Densification, microstructure, and fracture behavior of TiC/Si3N4 composites by spark plasma sintering

TiC/Si3N4 composites were prepared using the β-Si3N4 powder synthesized by self-propagating high-temperature synthesis (SHS) and 35 wt.% TiC by spark plasma sintering. Y2O3 and A12O3 were added as sintering additives. The almost full sintered density and the highest fracture toughness (8.48 MPa·m1/2) values of Si3N4-based ceramics could be achieved at 1550℃. No interfacial interactions were noticeable between TiC and Si3N4. The toughening mechanisms in TiC/Si3N4 composites were attributed to crack deflection, microcrack toughening, and crack impedance by the periodic compressive stress in the Si3N4 matrix. However, increasing microcracks easily led to excessive connection of microcracks, which would not be beneficial to the strength.     

Thermal shock fatigue behavior of TiC/Al2O3 composite ceramics

The thermal shock fatigue behaviors of pure hot-pressed alumina and 30 wt.% TiC/Al₂O₃ composites were studied. The effect of TiC and Al₂O₃ starting particle size on the mechanical properties of the composites was discussed. Indentation-quench test was conducted to evaluate the effect of thermal fatigue temperature difference (ΔT) and number of thermal cycles (N) on fatigue crack growth (Δa). The mechanical properties and thermal fatigue resistance of TiC/Al₂O₃ composites are remarkably improved by the addition of TiC. The thermal shock fatigue of monolithic alumina and TiC/Al₂O₃ composites is due to a “true” cycling effect (thermal fatigue). Crack deflection and bridging are the predominant reasons for the improvement of thermal shock fatigue resistance of the composites.     

Effect of rare earth La2O3 on the microstructure and mechanical properties of TiC/W composites

In this study, La₂O₃ was investigated as an additive to TiC/W composites. The composites were prepared by vacuum hot pressing, and the microstructure and mechanical properties of the composites were investigated. Experimental results show that the grain size of the TiC/W composites is reduced by TiC particles. When 0.5 wt.% La₂O₃ is added to the composites, the grain size is reduced further. According to TEM analysis, La₂O₃ can alleviate the aggregation of TiC particles. With La₂O₃ addition, the relative density of the TiC/W composites can be improved from 95.1% to 96.5%. The hardness and elastic modulus of the TiC/W + 0.5 wt.% La₂O₃ composite are little improved, but the flexural strength and the fracture toughness increase to 796 MPa and 10.07 MPa·m^1/2 respectively, which are higher than those of the TiC/W composites.     

Oxidation and corrosion of silicon nitride ceramics with different sintering additives at 1200 and 1500 °C in air, water vapour, SO2 and HCl environments - A comparative study

The effect of different sintering additives on the high temperature oxidation and corrosion behaviour of silicon nitride based ceramics was investigated. Comparative tests were conducted at 1200 and 1500 °C in air, in water vapour, and with the highly corrosive gases HCl and SO₂. Si₃N₄ was prepared with MgO, Al₂O₃, Y₂O₃ and Al₂O₃ + Y₂O₃ sintering additives. Hot pressed discs were tested for a total time of up to 128 h. The electrically conductive ceramic composites Si₃N₄ + TiN and Si₃N₄ + MoSi₂ were also tested under the same conditions. The effects that the different corrosion environments have on the different ceramics are presented. SEM studies of the oxidised ceramics show the direct transformation of Si₃N₄ grains into SiO₂ through a reaction interface layer.     

