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.     

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 talc and clay addition on pressureless sintering of porous Si<Subscript>3</Subscript>N<Subscript>4</Subscript> ceramics

Porous Si₃N₄ ceramics were successfully synthesized using cheaper talc and clay as sintering additives by pressureless sintering technology and the microstructure and mechanical properties of the ceramics were also investigated. The results indicated that the ceramics consisted of elongated β-Si₃N₄ and small Si₂N₂O grains. Fibrous β-Si₃N₄ grains developed in the porous microstructure, and the grain morphology and size were affected by different sintering conditions. Adding 20% talc and clay sintered at 1700°C for 2 h, the porous Si₃N₄ ceramics were obtained with excellent properties. The final mechanical properties of the Si₃N₄ ceramics were as follows: porosity, P ₀ = 45·39%; density, ρ = 1·663·g·cm⁻³; flexural strength, σ _b (average) = 131·59 MPa; Weibull modulus, m = 16·20.     

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.     

Role of Ti diffusion on the formation of phases in the Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–Al<Subscript>2</Subscript>O<Subscript>3</Subscript> brazed interface

Diffusivities of Ti, Cu, Al and Ag in the interface of Al₂O₃–Al₂O₃ braze joints using Ag–Cu–Ti active filler alloy, have been calculated by Matano–Boltzman method. The Matano plane has been identified for each elemental diffusion at various brazing temperatures. The diffusivities of Ag, Cu and Al are almost insignificant on formation of interface during brazing, whereas the diffusivity of Ti changes significantly with the brazing temperature and controls the formation of different reaction product in the interface. Presence of TiO and Ti₃Cu₃O phases in the interface has been confirmed by transmission electron microscopy (TEM).     

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.     

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.     

Joining Joining of silicon nitride with Al-Cu alloys

The sessiie drop technique was used to evaluate the equilibrium contact angle and work of adhesion of molten Al-Cu alloys on Si₃N₄ at 1373 K under vacuum. The wettability of Al-Cu alloys on Si₃N₄ is improved by an addition of copper content up to 20 at%. The joining of Si₃N₄ to Si₃Ni₄ was also conducted using Al-Cu filler metal at a brazing condition of 1373 K for 3.8 ksec. The dependence of strength of the Si₃N₄ joint against the copper content in the filler corresponds to the copper content dependence of work of adhesion for molten Al-Cu alloy on Si₃N₄. The superior wettability and mechanical property of filler provide the superior strength of Si₃N₄ brazed with the filler. In particular, the Si₃N₄ joint brazed with Al-1.7 at% Cu filler exhibits the maximum fracture shear strength of 188.3 MPa at room temperature. This superior strength of Si₃N₄ brazed with Al-1.7 at% Cu filler is maintained at elevated temperatures up to 850 K.     

Microstructure characterization of in situ synthesized porous Si<Subscript>3</Subscript>N<Subscript>4</Subscript>–Si<Subscript>2</Subscript>N<Subscript>2</Subscript>O composites using feldspar additive

Porous Si₃N₄–Si₂N₂O bodies fabricated by multi-pass extrusion process were investigated depending on the feldspar addition content (4–8 wt% Si) in the raw silicon powder. The diameter of the continuous pores was about 250 μm. The polycrystalline Si₂N₂O fibers observed in the continuous pores as well as in the matrix regions of the nitrided bodies can increase the filtration efficiency. In the 4 wt% feldspar addition, the diameter of the Si₂N₂O fibers in the continuous pores of the nitrided bodies was about 90–150 nm. A few number of rope typed Si₂N₂O fibers (∼4 μm) was found in the case of 8 wt% feldspar addition. However, in the 8 wt% feldspar addition, the matrix showed highly porous structure composed of large number of the Si₂N₂O fibers (∼60 nm). The relative densities of the Si₃N₄–Si₂N₂O bodies with 4 wt% and 8 wt% feldspar additions were about 65% and 61%, respectively.     

Intermetallic Fe<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Al<Subscript><Emphasis Type="Italic">y</Emphasis></Subscript>-phases in a steel/Al-alloy fusion weld

The microstructure of joints between an Al-alloy and a zinc coated ferritic steel sheet manufactured by the so-called CMT joining method is investigated. The joint consists of a weld between the Al-alloy and Al 99.8 filler and a brazing of the filler to the zinc coated steel. The morphology, the structure and the defects of the intermetallic phases that developed at the interface between the steel and the Al 99.8 filler are characterised using scanning and transmission electron microscopy. The intermetallic phase seam is only about 2.3 μm thick and consists of trapezoidal nearly equiaxial Fe₂Al₅ grains surrounded by finger-like remains of the steel and mostly elliptical FeAl₃ grains extending into the Al 99.8 filler material. Both the Fe₂Al₅ and the FeAl₃ grains contain crystal defects.     

