Oxidation resistance of Ti3AlC2 and Ti3Al0.8Sn0.2C2 MAX phases: A comparison

Ti₃AlC₂ and Ti₃Al_0.8Sn_0.2C₂ MAX phase powders are densified using Spark Plasma Sintering (SPS) technique to obtain dense bulk materials. Oxidation tests are then performed over the temperature range 800°C-1000°C under synthetic air on the two different materials in order to compare their oxidation resistance. It is demonstrated that, in the case of the Ti₃Al_0.8Sn_0.2C₂ solid solution, the oxide layers consist in TiO₂, Al₂O₃, and SnO₂. The presence of Sn atoms in the A planes of the solid solution leads to an easy diffusion of Sn out of the MAX phase which promote the formation of the nonprotective and fast growing SnO₂ oxide. Moreover, the small Al/Ti atom's ratio promotes the growth of a nonprotective rutile-TiO₂ scale as well. In the case of the Ti₃AlC₂ MAX phase, the oxide layer consists in a protective alumina scale; a few TiO₂ grains being observed on the top of the Al₂O₃ layer. The parabolic oxidation rate constants are about 3 orders of magnitude smaller for Ti₃AlC₂ compared to Ti₃Al_0.8Sn_0.2C₂.     

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.     

Comparison of corrosion behavior of Ti3SiC2 and Ti3AlC2 in NaCl solutions with Ti

Corrosion behavior of self-sintered, ternary-layered titanium silicon carbide (Ti₃SiC₂) and titanium aluminum carbide (Ti₃AlC₂) fabricated by an in-situ solid-liquid reaction/hot pressing process was investigated by potentiodynamic polarization, potentiostatic polarization and electrochemical impedance spectroscopy in a 3.5% NaCl solution. Commercially pure titanium (Ti) was selected for comparison through XRD, XPS, SEM and EDS examinations for elucidating both the passivation behavior and corrosion mechanism of the alloys. Both Ti₃SiC₂ and Ti₃AlC₂ exhibited significantly superior passivation characteristics compared to Ti; Ti₃SiC₂ also showed better corrosion resistance. The silicon/aluminum site is prone to attack, and the difference in the diffusion rate between the A-site atoms and titanium decreases the passivation ability of the MAX phase. CP titanium exhibited a lower passivation current density and did not undergo breakdown in the test potential region while two MAX phases are destroyed. Nevertheless, the corrosion resistances of Ti₃SiC₂ and Ti₃AlC₂ are comparable to that of CP titanium.     

Reducing the self-healing temperature of Ti2AlC MAX phase coating by substituting Al with Sn

In an effort to overcome the property degradation of Ti₂AlC MAX phase coating used in harsh environments, we fabricated a solid solution Ti₂(Al_0.6Sn_0.4)C coating with amount of Ti₅Sn₃ (20 wt.%) by a combined technique composing of magnetron sputtering and post-heat treatment. The cracks induced by Vickers indentation on coating surface were self-healed at 700 ℃, which is the lowest self-healing temperature among the Al-based MAX phase coatings till now. The structural evolution and kinetic diffusion revealed that the formation of SnO₂ is the key factor to achieve the crack self-healing at such a low temperature for Al-based MAX phase coatings. Additionally, the self-healed Ti₂(Al_0.6Sn_0.4)C coating exhibited better oxidation resistance compared to the unhealed one at 800 ℃. The results provide a novel and facile strategy to develop the protective MAX phase coatings with high performance at high temperature by partially substituting Al with Sn.     