六方-BN对非晶前驱体制备不含添加剂的Si3N4/SiC复合材料相变的影响（英文）

Si3N4/SiC纳米复合材料由于具有优良的力学和热性能,广泛应用于涡轮发动机、热交换器和其他复杂情况中。然而,不添加添加剂很难制备出Si3N4/SiC复合材料。添加剂在烧结过程形成液相从而促进复合材料的致密化。然而,添加剂的存在降低了复合材料的高温力学性能。通常在不添加添加剂的情况下,采用电场辅助烧结,利用聚合物前体路线制备Si3N4/SiC复合材料。本研究中,在无添加剂、温度1700°C、真空50MPa条件下,热压烧结2h,利用非晶前体路线成功制备了六方-BN致密化的Si3N4/SiC复合材料。聚合物前驱体和BN的作用减少了的SiC含量。并对相变、致密化、微观组织和力学性能进行了讨论。     

Selective Laser Melting of in-situ TiC/Ti5Si3 composites with novel reinforcement architecture and elevated performance

A novel Selective Laser Melting (SLM) process was applied to prepare bulk-form TiC/Ti₅Si₃ in-situ composites starting from Ti/SiC powder system. The influence of the applied laser energy density on densification, microstructure, and mechanical performance of SLM-processed composite parts was studied. It showed that the uniformly dispersed TiC reinforcing phase having a unique network distribution and a submicron-scale dendritic morphology was formed as a laser energy density of 0.4 kJ/m was properly settled. The 96.9% dense SLM-processed TiC/Ti₅Si₃ composites had a high microhardness of 980.3HV_0.2, showing more than a 3-fold increase upon that of the unreinforced Ti part. The dry sliding wear tests revealed that the TiC/Ti₅Si₃ composites possessed a considerably low friction coefficient of 0.2 and a reduced wear rate of 1.42 × 10^− 4 mm³/Nm. The scanning electron microscope (SEM) characterization of the worn surface morphology indicated that the high wear resistance was due to the formation of adherent and strain-hardened tribolayer. The densification rate, microhardness, and wear performance generally decreased at a higher laser energy density of 0.8 kJ/m, due to the formation of thermal cracks and the significant coarsening of TiC dendritic reinforcing phase.     

Mechanical properties improvement related to the isothermal holding time in Si3N4 ceramics sintered with an alternative additive

In the present work, the influence of the isothermal holding time on the physical (relative density and mass loss), chemical (α–β transformation and intergranular phase crystallization) and mechanical (hardness and fracture toughness) properties of Si₃N₄ ceramics with Al₂O₃ and CTR₂O₃ as additives has been studied. CTR₂O₃ is a natural rare earth oxide mixture, produced at DEMAR-FAENQUIL from the mineral xenotime, consisting mainly of Y₂O₃, Yb₂O₃, Er₂O₃ and Dy₂O₃. The increase in hardness and fracture toughness with increasing duration of isothermal sintering is discussed in regard of densification, α–β Si₃N₄ phase transformation and microstructure. The microstructural variations were decisive for the increase of fracture toughness, because larger grains (>4 μm) with higher aspect ratios (>6) developed during increased sinter periods, enhancing crack deflection and crack-bridging mechanism. In this way longer isothermal holding times contribute to the improvement of the physical and mechanical properties of silicon nitride based ceramics.     

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.     

On the wide range of mechanical properties of ZTA and ATZ based dental ceramic composites by varying the Al2O3 and ZrO2 content

In this work the influence of pressureless sintering on the Vickers hardness and fracture toughness of ZrO₂ reinforced with Al₂O₃ particles (ATZ) and Al₂O₃ reinforced with ZrO₂ particles (ZTA) has been investigated. The ceramic composites were produced by means of uniaxial compacting at 50 MPa and the green compacts were heated to 1250 °C using a heating rate of 10 °C min⁻¹, then to 1500 °C at 6 °C min⁻¹ and maintained at this temperature during 2 h. After sintering, relative density over 94%, hardness values between 9.5 and 21.9 GPa, and fracture toughness as high as 3.6 MPa m^1/2 were obtained. The presence of TZ-3Y particles on the grain boundaries suggests that they inhibit notably the alumina grain growth. The grain sizes of pure Al₂O₃ and TZ-3Y as well as Al₂O₃ and TZ-3Y in the 20 wt% Al₂O₃+80 wt% TZ-3Y composite were 1.27 ± 0.51 μm, 0.57 ± 0.12 μm, 0.65 ± 0.19 μm and 0.41 ± 0.14 μm, respectively. The 20 wt% Al₂O₃ + 80 wt% ZrO₂ + 3 mol% Y₂O₃ (TZ-3Y) composite showed a hardness of 16.05 GPa and the maximum fracture toughness (7.44 MPa m^1/2) with an average grain size of 0.53 ± 0.17 μm. On the other side, the submicron grain size and residual porosity seem to be responsible for the high hardness and fracture toughness obtained. The reported values were higher than those obtained by other authors and are in concordance with international standards that could be suitable for dental applications.     

