Fabrication of transparent γ-AlON by direct 2-step pressureless sintering of Al2O3 and AlN using an AlN-deficient composition

Transparent polycrystalline aluminum oxynitride (γ-AlON) was fabricated by the pressureless two-step sintering of α-Al₂O₃ and AlN after adding a small amount of MgO and Y₂O₃. The process was based on two assumptions. The first was the utilization of AlN-deficient non-stoichiometric composition to increase the cationic vacancies and the second was the selection of the 1st step sintering temperature that suppresses the formation of γ-AlON phase to achieve a high density after the 2nd sintering step. The 1st and 2nd sintering steps were performed at 1610–1650 and 1940–1990 °C, respectively, for 10 h in a 2.5 atmospheric nitrogen pressure, and the optimal sintering conditions were determined. The fabricated γ-AlON showed a mean grain size of 164–248 μm without the presence of significant scattering centers, where the sample prepared using an optimal condition revealed a very high transmittance of 84.7% along with comparable mechanical properties.     

A critique of master sintering curve analysis

In this work, we explore factors affecting the accuracy of the master sintering curve (MSC) approach for analyzing the complete sintering profile of ceramic powders. We show that the instantaneous anisotropic shrinkage must be accounted for to develop an accurate MSC. The MSC diverges at >90% density because of basic assumptions that oversimplify the analysis of the densification process. We also show that powder chemistry and forming techniques can affect the fitting parameter Q. Q should not be interpreted as the sintering activation energy, or used to interpret mechanistic differences since it is comprised of several mechanisms that influence densification throughout the sintering cycle. Despite these limitations, the MSC is a useful and practical tool for predicting thermal load (i.e. time and temperature) effects on the densification of a ceramic part fabricated from a singular powder that is fabricated by a singular forming 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.     

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.     

A geometrical sintering model (GSM) to predict surface area change

A geometrical sintering model (GSM) to predict the surface area variation with time is proposed. Predictions of the GSM are compared to the commonly used Koch and Friedlander [(1990). The effect of particle coalescence on the surface-area of a coagulating aerosol. Journal of Colloid and Interface Science, 140, 419–427] model, mass transport based viscous flow sintering models and to experimental data reported in the literature. Closed form expressions for the normalized surface area variation with time are derived for specific sintering mechanisms such as overall diffusion and viscous flow. For other sintering mechanisms such as surface, grain boundary, and volume diffusion, closed form expressions could be derived by making simplifying assumptions of a reference radius for the primary particles.     

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.     

Construction and validation of master sintering curve for TiO2 for pressureless sintering

Abstract

One of the ultimate objectives for sintering research is to predict densification results under different thermal profiles for a given processing method. This paper studies the construction and validation of the master sintering curve (MSC) for rutile TiO₂ for pressureless sintering. The MSC was constructed using dilatometry data at two heating rates and was then validated using isothermal holds at three different temperatures. The scanning electron microscopy (SEM) observation shows that the partially sintered samples have the same density under different heating procedures, which demonstrates that the assumptions of the model are reliable. The concept of the MSC could be used to predict the sintering shrinkage and final density and calculate the activation energy. A value of 105 kJ mol^-1 for TiO₂ was obtained. The MSC could be applied to predict the sintering profile to prepare ceramics with required density and a minimum of grain growth.     

Modelling gas-phase synthesis of single-walled carbon nanotubes on iron catalyst particles

A simple model for the gas-phase synthesis of carbon nanotubes on iron catalyst particles has been developed. It includes a growth model for the catalyst particles and describes nanotube growth processes through carbon monoxide disproportionation and hydrogenation. Models for particle-particle interactions and sintering are also included. When carbon arrives at a catalyst particle it can either dissolve in the particle until a saturation limit is reached, or form a graphene layer on the particle, or go on to form a nanotube. Two models for incipient nanotube growth are considered. The first allows nanotubes to form once a catalyst particle reaches the saturation condition. The second only allows nanotubes to form on the collision of two saturated particles. The particle system is solved using a multivariate stochastic solver coupled to the gas-phase iron chemistry using an operator splitting algorithm. Comparison with experimental data gives a good prediction of the nanotube length, and reasonable values of catalyst particle diameter and nanotube diameter. A parametric study is presented in which the carbon monoxide reaction rate constants are varied, as is the fraction of carbon allowed to form nanotubes relative to surface layers. The assumptions of the coagulation and sintering models are also discussed.     

