Effect of grain width and aspect ratio on mechanical properties of Si<Subscript>3</Subscript>N<Subscript>4</Subscript> ceramics

Sintering additives Y₂O₃ and Al₂O₃ with different ratios ((Y₂O₃/Al₂O₃) from 1 to 4) were used to sinter Si₃N₄ to high density and to induce microstructural changes suitable for raising mechanical properties of the resultant ceramics. The sintered Si₃N₄ ceramics have bi-modal microstructures with elongated β-Si₃N₄ grains uniformly distributed in a matrix of equiaxed or slightly elongated grains. Pores were found within the grain boundary phase at the junction regions of Si₃N₄ grains. The highest average aspect ratio (length/width of the grains) of ∼4.92 was found for Y₂O₃/Al₂O₃ ratio of 2.33 with fracture toughness and strength values of ∼7 MPam^1/2 and 800 MPa, respectively. The effect of microstructure, specifically grain morphology, on mechanical properties of sintered Si₃N₄ were investigated and found that the aspect ratio of the elongated grains is the most important microstructural feature which controls mechanical properties of these ceramics.     

Preparation and characterization of porous Si<Subscript>3</Subscript>N<Subscript>4</Subscript> ceramics prepared by compression molding and slip casting methods

Porous silicon nitride (Si₃N₄) ceramics were fabricated by compression molding and slip casting methods using petroleum coke as pore forming agent, and Y₂O₃-Al₂O₃ as sintering additives. Microstructure, mechanical properties and gas permeability of porous Si₃N₄ ceramics were investigated. The mechanical properties and microstructure of porous Si₃N₄ ceramics prepared by compression molding were better than those which were prepared by slip casting method, whereas slip casting method is suitable for the preparation of porous Si₃N₄ ceramics with higher porosity and excellent gas permeability.     

Effects of organic additives on microstructure and mechanical properties of porous Si<Subscript>3</Subscript>N<Subscript>4</Subscript> ceramics

Green bodies of porous Si₃N₄ ceramics were shaped by extrusion technique using different organic additives as binder during extrusion molding. Different porosity, microstructures and mechanical properties after the extrusion, drying, debinding and sintering stages were investigated. The solid slurry content of 70–75% and extrusion pressure of 0.5–1.0 MPa had played a decisive role in the smooth realization of extrusion molding. The porous Si₃N₄ ceramics were obtained with excellent properties using 4% hydroxypropyl methyl cellulose (HPMC) as binder and polyethylene glycol (PEG) of molecular weight, 1000, as plasticizer with a density of 1.91 g cm⁻³, porosity of 41.70%, three-point bending strength of 166.53 ± 20 MPa, fracture toughness of 2.45 ± 0.2 MPa m^1/2 and Weibull modulus (m) of 20.75.     

Si<Subscript>3</Subscript>N<Subscript>4</Subscript>/TiN composites produced from TiO<Subscript>2</Subscript>-Modified Si<Subscript>3</Subscript>N<Subscript>4</Subscript> powders

Si₃N₄/TiN composites have been produced by hot pressing at temperatures from 1600 to 1800°C in a nitrogen atmosphere, using silicon nitride powders prepared by self-propagating high-temperature synthesis and surface-modified with titanium dioxide nanoparticles. We examined the effect of TiO₂ content on the microstructure, phase composition, and mechanical strength of the ceramics. It is shown that titanium nitride can be formed by the reaction Si₃N₄ + TiO₂ → TiN + NO + N₂O + 3Si. The Si₃N₄/TiN composites containing 5–20% TiN have a low density, high porosity, and a bending strength of 60 MPa or lower. In Si₃N₄/TiN ceramics produced using calcium aluminates as sintering aids, the silicon nitride grains are densely packed, which ensures an increase in strength to 650 MPa.     

