Development of Si_3N_4/Al composite by pressureless melt infiltration

1 Introduction Composites of ceramic/metal or metal/ceramic are expected to have properties superior to their constituents alone[1?4]. However, the fundamental difference in atomic bonding between metals and ceramics results in quite different physical a…     

The production of AlN-rich matrix composites by the reactive infiltration of Al alloys in nitrogen

Aluminium nitride (AlN)–Al matrices reinforced with Al₂O₃ particulate have been fabricated by reactive infiltration of Al–2% Mg alloy into Al₂O₃ preforms in N₂ in the temperature range of 900–1075 °C. The growth of composites of useful thickness was facilitated by the presence of a Mg-rich external getter, in the absence of which composite growth is self-limiting and terminates prematurely. Successful growth of composites has been attributed to the reduction in residual oxygen partial pressure brought about by the reaction with oxygen of highly volatile Mg in the getter alloy. The microstructure of the matrix consists of AlN-rich regions contiguous with the particulate with metal-rich channels in-between, thereby suggesting that nitridation initiates by preferential wicking of alloy along the particle surfaces. The increase in nitride content of the matrix with temperature is consistent with hardness values that vary between ~3 and 10 GPa.     

Ti3AlC2-Al2O3-TiAl3 composite fabricated by reactive melt infiltration

Porous preforms were fabricated by cold-pressing process using powder mixture of TiC, TiO₂ and dextrin. After pyrolysis and sintering, Al melt was infiltrated into the porous preforms, leading to the formation of Ti₃AlC₂-Al₂O₃-TiAl₃ composite. Effects of cold-pressing pressure of preforms on microstructures and mechanical properties of the composites were studied. Synthesis mechanism and toughening mechanism of composite were also analyzed. The results shows that TiO₂ is reduced into Ti₂O₃ by carbon, the decomposition product of dextrin, which causes the spontaneous infiltration of Al melt into TiC/Ti₂O₃ preform. Then, Ti₃AlC₂-Al₂O₃-TiAl₃ composite is in-situ formed from the simultaneous reaction of Al melt with TiC and Ti₂O₃. With the increase of cold-pressing pressure from 10 MPa to 40 MPa, the pore size distribution of the preforms becomes increasingly uniform after pre-sintering, which results in the reduction of defects, and the decrease of property discrepancy of composites. Nano-laminated Ti₃AlC₂ grains and Al₂O₃ particles make the fracture toughness of TiAl₃ increase remarkably by various toughening mechanisms including stress-induced microcrack, crack deflection and crack bridging.     

Thermal properties of pressureless melt infiltrated AlN–Si–Al composites

Thermal properties of AlN-Si-Al composites produced by pressureless melt infiltration of Al/Al alloys into porous α-Si₃N₄ preforms were investigated in a temperature range of 50-300 °C. SEM and TEM investigations revealed that the grain size of AlN particles was less than 1 μm. In spite of sub-micron grain size, composites showed relatively high thermal conductivity (TC), 55-107 W/(m.K). The thermal expansion coefficient (CTE) of the composite produced with commercial Al source, which has the highest TC of 107 W/(m.K), was 6.5×10^?6 K^?1. Despite the high CTE of Al (23.6×10^?6 K^?1), composites revealed significantly low CTE through the formation of Si and AlN phases during the infiltration process.     

Effects of the injection temperature of N2 gas on pressureless infiltration for fabricating Al−Mg/Al2O3 composites

Pressureless infiltration of molten Al−Mg alloys into particulate Al₂O₃ preforms has been known to occur only in a nitrogen atmosphere. In order to understand the pressureless infiltration mechanism of Al−Mg alloys into particulate Al₂O₃ preforms, nitrogen was injected at 25°C, 300°C, and 600°C. The higher the injection temperature of the nitrogen gas was, the lower the infiltration temperature of the molten Al−Mg alloys into the particulate Al₂O₃ preform was. Pressureless infiltration of the Al−6Mg alloy occurred at 700°C when the nitrogen gas was injected at 600°C. The formation of an Mg−N compound (Mg₃N₂) on Al₂O₃ particles, which improves wettability by decreasing the interfacial energy between the Al−Mg alloys and the Al₂O₃ particles, enabled the formation of the Al−Mg alloy/Al₂O₃ composite via pressureless infiltration. Increasing the injection temperature close to the melting point of the Al−Mg alloys appeared to enhance the formation of Mg₃N₂ on the surface of the Al₂O₃ particles.     

