Temperature-driven deintercalation and structure evolution of Ag/Ti3AlC2 composites

Ag/Ti₃AlC₂ composites are promising sliding contact material. Here, Ag/Ti₃AlC₂ composites were obtained via the hot pressing technique and their structure evolutions upon sintering temperature were investigated. Sintering temperature controlled the deintercalation of Al layers from Ti₃AlC₂, thus controlling the interfacial structure of Ag/Ti₃AlC₂ composites. Amorphous interface was found after sintering at 750?°C. TiC_x particles with a size of around 10?nm were found in the interfacial region after sintering at 800?°C. Increasing sintering temperature to 850?°C, stripy structures composed of alternately arranged silver-rich phase and TiC_x phase appeared around the edges of Ti₃AlC₂ particles. The over-saturated Al precipitates found in 850?°C sintered composites are cubic μ-Ag₃Al inter-metallic compounds, which have the coherent relationship with Ag matrix.     

Wetting and interfacial behavior of Al–Ti/4H–SiC system:A combined study of experiment and DFT simulation

Wetting and interfacial behavior of molten Al-(10, 20, 30, 40) at.%Ti alloys on C-terminated 4H–SiC at 1500 and 1550 °C were investigated experimentally, and theoretical bonding strength, structure stability and electronic structure of interfacial reaction products/C-terminated 4H–SiC interfaces were evaluated by first-principle calculations. The wetting experiments show that the Al–Ti/SiC systems present excellent wettability with contact angle of less than 15° except the Al–40Ti/SiC system performed at 1500 °C × 30 min. The SEM-EDS and TEM analyses demonstrate that the reaction products are mainly composed of Al₄C₃, TiC, Ti₃SiC₂, Ti₅Si₃C_X and τ phase, and their formation and evolution can be mainly affected by the Ti concentration in the Al–Ti alloys and wetting temperature. Moreover, the calculated results show that the SiC/C-terminated TiC interface presents the highest work of separation and its electronic property reveals that the localization of electrons and formation of covalent bond between interfacial C atoms lead to the excellent bonding strength of SiC/TiC interface.     

Infiltration behavior of Cu and Ti fillers into Ti2AlC/Ti3AlC2 composites during tungsten inert gas (TIG)brazing

Herein we study the infiltration behavior of Ti and Cu fillers into a Ti₂AlC/Ti₃AlC₂MAX phase composites using a TIG-brazing process. The microstructures of the interfaces were investigated by scanning electron microscopy and energy dispersive spectrometry. When Ti₂AlC/Ti₃AlC₂ comes into contact with molten Ti, it starts decomposing into TiC_x, a Ti-richandTi₃AlC; when in contact with molten Cu, the resulting phases are Ti₂Al(Cu)C, Cu(Al), AlCu₂Ti and TiC. In the presence of Cu at approximately 1630 °C, a defective Ti₂Al(Cu)C phase was formed having a P63/mmc structure. Ti₃AlC₂ MAX phase was completely decomposed in presence of Cu or Ti filler-materials. The decomposition of Ti₂AlC to Ti₃AlC₂ was observed in the heat-affected zone of the composite. Notably, no cracks were observed during TIG-brazing of Ti₂AlC/Ti₃AlC₂ composite with Ti or Cu filler materials.     

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.     

Preparation and tribological behaviour of laminated Ti3AlC2 crystals as additive in base oil

Abstract

Laminated ternary compound Ti₃AlC₂ crystals were synthesised by pressureless sintering the mixture powders of 3Ti/1·1Al/1·8C, 3Ti/1Al/1·8C/0·2Sn, 1Ti/1·8TiC/1Al and 1Ti1·8TiC1Al0·1Sn at 1400°C with preliminary liquid magnetic stirring mixing. The X-ray diffraction results indicate that Ti₃AlC₂ prepared from 3Ti/1Al/1·8C/0·2Sn has the highest purity, and the addition of appropriate Sn favours the synthesis of high purity Ti₃AlC₂. Scanning electron microscopy images show that Ti₃AlC₂ samples exhibit lamellar-like microstructure with thickness of ～100 nm. The tribological properties of Ti₃AlC₂ as an additive in 100SN base oil were evaluated with a ball on disc tester. The results show that the Ti₃AlC₂ additives exhibited good friction reduction and wear resistance at 5 wt-% concentration. Under determinate conditions, the base oil containing 5 wt-% Ti₃AlC₂ samples presented good tribology performance under the load of 15 N. The improved tribological properties of the Ti₃AlC₂ samples could be attributed to the formation of tribofilm in friction process.     

