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.     

Postsintering Hot Isostatic Pressing of Ceria-Doped Tetragonal Zirconia/Alumina Composites in an Argon–Oxygen Gas Atmosphere

Ceria-doped tetragonal zirconia (Ce-TZP)/alumina (Al₂O₃) composites were fabricated by sintering at 1450° to 1600°C in air, followed by hot isostatic pressing (postsintering hot isostatic pressing) at 1450°C and 100 MPa in an 80 vol% Ar–20 vol% O₂ gas atmosphere. Dispersion of Al₂O₃ particles into Ce-TZP was useful in increasing the relative density and suppressing the grain growth of Ce-TZP before hot isostatic pressing, but improvement of the fracture strength and fracture toughness was limited. Postsintering hot isostatic pressing was useful to densify Ce-TZP/Al₂O₃ composites without grain growth and to improve the fracture strength and thermal shock resistance.     

Sintering Behavior and Optical Properties of Yttria

Sintering in air of a pure yttria powder was investigated on green samples shaped by slip casting. The "relative density/grain size" trajectory has been drawn and hypotheses concerning the mechanisms controlling grain growth and densification were formulated. Samples were fully densified by an additional hot isostatic pressing step on pre-sintered samples. After optimal polishing, optical properties were measured in the UV, visible, and infrared ranges.     

Grain Growth Behavior of Aluminum Oxide Reinforced with Carbon Nanotube During Plasma Spraying and PostSpray Consolidation

Grain-boundary mobility of the plasma sprayed aluminum oxide (Al₂O₃)–carbon nanotube (CNT) composites is evaluated in the current work. Grain mobility is evaluated from the grain growth within the spray-dried particles and thermal history experienced during high-temperature plasma processing. CNTs form an interfacial grain boundary layer during thermal exposure, limiting the grain growth of plasma-sprayed coatings. Consequent hot isostatic pressing (HIPing) of CNT-reinforced Al₂O₃ at 1773 K shows differences in grain growth kinetics, degree of densification, and pore shrinkage. Densification of HIPed coatings is observed to be dictated by CNTs, phase transformation, initial grain size, and time of thermal processing. CNTs have shown to impede the Al₂O₃ grain growth by serving as grain pinning obstacles. Impediment of grain-boundary mobility with variation of CNT content, and time and temperature of the heat treatment of aluminum oxide (Al₂O₃)–CNT nanocomposite is addressed in detail.     

Hot Isostatic Pressing of Alumina and Examination of the Hot Isostatic Pressing Map

The hot isostatic pressing (HIP) of four alumina powders is studied in the temperature range 1100° to 1400°C, at 5- to 200-MPa applied pressure, and for times ranging from 0.5 to 4 h. Density increases with increasing HIP temperature, pressure, and time; decreasing grain size results in increased density after HIP. An empirical relation is derived for grain growth during HIP, and the HIP map proposed by Helle et al. is found applicable to the present results. Densification is governed by the grain-boundary diffusion of aluminum ions; with the transport coefficient and the grain-growth values found in the present study, the map can be used to express experimental results to within a factor of 4 for all densification stages except near full density.     

Densification and Grain Growth of Porous Alumina Compacts

Densification and grain growth of porous alumina compacts during various high-temperature processes were investigated. Experimental data were obtained for densification and grain growth of alumina powder during hot pressing. A set of constitutive equations was proposed based on the constitutive equations by Helle et al. ¹ for hydrostatic response and by Rahaman et al. ² for deviatoric response. Theoretical results from the proposed constitutive equations were compared with various experimental data for alumina powder compacts in the literature, including pressureless sintering, sinter forging, and hot pressing. The proposed model well predicts the densification and grain growth of alumina compacts.     

Interface-Reaction-Controlled Kinetics in the Hot Isostatic Pressing of Submicrometer Alumina Powder

The kinetics of densification of alumina powder compacts at 1000° to 1200°C were studied by using a dilatometer to monitor volumetric changes during hot isostatic pressing. The densification rate is proportional to the square of the applied pressure, and densification does not occur below a threshold pressure. Results are interpreted in terms of an interface-controlled reaction mechanism involving the movement of grain-boundary dislocations.     