Low-firing Li<Subscript>2</Subscript>ZnTi<Subscript>3</Subscript>O<Subscript>8</Subscript> microwave dielectric ceramics with BaCu(B<Subscript>2</Subscript>O<Subscript>5</Subscript>) additive

Phase purity, microstructure, sinterability and microwave dielectric properties of BaCu(B₂O₅)-added Li₂ZnTi₃O₈ ceramics and their cofireability with Ag electrode were investigated. A small amount of BaCu (B₂O₅) can effectively reduce the sintering temperature from 1075°C to 925°C, and it does not induce much degradation of the microwave dielectric properties. Microwave dielectric properties of ε _r = 23·1, Q × f = 22,732 GHz and τ _f = − 17·6 ppm/°C were obtained for Li₂ZnTi₃O₈ ceramic with 1·5 wt% BaCu(B₂O₅) sintered at 925°C for 4 h. The Li₂ZnTi₃O₈ +BCB ceramics can be compatible with Ag electrode, which makes it a promising microwave dielectric material for low-temperature co-fired ceramic technology application.     

Microstructure and property enhancement of silicon nitride-barium aluminum silicate composites with β-Si3N4 seed addition

Si₃N₄-barium aluminum silicate (BAS) self-reinforced composites have been prepared by pressureless sintering at 1800 °C for 2 h. The β-Si₃N₄ seeds incorporated in the starting α-Si₃N₄ powders encouraged the α- to β-Si₃N₄ phase transformation, and the final bimodal microstructure with large grains, consequently, led to the improvement of the fracture toughness, from 7.74 to 8.34 MPa m^1/2. The almost-complete crystallized BAS benefited the high-temperature mechanical properties. The residual stress, crack deflection, grain bridging, and pullout were considered as the major toughening mechanisms in this composite.     

Microstructure characterization of hot-pressed β-silicon nitride containing β-Si3N4 seeds

Self-reinforced silicon nitride ceramics were synthesized by introducing 5 wt% previously prepared β-Si₃N₄ seeds into a mixture of α-Si₃N₄ and 8 wt.% of sintering additive. The microscopic evidence indicates that β-Si₃N₄ seeds play an important role in microstructural development and mechanical properties for silicon nitride ceramics. The growth of β-Si₃N₄ grains is initiated from the seeds, resulting in a core/shell microstructure observed in the abnormal grain growth. The internal dislocation, π-boundary, and Moire fringes are present in Si₃N₄ grains, which were formed to compensate the mismatch and compositional differences between the two grains. Coalescence can occur at the final stage of sintering.     

Room-Temperature Photomagnetic Effect of Fe<Subscript>3</Subscript>Ga<Subscript>4</Subscript> Grown on GaAs Substrates

Ga–As–Fe composite films prepared by molecular beam epitaxy at 600°C on GaAs(100) substrates with the stacking sequence of [100-nm GaAs/50-nm Fe₃Ga_{2− x} As _x /100-nm GaAs] exhibit the distinct photo-enhanced magnetization at room temperature. Transmission electron microscopy reveals the formation of metamagnetic Fe₃Ga₄ grains on the sample surface. Illumination power dependence of the enhanced magnetization has been carefully compared with the antiferromagnetic-type magnetization–temperature (M–T) curve (Neel temperature of T _N = 340–390 K), from which we have discussed the existence of photon-mode photo-enhanced magnetization of some sort in addition with the enhancement due to the light-induced heating.     

Varistor properties and aging behavior of ZnO-V<Subscript>2</Subscript>O<Subscript>5</Subscript>-Mn<Subscript>3</Subscript>O<Subscript>4</Subscript> ceramics with sintering process

The microstructure, electrical properties, and DC-accelerated aging behavior of the ZnO-V₂O₅-Mn₃O₄ ceramics were investigated at different sintering temperatures of 850–925°C. The microstructure of the ZnO-V₂O₅-Mn₃O₄ ceramics consisted of ZnO grain as a primary phase, and Zn₃(VO₄)₂ which acts as a liquid-phase sintering aid, in addition to Mn-rich phase as secondary phases. The maximum value (3,172 V/cm) and minimum value (977 V/cm) of breakdown field were obtained at sintering temperature of 850 and 900°C, respectively. The nonlinear coefficient exhibited the highest value, reaching 30 at 925°C and the lowest value, reaching 4 at 850°C. The optimum sintering temperature was 900°C, which exhibited not only high nonlinearity with 24 in nonlinear coefficient, but also the high stability, with %ΔE_1mA = −0.9% and %∆α = −12.5% for DC-accelerated aging stress of 0.85 E_1mA/85°C/24 h.     