Advances in brazing of ceramics

The main parameters in direct brazing of ceramics to ceramics and to metals are reviewed, with primary emphasis on those influencing wetting of solid ceramics by liquid filler metals. In general, wetting of ceramics by conventional brazing alloys has been regarded as difficult. As a consequence, premetallization of the faying surfaces is frequently used to facilitate the brazing of ceramics. However, it is evident from the literature that recent developments in filler metals, based on active metal (e.g. Ti) additions (the amount depending on alloy composition and type of ceramic), have provided a basis for a substantial reduction of the contact angle. This favourable effect is caused by their reactivity, resulting in the formation of oxides when joining oxide ceramics (e.g. Al₂O₃), and nitrides or carbides and suicides in the case of nonoxide ceramics (e.g. Si₃N₄ or SiC). In addition to insufficient wetting, the mismatch in thermal expansion between the joint members may give rise to a low strength level due to the formation of high residual stresses on cooling. These stresses may limit the maximum allowable flaw size in ceramics to a few micrometres, i.e. of a similar size to that of pores.     

The wetting of silicon nitride by chromium-containing alloys

The wetting of ceramic materials by metallic melts is the most important characteristic of brazing alloys. The effect of chromium additions to copper-base alloys on the wetting of silicon nitride was investigated. Wetting experiments were carried out on Si₃N₄ using liquid Cu-Cr, Cu-Ni-Cr, Cu-Si-Cr and Cu-Ni-Si-Cr alloys. The addition of chromium to liquid copper up to its solubility limit promoted wetting on Si₃N₄. Improved wetting with a higher chromium content was achieved by the addition of nickel to the Cu-Cr alloys. The formation of an interfacial reaction layer, which is detrimental for brazing ceramics, was suppressed by the addition of silicon to the chromium-containing brazing alloys.     

Design of Si<Subscript>3</Subscript>N<Subscript>4</Subscript>-based ceramic laminates by the residual stresses

Ceramic laminates with strong interfaces between layers are considered a very promising material for different engineering applications because of the potential for increasing fracture toughness by designing high residual compressive and low residual tensile stresses in separate layers. In this work, Si₃N₄/Si₃N₄-TiN ceramic laminates with strong interfaces were manufactured by rolling and hot pressing techniques. The investigation of their mechanical properties has shown that the increase in apparent fracture toughness can be achieved for the Si₃N₄/Si₃N₄-20 wt.%TiN composite, while further increase of TiN content in the layers with residual tensile stresses lead to a formation of multiple cracks, and as a result, a significant decrease in the mechanical performance of the composites. Micro-Raman spectroscopy was used to measure the frequency shift across the Si₃N₄/Si₃N₄-20 wt.%TiN laminate. These preliminary Raman results can be useful for further analysis of residual stress distribution in the laminate.     

Effect of Oxygen Impurities on the Phase Composition of Self-Propagating High-Temperature Synthesis Products in the α-Si<Subscript>3</Subscript>N<Subscript>4</Subscript>–MgO System

It has been shown that raising the oxygen impurity concentration in starting-mixture components from 0.5 to 2.7 wt % reduces the content of the α-phase form 98 to 83 wt % at synthesis temperatures between 1400 and 1550°C. The role of magnesium oxide as a catalyst of the α → β phase transition becomes more important as the oxygen impurity concentration rises to 2.5 wt % and above. The use of starting-mixture components containing less than 0.3–0.6 wt % oxygen impurities has enabled the synthesis of Si₃N₄–MgO composites containing up to 95 wt % α-Si₃N₄ at temperatures in the range 1600–1700°C.     

Development of novel CsF–RbF–AlF3 flux for brazing aluminum to stainless steel with Zn–Al filler metal

Brazing 6061 Al alloy to 304 stainless steel by flame brazing has been carried out with an improved CsF–RbF–AlF₃ flux which matched Zn–xAl filler metals. The results showed that, the spreading area on stainless steel of Zn–xAl filler metals has been improved with the addition of RbF to CsF–AlF₃ flux. It is found that a Zn-rich phase appeared between the brazing seam and the intermetallic compound (IMC) layer in the joints brazed with Zn–2Al and Zn–5Al filler metals, and the thickness of the IMC layer was approximately 1.76–6.45 μm which increased with the increase of Al added to the filler metals. Moreover, a Fe₄Al₁₃ phase formed in the IMC layer, while a Fe₂Al₅ phase appeared as the second layer in Zn–25Al brazed joint. Neither the Zn-rich phase nor Fe₂Al₅ phase was found in the joint brazed with Zn–15Al filler metal, so that the joint was exhibited the maximum shear strength which was up to 131 MPa. All the lap joints were fractured at the interfacial layer of the brazing seam and stainless steel.     

