Processing and Mechanical Properties of Ti3SiC2: I, Reaction Path and Microstructure Evolution

In this article, the first part of a two-part study, we report the reaction path and microstructure evolution during the reactive hot isostatic pressing of Ti₃SiC₂, starting with titanium, SiC, and graphite powders. A series of interrupted hot isostatic press runs have been conducted as a function of temperature (1200°–1600°C) and time (0–24 h). Based on X-ray diffractometry and scanning electron microscopy, at 1200°C, the intermediate phases are TiC _x and Ti₅Si₃C _x . Fully dense, essentially single-phase samples are fabricated in the 1450°–1700°C temperature range. The time-temperature processing envelope for fabricating microstructures with small (3–5 μm), large (∼200 μm), and duplex grains, in which large (100–200 μm) Ti₃SiC₂ grains are embedded in a much finer matrix, is delineated. The microstructure evolution is, to a large extent, determined by (i) the presence of unreacted phases, mainly TiC _x , which inhibits grain growth; (ii) a large anisotropy in growth rates along the c and a directions (at 1450°C, growth normal to the basal planes is about an order of magnitude smaller than that parallel to these planes; at 1600°C, the ratio is 4); and (iii) the impingement of grains. Ti₃SiC₂ is thermally stable under vacuum and argon atmosphere at temperatures as high as 1600°C for as long as 24 h. The influence of grain size on the mechanical properties is discussed in the second part of this study.     

Large-Scale Synthesis of Magnenium Silicon Nitride Powders at Low Temperature

Magnesium silicon nitride (MgSiN₂) powders have been synthesized by the reaction of SiCl₄, N₂H₄·HCl, and Mg in an autoclave at 450°C for 5 h. The yield of the products is calculated to be about 90% according to the amount of SiCl₄. X-ray powder diffraction patterns indicated that the products are orthorhombic MgSiN₂ (cell parameters: a =5.252 Å, b =6.426 Å, and c =4.979 Å) together with little amount of Si. The results of scanning electron microscopy and transmission electron microscopy (TEM) observations indicate that the particles have rough surfaces and have diameters in the range of 0.5–3 μm. The high-resolution TEM image shows clearly resolved fringes separated by 0.248 nm, which corresponds to the (002) d -spacing of the orthorhombic MgSiN₂. The effects of different synthesis conditions on the final formation of MgSiN₂ powder, such as the different ratios of the precursors, reaction temperature, and nitrogen sources were also investigated.     

CO2 Decomposition by Oxide Ceramics Intercalated in Layered Compound

Iron oxide polymers intercalated and/or loaded within täniolite have been studied as a CO₂ decomposition medium. Fe²⁺ was exchanged for Li⁺ in täniolite, oxidized by air-bubbling at 60°–70°C. The basic d -spacing (13.75 Å in the Li⁺ form) was expanded to give 14.86 Å in the Fe²⁺ form. Oxidation by air in the form of suspension gave a 15.3-Å phase, which was ascribed to formation of magnetite within the interlayer. The interlayer distance of the intercalated phase remained the same upon heating at 300°C. The magnetite–intercalated täniolite was heated to activate in a H₂ and/or H₂O steam. CO₂ decomposition reactivity at 300°C has been evidenced by evolution of CO gas. The high reactivity for CO₂ decomposition is ascribed to the highly dispersed iron oxide ceramics within the interlayer of täniolite Li[(Mg₂Li)(Si₄O₁₀)]F₂ n H₂O.     

