Inter-Conversion of Mn+1AXn Phases in the Ti–Al–C System

It is demonstrated that the M _{n +1}AX _n phase Ti₃AlC₂ may be readily synthesized by sintering a stoichiometric mixture of the lower order MAX phase Ti₂AlC mixed with a stoichiometric amount of TiC in the temperature range 1350°–1450 °C. High-quality Ti₃AlC₂ was readily produced using sintering times in the range 2–5 h. In general, <2% of unwanted or remnant phases were found to be present and in some samples none could be detected at all.     

Stability Domains of TiO2–Ti3O5–Ti2O3–TiC/Ti(CN) Systems During Reduction Process

The phase domain of Ti₃O₅–Ti₂O₃–Ti(CO) at 1580 K was determined from the formation energies of Ti(C _x O _y ), as calculated via the Gibbs–Duhem equation. An extensive Ti(CO) domain is attributed to the high affinity between TiC and TiO. The phase domain of Ti₃O₅–Ti₂O₃–Ti(CN) was obtained at 1673 K using the formation energies of Ti(C _x N _y ). This study shows that the stable region for Ti₂O₃ is significantly small in the Ti₃O₅–Ti₂O₃–Ti(CN) phase domain. It demonstrates the absence of TiO and Ti₂O₃ in the normal syntheses of TiC and Ti(CN) from TiO₂, respectively.     

Crystal Structure of V4AlC3: A New Layered Ternary Carbide

V₄AlC₃, a new MAX phase, was synthesized by reactive hot pressing of a V, Al, and C powder mixture at 1700°C. Using a combination of Rietveld refinement with X-ray diffraction data and ab initio calculations, the crystal structure was determinated. It was found that V₄AlC₃ has a Ti₄AlN₃-type crystal structure. The lattice constants are a =0.29310 nm and c =2.27192 nm. And the atomic positions are V1 at (4 f ) (1/3, 2/3, 0.0544), V2 at (4 e ) (0, 0, 0.1548), Al at (2 c ) (1/3, 2/3, 1/4), C1 at (2 a ) (0, 0, 0), and C2 at (4 f ) (2/3, 1/3, 0.1080).     

Synthesis and Mechanical Properties of Fully Dense Ti2SC

Because the layered machinable ternary carbide, Ti₂SC, has a significantly shorter c -lattice parameter—as compared with most of the 50+ other so-called M_n+1AX_n (MAX) phase family (M=early transition metal; A=A group element and X=C or N and n=1–3) to which it belongs—it was postulated that its mechanical properties would be significantly different than the other MAX phases. In this work, fine-grained (FG) and coarse-grained (CG) polycrystalline fully dense Ti₂SC samples were fabricated. Hot pressing Ti₂SC powders, at 1500°C under a stress of ∼45 MPa for 5 h resulted in FG (2–4 μm) samples which and upon further annealing for 20 h at 1600°C resulted in CG (10–20 μm) ones. No peaks other than those associated with Ti₂SC and an impurity anatase phase, with a volume fraction of ∼6 vol% were observed in the XRD patterns and micrographs. The average Vickers hardness in the 2–300 N range is 8±2 GPa with the FG samples being slightly harder. This hardness is the highest of any of the MAX phases characterized to date. Also in contrast to all MAX phases, cracks extended from the corners of Vickers indents in the FG samples. From these cracks the fracture toughness was estimated and found to increase more or less linearly with load from ≈4 to 6 MPa·m^1/2 as the Vickers force was increased from 50 to 300 N, respectively. The room temperature compressive stress of the FG samples was 1.4±0.2 GPa; the failure mode was brittle. Its Young's modulus—also one of the highest for a M₂AX phase measured to date—was 316±2 GPa. There was no evidence for incipient kink band formation during simple compression. The latter is attributed, in part, to the fine grain size of the hot-pressed material.     

Phase Relations in the Pseudobinary System Na2TiSi4O11-Na2Ti2Si2O9

The quenching technique was used to study subliquidus and subsolidus phase relations in the pseudobinary system Na₂ Ti₂Si₂ O₁₁-Na₂ Ti₂ Si₂ O₉. Both narsarukite (Na₂TiSi₄O₁₁) and lorenzenite (Na₂Ti₂Si₂O₉) melt incongruently. Narsarsukite melts at 911°±°C to SiO₂+liquid, with the liquidus at 1016°C. Lorenzenite melts at 910°±5°C to Na₂ Ti₆ O₁₃+liquid; Na₂ Ti₆ O₁₃ reacts with liquid to form TiO₂ and is thus consumed by 985°±5°C. The liquidus occurs at 1252°C.     

