Development of microstructure during the fabrication of Si3N4 by nitridation and pressureless sintering of Si:Si3N4 compacts

The technique for the fabrication of Si₃N₄ which was investigated involves the nitridation of Si:Si₃N₄ powder compacts containing additions of sintering aids (e.g. Y₂O₃ and Al₂O₃) followed by pressureless sintering. The development of microstructure during fabrication by this method has been followed by X-ray diffraction and analytical electron microscopy. As well as being important for the sintering process, it was found that the sintering aids promote nitridation through reaction with the surface silica on the powder particles. During nitridation extremely fine grained Si₃N₄ forms at silicon powder particle surfaces and at tunnel walls extending into the interior of these powder particles. Secondary crystalline phases which form during nitridation are eliminated from the microstructure during sintering. The- to-Si₃N₄ phase transformation is completed early in the sintering process, but despite this the fully sintered product contains fine-Si₃N₄ grains. The grains are surrounded by a thin intergranular amorphous film.     

Microwave and conventional sintering of rapidly solidified Al2O3-ZrO2 powders

The Al₂O₃-ZrO₂ eutectic composition was rapidly solidified, forming amorphous and crystalline structures. The as-quenched material was crushed and pressed into pellets which were sintered conventionally or with microwaves. Conventional and microwave sintering at temperatures up to 1600 °C resulted in a microstructure where 100–200 nm ZrO₂ grains were present intergranularly in the -Al₂O₃ grains. Larger ZrO₂ grains (1 m) were found intergranularly. The as-quenched lamellar structure spheroidized during sintering at high temperatures. Boron contamination of the powders resulted in more homogeneous and dense as-fired samples but promoted the ZrO₂ tetragonal-to-monoclinic transformation, which was attributed to increased grain boundary diffusivity. Conventional sintering at low temperatures resulted in the formation of rods of an Al₂O₃-rich phase which grew from a low-melting B₂O₃-rich liquid.     

Formation of intergranular amorphous films during the microstructural development of liquid phase sintered silicon carbide ceramics

The microstructure of liquid phase sintered SiC ceramics was characterised by means of high resolution transmission electron microscopy (HRTEM). The SiC ceramics were pressureless sintered with the additions of Al₂O₃ and Y₂O₃ at sintering temperatures of 1800 and 1950°C, respectively. At a sintering temperature of 1800°C the microstructure of the SiC ceramics has no crystallised secondary phase and the SiC grains are separated by an intergranular amorphous film. In contrast, in the case of the microstructure of SiC ceramics sintered at 1950°C a clean interface without any amorphous layer between the SiC grains was observed. The secondary phase is crystallised into the Y₃Al₅O₁₂ phase and exhibits a clean interface between the SiC grains. An explanation for the existence or the absence of the intergranular glass films are given by an extended Clarke's model of the force balance of attractive van der Waals forces and repulsive steric forces. The chemical decomposition of the intergranular glass film at elevated temperature was considered.     

Effect of Powder Processing and Sintering Conditions on the Microstructural,Thermal, and Mechanical Properties of Reticulated Zinc Oxide Ceramic Foams

Ceramic foams are made of zinc oxide using different amounts of Sb₂O₃ and Bi₂O₃ as sintering aids. The effect of a ball milling processing of the starting powders and the sintering temperature on the microstructure and the properties of the ZnO foams is investigated. The focus is set on the evolution of the secondary phases formed within the microstructure of ZnO. A determining effect is identified in the amount of an Al₂O₃ impurity which is introduced by abrasion of the milling vessels during ball milling. Alumina is partially dissolved in a spinel α–Zn₇Sb₂O₁₂ secondary phase which is stabilized by a reduction of the unit cell volume. Remaining Al₂O₃ is incorporated into zinc oxide under formation of a defect wurtzite phase. The phase evolution is a complex function of the content of sintering aids, the Al₂O₃ impurity level and the sintering temperature. The shrinkage during sintering and the porosity evolution are correlated to the phase composition within the ZnO material. The thermal conductivity and the compressive strength of the foams are determined, normalized with respect to their porosity, and correlated to the microstructure and phase composition of the ZnO strut material.     

Influence of chemical composition on sintering of bismuth-titanium-doped zinc oxide

Liquid-phase sintering (LPS) of ceramics issued from powders of bismuth-titanium-doped zinc oxide, made of spherical grains constituted of small crystallites, were studied by dilatometry. A correlation can be established between the shape of the shrinkage curves and the microstructure of the ceramics. During sintering the spherical grains are destroyed as soon as the liquid phase appears and the rearrangement proceeds directly between crystallites. Systematic studies were carried out on bismuth-titanium-doped ZnO. For small Bi contents, the beginning of a solid-phase sintering process occurs. For 1 at % Bi in the binary system Bi-doped ZnO, rapid shrinkage leads to a well-densified ceramic with a grain size of 70 m on average. The influence of the amount of titanium iny% Ti-1% Bi-doped ZnO is discussed. Whatever the amount of Ti, LPS is observed. The shrinkage curves depend greatly on the amount of Ti: only a Ti content ofy=0.6 % leads to an increase in grain size (100 m on average).     

