Crystallographic relations between Ti<Subscript>3</Subscript>SiC<Subscript>2</Subscript> and TiC

Ti₃SiC₂ is a so-called not-so-brittle ceramic that combines the merits of both metals and ceramics. However, many previous works demonstrated that its bonding nature and properties were strongly related to TiC. In this paper the crystallographic relations between Ti₃SiC₂ and TiC were established and described based on the transmission electron microscopy investigation on the Ti₃SiC₂/TiC interface in Ti₃SiC₂ based material. At Ti₃SiC₂/TiC interface, the following crystallographic relationships were identified: (111)TiC//(001)Ti₃SiC₂, (002) TiC//(104)Ti₃SiC₂, and [11ˉ0]TiC//[110]Ti₃SiC₂. Based on the above interfacial relations an interfacial structure model was established. The structure of Ti₃SiC₂ could be considered as two-dimensional closed packed layers of Si periodically intercalated into the (111) twin boundary of TiC_0.67 (Ti₃C₂). The intercalation resulted in the transformation from cubic TiC_0.67 to hexagonal Ti₃SiC₂. In the opposite case, de-intercalation of Si from Ti₃SiC₂ caused the transformation from hexagonal Ti₃SiC₂ to cubic TiC_0.67. Understanding the crystallographic relations between Ti₃SiC₂ and TiC is of vital importance in both understanding the properties and optimizing the processing route for preparing pure Ti₃SiC₂. Received: 10 February 2000 / Reviewed and accepted: 17 March 2000     

Formation of Ti<Subscript>3</Subscript>SiC<Subscript>2</Subscript> from Ti-Si-TiC powders by pulse discharge sintering (PDS) technique

Ti/Si/TiC powder mixture with molar ratios of 2:2:3 were sintered at various temperatures from 700–1300 °C for 15 min by PDS technique. X-ray diffraction (XRD) and scanning electron microscopy (SEM) were used for the evaluation of phase composition in different samples for the understanding of the sintering mechanism for this system. Results showed that Ti₅Si₃ formed as the intermediate phase during sintering. The reaction between Ti₅Si₃ and TiC as well as Si induces the formation of Ti₃SiC₂, and TiSi₂ appears as the byproduct in this process. At temperature above 1000 °C, TiSi₂ reacts with TiC to form Ti₃SiC₂. High Ti₃SiC₂ phase content bulk material can be synthesized at 1300 °C for 15 min.     

Effect of Ti<Subscript>3</Subscript>SiC<Subscript>2</Subscript> addition on microwave absorption property of plasma sprayed Ti<Subscript>3</Subscript>SiC<Subscript>2</Subscript>/NASICON coatings

The work attempted to develop a kind of high temperature microwave absorption coating. The Ti₃SiC₂/NASICON composite coatings with different Ti₃SiC₂ concentrations were fabricated by atmospheric plasma spraying. The effect of Ti₃SiC₂ addition on phase, density, microstructure, dielectric property and microwave absorption property of as-sprayed coatings was investigated. Results show that the complex permittivity increases with increasing the content of Ti₃SiC₂ due to the enhanced space charge polarization, decreased porosity and increased conduction loss. When the content of Ti₃SiC₂ increases to 30 wt%, the coating exhibits the optimal microwave absorption property with a bandwidth (below ??5 dB) of 4.01 GHz and lowest reflection loss of ??12.4 dB at 9.63 GHz in 1.4 mm thickness. It indicates that the Ti₃SiC₂/NASICON composite coating can be a potential candidate for microwave absorption.     

Superhard pcBN tool materials with Ti<Subscript>3</Subscript>SiC<Subscript>2</Subscript> MAX-phase binder: Structure,properties, application

Superhard cutting tool materials were sintered in cBN–(Ti₃SiC₂–TiC) system via high pressure–high temperature method. Sintering was performed under the pressure 8 GPa in the 1400–2400°C temperature range. The initial mixtures of three compositions were chosen with 90, 80 and 60 vol % cBN. The mixtures were prepared by mixing cBN (1–3 μm) and Ti₃SiC₂–TiC (< 2 μm). It was found, that upon sintering, the compositions of the obtained samples differed from the initial mixtures in all cases as a result of chemical reactions. Microstructure observations, phase composition estimation, and mechanical properties of the obtained tool materials were carried out. The results indicate that both the varying cBN content and the applied sintering conditions have a direct effect on the structure, properties, and kinetics of reactions.     