High-Resolution Transmission Electron Microscopy of Ti4AlN3, or Ti3Al2N2 Revisited

The structure and chemistry of what initially was proposed to be Ti₃Al₂N₂ are incorrect. Using high-resolution transmission electron microscopy, together with chemical analysis, the stoichiometry of this compound is concluded to be Ti₄AlN_3-delta (where delta = 0.1). The structure is layered, wherein every four layers of almost-close-packed Ti atoms are separated by a layer of Al atoms. The N atoms occupy ∼97.5% of the octahedral sites between the Ti atoms. The unit cell is comprised of eight layers of Ti atoms and two layers of Al atoms; the unit cell is hexagonal with P 6₃/ mmc symmetry (lattice parameters of a = 0.3 nm and c = 2.33 nm). This compound is machinable and closely related to other layered, ternary, machinable, hexagonal nitrides and carbides, namely M₂AX and M₃AX₂ (where M is an early transition metal, A is an A-group element, and X is carbon and/or nitrogen).     

Mechanical-Alloying-Assisted Synthesis of Ti3SiC2 Powder

Mechanical alloying (MA) has been used to synthesize Ti₃SiC₂ powder from the elemental Ti, Si, and C powders. The MA formation conditions of Ti₃SiC₂ were strongly affected by the ball size for the conditions used. MA using large balls (20.6 mm in diameter) enhanced the formation of Ti₃SiC₂, probably via an MA-triggered combustion reaction, but the Ti₃SiC₂ phase was not synthesized only by the MA process using small balls (12.7 mm in diameter). Fine powders containing 95.8 vol% Ti₃SiC₂ can be obtained by annealing the mechanically alloyed powder at relatively low temperatures.     

Interdiffusion Between Ti3SiC2–Ti3GeC2 and Ti2AlC–Nb2AlC Diffusion Couples

In this work, we report on the interdiffusion of Ge and Si in Ti₃SiC₂ and Ti₃GeC₂, as well as that of Nb and Ti in Ti₂AlC and Nb₂AlC. The interdiffusion coefficient, D _int, measured by analyzing the diffusion profiles of Si and Ge obtained when Ti₃SiC₂–Ti₃GeC₂ diffusion couples are annealed in the 1473–1773 K temperature range at the Matano interface composition (≈Ti₃Ge_0.5Si_0.5C₂), was found to be given by
D _int increased with increasing Ge composition. At the highest temperatures, diffusion was halted after a short time, apparently by the formation of a diffusion barrier of TiC. Similarly, the interdiffusion of Ti and Nb in Ti₂AlC–Nb₂AlC couples was measured in the 1723–1873 K temperature range. The D _int for the Matano interface composition, viz. ≈(Ti_0.5,Nb_0.5)₂AlC, was found to be given by
At 1773 K, the diffusivity of the transition metal atoms was ≈7 times smaller than those of the Si and Ge atoms, suggesting that the former are better bound in the structure than the latter.     

Effect of Vacuum Annealing on the Phase Stability of Ti3SiC2

The effect of vacuum annealing on the thermal stability and phase transition of Ti₃SiC₂ has been investigated by X-ray diffraction (XRD), neutron diffraction, synchrotron radiation diffraction, and secondary ion mass spectroscopy (SIMS). In the presence of vacuum or a controlled atmosphere of low oxygen partial pressure, Ti₃SiC₂ undergoes a surface dissociation to form nonstoichiometric TiC and/or Ti₅Si₃C _x that commences at ∼1200°C and becomes very pronounced at ≥1500°C. Composition depth profiling at the near surface of vacuum-annealed Ti₃SiC₂ by XRD and SIMS revealed a distinct gradation in the phase distribution of TiC and Ti₅Si₃C _x with depth.     

Phase Relations in the Pyrochlore-Rich Part of the Bi2O3−TiO2−Nd2O3 System

In this study we used solid-state synthesis to determine the phase relations in the pyrochlore-rich part of the Bi₂O₃−TiO₂−Nd₂O₃ system at 1100°C. The samples were analyzed using X-ray powder diffraction and scanning electron microscopy with energy- and wavelength-dispersive spectroscopy. A single-phase pyrochlore ceramic was obtained with the addition of 4.5 mol% of Nd₂O₃. We determined the solubility limits for the three solid solutions: (i) the pyrochlore solid solution Bi_{(1.6–1.08 x )}Nd _x Ti₂O_{(6.4+0.3 x )}, where 0.25< x <0.96; (ii) the solid solution Bi_{4− x} Nd _x Ti₃O₁₂, where 0< x <2.6; and (iii) the Nd_{2− x} Bi _x Ti₂O₇ solid solution, where 0< x <0.35. The determined phase relations in the pyrochlore-rich part are presented in a partial phase diagram of the Bi₂O₃−TiO₂−Nd₂O₃ system in air at 1100°C.     