Effect of si addition on mechanical alloying behavior and creep properties of Al-10Ti-xSi alloys

Al-10Ti-xSi alloys (x=0∼6wt.%) have been mechanically alloyed under Ar atmosphere using an attritor and the alloying process has been investigated. From Al-10Ti composite powders, supersaturated Al(Ti) powders were obtained after mechanical alloying. In the ternary mixture, fine Si particles were observed to be distributed in the Al(Ti) matrix due to both the negligible solid solubility of Si in the Al matrix and the weaker chemical interaction of Si with Al, as compared with Ti. The sealed compacts were hot extruded to full density at 450°C with an extrusion ratio of 12:1. The microstructures and creep properties of the hot extruded alloys were examined. During consolidation, Si particles were dissolved in Al₃Ti up to 4 wt.% Si to form the (Al(Si))₃Ti phase, and the Ti₇Al₅Si₁₂ phase was formed beyond the solubility limit of Si in Al₃Ti. The transition from the Coble creep mechanism at low stresses and temperatures to dislocation one at high stresses and temperatures was observed. The stress and temperature of the transition from diffusional to dislocation creep became higher as Si concentration increased. This was due to an enhancement of Al₃Ti particle strength with increasing Si content as a result of Si incorporation. Thus, the addition of Si enhances the creep resistance of the MA Al-10Ti alloy.     

Microstructure and Strength of Al2O3 and Carbon Fiber Reinforced 2024 Aluminum Alloy Composites

The microstructure and mechanical properties of 2024 aluminum alloy composite materials strengthened with Al₂O₃ Saffil fibers or together with addition of carbon fibers were investigated. The fibers were stabilized in the preform with silica binder strengthened by further heat treatment. The preforms with 80-90% porosity were infiltrated by direct squeeze casting method. The microstructure of the as-cast specimens consisted mainly of α-dendrites with intermetallic compounds precipitated at their boundaries. The homogenization treatment of the composite materials substituted silica binder with a mixture of the Θ phase and silicon precipitates distributed in the remnants of SiO₂ amorphous phase. Outside of this area at the binder/matrix interface, fine MgO precipitates were also present. At surface of C fibers, a small amount of fine Al₃C₄ carbides were formed. During pressure infiltration of preforms containing carbon fibers under oxygen carrying atmosphere, C fibers can burn releasing gasses and causing cracks initiated by thermal stress. The examination of tensile and bending strength showed that reinforcing of aluminum matrix with 10-20% fibers improved investigated properties in the entire temperature range. The largest increase in relation to unreinforced alloy was observed for composite materials examined at the temperature of 300 °C. Substituting Al₂O₃ Saffil fibers with carbon fibers leads to better wear resistance at dry condition with no relevant effect on strength properties.     

Phase reaction and sintering behavior of a Al2O3–20wt%AlN–5wt%Y2O3 system

Two major problems exist in the processing of AlN. The first is the difficulty in achieving full densification even at relatively high sintering temperatures. The second is the formation of the spinel phase, AlON. Pure AlN sintered at temperatures up to 2000°C have produced no more than 90–93% densification in the former case, while AlN rich ternary systems (AlN–Al₂O₃-sintering agent) have resulted in the detrimental formation of AlON well before full densification can occur. This paper reports on the phase reaction and sintering behavior of a ternary Al₂O₃–AlN–Y₂O₃ system near the critical temperature range of 1600–1700°C, in a carbo-thermal reduction furnace in a fully nitrogen environment. Full densification (>98%) for AlN without the formation of AlON was achieved by sintering an initial Al₂O₃ rich ternary system (Al₂O₃–20wt%AlN–5wt% Y₂O₃) at a relatively low temperature of 1680°C. Formation of the AlON was delayed until 1700°C, at which a stoichiometric γ-AlON (Al₃O₃N) with spinel type structure was obtained. Thermal conductivity values for a sintered substrate obtained with low oxygen content within the AlN matrix reached 125 W m⁻¹ K⁻¹.     

