alumina manufactured via laser stereolithography (SLA) has been investigated. The microstructural characteristics of the developed ceramic parts and components are still unknown and require detailed investigation. A combination of optical microscopy and scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), image analysis, X-ray diffraction (XRD) analysis, transmission electron microscopy (TEM) and micro-computed tomography (micro-CT) scans was used to evaluate the microstructural features of the alumina samples after each step of the manufacturing process (i.e. printing, debinding and sintering). In addition, the apparent density of each sample was measured using water displacement method. Results indicated that the porosity of printed alumina samples was significantly reduced after sintering process. EDS analysis confirmed elimination of binder material after debinding and sintering processes. XRD analysis detected existence of α-Al₂O₃ in initial printed samples which was not changed during debinding and sintering processes. Due to detection of identical peaks for all samples, only one set of lattice parameters ($\mathrm{a}$ and $\mathrm{c}$) was calculated from XRD patterns of all samples which was close to the ones reported in literature for alumina. TEM micrographs and corresponding diffraction patterns confirmed polycrystalline structure from different layers of the samples. High resolution transmission electron microscopy (HRTEM) and diffraction patterns from single layers were used to calculate lattice parameters for each sample. A slight increase was noticed in unit cell and grain size after sintering process. The obtained results help for better understanding of the properties through microstructural characteristics of the 3D printed ceramic parts.     

A general method to determine optimal thermal cycles based on solid-state sintering fundamentals

Most technical ceramics require processing up to and including final-stage sintering to obtain a high-density bulk while inhibiting grain growth as dominant sintering process as far as possible. The literature typically highlights the qualitative interdependence of the sintering variables and microstructural parameters, focusing on very simple particulate systems. However, a quantitative method to achieve optimum sintering of actual polycrystalline solids is still lacking.This paper puts forward such a method, which has been satisfactorily tested by the authors. The method consists of a mathematical model, based on the physical phenomena that take place during solid-state sintering. The method leads to two differential equations: a densification rate and a pore-dragged normal grain growth rate equation during final-stage sintering, which mainly depend on sintering temperature and shaping conditions. Simultaneous numerical integration of these two rate equations allows design of an optimal thermal cycle (enhancing densification and controlling grain growth) to obtain the targeted sintered polycrystalline microstructure. Application of this method yields staggered thermal cycles, in addition to the number of steps, as well as the sintering temperature and dwell time in each step.     

Experimental Analysis of Sintering of MgO Compacts

Experimental sintering studies On undoped and cao-doped Mgo powder compacts in Static air and flowing Water Vapor atmospheres were conducted at 1230° to 1600°C. Corresponding microstructural changes of specimens during sintering were examined by scanning electron microscopy. Kinetic and microstructural data were analyzed to determine sintering mechanisms during the initial and intermediate stages of sintering.     

Evolution of Macropores in a Glass-Ceramic Under Microwave and Conventional Sintering

Densification and microstructural evolution of a CaO-ZrO₂-SiO₂ glass powder were studied during heating in order to produce a glass-ceramic material. Microwave (2.45 GHz) and conventional heating were used for different soaking times and temperatures. Macropores, as visible from the last stage of glass sintering, were monitored as a function of temperature by SEM microscopy and image elaboration. The porosity as a results of micropores has proved to be negligible. Other important densification parameters, such as initial powder size distribution and green pellet density, which would have affected macropores evolution were kept constant. Microwave prepared samples have been compared to conventionally treated ones. The effect of microwaves was to speed up the sintering process, but did not affect the crystallization evolution of glass-ceramic materials differently when compared to the conventional sintering.     

Phase transition between sphalerite and wurtzite in ZnS optical ceramic materials

The phase transition behavior of zinc sulfide (ZnS) ceramics consolidated via pressureless and hot press sintering has been investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM), and electron backscatter diffraction (EBSD) analyses. Two types of ZnS powders with different particle sizes and morphologies were employed to study the influence of microstructural features of starting powders on the ZnS phase transition behaviors. The present work has revealed that during sintering of ZnS ceramics, the phase transition behavior varies based on the starting powder particle size and magnitude of the applied pressure. It has been demonstrated that smaller particle sizes lead to an increased degree of “early” phase transformation from sphalerite to wurtzite at 1000 °C. Additionally, the application of uniaxial pressure during sintering can lead to a reverse phase transition from wurtzite to sphalerite while simultaneously inducing twinning, resulting in improved optical transmittance and mechanical hardness.     