Microstructure and mechanical properties of plasma sprayed TiC/Ti5Si3/Ti3SiC2 composite coatings with Al additions

The mass production of MAX phase coatings such as Ti₃SiC₂ and Ti₃AlC₂ using the plasma spraying method is highly challenging due to its ultra-high temperature and short reaction time. In this study, agglomerate powders of 3Ti/SiC/C/xAl with various Al contents (x = 0–1.5) were prepared to form TiC/Ti₅Si₃/Ti₃SiC₂ composite coatings using the plasma spraying technique. The effect of the Al addition on the microstructures and mechanical performances of the as-sprayed coatings was investigated. The addition of Al decreased the TiC content of the coatings while increasing their Ti₃SiC₂ content significantly. The addition of even small amounts of Al improved the MAX phase fraction of the coatings from 8.95 wt% (x = 0) to 34.05 wt% (x = 0.2) and 41.60 wt% (x = 0.5). Excess Al did not affect the Ti₃SiC₂ content of the coatings. The composite coatings showed a lamellar structure with pores and microcracks. With the addition of Al, the microhardness of the coatings increased slightly, while the fracture toughness improved significantly. The composite coatings with Al showed better wear resistance than those without Al. The wear mechanism of the coatings was a combination of adhesive wear, abrasive wear, and oxidative wear.     

Multifunctional performance of Ti2AlC MAX phase/2D braided alumina fiber laminates

The processing and characterization of laminates based on Ti₂AlC MAX phase, as matrix, and triaxial alumina braids, as reinforcing phase, are presented. Ti₂AlC powders with a mean particle size below 1 µm are synthesized, while commercial 3M Nextel 610 alumina fibers are braided in a three-stage process consisting of spooling, braiding with an angle of 0° and ±60° and the separation to single-layer fabric. The laminates are processed by layer-by-layer stacking, where 3 two-dimensional alumina braids are interleaved between Ti₂AlC layers, followed by full densification using a Field-Assisted Sintering Technology/Spark Plasma Sintering. The multifunctional response of the laminates, as well as for the monolithic Ti₂AlC, is evaluated, in particular, the thermal and electrical conductivity, the oxidation resistance, and the mechanical response. The laminates exhibit an anisotropic thermal and electrical behavior, and an excellent oxidation resistance at 1200℃ in air for a week. A relatively lower characteristic biaxial strength and Weibull modulus (i.e., σ₀ = 590 MPa and m = 9) for the laminate compared to the high values measured in the monolithic Ti₂AlC (i.e., σ₀ = 790 MPa and m = 29) indicates the need but also the potential of optimizing MAX-phase layered structures for multifunctional performance.     

Microstructure evolution,mechanical and tribological properties of Ti3(Al,Sn)C2/Al2O3 composites

In this paper, in situ formed Ti₃(Al,Sn)C₂/Al₂O₃ composites were fabricated by sintering the mixture of Ti₃AlC₂ and SnO₂. The Al atoms could diffuse out of the Ti₃AlC₂ layered structure to react with SnO₂, resulting in the formation of Ti₃(Al,Sn)C₂ solid solution and Al₂O₃. When the SnO₂ content was 20?wt.%, the sintered Ti₃(Al,Sn)C₂/Al₂O₃ composite exhibited the best overall mechanical properties, because of the optimized cooperative strengthening effect of solution strengthening and Al₂O₃ enhancement. When the SnO₂ content increased up to 30?wt.%, the flexural strength and fracture toughness of Ti₃(Al,Sn)C₂/Al₂O₃ composite dramatically decreased on account of the large accumulation of generated Al₂O₃. Moreover, according to the SiC ball-on-flat wear tests, it was found that the wear resistance of Ti₃(Al,Sn)C₂/Al₂O₃ composites was significantly improved as the SnO₂ content increased.     

Synthesis and formation mechanism of high-purity Ti3AlC2 powders by microwave sintering

High-purity titanium aluminum carbide (Ti₃AlC₂) powders were synthesized by a microwave sintering method using different titanium sources as raw materials. The prepared products were characterized by differential scanning calorimetry (DSC), X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The results indicated that the synthesized Ti₃AlC₂ powders have high purity (97.5%) and even distribution of the grain size when using a 3TiH₂/1.2Al/2C mixture as raw materials when the microwave sintering temperature and time were 1300°C and 30 minutes, respectively. The formation mechanism of the Ti₃AlC₂ is described as proceeding via four stages. The solid-phase reaction between titanium and aluminum occurs below the melting point of aluminum and the main product is a Ti₃Al phase, which is an observed intermediate compound for the formation of Ti₂AlC and Ti₃AlC₂. Thus, this study provides a beneficial approach to low-temperature synthesis of high-purity Ti₃AlC₂ materials.     