La2O3对镁铝尖晶石透明陶瓷致密化及其性能的影响

镁铝尖晶石透明陶瓷兼具了良好的光学和力学性能,在军、民两用领域有着广泛的实际和潜在应用前景。由于其致密化速率低,在烧结过程中往往需要引入烧结助剂。稀土倍半氧化物熔点高,高温不易挥发,近些年被证实可以促进镁铝尖晶石陶瓷的致密化,但其促烧机理尚不明确。本文以高纯商业化镁铝尖晶石粉体为原料,La₂O₃为烧结助剂,采用无压预烧结合热等静压烧结,制备镁铝尖晶石透明陶瓷,通过XRD、SEM、紫外-可见分光光度计、万能试验机等测试手段对其致密化过程及其力学和光学性能进行表征和分析,研究了La₂O₃对镁铝尖晶石透明陶瓷致密化过程的影响规律和作用机制。结果表明,La₂O₃通过与尖晶石反应或固溶产生晶格畸变,增加缺陷浓度,从而起到促进致密化的作用,一定程度上降低了预烧温度和热等静压温度。对于190 MPa、1 500 ℃热等静压烧结3 h的样品,La₂O₃掺杂可以显著提高紫外区域的透过率;同时,La偏析到晶粒表面,抑制了尖晶石晶粒的生长,从而提高了样品的力学强度。掺杂0.05%(质量分数)La₂O₃样品较未掺的样品,400 nm处透过率从63%提高到81%,弯曲强度从263.7 MPa提高至319.0 MPa,断裂韧性从1.69 MPa·m^1/2提高至1.82 MPa·m^1/2。     

The influence of MgO,Y2O3 and ZrO2 additions on densification and grain growth of submicrometre alumina sintered by SPS and HIP

Spark plasma sintering followed by hot isostatic pressing was applied for preparation of polycrystalline alumina with submicron grain size. The effect of additives known to influence both densification and grain growth of alumina, such as MgO, ZrO₂ and Y₂O₃ on microstructure development was studied. In the reference undoped alumina the SPS resulted in some microstructure refinement in comparison to conventionally sintered materials. Relative density >99% was achieved at temperatures >1200 °C, but high temperatures led to rapid grain growth. Addition of 500 ppm of MgO, ZrO₂ and Y₂O₃ led, under the same sintering conditions, to microstructure refinement, but inhibited densification. Doped materials with mean grain size <400 nm were prepared, but the relative density did not exceed 97.9%. Subsequent hot isostatic pressing (HIP) at 1200 and 1250 °C led to quick attainment of full density followed by rapid grain growth. The temperature of 1250 °C was required for complete densification of Y₂O₃ and ZrO₂-doped polycrystalline alumina by HIP (relative density >99.8%), and resulted in fully dense opaque materials with mean grain size<500 nm.     

Analysis of Hot Isotatic Pressing of Presintered Zirconia

Hot isostatic pressing (HIP) of presintered Y-TZP was studied at 1100° to 1400°C, 5 to 200 MPa, for 0.5 to 4 h. The effects of process variables of HIP and the characteristics of the presintered specimens on the densification behavior of HIP were examined. The microstructural development after HIP was also examined. Grain growth occurred during the densification in HIP. Empirically, a linear relation having a rather constant slope was found between the logarithms of porosities and grain sizes, for each starting condition. Provided this relationship was taken into account, the Ashby's model for HIP could express the densification process for this system satisfactorily.     