高压烧结高纯微晶氧化铝陶瓷

以商业生产的高纯纳米α-Al2O3粉(99.9%,质量分数)、分析纯Mg(NO3)2为原料,以两面顶压机高压烧结,制备了纯Al2O3陶瓷及微量MgO掺杂的Al2O3陶瓷,并进行了密度测试与显微结构分析.与常压烧结相比,高压烧结可显著降低高纯Al2O3陶瓷的烧结温度,提高传质速率,大幅度缩短烧结时间,达到快速、低温烧结的效果.与常压烧结明显不同,在高压烧结时,MgO对高纯AlO3陶瓷的烧结致密化几乎没有影响.在4.5GPa,100 ℃高压烧结30 min,制备的纯Al2O3陶瓷的相对密度为97.65%,微量MgO掺杂的Al2O3陶瓷的相对密度达97.93%、平均晶粒尺寸约为4 μm.     

烧结工艺对Si_3N_4/TiC纳米复合陶瓷材料微观结构及力学性能的影响

以La2O3和Y2O3作为复合烧结助剂,采用热压烧结法制备了Si3N4基复合陶瓷材料。研究了保温时间和烧结助剂含量对复合材料微观结构及力学性能的影响。研究表明:所制备的Si3N4/TiC陶瓷复合材料的微观结构呈现纵横交错、相互嵌套的结构,晶粒尺寸呈现明显的双峰分布特征,单位面积内晶粒数量与烧结助剂含量之间呈线性降低关系。当烧结助剂质量含量为8%时,该复合陶瓷材料具有最优的力学性能,其抗弯强度、断裂韧性和Vickers硬度分别达到943MPa,8.38MPa·m1/2和16.67GPa。     

Composition,microstructure and electrical properties of K0.5Na0.5NbO3 ceramics fabricated by cold sintering assisted sintering

In this paper, cold sintering was served as a forming method to assist the conventional sintering, which is so-called cold sintering assisted sintering (CSAS) method. Lead-free K_0.5Na_0.5NbO₃ piezoelectric ceramics were prepared by the CSAS method, and the effects of the different procedures on the sintering behaviors and electrical properties of KNN ceramics were studied. Compared with conventional sintering (CS), cold sintering process can induce potassium-rich phase on the KNN particle surface, and remarkably increase both the green and sintering density of KNN ceramics. Meanwhile, the potassium-rich phase would transform to K₄Nb₆O₁₇ second phase on the grain surface, and subsequently suppress the volatilization of potassium element. The sinterability and electrical properties were greatly improved, and KNN piezoelectric ceramics with high performance can be manufactured in a wide sintering temperature range (1055 °C–1145 °C), which proves that CSAS has the potential to be an excellent sintering technique for producing KNN based ceramics.     

微波强化烧结制备铁钴基金刚石锯片刀头

采用微波烧结技术制备了低钴型Fe-Co基金刚石锯片刀头,利用圆柱谐振腔微扰法电磁特性测试系统评价了配方物料压坯的吸波特性,并结合物料在微波场中的升温特性设计了可行的微波烧结制度。采用SEM、致密度和硬度测试对比研究了微波烧结和常规烧结所得样品的微结构信息和力学性能。结果表明,对于低钴高铁型配方,在850℃下微波烧结获得的样品,其相对致密度和硬度即可分别达到96.63%和99.4HRB,微波烧结在最大升温速率为32.5℃/min时能保证烧结体组织均匀。与常规烧结方法相比,在获得同等级力学性能的前提下,微波强化烧结可将温度降低至900℃以下,显著缩短了烧结总时间,在金属基金刚石工具刀头烧结方面表现出良好的应用前景。     

