Preparation of Ti<Subscript>2</Subscript>AlN by reactive sintering

Reactive sintering of 2Ti–AlN mixtures at T = 1300°C for τ = 2 h in an argon atmosphere was used to prepare Ti₂AlN containing below 1 wt % TiN and exhibiting a laminate structure typical of MAX compounds. At lower values of T and τ, the TiN content of products increased. Sintering in vacuum yielded a material containing up to 20 wt % TiN. Contrary to our expectations, mechanical activation of green blends was found to increase the TiN content of sintered materials, due to intensification of thermal dissociation of AlN and elimination of Al, which shifts equilibrium toward two-phase Ti₂AlN–TiN composite. Relative density of green compacts was found to produce little or no influence on phase composition of products.     

热压法制备Al2O3/TiB2/AlN/TiN复合陶瓷

将金属Al,Al3Ti和TiB2以AlTiB中间合金的形式引入Al2O3基体材料中,利用热压法制备Al2O3/TiB2/AlN/TiN复合陶瓷.探讨了复合陶瓷致密化程度与AlTiB体积含量之间的关系.复合陶瓷在烧结过程中属过渡液相烧结.烧结过程中Al,Ti和N2(保护气氛)通过化学反应生成新相AIN和TiN.对热压烧结后材料的硬度、断裂韧性和抗弯强度进行了测试和分析.分析了复合陶瓷的力学性能随AlTiB体积含量变化的规律.比较了复合陶瓷1500℃和1600℃的相对密度及力学性能.探讨了复合陶瓷断面断裂方式的变化对其力学性能的影响,并分析了AlTiB中间合金的细化特性.     

Addition of Al–Ti–B master alloys to improve the performances of alumina matrix ceramic materials

In the present work, a new technique to improve the performances of alumina matrix ceramic materials is presented, in which Al, Al₃Ti and TiB₂ are incorporated into alumina matrix ceramic materials in the form of Al–Ti–B master alloys. Composites of Al₂O₃/TiB₂/AlN/TiN are fabricated by the technology of transient liquid phase sintering, during which new phases such as AlN and TiN are produced by the chemical reactions taking place among Al, Ti and N₂ (the protective atmosphere). The densification rate of the composites as a function of Al–Ti–B volume content is discussed. The fundamental properties of the composites such as hardness, fracture toughness and bending strength are examined. The relations of volume content of Al–Ti–B master alloys and mechanical properties of alumina matrix ceramic materials are analyzed. The effects of fracture mechanism on mechanical properties of the composites are researched together with the refining performances of Al–Ti–B master alloys.     

Effects of TiN addition on the properties of hot pressed TiN–Ti/Al2O3 composites

TiN–Ti/Al₂O₃ composites of varying TiN content (0–20?vol%) were prepared by vacuum hot-pressing sintering at different temperatures (1400?°C and 1500?°C) to investigate how TiN affected the mechanical properties and electrical conductivity of the composites. Sintered samples with added TiN exhibited better performance than those without it. The sample with 20?vol% TiN sintered 1500?°C had an optimal relative density of 99.49, Vickers hardness of 14.94?GPa, flexural strength of 321.55?MPa, and electrical resistivity of 1474.7?μΩ?cm. However, this increased temperature did not improve the best sample resistivity of 930.3?μΩ?cm, which was obtained at 1400?°C. Form SEM images and XRD patterns, the positive effect of TiN on composite mechanical properties may be ascribed to its good performance of high hardness and strength, a decrease of the brittle intermetallic phase, the form of AlTi₃N, and the impact of the fine-grained strength of the TiN phase.     