Influence of Ti3AlC2 content and load on the tribological behaviors of Ti3AlC2p/Al composites

In this study, Ti₃AlC₂ particles doped aluminum matrix composites were prepared by ultrasonic agitation casting method. Microstructure, mechanical properties, and tribological properties of pure aluminum and Ti₃AlC_2p/Al composites were characterized. Influence of different loads (10, 20, 30, and 40 N) and Ti₃AlC₂ contents (1.0, 2.0, 3.0, and 4.0 wt%) on the tribological behaviors of the composites were studied. Scanning electron microscopy (SEM), X-ray diffraction (XRD), Energy dispersion spectroscopy (EDS), and 3D laser confocal were used to assist the analysis. The results indicated that fine and uniformly microstructure and the optimum comprehensive mechanical properties were exhibited on 2.0 wt%-Ti₃AlC_2p/Al composites. The abrasive grooves were widened and deepened with an increase in the load. The abrasion performance of composites improved distinctly with the addition of the Ti₃AlC₂ particles, which changed the wear mechanism from adhesive wear to abrasive wear. The 30 N load and the composites of 2.0 wt% Ti₃AlC₂ revealed the optimum tribological properties. The improvement of the tribological behavior of composites was attributed to the refinement of microstructure, the improvement mechanical properties and the three dimensional layered Ti₃AlC₂ phases with self-lubricating properties.     

Tailoring Magnetic Properties of MAX Phases,a Theoretical Investigation of (Cr2Ti)AlC2 and Cr2AlC

(Cr₂Ti)AlC₂ is a newly discovered MAX phase with ordered occupations of Ti and Cr atoms on M sites. The Cr‐containing MAX phase is expected showing magnetic property, which provides functional applications in spintronics and as self‐monitoring smart coating. The magnetic states of (Cr₂Ti)AlC₂ are predicted by GGA and GGA + U methods and compared to those of Cr₂AlC. The ground states are predicted as FM or AFM‐XX configurations depending on the calculation methods. Analysis of the electronic structure shows that the magnetic moments mainly originate from the net spins of Cr 3d valence electrons, whereas the contribution of other atoms is negligible. The calculated magnetic moments of Cr atoms in (Cr₂Ti)AlC₂ are higher than those in Cr₂AlC due to the larger distance between the out‐plane Cr atoms separated by the intercalated nonmagnetic Ti–C slab. This work provides an insight on tailoring magnetic properties of MAX phases by modifying the crystal structure.     

Molten salt dynamic sealing synthesis of MAX phases (Ti3AlC2, Ti3SiC2 et al.) powder in air

Since the synthesis of non-oxidized ceramic and alloy powders requires both high temperature and oxygen insulation conditions, here we demonstrate a cost-efficient molten salt sealing/shielded synthesis method with dynamic gas tightness. Compared to conventional synthesis method, it can prevent the loss of reaction materials at high temperature, cut off the connection between reacting material and outside air, and does not require long-time ball milling mixing treatment or provision of applied pressing before or during heating. Only low-cost salts (e.g., NaCl, KCl), a few minutes of raw material mixing, and regular heating molds are required to obtain high-purity (>96 wt%), micron-sized Ti₃AlC₂ and Ti₃SiC₂ powders with narrow size distribution, which significantly decreased the complexity and production costs in the synthesis process. The effect of temperature and raw material content on the products were investigated. The mechanism of diffusion reaction between reactants in molten salt environment was analyzed. The new method developed here was also applicable to Ti₂AlC, V₂AlC and Cr₂AlC MAX phases, as well as provided new ideas for the preparation of other MXenes precursors with certain stoichiometric ratios, air-sensitive materials and nanopowders.     