Preparation and Characterization of Submicron Hafnium Oxide

Submicron hafnium oxide powder prepared by hydrolytic decomposition of alkoxides was studied. The particle size range of this powder was 10 to 50 Å. Emission spectrographic analysis of the powder after it was calcined at 250°C for 0.5 h indicated a purity of >99.995%. Up to 320°C, the powder showed no crystallinity by X-ray analysis. The amorphous HfO₂ was isothermally aged at 5° to 10°C intervals between 200° and 500°C. X-ray diffraction patterns indicate a sharp transition from an amorphous state to the monoclinic phase at 325°C. High-temperature X-ray studies and DTA suggest nucleation and growth of small crystallites at 420°C leading to conversion to monoclinic HfO₂ at 480°C. BET surface area measurements and TGA of the powders were also conducted. A powder which transformed at 325°C to the monoclinic phase was isothermally aged below 325°C for 150 h without change.     

High-Temperature Structural Phase Transition in Ca0.7Ti0.7La0.3Al0.3O3: Investigation by Synchrotron X-Ray Diffraction

Mixed-oxide prepared Ca_0.7Ti_0.7La_0.3Al_0.3O₃ (CTLA) ceramics (≈96% dense), grain size 6–7 μm, with dielectric properties (at 4 GHz) of ɛ_r≈46, Q × f ≈38 000 GHz, and τ_f+13 ppm/°C, were studied at 25°–1300°C using synchrotron X-ray powder diffraction. At room temperature, CTLA exhibits a distorted orthorhombic structure, with two tilt systems: a =5.40383 (4) Å, b =5.41106 (6) Å, and c =7.64114 (7) Å with space group Pbnm . At 1050°±25°C, there is a transition from orthorhombic ( Pbnm ) to tetragonal ( I 4/ mcm ), with a simpler tilt arrangement. The lattice parameters at 1100°C were: a =5.44285 (4) Å and c =7.68913 (8) Å.     

Aluminum Nitride Prepared by Nitridation of Aluminum Oxide Precursors

Aluminum nitride (AlN) powders were prepared from the oxide precursors aluminum nitrate, aluminum hydroxide, aluminum 2-ethyl-hexanoate, and aluminum isopropoxide (i.e., Al(NO₃)₃, Al(OH)₃, Al(OH)(O₂CCH(C₂H₅)(C₄H₉))₂, and Al(OCH(CH₃)₂)₃). Pyrolyses were performed in flowing dry NH₃ and N₂ at 1000°–1500°C. For comparison, the nitride precursors aluminum dimethylamide (Al(N(CH₃)₂)₃) and aluminum trimethylamino alane (AlH₃·N(CH₃)₃) were exposed to the same nitridation conditions. Products were investigated using XRD, TEM, EDX, SEM, and elemental analysis. The results showed that nitridation was primarily controlled by the water:ammonia ratio in the atmosphere. Single-phase AlN powders were obtained from all oxide precursors. Complete nitridation was not obtained using pure N₂, even for the non-oxide precursors.     

Preparation of Aluminum Nitride–Silicon Carbide Nanocomposite Powder by the Nitridation of Aluminum Silicon Carbide

Aluminum nitride (AlN)–silicon carbide (SiC) nanocomposite powders were prepared by the nitridation of aluminum-silicon carbide (Al₄SiC₄) with the specific surface area of 15.5 m²·g⁻¹. The powders nitrided at and above 1400°C for 3 h contained the 2H-phases which consisted of AlN-rich and SiC-rich phases. The formation of homogeneous solid solution proceeded with increasing nitridation temperature from 1400° up to 1500°C. The specific surface area of the AlN–SiC powder nitrided at 1500°C for 3 h was 19.5 m²·g⁻¹, whereas the primary particle size (assuming spherical particles) was estimated to be ∼100 nm.     

Synthesis of Uniform Titanium Nitride Nanocrystalline Powders via a Reduction–Hydrogenation–Dehydrogenation–Nitridation Route

A novel reaction of TiCl₄ and NaNH₂ at 450°–500°C for 12–24 h was performed for the preparation of TiN nanocrystalline powders. Powder XRD patterns indicated that the as-synthesized powder was cubic-phase TiN with a lattice constant a =4.225 Å. Transmission electron microscopy images showed that the TiN powders consisted of uniform particles with an average diameter of 10–20 nm. The binding energies of Ti2p_3/2 and N1s core levels at the position of 455.50 and 396.96 eV, respectively, were detected by X-ray photoelectron spectra. Four peaks, related to transverse acoustic, longitudinal acoustic, second-order acoustic, and transverse optical (TO) modes of TiN, respectively, were observed in the Raman spectra of TiN particles. A very reasonable formation mechanism of TiN nanocrystalline powders was proposed.     