Fabrication and mechanical performance of Ti2AlN prepared by FAST/SPS

Highly dense bulk Ti₂AlN with high purity was successfully fabricated at 1400 °C by Field Assisted Sintering Technology (FAST/SPS) using Ti, Al, TiN as starting powders. Aluminum content appears to play a determinant role to attain high phase purity, where the optimum content has been achieved for a starting molar composition of 1:1.02:1 for Ti, Al, and TiN, respectively. Elastic modulus and hardness were determined via micro-indentation testing at room temperature. Regarding abrasive behavior, sandblasting tests with compressed air of 2 bar were carried out. In addition, creep tests in air in the temperature range of 900−1200 °C were performed to characterize the steady state deformation behavior under constant applied stresses ranging from 20−100 MPa.     

Synthesis mechanism of AlN–SiC solid solution reinforced Al2O3 composite by two-step nitriding of Al–Si3N4–Al2O3 compact at 1500 °C

The in-situ controllable synthesis of AlN–SiC solid solution reinforcement in large-sized Al–Si₃N₄–Al₂O₃ composite refractory by two-steps nitriding sintering was examined. In the first step, a dynamic Al@AlN structure was constructed in the composite by pre-nitriding at 580 °C. During the subsequent sintering process, it cracked above ∼900 °C, and micronized Al cluster (mixture of droplets and vapor) was extracted out gradually. As a result, multiple AlN mesophases were formed through different reaction paths, including i) initial AlN shell formed by solid Al with N₂, ii) reaction of Al cluster with N₂, and iii) reaction of Al cluster with Si₃N₄ from 900 °C to 1500 °C. The Si₃N₄ precursor serves as both a solid nitrogen source and an active Si source, and the controllable reaction between Al and Si₃N₄ leading to uniformly distributed AlN and Si mesophases. AlN–SiC solid solution is significantly formed when liquid Si appears. The shell, granule and whisker SiC–AlN solid solution were observed mainly depending on the dynamic AlN mesophase. The SiC–AlN solid solution reinforced Al₂O₃ materials is a novel promising refractory for large-scale blast furnace lining.     

Reactive consolidation of layered-ternary Ti2AlN ceramics by spark plasma sintering of a Ti/AlN powder mixture

A reactive consolidation process for preparing ternary Ti₂AlN ceramics was investigated by spark plasma sintering (SPS). A Ti/AlN powder mixture with a molar ratio of 2:1 was consolidated at temperatures ranging from 800 to 1450 °C. The phase composition and microstructure evolution during the process were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM) equipped with an energy dispersive spectroscopy (EDS). A series of intermediate phases, namely TiN, Ti₃Al, Ti₃AlN and TiAl were indentified, which revealed a reaction pathway towards the formation of Ti₂AlN.     

Reaction joining of SiC ceramics using TiB2-based composites

SiC ceramics were reaction joined in the temperature range of 1450–1800 °C using TiB₂-based composites starting from four types of joining materials, namely Ti–BN, Ti–B₄C, Ti–BN–Al and Ti–B₄C–Si. XRD analysis and microstructure examination were carried out on SiC joints. It is found that the former two joining materials do not yield good bond for SiC ceramics at temperatures up to 1600 °C. However, Ti–BN–Al system results in the connection of SiC substrates at 1450 °C by the formation of TiB₂–AlN composite. Furthermore, nearly dense SiC joints with crack-free interface have been produced from Ti–BN–Al and Ti–B₄C–Si systems at 1800 °C, i.e. joints TBNA80 and TBCS80, whose average bending strengths are measured to be 65 MPa and 142 MPa, respectively. The joining mechanisms involved are also discussed.     

Si3N4/Al反应烧结制备AlN/Al复合材料

研究了采用Si3N4与Al的混合粉,经压制、烧结制备AlN/Al-Si复合材料的技术方法.试验结果表明:AlN的反应生成机制属于一种连续渐进式反应形成过程,即于高温下液相Al中的Al原子渗入Si3N4的晶体点阵取代Si原子而逐渐使之向AlN晶体点阵转化的过程.被取代的Si原子从固相Si3N4中析出,扩散溶入液相Al中,冷却后形成Al-Si合金固溶体,一般呈网状分布于AlN晶体相的周围.新生成的AlN与Al-Si合金相之间表现出很好的界面亲和性.     