Cutting performance and failure mechanisms of an Al2O3/WC/TiC micro- nano-composite ceramic tool

An Al₂O₃-based composite ceramic tool material reinforced with WC microparticles and TiC nanoparticles was fabricated by using hot-pressing technique. The cutting performance, failure modes and mechanisms of the Al₂O₃/WC/TiC ceramic tool were investigated via continuous and intermittent turning of hardened AISI 1045 steel in comparison with those of an Al₂O₃/(W, Ti)C ceramic tool SG-4 and a cemented carbide tool YS8. Worn and fractured surfaces of the cutting tools were characterized by scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS). The results of continuous turning revealed that tool lifetime of the Al₂O₃/WC/TiC ceramic tool was higher than that of the SG-4 and YS8 tools at all the tested cutting speeds. As for the intermittent turning, tool life of the Al₂O₃/WC/TiC ceramic tool was equivalent to that of YS8, but shorter than that of the SG-4 at lower cutting speed (110 m/min). However, tool life of the Al₂O₃/WC/TiC ceramic tool increased when the cutting speed increased to 170 m/min, becoming much longer than that of the SG-4 and YS8 tools. The longer tool life of the Al₂O₃/WC/TiC composite ceramic tool was attributed to its synergistic strengthening/toughening mechanisms induced by the WC microparticles and TiC nanoparticles.     

Study of the mechanical properties,toughening and strengthening mechanisms of Si3N4/Si3N4w/TiN nanocomposite ceramic tool materials

Si₃N₄/Si₃N_4w/TiN nanocomposites were fabricated by a hot-pressing technology with different sintering processes. The effect of nanoscale TiN and Si₃N_4w on the mechanical properties was investigated. The microstructure and indention cracks were observed by scanning electron microscopy, transmission electron microscopy and energy-dispersive spectrometry investigations. The research results showed that Si₃N₄/Si₃N_4w20/TiN5 nanocomposites containing 5 vol.% of nanoscale TiN and 20 vol.% of nanoscale Si₃N_4w, which were sintered under a pressure of 30 MPa at a temperature of 1650 °C for 40 min, had optimum mechanical properties. The addition of both nanoscale TiN and nanoscale Si₃N_4w contributed to the microstructural evolution and an improvement of the mechanical properties. The toughening and strengthening mechanisms are discussed for Si₃N₄/Si₃N_4w20/TiN5 nanocomposites.     

Preparation and characterization of Si3N4/TiN nanocomposites ceramic tool materials

Si₃N₄/TiN nanocomposites ceramic tool materials were sintered under 30 MPa at 1650 °C for 40 min. The effects of nano-scale TiN on the mechanical properties and microstructure were investigated. The strengthening and toughening mechanisms of Si₃N₄/TiN nanocomposites were studied by observing the fracture surfaces, samples for TEM and cracks. The oxidation resistance of Si₃N₄/TiN nanocomposites was also discussed based on the observation of microstructure. The results showed that the elongated Si₃N₄ grains which were pulled out from the fracture surfaces were reduced with the increase of the addition of nano-scale TiN, and many intragranular TiN grains were observed in Si₃N₄/TiN nanocomposites. The greater crack deflection and microcrack provided the contributions to the strengthening and toughening mechanisms for Si₃N₄/1 vol%TiN nanocomposite. However, Si₃N₄/TiN nanocomposites were oxidized strongly at higher temperature.     

