Reaction,densification, and mechanical properties of Ti2AlCx ceramics at low applied pressure and temperature

Ti₂AlC_x ceramic was produced by reactive hot pressing (RHP) of Ti:Al:C powder mixtures with a molar ratio of 2:1:1–.5 at 10–20 MPa, 1200–1300°C for 60 min. X-ray diffraction analysis confirmed the Ti₂AlC with TiC, Ti₃Al as minor phases in samples produced at 10–20 MPa, 1200°C. The samples RHPed at 10 MPa, 1300°C exhibited ≥95 vol.% Ti₂AlC with TiC as a minor phase. The density of samples increased from 3.69 to 4.04 g/cm³ at 10 MPa, 1200°C, whereas an increase of pressure to 20 MPa resulted from 3.84 to 4.07 g/cm³ (2:1:1 to 2:1:.5). The samples made at 10 MPa, 1300°C exhibited a density from 3.95 to 4.07 g/cm³. Reaction and densification were studied for 2Ti–Al–.67C composition at 10 MPa, 700–1300°C for 5 min showed the formation of Ti–Al intermetallic and TiC phases up to 900°C with Ti, Al, and carbon. The appearance of the Ti₂AlC phase was ≥1000°C; further, as the temperature increased, Ti₂AlC peak intensity was raised, and other phase intensities were reduced. The sample made at 700°C showed a density of 2.87 g/cm³, whereas at 1300°C it exhibited 3.98 g/cm³; further, soaking for 60 min resulted in a density of 4.07 g/cm³. Microhardness and flexural strength of Ti₂AlC_0.8 sample were 5.81 ± .21 GPa and 445 ± 35 MPa.     

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.     

Microstructure and High‐temperature Oxidation Behavior of Ti3AlC2/W Composites

Using spark plasma sintering, Ti₃AlC₂/W composites were prepared at 1300°C. They contained “core‐shell” microstructures in which a Ti_xW_1?x “shell” surrounded a W “core”, in a Ti₃AlC₂ matrix. The composite hardness increased with W addition, and the hardening effect is likely achieved by the Ti_xW_1?x interfacial layer providing strong bonding between Ti₃AlC₂ and W, and by the presence of hard W. Microstructural development during high‐temperature oxidation of Ti₃AlC₂/W composites involves α‐Al₂O₃ and rutile (TiO₂) formation ≥1000°C and Al₂TiO₅ formation at ~1400°C while tungsten oxides appear to have volatilized above 800°C. Likely due to exaggerated, secondary grain growth of TiO₂‐doped alumina and the effect of W addition, fine (<1 μm) Al₂O₃ grains formed dense, anisomorphic laths on Ti₃AlC₂/5 wt%W surfaces ≥1200°C and coarsened to large (>5 μm), dense, TiO₂‐doped Al₂O₃ clusters on Ti₃AlC₂/10 wt%W surfaces ≥1400°C. W potentially affects the oxidation behavior of Ti₃AlC₂/W composites beneficially by causing formation of Ti_xW_1?x thus altering the defect structure of Ti₃AlC₂, resulting in Al having a higher activity and by changing the scale morphology by forming dense Al₂O₃ laths in a thinner oxide coating, and detrimentally through release of volatile tungsten oxides generating cavities in the oxide scale. For Ti₃AlC₂/5 wt%W oxidation, the former beneficial effects appear to dominate over the latter detrimental effect.     

Improving the High‐Temperature Oxidation Resistance of Nb4AlC3 by Silicon Pack Cementation

Niobium aluminum carbide (Nb₄AlC₃), as a member of the MAX phases, can retain its stiffness and strength up to over 1400°C. However, its applications are limited due to its poor oxidation resistance at high temperatures. In this work, silicon pack cementation has been applied to improve the oxidation resistance of Nb₄AlC₃. After Si pack cementation at 1200°C for 6 h, a dense and uniform silicide coating which was mainly composed of NbSi₂ and SiC and well bonded to the matrix was successfully formed on the surface of Nb₄AlC₃. The Si pack cemented Nb₄AlC₃ shows excellent oxidation resistance up to 1200°C due to the formation of protective Al₂O₃ layer. The oxidation kinetics of the cemented Nb₄AlC₃ obey parabolic law all the way to up to 1200°C, and the parabolic rate constants of cemented Nb₄AlC₃ are in the same order of magnitude as those of Ti₃AlC₂ in the temperature range 1000°C–1200°C. However, the oxidation of the cemented Nb₄AlC₃ was accelerated after oxidation at 1300°C for about 15 h due to the formation of NbAlO₄.     

