Sintering behavior of mechanically alloyed Ti-48Al-2Nb aluminides

Ti-Al intermetallics have been produced using mechanical alloying technique. A composition of Ti-48Al-2Nb at % powders was mechanically alloyed for various durations of 20, 40, 60, 80 and 100 h. At the early stages of milling, a Ti (Al) solid solution is formed, on further milling the formation of amorphous phase occurs. Traces of TiAl and Ti₃Al were formed with major Ti and Al phases after milling at 40 h and beyond. When further milled, phases of intermetallic compounds like TiAl and Ti₃Al were formed after 80 hours of milling and they also found in 100 h milled powders. The powders milled for different durations were sintered at 785°C in vacuum. The mechanically alloyed powders as well as the sintered compacts were characterized by XRD, FESEM and DTA to determine the phases, crystallite size, microstructures and the influence of sintering over mechanical alloying.     

In Situ Synthesis of Ti5Si3 Matrix Nanocomposites Reinforced with Nanoparticles by High‐Energy Mechanical Alloying

In the present work, in situ TiN/Ti₅Si₃ nanocomposite powder was prepared by high‐energy mechanical alloying of a Ti and Si₃N₄ powder mixture via the following route: 9Ti + Si₃N₄ = Ti₅Si₃ + 4TiN. Constitution phases and microstructural features of the milled powders at different milling times were studied by XRD, SEM, and TEM. The operative formation mechanisms behind the microstructural developments were disclosed. It showed that the original Si₃N₄ and Ti constituents demonstrated two different reaction mechanisms during milling, i.e., a progressive mechanism of Si₃N₄ (≤20 h) and a speedy mechanism of Ti (≤10 h). The morphologies of the milled composite powders experienced a successive change: pre‐refining – coarsening – re‐refining on increasing the applied milling time. The variation of the operative mechanisms was ascribed to the existence/exhaustion of the ductile Ti constituent in the milling system due to the nonoccurrence/initiation of the in situ reaction. The 20 h milled powder was the typical nanocomposites featured by the nanocrystalline Ti₅Si₃ matrix reinforced with in situ TiN nanoparticles. The grain sizes of the in situ formed Ti₅Si₃ and TiN phases were generally ≤15 nm, exhibiting coherent interfacial structure between reinforcement and matrix.     

Metastable phases formation induced by mechanical alloying

Elemental aluminium, titanium and iron powders with compositions of Al₉₀Ti₁₀, Al₅₅Ti₄₅, Al₆₅Ti₂₅Fe₁₀, respectively, were mechanically alloyed in a planetary ball mill. The sequence of phase formation was characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), and differential scanning calorimetry (DSC). Various metastable phases were experimentally observed: supersaturated solid solution Al(Ti) for Al₉₀Ti₁₀, amorphous phase and L1₂-Al₃Ti compound for Al₅₅Ti₄₅, amorphous phase and supersaturated solid solution Al(Ti,Fe) for Al₆₅Ti₂₅Fe₁₀, and an fcc crystalline phase was inevitably found in those alloys. The formation of the fcc crystalline phase has been critically assessed. The results suggest that the fcc crystalline phase seems to be metastable and it cannot be solely attributed to the contamination from the milling atmosphere underthe present experimental conditions.     

放电等离子烧结Ti-Al系金属间化合物

用机械合金化法(MA)制备了Ti-45% Al纳米晶合金粉末,并对其进行放电等离子烧结(SPS),烧结时间仅为5min.用D-maxIIA型X射线衍射仪、JEM-2000EX型透射电子显微镜对粉末和烧结块体的微观组织及机械性能进行了研究.研究表明:Ti和Al的粉末随着球磨时间的延长,粉末有明显的细化趋势,球磨5h即有非晶产生,球磨20h后得到接近完全非晶相;采用SPS烧结技术,在1200℃下能够制备出较高硬度的TiAl金属间化合物块体材料.     