Molten salt synthesis and formation mechanism of Ti3AlC2: A new path from Ti2AlC to Ti3AlC2

Fine, pure Ti₃AlC₂ powder is prepared in a very mild condition via Ti₃Al alloy and carbon black with the assistance of molten salts. X-ray diffraction, scanning electron microscopy, TG-DSC, and transmission electron microscopy (TEM) characterizations show that the high purity, nanosized Ti₃AlC₂ can be obtained at 900°C with the 1:1 salt-to-material ratio. The formation mechanism of Ti₃AlC₂ through this strategy of alloy raw material is fully studied under further TEM investigations, showing that the reaction process can basically be described as Ti₃Al and C → TiAl and TiC → Ti₂AlC and TiC → ψ and TiC → Ti₅Al₂C₃ and TiC → Ti₃AlC₂, where the key ψ, a modulated Ti₂AlC structure, is determined for the first time containing alternate-displacement Al layers along (0 0 0 2) of Ti₂AlC phase with a distinct selected area electron diffraction pattern. Such alternant displacement is considered a precondition of forming Ti₅Al₂C₃ through topotactic transition, followed by Ti₅Al₂C₃ converting into Ti₃AlC₂ by the diffusion of Ti, C atoms in the outside TiC. Several parallel orientations can be observed through the phase transition process: Ti₂AlC (0 0 0 2)//ψ (0 0 0 1), ψ (0 0 0 1)//Ti₅Al₂C₃ (0 0 0 3), Ti₅Al₂C₃ (0 0 0 3)//Ti₃AlC₂ (0 0 0 2). Such parallel orientations among these phases apply an ideal condition for the topotactic reaction. The distinct path of the phase transition brings a significant change of heat effect compared with the traditional method, leading to a fast reaction rate and a mild reaction condition.     

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.     

Oxidation and hot corrosion behaviors of MAX-phase Ti3SiC2, Ti2AlC,Cr2AlC

Oxidation and hot corrosion behaviours of Ti₃SiC₂, Ti₂AlC and Cr₂AlC at 750 °C were investigated in this work. Ti₃SiC₂ and Ti₂AlC showed a linear increase in mass gain and a relatively poor oxidation resistance. This might be attributed to the porous TiO₂ scale. A dense α-Al₂O₃ layer was formed during the oxidation test. Cr₂AlC exhibited the best oxidation resistance. This dense oxide scale can effectively isolate the substrate from contact with oxygen leading to excellent oxidation resistance. In contrast to the oxidation test, Ti₃SiC₂ and Ti₂AlC showed relatively better resistance to hot corrosion, while Cr₂AlC showed inferior resistance to NaCl introduced hot corrosion. The hot corrosion mechanism of the MAX phases was analyzed. Due to the formation of Na₂TiO₃, Ti containing MAX phases showed a continuous increase in the mass gain. The corrosion products of Cr₂AlC were Al₂O₃, Cr₂O₃ and Na₂CrO₄. However, due to the volatilization of Na₂CrO₄, Cr₂AlC showed a mass loss during the hot corrosion test. The chemical reaction process of the MAX phase was also analyzed.     

Preparation of TiC/Ti2AlC coating on carbon fiber and investigation of the oxidation resistance properties

MAX phases were proposed as the interphase materials for carbon fiber reinforced ceramic matrix composites toward the applications in high‐dose irradiation and oxidation environments. A thickness‐controllable TiC/Ti₂AlC coating was fabricated on carbon fiber using an in situ reaction in a molten salt bath. The coating showed a multilayered structure, in which the inner layer was TiC and the outer layer was Ti₂AlC. The influence of the reaction conditions on the morphology, composition, and thickness of the coating was investigated. The oxidation resistance properties of the as‐prepared TiC/Ti₂AlC‐coated carbon fiber in static air and water vapor flow at elevated temperatures were investigated. The results showed that the as‐prepared TiC/Ti₂AlC coating could provide good protection to the carbon fiber in both static air and water vapor flow up to 800°C. As these TiC and Ti₂AlC materials have good irradiation resistance, the present work provides a potential way to develop an irradiation‐resistant interphase of carbon‐fiber‐reinforced ceramic matrix composites for nuclear applications. Furthermore, this work also provides a feasible way to prepare carbide/MAX phase coating on other carbon materials.     