Transient creep behaviour of hot isostatically pressed silicon nitride

Transient creep is shown to dominate the high-temperature behaviour of a grade of hot isostatically pressed silicon nitride containing only 4 wt% Y₂O₃ as a sintering aid. Contributing factors to transient creep are discussed and it is concluded that the most likely cause of longterm transient creep in the present study is intergranular sliding and interlocking of silicon nitride grains. In early stages of creep, devitrification of the intergranular phase, and intergranular flow of that phase may also contribute to the transient creep process. The occurrence of transient creep precluded the determination of an activation energy on the as-received material. However, after creep in the temperature range 1330–1430°C for times exceeding approximately 1100 h, an apparent activation energy of 1260 kJ mol^–1 was measured. It is suggested that the apparent activation energy for creep is determined by the mobility and concentration of diffusing species in the intergranular glassy phase. The time-to-rupture was found to be a power function of the minimum strain rate, independent of applied stress or temperature. Hence, creep-rupture behaviour followed a Monkman-Grant relation. A strain rate exponent of – 1.12 was determined.     

Influence of powder characteristics on gas pressure sintering of Si3N4

The sintering behaviours of four kinds of Si₃N₄ powders were investigated by dilatometry in 10 atm N₂ at 1890, 1930 and 2050° C. The sinterabilities of powders were compared and discussed in relation to the powder characteristics. A large size distribution in the powder accelerated grain and pore growth at <1800° C, which resulted in the inhibition of further densification at >1800° C. The presence of carbon in a powder prevented densification. A powder with a uniform grain size kept the microstructure of the sintered material uniform during sintering at <1800° C and gave a high degree of shrinkage at >1800° C. Densification at >1800° C was accompanied by the dissolution of equi-axial -Si₃N₄ grains and reprecipitation as elongated -Si₃N₄ grains from the oxynitride liquid. The relation between the densification and microstructure is discussed in terms of the relative rates of densification and grain growth.     

Piezoelectricity and microstructures of modified lead titanate ceramics

Modified lead titanate ceramics with the composition Pb_0.70 Ca_0.30 Ti_0.94 (Co_1/2W_1/2)_0.06 O₃ with 1 mol% MnO were prepared by the mixed oxide route. By varying the sintering temperature, ceramics with average grain sizes between 2.8 and 5m were obtained. An increase in grain size resulted in an increased electromechanical anisotropy and a decreased dielectric constant. Transmission electron microscopy was used to examine the ferroelectric domain boundaries and intergranular phases. Indications are that during poling favourably oriented domains approximately doubled in size by 90 ° type domain wall switching. Evidence was found for the existence of a vitreous intergranular phase at multiple grain junctions. EDS microanalysis indicated that the amorphous grain boundary phase had a lower lead content than the bulk material.     

Effect of annealing on mechanical properties of self-reinforced alpha-silicon carbide

Alpha-SIC powder containing 7.2 wt % Y₃Al₅O₁₂ (YAG, yttrium aluminum garnet) and 4.8 wt % SiO₂ as sintering aids were hot-pressed (SC0) at 1820°C for 1 h and subsequently annealed at 1920°C for 2 h (SC2), 4 h (SC4) and 8 h (SC8). When the annealing time was increased, the microstructure changed from equiaxed to elongated grains and resulted in self-reinforced microstructure consisted of large elongated grains and small equiaxed grains. Development of self-reinforced microstructure, consisted of mostly 6H phase, resulted in significant improvements in toughness. However, the improved toughness was offset by a significant reduction in strength as in the materials consisted of 4H originated from -SiC. The fracture toughness and strength of the 8-h annealed materials were 5.5MPa · m^1/2 and 490 MPa, respectively.     

Spark plasma sintering of a p-type Si1?x Ge x alloy: identification of the densification mechanism by isothermal and anisothermal methods

Spark plasma sintering of a p-type Si_0.795Ge_0.200B_0.005 alloy has been investigated in vacuum, in the 400–1200 °C temperature range. The densification mechanism has been determined using isothermal and anisothermal methods. In spite of a slight material degradation for the highest sintering temperatures (occurrence of cristobalite nodules homogeneously dispersed in intergranular and intragranular positions), it is proposed that densification proceeds by grain boundary sliding accommodated most probably by silicon volume diffusion. The microstructure observation of several sintered samples using transmission electron microscopy supports the densification mechanism advanced. Because the elemental grains remain mostly equiaxe whatever the sintering conditions, a grain intercalation mechanism may be also implicated during densification.     