On the mechanism of mechanochemical synthesis of Ti2SC from Ti/FeS2/C mixture

In this study, the synthesis of Ti₂SC MAX phase by high energy ball milling, and the effects of heat treatment on ball milled powder was investigated. To this aim, a mixture of Ti, FeS₂ (as sulfur source), and C according to Ti₂SC stoichiometry, were ball milled by a planetary ball mill for different milling periods up to 10 h. The structural evolution, and the morphology of the products was studied by x-ray diffraction (XRD), and scanning electron microscopy (SEM) equipped with energy-dispersive spectroscopy (EDS), respectively. The results showed that after 10 h of ball milling, the raw materials reacted together and resulted in the formation of Ti₂SiC and TiC phases. The ball milled powder was then compacted and heat treated at 1000 and 1200 °C. Heat treatment caused the progressing of synthesis reactions, and led to increasing the purity of Ti₂SC phase. The heat-treated powder was leached in 1 M HCl for 2 h to remove iron from the product. The XRD results confirmed successful iron removal by leaching. SEM micrographs of the final product revealed the specific lamellar structure of MAX phases. Elemental mapping confirmed the homogeneous distribution of Ti, S and C elements.     

Role of intensive milling in mechano-thermal processing of TiAl/Al2O3 nano-composite

In this research a nano-composite structure containing of an intermetallic matrix with dispersed Al₂O₃ particles was obtained via mechanical activation of TiO₂ and Al powder mixture and subsequent sintering. The mixture has been milled for different lengths of time and then as a subsequent process it has been sintered. Phase evolutions in the course of milling and subsequent sintering of the milled powder mixture were investigated. Samples were characterized by XRD, SEM, DTA and TEM techniques.The results reveal that the reaction begins during milling by formation of Al₂O₃ and L1₂ Al₃Ti and further milling causes partial amorphization of powder mixture. DTA results reveal that milling of the powder mixture causes solid state reaction between Al and TiO₂ rather than liquid–solid reaction. Also, it was observed that the exothermicity of aluminothermic reduction is reduced by increasing the milling time and the exothermic peak shifts to lower temperatures after partial amorphization of powder mixture during milling. Phase evolutions of the milled powders after being sintered reveal that by increasing the milling time and formation of L1₂ Al₃Ti in the milled powder, intermediate phase formed at 500 °C changes from D0₂₂ Al₃Ti to Al₂₄Ti₈ phase.     

Microstructure and oxidation behaviour of TiAl(Nb)/Ti<Subscript>2</Subscript>AlC composites fabricated by mechanical alloying and hot pressing

TiAl-based intermetallic matrix composites with dispersed Ti₂AlC particles and different amounts of Nb were successfully synthesized by mechanical alloying and hot pressing. The phase evolution of Ti–48 at%. Al elemental powder mixture milled for different times with hexane as a process control agent was investigated. It was found that after milling for 25 h, a Ti(Al) solid solution was formed; also with increase in the milling time to 50 h, an amorphous phase was detected. Formation of a supersaturated Ti(Al) solid solution after 75 h milling was achieved by crystallization of amorphous phase. Addition of Nb to system also exhibited a supersaturated Ti(Al,Nb) solid solution after milling for 75 h, implying that the Al and Nb elements were dissolved in the Ti lattice in a non-equilibrium state. Annealing of 75 h milled powders resulted in the formation of equilibrium TiAl intermetallic with Ti₂AlC phases that showed the carbon that originates from hexane, participated in the reaction to form Ti₂AlC during heating. Consolidation of milled powder with different amounts of Nb was performed by hot pressing at 1000°C for 1 h. Only the presence of γ-TiAl and Ti₂AlC was detected and no secondary phases were observed on the base of Nb. Displacement of γ-TiAl peaks with Nb addition implied that the Nb element was dissolved into TiAl matrix in the form of solid solution, causing the lattice tetragonality of TiAl to increase slightly. The values for density and porosity of samples indicated that condition of hot pressing process with temperature and pressure was adequate to consolidate almost fully densified samples. The isothermal oxidation test was carried out at 1000°C in air to assess the effect of Nb addition on the oxidation behaviour of TiAl/Ti₂AlC composites. The oxidation resistance of composites was improved with the increase in the Nb content due to the suppression of TiO₂ growth, the formation and stabilization of nitride in the oxide scale and better scale spallation resistance.     

