Synthesis of single-phase Ti3SiC2 powder

In this study, free 2Ti/2Si/3TiC powder mixture was heated at high temperatures in vacuum, in order to reveal the possibility for the synthesis of high Ti₃SiC₂ content powder. X-ray diffraction (XRD) and scanning electron microscopy (SEM) were used for the evaluation of phase identities and the morphology of the powder after different treatments. Results showed that almost single phase Ti₃SiC₂ powder (99.3 wt.%) can be synthesized by heat treatment with free 2Ti/2Si/3TiC powders in vacuum at 1210°C for about 3 h. The nucleation and growth of Ti₃SiC₂ within TiC particles was observed. The typical appearance of the formed Ti₃SiC₂ is equiaxed with particle size of 2–4 μm. Effects of temperature and heating time on the morphology and the particle sizes of the synthesized Ti₃SiC₂ powders are not obvious.     

Preparation and characterization of Ti3SiC2 powder

Pressureless sintering in vacuum was applied to synthesize Ti₃SiC₂ from elemental powders of Ti, Si and C. Based on the phase compositions and purities of the products obtained by X-ray diffraction, the elemental powders composition and sintering condition were optimized. It was found that the sample sintered at 1450 °C for 240 min from a mixture of 3Ti/1.75Si/2C (molar ratio) contained Ti₃SiC₂ with the volume fraction as high as 93%. It was proposed that loss of Si through gaseous vaporization and contamination of C might be the main obstacles against obtaining high-purity material by this way.     

Effect of Al addition on the synthesis of Ti3SiC2 bulk material by pulse discharge sintering process

Ti₃SiC₂ bulk materials were synthesized from the starting powders of 1Ti/1Si/2TiC–xAl and 3Ti/1SiC/1C–xAl (molar ratios, x ranges from 0.05 to 0.15) at temperatures between 1100 and 1400 °C for 15 min by pulse discharge sintering technique. X-ray diffraction and scanning electron microscopy were used to characterize the synthesized materials. It was found that the addition of Al decreases the content of TiC in the sintered samples and expands the optimal temperature range for the synthesis of Ti₃SiC₂ bulk materials. By addition of Al, Ti₃SiC₂ bulk materials of high phase-purity have been synthesized at 1100 and 1200 °C from 1Ti/1Si/2TiC and 3Ti/1SiC/1C starting powders, respectively.     

Fabrication and Microstructure Characterization of Ti3SiC2 Synthesized from Ti/Si/2TiC Powders Using the Pulse Discharge Sintering (PDS) Technique

Ti/Si/2TiC powders were prepared using a mixture method (M) and a mechanical alloying (MA) method to fabricate Ti₃SiC₂ at 1200°–1400°C using a pulse discharge sintering (PDS) technique. The results showed that the Ti₃SiC₂ samples with <5 wt% TiC could be rapidly synthesized from the M powders; however, the TiC content was always >18 wt% in the MA samples. Further sintering of the M powder showed that the purity of Ti₃SiC₂ could be improved to >97 wt% at 1250°–1300°C, which is ∼200°–300°C lower than that of sintered Ti/Si/C and Ti/SiC/C powders using the hot isostatic pressing (HIPing) technique. The microstructure of Ti₃SiC₂ also could be controlled using three types of powders, i.e., fine, coarse, or duplex-grained, within the sintering temperature range. In comparison with Ti/Si/C and Ti/SiC/C mixture powders, it has been suggested that high-purity Ti₃SiC₂ could be rapidly synthesized by sintering the Ti/Si/TiC powder mixture at relatively lower temperature using the PDS technique.     

Surface strengthening of Ti3SiC2 through magnetron sputtering Cu and subsequent annealing

Magnetron sputtering deposition Cu and subsequent annealing in the temperature range of 900–1100 °C for 30–60 min were conducted with the motivation to modify the surface hardness of Ti₃SiC₂. Owing to the formation of TiC following the reaction Ti₃SiC₂ + 3Cu → 3TiC_0.67 + Cu₃Si, the surface hardness was enhanced from 5.08 GPa to a maximum 9.65 GPa. In addition, the surface hardness was dependent on the relative amount of TiC, which was related to Cu film thickness, heat treatment temperatures and durations of annealing. Furthermore, after annealing at 1000 °C for 30 min the Cu-coated Ti₃SiC₂ has lower wear rate and lower COF at the running-in stage compared with Ti₃SiC₂ substrate. The reaction was triggered by the inward diffusion of Cu along the grain boundaries and defects of Ti₃SiC₂. At low temperature and short annealing time, i.e. 900 or 1000 °C for 30 min, Cu diffused inward Ti₃SiC₂ and accumulated at the trigonal junctions first. At higher temperature of 1100 °C or prolonging the annealing time to 60 min, considerable amount of Cu diffused to Ti₃SiC₂ and filled up the grain boundaries leaving a mesh structure.     