Synthesis of high-purity bulk Ti2AlN by spark plasma sintering (SPS)

Single-phase bulk Ti₂AlN was prepared by spark plasma sintering (SPS) at 1200 °C of Ti/Al/TiN powders in stoichiometric proportion. Investigated by X-ray diffraction (XRD) of samples and the sintering process parameter, the reaction procedure could be analyzed. Scanning electron microscopy (SEM) and electron probe micro-analysis (EPMA) coupled with energy-dispersive spectroscopy (EDS) were utilized to investigate the morphology characteristics. When sintered at 1200 °C, Ti₂AlN phase was well developed with a close and lamellated structure. The distribution of Ti₂AlN grains was homogeneous.     

Two‐Step Carbothermal Synthesis of AlN–SiC Solid Solution Powder Using Combustion Synthesized Precursor

In the present work, a two‐step carbothermal reduction method is employed to prepare the AlN–SiC solid solution (AlN–SiCss) powders by using a combustion synthesized precursor. The precursor is prepared by low‐temperature combustion synthesis (LCS) method using a mixed solution of aluminum nitrate, silicic acid, polyacrylamide, glucose, and urea. The synthesized LCS precursor exhibits a porous and foamy uniform mixture of Al₂O₃ + SiO₂ + C consisting of flaky particles. The carbothermal reduction in the LCS precursor is carried out in two steps. First, the precursors are calcined at 1600°C in argon for 3 h. Subsequently, the precursors are further calcined at 1600°C–1900°C in nitrogen for 3 h. The results indicate that the precursor calcined at and above 1850°C in nitrogen for 3 h yields the single‐phase AlN–SiCss powders. The synthesized AlN–SiCss powder exhibits near‐spherical particles with diameter of 200–500 nm. The experimental and thermodynamical results reveal that the formation of AlN–SiCss occurs via the diffusion of AlN into SiC by virtue of formation of a highly defective β′ intermediate during the second step reaction.     

Oxidation Behavior of MAX Phase Ti2Al(1−x)SnxC Solid Solution

MAX phase Ti₂Al_(1?x)Sn_xC solid solution with x = 0, 0.32, 0.57, 0.82, and 1 was synthesized by pressureless sintering of uniaxially pressed Ti, Al, Sn, and TiC powder mixtures. Annealing in air atmosphere at 200°C–1000°C triggered a sequence of oxidation reactions which reveal a distinct influence of solid solution composition on the oxidation process. With decreasing Al/Sn ratio, the characteristic temperature of accelerated oxidation reaction of A‐element was reduced from 900°C (x = 0) to 460°C (x = 1). SnO₂ was formed at temperatures significantly lower than TiO₂ (rutile) and Al₂O₃. Substitution of A‐element in MAX phase solid solution by low‐melting elements such as Sn may offer potential for reducing oxidation‐induced crack healing temperatures.     

Synthesis and microstructure of Ti2AlN ceramic by thermal explosion

Ti₂AlN ceramic with a small amount of TiN was rapidly synthesized by the thermal explosion (TE) technique using Ti, Al and TiN as starting materials. The effects of the starting composition, the particle size of TiN and the compacts’ height on the phase composition and microstructure of obtained Ti₂AlN ceramic were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The results showed that high purity Ti₂AlN ceramic containing 4% TiN could be fabricated at 700 °C for 2 min with a molar ratio of 1.1:1.1:1(Ti: Al: TiN). It was further found that small particle size of TiN and compacts’ height of 2–8 mm were beneficial to obtain high purity Ti₂AlN. Finally, the formation mechanism of Ti₂AlN ceramic via thermal explosion was proposed.     