Oxidation behavior of Ti3SiC2 powder synthesized by using biochar,Si and Ti

Biochar was proposed as a novel carbon source for synthesizing Ti₃SiC₂ powder with high purity by a simple pressureless sintering at 1673 K, and Ti₃SiC₂ grains exhibited the typical nanolayered structure. The oxidation behavior of Ti₃SiC₂ powder showed the parabolic law during isothermal oxidation from 1273 K to 1473 K. Dense and continuous oxidation layer consisting of mixed TiO₂ and SiO₂ was formed rapidly on the surface of Ti₃SiC₂ particles as a diffusion barrier, which effectively retarded the inward diffusion of oxygen, conferring good oxidation resistance of the powder.     

Influence of Cu on the mechanical and tribological properties of Ti3SiC2

Ti₃SiC₂/Cu composites with different contents of Cu were fabricated by mechanical alloying and spark plasma sintering method. The phase composition and structure of the composites were analyzed by X-ray diffractometry and scanning electron microscopy equipped with energy dispersive spectroscopy. The mechanical and tribological properties of Ti₃SiC₂/Cu composites were tested and analyzed compared with monolithic Ti₃SiC₂ in details. The results show that the Cu leads to the decomposition of Ti₃SiC₂ to produce TiC_x, Ti₅Si₃C_y, Cu₃Si, and TiSi₂C_z. The friction coefficient and wear rate of the composites are lower than that of monolithic Ti₃SiC₂, which is ascribed to the fixing effect of hard TiC_x, Ti₅Si₃C_y, and Cu₃Si to inhibit the abrasive friction and wear. However, at elevated temperatures (ranging from room temperature to 600 °C) the friction and wear of the composites are higher than those at room temperature. Plastic flowing and tribo-oxidation wear accompanied by material transference contribute to the increased friction and wear at elevated temperatures.     

Yttrium incorporation in Cr2AlC: On the metastable phase formation and decomposition of (Cr,Y)2AlC MAX phase thin films

Herein we report on the synthesis of a metastable (Cr,Y)₂AlC MAX phase solid solution by co-sputtering from a composite Cr–Al–C and elemental Y target, at room temperature, followed by annealing. However, direct high-temperature synthesis resulted in multiphase films, as evidenced by X-ray diffraction analyses, room-temperature depositions, followed by annealing to 760°C led to the formation of phase pure (Cr,Y)₂AlC by diffusion. Higher annealing temperatures caused a decomposition of the metastable phase into Cr₂AlC, Y₅Al₃, and Cr-carbides. In contrast to pure Cr₂AlC, the Y-containing phase crystallizes directly in the MAX phase structure instead of first forming a disordered solid solution. Furthermore, the crystallization temperature was shown to be Y-content dependent and was increased by ∼200°C for 5 at.% Y compared to Cr₂AlC. Calculations predicting the metastable phase formation of (Cr,Y)₂AlC and its decomposition are in excellent agreement with the experimental findings.     

Compressive Behavior of Ti3AlC2 and Ti3Al0.8Sn0.2C2 MAX Phases at Room Temperature

In this study, we report on the compressive behavior of Ti₃AlC₂ and Ti₃Al_0.8Sn_0.2C₂ MAX phases at room temperature. We found that these two phases could be classified as Kinking Nonlinear Elastic (KNE) solids. The cyclic compressive stress–strain loops for Ti₃AlC₂ and Ti₃Al_0.8Sn_0.2C₂ are typical hysteretic and fully reversible. At failure, both compositions fracture in shear with maximum stresses of 545 MPa for Ti₃AlC₂ and 839 MPa for Ti₃Al_0.8Sn_0.2C₂. Consequently, the macroshear stresses for failure, τ_c, are 185 MPa and 242 MPa for Ti₃AlC₂ and Ti₃Al_0.8Sn_0.2C₂, respectively. In addition to the grain size effects, the presence of a ductile Ti_xAl_y intermetallic distributed in the grain boundaries plays an important role in the enhancement of the ultimate compressive and macroshear stresses for Ti₃Al_0.8Sn_0.2C₂. SEM observations reveal that these two MAX phases exhibit crack deflections, intragranular fractures, kink band formation and delaminations, grain push‐in and pull‐out.