Complex permittivity and electromagnetic interference shielding properties of Ti<Subscript>3</Subscript>SiC<Subscript>2</Subscript>/polyaniline composites

Ti₃SiC₂/insulating polyaniline (Ti₃SiC₂/PANI) composites were prepared by solution blending and subsequently by hot-pressing process. The dielectric permittivity and electromagnetic interference (EMI) shielding effectiveness (SE) of the composites were determined in the frequency range of 8.2–12.4 GHz (X-band). Both real and imaginary permittivities increase with the increasing Ti₃SiC₂ content, and which are attributed to the enhanced displacement current and conduction current. The EMI SE of the composites can be greatly improved by addition of Ti₃SiC₂ filler, which may be ascribed to the increase of electrical conductivity of the composites. It is also found that the reflection of electromagnetic radiation is a dominant mechanism for EMI shielding of the composite. An average EMI SE of 23 dB can be achieved in the X-band range for the composite with 25 wt% Ti₃SiC₂ content, which shows the potential of the Ti₃SiC₂/PANI composites as EMI shielding materials for commercial applications.     

Preparation of Ti<Subscript>3</Subscript>SiC<Subscript>2</Subscript> through reduction of titanium dioxide with silicon carbide

This paper describes the reduction of titanium dioxide with a mixture of silicon carbide and silicon powders at a temperature of 1550°C under vacuum. It has been shown that the use of the combined reductant enables the preparation of the ternary phase Ti₃SiC₂ through concurrent carboand silicothermic processes. The optimal compositions for Ti₃SiC₂ formation are TiO₂ + (1.5–x)SiC + 2xSi with x = 0.4–0.5. The Ti₃SiC₂ yield then reaches 96 wt %.     

Optimization of the Carbosilicothermic Synthesis of the Ti<Subscript>4</Subscript>SiC<Subscript>3</Subscript> MAX Phase

We have studied the formation of the Ti4SiC3 MAX phase during the vacuum carbosilicothermic reduction of TiO₂ with a combined reducing agent consisting of SiC and elemental Si and analyzed the effects of the synthesis temperature, heat treatment time, and percentage of elemental silicon in the starting mixture on the Ti₄SiC₃ yield. Optimal Ti₄SiC₃ synthesis conditions are as follows: temperature from 1550 to 1650°C, isothermal holding time of 360 min, and the starting-mixture composition TiO₂ + 1.2SiC + 0.6Si. The Ti₄SiC₃ yield then reaches 92 wt %.     

Wettability of Ti<Subscript>3</Subscript>SiC<Subscript>2</Subscript> by Ag–Cu and Ag–Cu–Ti melts

Recently, the ternary carbide Ti₃SiC₂ has gained much attention due to its unique characteristics combining the properties of metals and ceramics (i.e., a low density, decent thermal and electrical conductivities, an excellent thermal shock resistance, a good machinability, damage tolerance, low friction, and so on). This study describes an investigation of the wettability in high vacuum of bulk Ti₃SiC₂ by a classical braze alloy based on the Ag–Cu–Ti system. Two techniques, i.e., the sessile drop and dispensed drop methods, were utilized. The results indicated that spreading kinetics is controlled by deoxidation kinetics of Ti₃SiC₂ surface under vacuum. The final contact angle on clean Ti₃SiC₂ is very small (~10°), testifying the development of strong, metallic interactions across the liquid–solid interface. The reactivity between the ternary carbide and the liquid phase during isothermal heating at 800 °C was also considered.     

Investigation on reliability of nanolayer-grained Ti<Subscript>3</Subscript>SiC<Subscript>2</Subscript> via Weibull statistics

Weibull modulus of bending strength of nanolayer-grained ceramic Ti₃SiC₂ was estimated with over 50 specimens, using the least square method, the moment method and the maximum likelihood technique, respectively. The result demonstrated that the m-value of this layered ceramic ranged from 25 to 29, which is much higher than that of traditional brittle ceramics. The reason of high Weibull modulus was due to high damage tolerance of this material. Under stress, delamination and kinking of grains and shear slipping at interfaces give this material high capacity of local energy dissipation and easy local stress relaxation, leading to the excellent damage tolerance of Ti₃SiC₂. The effect of amounts of specimens on the reliability of the estimated m-values was also investigated. It was confirmed that the stability of the estimated m-value increased with increasing numbers of specimens. The parameter obtained using the maximum likelihood technique showed the highest reliability than other methods. The ranges of failure probability were determined using the Weibull estimates calculated from the maximum likelihood technique.     

