Effect of Seeding on the Microstructure and Mechanical Properties of α-SiAlON: II, Ca-α-SiAlON

Seeding effects on the microstructure and mechanical properties of single-phase Ca-α-SiAlON ceramics have been investigated. Whereas a small amount of seeds can transform the microstructure from one of fine equiaxed grains to one consisting of many needle-like grains, the highest fracture toughness of 8 MPa·m^1/2 is not reached until 8% seeding. This contrasts with the much higher seed efficiency in Y-SiAlON, where the peak toughness is reached at 1% seeding. The difference and the general trend of mechanical properties of seeded α-SiAlONs are discussed in terms of α-SiAlON formation and toughening mechanisms.     

Photoluminescence of Cerium-Doped α-SiAlON Materials

Cerium-doped α-SiAlON (M _x Si_{12−( m + n )}Al _{m + n} O _n N_{16– n} ) materials have been prepared by gas-pressure sintering and post-hot-isostatic-press (HIP) annealing, using four powder mixtures of α-Si₃N₄, AlN, and either (i) CeO₂, (ii) CeO₂+ Y-α-SiAlON seed, (iii) CeO₂+ Y₂O₃, or (iv) CeO₂+ CaO. Cerium-containing CeAl(Si_{6– z} Al _z )(N_{10– z} O _z ) (JEM) phase, rather than Ce-α-SiAlON phase, forms in the sample with only CeO₂, whereas a single-phase α-SiAlON generates in samples with dual doping (CeO₂+ Y₂O₃ and CeO₂+ CaO). On ultraviolet-light excitation, JEM gives one broad emission band with maximum at 465 nm and a shoulder at 498 nm; α-SiAlON shows an intense and broad emission band that peaks at 500 nm. The unusual long-wavelength emissions in JEM and α-SiAlON are due to increases in the nephelauxetic effect and the ligand-field splitting of the 5 d band, because the coordination of Ce³⁺ in JEM and α-SiAlON is nitrogen enriched.     

Microstructural Tailoring and Characterization of a Calcium α-SiAlON Composition

Three calcium α-SiAlON microstructures—namely, fine-grained, bimodal, and large elongated—were developed using powders of the same composition and then characterized. The evolution of grain size and morphology was determined to be a process of nucleation and growth that could be controlled with a two-step sintering technique. The extent of texture was identified in the as-hot-pressed materials as a function of sintering conditions. Samples with different microstructures exhibited different hardness and fracture toughness. The true hardness was derived from the intrinsic relation between applied loads and indent sizes. The effect of microstructure on hardness and fracture toughness was analyzed.     

白光LED用新型红色荧光粉的组成与发光性能的关系

白光LED有望发展成为新一代绿色照明光源.荧光粉作为配套材料,其性能优劣直接影响白光LED的发光效率、亮度以及显色性等.高效红色荧光粉已经成为白光LED发展的瓶颈.概述了Eu3+激活的钨/钼酸盐、氧化钇铋和钛酸盐,Sm3+激活的锌酸锶,Pr3+和Bi3+共激活的钛酸钙,Eu2+激活的氮化物,Ce3+激活的硅锗酸盐石榴石以及Mn4+激活的多铝酸钙和Mn2+激活的硫氧化锌钙等白光LED用新型红色荧光粉的发光性能的研究进展;着重分析了它们的组成变化对荧光性能的影响;并对今后的研究提出了一些设想.     

Highly Transparent Lu-α-SiAlON

Novel Lu-α-SiAlON ceramics were produced by hot pressing mixtures of Si₃N₄, Lu₂O₃, AlN, and Al₂O₃ at 1950°C for 2 h in a nitrogen atmosphere. The resultant SiAlON was fully dense and possessed a uniform, equiaxed microstructure with a grain size of ∼1 μm, which resulted in a high hardness of >19 GPa. In addition to high hardness, the sample showed very high optical transparency in the visible light region, with >70% transmission at higher wavelengths. This high transparency was attributed to the uniform, dense microstructure and lack of residual grain-boundary phase.     

Synthesis of α-SiAlON Seed Crystals

Single-phase seed crystals of Ca- and Y-α-SiAlONs have been synthesized for tailoring microstructure of α-SiAlON ceramics. The influence of composition, sintering temperature, and nitrogen pressure on the size and morphology of seeds has been explored. Guidelines for α-SiAlON seed preparation and morphology control are provided.     

