Functionally graded laminated composites fabricated from MAX-phase filled preceramic papers: Microstructure,mechanical properties and oxidation resistance

This paper describes the fabrication and characterization of novel preceramic paper-derived functionally graded materials (FGMs) based on Ti₃(Si,Al)C₂ MAX phase. The FGMs with different architecture were fabricated via spark plasma sintering of stacked preceramic papers at 1250 °C for 5 min. Microstructure, phase composition and elemental distribution were analyzed by scanning electron microscopy, X-ray diffraction and energy-dispersive X-ray spectroscopy, respectively. Oxidation tests were performed in air at 1300 °C for 5 h. FGMs containing Al- and Si-enriched MAX-phase layers were formed. The fabricated materials exhibit high flexural strength (over 600 MPa), which are dependent on microstructure and composition of individual layers as well as the architecture of composites. It was found that texturing of MAX phase grains during SPS results in anisotropic hardness of the composite. The difference in the composition of the individual layers also provides a hardness gradient in the composite. It was shown that the formation of the outer layer from the Al-enriched Ti₃Al(Si)C₂ MAX phase increases the corrosion resistance of Ti₃SiC₂-based composites. The high corrosion resistance of FGMs is due to the growth of a continuous and dense Al₂O₃ oxide layer.     

Ti3Si(Al)C2-based ceramics fabricated by reactive melt infiltration with Al70Si30 alloy

Dense Ti₃Si(Al)C₂-based ceramics were synthesized using reactive melt infiltration (RMI) of Al₇₀Si₃₀ alloy into the porous TiC preforms. The effects of the infiltration temperature on the microstructure and mechanical properties of the synthesized composites were investigated. All the composites infiltrated at different temperatures were composed of Ti₃Si(Al)C₂, TiC, SiC, Ti(Al, Si)₃ and Al. With the increase of infiltration temperature from 1050 °C to 1500 °C, the Ti₃Si(Al)C₂ content increased to 52 vol.% and the TiC content decreased to 15 vol.%, and the Vickers hardness, flexural strength and fracture toughness of Ti₃Si(Al)C₂-based composite reached to 9.95 GPa, 328 MPa and 4.8 MPa m^1/2, respectively.     

Low-temperature sintering and microstructure control of mullite–Mo composites

Dense mullite–Mo (45 vol%) composites with homogeneous microstructure have been obtained by plasma activated sintering of a mixture of Mo and mullite precursors at a relatively low temperature (1350 °C) and a pressure of 30 MPa. The mullite precursor was synthesized by a sol–gel process followed by a heat-treatment at 1000 °C. The influence of different mullite precursors on the densification behavior and the microstructure of mullite–Mo composites has been studied. The precursor powder heat-treated at 1000 °C with only Si–Al spinel but no mullite phase shows an excellent sintering activity. Following the sintering shrinkage curves, a two-stage sintering process is designed to enhance the composite densification for further reducing the sintering temperature. The study reveals that viscous flow sintering of amorphous SiO₂ at low temperatures effectively enhances the densification. Moreover, microstructure of these composites can be controlled by selecting different precursors and sintering temperatures.     

An experimental approach to delineate the reaction mechanism of Ti3AlC2 MAX-Phase formation

A comprehensive reaction mechanism of Ti₃AlC₂ MAX-phase formation from its elemental powders while spark plasma sintering has been proposed. Microstructural evaluation revealed that Al-rich TiAl₃ intermetallic forms at around 660 °C once Al melts. Gradual transition from TiAl₃ to Ti-rich TiAl and Ti₃Al intermetallic phases occurs between 700 °C and 1200 °C through formation of layered structure due to diffusion of Al from periphery toward the centre of Ti particles. Formation of TiC and Ti₃AlC transient carbide phases were observed to occur through two different reactions beyond 1000 °C. Initially, TiC forms due to interaction of Ti and C, which further reacts with TiAl and Ti and gives rise to Ti₃AlC. Later, Ti₃AlC also forms due to diffusion of C into Ti₃Al above 1200 °C. Above 1300 °C, Ti₃AlC phase decomposes into Ti₂AlC MAX-phase and TiC in presence of unreacted C. Finally, Ti₂AlC and TiC reacts together to from Ti₃AlC₂ MAX-phase above 1350 °C and completes at 1500 °C.     