Effects of TiC/TiN addition on the microstructure and mechanical properties of ultra-fine grade Ti (C, N)–Ni cermets

Two series of Ti (C, N)-based cermets, one with TiC addition and the other with TiN addition, were fabricated by conventional powder metallurgy technique. The initial powder particle size of the main hard phase components (Ti (C, N), TiC and TiN) was nano/submicron-sized, in order to achieve an ultra-fine grade final microstructure. The TiC and TiN addition can improve the mechanical properties of Ti (C, N)-based cermets to some degree. Ultra-fine grade Ti (C, N)-based cermets present a typical core/rim (black core and grayish rim) as well as a new kind of bright core and grayish rim structure. The average metallic constituent of this bright core is determined to be 62 at% Ti, 25 at% Mo, and 13 at% W by SEM–EDX. The bright core structure is believed to be formed during the solid state sintering stage, as extremely small Ti (C, N)/TiC/TiN particles are completely consumed by surrounding large WC and Mo₂C particles. Low carbon activity in the binder phase will result in the formation (Ni₂Mo₂W)C_x intermetallic phase, and the presence of this phase plays a very important role in determining the mechanical properties of TiN addition cermets.     

Processing of 0.7BaTiO3–0.3BiScO3 Solid‐Solution Coatings

Coatings with the 0.7BaTiO₃–0.3BiScO₃ solid‐solution composition were formed on palladium and single‐crystal (001) SrTiO₃ substrates using a polymeric metal citrate precursor. Solutions of TiOCl₂, Ba(NO₃)₂, Sc(NO₃)₃, and Bi(NO₃)₃ were mixed with citric acid and polymerized with ethylene glycol. Stable mixed‐metal citrate solutions were formed at pH > 9 and used for coatings. The phase and composition of powders and coatings were characterized using DTA, TGA, SEM, TEM, and X‐ray diffraction. Single‐phase cubic 0.7BaTiO₃–0.3BiScO₃ solid solutions formed at 600°C. Coatings on Pd using precursors doped with 5 wt% lithium nitrate were dense after sintering at 950°C/1 h. Coatings without lithium nitrate required 1050°C/50 h to densify. Coatings on SrTiO₃ heat‐treated at 1150°C were dense but formed a (Sc,Ti)‐rich second phase.     

C–(N)–S–H and N–A–S–H gels: Compositions and solubility data at 25°C and 50°C

Calcium silicate hydrates containing sodium [C–(N)–S–H], and sodium aluminosilicate hydrates [N–A–S–H] are the dominant reaction products that are formed following reaction between a solid aluminosilicate precursor (eg, slags, fly ash, metakaolin) and an alkaline activation agent (eg NaOH) in the presence of water. To gain insights into the thermochemical properties of such compounds, C–(N)–S–H and N–A–S–H gels were synthesized with compositions: 0.8≤Ca/Si≤1.2 for the former, and 0.25≤Al/Si≤0.50 (atomic units) for the latter. The gels were characterized using thermogravimetric analysis (TGA), scanning electron microscopy with energy‐dispersive X‐ray microanalysis (SEM‐EDS), and X‐ray diffraction (XRD). The solubility products (K_S0) of the gels were established at 25°C and 50°C. Self‐consistent solubility data of this nature are key inputs required for calculation of mass and volume balances in alkali‐activated binders (AABs), and to determine the impacts of the precursor chemistry on the hydrated phase distributions; in which, C–(N)–S–H and N–A–S–H compounds dominate the hydrated phase assemblages.     

Preparation and oxidation of composite TiN–AlN films from alkoxide solutions by plasma-enhanced CVD

Composite and compositionally graded (CGed) TiN–AlN films were deposited on Si wafers at 600 °C from Ti- and Al-alkoxide solutions by N₂ plasma-enhanced chemical vapor deposition (CVD). The films were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and Vickers micro-hardness. In the composite TiN–AlN films, the Ti and Al contents varied linearly and complementarily with solution composition, the N content ranging from 35 to 40 at.%. In the CGed films, the Al component decreased complementarily with increasing Ti toward the substrate. Cross-sectional SEM observation showed both films to be about 1 μm thick with a columnar structure. Oxidation of the composite and CGed films was performed at 500, 700, and 900 °C in air for 1 h. The improvement of oxidation resistance in both composite and CGed films is discussed on the basis of the XRD and SEM observations, and the XPS analysis of the oxidized films.     