Toughening of SiC with Ti3SiC2 Particles

Composites in the SiC–TiC–Ti₃SiC₂ system were synthesized using reactive hot pressing at 1600°C. The results indicate that addition of Ti₃SiC₂ to SiC leads to improved fracture toughness. In addition, high microhardness can be retained if TiC is added to the material. The best combination of properties obtained in this study is K _{I c} =8.3 MPa·m^1/2 and H _v=17.6 GPa. The composition can be tailored in situ using the decomposition of Ti₃SiC₂. Ti₃SiC₂ decomposed rapidly at temperatures above 1800°C, but the decomposition could be conducted in a controlled manner at 1750°C. This can be used for synthesis of fully dense composites with improved properties by first consolidating to full density a softer Ti₃SiC₂-rich initial composition, and then using controlled decomposition of Ti₃SiC₂ to achieve the desired combination of microhardness and fracture toughness.     

Machinable Ti3SiC2/Hydroxyapatite Bioceramic Composites by Spark Plasma Sintering

In this paper, we report a machinable Ti₃SiC₂/hydroxyapatite (HAp) composite prepared by spark plasma sintering. The experimental results of a drilling test demonstrated that the composites exhibit excellent machinability when the Ti₃SiC₂ content is higher than 20 vol%, which can be attributed to the improvement in the mechanical and machinable properties of the composites by addition of Ti₃SiC₂ phase, which possessess unique mechanical and machinable properties and energy-absorbing mechanisms. The superior mechanical and machinable properties of Ti₃SiC₂/HAp composites suggest that the composite system could be attractive for practical applications of novel biomaterials.     

Crossover of Ba(Ti,Y)O3 Solid Solutions to Ba3Ti2YO8.5–BaTiO3 Composites and their Dielectric Properties

Ceramic samples with the nominal composition (1− x ) BaTiO₃+ x Ba₃Ti₂YO_8.5 ( x =0−0.535) were prepared by the mixed oxide method. X-ray diffraction (XRD) analysis shows that the materials are of single phase with a cubic symmetry as x ≤0.16. The compositions of the solid solutions ( x ≤0.16) can be expressed equivalently as Ba(Ti_{1− y} Y _y )O_3−δ ( y ≤0.122, y = x /(1+2 x )). For x >0.16, the materials are diphasic composites consisting of Ba(Ti_{1− y} Y _y )O₃ ( y =0.122) and Ba₃Ti₂YO_8.5. The microstructure observation by scanning electron microscopy supports the XRD result. The dielectric behavior and phase transitions of the solid solutions ( x ≤0.16) vary with different Y concentrations. The dielectric constant of the composites ( x >0.16) follows approximately the Lichteneker relation in a wide temperature range.     

Synthesis of Ti3SiC2 Powders: Reaction Mechanism

Titanium silicon carbide (Ti₃SiC₂) and Ti₃SiC₂-based composite powders were synthesized by isothermal treatment in an inert atmosphere as a function of initial compositions (mixtures). A high content of TiC was obtained in the final product when the initial mixtures contained free carbon. The use of TiC as a reagent was unsuccessful in obtaining Ti₃SiC₂. High Ti₃SiC₂ conversion was found for the initial mixtures containing SiC as the main source for silicon and carbon. An initial mixture with a large excess of silicon, 3Ti/1.5SiC/0.5C, was needed to obtain high-purity Ti₃SiC₂. A reaction mechanism, where Ti₃SiC₂ nucleates on Ti₅Si₃C crystals and grows by long-range diffusion of Ti and C, is proposed. The reaction mechanism was proposed to be based on silicon loss during the formation of Ti₃SiC₂.     

Self-Propagating High-Temperature Synthesis of Ti3SiC2: Study of the Reaction Mechanisms by Time-Resolved X-Ray Diffraction and Infrared Thermography

Ti₃SiC₂ is synthesized by self-propagating high-temperature synthesis (SHS) of elemental titanium, silicon, and graphite powders. The reaction paths and structure evolution are studied in situ during the SHS of the 3Ti+Si+2C mixture by time-resolved X-ray diffraction coupled with infrared thermography. The proposed reaction mechanism suggests that Ti₃SiC₂ might be formed from Ti–Si liquid phase and solid TiC _x . Finally, the effect of the powders starting composition on the Ti₃SiC₂ synthesis is studied. For the investigated initial mixtures, TiC _x is always formed as a major impurity together with the Ti₃SiC₂ phase.     