Wear characteristics of Al−Si−Mg−(Cu)/Al2O3 composites fabricated by thermit reaction

Al₂O₃ particles could be formed by a thermit reaction in an Al-12Si-4Mg-1.5Cu/Al₂O₃ composite due to thein-situ reaction between Al-12Si-4Mg-(1.5Cu) molten metal and SiO₂ particles in preform, which took place at 1173 K for 24 hours, resulting in the decomposition of SiO₂ particles and the formation of Al₂O₃ particles simultaneously. The mechanically mixed layers (MMLs) consisting of α-Fe and Fe oxides existed on the subsurface layers beneath the worn surface in composites or mother alloys, which improved the wear resistance. The characteristics of wear resistance and hardening of an Al-12Si-4Mg-1.5Cu/Al₂O₃ composite are superior to those of the Al-12Si-4Mg/Al₂O₃ composite and Al-12Si-4Mg-1.5Cu alloy.     

Synthesis of AlN–SiC solid solution through nitriding combustion of Al–C–Si3N4 in air

A simple way of fabricating AlN–SiC solid solutions (AlN–SiCss) through the combustion reaction of aluminum, carbon and Si₃N₄ powder mixtures in air is reported. X-ray diffraction analysis, scanning electron microscopy and energy dispersive spectroscopy are employed to analyze the phase composition and microstructure of the as-synthesized products. It is found that the phase composition of the product changes gradually with the increase in air infiltration distance, accompanied by variation in the partial pressure of N₂/O₂ at different locations of the powder compacts. Homogeneous single-phase AlN–SiCss powders with well-crystallized hexagonal morphologies and a fine particle size of 3 μm can be obtained within a suitable distance range of N₂ infiltration. Thermodynamic analysis of the Al–C–Si₃N₄–air combustion reaction system was conducted based on the N₂/O₂ diffusion kinetic model, and the calculated results are in good agreement with the experimental phenomenon.     

Effects of α-Si3N4 and AlN addition on formation of α-SiAlON by combustion synthesis

Preparation of Yb α-SiAlON was investigated by self-propagating high-temperature synthesis (SHS) from α-Si₃N₄- and α-Si₃N₄/AlN-diluted powder compacts under nitrogen of 2.17 MPa. For the AlN-free samples, the molar ratio of Si₃N₄/Si varies between 0.22 and 0.5. The starting stoichiometry of the AlN-added samples comprises a constant proportion of Si₃N₄/Si equal to 0.22, but a broad range of AlN/Al from 0.33 to 1.0. The self-sustaining combustion wave propagated in the spinning mode on account of highly diluted samples adopted in this study. The overall reaction exothermicity increases with Si₃N₄/Si ratio for the AlN-free samples, while decreases with AlN/Al ratio for the AlN-added powder compacts. As a result, the amount of unreacted Si left in the final product was significantly reduced and the formation of nearly single-phase Yb α-SiAlON was achieved in the sample with Si₃N₄/Si = 0.5. Moreover, the growth of elongated α-SiAlON grains was enhanced in the samples with high contents of Si₃N₄. In contrast, the nitridation of Si was only improved to a certain extent with the addition of AlN and no further improvement was attained by increasing the AlN content. Due to the lack of sufficient liquid phases during combustion and the weak reaction exothermicity, the samples with high contents of AlN were inclined to produce α-SiAlON grains in a fine equiaxed form.     

Secondary phases and interfaces in a nitrogen-atmosphere sintered Al alloy: Transmission electron microscopy evidence for the formation of AlN during liquid phase sintering

A comprehensive transmission electron microscopy study has been made of the secondary phases and their interfaces with the matrix in an alloy of Al–2Mg–2Si–0.25Cu sintered in nitrogen. AlN was detected both at the Al–Mg₂Si interface and inside Mg₂Si grains as strings of nanocrystallites. Mg₂Si did not exist at the sintering temperature; it was the solidified residue of the sintering liquid. The observation confirms the formation of AlN during liquid phase sintering of aluminium alloys in nitrogen. The likely pore filling processes are discussed in the light of the distribution of the AlN nanocrystallites. Two Al-, Si- and O-rich secondary phases were also identified, suggesting that, in addition to Mg, Si may have also played a role in disrupting the Al₂O₃ film that enveloped each Al powder particle. These findings improve the fundamental basis for understanding the sintering of aluminium alloys in nitrogen and the role of Si.     