High-temperature oxidation behaviour of Ti<Subscript>3</Subscript>Si<Subscript>(1−<Emphasis Type="Italic">x</Emphasis>)</Subscript>Al<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>C<Subscript>2</Subscript> in air

The oxidation behaviours of bulk Ti₃Si_(1−x)Al _x C₂ prepared by hot pressing were investigated. The results showed that the isothermal oxidation behaviour of Ti₃SiC₂ obeyed a parabolic law between 900 and 1100°C, and followed a two-step parabolic rate law between 1200°C and 1300°C. The cyclic oxidation behaviour of material is assumed to obey a three-step parabolic rate law at 1100°C and 1200°C. The calculated activation energy of isothermal oxidation is 101·43 kJ·mol⁻¹. The oxide layers consisted of a mass of α-Al₂O₃ and little TiO₂ and SiO₂ are observed on Ti₃SiC₂ as a dense and adhesive protect scale. The oxidation mechanism varies with the additive aluminum that greatly improves the oxidation resistance of Ti₃SiC₂.     

Diffusion bonding of Ti<Subscript>3</Subscript>AlC<Subscript>2</Subscript> ceramic via a Si interlayer

Based on the structure characteristic of Ti₃AlC₂ and the easy formation of Ti₃Al_{1 − x} Si _x C₂ solid solution, a Si interlayer was selected to join Ti₃AlC₂ layered ceramic by diffusion bonding method. Joining was performed at 1,300–1,400 °C for 120 min under 5 MPa load in an Ar atmosphere. The phase composition and interface microstructure of the joints were investigated by XRD, SEM and EPMA. The results revealed that Ti₃Al(Si)C₂ solid solution formed at the interface. The mechanism of bonding is attributed to silicon diffusing inward the Ti₃AlC₂. The strength of joints was evaluated by a 3-point bending test. The jointed specimens exhibit a high flexural strength of 285 ± 11 MPa, which is about 80% of that of the Ti₃AlC₂; and retain this strength up to 1,000 °C. The high mechanical performance of the joints indicates that diffusion bonding via a Si interlayer is effective to bond Ti₃AlC₂ ceramic.     

Effects of infiltration parameters on the synthesis of nano-laminated Ti3SiC2

In this paper, the nano-laminated Ti₃SiC₂ ceramics were fabricated by liquid silicon infiltration of gelcast porous titanium carbide (TiC) preforms. The phase compositions and microstructures of the synthesized samples at various infiltration times and temperatures were analyzed by the X-ray diffraction (XRD) technique and were observed by field emission scanning electron microscopy (FESEM). The results showed that the formed Ti₃SiC₂ decomposes to the TiC phase with the increase of infiltration time. It was found from the XRD patterns that the samples with an 88?wt% Ti₃SiC₂ MAX phase can be produced with infiltration at 1500°C for 1?h with 50 vol% solid loading and 10?wt% monomer content. It is found that the hardness and flexural strength of Ti₃SiC₂-based ceramic has been reduced with a decrease in SiC and TiC impurities and reach 5.8?GPa and 420?MPa, respectively, for the sample with 15?wt% impurity. The microstructure evaluation revealed that the purity and properties of samples were affected both through the gelcasting and infiltration parameters.     

Self-propagating high-temperature synthesis of Al<Subscript>2</Subscript>O<Subscript>3</Subscript>/TiC-based ceramic materials

Dense Al₂O₃/TiC composite ceramic materials are synthesized using the SHS compaction of mixtures based on TiO₂ + Al + C. Mineralizing and heating additives are introduced into compounds. The phase composition and microstructure of combustion products are investigated by x-ray phase analysis, electron microscopy, and microprobe techniques. Two Al₂O₃ modifications are revealed. Special attention is devoted to the presence of residual graphite. The mechanisms of phase formation and formation of the microstructure of combustion products are considered.     

Effect of excess PbO and sintering temperature on the templated grain growth of Pb(Mg<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>)<Subscript>0.67</Subscript>Ti<Subscript>0.33</Subscript>O<Subscript>3</Subscript> polycrystals

The effect of excess lead oxide and sintering temperature on the microstructure evolution in the templated grain growth (TGG) of the Pb(Mg_1/3Nb_{2/ 3})_0.67Ti_0.33O₃ (PMNT67/33) polycrystals was investigated. By adding excess PbO in the precursor of PMNT ceramics, the textured structure of PMNT polycrystals was obtained near SrTiO₃ (ST) template by the conventional ceramic technique. The texture profiles developed progressively with increasing the concentration of excess PbO. A suitable sintering temperature is also very essential to grow a thick textured layer and avoid a second phase. Furthermore, the through-thickness of the PMNT textured layer is strongly influenced by the uniaxial compact-pressure of preparing the ST seeded PMNT specimen.     