Characteristics of the mechanically-alloyed Ni60Ti40 amorphous powders during mechanical milling in different atmospheres

Mechanically alloyed Ni₆₀Ti₄₀ amorphous powders were further milled in argon, nitrogen and oxygen atmospheres. X-ray diffraction, differential scanning calorimetry and transmission electron microscopy analyses were made to investigate the structural changes during each process. No distinguishable structural changes during further milling of the amorphous powders in argon or nitrogen atmospheres were observed. However, in an oxygen atmosphere, the amorphous phase was crystallized into intermetallic compounds and was accompanied by the occurrence of titanium oxides in the initial stage. On further milling in an oxygen atmosphere, the intermetallic compounds decomposed and only the nickel saturation solution and titanium oxides remained. A thermodynamic explanation of the crystallization and decomposition has been proposed.     

Nano-structured intermetallic compound TiAl obtained by crystallization of mechanically alloyed amorphous TiAl, and its subsequent grain growth

The amorphization process during mechanical alloying (MA) was investigated for the Al-50at%Ti and Al-50at%Ti-10vol%TiB₂ powder mixtures. Pure metallic powders of Al and Ti were finely mixed and transformed to the amorphous phase after being milled for about 2880 ks. In the case of Al-50at%Ti-10vol%TiB₂ powder, the amorphous alloys with a fine dispersion of TiB₂ particles could be obtained for a shorter milling times than that required for the powders without TiB₂ ceramics. As a result of heat treatment for the mechanically alloyed amorphous powders, a nanocrystalline intermetallic compound of TiAl () could be produced. Subsequent grain growth of the phase during heat treatment was investigated by estimating the grain-growth exponent and the activation energy for grain growth. It was found from this estimation that the grain growth was further suppressed as the powders were mechanically alloyed for longer times. Furthermore, the addition of the TiB₂ particles that could be dispersed during MA finely and homogeneously in the amorphous matrix was found to be effective for suppression of the grain growth especially at elevated temperatures as well as for a long annealing.     

Synthesis and Characterization of CuNi Magnetic Nanoparticles by Mechano-Thermal Route

In the present investigation, Cu_0.5Ni_0.5 nanoparticles were synthesized using high energy ball milling of a mixture of Cu₂O, NiO, and graphite powders. The mixture of powders was milled up to 50 h. The 30 h milled sample was heat treated at various temperatures for 1 h in a vacuum tube furnace. The effects of milling time and heat treatment temperature on the powder particle characteristics were studied employing X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), differential thermal analysis (DTA), and vibrating sample magnetometer (VSM) techniques. XRD results indicated incomplete formation of Cu_0.5Ni_0.5 after 30 h of milling. Further heat treatment at 500 ^°C led to the formation of a single phase Cu_0.5Ni_0.5 powder. FESEM and TEM images of the heat treated sample showed spherical Cu_0.5Ni_0.5 nanoparticles with a mean particle size of 15 nm. Magnetic properties data measured by VSM of the above sample are correlated well with the XRD results. Coercivity and saturation magnetization have been approximately achieved at 25 Oe and 18 emu/g, respectively.     

