Effect of Excess PbO on the Densification of PLZT Ceramics

The densification behavior and electrical properties of PLZT ceramics as a function of excess PbO in the starting powder have been investigated. The hot-pressed PLZT ceramics, prepared from powders containing 0% to 4% excess PbO, were transparent, and their electrical properties were similar in general. PLZT with PbO deficiency up to 1.4 mol% from stoichiometry can be regarded as a single phase-PLZT.     

Sintering of PZT Ceramics: I, Atmosphere Control

Methods of PbO atmosphere control during the sintering of PZT ceramics are briefly reviewed. The problem of atmosphere control of PZT compositions containing a PbO excess (PbO/(Zr,Ti)O₂>1) is discussed. Weight-loss experiments were performed to compare with behavior predicted by reference to the PbO-rich part of the ternary PbO-ZrO₂-TiO₂ phase diagram. The results indicated that the PbO activity of a PZT composition is a function of the excess PbO content, contrary to earlier reports. Experimental procedures were established in order to control the PbO content within satisfactory limits. The effects of various packing powders on the PbO content of sintered PZT compacts were evaluated.     

Densification and Sintering Viscosity of Low-Temperature Co-Fired Ceramics

In this paper, we present sintering and uniaxial viscosity data of three commercial low-temperature co-sintered ceramic systems, i.e., DuPont 951Tape (DU), Heraeus CT2000 (CT), and Ferro A6M (FE), measured by cyclic loading dilatometry. The viscosity initially decreases with temperature, changes little during the intermediate stage, and increases towards the end of densification. The viscosity increases sharply beyond the onset of crystallization. At slower heating rates, the viscosity increases at lower temperature, because of densification and crystallization. The isothermal viscosity data range from 0.1 to 100 GPa·s between 73% and 95% density. Ceramic particle-filled glasses show a higher isothermal viscosity compared with pure glass system, i.e., FE. From master viscosity curves based on isothermal data, the activation energies for viscous flow were ∼375±30 and 450±10 kJ/mol for DU and FE, respectively. These energies are comparable to values obtained from the master sintering curve approach.     

Diffusion Sintering: II, Initial Sintering Kinetics of Alumina

The initial sintering kinetics of alumina have been studied by measuring the isothermal shrinkage of compacts of several alumina powders in air. The shrinkage of these compacts can best be described by a grain-boundary vacancy diffusion model for the temperature range 1200° to 1600°C. The behavior of the compacts is consistent with the model after an initial shrinkage has occurred. The magnitude of this initial shrinkage is constant for identical specimens and is independent of the sintering temperature.     

烧结温度对多孔陶瓷压电性能的影响

研究了烧结温度对海藻酸钠离子凝胶法制备3-1型多孔PZT压电陶瓷和凝胶注模法制备3-3型多孔PZT压电陶瓷性能的影响.结果表明:当烧结温度从1150℃升至1250℃,多孔PZT陶瓷的孔隙率降低,晶粒尺寸、介电常数、压电系数、厚度机电耦合系数和抗压强度增大,静水压压电系数与静水压品质因数随之降低.3-1型PZT陶瓷具有定...     

Densification of Yttria Transparent Ceramics: The Utilization of Activated Sintering

Highly transparent 0.5 at.% Tm:Y₂O₃ ceramics were prepared by using solid‐state reaction combined with vacuum sintering method, with ZrO₂ and Al₂O₃ as sintering aids. Doping amount of ZrO₂ was fixed at 1 at.%, while the effect of Al₂O₃ on densification, microstructure evolution, and transmittance of the Y₂O₃ ceramics was carefully studied. It was found that the addition of Al₂O₃ was very effective in improving densification of Y₂O₃, due to the formation of an Al‐rich eutectic phase Y₄Al₂O₉ (YAM) during the sintering process. As the content of Al₂O₃ was increased from 0 to 81.8 wt ppm, porosity of the ceramics was decreased and transmittance was increased. However, when the content of Al₂O₃ was increased to 137 wt ppm, a secondary phase began to segregate at grain junctions. Further increase in the amount of Al₂O₃ led to an increase in both amount and size of the secondary phase. At the optimized content of Al₂O₃ with 81.8 wt ppm, the Tm:Y₂O₃ ceramics sintered at 1860°C for 13 h exhibited an in‐line transmittance of 83.0% at 2000 nm and 76.5% at 600 nm. It is expected that this finding can be readily applied to other transparent ceramics.     

Fast Densification of Ultra-High-Temperature Ceramics by Spark Plasma Sintering

This work investigated suitability and efficacy of the sintering technique known as spark plasma sintering to produce ultra-high-temperature-based Hf and Zr borides. Ceramic–matrix composites in the systems HfB₂–SiC, ZrB₂–MoSi₂, and ZrB₂–ZrC–SiC were processed by spark plasma sintering and hot pressing. The effects of processing were evaluated comparing the materials microstructure and properties. Compared with hot-pressing technique, spark plasma sintering offers the great advantage to fabricate successfully in short time (i.e., cuts in costs) poorly sinterable powder compositions without the help of any sintering activators.     