Dielectric properties of B<Subscript>2</Subscript>O<Subscript>3</Subscript> doped Sm(Co<Subscript>1/2</Subscript>Ti<Subscript>1/2</Subscript>)O<Subscript>3</Subscript> ceramics at microwave frequency

The microwave dielectric properties and the microstructures of Sm(Co_1/2Ti_1/2)O₃ ceramics with B₂O₃ additions (0.25 and 0.5 wt%) prepared by conventional solid-state route have been investigated. The prepared Sm(Co_1/2Ti_1/2)O₃ exhibited a mixture of Co and Ti showing 1:1 order in the B-site. Doping with B₂O₃ (up to 0.5 wt%) can effectively promote the densification of Sm(Co_1/2Ti_1/2)O₃ ceramics with low sintering temperature. It is found that Sm(Co_1/2Ti_1/2)O₃ ceramics can be sintered at 1,260 °C due to the grain boundary phase effect of B₂O₃ addition. At 1,290 °C, Sm(Co_1/2Ti_1/2)O₃ ceramics with 0.5 wt% B₂O₃ addition possess a dielectric constant (ε _r) of 27.7, a Q × f value of 33,600 (at 9 GHz) and a temperature coefficient of resonant frequency (τ_f) of −11.4 ppm/ °C. The B₂O₃-doped Sm(Co_1/2Ti_1/2)O₃ ceramics can find applications in microwave devices requiring low sintering temperature.     

Structural evolution of the intergrowth bismuth-layered Bi<Subscript>7</Subscript>Ti<Subscript>4</Subscript>NbO<Subscript>21</Subscript>

A series of intergrowth bismuth-layered ferroelectric Bi₇Ti₄NbO₂₁ materials are reactive-sintered at 1050 to 1150 °C from Bi₃TiNbO₉ and Bi₄Ti₃O₁₂ parent phases to infer their structural characters and microstructure relations. Various types of stacking faults are revealed in the intergrowth structure with extra Bi₃TiNbO₉ or Bi₄Ti₃O₁₂ layer(s) by high-resolution transmission electron microscopy; some faults with even spacing form locally new intergrowths of Bi₁₀Ti₅Nb₂O₃₀ and Bi₁₁Ti₇NbO₃₃. Co-growth of Bi₇Ti₄NbO₂₁ epitaxially grown onto the remaining Bi₄Ti₃O₁₂ grains is found in the low temperature sintered samples, while the Bi₄Ti₃O₁₂ co-growth onto the intergrowth grains is also found in the high temperature samples. Both co-growths are created from intergranular melts during a solution-precipitation process, which is consistent with the anisotropic growth of the intergrowth structure and the presence of a Bi-rich intergranular phase. The populations of different stacking faults are found to decrease with the increase of their thickness and also with the increase of sintering temperature, indicating that they are remnants survived from dissolution to imbed via precipitation into the intergrowth structure, which should be created from the smaller but much abundant one-layered remnants of the parent phases. This leads to a new model of structural reorganization by such one-layered units to form the intergrowth structure in this solution-precipitation process. Such incomplete dissolution is initiated by the preferential melting of interleaved [Bi₂O₂]²⁺ sheets to enable the exfoliation of perovskite layers to re-order into the intergrowth structure. This reorganization model re-defines the reactive sintering as an evolution process of Bismuth-layered structures.     

Formation behavior of CaCu<Subscript>3</Subscript>Ti<Subscript>4</Subscript>O<Subscript>12</Subscript> from CaTiO<Subscript>3</Subscript>, CuO and TiO<Subscript>2</Subscript>

The formation behavior of CaCu₃Ti₄O₁₂ (CCTO) had been investigated via solid state reaction from CaTiO₃, CuO and TiO₂ powders. In the temperature range from 750 to 1,200 °C, the reaction sequence was traced by XRD, and the microstructure evolution of calcined powders was also investigated by SEM. CCTO began to form owing to the reaction between CaTiO₃, CuO and TiO₂ at around 850 °C, and became the major phase at 1,000 °C. Finally, the single phase CCTO was obtained at 1,150 °C. However, CCTO was decomposed at CaTiO₃, CuO and TiO₂ when the temperature increased to 1,200 °C. In addition, no other intermediate phases occurred in the synthesized process. The formation behaviors indicated that CaTiO₃ prevented the formation and growth of CCTO.     