The Crystal Structure of LaAlO3-Stabilized La2/3TiO3 Ceramics: An HRTEM Investigation

LaAlO₃-stabilized La_2/3TiO₃ (LT) ceramics were prepared by the conventional mixed oxide route. Small amounts of manganese oxide were added to eliminate Ti⁴⁺ reduction. The powders were calcined at 1150°C and sintered at 1400°–1500°C for 4 h and cooled at rates of 900°–15°C/h. The products were high density and single phase, with an average grain size of 6 μm. The LaAlO₃-stabilized LT ceramics exhibited a relative permittivity (ɛ_r) of 64, a positive temperature coefficient of resonant frequency (τ_f) of 84, and dielectric Q value × resonant frequency ( Q × f ) values of 16 400 GHz. The crystal structure and microstructures have been investigated using high-resolution transmission electron microscopy (HRTEM) in conjunction with X-ray diffraction (XRD). One candidate crystal structure, a ≈2 a _p (where a _p is the lattice parameter of the high-temperature form of the cubic perovskite), b ≈2 a _p, and c ≈2 a _p with a space group Cmmm (65), has been confirmed by XRD, electron diffraction, and lattice imaging techniques. Microtwins, with twin boundaries parallel to the {100} planes, were observed in the microstructures.     

Synthesis of Nanocrystalline Aluminum Nitride by Nitridation of δ-Al2O3 Nanoparticles in Flowing Ammonia

Nanocrystalline aluminum nitride (AlN) with surface area more than 30 m²/g was synthesized by nitridation of nanosized δ-Al₂O₃ particles using NH₃ as a reacting gas. The resulting powders were characterized by CHN elemental analysis, X-ray diffraction (XRD), Fourier transform infrared spectra, X-ray photoelectron spectra, field-emission scanning electron microscopy, transmission electron microscopy, and Brunauer–Emmett–Teller surface area techniques. It was found that nanocrystalline δ-Al₂O₃ was converted into AlN completely (by XRD) at 1350°–1400°C within 5.0 h in a single-step synthesis process. The complete nitridation of nanosized alumina at relatively lower temperatures was attributed to the lack of coarsening of the initial δ-Al₂O₃ powder. The effect of precursor powder types on the conversion was also investigated, and it was found that α-Al₂O₃ was hard to convert to AlN under the same conditions.     

Gas-Sensing Properties of Zinc Ferrite Nanoparticles Synthesized by the Molten-Salt Route

Zinc ferrite (ZnFe₂O₄) nanoparticles have been synthesized at 700°C using sodium chloride as a growth inhibitor. Single-phase formation of spinel zinc ferrite having crystallite size in the range of 15–20 nm was observed by XRD and confirmed by TEM. In the present work, the gas-sensing properties of these zinc ferrite nanoparticles toward ethanol, LPG, H₂, NO _x . SO _x , and H₂S have been studied. It was found that they exhibit excellent selective sensitivity toward 200 ppm of H₂S at the operating temperature of 250°C, and thus this nanosized ferrite is expected to be useful in an industrial application as a potential H₂S gas sensor.     