Densification and Sintering Kinetics in Sintered Silicon Nitride

The sintering sequence of Y₂O₃-Al₂O₃-doped Si₃N₄ was investigated with respect to the relationship between densification, α→β transformation, and microstructural development. Quenching studies were performed to reveal these interactions during a complete sintering cycle. Isothermal studies were conducted to examine the sintering kinetics and compared to Kingery's liquid-phase sintering model. The bulk density increased to ≥90% of theoretical density with only minor transformation taking place. Major transformation occurred in a late sintering stage and was accompanied by the development of elongated grains. The kinetic order of the densification process, taking into account an appropriate correction, was larger than any of the rate exponents predicted by the Kingery model, indicating that other single or mixed mechanisms were active.     

Densification of Large Pores: II, Driving Potentials and Kinetics

A kinetic analysis of densification is presented for the case of isolated, identical pores separated by dense, polyerystal-line material where the grain size is a variable (smaller to larger, relative to the pore size). The analysis includes the influence of both grain growth and mass transport rates on the driving potential for mass transport to the pore. For the expected condition where the rate of grain growth is much greater than the rate of pore shrinkage, it is shown that the driving potential is relatively independent of pore surface curvature, and approaches (2γ_s/ R _po) sin (ψ_e/2) during grain growth, where γ_s is the surface energy per unit area of the material, ψ_e is the dihedral angle, and R _po is the initial pore radius. Using this driving potential, an expression is derived for the current densification rate. The proposed mechanism for mass transport is radial diffusion through a spherical polycrystalline unit cell containing a spherical pore, where diffusion is restricted to grain boundaries that intersect the pore. The expression includes the average separation distance between pores and the grain boundary area intersecting each pore. This expression is in qualitative agreement for data reported in Part I for a Zr(3Y)O₂ material where the grain size is always smaller than the pore size, and a Zr(8Y)O₂ material where the grain size is larger than the pore size.     

烧结工艺对β-氮化硅陶瓷的影响

以β-Si3N4粉末为原料,以YAG（钇铝石榴石）为烧结助剂,通过气氛压力烧结（GPS）制备出致密的β-氮化硅陶瓷材料,形成大小均匀的柱状颗粒和小球状颗粒复合显微结构,研究了烧结助剂质量分数、烧结温度以及保温时间对β-氮化硅陶瓷致密化程度及力学性能的影响.     

Effect of Inclusions on Densification: II, Numerical Model

Experimental studies conducted in conjunction with a numerical analysis of strain-rate gradients have established the origin of the damage process that occurs upon the densification of powders containing nonsintering inclusions and reinforcements. The underlying phenomenon is the development of localized compressive strains in the porous matrix, both around high-aspect ratio reinforcements and between closely spaced reinforcements. These regions of compression densify first and then support grain growth. This process produces nondeformable networks that constrain the shrinkage of the adjacent, porous matrix. The constraint causes desintering and cracklike void formation in the lowdensity regions. The variables shown to be of importance are the volume fraction and aspect ratio of the reinforcements. The process is shown to be sensitive to the green density, such that a high initial density reduces initial damage and lowers the differential in densification.     

Sintering Kinetics of Porous Ceramics from Natural Diatomite

The sintering kinetics of the porous ceramics from natural diatomite is investigated by means of stepwise isothermal dilatometry (SID) accompanied with XRD, scanning electron microscope (SEM), and porosity measurement. We find that the isothermal shrinkage data from SID could be well analyzed to get kinetic parameters according to the empirical rate equation developed by Makipirtti–Meng , where Y is the fractional volume shrinkage during sintering process and n a dimensionless exponent. The apparent activation energy Δ E values obtained for 850°–1000°C and 1050°–1150°C are 911.8 and 610.5 kJ/mol, respectively. Correspondingly, the exponent n values for the two temperature ranges are also much different and can be served to reveal the morphology changing during the sintering process, which is well consistent with the SEM observation.     

比表面积对TiO2陶瓷烧结初期致密化行为的影响

将比表面积分别为30 m2/g和1 m2/g的纳米(50 nln)和微米(2 μm)金红石TiO2陶瓷坯体在高温热膨胀仪中自室温至1200℃进行恒速无压烧结,升温速率为1℃/min,3℃/min和5℃/min,热膨胀仪自动记录烧结收缩.为阐明比表面对无压烧结初期致密化行为的影响,研究了氧化钛陶瓷的烧结收缩行为.同时,利用Arrhenius曲线研究了纳米和微米氧化钛陶瓷的烧结激活能.结果表明:随烧结温度的增加,比表面积的增加加速了致密化速率;纳米和微米氧化钛的烧结激活能分别为115±10 kJ/mol和302±15 kJ/mol;对于纳米氧化钛,当烧结体的瞬时相对密度为70～80%时,出现最大致密化速率,而对于微米氧化钛陶瓷,最大致密化速率出现在相对密度为75～85%.     