A dense and fine-grained SiC/Ti3Si(Al)C2 composite and its high-temperature oxidation behavior

A dense SiC/Ti₃Si(Al)C₂ composite was synthesized by in situ hot pressing powders of Si, TiC and Al as a sintering additive at 1500 °C for 2 h under 30 MPa in Ar atmosphere. This composite has a fine-grained and homogeneous microstructure with grain sizes of 5 μm for Ti₃Si(Al)C₂ and of 1 μm for SiC. The SiC/Ti₃Si(Al)C₂ composite possesses an improved oxidation resistance, with parabolic rate constants of 4.57 × 10^?8 kg²/m⁴/s at 1200 °C and 1.31 × 10^?7 kg²/m⁴/s at 1300 °C. This study provides an experimental evidence to confirm the formation of amorphous phases in the oxide scale of the SiC/Ti₃Si(Al)C₂ composite. Microstructure and phase composition of the SiC/Ti₃Si(Al)C₂ composite and oxide scales were identified by X-ray diffractometry and scanning electron microscopy. The mechanism for the enhanced oxidation resistance has been discussed.     

Sintering,mechanical, electrical and oxidation properties of ceramic intermetallic TiC–Ti3Al composites obtained from nano-TiC particles

The paper discusses the development of a new material system for interconnect application in Solid Oxide Fuel Cells (SOFC) based on TiC–Ti₃Al. Nano-sized TiC powders utilized in this research were synthesized using carbon coated TiO₂ precursors from a patented process. The pressureless sintering of TiC–Ti₃Al in a vacuum was applied at temperatures between 1100 °C and 1500 °C and content of Ti₃Al was varied in the range of 10–40 wt%. X-ray diffraction (XRD) and scanning electron microscope (SEM) were used for phase evaluation and sintering behavior. Relative density increased markedly with increasing sintering temperature because of grain growth and formation of the Ti₃AlC₂ secondary phase. Dense products (>95% TD) were prepared from nanosized TiC powders with 10 and 20 wt% Ti₃Al, but with about 8 to 10% porosity for 30 and 40 wt% Ti₃Al. The mechanical properties were determined from Vickers hardness and fracture toughness calculations. Vickers hardness decreased and fracture toughness increased with increasing Ti₃Al content. The electrical conductivity and oxidation behavior of TiC–Ti₃Al composites were investigated to evaluate the feasibility for SOFC interconnect application. The electrical conductivity measurements in the air at 800 °C for 100 h were made using the Kelvin 4-wire method.     

Low-temperature diffusion bonding of Ti3Si(Al)C2 ceramic with Au interlayer

Herein, a reliable diffusion bonding of Ti₃Si(Al)C₂ ceramic is achieved by applying Au foil as an interlayer at 650 °C for 30 min with an axial pressure of 20 MPa. This novel method significantly decreases the bonding temperature, which is about 150 °C lower than the lowest bonding temperature from current research to the best of our knowledge. Maximum shear strength of 58 MPa is achieved at 650 °C among the bonding temperature range of 600 °C~800 °C. The microstructure evolution mechanism and the relationship between microstructure and mechanical property are discussed. The facile mutual diffusion of Au with de-intercalated Al and Si from Ti₃Si(Al)C₂ is considered critical in achieving sound interfacial bonding.     

Effect of short carbon fiber content on the mechanical properties of TiB2-based composites prepared by spark plasma sintering

In this study, TiB₂-30 vol% SiC composites containing 0, 5, 10, and 15 vol% short carbon fibers (C_f) were produced by spark plasma sintering (SPS). The effect of carbon fiber content on microstructure, density, and mechanical properties (micro-hardness and flexural strength) of the fabricated composites was studied. Scanning electron microscopy (SEM) results indicated that the fibers were uniformly dispersed in the TiB₂–SiC matrix using wet ball milling before SPS process. Fully dense TiB₂–SiC–C_f composites were achieved by SPS process at 1900°C for 10 min under 30 MPa. With the addition of fibers, the relative density of the composites did not change considerably. Mechanical tests revealed that microhardness was reduced about 19% by the incorporation of carbon fibers, whereas the flexural strength improved significantly. However, the flexural strength diminished by adding carbon fibers above to critical value (5 vol%) due to residual thermal stresses, nonhomogeneous structure and graphitization of carbon fibers. It was found that the composite with 5 vol% C_f had the highest flexural strength (482 MPa), which was enhanced by 20% compared with the TiB₂–SiC composite.     