Sintering behavior of Al2TiO5 base ceramics and their thermal properties

Sintering behavior of Al₂TiO₅ without and with various additives and the thermal properties of the sintered material—thermal expansion and decomposition—were investigated. The precursors of Al₂TiO₅ powders were prepared by homogeneous precipitation and coprecipitation. Sintering of pure Al₂TiO₅ gave a fine grained-structure at 1300°C, but resulted in large-grained and cracked microstructures at 1400 and 1500°C. Addition of ZrO₂ or BaO gave fine-grained microstructures with a small increase in thermal expansion. Addition of ZrO₂, BaO or ZrSiO₄, especially ZrSiO₄, was effective in suppressing the thermal decomposition of Al₂TiO₅ at 1100°C. ©     

Sintering of Si3N4 with liquid in the system Ce2O3---AIN---SiO2

Liquid phase sintering of Si₃N₄ with melts from the system Ce₂O₃---AIN---SiO₂ has been studied. The glass forming region in this system and the reaction products formed during sintering at 1750–1800°C were analysed. Sintering of Si₃N₄ with two melt compositions selected from outside the glass forming region yields fully dense Si₃N₄. Post sintering treatment at 1300°C resulted in devitrification with consequent improvement of high temperature mechanical properties. The mechanical properties of Si₃N₄ sintered with liquids in the system Ce₂O₃---AIN---SiO₂ were found to be inferior to those of liquids selected from Y₂O₃---AIN---SiO₂, but superior to those selected from the system MgO---AIN---SiO₂.     

Ordering and quality factor in 0.95BaZn1/3Ta2/3O3–0.05SrGa1/2Ta1/2O3 production resonators

Ordering of the B-site cations in UMTS (universal mobile telecommunications systems) standard resonator pucks composed of perovskite structured, 0.95BaZn_1/3Ta_2/3O₃–0.05SrGa_1/2Ta_1/2O₃ (BZT–SGT) has been investigated using transmission electron microscopy (TEM), X-ray diffraction (XRD) and powder neutron diffraction (PND). XRD patterns from samples sintered at 1550 °C/2 h but annealed and quenched at 50 °C intervals between 1400 and 1600 °C revealed that the order–disorder phase transition was at 1500 °C. In addition, a peak at 29.5° 2θ attributed to a Ba₈ZnTa₆O₂₄ phase was present due to ZnO loss. Electron diffraction patterns revealed that samples heat treated 1500 °C (including as sintered samples, 1525 °C/2h,) exhibited short-range 1:2 ordering along all <111> directions giving rise to an average short-range face centred cubic structure. Samples annealed and quenched from below 1500 °C showed 1:2 order. To avoid excessive ZnO loss, an annealing temperature was chosen at 1275 °C (for 24 and 168 h). Neutron diffraction data were best refined using two ordered BZT phases with slightly different lattice parameters. TEM revealed a microstructure in each case consisting of 1:2 small ordered domains in the centre of all grains but with every second grain exhibiting a concentric shell composed of an ordered single domain, containing elongated translational (APBs) but not orientational domains. The formation of the concentric ordered shell was attributed to grain boundary migration during grain growth. As-sintered samples gave unloaded quality factors (Q)=54,000 at 2 GHz which rose to 78,000 at 2 GHz after annealing for 24 h. No further improvement in Q was observed for longer annealing times.     