Giant dielectric and electrical properties of sodium yttrium copper titanate: Na<Subscript>1/2</Subscript>Y<Subscript>1/2</Subscript>Cu<Subscript>3</Subscript>Ti<Subscript>4</Subscript>O<Subscript>12</Subscript>

The electrical properties and dielectric response in Na_1/2Y_1/2Cu₃Ti₄O₁₂ ceramic prepared by conventional solid-state reaction method and sintered at 1,090 °C for 5 h were investigated as functions of frequency and temperature. Main phase of Na_1/2Y_1/2Cu₃Ti₄O₁₂ with CaCu₃Ti₄O₁₂-like crystallographic structure and CuO secondary phase were observed in the X-ray diffraction pattern. Abnormal grain growth was observed just as observed in CaCu₃Ti₄O₁₂ ceramics. The Na_1/2Y_1/2Cu₃Ti₄O₁₂ ceramic exhibits a high ε′ of ~2.04 × 10⁴ at 20 °C and 1 kHz and low tan δ (with the minimum 0.080 at 5 kHz). Impedance spectroscopy analysis reveals that Na_1/2Y_1/2Cu₃Ti₄O₁₂ ceramic is electrically heterogeneous, consisting of semiconducting grains and insulating grain boundaries. Giant ε′ response in Na_1/2Y_1/2Cu₃Ti₄O₁₂ ceramic is therefore attributed to an internal barrier layer capacitor effect.     

Investigation of Li<Subscript>2</Subscript>Zn<Subscript>3</Subscript>Ti<Subscript>4</Subscript>O<Subscript>12</Subscript>-based temperature stable dielectric ceramics for LTCC applications

A low temperature co-fired ceramic (LTCC) was fabricated at 910 °C /2 h from the powder mixture of Li₂Zn₃Ti₄O₁₂, TiO₂ and a B₂O₃–La₂O₃–MgO–TiO₂ glass (BLMT), and the influence of TiO₂ on microstructure and dielectric properties of the composite was investigated in the composition range (wt%) of 20BLMT–(80???x)Li₂Zn₃Ti₄O₁₂–xTiO₂ (x?=?0, 2.5, 5, 7.5, 9 and 10). The results showed that all samples consisted of Li₂Zn₃Ti₄O₁₂, TiO₂, LaBO₃ and LaMgB₅O₁₀ phase. And LaBO₃, LaMgB₅O₁₀ and a small amounts of TiO₂ were crystallized from BLMT glass during sintering process. As x increases, dielectric constant and temperature coefficient of resonance frequency of the composites demonstrated gradually increase, whereas the quality factor of the sample of x?=?0 wt% was about 41,500 GHz and the ones maintained stable at a high level of 49,000–51,000 GHz for other samples. The composite with x?=?9 wt% had an optimal microwave dielectric properties with the dielectric constant of 20.2, quality factor of 50,000 GHz and temperature coefficient of resonant frequency of ??0.33 ppm/°C.     

A new synthesis reaction of Ti3SiC2 from Ti/TiSi2/TiC powder mixtures through pulse discharge sintering (PDS) technique

Ti/TiSi₂/TiC powder mixtures with molar ratios of 1:1:4 (M1) and 1:1:3 (M2) were first employed for the synthesis of Ti₃SiC₂ through pulse discharge sintering (PDS) technique in a temperature range of 1100–1325 °C. It was found that Ti₃SiC₂ phase began to form at the temperature above 1200 °C and its purity did not show obvious dependence on the sintering temperature at 1225–1325 °C. The TiC contents in M2 samples is always lower than that of the M1 samples, and the lowest TiC contents in the M1 and M2 samples were calculated to be about 7 wt% and 5 wt% when the sintering was conducted at the temperature near 1300 °C for 15 minutes. The relative density of the M1 samples is always higher than 99% at sintering temperature above 1225 °C, indicating a good densification effect produced by the PDS technique. A solid-liquid reaction mechanism between Ti-Si liquid phase and TiC particles was proposed to explain the rapid formation of Ti₃SiC₂. Furthermore, it is suggested that Ti/TiSi₂/TiC powder can be regarded as a new mixture to fabricate ternary carbide Ti₃SiC₂. Received: 5 September 2001 / Accepted: 11 September 2001