Effect of TiO2 addition on the properties of Ti3Si(Al)C2 based ceramics fabricated by reactive melt infiltration

In this paper, Ti₃Si(Al)C₂ based ceramics were fabricated by reactive melt infiltration (RMI) of TiC/TiO₂ preforms with liquid silicon. The microstructure, phase composition, and mechanical properties of the Ti₃Si(Al)C₂ based ceramics have been investigated to understand the effect of phase composition of the preforms on the formation mechanisms of Ti₃Si(Al)C₂. The preforms with different content of TiO₂ infiltrated at 1500 °C with liquid silicon for 1 h were composed of Ti₃Si(Al)C₂, Al₂O₃, TiC, TiSi_xAl_y and residual Al. The prior generated Al₂O₃ phases inhibited the dispersion of Ti₃Si(Al)C₂ phases, resulting in the drastically grain growth of Ti₃Si(Al)C₂. Subsequently, the microstructure with gradually increasing Ti₃Si(Al)C₂ grain size resulted in the decrease of the bending strength and fracture toughness of samples. When the content of TiO₂ reached 20 wt%, the bending strength reached the maximum, 326.6 MPa. The fracture toughness attained the maximum, 4.3 MPa m^1/2, when the content of TiO₂ was 10 wt%.     

The synthesis and mechanical properties of high pure Ti2Al(Sn)C solid solution

High pure Ti₂Al_(1?x)Sn_xC (x = 0‐1) powders were synthesized using Ti, Al, Sn, and TiC powders as raw materials by pressureless sintering method. The influence of sintering temperature and raw material ratio on the purity of Ti₂AlC and Ti₂Al_0.8Sn_0.2C powders were investigated. The results show that pure Ti₂AlC and Ti₂Al_0.8Sn_0.2C powders were obtained from the mixed raw materials ratio of Ti:1.1Al:0.9TiC and Ti:0.9Al:0.2Sn:0.9TiC at 1450°C, respectively. Subsequently, fully dense Ti₂AlC and Ti₂Al_0.8Sn_0.2C bulks were prepared using mechanically alloying and hot pressed sintering method. The Vickers hardness of Ti₂AlC and Ti₂Al_0.8Sn_0.2C approaches approximately about 6 GPa and 4 GPa, the flexural strength was measured to be 650 ± 36 MPa and 521 ± 33 MPa, respectively. Microstructural analysis reveals that grain delamination, kink bands, and crack deflection occurred around the indentation area and at the fracture surface.     

Reaction synthesis of layered ternary Ti2AlC ceramic

Reactive sintering of 8Ti:Al₄C₃:C powder mixtures to form the ternary carbide Ti₂AlC is studied in the temperature range 570–1400 °C. After sintering at 1400 °C for 1 h, only the MAX phase Ti₂AlC and some TiC are produced. A series of intermediate phases, such as TiC, Ti₃Al, Ti₃AlC are detected during the reactive sintering process. From X-ray diffraction (XRD) and scanning electron microscopy (SEM) characterizations, a reaction path is proposed for the intermediate phases and Ti₂AlC formation. Results show that reaction kinetics may play an important role in the understanding of the reaction mechanisms.     

Enhancement mechanical properties of in-situ preparated B4C-based composites with small amount of (Ti3SiC2+Si)

B₄C-based composites were synthesized by spark plasma sintering using B₄C、Ti₃SiC₂、Si as starting materials. The effects of sintering temperature and second phase content on mechanical performance and microstructure of composites were studied. Full dense B₄C-based composites were obtained at a low sintering temperature of 1800 °C. The B₄C-based composite with 10 wt% (TiB₂+SiC) shows excellent mechanical properties: the Vickers hardness, fracture toughness, and flexural strength are 33 GPa, 8 MPa m^1/2, 569 MPa, respectively. High hardness and flexural strength were attributed to the high relative density and grain refinement, the high fracture toughness was owing to the crack deflection and uniform distribution of the second phase.     