Phase Evolution,Microstructure, and Mechanical Properties of Alumina–Mullite–Zirconia Composites Prepared by Iranian Andalusite

This paper investigates the effects of Iranian andalusite and short milling times on alumina–mullite–zirconia composites. Andalusite powder was added at 0, 2.5, 5, and 10 wt% to an alumina–zircon mixture and the raw materials were milled for 1 or 3 h. The sintering of samples was carried out at the temperatures of 1550°C, 1600°C, and 1650°C for 3 h. Microstructural changes, phase composition, physical properties, and mechanical strength of the sintered composites were characterized by scanning electron microscopy, X‐ray diffraction, density, and strength measurement tests. Results show that andalusite promoted the decomposition of zircon and accelerated the reaction sintering of alumina–zircon, which leads to the formation of much more mullite phase and improvements to the composites’ thermal shock resistance up to about 50%.     

Effect of pressure and treatment temperature on the structural evolution of mechanically alloyed Ti(W)(C,N)–Al admixes in boron nitride

The effect of pressure and temperature on the structural changes of admixtures of cBN, Al and Ti(C_0.5N_0.05) or Ti(C_0.5N_0.5)_0.6 mechanically alloyed powders with 40 mass% W were investigated by means of the X-ray diffraction technique. It emerged that pressure and temperature affected the crystal structures and compositions of the binder phases as well as the behaviour of the contaminating Fe. High pressure–high temperature (HPHT) sintering favoured the formation of Ti(W,Al)(C,N) solid-solutions, whereas vacuum annealing favoured the formation of W(Ti,Al) solid-solutions. Products of Ti(C,N)-based crystal lattices remained stable under high pressure (5 GPa), whereas W based crystal lattices were more stable under vacuum (0.001 Pa). Inert single phase binders were formed in HPHT sintered PcBN compacts. Formation of Ti(W,Al)(C,N) by reactions between mechanical alloyed Ti(W)(C,N) powder particles and liquid Al prevented the formation of AlN, AlB₂, α-AlB₁₂, TiN and TiB₂ particles in PcBN compacts. Sintering of PcBN occurred by dissolution of B and N atoms in Ti(W,Al)(C,N) and re-precipitation on cBN particles.     

Novel nanoceramics from in situ made nanocrystalline powders of pure nitrides and their composites in the system aluminum nitride AlN/gallium nitride GaN/aluminum gallium nitride Al0.5Ga0.5N

Presented are investigations of in situ preparation of composite nanopowders of AlN, GaN, and, optionally, solid solution Al_0.5Ga_0.5N, which were used in no-additive, high-pressure/high-temperature sintering. Two precursor synthesis pathways and two nitridation temperatures afforded nanopowders containing both (i) mixed AlN and GaN and (ii) such AlN and GaN admixed with Al_0.5Ga_0.5N as well as (iii) reference individual AlN and GaN. The applied sintering temperatures were either to preserve powder nanocrystallinity (650 °C) or promote crystallite growth and sintering-mediated Al_0.5Ga_0.5N formation (1000 °C). One specific route led to the novel nanoceramics of Al_0.5Ga_0.5N. The powders and nanoceramics were characterized by XRD, FT-IR, SEM/EDX, ²⁷Al/⁷¹Ga MAS NMR, BET/BJH surface areas, and helium densities. Vicker’s hardness tests confirmed many of the sintered composites and individual nitrides having high hardness comparable with monocrystalline AlN and GaN. Formation of pure Al_0.5Ga_0.5N nanoceramics was associated with closed pore evolution and had a detrimental effect on hardness.