Effect of TiO2 on sinterability and physical properties of pressureless sintered Ti3AlC2 ceramics

TiO₂ was selected as effective sintering aid for pressureless sintering of Ti₃AlC₂ ceramics in this study. The addition of only 5?wt% TiO₂ largely promotes the densification and nearly dense Ti₃AlC₂ ceramic was obtained by pressureless sintering at 1500?°C. Significant strengthening and toughening effects were observed with the addition of TiO₂. High Vickers hardness, flexural strength and fracture toughness of 3.22?GPa, 298?MPa and 6.2?MPa?m^?1/2, respectively, were achieved in specimen pressureless sintered with 10?wt% TiO₂. Additionally, the addition of 5?wt% TiO₂ had no deleterious effect on the excellent oxidation resistance of Ti₃AlC₂ ceramic under 1200?°C water vapor atmosphere, while addition of 10?wt% TiO₂ accelerates the oxidation rate by two orders of degree.     

Fabrication of toughened B4C composites with high electrical conductivity using MAX phase as a novel sintering aid

MAX phase Ti₃AlC₂ was chosen as a novel sintering aid to prepare electrically conductive B₄C composites with high strength and toughness. Dense B₄C composites can be obtained at a hot-pressing temperature as low as 1850 °C with 15 vol% Ti₃AlC₂. The enhanced sinterability was mainly ascribed to the in situ reactions between B₄C and Ti₃AlC₂ as well as the liquid phase decomposed from Ti₃AlC₂. Both the Vickers hardness and fracture toughness increase with increasing Ti₃AlC₂ amount, and high hardness and toughness values of 28.5 GPa and 7.02 MPa m^−1/2 respectively were achieved for B₄C composites sintered with 20 vol% Ti₃AlC₂ at 1900 °C. Crack deflection by homogenously distributed TiB₂ particles was identified as the main toughening mechanism. Besides, B₄C composites sintered with Ti₃AlC₂ show significantly improved electrical conductivity due to the percolation of highly conductive TiB₂ phase, which could enhance the machinability of B₄C composites largely by allowing electrical discharge machining.     

Microstructure and mechanical properties of titanium aluminum carbides neutron irradiated at 400–700 °C

This work reports the first mechanical properties of Ti₃AlC₂-Ti₅Al₂C₃ materials neutron irradiated at ∼400, 630 and 700 °C at a fluence of 2 × 10²⁵ n m⁻² (E > 0.1 MeV) or a displacement dose of ∼2 dpa. After irradiation at ∼400 °C, anisotropic swelling and loss of 90% flexural strength was observed. After irradiation at ∼630–700 °C, properties were unchanged. Microcracking and kinking-delamination had occurred during irradiation at ∼630–700 °C. Further examination showed no cavities in Ti₃AlC₂ after irradiation at ∼630 °C, and MX and A lamellae were preserved. However, disturbance of (0004) reflections corresponding to M-A layers was observed, and the number density of line/planar defects was ∼10²³ m⁻³ of size 5–10 nm. HAADF identified these defects as antisite Ti_Al atoms. Ti₃AlC₂-Ti₅Al₂C₃ shows abrupt dynamic recovery of A-layers from ∼630 °C, but a higher temperature appears necessary for full recovery.     

Effect of Al atomic layer on the wetting behavior,interface structure and electrical contact properties of silver reinforced by Ti3AlC2 ceramic

Ti₃AlC₂ ceramic exhibits potential in Ag-based composite electrical contact materials, but its interface characteristic with Ag matrix remains unexplored. In this work, sessile drop experiment is carried out to investigate the high-temperature wetting behavior of molten Ag with Ti₃AlC₂. Stable Ti₃AlC₂ is hardly wetted by molten Ag below 1000 °C(contact angle of 148.5°), but the wettability of Ag/Ti₃AlC₂ improves with the increasing temperature(final 14° at ～1130 °C). In contrast, the Ti₃C_2, a MXene with Al layer removed from its parent Ti₃AlC₂, exhibits inferior wettability with Ag(final 56.5° at ～1130 °C). Wetting mechanism of Ag/Ti₃AlC₂ is proposed on the basis of the interfacial structure and chemical composition. Increasing temperature accelerates dissociation of Ti₃AlC₂, and outward-escaping Al reacts with Ag to form interface layer with a composition of Ag_4.86Ti_8.66AlC_7.59, Ag also diffuses along Ti₃AlC₂ grain boundaries and forms gradient reactive products(Ag–Ti–Al–C), which promotes their wettability. Finally comprehensive properties of Ag/Ti₃AlC₂ and Ag/Ti₃C₂ are compared. Al–Ag interdiffusion slightly decreases the electrical conductivity of Ag/Ti₃AlC₂ bulk material, but strengthen the interface bonding of composite and promote the viscosity of the molten pool, leading to the superior mechanical and anti-arc erosion properties. Absence of Al–Ag interdiffusion does remarkably improve the electrical conductivity of Ag/Ti₃C₂ bulk materials, but lack of Al layer damages the mechanical core and wettability with Ag, resulting in a drastic decrease of anti-arco erosion property.     