Sintering of Alumina in Microwave-Induced Oxygen Plasma

Small cylindrical tubes were sintered in a microwave- induced oxygen plasma, initiated and sustained inside a tunable, single-mode cavity. Temperature and shrinkage measurements of the specimens were achieved using an optical-fiber thermometer black-body sensor and a dilatometer, respectively. Sintering experiments at constant heating rate were accomplished to obtain the activation energy for sintering of alumina in the plasma and in a conventional rapid-heating furnace. Diffusion of aluminum interstitials along grain boundaries was believed to be the dominant sintering mechanism, with an estimated activation energy of 488 ± 20 kj/mol for conventional sintering and an average activation energy of 468 ± 20 kj/mol for plasma sintering. A comparison of specimens sintered in the plasma to those sintered in a conventional furnace under the same temperature-time excursions and oxygen pressures showed an athermal effect due to the plasma. To further explore this athermal effect, sintering experiments in plasmas of different oxygen pressure were conducted. The athermal effect was ascribed to an increase of aluminum interstitial concentration during plasma sintering. Sintering data were interpreted using the combined-stage sintering model.     

Transient liquid phase sintering of high-purity mullite for high-temperature structural ceramics

High-purity mullite ceramics, promising engineering ceramics for high-temperature applications, were fabricated using transient liquid phase sintering to improve their high-temperature mechanical properties. Small amounts of ultrafine alumina or silica powders were uniformly mixed with the mullite precursor depending on the silica-alumina ratio of the resulting ceramics to allow for the formation of a transient liquid phase during sintering, thus, enhancing densification at the early stage of sintering and mullite formation by the reaction between additional alumina and the residual glassy phase (mullitization) at the final stage of sintering. The addition of alumina powder to the silica-rich mullite precursor resulted in a reaction between the glassy silica and alumina phases during sintering, thereby forming a mullite phase without inhibiting densification. The addition of fine silica powder to the mullite single-phase precursor led to densification with an abnormal grain growth of mullite, whereas some of the added silica remained as a glassy phase after sintering. The resulting mullite ceramics prepared using different powder compositions showed different sintering behaviors, depending on the amount of alumina added. Upon selecting an optimum process and the amount of alumina to be added, the pure mullite ceramics obtained via transient liquid phase sintering exhibited high density (approximately 99%) and excellent high-temperature flexural strength (approximately 320 MPa) at 1500 °C in air. These results clearly demonstrate that pure mullite ceramics fabricated via transient liquid phase sintering with compositions close to those of stoichiometric mullite could be a promising process for the fabrication of high-temperature structural ceramics used in an ambient atmosphere. The transient liquid phase sintering process proposed in this study could be a powerful processing tool that allows for the preparation of superior high-temperature structural ceramics used in the ambient processing atmosphere.     

Agglomerate and Particle Size Effects on Sintering Yttria-Stabilized Zirconia

The initial-, intermediate-, and final-stage sintering of fine crystallite yttria-stabilized zirconia was studied. Experiments were conducted on powder lots of differing agglomerate size and one specially prepared agglomerate-free powder. Initial-stage sintering kinetics were compared with a sintering study on larger crystallite size calcia-stabilized zirconia to access the Herring scaling law. It was found that agglomerates limit attainable green density, interfere with the development of microstructure, impede initial-stage sintering kinetics, and limit the potential benefit of fine crystallites on final-stage sintering. An gglomerate free powder centrifuge-cast to 74% green density was sintered to 99.5% of theoretical density in a 1 h 1100°C cycle, which is ∼300°C lower than necessary for an agglomerated but equal crystallite size powder.     