TIOx/Al2O3 Multilayer Ceramic Thin Films

Titanium oxide/aluminum oxide films have been deposited using molecular beam epitaxy methods and characterized by reflection high-energy electron diffraction and transmission electron microscopy techniques. Growth on silicon substrates below 973 K resulted in primarily amorphous multilayers. At 1323 K, the deposition of titanium in an oxygen atmosphere on (0001) Al₂O₃ substrates resulted in films of Ti₂O₃. These films consisted of small domains, up to 60 nm, slightly misoriented from a [1120] ∥ [1120] orientation relationship. Two variants of Ti₂O₃ were observed due to multiple positioning during growth. Closing the titanium shutter during growth resulted in an oriented TiO₂ film.     

Microstructure and Grain Boundary Structure of Na+-Diffused (Sr,Ca)TiO3 Capacitor-Varistor Ceramics

The microstructure of (Sr,Ca)TiO₃ capacitor-varistor materials has been investigated by employing electron microscopy techniques (TEM, STEM, HREM, EDX, and EPA). The material is found to contain (Sr,Ca)TiO₃ grains (∼30 μm) having perovskite crystal structure with domains, a Na⁺-diffused layer at the grain boundaries which is dependent on thermal diffusion conditions, and multiple-grain junctions in which the Ti _n O_2n–1 Magneli phase coexists with an amorphous intergranular phase. In addition, wider grain boundaries (10–30 nm), thin grain boundaries (∼1 nm), and clean grain boundaries which are free from intergranular phase were observed, and the effects of different grain boundaries on the diffusion of Na⁺are discussed.     

Reinforcement of Hydroxyapatite Bioceramic by Addition of Ti3SiC2

Ti₃SiC₂/HAp composites with different Ti₃SiC₂ volume fractions were fabricated by spark plasma sintering (SPS) at 1200°C. The effects of Ti₃SiC₂ addition on the mechanical properties and microstructures of the composites were investigated. The bending strength and fracture toughness of the composites increased with increasing of Ti₃SiC₂ content, whereas the Vickers hardness decreased. The bending strength and fracture toughness reached 252±10 MPa and 3.9±0.1 MPa·m^1/2, respectively, with the addition of 50 vol% Ti₃SiC₂. The increases in the mechanical properties were attributed to the matrix strengthening and interactions between cracks and the Ti₃SiC₂ platelets.     

Three-Dimensional Printing of Nanolaminated Ti3AlC2 Toughened TiAl3–Al2O3 Composites

Nanolaminates with a layered M _{N +1}AX _N crystal structure (with M: transition metal, A: group element, X: carbon or nitrogen, and N =1, 2, 3) offer great potential to toughen ceramic composites. A ternary Ti₃AlC₂ carbide containing ceramic composite was fabricated by three-dimensional printing of a TiC+TiO₂ powder mixture and dextrin as a binder. Subsequent pressureless infiltration of the porous ceramic preform with an Al melt at 800°–1400°C in an inert atmosphere, followed by reaction of Al with TiC and TiO₂ finally resulted in the formation of a dense multiphase composite of Ti₃AlC₂–TiAl₃–Al₂O₃. A controlled flaw/strength technique was utilized to determine fracture resistance as a function of crack extension. Rising R -curve behavior with increasing crack extension was observed, confirming the operation of wake-toughening effects on the crack growth resistance. Observations of crack/microstructure interactions revealed that extensive crack deflection along the (0001) lamellar sheets of Ti₃AlC₂ was the mechanism responsible for the rising R -curve behavior.     

Preparation and Properties of Ternary Ti3AlC2 and its Composites from Ti–Al–C Powder Mixtures With Ceramic Particulates

A layered ternary carbide phase, Ti₃AlC₂, was synthesized by hot pressing from the starting materials of Ti, aluminum, and activated carbon at 1400°C for 2 h. Its composites were also fabricated through addition of micro-sized SiC and partially stabilized zirconia particulates to the pulverized Ti₃AlC₂ powders. The polycrystalline Ti₃AlC₂ ceramic obtained has a flexural strength of 172 MPa and a fracture toughness of 4.6 MPa·m^1/2, respectively. This compound is relatively soft (Vikers hardness of 2.7 GPa) and exhibits good electrical conductivity with an electrical resistivity of 8.2 μΩ·m. Both the Ti₃AlC₂/SiC and Ti₃AlC₂/ZrO₂ composites are superior to the monolithic Ti₃AlC₂ ceramic in strength, fracture toughness, and micro-hardness.