HiPIMS induced high-purity Ti3AlC2 MAX phase coating at low-temperature of 700 °C

Ti₃AlC₂, one of Ti-Al-C MAX phases, has received extensive attention due to its unique nano-laminated structure and combined properties of metals and ceramics. However, ultra-high synthesis temperature exceeding 800 °C is a critical challenge for broad application of Ti₃AlC₂ coatings on temperature-sensitive substrates. In this study, Ti-Al-C coatings were deposited on Ti-6Al-4V substrates using high-power impulse magnetron sputtering (HiPIMS) and DC sputtering (DCMS) for comparison. Different from as-deposited amorphous Ti-Al-C coating by DCMS, nanocrystalline TiAl_x compound was achieved by HiPIMS deposition due to highly ionized plasma flux with high kinetic energy. Furthermore, HiPIMS promoted the generation of dense and smooth Ti₃AlC₂ phase coating after low-temperature annealing at 700 °C, while annealed DCMS coating only obtained Ti₂AlC. In-situ XRD demonstrated such Ti₃AlC₂ phase could be early involved in crystallization at 450 °C, lowest than synthesis temperature ever reported. The mechanical properties of Ti₃AlC₂ coating were also discussed in terms of structural evolution.     

Nb doping in Ti3AlC2: Effects on phase stability,high-temperature compressive properties,and oxidation resistance

Nb-based ‘312’ MAX phase has not been recognized so far, raising a hypothesis that Nb doping would destabilize the isostructural Ti₃AlC₂. Here we report that (Ti_1−xNb_x)₃AlC₂ could persist with a doping limitation up to x = 0.15. As demonstrated by HAADF-STEM analysis, Nb dopants homogeneously distribute among polycrystalline grains at the microscale and randomly occupy the Ti sites at the atomic level. Beyond the limitation, Nb-doped ‘312’ phase Ti₃AlC₂ decomposes into (Ti,Nb)C, Nb-doped ‘211’ phase Ti₂AlC, and Nb-based ‘413’ phase. Compared to pristine Ti₃AlC₂, the compressive strength of (Ti_0.9Nb_0.1)₃AlC₂ at 1200 °C increases by 130%, whereas doping at this level impairs the oxidation resistance. Improving high-temperature strength without deteriorating oxidation resistance can be achieved by 5% Nb doping.     

Low-temperature synthesis of high-purity Ti3AlC2 by MA-SPS technique

Ternary carbide Ti₃AlC₂ was synthesized by mechanical alloying (MA) and spark plasma sintering (SPS) from elemental powder mixtures of Ti, Al and C, and the effect of Al content on formation of Ti₃AlC₂ during both processes was investigated. The results showed that adding proper Al content in the staring materials significantly increased the phase purity of Ti₃AlC₂ in the synthesized samples. Dense and high-purity Ti₃AlC₂ with <1 wt.% TiC could be successfully obtained by spark plasma sintering of powders mechanically alloyed for 9.5 h from a starting powder mixtures of 3Ti/1.1Al/2C at a lower sintering temperature of 1050 °C for 10–20 min.     

Influence of Mo doping on the tribological behavior of Ti3AlC2 ceramic at different temperatures

(Ti_0·8Mo_0.2)₃AlC₂ solid solutions were successfully synthesized from Ti, Al, TiC, and Mo powders using the in situ hot-pressing sintering method. The tribological properties of (Ti_0·8Mo_0.2)₃AlC₂ and the reference Ti₃AlC₂ in the temperature range 25–800 °C were evaluated in ambient air with the counterpart of Al₂O₃ balls. The results show that (Ti_0·8Mo_0.2)₃AlC₂ has improved lubricating properties and wear resistance above 400 °C compared with Ti₃AlC₂. This can be contributed to the formation of tribo-oxidation films containing MoO₃ and MoO_3-x. Structural characterization of the tribo-oxidation films was conducted using SEM, EDS, Raman spectroscopy, and XPS to evaluate the effect of Mo doping on the wear mechanisms of Ti₃AlC₂ in detail.     