Properties and microstructure of sintered incinerator bottom ash

The fraction of incinerator bottom ash with a particle size less than 8 mm produced at a commercial municipal solid waste incinerator was wet milled, dried, compacted and sintered at a range of temperatures to form ceramic materials. The effects of milled ash particle size distribution, powder compaction pressure and sintering temperature were investigated, and the materials formed characterised by X-ray diffraction (XRD), scanning electron microscopy (SEM) and thermal analysis (TG/DTA). The main minerals present in the milled ash were quartz (SiO₂) and calcite (CaCO₃). Sintered densities of materials produced from ash milled to 95% less than 27 μm increased from 1.38 to 2.63 g/cm³ on increasing the sintering temperature from 1020 to 1080 °C. Firing above 1080 °C caused a rapid decrease in density and sample expansion. The principal crystalline phase present in the high-density material was diopside (CaMgSi₂O₆). This work shows that a significant fraction of incinerator bottom ash can be processed to form sintered materials with properties controlled by ash particle size distribution and sintering conditions.     

Thermal conductivity of AlN ceramics sintered with CaF2 and YF3

Dense AlN ceramics with a thermal conductivity of 180W/m·K were obtained at the sintering temperature of 1750 °C using CaF₂ and YF₃ as additives. At temperatures below 1650 °C, the shrinkage of AlN ceramics is promoted by liquid (Ca,Y)F₂ and Ca₁₂Al₁₄O₃₂F₂. Liquid CaYAlO₄ mainly improves the densification of the sample when the sintering temperature increases to 1750 °C. The formation of liquid (Ca,Y)F₂ at a relatively low temperature results in homogeneous YF₃ distribution around the AlN particles, which benefits the removal of oxygen impurity in the AlN lattice, and thus a higher thermal conductivity.     

Thermoelectric characterization of NaxMx/2Ti1−x/2O2 (M=Co, Ni and Fe) polycrystalline materials

Layered -titanate materials, Na_xM_x/2Ti_1−x/2O₂ (M=Co, Ni and Fe, x=0.2–0.4), were synthesized by flux reactions, and electrical properties of polycrystalline products were measured at 300–800 °C. After sintering at 1250 °C in Ar, all products show n-type thermoelectric behavior. The values of both d.c. conductivity and Seebeck coefficient of polycrystalline Na_0.4Ni_0.2Ti_0.8O₂ were ca. 7×10³ S/m and ca. −193 μV/K around 700 °C, respectively. The measured thermal conductivity of layered -titanate materials has lower value than conductive oxide materials. It was ca. 1.5 Wm⁻¹ K⁻¹ at 800 °C. The estimated thermoelectric figure-of-merit, Z, of Na_0.4Ni_0.2Ti_0.8O₂ and Na_0.4Co_0.2Ti_0.8O₂ was about 1.9×10⁻⁴ and 1.2×10⁻⁴ K⁻¹ around 700 °C, respectively.     

Sintering behavior and mechanical properties of nano-sized Cr3C2/Al2O3 composites prepared by MOCVI process

A process using metal-organic chemical vapor infiltration (MOCVI) conducted in fluidized bed was employed for the preparation of nano-sized ceramic composites. The Cr-species was infiltrated into Al₂O₃ granules by the pyrolysis of chromium carbonyl (Cr(CO)₆) at 300–450 °C. The granulated powder was pressureless sintered or hot-pressed to achieve high density. The results showed that the dominant factors influencing the Cr-carbide phases formation, either Cr₃C₂ or Cr₇C₃, in the composite powders during the sintering process were the temperature and oxygen partial pressure in the furnace. The coated Cr-phase either in agglomerated or dispersive condition was controlled by the use of colloidal dispersion. The microstructures showed that fine (20 –600 nm) Cr_xC_y grains (≤8 vol.%) located at Al₂O₃ grain boundaries hardly retarded the densification of Al₂O₃ matrix in sintering process. The tests on hardness, strength and toughness appeared that the composites with the inclusions (Cr₃C₂) had gained the advantages over those by the rule of mixture. Even 8 vol.% ultrafine inclusions have greatly improved the mechanical properties. The strengthening and toughening mechanisms of the composites were due to grain-size reduction, homogenous dispersion of hard inclusions, and crack deflection.     