Modelling of elimination of strength-limiting defects by pressure-assisted sintering at low stress levels

The structural reliability of sintered products depends on large defects introduced during powder processing, which cannot be removed by pressureless sintering. Here, we present a model how a large single ellipsoidal void is deformed, and finally disappears by pressure-assisted sintering. Taya-Seidel’s model is applied to predict the shrinkage of a large void in a compressible linear viscous material by using bulk viscosity, shear viscosity, and sintering stress that are determined experimentally for sintering of alumina powder at low stress levels. The application of mechanical stress promotes the densification rate. Its effect is maximum for hot isostatic pressing (HIP) and minimum for sinter forging. The effect is intermediate for hot pressing (HP) and spark plasma sintering (SPS), because the hydrostatic component of stress varies with densification. While a crack-like defect can be removed during densification, a spherical void must be eliminated by shear deformation in the final stage during dwell time.     

Rubber isostatic pressing of metal powder under warm temperatures

The effect of a rubber mould on densification and deformation of aluminum alloy powder was investigated during warm isostatic pressing. The hyperelastic constitutive equations based on various strain energy potentials were employed to analyze deformation of a rubber mould. The parameters in the strain energy potentials were obtained from experimental data for uniaxial and volumetric responses of Viton rubber at elevated temperatures. The yield function of Shima and Oyane was implemented into a finite element program (ABAQUS) to predict compaction responses of metal powder during warm isostatic pressing. Finite element results were compared with experimental data for densification and deformation of aluminum alloy powder during warm die pressing and warm isostatic pressing.     

Hot‐Pressing Kinetics and Densification Mechanisms of Boron Carbide

The hot‐pressing kinetics of boron carbide at different stages in the hot‐pressing process was investigated. Based general densification equation and pore‐dragged creep model, the densification and grain growth kinetics were analyzed as a function of various parameters such as sintering temperature, sintering pressure and dwell time. Stress exponent of n ≈ 3 at the initial dwell stage suggests the plastic deformation may dominates the densification. The further TEM observations and the calculation based on effective stress and plastic yield stress also indicate that plastic deformation may occur and account for the large increase in density at the initial stage of sintering. Calculated grain size exponent of m ≈ 3 suggests that the grain‐boundary diffusion dominates the densification at the final stage. During the final stage of sintering, grain growth may be determined by evaporation/condensation and grain‐boundary migration.     

Gas Diffusion During Containerless Hot Isostatic Pressing of Liquid-Phase Sintered Ceramics

Diffusion and dissolution of gases are considerably higher in glasses than in most crystalline materials. Thus, materials with a glassy grain-boundary phase are susceptible to gas permeation when they are containerless hot isostatic pressed. Annealing of sinter-hot isostatic pressed alumina—magnesium aluminosilicate glass (3 to 10 vol%) composites and pure glass samples at 1200° to 1600°C results in dedensification by matrix bloating and swelling. The degree of dedensification increases with the hot isostatic pressing pressure, temperature, and time and increasing annealing temperature. A theoretical prediction of high-pressure gas permeation is developed based on a diffusion model. The analysis allows a satisfactory explanation for the gas diffusion effect on hot isostatic press densification. The analysis is also useful for developing design criteria for the hot isostatic press schedule and encapsulation materials. Annealing of hot isostatic pressed samples at 1100°C prior to high-temperature annealing results in no dedensification as a result of out-diffusion of the internal gases.     

Hot Isostatic Pressing of Transparent Nd:YAG Ceramics

This paper demonstrates that fine-grained (2–3 μm), transparent Nd:YAG can be achieved at SiO₂ doping levels as low as 0.02 wt% by the sinter plus hot isostatic pressing (HIP) approach. Fine grain size is assured by sintering to 98% density, in order to limit grain growth, followed by HIP. Unlike dry-pressed samples, tape-cast samples were free of large, agglomerate-related pores after sintering, and thus high transparency (i.e., >80% transmission at 1064 nm) could be achieved by HIP at <1750°C along with lower silica levels, thereby avoiding conditions shown to cause exaggerated grain growth. Grain growth was substantially limited at lower SiO₂ levels because silica is soluble in the YAG lattice up to ∼0.02–0.1 wt% at 1750°C, thus allowing sintering and grain growth to occur by solid-state diffusional processes. In contrast, liquid phase enhanced densification and grain growth occur at ∼0.08–0.14 wt% SiO₂, especially at higher temperatures, because the SiO₂ solubility limit is exceeded.     