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.     

Reactive synthesis of porous Mo2Ti2AlC3 ceramic and its basic application properties

Porous Mo₂Ti₂AlC₃ was synthesized by reactive synthesis of the mixed powder of molybdenum, aluminum, titanium hydride and graphite at 1500 °C. The effects of sintering temperature on the phase transition and pore structure parameters of porous Mo₂Ti₂AlC₃ were deeply discussed, and the pore forming mechanism in the sintering process was further deduced. The results showed that the pore formation of porous Mo₂Ti₂AlC₃ consists of the following aspects: (i) At 500 °C, stearic acid was completely pyrolyzed; (ii) At 700 °C, titanium hydride was completely decomposed into titanium and hydrogen via endothermic reaction; (iii) The partial diffusion effect of aluminum in the formation of TiAl and Mo₃Al intermetallic compounds; (iv) The solid-solid reaction of titanium and molybdenum with graphite generated TiC and Mo₂C; (v) TiC, Mo₂C, Ti₂AlC, Mo₃Al and graphite further reacted to form Mo₂Ti₂AlC₃,where pore formation was mainly controlled by (iii) and (v). In addition, the corrosion resistance and mechanical properties of porous Mo₂Ti₂AlC₃ were also explored.     

Synthesis and mechanism of ternary carbide Ti3AlC2 by in situ hot pressing process in TiC–Ti–Al system

Abstract

Ti₃AlC₂ is successfully synthesised by in situ hot pressing process from 2TiC/xAl/Ti (x?=?1, 1·2) raw powders. The phases and microstructure of the samples are identified by X-ray diffraction and scanning electron microscopy. It is found that aluminium content influences on the generating content of Ti₃AlC₂ significantly. High purity Ti₃AlC₂ can be obtained from a compacted cylinder composed of TiC–Ti–1·2Al at 1350°C for 2 h, and the purity of Ti₃AlC₂ is nearly 96·9 wt-%. The corresponding density and compressive strength are 3·93 g·cm^?3 and 377·34 MPa respectively. Ti₃AlC₂ grain exhibits typical plate-like structure. When aluminium melts, a mass of Al atoms diffuse to Ti grain rapidly, and Ti–Al intermetallic compounds generate. Then, Ti–Al intermetallic compounds react with TiC to form Ti₃AlC₂ directly. Using TiC powders as the raw materials provides Ti₆C octahedra directly. At elevated temperature, a part of aluminium will evaporate and lose. This will result in that every two layers of Ti₆C octahedra are linked by aluminium planes directly and Ti₃AlC₂ can be formed.     

Mo-doped Cr-Ti-Mo ternary o-MAX with ultra-low wear at elevated temperatures

In this work, the Cr-Ti-Mo ternary o-MAX ceramics based on the Cr₂TiAlC₂ phase are synthesized, and their tribological performance at elevated temperatures up to 800 ºC in the air is evaluated. With Si₃N₄ as a tribocouple, an unexpected ultra-low wear rate reaching 6.1 × 10^?8 mm³ N^?1 m^?1 is observed in Cr_1.9Ti_0.9Mo_0.2AlC₂ at 800 ºC, accompanied by a stable coefficient of friction (COF) around 0.33 in a wide temperature range. X-ray photoelectron spectroscopy (XPS) depth profiling confirms a tribofilm with gradient composition, which simultaneously offers fluid lubricating at elevated temperatures and self-healing after cooling. Particularly, confirmed by the theoretical simulations, the doping of Mo improves the interlayer binding as well as alters the oxidation behaviors of Cr₂TiAlC₂. With an optimal interlayer binding strength and oxidation rate, the Cr_1.9Ti_0.9Mo_0.2AlC₂ can generate a tribofilm possessing ideal composition, which simultaneously promotes lubrication and anti-wear performance at elevated temperatures.     

Spark plasma sintering of TiB2-based ceramics with Ti3AlC2

A TiB₂–Ti₃AlC₂ ceramic was manufactured by spark plasma sintering at 1900 °C temperature for 7 min soaking time under 30 MPa biaxial pressure. The role of Ti₃AlC₂ additive on the microstructure development, densification behavior, phase evolution, and hardness of the ceramic composite were studied. The phase characterization and microstructural investigations unveiled that the Ti₃AlC₂ MAX phase decomposes at the initial stages of the sintering. The in-situ formed phases, induced by the decomposition of Ti₃AlC₂ additive, were identified and scrutinized by XRD and FESEM/EDS techniques as well as thermodynamics principles. The sintered TiB₂–Ti₃AlC₂ ceramic approached a near full density of ~99% and a hardness of ~28 GPa. The densification mechanism and sintering phenomena were discussed and graphically illustrated.     