Thermal shock behavior of Si3N4-TiN nano-composites

Si₃N₄-TiN nano-composites were fabricated by hot press sintering nano-sized Si₃N₄ and TiN powders. The microstructure, mechanical properties and thermal shock behavior of Si₃N₄-TiN nano-composites were investigated. The addition of proper amount TiN particles can significantly increase the flexural strength and the fracture toughness. Si₃N₄-TiN nano-composites showed both higher critical temperature difference and higher residual strength compared with those of monolithic silicon nitride nano-ceramic when the amount of TiN is less than 15 wt.%. But a further increase in the amount of TiN leaded to a decrease in the thermal shock resistance.     

Sintering behavior and mechanical properties of spark plasma sintered β–SiAlON/TiN nanocomposites

In this study, fully dense β-SiAlON/TiN composites were produced by Spark Plasma Sintering (SPS) method. Si₃N₄, Al₂O₃, AlN and TiO₂ powders were used as precursors. Starting powders were mixed with high energy ball milling and then were sintered by SPS method (at 1750 °C under pressure of 30 MPa for 12 min.). The milled powders had an average particle size of below ~ 155 nm. The XRD patterns of SPS-ed composites showed that the entire β-SiAlON phase constituent was in the form of Si₄Al₂O₂N₆ phase and cubic TiN phase can be formed by the phase transformation of TiO2 in relation with other precursors. FESEM micrographs confirmed that TiN particles were distributed homogeneously throughout β-SiAlON matrix. Mechanical properties evaluation revealed that by adding micro sized TiO₂, optimal mechanical properties with a hardness ~ 14.6 GPa and a fracture toughness ~ 6.3 MPa m^1/2 were obtained. The improvement in the fracture toughness was attributed to the presence of the crack deflection as the dominant toughening mechanism in the SPS-ed β–SiAlON/TiN composites.     

Corrosion of hot pressed Si3N4-TiN composite in sulphuric acid aqueous solution

The corrosion behaviour of an electroconductive Si₃N₄-35 vol% TiN composite, hot pressed with the addition of Al₂O₃ and Y₂O₃ as sintering aids, was studied in 1.8 M sulphuric acid aqueous solution at RT, 40 and 70 °C up to 400 h. The corrosion follows linear kinetics at RT and at 40 °C, involving only the progressive chemical dissolution of grain boundary phases, in the system Al-Y-Si-Ti-O-N. Chemical attack of TiN occurs at 70 °C, while Si₃N₄ is not affected by the selected corrosive environment.The effect of the corrosion on flexural strength, fracture toughness and electrical resistivity were investigated. Very high strength levels are maintained after corrosion for 400 h at room temperature, while the strength decreases of about 10% and 16% after the treatment at 40 and 70 °C, respectively. The electrical resistivity rises after corrosion at 40 and 70 °C, in line with the progressive chemical dissolution of the conductive TiN particles.     

Direct measurement of residual stresses and their effects on the microstructure and mechanical properties of heat-treated Si3N4 ceramics II: With CeO2 as a single additive

The heat treatment of silicon nitride ceramics with only CeO₂ as a sintering additive was carried out at different temperatures. Large residual stress was induced only by the non-relaxed volume changes and not by the relaxed volume changes (i.e. the crystallized phases with cavities or microcracks). The fact that the liquid formation temperature of the Si–Ce–O–N system (∼1470 °C) is much lower than that of the Si–Yb–O–N system (∼1650 °C) is the reason why the residual stress is comparable almost to each other in CeO₂-doped Si₃N₄, but increases steadily with heat-treatment temperature in Yb₂O₃-doped Si₃N₄. The large residual stress and the induced cavities and microcracks are the dominant factors for the reduction in room-temperature strength of the heat-treated samples. The defects in β-Si₃N₄ grains of heat-treated samples were caused by the large residual stress, and may lead to the reduction of both room- and high-temperature strengths. These results significantly extends our previous study (Guo GF, Li JB, Yang XZ, Lin H, Liang L, He MS, Tong XG, Yang J. Acta Mater 2006;54:2311) on heat-treated Si₃N₄ ceramics with only Yb₂O₃ (one of the heavier lanthanide oxides) as a sintering additive.     