Mechanical and wear properties of Mo5Si3–Mo3Si–Al2O3 composites

Mo₅Si₃ and Mo₅Si₃–Mo₃Si–Al₂O₃ composite were synthesized use MoO₃, Mo, Si and Al as raw materials by mechanically induced self propagating reaction and then consolidated by hot-pressing. The microstructure of the materials was characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM) with X-ray energy dispersive spectroscopy (EDS). The effects of the Al₂O₃ on the mechanical and tribological properties of Mo₅Si₃–Mo₃Si–Al₂O₃ composite have been studied. It was found that benefits associated with the addition of the Al₂O₃ to Mo₅Si₃ and Mo₃Si include finer microstructure, higher strength, higher fracture toughness and higher hardness. The dry sliding wear properties of the composite were investigated using against GCr15 bearing steel in ball-on-disk system at room temperature. The results indicated that the friction coefficients and specific wear rates of Mo₅Si₃–Mo₃Si–Al₂O₃ composite were significantly reduced by the addition of Al₂O₃, and its specific wear rates decreased by an order of magnitude compare with the monophase Mo₅Si₃. The friction coefficients of test materials decrease with an increasing load. The dominant wear mechanism of the composites was interpreted by several different wear models involving plastic deformation, adhesion, brittle fracture and reaction to form a tribo-oxidation layer.     

Tribological Properties of Ni<Subscript>3</Subscript>Al Matrix Composite Sliding Against Si<Subscript>3</Subscript>N<Subscript>4</Subscript>, SiC and Al<Subscript>2</Subscript>O<Subscript>3</Subscript> at Elevated Temperatures

The Ni₃Al matrix self-lubricating composite was fabricated by powder metallurgy technique. The tribological behavior of the composite sliding against commercial Si₃N₄, SiC and Al₂O₃ ceramic balls was investigated from 20 to 1000 °C. It was found that the composite demonstrated excellent lubricating properties with different friction pairs at a wide temperature range, which can be attributed to the synergetic effect of Ag, fluorides, and molybdates formed by oxidations. The Ni₃Al matrix self-lubricating composite/Si₃N₄ couple possessed the stable friction coefficient and wear rate.     

Near-net shaped Al/SiCP composites via vacuum-pressure infiltration combined with gelcasting

To solve the problem of difficult machining, the near-net shaped Al/SiC_P composites with high volume fraction of SiC particles were fabricated by vacuum-pressure infiltration. The SiC_P preform with a complex shape was prepared by gelcasting. Pure Al, Al4Mg, and Al4Mg2Si were used as the matrices, respectively. The results indicate that the optimal parameters of SiC_P suspension in gelcasting process are pH value of 10, TMAH content of 0.5 wt.%, and solid loading of 52 vol.%. The Al matrix alloyed with Mg contributes to improving the interfacial wettability of the matrix and SiC particles, which increases the relative density of the composite. The Al matrix alloyed with Si is beneficial to inhibiting the formation of the detrimental Al₄C₃ phases. The Al4Mg2Si/SiC_P composite exhibits high relative density of 99.2%, good thermal conductivity of 150 W·m⁻¹·K⁻¹, low coefficient of thermal expansion of 10.1×10⁻⁶ K⁻¹, and excellent bending strength of 489 MPa.     

P-Cr-Ti复合变质Al-25%Si合金时Cr-Ti作用机理

采用P-Cr-Ti复合变质处理Al-25%Si(质量分数)合金,重点研究了凝固组织的变化以及Cr、Ti元素的作用机理。结果表明:与单一的P变质相比,经P-Cr-Ti复合变质后,Al-25%Si合金凝固组织中初生Si的尺寸减小了12.2%~51.7%,并且初生Si分布的均匀程度增加。Al-25%Si合金中Cr、Ti主要以TiAl_3、Ti_7Al_5Si_(12)、Al_7Cr、Al_(13)Cr_4Si_4化合物的形式存在,同时有少量的P分布在含Ti化合物中。含Ti化合物呈长条状、短杆状;含Cr化合物呈菊花状、网状,分布在初生Si之间。含Cr、Ti化合物的数量随冷却速度的增加而增加。变质处理时Al-6.5%Ti合金带入的TiAl_3相,具有使初生Si持续析出和细化初生Si的作用,但细化能力有限。凝固过程中初生Si周围形成的含Cr化合物和αCr阻止初生Si的长大与聚集,促使增加初生Si分布均匀程度。     

Effects of oxide precursors on fabrication of Mo5Si3–Al2O3 composites via thermite-based combustion synthesis