Self-Reinforced Nitrogen-Rich Calcium–α-SiAlON Ceramics

Nitrogen-rich Ca–α-SiAlON ceramics with nominal compositions Ca _x Si_{12−2 x} Al_{2 x} N₁₆ and 0.2≤ x ≤2.6, extending along the Si₃N₄–1/2Ca₃N₂:3AlN tie line, were prepared from Si₃N₄, AlN, and CaH₂ precursors by hot pressing at 1800°C. The x values attained were determined by energy-dispersive X-ray (EDX) microanalysis and X-ray powder diffraction (XRPD) data using the Rietveld method. The results show that Ca–α-SiAlONs form continuously within the compositional range x =0 to at least x =1.82. Phase assemblages, lattice parameters, Vickers hardness, and fracture toughness were determined and correlated to the calcium content, x . Owing to a high sintering temperature and the use of CaH₂ as a precursor, grain growth was kinetically enhanced, resulting in self-reinforced microstructures with elongated grains. The obtained Ca–α-SiAlON ceramics demonstrate a combination of both high hardness ∼21 GPa, and high fracture toughness ∼5.5 MPa·m^1/2.     

Machinable α-SiAlON/BN Composites

Dense machinable α-SiAlON/BN composites were fabricated by hot-pressing using turbostratic boron nitride (tBN) obtained from nitridation of melamine diborate. The tBN was added to the starting powders, or introduced as a coating that formed in situ on α-Si₃N₄ carrier powders during nitridation, and was subsequently converted to hexagonal boron nitride (hBN) during hot pressing by solution reprecipitation. These composites maintain high strength at 1000°C and their strength/hardness are much higher than similar composites prepared using commercial hBN powder, which yielded a coarser microstructure. Good machinability was achieved despite a flat R curve.     

Preparation of Multication α-SiAlON Containing Strontium

The possibility of having Sr as an interstitial metal cation in α-SiAION has been investigated in two systems: a single-cation system (Si₃N₄-SrO-AlN) and a multication system (Si₃N₄-(Y₂O₃/SrO/CaO)-AlN). It was found that Sr alone does not form α-SiAlON and that Sr could only be accommodated in α -SiAION in conjunction with Y and Ca. The Sr content of α-SiAION increased as the total content of (Y + Ca) increased and appeared to reach a limit at 0.5 at.%, or 0.15 atom per α-SiAlON. Unexpectedly, some of the α-SiAlON that contained (Sr + Y + Ca) was present as laths or fibers with the c -axis perpendicular to the hot-press direction.     

Microstructure Control of In-Situ-Toughened α-SiAlON Ceramics

Single-phase α-SiAlON with elongated grains is obtained from α-Si₃N₄ powder for a broad range of compositions of practical interest. Following the concept of nucleation and growth, two-step firing is used for microstructure control. This method takes advantage of the slow transformation reaction from α-Si₃N₄ to α-SiAlON at low temperature when the composition is near the α-SiAlON phase boundary and, hence, is marginally stable. For more-stable compositions, the seeding of α-SiAlON crystals is more effective, because it allows elongated grains to grow onto the seed crystals. The fracture toughness is strongly correlated with the microstructure and is enhanced greatly in the optimized materials.     

Control of Microstructures in α-SiAlON Ceramics

The effects of sintering cycles and doping elements on the microstructures of Ln-α-sialon were studied. The results showed that microstructures with an elongated α-sialon morphology could be obtained through high-temperature post-heat treatment (1800–1900°C) or by prolonging soaking times during sintering. Different rare-earth elements had a profound effect on the microstructure of the resulting α-sialon. The Ln-α-sialon doped with low- Z -value elements could easily develop elongated grains with higher aspect ratio.     

Formation of an α-SiAlON Layer on ß-SiAlON and Its Effect on Mechanical Properties

We have developed a technique for in situ formation of an alpha-SiAlON layer on sintered ß-SiAlON. The technique consists of packing a powder compact of ß-SiAlON composition with alpha-SiAlON composition powder, presintering, and sintering. Using this technique, it is possible to control the thickness of the layer by changing the presintering conditions during heating to a sintering temperature. The introduction of an alpha-SiAlON layer increases the surface hardness and improves the wear and oxidation resistance, with a moderate reduction of flexural strength. The surface modification of ß-SiAlON may provide opportunities of wider application of ß-SiAlON to wear- and oxidation-resistant components.     

Formation of AlN-Polytypoid Phases during α-SiAlON Decomposition

Phase transformations from α– to ß–SiAlONs (i.e., from α' to ß') have been recently reported in a number of rare-earth SiAlON systems during postsintering heat treatment. In the present work, this transformation process in a Sm (α+ß)-SiAlON material is studied by using XRD, TEM, and EDS X-ray mapping techniques. It is observed that in addition to the formation of ß' and M' phases, the α'-to-ß' transformation is accompanied by a significant increase in the amount of an AlN-polytypoid phase. The results suggest that some α' phases are thermodynamically unstable at temperatures lower than the material sintering temperature and will decompose when conditions allow. For the composition studied in this work, the α-SiAlON decomposition can be described in general as α'→ß'+ M'+ AlN polytypoid.     