Synthesis of titanium carbide and TiC–SiO2 nanocomposite powder using rutile and Si by mechanically activated sintering

High-energy ball milling was applied with subsequent heat treatment for synthesizing nanoparticles of TiC powders by the carbothermic and carbosilisisothermic reduction of titanium oxide (rutile type). The milling procedure involved milling of TiO₂/C and TiO₂/Si/C powders at room temperature in an argon atmosphere. The progress of the mechanically induced solid state reaction was monitored using X-ray diffraction (XRD) and scanning electron microscopy (SEM). The XRD results showed that TiC nanoparticles were duly synthesized in the TiO₂/C system at 1700 °C in 60-h milled samples. In the non-milled samples, although heated at the same temperature, only a minor amount of a lower degree of titanium oxide (Ti₃O₅) was observed to form. Further, in other non-milled samples, but with Si initially present, despite heating to 1550 °C no TiC phase was detected. However, using Si as a reducing agent accompanied by graphite, after 60 h ball milling, only Si remained as a distinguishable crystalline phase. Further, heat treatment of activated powders by forming the interphase compounds (such as Ti₃Si₅ and Ti₅Si₃) remarkably decreased the synthesis temperature to 900 °C for the 60 h milled samples.     

反应球磨钛与尿素制备氮化钛的反应机理研究

将Ti粉与尿素在室温下进行反应球磨制备了TiN粉末,对球磨不同时间后的粉末进行XRD分析,采用TG-FTIR技术分析了尿素的分解温度与产物,利用TEM及EELS观察和分析了球磨70h粉末的微观形貌、结构及成分. 结果发现,球磨70h合成了纳米TiN粉末,晶粒度为6~7nm,Ti/N原子比约为1.0∶0.6. 经800℃,5h真空退火处理后粉末的XRD谱图表明粉末组成为单相TiN. 在反应球磨过程中,Ti与尿素的分解产物NH₃与HNCO发生反应形成TiN,随球磨时间延长,Ti的缺陷能增大、活性增加,N在Ti中的扩散激活能减小,在球磨作用下N的扩散距离变短,TiN的含量逐渐增加形成晶核并逐渐长大形成纳米晶.     

Amorphisation and phase transformations in mechanically alloyed Ti–Al powders: electron microscopy investigation

Abstract

The microstructural evolution during mechanical alloying of Ti and Al powders has been investigated by X-ray diffraction, scanning electron microscopy (SEM)–energy dispersive spectroscopy, and transmission electron microscopy (TEM). Observations by SEM showed a progressive change of the powders' morphology as a function of milling time. Observations by TEM, performed on a sample milled for 20 h, revealed the simultaneous occurrence of amorphous zones and nanocrystalline domains. The observed amorphous phase is not the final milling product. After 34 h of milling it was possible to identify by TEM fcc (a=0·41 nm) nanocrystalline zones, with a mean size of about 10 nm. By irradiating the powder milled for 20 h with high density electron beams, a sudden in situ crystallisation took place. The crystallite (fcc with a=0·41 nm) size was between 0·1 and 0·5 μm.

MST/1281     

Thermodynamic aspects of nanostructured Ti5Si3 formation during mechanical alloying and its characterization

Mechanical alloying (MA) was used to produce Ti₅Si₃ intermetallic compound with nanocrystalline structure from elemental powders. The structural changes and characterization of powder particles during milling were studied by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), particle size analyser (PSA) and microhardness measurements. MA resulted in gradual formation of disordered Ti₅Si₃ intermetallic compound with crystallite size of about 15 nm after 45 h of milling. Also a thermodynamic analysis of the process was carried out using Miedema model. The results showed that in the nominal composition of Ti₅Si₃ intermetallic phase (X _Si ?=?0·375), formation of an intermetallic compound has the lowest Gibbs free energy rather than solid solution or amorphous phases. So the MA product is the most stable phase in nominal composition of Ti₅Si₃. This intermetallic compound exhibits high microhardness value of about 1235 HV.     