Fabrication of the Mo₅Si₃–Al₂O₃ composite with a broad composition range was studied by thermite-based combustion synthesis. The addition of two thermite mixtures composed of 0.6MoO₃ + 0.6SiO₂ + 2Al and MoO₃ + 2Al into the Mo–Si reaction system was thermally beneficial for the self-sustaining combustion process. The former thermite reagent is less exothermic than the latter. Moreover, experimental results showed that the combustion temperature and flame-front velocity decreased with increasing molar ratio of Mo₅Si₃ to Al₂O₃ formed in the composite. As a consequence, the MoO₃/SiO₂/Al-based reaction scheme was adopted to synthesize composites with Mo₅Si₃/Al₂O₃ from 0.4 to 0.7, and MoO₃/Al-based system was for the products with Mo₅Si₃/Al₂O₃ from 0.8 to 1.6. The XRD pattern indicated Mo₅Si₃ as the dominant silicide. Mo₃Si was formed as the minor phase, because a small amount of Si dissolved in Al₂O₃. This was confirmed by the presence of both Al₂O₃ and aluminum silicate, a solid solution of Al₂O₃ and SiO₂, in the final products.     

Effect of Al2O3 addition on properties of non-sintered SiC–Si3N4 composite refractory materials

Preparation of SiC–Si₃N₄ composite refractory materials without sintering entails only low energy consumption and incurs little cost compared with traditional preparation methods. This paper investigated the effect of Al₂O₃ addition on bulk density, apparent porosity, linear shrinkage and oxidation resistance of as-fabricated non-sintered SiC–Si₃N₄ composite refractory materials. Meanwhile, the compressive and flexural strengths both before and after heat treatment were analyzed. The mechanisms of oxidation resistance and cryolite resistance of the SiC–Si₃N₄ composite refractory materials are discussed. Increasing amounts of Al₂O₃ reduced linear shrinkage but increased oxidation resistance and cryolite resistance. Moreover, compressive and flexural strengths initially increased and then decreased, with maximum values achieved at an Al₂O₃ addition of 8% w/w.     

Effect of SiC, Si3N4 and TiB2 additions on the oxidation resistance of TiAl alloys

The oxidation behavior of TiAl alloys containing dispersed particles of (5, 10, 15 wt.%) SiC, (3,5 wt.%) Si₃N₄ or (3, 5, 10 wt.%) TiB₂ was studied between 800 and 1200°C in atmospheric air. The TiAl−(SiC, Si₃N₄) alloys oxidized to TiO₂, Al₂O₃, and SiO₂. The TiAl−TiB₂ alloys oxidized to TiO₂, Al₂O₃, and B₂O₃ which evaporated during oxidation. Improvement in oxidation resistance accompanied by thin, dense scale formation due to the addition of dispersoids originated primarily from the enhanced alumina-forming tendency, improved scale adhesion by oxide grain refinement owing to the beneficial effect of dispersoids, and the incorporation of SiO₂ within the oxide scale in the case of TiAl−(SiC, Si₃N₄) alloys.     

Effects of SiC volume fraction and aluminum particulate size on interfacial reactions in SiC nanoparticulate reinforced aluminum matrix composites

The SiC nanoparticulate reinforced Al-3.0 wt.% Mg composites were fabricated by combining pressureless infiltration with ball-milling and cold-pressing technology at 700 °C for 2 h. The effects of SiC nanoparticulate volume fractions (6%, 10% and 14%) and Al particulate sizes (38 μm and 74 μm) on interfacial reactions were investigated by SEM, TEM and X-ray diffraction. The results show that the MgO at the interface between SiC nanoparticulate and molten Al can provide a barrier for the diffusion of Si, C and Al. Using Al particulate (74 μm) as raw material, the Al₄C₃ phase was not found in the composites containing 6 vol.% and 10 vol.% SiC, but presented in the composites containing 14 vol.% SiC. When SiC content up to 14 vol.%, the products of MgO around SiC nanoparticulate are not enough to provide effective protection from the reaction between SiC and molten Al, therefore the diffusion of Si, C and Al can take place to produce Al₄C₃ and Si phases. Using 38 μm Al particulate as raw material, the fine Al particulate possesses the high reaction activity and can easily be embedded into the gap among the big Mg particulate segregated at the interface, resulting in the appearance of exposure surface of SiCp to the Al and the forming of diffusion channels for the atomics C, Si and Al. So, the formations of Al₄C₃ and Si phases were occurred.