Electrically conductive and corrosion resistant MAX phases with superior electromagnetic wave shielding performance

MAX phases have emerged as promising corrosion-resistant electromagnetic interference (EMI) shielding materials. Herein, four MAX phases: Ti₃SiC₂, Ti₃AlC₂, V_0.5Cr_1.5AlC, and Nb₄AlC₃, were synthesized via solid–liquid reactions. The electrical conductivities of Ti₃SiC₂, Ti₃AlC₂, V_0.5Cr_1.5AlC, and Nb₄AlC₃ are 14.7 × 10³, 15.5 × 10³, 5.1 × 10³, 8.0 × 10³ S/cm, respectively, and the corresponding average EMI shielding effectiveness values in the frequency of 18–26.5 GHz are 53.9, 69.2, 19.4, and 29.0 dB, respectively. Most importantly, these MAX phases are highly corrosion resistant under acidic conditions. Despite the exposure to the acidic environment and a slight decrease in the electrical conductivity, the corroded MAX phases exhibited excellent EMI shielding properties compared to the pristine MAX phases. Additional analysis showed that reflection was the primary EMI blocking mechanism. The study offers a guide for designing MAX phase ceramics that exhibit high EMI shielding performance in corrosive environments.     

Uniaxial plastic deformation in the zirconia-based nanocrystalline ceramics containing a silicate glass

Nanocrystalline yttria-stabilized tetragonal zirconia polycrystal (nc-Y-TZP) powders coated with silicate based glasses were cold isostatically pressed and sintered near to the full density (98–99%). Two glasses with different compositions were used: 93 SiO₂–1 Na₂O–6 SrO (mol%) (designated as SNS glass) and 58 SiO₂–29 Al₂O₃–13 SrO (designated as SAS glass). Uniaxial compression tests of the pure (glass-free) nc-Y-TZP samples yielded strain rates as high as 2·10⁻⁴ s⁻¹ under 60 MPa at 1300 °C. Comparable strain rates were measured in the SNS glass-containing samples, with the maximum of 3·10⁻⁴ s⁻¹ at 1300 °C under a stress of 80 MPa (5 vol.% SNS glass content). Compression tests under 100 MPa exhibited relatively high strain rates of 5·10⁻⁴ and 10⁻⁴ at 1300 °C and 1200 °C, respectively, in the 15 vol.% SAS glass samples. The strain rates measured in the SAS glass-containing samples were achieved at temperatures lower by 100 °C compared to the similar strain rates in the glass-free and SNS glass-containing samples. The microstructure of the deformed samples was similar to that of samples before deformation, within which the ultrafine and equiaxed character of the grains was preserved. Clear evidence for cooperative grain boundary sliding was observed in the SAS glass-containing samples.     

Synthesis,sintering, and effect of surface roughness on oxidation of submicron Ti2AlC ceramics

Submicron Ti₂AlC MAX phase powder was synthesized by molten salt shielded synthesis (MS³) using a Ti:Al:C molar ratio of 2:1:0.9 at a process temperature of 1000°C for 5  hours. The synthesized powder presented a mean particle size of ~0.9 µm and a purity of 91 wt. % Ti₂AlC, containing 6 wt. % Ti₃AlC₂. The Ti₂AlC powder was sintered by pressureless sintering, achieving a maximal relative density of 90%, hence field-assisted sintering technology/spark plasma sintering was used to enhance densification. The fine-grained microstructure was preserved, and phase purity of Ti₂AlC was unaltered in the latter case, with a relative density of 98.5%. Oxidation was performed at 1200°C for 50 hours in static air of dense monolithic Ti₂AlC with different surface finish, (polished, ground and sandblasted) which resulted in the formation of an approx. 8 µm thin aluminum oxide (Al₂O₃) layer decorated with titanium dioxide (rutile, TiO₂) colonies. Surface quality had no influence on Al₂O₃ scale thickness, but the amount and size of TiO₂ crystals increased with surface roughness. A phenomenon of rumpling of the thermally grown oxide (TGO) was observed and a model to estimate the extent of deformation is proposed.