Low-temperature sintering of SiC reticulated porous ceramics with MgO–Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–SiO<Subscript>2</Subscript> additives as sintering aids

SiC reticulated porous ceramics (SiC RPCs) was fabricated with polymer replicas method by using MgO–Al₂O₃–SiO₂ additives as sintering aids at 1,000∼1,450 °C. The MgO–Al₂O₃–SiO₂ additives were from alumina, kaolin and Talc powders. By employing various experimental techniques, zeta potential, viscosity and rheological measurements, the dispersion of mixed powders (SiC, Al₂O₃, talc and kaolin) in aqueous media using silica sol as a binder was studied. The pH value of the optimum dispersion was found to be around pH 10 for the mixtures. The optimum condition of the slurry suitable for impregnating the polymeric sponge was obtained. At the same time, the influence of the sintering temperature and holding time on the properties of SiC RPCs was investigated. According to the properties of SiC RPCs, the optimal sintering temperature was chosen at 1,300 °C, which was lower than that with Al₂O₃–SiO₂ additives as sintering aids.     

Chemical solution deposition of CaCu<Subscript>3</Subscript>Ti<Subscript>4</Subscript>O<Subscript>12</Subscript> thin film

CaCu₃Ti₄O₁₂ (CCTO) thin film was successfully deposited on boron doped silica substrate by chemical solution deposition and rapid thermal processing. The phase and microstructure of the deposited films were studied as a function of sintering temperature, employing X-ray diffractometry and scanning electron microscopy. Dielectric properties of the films were measured at room temperature using impedance spectroscopy. Polycrystalline pure phase CCTO thin films with (220) preferential orientation was obtained at a sintering temperature of 750°C. There was a bimodal size distribution of grains. The dielectric constant and loss factor at 1 kHz obtained for a film sintered at 750°C was k ∼ 2000 and tan δ ∼ 0.05.     

Effect of solid content on pore structure and mechanical properties of porous silicon nitride ceramics produced by freeze casting

Porous Si₃N₄ ceramics were prepared by freeze casting using liquid N₂ as refrigerant. The pore structure, porosity, α → β-Si₃N₄ transformation and mechanical properties of the obtained materials were strongly affected by the solid contents of the slurries. Increasing the solid content would reduce the porosity, decrease the pore size and change the pore structure from the aligned channels with dendrites to the round pores with decreased pore size. The formation of this round pores impeded the α → β-Si₃N₄ phase transformation, but was beneficial to the mechanical properties of the obtained porous Si₃N₄ due to its unique pore structure.     

Properties of reaction bonded silicon nitride obtained from slip cast preforms

Fabrication of silicon preforms of high green density (>1·2 g/cm³) by slip casting of silicon (in aqueous medium) has been studied. The nitridation product consists of 59–85% α-Si₃N₄, 7–22%β-Si₃N₄ and 7–23% Si₂N₂O phase. The amounts of un-nitrided silicon were negligible. The microstructure is either granular or consists of needle-like grains (α-Si₃N₄) and whiskers deposited in the large pores. MOR values of the specimens are almost constant up to 1000°C or 1400°C or show slight increase up to 1000°C or 1200°C. In some cases a little dip around 1200°C, then a sharp increase in MOR up to 1400°C was observed.K _ic values are almost constant up to 1000°C, and thereafter increase sharply. Pore size distribution, existence of Si₂N₂O phase and oxidation of RBSN at high temperatures have been considered for the explanation of the observed behaviour.     