Microstructure and mechanical properties of hot-pressed B4C/TiC/Mo ceramic composites

Boron carbide (B₄C)/TiC/Mo ceramic composites with different content of TiC were produced by hot pressing. The effect of TiC content on the microstructure and mechanical properties of the composites has been studied. Results showed that chemical reaction took place for this system during hot pressing sintering, and resulted in a B₄C/TiB₂/Mo composite with high density and improved mechanical properties compared to monolithic B₄C ceramic. Densification rates of the B₄C/TiC/Mo composites were found to be affected by additions of TiC. Increasing TiC content led to increase in the densification rates of the composites. The sintering temperature was lowered from 2150 °C for monolithic B₄C to 1950 °C for the B₄C/TiC/Mo composites. The fracture toughness, flexural strength, and hardness of the composites increased with increasing TiC content up to 10 wt.%. The maximum values of fracture toughness, flexural strength, and hardness are 4.3 MPa m^1/2, 695 MPa, and 25.0 GPa, respectively.     

Effects of TiN content on the properties of hot pressed TiB2–SiC ceramics

This research intended to study the impacts of different contents of the TiN additive on the mechanical properties and microstructural features of the TiB₂–SiC-based composites. Three different samples of TiB₂-15 vol% SiC- x vol% TiN (x = 0, 3.5, and 7) were produced by hot-pressing at 2000 °C under 35 MPa for 120 min. Thanks to advancement of some reactions among the TiB₂ surface oxides and the SiC reinforcement, two in-situ phases of TiC and SiO₂ were produced during the sintering. Nevertheless, the TiN incorporation resulted in generating another in-situ compound (TiC_0.3N_0.7) in the relevant as-sintered ceramics. Moreover, introducing TiN significantly refined the microstructure of the composites, leading to higher mechanical characteristics. Finally, the highest flexural strength (781 MPa) and Vickers hardness (27.1 GPa) values were attained for the sample introduced by 7 vol% TiN.     

Reactive Hot Pressing and Properties of Zr1−xTixB2–ZrC Composites

Reactive hot pressing was used to prepare Zr_1?xTi_xB₂–ZrC composites with advantageous microstructure and mechanical properties from ZrB₂–TiC powders. The reaction mechanisms and the effects of different levels of TiC on the physical and mechanical properties of the resulting composite were explored in detail and compared to conventionally hot‐pressed ZrB₂ and ZrB₂–ZrC. Incorporation of 10 to 30 vol% TiC enabled full densification and restrained grain growth, reducing the final average grain size from 5.6 μm in pure ZrB₂ to a minimum of 1.4 μm in samples with 30 vol% TiC. The flexural strengths and hardnesses of the composites sintered with TiC were consequently greater than the conventionally processed ZrB₂–ZrC materials, increasing from 440 MPa and 17.4 GPa to a maximum of 670 MPa and 24.2 GPa at 10 vol% TiC. However, despite a decrease in the total average grain size, the flexural strength at higher TiC levels was limited by an increase in ZrC grain growth, which was observed to determine the flexural strength of the reaction sintered composites similar to the case of ZrB₂–SiC.     

Microwave Sintering of Ti3Si(Al)C2 Ceramic

In this work, microwave sintering (MWS) method was successfully applied for fabrication of dense layered ternary Ti₃Si(Al)C₂ ceramic. Compared to conventional pressureless approaches, MWS could significantly decrease preparation temperature from 1600°C to 1400°C. The activation energy of the MWS process was estimated as 233 ± 18 kJ/mol, which was much lower than those in previous sintering techniques. The low sintering temperature likely originates from the low activation energy during MWS process. Such low temperature do not only make the as‐received Ti₃Si(Al)C₂ ceramic much smaller grain size and better mechanical properties, but also indicate higher energy converting efficiency during the sintering processes. Wide application of MWS techniques in MAX phases is expected to promote the practical applications of these materials and contribute to the energy saving during sintering process.     