Compositional effects on densification and microstructural evolution of bismuth titanate

The effects of small compositional variations on the densification and microstructural evolution of bismuth titanate (Bi₄Ti₃O₁₂) powder compacts were investigated during sintering and during hot forging. For a nominally stoichiometric Bi₄Ti₃O₁₂ composition, sintering commenced at 870°C, leading to a relatively dense microstructure (relative density >97% of the theoretical value) with randomly aligned elongated grains after 1 h at 1100°C. Small additions (1 weight percent) of Bi₂O₃ or TiO₂ to the nominally stoichiometric Bi₄Ti₃O₁₂ composition shifted the onset of sintering to lower or higher temperatures, respectively, but did not significantly alter the final density. Hot forging produced a microstructure of aligned, elongated grains. The small compositional variations did not seriously influence the ability to develop the elongated grain alignment. However, subsequent annealing of the hot forged materials produced significant changes in the aligned grain microstructure. The elongated grain alignment in the nominally stoichiometric Bi₄Ti₃O₁₂ composition was destroyed during subsequent annealing for less than 2 h at 1100°C.     

Yb2O3-fluxed sintered silicon nitride

Microstructural development and crystallization behaviour of Yb₂O₃-fluxed sintered silicon nitride materials was investigated using CTEM and HREM. The materials contained 5 and 10 vol% Yb₂O₃ as sintering additives. After densification, both compositions were subsequently heat treated to crystallize the residual amorphous secondary phases present at triple-grain regions. In the material doped with 5 vol% Yb₂O₃, only an amorphous secondary phase was observed after sintering, which was about 80% crystalline (Yb₂Si₂O₇) after the post-sintering heat treatment. A metastable phase was formed in the material with 10 vol% additives after sintering, with about 70% crystallinity in the triple-point pockets. Upon postsintering heat treatment, the material could be completely crystallized. During heat treating, the metastable phase combined with the remaining glass to form Yb₂SiO₅ plus Yb₂Si₂O₇ and a small amount of Si₃N₄ which deposited epitaxially on pre-existing Si₃N₄ grains in areas of low-energy within the triple-point pockets. All materials contained thin amorphous films separating the grains. The amorphous intergranular films along grain boundaries (homophase boundaries) revealed excess ytterbium and oxygen. The thickness of the intergranular films was about 1.0 and 2.5 nm for the grain boundaries and the phase boundaries, respectively, independent of additive content and heat-treatment history.     

Sintering of 3 mol % Y2O3-TZP and its fracture after ageing treatment

TZP ceramic of 99.7% theoretical relative final density was obtained by pressureless sintering a commercial co-precipitated 3 mol % Y₂O₃-ZrO₂ powder at 1400° C for 10 h. Fracture surfaces of the aged material revealed that the fracture of TZP ceramic was typified by an intergranular mode in areas where the phase was mainly tetragonal, whereas the transgranular mode was found predominantly in the area containing more monoclinic phase. Microcracks induced by the (t) (m) transformation provided short paths for water to accelerate the property degradation of TZP upon low-temperature ageing in a humid atmosphere.     

Microstructure and mechanical properties of a Si3N4/Al2O3 nanocomposite

A nanocomposite material fabricated by hot pressing in the form of nanometre-sized Si3N4 particles dispersed in an Al2O3 matrix has been shown to exhibit enhanced mechanical properties compared with monolithic matrix material. It was observed by transmission electron microscopy (TEM) for the first time that the alumina grains were in the shape of elongated columns with aspect ratios in the range 2.5–4. The presence of liquid phase during sintering was found to be responsible for the appearance of columnar grains. Regular hexagon-shaped larger -Sialon grains formed during sintering were mainly situated at grain boundaries of the matrix material while irregular smaller dispersoids were trapped within the alumina grains. The improvement in the mechanical properties of the nanocomposite is attributed to the change in fracture mode from intergranular fracture to transgranular fracture, the self-reinforcement effect arising from the elongated columnar grains of the matrix, as well as the pinning effect due to the existence of intergranular -sialon particles. It was revealed that the trapped particles have an -Al2O3 structure with partial sites of aluminium and oxygen atoms substituted by silicon and nitrogen atoms, which is also likely to lead to the strengthening of the composite.     