低温无压烧结氮化硅陶瓷的相变及致密化研究

采用氧化铝（Al2 O3）和氧化钇（Y2 O3）为烧结助剂,利用无压烧结工艺在低温下制备氮化硅陶瓷材料。利用XRD和SEM等着重研究了无压烧结氮化硅陶瓷低温阶段时的物相组成及其致密化。结果表明：当添加剂含量为10％,烧结温度高于1430℃时,α→β相转变较快;当烧结温度达到1510℃时,α相全部转变为β相。     

热压烧结BN-AlN复相陶瓷致密化研究

研究了热压烧结BN-AlN复相陶瓷的致密化行为，研究了添加剂的加入量、AlN第二相的含量以及热压温度、保温时间等工艺参数对复相陶瓷致密化的影响。结果表明：当Y2O3的添加量为10％，AlN加入量为50％时，在1900℃，保温2h，压力为30MPa，N2气氛下可以制备出致密的BN—AlN复相陶瓷，对BN—AlN的相组成及显微结构进行了观察分析。     

Effect of Green Density on Densification and Creep During Sintering

The effect of green density on both the densification rate and the creep rate was measured simultaneously during sintering by loading dilatometry. The experiments were performed on zinc oxide powder compacts with five different green densities covering a range of 0.39 to 0.73 of theoretical. The samples were heated at a constant rate of 4°C/min up to 1100°C in air. The densification rate at any temperature increases significantly with decreasing green density. The data for the densification rate and creep rate as a function of density show two quite distinct regimes of behavior; the rates were strongly dependent on density below 0.80, while above this value they were weakly dependent on density. The ratio of the densification rate to the creep rate was almost independent of temperature but increased almost linearly with increasing green density. The representation of the data in terms of models for sintering and creep is discussed.     

Normal Sintering of (K,Na)NbO3-Based Ceramics: Influence of Sintering Temperature on Densification, Microstructure, and Electrical Properties

Normal sintering of Li-doped and Li/Ta-codoped potassium sodium niobate (KNbO₃–NaNbO₃, KNN)-based ceramics was investigated to clarify the optimal sintering condition for densification, microstructure, and electrical properties. It was found that density increased greatly within a narrow temperature range but tended to decrease when the sintering temperature slightly exceeded the optimal one, accompanied by the appearance of abnormal grain growth, which was considered to be due to the intensified volatilization of alkali metal oxides. Piezoelectric and dielectric properties also showed a similar relationship between the density and sintering temperature, but the highest piezoelectric strain coefficients were obtained at the temperatures lower than that for the highest density, because both densification and composition affect the electrical properties. The highest d ₃₃ value of 206 pC/N was obtained for the Li- and Ta-codoped KNN ceramics prepared at 1090°C.     

Effect of Matrix Grain Growth Kinetics on Composite Densification

The effect of matrix grain growth kinetics on the densification behavior of a particulate composite has been investigated. Large alumina inclusions were added to two types of zirconia matrices having different grain growth kinetics, i.e., Zr(8Y)O₂ and Zr(3Y)O₂. Despite the evolution of different grain sizes, both matrices reached an end-point relative density of 0.92 and 0.94, respectively, even though they contained 0.25 volume fraction of inclusions (based on total solid volume). However, the morphology and spatial distribution of the residual pores were distinct. The Zr(8Y)O₂ matrix, which developed very large grains, had a dual microstructure with porous regions surrounded by a connective, denser region, as previously reported for an alumina matrix containing zirconia inclusions. Conversely, the Zr(3Y)O₂ matrix was fully dense and uniform, but the composite contained large cracklike voids at inclusion/matrix interfaces. The large opening displacement of these cracklike voids locally relaxed the constraint to matrix shrinkage imposed by the inclusion network.     

热压烧结制备高致密度B4C陶瓷及其致密化

以B4C粉末为原料,以酚醛树脂热解碳为烧结助剂,采用真空热压烧结工艺制备出高致密度的B4C陶瓷材料,探讨了酚醛树脂含量和烧结温度对材料致密化的影响,对比分析了纯B4C和掺碳B4C的热压烧结致密化过程.研究显示,烧结温度的升高有利于材料的致密化,酚醛树脂的添加则显著活化了B4C的烧结.实验条件下酚醛树脂的最优添加量为3％（质量分数）,烧结过程中热解碳固溶于B4C晶格,显著加速了其在1600℃至1800℃区间的致密化速率.     

Al2O3对氮化硅陶瓷致密度的影响

用自蔓延高温燃烧合成氮化硅粉料,采用Y203-Al2O3-AlN液相烧结体系,通过改变Al2O3的含量考察了Al2O3成分对烧结体及素坯致密度的影响.测试了烧结体收缩率、烧失率.并对比了两种不同粒度氮化硅原料的烧结情况.结果表明,烧结体密度随着Al2O3的加入和含量的增多而降低,素坯密度在Al2O3含量小于7%时基本保持不变,当增加至7%质量分数后也趋于下降.含量达到10%以后,样品的烧失率和收缩率急剧增高.粒度小的粉料烧结体密度高.