Graded evolution of anisotropic microstructure during sintering from crystal-oriented powder compact

Anisotropic sintering, including shrinkage and grain growth, was examined for c-axis-oriented (Sr,Ca)₂NaNb₅O₁₅ (SCNN) ceramics, which were prepared by colloidal processing under a magnetic field. In the c-axis-oriented SCNN powder compact, shrinkage and grain growth along the c-axis were higher than those along the a-axis. The anisotropic microstructural development was clearly associated with anisotropic sintering shrinkage. X-ray diffraction, scanning electron microscopy, and energy back scattering diffraction showed that the grain growth of oriented particles by including random grains contribute to the development of the oriented microstructure. Finally, the highly crystal-oriented SCNN ceramics with a densified microstructure were obtained through anisotropic sintering. These results clearly showed the potential to develop a well-defined anisotropic microstructure during sintering by designing and controlling the particle packing structure in a powder compact.     

Effect of porosity and hexagonality on the infrared transmission of spark plasma sintered ZnS ceramics

Tailoring phase transition and microstructural evolution during sintering is crucial for the fabrication of ZnS ceramics transparent to infrared (IR) radiation. Herein, we have described the phase transition, microstructure, and related IR transmission of spark-plasma-sintered ZnS ceramics in terms of sintering temperature and pressure. The pore characteristics of spark-plasma-sintered ZnS ceramics were evaluated using Mie scattering theory. Changes in hexagonality and residual pore characteristics of the microstructure affected IR transmission of the sintered specimens. High temperature and pressure condition of SPS were found to increase excessive hexagonal phase (>20%), mainly contributing to a transmittance decay in the range 2–4 μm.     

In situ characterization of ceramic cold sintering by small-angle scattering

The first in situ characterization of the pore morphology evolution during the cold sintering process (CSP) is presented using small-angle X-ray scattering methods. For practical reasons, measurements have been made on a model system, KH₂PO₄ (KDP). The scattering signal revealed a striking behavior that could be modeled with nanoscale structural features associated with the dissolution and reprecipitation of KDP close to the grain/pore interface during CSP. The prospects for future more quantitative experiments under a range of temperature and pressure conditions, as well as for studies of more technologically important materials such as ZnO are considered.     

3D analysis of ceramic powder sintering by synchrotron X-ray nano-tomography

In-depth investigation of the sintering phenomena in ceramic powders remains challenging, with the typical size of the individual particles being around 1 µm or less, i.e., at the resolution limit of X-ray micro-tomography (μCT). This has been dealt with, thanks to the state-of-the-art hard X-ray nano-analysis beamline at the upgraded European Synchrotron Radiation Facility (ESRF). Complete 3D images were obtained for representative ceramic powder systems with a voxel size as low as 25 nm, so as to depict particles and pores with adequate details and follow the entire sintering process. Subsequent quantitative image analyses were used to explore microstructural changes, including the evolution of relevant sintering parameters with respect to the grains and the pores. Notably, a study adopted in this research on the advancement of pore curvatures can be linked to tracking the stages of sintering.     

Competition between densification and microstructure development during spark plasma sintering of B4C–Eu2O3

The densification of nonoxide ceramics has been a known challenge in the field of engineering ceramics. The amount and type of sinter‐aid together with sintering conditions significantly influence the densification behavior and microstructure in nonoxide ceramics. In this perspective, the present work reports the use of Eu₂O₃ sinter‐aid and spark plasma sintering towards the densification of B₄C. The densification is largely influenced by the solid‐state sintering reactions during heating to 1900°C. Based on the careful analysis of the heat‐treated powder mixture (B₄C–Eu₂O₃) and sintered compacts, the competitive reaction pathways are proposed to rationalize the formation of EuB₆ as dominant microstructural phase. An array of distinctive morphological features, including intragranular and intergranular EuB₆ phase as well as characteristic defect structures (asymmetric twins, stacking faults and threaded dislocations) are observed within dense B₄C matrix. An attempt has been made to explain the competition between microstructure development and densification.