Influence of pores distribution on fracture toughness of FeSi/Si3N4 composite

FeSi/Si₃N₄ ceramic composite was fabricated by hot pressing technique, using α-Si₃N₄ and Fe₃Al. The toughening effect of Fe₃Al on the Si₃N₄ matrix is explained on the basis of microstructural characterizations and schematic representations. Results indicate that the reaction between α-Si₃N₄ and Fe₃Al results in the formation of FeSi and sialon phases at the interface. Both phases effectively restrain coalescence and movement of the gaseous reaction product, N₂, retaining it in situ to form small separated pores. The dominant toughening effect of these pores reduces the interface bonding strength, consumes the crack propagation energy, and decreases the stress-concentration at the crack tip, thereby improving the fracture toughness of the matrix.     

Reticulated Porous Multiphase Ceramics with Improved Compressive Strength and Fracture Toughness

A multiphase reticulated porous ceramic (RPC) as Si₃N₄–Al₂O₃–SiO₂ was fabricated by replication techniques. Proper volumes of additives and twice sinter- twice immerse process endow the RPC an excellent crack healing and submerging property. The compressive strength and fracture toughness improved owing to the crack bridging behavior. The existence of pores in struts in RPC blunt the crack tip and increased the external force needed to propagate the crack. The mechanisms play a beneficial role in enhancing the compressive strength and fracture strength. Si₃N₄ RPC with additives of 5%Al and 5% Al₂O₃ yielded the compressive strength of 9.8 MPa and fracture toughness of 0.3 MPa m^1/2.     

One-pot synthesis of polyaniline/Fe3O4 nanocomposites with magnetic and conductive behaviour. Catalytic effect of Fe3O4 nanoparticles

Polyaniline/Fe₃O₄ nanocomposites were prepared by a one-pot synthesis using N-(4-aminophenyl)aniline as the reagent, molecular oxygen or hydrogen peroxide as the oxidizing agents in the presence of Fe₃O₄ nanoparticles (NPs) in powder and ferrofluid form. Both magnetic NPs in powder and ferrofluid form showed similar catalytic behaviour. The catalytic effect is particularly evident when molecular oxygen was used as the oxidizing agent. However, concerning the morphological aspects, only the composites prepared in the presence of ferrofluid-type Fe₃O₄ NPs showed a preferential morphology of nanorods (between 30 and 110 nm in diameter). All the composites are superparamagnetic at room temperature but at low temperature they are in a blocked state. Inter-particle interactions significantly affect the magnetic properties of the composites. The electrical conductivity of the composites is about 10⁻² S cm⁻¹, in agreement with the values obtained for polyaniline prepared by chemical route. A mechanism of the nanorods formation is proposed.     

Bulk WC-Al2O3 composites prepared by spark plasma sintering

WC and WC-Al₂O₃ materials without metallic binder addition were densified by spark plasma sintering in the range of 1800-1900 °C. The densification behavior, phase constitution, microstructure and mechanical properties of pure WC and WC-Al₂O₃ composite were investigated. The addition of Al₂O₃ facilitates sintering and increases the fracture toughness of the composites to a certain extent. An interesting phenomenon is found that a proper content of Al₂O₃ additive helps to limit the formation of W₂C phase in sintered WC materials. The pure WC specimen possesses a hardness (HV₁₀) of 25.71 GPa, fracture toughness of 4.54 MPa·m^1/2, and transverse fracture strength of 862 MPa, while those of WC-6.8 vol.% Al₂O₃ composites are 24.48 GPa, 6.01 MPa·m^1/2, and 1245 MPa respectively. The higher fracture toughness and transverse fracture strength of WC-6.8 vol.% Al₂O₃ are thought to result from the reduction of W₂C phase, the crack-bridging by Al₂O₃ particles and the local change in fracture mode from intergranular to transgranular.