Hydrothermal synthesis of Ba(Ti, Sn)O3 fine powders and dielectric properties of the corresponding ceramics

Fine powders of submicron-sized crystallites of BaTiO₃ were prepared at 85–130°C by the hydrothermal method, starting from TiO₂.ξH₂O gel and Ba(OH)₂ solution. The products obtained below 110°C incorporated considerable amounts of H₂O and OH⁻ in the lattice. As-prepared BaTiO₃ is cubic and converts to the tetragonal phase after heat treatment at 1200°C, accompanied by the loss of residual OH⁻ ions. Hydrothermal reaction of SnO₂.ξH₂O gel with Ba(OH)₂ at 150–260°C gives rise to the hydrated phase, BaSn(OH)₆.3H₂O, due to the amphoteric nature of SnO₂.ξH₂O which stabilises Sn(OH)₆²⁻ anions in basic media. On heating in air or releasing the pressure in situ at 260°C, BaSn(OH)₆.3H₂O converts to BaSnO₃ through an intermediate, BaSnO(OH)₄. Solid solutions of Ba(Ti,Sn)O₃ are directly formed from (TiO₂ + SnO₂)..ξH₂O gel up to 35 mol% SnO₂. At higher Sn contents, the hydrothermal products are mixtures of BaSn(OH)₆.3H₂O and BaTiO₃, which on annealing at 1000°C result in monophasic Ba(Ti,Sn)O₃. The sintering characteristics and the dielectric properties of the ceramics prepared out of these fine powders are presented. The dielectric properties of fine-grained Ba(Ti,Sn)O₃ ceramics are explained on the basis of the prevailing diffuse phase transition behaviour.     

Effect of Al2O3 on mechanical properties of Ti3SiC2/Al2O3 composite

The effect of Al₂O₃ on mechanical properties of Ti₃SiC₂/Al₂O₃ composite fabricated by SPS was studied systematically. The results show that the hardness of the Ti₃SiC₂/Al₂O₃ composite can reach 10.28 GPa, 50% higher than that of pure Ti₃SiC₂. However, slight decrease in the other mechanical properties was observed with Al₂O₃ addition higher than 5–10 vol.%, which is believed to be due to the agglomeration of Al₂O₃ in the composite.     

In-situ growth of needlelike LaAl11O18 for reinforcement of alumina composites

In situ growth of needlelike LaAl₁₁O₁₈ grains reinforcing Al₂O₃ composites can be fabricated by a coprecipitation method using La(NO₃)₃√6H₂O and Al(NO₃)₃√9H₂O as starting materials. The new two-step process involved firstly preparing needlelike LaAl₁₁O₁₈ grains distributed homogeneously in Al₂O₃ powder and then pressureless sintering the composite powders. The Al₂O₃/25 vol.%LaAl₁₁O₁₈ samples pressureless sintered at 1550°C for 4 h achieve relative density up to 96.5% and exhibit a bending strength of 420±30 MPa and a fracture toughness of 4.3±0.4 MPa m^1/2.     

Microstructures and mechanical properties of 8Y-FSZ ceramics with BaTiO3 additive

The microstructure and mechanical properties of 8 mol% Y₂O₃ fully stabilized zirconia (8Y-FSZ) with BaTiO₃ additive were investigated. The introduction of BaTiO₃ additive would significantly increase the density and the grain size of 8Y-FSZ ceramics. XRD, Raman spectroscopy, and dielectric measurement were performed. A rhombohedral Ba(Ti_1−xZr_x)O₃ ferroelectric phase resulted in the composite with 5 mol% additive, while for those with higher additive content, the secondary phase changes to cubic Ba(Ti_1−xZr_x)O₃. The fracture toughness of the xBaTiO₃/(1−x)8Y-FSZ composites reached a maximum and then decreased with increasing the amount of additive. The highest value reached 6.1 MPa m^1/2 for 0.05BaTiO₃/0.95(8Y-FSZ) sintered at 1475 °C for 3 h, where the piezoelectric/ferroelectric secondary phase toughening played an important role. Moreover, the fracture toughness of the composites increased firstly and then decreased with increasing sintering temperature.     