Determination of interdiffusion coefficients of Si and Al in Ti3SiC2–Ti3AlC2 diffusion couple at 1373-1673 K

In the diffusion couple of Ti₃SiC₂ and Ti₃AlC₂, only interdiffusion of Si and Al occurred during diffusion treatment process. Based on the concentration profiles of Si and Al measured by electron probe microanalysis (EPMA), the interdiffusion coefficients of Si and Al at 1373-1673 K in Ti₃SiC₂–Ti₃AlC₂ diffusion couple were determined by both the Boltzmann-Matano (B-M) method and the Saucer-Freise (S-F) method. At the position of Matano plane with the composition of Ti₃Al_0.5Si_0.5C₂, the interdiffusion coefficient could be expressed as D_int (m²/s) = 5.6 × 10⁻⁴⋅exp [−246 ± 14 (kJ/mol)/RT]. Based on the two methods, the calculated interdiffusion coefficients increased with increasing temperature, and the magnitudes of their absolute values were on the order of 10^–13-10^–11 m²/s at 1373-1673 K. At 1373-1573 K, the calculated interdiffusion coefficients decreased monotonously with the increase of Si concentration, that is, x_Si/(x_Al + x_Si). But at 1673 K, the variation trend of interdiffusion coefficients with x_Si/(x_Al + x_Si) was no longer monotonous, probably due to the presence of Ti₅Si₃ phase and voids on Ti₃AlC₂ side.     

Molten salt synthesis of MAX phases in the Ti-Al-C system

The molten salt method was used to synthesise the MAX phase compounds Ti₂AlC and Ti₃AlC₂ from elemental powders. Between 900–1000?°C, Ti₂AlC was formed alongside ancillary phases TiC and TiAl, which decreased in abundance with increasing synthesis temperature. Changing the stoichiometry and increasing the synthesis temperature to 1300?°C resulted in formation of Ti₃AlC₂ alongside Ti₂AlC and TiC. The type of salt flux used had little effect on the product formation. The reaction pathway for Ti₂AlC was determined to be the initial formation of TiC_1-x templating on the graphite and titanium aluminides.     

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.     

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.     

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.     

Synthesis and characterization of a new (Ti1-ε,Cuε)3(Al,Cu)C2 MAX phase solid solution

A new (Ti_1-εCu_ε)₃(Al,Cu)C₂ MAX phase solid solution has been synthesized by sintering at 760 °C compacted Ti₃AlC₂-40 vol.% Cu composite particles produced by mechanical milling. Using XRD and TEM-EDXS, it has been demonstrated that Cu can enter the crystallographic structure of the Ti₃AlC₂ MAX phase, whereas a Cu(Al,Ti) solid solution is also formed during thermal treatment. TEM-EELS analyses have demonstrated that Cu is mainly located on the A site of the MAX phase. The composition of the MAX phase solid solution, determined after selective chemical etching of the Cu(Al,Ti) matrix, by analyzing the filtrate and the solid phase using ICP-OES end EDXS methods respectively, is (Ti_0.93–0.97Cu_0.07–0.03)₃(Al_0.49–0.52Cu_0.51–0.48)C_2.     

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.     

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.     

Fabrication of SiC ceramics with invariable value resistivity in the range of 20–400 ℃ using MAX phase- Ti3AlC2 additives

SiC ceramics were fabricated by SPS sintering at 1850 ℃ with different amounts of Ti₃AlC₂. The effects of Ti₃AlC₂ content on the microstructure and electrical properties of the material were discussed. The densification and electrical properties of SiC ceramics have been improved by adding MAX phase Ti₃AlC₂. Ti₃AlC₂ decomposes to produce TiC and Al in the sintering process. The conductivity of SiC ceramics is elevated by TiC serving as a conductive second phase, and Al is dissolved into SiC lattice to promote the densification of SiC ceramics. With the addition of 15 wt% Ti₃AlC₂, the voltage-current curve of the sample changes from nonlinear to linear electrical characteristics with the resistivity dropping to 52 Ω cm. Moreover, the introduction of Ti₃AlC₂ reduces the temperature sensitivity of SiC ceramics. When the Ti₃AlC₂ content reaches 15 wt%, the resistivity of SiC ceramics remains relatively constant within the range of 20–400 ℃.     