High temperature interfacial phase stability of a Mo/Ti3SiC2 laminated composite

A Mo/Ti₃SiC₂ laminated composite is prepared by spark plasma sintering at 1300 °C under a pressure of 50 MPa. Al powder is used as sintering aid to assist the formation of Ti₃SiC₂. The fabricated composites were annealed at 800, 1000 and 1150 °C under vacuum for 5, 10, 20 and 40 h to study the composite's interfacial phase stability at high temperature. Three interfacial layers, namely Mo₂C layer, AlMoSi layer and Ti₅Si₃ solid solution layer are formed during sintering. Experimental results show that the Mo/Ti₃SiC₂ layered composite prepared in this study has good interfacial phase stability up to at least 1000 °C and the growth of the interfacial layer does not show strong dependence on annealing time. However, after being exposed to 1150 °C for 10 h, cracks formed at the interface.     

Hot-pressing and characterization of TiB2–SiC composites with different amounts of BN additive

This research aimed to study the influence of different amounts of hBN additive on the mechanical properties and microstructure of TiB₂-15 vol% SiC samples. All ceramics, containing 0, 3.5, and 7 vol% hBN, were sintered at 2000 °C using a hot-pressing route and reached their near full densities. Thanks to two different chemical reactions among the SiC reinforcement and the TiB₂ surface oxides (B₂O₃ and TiO₂), the in-situ phases of SiO₂ and TiC were generated over the sintering process. The intergranular mode was identified as the predominant fracture type in all three composite samples. The hBN additive could contribute to grain refining of composites so that the sample containing 7 vol% hBN reached the finest microstructure. Finally, the highest Vickers hardness of 25.4 HV_0.5 kg and flexural strength of 776 MPa were attained for the TiB₂–SiC and TiB₂–SiC-7 vol% hBN samples, respectively.     

Advantages and disadvantages of graphite addition on the characteristics of hot-pressed ZrB2–SiC composites

ZrB₂–SiC–graphite composites with 0–35 vol% graphite flakes were densified via hot-pressing route at the temperature of 1800 °C under the uniaxial pressure of 40 MPa for 1 h. Consolidation, mechanical properties, and microstructure of hot-pressed composites were investigated by variation of graphite content. By the addition of graphite, the relative density of composites increased, and at this hot pressing condition, fully densified composites were fabricated. The highest flexural strength of 366 MPa was measured for composite containing 7.5 vol% graphite, while the maximum Vickers hardness resulted in 2.5 vol% graphite doped one, and its value was equal to 20.8 GPa. Phase analysis of hot-pressed samples revealed the formation of the Zr₃C₂ and B₄C phases besides the main existing ZrB₂, SiC, and graphite phases. The newly carbide phases formed at the surface of ZrB₂ grains. The addition of graphite into the ZrB₂–SiC composites improved the sintering process and caused a fine-grained microstructure.     

Effect of Ti5Si3 on wear properties of Ti3Si(Al)C2

Near-fully dense Ti₃Si(Al)C₂/Ti₅Si₃ composites were synthesized by in situ hot pressing/solid–liquid reaction process under a pressure of 30 MPa in a flowing Ar atmosphere at 1580 °C for 60 min. Compared to monolithic Ti₃Si(Al)C₂, Ti₃Si(Al)C₂/Ti₅Si₃ composites exhibit higher hardness and improved wear resistance, but a slight loss in flexural strength (about 26% lower than Ti₃Si(Al)C₂ matrix). In addition, Ti₃Si(Al)C₂/Ti₅Si₃ composites maintain a high fracture toughness (K_IC = 5.69–6.79 MPa m^1/2). The Ti₃Si(Al)C₂/30 vol.%Ti₅Si₃ composite shows the highest Vickers hardness (68% higher than that of Ti₃Si(Al)C₂) and best wear resistance (the wear resistance increases by 2 orders of magnitude). The improved properties are mainly ascribed to the contribution of hard Ti₅Si₃ particles, and the strength degradation is mainly due to the lower Young's modulus and strength of Ti₅Si₃.