Effective diffusion distance for isothermal sintering of hydroxyapatite

Abstract

The microstructural evolution of hydroxyapatite (HAp) was quantified for isothermal sintering at 1100°C. The aggregated state of the powder particles is thought to be responsible for the relatively high value of the average pore separation throughout isothermal sintering. The measured grain size exponent of 6·7 is not compatible with the values expected for volume diffusion or grain boundary diffusion under the assumptions of the Combined Stage Sintering Model and hence the Master Sintering Curve. The measured exponent for a previously defined flux weighted effective diffusion distance gave a more reasonable value of 3·4. The theoretical exponent in the Combined Stage Sintering Model was then corrected to accommodate a non-linear relationship between the effective diffusion length and pore size. The results demonstrate how the effective lengthscale in the Combined Stage Sintering Model can be corrected to accommodate aggregation in the microstructure.     

Sintering deformation caused by particle orientation in uniaxially and isostatically pressed alumina compacts

Effect of particle orientation on deformation during sintering is reported for model systems; one made with industrial grade low soda alumina, which has an elongated particle shape, and the other a special alumina with a spherical particle shape. To ensure the homogeneous packing density of particles, compacts were made by uniaxial pressing followed by cold isostatic pressing. The particle orientation was examined with a polarized light microscope and was found to be an important cause of sintering deformation. In a green body, for elongated shape of particles, the particle orientation occurred during uniaxial pressing, causing the anisotropic sintering shrinkage during sintering and thus the sintering deformation. No particle orientation nor shrinkage anisotropy was noted in the system made with the powder of spherical particle shape.     

Effect of tungsten particle size on sintered properties of heavy alloys

In the present investigation, the sintering of CuNi (10 wt.%) bonded heavy alloys has been studied using two different particle sizes of tungsten, submicron range (0.74 μm) and micron range (3.03 μm). The sintering temperatures were 1400, 1450 and 1500 °C, and the sintering time was 1 h. Results show that an increase in the sintering temperature and/or the nickel content of the binder, enhances densification. The properties of the heavy alloys reveal an improvement when the fine tungsten powder is used. The results have been discussed on the basis of a solution-reprecipitation mechanism for liquid phase sintering, which correlates well with the spheroid coarsening of the tungsten particles.     

Low-Sintering High-k Materials for an LTCC Application

High-k LTCC tapes with ultralow sintering temperatures were developed from lead-free perovskite powders. Lowering of the sintering temperature from 1250°C down to 900°C has been achieved by means of ultrafine ceramic powders in combination with suitable sintering aids. The tape-casting process has been optimized for ultrafine powders with an enhanced sintering activity. Low-sintering high-k tapes of a thickness down to 40 μm, suitable for LTCC processing, were obtained. The sintering behavior of these high-k tapes has been studied and compared with other LTCC materials. Dielectric properties of the high-k material have been investigated on a multilayer test structure consisting of up to 20 dielectric layers. After metallization with an Ag conductor, the green tapes were stacked and laminated. Sintering of these multilayer stacks at 900°C gives dense ceramic samples. Permittivities up to 2000 have been obtained, together with low dielectric losses. Material compatibility with several Ag/Au-thick-film-paste systems has been tested.     

A comparison of sintering techniques using different particle sized β-SiAlON powders

In the present study sintering behavior and mechanical properties of β-SiAlON ceramics were investigated using different sintering techniques (gas pressured sintering (GPS), pressureless sintering and spark plasma sintering (SPS)) and different particle sized powders (with D_BET 216 and 130 nm). After sintering of the microstructure and phase characterization were carried out using a scanning electron microscope (SEM) and the X-ray diffraction (XRD) method, respectively. All the samples, prepared using fine powder, were sintered at lower temperatures than samples prepared by conventional powder, by two sintering techniques (GPS and pressureless). Additionally, the results showed that cooling rates had an important effect on the formation and the amount of intermediate phase in the sample. As a result, it was shown that the particle size of starting raw materials, the amount of additive, the sintering temperature and the technique had a significant effect on the microstructure and mechanical properties of the SiAlON samples.