Spark Plasma Sintering of Nano-Sized TiN Prepared from TiO2 by Controlled Hydrolysis of TiCl4 and Ti(O-i-C3H7)4 Solution

Nano-sized TiO₂ powders were prepared by controlled hydrolysis of TiCl₄ and Ti(O-i-C₃H₇)₄ solutions and nitrided in flowing NH₃ gas at 700°–1000°C to form TiN. Nano-sized TiN was densified by spark plasma sintering at 1300°–1600°C to produce TiN ceramics with a relative density of 98% at 1600°C. The microstructure of the etched ceramic surface was observed by SEM, which revealed the formation of uniformly sized 1–2 μm grains in the TiCl₄-derived product and 10–20 μm in the Ti(O-i-C₃H₇)₄-derived TiN. The electric resisitivity and Vickers micro-hardness of the TiN ceramics was also measured.     

A Chemical Co-Reduction Route to Synthesize Nanocrystalline Vanadium Carbide

Nanocrystalline vanadium carbide (VC) was synthesized via a chemical co-reduction process, in which VCl₄ and CCl₄ were used as the vanadium source and the carbon source, respectively, and metallic Na as a reductant in an autoclave at 500°C for 12 h. X-ray powder diffraction indicated that the product was an NaCl type of VC with a cell constant a =4.171 Å. A transmission electron microscopy image showed the VC particles were 10–40 nm in size. X-ray photoelectron spectrum and Raman spectrum showed the surface covered with oxide and graphite. The formation of nanocrystalline VC was discussed based on thermodynamics.     

Relations Among Particle Size, Shape, and Surface Area of Mg(OH)2 and Its Calcination Product

Precipitated Mg(OH)₂ particles 0.05 to 1 μm in diam. and of various shapes were calcined in air for 1/2 h at 704°, 816°, 954°, 1093°, or 1232°C. At 704°C, BET surface areas, initially 11 to 32 m²/g, increased 1.4- to 7.6-fold, and TEM observations showed pseudomorphs. Depending on the parent crystal size and shape, these particles contained either single layers or multilayers of MgO crystallites 40 to 260 Å in diam., roughly perpendicular to the original c axis. Pseudomorph stability varied greatly, even between particles of different shape in the same sample. Coalescence into single or linked angular particles occurred at 1093° and 1232°C, but one sample retained single-layer pseudomorphs containing cubic crystallites. One observation indicated that sodium cation impurity decreased the surface area of oxide formed at 704°C.     

Wetting of AlN and TiC by Liquid Ag and Liquid Cu

The wetting of AlN and TiC by liquid Ag and liquid Cu was investigated by the sessile drop technique at 10⁻⁶ torr or less. An empirical relation was established between the cosine of the contact angle and the temperature or surface tension of the liquid drop. The critical surface tension for spreading and its physical significance are discussed. A method for estimating the surface energies of ceramics is proposed. The surface tension of TiC is estimated to be 1242±158 dynes/cm and that of AlN 990±110 dynes/cm. The surface tension of liquid Ag followed the equation γ _Lv (Ag) (dynes/cm) = 1092–0.14T (°C) and that of liquid Cu γ _LV (Cu) (dynes/cm) = 1462–0.27T (°C).     

Hydrothermal Synthesis of Acicular Lead Titanate Fine Powders

A pure, acicular lead titanate (PbTiO₃) fine powder with a white color has been prepared by hydrothermal synthesis. It is a new phase of PbTiO₃ with I 4 symmetry, cell parameters of a = 12.358 Å and b = 14.541 Å, and a density of 6.80 g.cm⁻³. The influences of pH (12.5 to 14.4), Pb/Ti ratio (1.0 to 1.6) in the feedstock, reaction temperature (130° to 230°C), time (0.25 to 4 h), starting materials, and additives on the formation of acicular PbTiO₃ under hydrothermal conditions have been investigated. The acicular PbTiO₃ with I 4 symmetry, referred to as the PX phase, can be converted to the perovskite-type (PE phase) of PbTiO₃ at about 605°C while its acicular morphology is essentially unchanged. The preferable conditions for preparing pure acicular PX-phase PbTiO₃ are that the pH is 13.0 to 14.0, Pb/Ti ratio is >1.3, reaction temperature is 170° to 200°C, time is 0.5 to 1.0 h, titanium butoxide (Ti[O(CH₂)₃CH₃]₄) is the starting material, and poly(vinyl alcohol) is an additive. The acicular grain of the PX phase is usually less than 100 nm in diameter and more than 1000 nm in length.     