Effect of Sintering Temperature on the Densification of Al2O3

Alumina powder compacts sintered at various temperatures were isostatically hot-pressed. The specimens sintered to the closed-pore state can be densified further by hot isostatic pressing. If the open pores are eliminated during sintering, sintering at a low temperature is desirable to achieve a full densification after hot-pressing. Sintering at high temperatures causes pores to be trapped inside the grains; these pores are difficult to eliminate by subsequent hot-pressing.     

Hot Isostatic Press Sintering and Properties of Silicon Nitride without Additives

Fully densified silicon nitride without additives was fabricated by means of hot isostatic pressing. The sintering process of highly pure powder was investigated with special interest in the evolution of α–β phase transformation, densification, and microstructure development. It was observed that the transformation occurred without a liquid phase below 1730°C, which corresponds to the melting point of SiO₂. Above 1730°C, the densification and β-grain elongation accelerated concurrently because of the appearance of liquid SiO₂. However, full densification was attained at 1950°C together with marked grain growth. Flexural strength, microhardness, fracture toughness, and Young's modulus of sintered bodies were measured as a function of temperature. In the sintered body started from highly pure powder, excellent MOR behavior was found up to 1400°C. Impurity content of a few hundred ppm was found to be sufficient to make densification easy and to degrade high-temperature strength.     

Al2O3/TiC Based Metal Cutting Tools by Microwave Sintering Followed by Hot Isostatic Pressing

The feasibility of producing Al₂O₃/TiC metal cutting tools by fast microwave sintering followed by hot isostatic pressing was examined. Microwave heating profiles able to ensure near-full densification of Al₂O₃/TiC ceramic components were determined. Simple-shape specimens could be sintered to a bulk density of 97% theoretical density (TD) while in the case of tool-shaped ones maximal densification levels attained were somewhat lower, i.e., ∼95% TD. Temperature uniformization—within the heating chamber—by using a particulate SiC susceptor noticeably reduced tool cracking propensity. Densification levels in the range acceptable for commercial tool manufacturing (≥98% TD) were achieved by hot isostatic pressing of the microwave-sintered parts. The isostatically pressed parts exhibited a Vickers hardness H _v≅ 2000 kg/mm² and a fracture toughness K _IC∼ 4.3 MPa·m^1/2.     

Pulsed Electric Current Sintering of Silicon Nitride

Pulsed electric current sintering (PECS) has been used to densify α-Si₃N₄ powder doped with oxide additives of Y₂O₃ and Al₂O₃. A full density (>99%) was achieved with virtually no transformation to β-phase, resulting in a microstructure with fine equiaxed grains. With further holding at the sintering temperature, the α-to-β phase transformation took place, concurrent with an exaggerated grain growth of a limited number of elongated β-grains in a fine-grained matrix, leading to a distinct bimodal grain size distribution. The average grain size was found to obey a cubic growth law, indicating that the growth is diffusion-controlled. In contrast, the densification by hot pressing was accompanied by a significant degree of the phase transformation, and the subsequent grain growth gave a broad normal size distribution. The apparent activation energy for the phase transformation was as high as 1000 kJ/mol for PECS, almost twice the value for hot pressing (∼500 kJ/mol), thereby causing the retention of α-phase during the densification by PECS.     

Compressive Creep of a Fine-Grained Poly crystal line Yttria

Compressive creep of a high-purity fine-grained polycrys-talline yttria ceramic processed by hot isostatic pressing has been investigated in the 1130–1210°C temperature range for stresses between 6 and 92 MPa. The main creep mechanism is grain boundary diffusion controlled by an interface reaction. The most striking feature is the strong dynamic grain growth whereas static grain growth is negligible in the studied temperature domain.