A high-resolution transmission electron microscope study of a zinc oxide varistor

Investigations were made of varistor microstructure, the morphology of Bi₂O₃ at multiple ZnO grain junctions, Bi₂O₃/ZnO grain boundaries and ZnO/ZnO grain boundaries (especially whether Bi₂O₃ is present or not at the ZnO/ZnO grain boundary) by means of high-resolution transmission electron microscopy and X-ray microanalysis in the scanning transmission electron microscope. Bi₂O₃ at multiple ZnO grain junctions consists of small particles of 0.1m in diameter, and they are vitrified to some extent. It is suggested that bismuth ions dissolve into ZnO grains over a 30 nm range from a Bi₂O₃/ZnO grain boundary; however, there is no bismuth at ZnO/ZnO grain boundaries.     

The effect of doping process on microstructure and dielectric properties of BaTiO3-based X7R materials

The effect of doping process on the dielectric properties, sintering behavior and microstructure were investigated on the BaTiO₃–Nb₂O₅–Co₃O₄ ternary system ceramic. Temperature stable dielectric ceramics were obtained by different doping processes if only appropriate Nb⁵⁺+Co³⁺ amount and Nb⁵⁺/Co³⁺ ratio were adopted. The dielectric constant was enhanced to the largest extent by nanometer oxide doping and the temperature characteristic satisfied the X7R specification. Two kinds of grains were observed in all the samples: matrix grains (BaTiO₃) and the secondary phase grains (Ba₆Ti₁₇O₄₀) formed by the incorporation of Nb⁵⁺ and Co³⁺ into BaTiO₃ lattice and Ti⁴⁺ segregation. The matrix grains were about 1 m in diameter and showed little grain growth with increasing temperature in all the doped samples, whereas the sizes of the secondary phase grains were strongly dependent on the doping process. The secondary phase formed liquid phase during firing, but the liquid phase contributed little to the densification of ceramics.     

Electronic paramagnetic resonance (EPR) study of the structure of ZnO varistors prepared by various chemical methods

The structure of ZnO varistors prepared by different chemical methods was studied by the electronic paramagnetic resonance (EPR) method. The presence of Mn²⁺ ions in both ZnO lattice and electroconductive phase was used as a sensitive probe for the analyses of structural changes which occur during sintering of ZnO varistors. Potential mechanisms which can contribute to the formation of resonant lines were considered. The concentration of paramagnetic centres was quantitatively analysed. The variation of EPR signals of Mn²⁺ ions in ZnO phase was registered as a function of the chemical methods used for the preparation of powders only when samples were sintered at lower temperatures and non-linear characteristics of varistor ceramics had not yet been reached. At higher sintering temperatures EPR signals of Mn²⁺ ions in electroconductive phase differed only in the case of powders obtained by NaOH coprecipitation.     

Silicon nitride ceramics with celsian as an additive

Four different Si₃N₄ ceramics using 10 wt% celsian (BaAl₂Si₂O₈) as an additive, have been prepared by hot pressing. Different celsian sources and hot-pressing conditions were used and their effects on densification, in situ crystallization of celsian, to phase transformation, microstructures and properties, were examined. The use of a presynthesized celsian as a raw material was found to enhance the rates of densification and phase transformation due to the excess silica from raw Si₃N₄ powders which, however, did not change the microstructure and crystallization behaviour of celsian. Increases in hot-pressing temperatures and times increased the total number of large elongated grains and resulted in coincidental increases in strength and toughness until the to transformation was complete. An intermediate quench-and-reheat step during hot pressing made the microstructure finer and more uniform by greatly reducing the large-sized elongated grains. The quenching step also disrupted complete crystallization of celsian which led to more grain-boundary glassy phase and compromised the material's high-temperature properties.     

Microstructure and properties of silicon nitride ceramics with calcium aluminate additions

Silicon nitride ceramics containing calcium aluminates as sintering aids have been prepared by hot pressing at 1650°C in a nitrogen atmosphere, and the effect of sintering aid content on their microstructure, phase composition, mechanical strength, and air oxidation resistance has been studied. The results demonstrate that the Si₃N₄ ceramic containing 10 wt % calcium aluminates has a uniform distribution of intergranular multicomponent oxide phases and consists of densely packed silicon nitride grains. Owing to this, it offers the maximum mechanical strength (850 MPa) and is stable to air oxidation up to 1300°C.     

Gas pressure sintering of β-silicon nitride

The sintering behaviour of -Si₃N₄ powder was investigated in 980 kPa (10 atm) nitrogen at 1800–2000 °C. It is shown that -Si₃N₄ has a higher sinterability than the finer -Si₃N₄. The solution of small grains and reprecipitation on large grains occurred during sintering at >1600 °C. The rate-determining step in the liquid-phase sintering is believed to be the diffusion of material through the liquid phase at grain boundaries. There was no abnormal grain growth during gas pressure sintering of -Si₃N₄. The microstructures of gas pressure sintered materials from -Si₃N₄ were more uniform than those from -Si₃N₄. The densification mechanism of -Si₃N₄ is discussed in relation to that of -Si₃N₄.