Influence of CuO and B<Subscript>2</Subscript>O<Subscript>3</Subscript> on sintering and dielectric properties of tungsten bronze type microwave ceramics: a case study in Ba<Subscript>4</Subscript>Nd<Subscript>9.3</Subscript>Ti<Subscript>18</Subscript>O<Subscript>54</Subscript>

The effect of CuO and B₂O₃ co-doping on the sintering behavior, microstructure and microwave dielectric properties of tungsten bronze type Ba₄Nd_9.3Ti₁₈O₅₄ (BNT) ceramics has been investigated by means of a traditional solid-state mixed oxide route. On the one hand, it was indicated that the mixture of CuO and B₂O₃ is an effective sintering aid for BNT matrix compositions owing to the existence of a low-temperature eutectic reaction. On the other hand, it was found that the addition of CuO and B₂O₃ has an obvious effect on microwave dielectric properties of BNT ceramics, depending on the amount of sintering aids, the sample density and microstructure. The liquid phases from sintering aids can promote densification, but simultaneously induce grain growth which tends to decrease the sintering driving force. BNT ceramics doped with 3 wt% CuO–B₂O₃ mixture can be well sintered at 950°C for 4 h and still exhibit relatively good microwave dielectric properties.     

Microstructure and properties of SiC-whisker-reinforced Si<Subscript>3</Subscript>N<Subscript>4</Subscript> ceramics with calcium aluminate additions

Silicon-nitride-based ceramics containing Al₂O₃-CaO sintering aids and reinforced with silicon carbide whiskers have been prepared by hot pressing at 1650°C in a nitrogen atmosphere, and their microstructure, phase composition, and mechanical properties have been studied. The results indicate that the Si₃N₄ ceramic containing 15 wt % calcium aluminate additions and 10 wt % SiC fibers has a dense microstructure with a uniform distribution of skeletal and dendritic silicon carbide crystals. The observed variations in the morphology of the crystals are tentatively attributed to the secondary crystallization of silicon carbide from the eutectic calcium aluminate melt during cooling.     

Magnetocaloric effect of Gd<Subscript>5</Subscript>Si<Subscript>2</Subscript>Ge<Subscript>2</Subscript> alloys in low magnetic field

The magnetocaloric effect of Gd₅Si₂Ge₂ alloys under heat treatment conditions are investigated in low magnetic fields. The magnetocaloric effect (MCE) is studied by measuring magnetic entropy change (ΔS _M) and adiabatic temperature change (ΔT _ad) in a magnetic field of 1·5 T using a vibrating sample magnetometer (VSM) and a home-made magnetocaloric effect measuring apparatus, respectively. The maximum ΔS _M of the alloys increases by 200% from 4·38 to 13·32 J kg⁻¹ K⁻¹, the maximum ·T _ad increases by 105% from 1·9 to 3·9 K when compared to the as-cast due to the homogeneous composition distribution and microstructure, while the magnetic ordering temperature is slightly reduced. These results indicate that the annealed Gd₅Si₂Ge₂ compounds are promising as high-performance magnetic refrigerants working room temperature in relatively low magnetic fields.     

Low-temperature sintering behavior and properties of <Emphasis Type="Italic">monoclinic</Emphasis>-SrAl<Subscript>2</Subscript>Si<Subscript>2</Subscript>O<Subscript>8</Subscript> ceramics prepared via an aqueous suspension milling process

In this work, by an aqueous suspension milling process, boric acid (H₃BO₃), calcium hydroxide [Ca(OH)₂], strontium carbonate (SrCO₃) and barium hydroxide octahydrate [Ba (OH)₂·8H₂O] are mixed with strontium carbonate (SrCO₃) and kaolin (Al₂O₃·2SiO₂·2H₂O) to prepare SrAl₂Si₂O₈ ceramics with a sintering temperature of 950 °C. According to chemical compositions of flux agents B₂O₃, CaO·2B₂O₃, SrO·2B₂O₃ and BaO·2B₂O₃, raw materials boric acid, calcium hydroxide, strontium carbonate and barium hydroxide octahydrate were introduced to the suspension slurries of strontium carbonate and kaolin to decrease the densification sintering temperature of SrAl₂Si₂O₈ ceramics. In addition, the Sr element in SrAl₂Si₂O₈ ceramics are partly substituted with Ba and Ca elements, respectively, to investigate the low-temperature sintering behavior of partly substituted SrAl₂Si₂O₈ ceramics. The results indicated that the addition of flux agents to SrAl₂Si₂O₈ ceramics can availably achieve the densification sintering of SrAl₂Si₂O₈ ceramics at 950 °C, whereas the substitution of Sr with Ca or Ba have a great effect on sintering behaviors and dielectric properties of SrAl₂Si₂O₈ ceramics. Additionally, main crystal phases of the SrAl₂Si₂O₈ ceramics are monoclinic- SrAl₂Si₂O₈ and small quartz, but the evolution of crystal phases also depend on flux agents.     