Structural investigations of Y2O3 dispersoids during mechanical milling and high-temperature annealing of Fe-15Y2O3-xTi (x = 0–15) model ODS alloys

A model Oxide Dispersion Strengthened (ODS) alloy powder of composition Fe – 15 wt. % Y₂O₃ – x wt. % Ti (x = 0, 2, 5, 10 and 15) were synthesized by high energy mechanical milling in Ar atmosphere for a prolonged duration of 60 h. Synchrotron X-ray diffraction (XRD) and transmission electron microscopy (TEM) observations suggested the amorphisation of Y₂O₃ nano-crystallites, irrespective of Ti content, which is further studied by Raman spectroscopy. The Raman spectroscopy analysis confirms the presence of YO bonding in the milled powder and ruled out the possibility of elemental dissociation of Y₂O₃ and dissolution into the Fe matrix. Annealing of the milled powders containing different amounts of Ti led to formation of different types of oxide complexes which were also studied using synchrotron XRD and TEM studies. The role of Ti in refining the dispersoids through formation of Y_1.6Ti_1.8Fe_0.4O_6.6 is established through these studies.     

Study on the formation mechanism of Y-Ti-O oxides during mechanical milling and annealing treatment

Y-Ti-O nano-scale oxides play important roles in ensuring the excellent performance of oxide dispersion strengthened (ODS) steels. In this study, a model powder system of Y₂O₃ and Ti was designed to investigate the formation and evolution mechanism of Y-Ti-O oxides. The morphology of powders tended to be stable after high energy ball milling for 240 min in Ar. X-ray diffraction (XRD) results suggested that there was no formation of new phase after mechanical milling. Thermo-gravimetric and differential thermal analysis (TG-DTA) was applied to analyze physical and chemical reactions of milled powders respectively in Ar and air. The corresponding annealing and XRD were performed to study the types and structures of oxides at different temperatures. It shows that oxygen concentration and temperature are the critical factors affecting the formation of oxides. Ti was evolved into Ti₆O, Ti₃O and TiO₂ in turn with temperature increasing. Then only TiO₂ was reacted with Y₂O₃ to form Y₂Ti₂O₇. The formation of Y₂Ti₂O₇ began at around 500 ℃ and was completed around 1004 ℃. A maximum formation rate occurred at about 779 ℃. High resolution transmission electron microscopy (HRTEM) suggested that the main phase in powders sintered at 1100 ℃ was identified as pyrochlore structure Y₂Ti₂O₇.     

Fabrication and characterization of NiTi shape memory alloy synthesized by Ni electroless plating of titanium powder

In this work NiTi shape memory alloy was fabricated from mixed elemental powders, Ni plated titanium powder and Ni heated/plated titanium powder by Ar-sintering. Electroless plating process was utilized to fabricate Ni plated titanium powder. For this purpose titanium powder was plated in an electroless Ni bath for 225?min and hydrazine hydrate was used as a reductant to deposit pure nickel on the titanium particles. Ni plated titanium powder was heat treated under an argon atmosphere at 1000?°C to prepare Ni heated/plated titanium powder. Finally, the three sample powders were pressed by CIP followed by sintering at 980?°C for 8?h to manufacture NiTi shape memory alloy. The prepared powders, as well as sintered samples, were characterized by scanning electronic microscopy (SEM), energy dispersive spectrometer analysis (EDS), X-ray fluorescence (XRF), X-ray diffraction (XRD) and differential scanning calorimetric (DSC). The results indicated the presence of NiTi phase and also non-transformable phases (NiTi₂ and Ni₃Ti) in the heated/plated Ti powder and sintered samples. NiTi compound was dominated phase in the heated/plated sintered sample. All three sintered samples, as well as heated/plated powder, showed one-step phase transformation (B2???B19′).     