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.     

Mechanical Behavior and Electromagnetic Interference Shielding Properties of C/SiC–Ti3Si(Al)C2

In this paper, a low‐temperature densification process of Al–Si alloy infiltration was developed to fabricate C/SiC–Ti₃Si(Al)C₂, and then the microstructure, mechanical, and electromagnetic interference (EMI) shielding properties were studied compared with those of C/SiC–Ti₃SiC₂ and C/SiC–Si. The interbundle matrix of C/SiC–Ti₃Si(Al)C₂ is mainly composed of Ti₃Si(Al)C₂, which can bring various microdeformation mechanisms, high damage tolerance, and electrical conductivity, leading to the high effective volume fraction of loading fibers and electrical conductivity of C/SiC–Ti₃Si(Al)C₂. Therefore, C/SiC–Ti₃Si(Al)C₂ shows excellent bending strength of 556 MPa, fracture toughness 21.6 MPa·m^1/2, and EMI shielding effectiveness of 43.9 dB over the frequency of 8.2–12.4 GHz. Compared with C/SiC–Si and C/SiC–Ti₃SiC₂, both the improvement of mechanical properties and EMI shielding effectiveness can be obtained by the introduction of Ti₃Si(Al)C₂ into C/SiC, revealing great potential as structural and functional materials.     

In situ synthesis,mechanical and cyclic oxidation properties of Ti3AlC2/Al2O3 composites

ABSTRACT

Ti₃AlC₂/Al₂O₃ composite materials were successfully fabricated from TiO₂/TiC/Ti/Al powders by the in situ reactive hot pressed technique. The microstructure, mechanical and oxidation properties of the composites were investigated in the paper. Vickers hardness increased with the Al₂O₃ content. The relative density of Ti₃AlC₂/Al₂O₃ composites exhibits a declining tendency with Al₂O₃ content especially exceeds 10 vol.?%. The Ti₃AlC₂/Al₂O₃ composites show excellent electrical conductivity. The flexural strength and fracture toughness of Ti₃AlC₂/10 vol. % Al₂O₃ are 461 ± 20?MPa and 6.2?±?0.2?MPa m^1/2, respectively. The cyclic oxidation behaviour of resistance of Ti₃AlC₂/10 vol. % Al₂O₃ composites at 800–1000°C generally obeys a parabolic law. The oxide scale of sample consists of a mass of α-Al₂O₃ and TiO₂, forming a dense and adhesive protect layer. The result indicates that the Al₂O₃ can greatly improve the oxidation resistance of Ti₃AlC₂.     

Synthesis and reaction path of Ti-Al-C MAX phases by reaction with Ti-Al intermetallic compounds and TiC

In this study, it was verified that the synthesis of Ti-Al-C MAX phases has advantages when using intermetallic compounds rather than using only elemental powders. The formation behavior of the MAX phases was presented through diffusion experiments. In the case of using elemental powder, Ti₂AlC is produced at 1300°C, and Ti₃AlC₂ is produced at 1400°C. When intermetallic compounds are used, Ti₂AlC is produced at 1000°C, and Ti₃AlC₂ is produced at 1300°C. In the case of the elemental powder, it is verified that Ti₃AlC₂ content is decreased and Ti₂AlC is increased when heat treatment is performed at 1400°C for 3 h. Rather Ti₃AlC₂ content is increased when intermetallic compounds are used. When an intermetallic compound is used, synthesis occurs more actively at high temperatures, and the tendency to be thermally decomposed can be prevented. When TiAl and TiC are heat treated, Al of the intermetallic compound is diffused into TiC, and C of TiC is diffused into the intermetallic compound. Furthermore, there are many two-dimensional defects in TiAl, which act as a C diffusion channel. C diffuses into TiAl to produce TiC_X, and the MAX phases is generated by the short-range diffusion of Al. At the region of TiC, TiC transforms into TiC_X after C diffuses into TiAl, which consequently structure of TiC changes from cubic to hexagonal. This is the same crystal structure as the MAX phases, and it is confirmed that the (110) surface is maintained. A Ti-C layer structure of the (110) surface is maintained, and it was determined that Al is diffused during this time to generate the MAX phases.     

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.     

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.