Low-Temperature Synthesis of β-Ca2SiO4 from Hillebrandite

Experiments on hydrothermal synthesis were conducted using quartz or silicic acid and lime as starting materials at Ca/Si = 2.0. It is possible to synthesize pure hillebrandite (Ca₂(SiO₃)(OH)₂) having the theoretical composition by heating at 200°C for 10 h or at 250°C for 5 h. The synthesized product is fibrous, open at each end, and has a length of 20 to 30 μm. Calcium silicate hydrate gels are produced at the initial stage of the reaction. These react further with the unreacted lime to give hillebrandite. However, when silicic acid is used as silica, hillebrandite with tricalcium silicate hydrate is observed at 250°C because of the high reaction rate of silica. On heating, hillebrandite starts to decompose at about 500°C and produces low-crystalline β-Ca₂SiO₄, which is stable at room temperature and has a remarkably large specific surface area of about 7 m²/g. The decomposition reaction rate in a single crystal is rapid, and the reaction is considered to proceed topotactically.     

Thermal Treatment of Titanate Derivatives Synthesized by Ion-Exchange Reaction

TiO₂ fibers were formed by thermal treatment of layered H₂Ti₄O₉ (hydrous titanium dioxide) and KHTi₄O₉ synthesized by ion-exchange reactions. The calcination of the former at 900° and 1050°C for 3 h yielded TiO₂ fibers with anatase and rutile phases, whose length and diameter were 15–20 and 2–5 μm and 10–15 and 3–5 μm, respectively. The thermal treatment of the latter at temperatures of 250° to 500°C yielded pure K₂Ti₈O₁₇, which tended to decompose to K₂Ti₆O₁₃ and TiO₂ at temperatures >600°C. At 1050°C, K₂Ti₆O₁₃ phase was formed with rutile TiO₂ fibers, whose length and diameter were 10–20 and 1–3 μm, respectively.     

Solution-Based Synthesis of Submicrometer ZrB2 and ZrB2–TaB2

Zirconium diboride and a zirconium diboride/tantalum diboride mixture were synthesized by solution-based processing. Zirconium n -propoxide was refluxed with 2,4-pentanedione to form zirconium diketonate. This compound hydrolyzed in a controllable fashion to form a zirconia precursor. Boria and carbon precursors were formed via solution additions of phenol–formaldehyde and boric acid, respectively. Tantalum oxide precursors were formed similarly as zirconia precursors, in which tantalum ethoxide was used. Solutions were concentrated, dried, pyrolyzed (800°–1100°C, 2 h, flowing argon), and exposed to carbothermal reduction heat treatments (1150°–1800°C, 2 h, flowing argon). Spherical particles of 200–600 nm for pure ZrB₂ and ZrB₂–TaB₂ mixtures were formed.     

Tin(IV) Oxide Coating of Aluminum Borate Whiskers and Alumina Particles by Chemical Vapor Deposition

Aluminum borate whiskers of 0.5–1.0 μ diameter and alumina particles of 10–20 μ diameter were coated with SnO₂ by the reaction of SnCl₄–H₂O–N₂ gas mixtures in a rotary kiln reactor. Prior to coating, the whiskers were slightly etched to ensure adhesion between the SnO₂ layer and the whisker surface. The whiskers were coated at 100°C for 1 h, and then at 300°C for 2 h. This procedure was effective for covering the entire whisker surface with a uniform SnO₂ layer. Precoating was not necessary for the alumina particles. A compressed disk of the coated whiskers had an electrical conductivity of 30–40 S/m.