Synthesis and sintering of nano-sized BaSnO<Subscript>3</Subscript> powders containing BaGeO<Subscript>3</Subscript>

The formation of solid solutions of the type [Ba(HOC₂H₄OH)₄][Sn_1−x Ge _x (OC₂H₄O)₃] as BaSn_1−x /Ge _x O₃ precursor and the phase evolution during its thermal decomposition are described in this paper. The 1,2-ethanediolato complexes can be decomposed to nano-sized BaSn_1−x /Ge _x O₃ preceramic powders. Samples with x = 0.05 consist of only a Ba(Sn,Ge)O₃ phase, whereas powders with x = 0.15 and 0.25 show diffraction patterns of both the Ba(Sn,Ge)O₃ and BaGeO₃ phase. The sintering behaviour was investigated on powders with a BaGeO₃ content of 5 and 15 mol%. These powders show a specific surface area of 15.4–15.9 m²/g and were obtained from calcination above 800 °C. The addition of BaGeO₃ reduced the sintering temperature of the ceramics drastically. BaSn_0.95Ge_0.05O₃ ceramics with a relative density of at least 90% can be obtained by sintering at 1150 °C for 1 h. The ceramic bodies reveal a fine microstructure with cubical-shaped grains between 0.25 and 0.6 μm. For dense ceramics, the sintering temperature could be reduced down to 1090 °C, when the soaking time was extended up to 10 h.     

Microstructure of brazed joints between mechanically metallized Si<Subscript>3</Subscript>N<Subscript>4</Subscript> and stainless steel

Brazing has been increasingly used to join metals to advanced ceramics. Brazing covalent materials requires either the use of active filler alloys or the previous metallization of the surface. To that end, a new and simple mechanical technique has been applied to metallize advanced ceramics, thus avoiding the use of costly Ti-based active filler alloys. The mechanical metallization of Si₃N₄ with Ti was employed as an alternative route to deposit active metallic films prior to brazing with stainless steel using 72% Ag--28% Cu or 82% Au—18% Ni eutectic alloys. The brazing temperatures were set to 40°C or 75°C above the eutectic temperature of each filler alloy. Ti-films of average thickness 4 μm produced adequate spreading of both filler alloys onto Si₃N₄ substrates, which were subsequently brazed to stainless steel. The interface of Si₃N₄/310 stainless steel basically consisted of a reaction layer, a precipitation zone and an eutectic microconstituent. Mechanically sound and vacuum-tight joints were obtained, especially upon brazing at relatively lower temperatures. Increasing the brazing temperature resulted in thermal cracking of the Si₃N₄, possibly due to increased thermal stress.     

Microstructure and properties of porous silicon nitride ceramics prepared by gel-casting and gas pressure sintering

Wave-transparent porous Si₃N₄ ceramics were prepared by gel-casting and gas pressure sintering, and the effects of solid loading on microstructure, mechanical and dielectric properties were investigated. Microstructures with interlocked elongated β-Si₃N₄ grains and uniformly distributed pores were observed, while both the β-Si₃N₄ phase content and grain aspect ratio reduced as the solid loading increased due to the restrained anisotropic growth of β-Si₃N₄ grains. As the solid loading increased from 30 to 45 vol.%, the porosity of ceramics declined from 57.6% to 36.4%. The flexural strength increased linearly from 108.3 to 235.1 MPa, and the dielectric constant and loss tangent of ceramics increased from 2.63 and 2.85 × 10⁻³ to 3.68 and 3.56 × 10⁻³ (10 GHz), respectively.