Microwave dielectric ceramics in the system BaO–Li2O–Nd2O3–TiO2

Ceramics in the system BaO-Li₂O–Nd₂O₃–TiO₂ (BNT–LNT) were prepared by the mixed oxide route. Powders were mixed, milled, calcined and sintered at 1475°C for 4 h. Fired densities decreased steadily along the series from BNT to LNT. The microstructures of samples rich in BNT were dominated by small needle-like grains; the LNT samples comprised larger (6 μm) cubic grains. X-ray diffraction showed that there was a transition from orthorhombic BNT to cubic LNT; small amounts of LNT could be accommodated in BNT, but between 10–20% LNT there was the development of the second phase. Small additions of LNT led to a small increase in relative permittivity, but decreased the dielectric Q-value (from the maximum of 1819 at 4 GHz). As BNT and LNT exhibit negative and positive temperature dependencies of permittivity respectively, the addition of 10–20% LNT to BNT should yield samples with zero temperature dependence of _r Impedance spectroscopy showed that data could only be acquired at elevated temperatures for BNT rich samples (above 500°C), but at modest temperatures (less than 100°C) for the more conductive LNT.     

Piezoelectric properties of Pb(Mn1/3Nb2/3)O3–PbZrO3–PbTiO3 ceramics with sintering aid of 2CaO–Fe2O3 compound

Since the electromechanical devices move towards enhanced power density, high mechanical quality factor (Q_m) and electromechanical coupling factor (k_p) are commonly needed for the high powered piezoelectric transformer with Q_m≥2000 and k_p=0.60. Although Pb(Mn_1/3Nb_2/3)O₃–PbZrO₃–PbTiO₃ (PMnN–PZ–PT) ceramic system has potential for piezoelectric transformer application, further improvements of Q_m and k_p are needed. Addition of 2CaO–Fe₂O₃ has been proved to have many beneficial effects on Pb(Zr,Ti)O₃ ceramics. Therefore, 2CaO–Fe₂O₃ is used as additive in order to improve the piezoelectric properties in this study. The piezoelectric properties, density and microstructures of 0.07Pb(Mn_1/3Nb_2/3)O₃–0.468PbZrO₃–0.462PbTiO₃ (PMnN–PZ–PT) piezoelectric ceramics with 2CaO–Fe₂O₃ additive sintered at 1100 and 1250 °C have been studied. When sintering temperature is 1250 °C, Q_m has the maximum 2150 with 0.3 wt.% 2CaO–Fe₂O₃ addition. The k_p more than 0.6 is observed for samples sintered at 1100 °C. The addition of 2CaO–Fe₂O₃ can significantly enhance the densification of PMnN–PZ–PT ceramics when the sintering temperature is 1250 °C. The grain growth occurred with the amount of 2CaO–Fe₂O₃ at both sintering temperatures.     

Sintering characteristics of in situ formed low expansion ceramics from a powder precursor in the form of hydroxy hydrogel

Lithium aluminosilicate powder precursors of compositions Li₂O:Al₂O₃:SiO₂ as 1:1:2; 1:1:2.5 and 1:1:3 were prepared in the hydroxy hydrogel form by wet interaction technique in aqueous medium followed by sintering for ultimate synthesis of low expansion ceramics. Phases formed in the sintered specimens were analyzed by XRD technique. Thermal expansion of the specimens sintered at 1100, 1200 and 1300 °C were also measured. It was found that β-spodumene, lithium aluminum oxide and silica were the predominat phases in all the specimens. Sintering was optimum up to 1200 °C beyond which no further noticeable shrinkage was observed. The sintered specimens remained highly porous even after firing at 1300 °C, whose bulk density and apparent porosity were in the range of 1.25–1.42 g/cm³ and 43–48%, respectively. Thermal expansion characteristics and density of the sintered specimens were found to be primarily related to the composition of the phases formed during sintering. A porous low expansion ceramic monolith could be prepared using the present technique.     

Dense ceramics of BaTiO3 produced from powders prepared by a chemical process

A sintering optimization of barium titanate ceramics from fine-grained and homogeneous reproducible powders obtained by the citric process is presented. Different sintering parameters are studied: heating rates, final temperature, dwelling times at this final temperature, and influence of the powder deagglomeration step. The sintering is followed by dilatometric measurements. The ceramics obtained by sintering at 1230 or 1300 °C are free of barium carbonate, the residual carbon content being estimated at about 400 ppm in the surface layer. They exhibit a grain size close to 1 μm, a structure in which the cubic and tetragonal phases coexist, and a density of about 96% of the theoretical density. Their permittivity and loss factor are respectively about 5000 and 2.5 × 10⁻² at 25 °C.