Synthesis of LaB<Subscript>6</Subscript>–Al<Subscript>2</Subscript>O<Subscript>3</Subscript> nanocomposite powders via ball milling-assisted annealing

In this study, LaB₆–Al₂O₃ nanocomposite powders were synthesized via ball milling-assisted annealing process starting from La₂O₃–B₂O₃–Al powder blends. High-energy ball milling was conducted at various durations (0, 3, 6 and 9 h). Then, the milled powders were annealed at 1200 °C for 3 h under Ar atmosphere in order to obtain LaB₆ and Al₂O₃ phases as reaction products. X-ray diffractometry (XRD), scanning electron microscopy/energy-dispersive spectrometry (SEM/EDS) and transmission electron microscopy (TEM) techniques were utilized to carry out microstructural characterization of the powders. No reaction between the reactants was observed in the XRD patterns of the milled powders, indicating that high-energy ball milling did not trigger any chemical reactions even after milling for 9 h. LaAlO₃ and LaBO₃ phases existed in the annealed powders which were milled for 0, 3 and 6 h. LaBO₃ phase was removed after HCl leaching. 9-h milled and annealed powders did not exhibit any undesired phases such as LaAlO₃ and LaBO₃ after leaching step, and pure nanocrystalline LaB₆–Al₂O₃ composite powders were successfully obtained. TEM analyses revealed that very fine LaB₆ particles (~?100 nm) were embedded in coarse Al₂O₃ (~?500 nm) particles.     

Mechanically activated combustion synthesis of Ti3AlC2/Al2O3 nanocomposite from TiO2/Al/C powder mixtures

Ti₃AlC₂/Al₂O₃ nanocomposite powder was synthesized by mechanical-activation-assisted combustion synthesis of TiO₂, Al and C powder mixtures. The effect of mechanical activation time of 3TiO₂-5Al-2C powder mixtures, via high energy planetary milling (up to 20?h), on the phase transformation after combustion synthesis was experimentally investigated. X-ray diffraction (XRD) was used to characterize as-milled and thermally treated powder mixtures. The morphology and microstructure of as-fabricated products were also studied by scanning electron microscopy (SEM) and field-emission gun electron microscopy (FESEM). The experimental results showed that mechanical activation via ball-milling increased the initial extra energy of TiO₂-Al-C powder mixtures, which is needed to enhance the reactivity of powder mixture and make it possible to ignite and sustain the combustion reaction to form Ti₃AlC₂/Al₂O₃ nanocomposite. TiC, AlTi and Al₂O₃ intermediate phases were formed when the initial 10?h milled powder mixtures were thermally treated. The desired Ti₃AlC₂/Al₂O₃ nanocomposite was synthesized after thermal treatment of 20?h milled powder and consequent combustion synthesis and FESEM result confirmed that produced powder had nanocrystalline structure.     

等离子旋转电极雾化法制备高品质Ti-6.5Al-1.4Si-2Zr-0.5Mo-2Sn合金粉末

旨在制备高品质Ti-6.5Al-1.4Si-2Zr-0.5Mo-2Sn粉末,为后续粉末高温钛合金构件的制备奠定基础。首先采用真空自耗电弧熔炼(VAR)技术制备Ti-6.5Al-1.4Si-2Zr-0.5Mo-2Sn合金铸锭,对铸锭进行化学成分检测,并分析其合金元素损耗、成分均匀性以及显微组织和物相组成。利用制得棒料,采用等离子旋转电极雾化法(PREP),选取不同转速制备得到钛合金粉末,将粉末筛分成不同粒度范围。研究了棒料转速与粉末理化性能间的关系。采用X射线衍射分析仪(XRD)、扫描电镜(SEM)、金相显微镜(OM)分别分析了粉末的物相组成、形貌和微观组织。研究表明:通过独特的压制电极设计,可制得成分均匀、元素损耗小的钛合金铸锭,且各合金元素含量满足国标的要求。铸锭微观组织为层片状结构,基体中存在少量大小不均的Ti5Si3硅化物相。PREP法制得的钛合金粉末呈正态分布,且球形度好,无空心球和卫星球。随着转速增加,小颗粒粉末占比增加,大颗粒粉末占比大幅度降低。粉末颗粒以胞状组织为主,存在少量的枝晶。合金粉末主要由α′马氏体相组成。相比合金铸锭,粉末中各合金元素略有损耗,O元素质量分数小于0.1%,有利于制得高性能的粉末钛合金。