Synthesis of Cerium α-SiAlON with Nuclei Addition

Cerium α-SiAlON ceramics were made from a powder mixture of Si₃N₄-AlN-CeO₂ that contained 1 wt% yttrium α-SiAlON powder. Plasma-activated sintering was used to examine the effect of the cooling rate on the formation of α-SiAlON. The formation of cerium α-SiAlON was suggested to be controlled by the nucleation at the surface of α-SiAlON nuclei, because α-phase formation could not occur without the addition of SiAlON powder. The solubility of cerium in the α-SiAlON was shown to be less than a previously predicted critical value.     

Hollow Beads Composed of Nanosize Ca α-SiAlON Grains

Carbothermal reduction—nitridation (CRN) of SiO₂ is an attractive method to manufacture Si₃N₄ powders with controlled grain morphology. Moreover, β-SiAlON powders could also be synthesized from either pure powder mixture or some inexpensive raw minerals by CRN and the resulting powders favored the sintering of SiAlON product. However, there have been few works on preparing α-SiAlON powders so far. In this work, Ca α-SiAlON powder was synthesized by CRN of a SiO₂—Al₂O₃—CaCO₃ mixture. An unusual morphology of hollow beads 200 to 500 nm in diameter with a great deal of nanosize α-SiAlON particles around 10 to 30 nm in diameter was observed from the resultant Ca α-SiAlON powders, which has not been reported for SiAlON ceramics before.     

Fabrication of Elongated α-SiAlON via a Reaction-Bonding Process

A reaction-bonding process, which offers low sintering shrinkage and is a low-cost process, was applied to fabricate Y–α-SiAlON ceramics. The green compacts composed of Si, Y₂O₃, Al₂O₃, and AlN were nitrided and subsequently postsintered. Dense single-phase Y–α-SiAlON with elongated grain morphology could be achieved in the specimen postsintered at 1900°C. The material exhibited high hardness (1850 HV10) and high fracture toughness (5.1 MPa·m^1/2).     

R-Curve Behavior of In Situ Toughened α-SiAlON Ceramics

R -curves of single-phase Y- and Ca-containing α-SiAlON ceramics have been measured. They range from flat ones for fine-grain ceramics to pronounced rising ones when large elongated grains are present. The highest toughness measured reached 11.5 MPa·m^1/2 over a crack extension of about 1000 μm.     

Grain Growth of α-SiAlON in the Calcium-Doped System

Two calcium-doped α-SiAlON compositions (Ca_0.6Si_10.2Al_1.8−O_0.6N_15.4 and Ca_1.8Si_6.6Al_5.4O_1.8N_14.2) were prepared by hot pressing at 1600° and 1500°C, respectively, for complete phase transformation from α-Si₃N₄ to α-SiAlON. Both samples were subsequently fired at different temperatures for different periods of time to study the grain growth of α-SiAlON. Elongated α-SiAlON grains were developed in both samples at high temperatures. The kinetics of grain growth was investigated based on the variations in length and width of the α-SiAlON grains under different sintering conditions. Different growth rates were found between the length and width directions of the α-SiAlON crystals, resulting in anisotropic grain growth in the microstructural development.     

The Effect of Powder Mixing Procedures on α-SiAlON

Various procedures of mixing starting powders for hot-pressing α-SiAlON ceramics were studied. They included different milling methods (attrition milling, ball milling, and sonication), liquid medium (water, isopropyl alcohol, and pyridine), and atmospheres (ambient air and nitrogen). These mixing procedures resulted in markedly different densification behavior and fired ceramics. As the powders experienced increasing oxidation because of mixing, the densification temperature decreased, the amount of residual glass increased, and α-SiAlON was destabilized and replaced by β-SiAlON and AlN polytypes during hot pressing. These effects were mitigated when pyridine, nitrogen, and sonication were used. Several protocols that yielded nearly phase-pure, glass-free dense α-SiAlON were thus identified.     

α-SiAlON Ceramics Obtained by Slip Casting and Pressureless Sintering

Dense α-SiAlON ceramics were obtained by pressureless sintering of green compacts prepared using slip casting. The rheological properties of the reaction SiAlON suspension were optimized to achieve a high degree of dispersion with a high solids volume fraction, which resulted in homogeneous and relatively dense green bodies with high sintering ability, which could be densified by pressureless sintering at 1750°C for 2 h. The sintered samples revealed a high degree of uniformity and almost fully dense microstructures that consisted of many small, elongated grains homogeneously dispersed in the fracture surfaces, which had properties comparable with those of other SiAlONs obtained using hot pressing.