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.     

Phase relations in the LaB<Subscript>6</Subscript>-W<Subscript>2</Subscript>B<Subscript>5</Subscript> system

The LaB₆-W₂B₅ join in the ternary system La-B-W is shown to have a eutectic phase diagram with t _e= 2220°C and a eutectic composition of 30 mol % LaB₆ + 70 mol % W₂B₅. Data are presented on LaB₆-containing systems potentially attractive for designing mixed-phase ceramics.     

Mechanical Properties and Thermal Shock Resistance Analysis of BNNT/Si<Subscript>3</Subscript>N<Subscript>4</Subscript> Composites

BNNT/Si₃N₄ ceramic composites with different weight amount of BNNT fabricated by hot isostatic pressing were introduced. The mechanical properties and thermal shock resistance of the composites were investigated. The results showed that BNNT-added ceramic composites have a finer and more uniform microstructure than that of BNNT-free Si₃N₄ ceramic because of the retarding effect of BNNT on Si₃N₄ grain growth. The addition of 1.5 wt.% BNNT results in simultaneous increase in flexural strength, fracture toughness, and thermal shock resistance. The analysis of the results indicates that BNNT brings many thermal transport channels in the microstructure, increasing the efficiency of thermal transport, therefore results in increase of thermal shock resistance. In addition, BNNT improves the residual flexural strength of composites by crack deflection, bridging, branching and pinning, which increase the crack propagation resistance.     

Silicon nitride-stainless steel braze joining with an active filler metal

Hot-pressed Si₃N₄ was brazed to 410-stainless steel using a Ag-Cu-Ti alloy foil in a vacuum. The occurrence of cracking due to processing was examined by systematically varying the brazing temperature and time between 840 and 900 °C and 6 and 60 min, respectively. Cracks were found in Si₃N₄ parallel to the bonding interface when the braze joints were processed at the lower temperatures (for all processing times at 840 °C and for times of 6 and 12 min at 860 °C). A reaction layer was observed to develop in the filler metal adjacent to Si₃N₄, rich in Ti and containing some Si. The thickness of this layer depended on brazing temperature and time. Microcracks were found in the reaction layer normal to the bonding interface in the joints processed at higher brazing temperatures (880 °C for 60 min and at 900 °C for 30 and 60 min). The low temperature cracks occurred, apparently, as a result of the incomplete relaxation of thermal stresses due to the presence of a hard continuous titanium strip in the filler metal; the high temperature microcracks seemed to be affected by the increase in thickness of the reaction layer and by the precipitation of intermetallic compounds. The compressive shear strength of the braze joints were evaluated and correlated with the cracking behaviour and microstructure changes in the joint. A strong braze joint was obtained when the reaction layer was relatively thin and no cracks were present in either the reaction layer or the Si₃N₄.     

Interfacial microstructure of Si3N4/Si3N4 brazing joint with Cu–Zn–Ti filler alloy

In this study, Si₃N₄ ceramic was jointed by a brazing technique with a Cu–Zn–Ti filler alloy. The interfacial microstructure between Si₃N₄ ceramic and filler alloy in the Si₃N₄/Si₃N₄ joint was observed and analyzed by using electron-probe microanalysis, X-ray diffraction and transmission electron microscopy. The results indicate that there are two reaction layers at the ceramic/filler interface in the joint, which was obtained by brazing at a temperature and holding time of 1223 K and 15 min, respectively. The layer nearby the Si₃N₄ ceramic is a TiN layer with an average grain size of 100 nm, and the layer nearby the filler alloy is a Ti₅Si₃N_x layer with an average grain size of 1–2 μm. Thickness of the TiN and Ti₅Si₃N_x layers is about 1 μm and 10 μm, respectively. The formation mechanism of the reaction layers was discussed. A model showing the microstructure from Si₃N₄ ceramic to filler alloy in the Si₃N₄/Si₃N₄ joint was provided as: Si₃N₄ ceramic/TiN reaction layer/Ti₅Si₃N_x reaction layer/Cu–Zn solution.