Phase Stability in Mechanically Alloyed Mg–Ni System Studied by Experiments and Thermodynamic Calculations

In this study, microstructural evolution of Mg–Ni alloy during mechanical alloying(MA) was investigated.Also, a thermodynamic approach was utilized to predict the most stable phases formed in Mg–Ni alloy after MA. The phase composition and microstructural properties of Mg–Ni alloy were assessed by X-ray diffractometry, high-resolution field emission scanning electron microscopy and high-resolution transmission electron microscopy. The results showed that ball milling of magnesium and nickel powder mixture for 70 h yields nanostructural Mg2Ni compound with an average grain size of ~20 nm. Thermodynamic calculations revealed that in the composition ranges of 0.0 \ XMg\ 0.03(at.%)and 0.97 \ XMg\ 1, there is no driving force for amorphous phase formation. In the composition range of 0.07 \ XMg\ 0.93, the change of Gibbs free energy for amorphous phase formation was more negative than solid solution.While for XMg= 0.66(nominal composition of Mg2Ni intermetallic phase), the change of Gibbs free energy for intermetallic phase was found to be more negative than both amorphous and solid solution phases indicating that Mg2Ni intermetallic compound is the most stable phase, in agreement with the experimental observations.     

Hot-press sintering of MA Fe-based nanocrystalline／amorphous soft magnetic powder

Microstructures and magnetic properties of Fe84 Nb7 B9, Fe80 Ti8 B12 and Fe32 Ni36 (Nb/Ⅴ) 7 Si8 B17 powders and their bulk alloys prepared by mechanical alloying(MA) method and hot-press sintering were studied. The results show that: 1) After MA for 20 h, nanocrystalline bcc single phase supersaturated solid solution forms in Fe84-Nb7 B9 and Fe8o Ti8 B12 alloys, amorphous structure forms in Fe32 Ni36 Nb7 Si8 B17 alloy, duplex microstructure composed of nanocrystalline γ-(FeNi) supersaturated solid solution and trace content of Fe2B phase forms in Fe32 Ni36-V7 Si8 B17 alloy. 2) The decomposition process of supersaturated solid solution phases in Fe84 Nb7 B9 and Fe80 Ti8 B12alloys happens at 710 -780 ℃, crystallization reaction in Fe32 Ni36 Nb7 Si8 B17 alloy happens at 530 ℃ (the temperature of peak value) and residual amorphous crystallized further happens at 760 ℃ (the temperature of peak value), phase decomposition process of supersaturated solid solution at 780 ℃ (the temperature of peak value) and crystallization reaction at 431 ℃ (the temperature of peak value) happens in Fe32 Ni36 V7Si8B17 alloy. 3) under 900 ℃, 30 MPa,0.5 h hot-press sintering conditions, bulk alloys with high relative density(94.7%- 95.8%) can be obtained. Except that the grain size of Fe84 Nb7B9 bulk alloy is large, superfine grains (grain size 50 - 200 nm) are obtained in other alloys. Except that single phase microstructure is obtained in Fe80 Ti8B12 bulk alloy, multi-phase microstructures are obtained in other alloys. 4) The magnetic properties of Fe80 Ti8 B12 bulk alloy(Bs = 1.74 T, Hc = 4.35 kA/m) are significantly superior to those of other bulk alloys, which is related to the different phases of nanocrystalline or amorphous powder formed during hot-press sintering process and grain size.     

Synthesis of TiAl-Ti2AlN composites by in-situ crystallization

The amorphization process during mechanical alloying （MA） was investigated for the Ti-50%/Al （mole fraction） powder mixtures with no special protection conditions. During the milling process, with the milling time prolonging, the metallic powder Ti and Al were finely mixed, gradually, aluminum completely dissolved into titanium to form an Ti（Al） hcp supersaturated solid solution, and finally, transformed to the amorphous phase after milled for about 39 h. As a result of heat treatment in hot press sintering processing for the mechanically alloyed amorphous powders in vacuum, a submicrostructure intermetallics of TiAl/TizAIN composite can be produced by in-situ crystallization. Furthermore, the structure evolution, phase formation and transformation during the heat treatment were also investigated by X-ray diffractometry and differential thermal analysis. The results show that the reaction involves many transitional stages, including formation of TiAl3 and transformation into TiAl and Ti3Al. The examination show that the composite materials fabricated by this in-situ crystallization from amorphization have good mechanical properties due to fine grain size and uniform microstructure.     

Structural evolution of Si-50%C powder during mechanical alloying and heat treatment

The nanocrystalline β-SiC powder was successfully synthesized by ball milling the Si-50%C elemental powder. During ball milling, a solid solution of C in Si, Si（C）, firstly forms, followed by SiC. The formation of SiC is controlled by the mixing mechanism of the gradual diffusion reaction（GDR） and the mechanically induced self-propagating reaction（MSR）. The amount of β-SiC increases with milling time increasing. After 40 h milling, there exists only β-SiC in the milled powder. The grain size of β-SiC is about 6.4 nm after the powder is milled for 60 h. After the 60 h-milled Si-50%C elemental powder is heat treated at 1 100℃for l h, the grain size of β-SiC does not change, but the lattice ordering degree offl-SiC increases.     

Characteristics of mechanical alloyed Ni-Al powder for sintering

Mechanical alloying was employed to obtain high-activity Ni-AI powder. The effects of mechanical alloying on the microstructure and characteristics of milled powder with a normal composition of Ni-22.89 at.% AI-0.5 at.% B were investigated by X-ray diffraction （XRD）, scanning electron microscopy （SEM）, and transmission electron microscopy （TEM）. The results show that a solution Ni （AI） was obtained after milling. During mechanical alloying, the milled powder obtains extra surface energy and crystalline energy because the crystallite size becomes free and the lattice strain increases with the milling time prolonging. Furthermore, about 0.5 mol% oxide in the particles were formed after milling, and this kind of dis- persed oxide is effective to improve the properties of the sintered alloy by dispersion strengthening. It is confirmed that Ni3AI alloy with outstanding properties has been prepared with mechanical alloyed powders.     

Preparation and Characterization of Amorphous W–B–C Alloy and Solid Solutions of C in Tungsten Borides

Mixtures of W and B_(13) C_2 powders were mechanically milled and subsequently annealed at 900–1200 °C. It is found that amorphous W–B–C alloy formed as the mixtures were milled for 20–80 h. After annealing the 80 h-milled mixtures at 900–950 °C, solid solutions of C and/or B in tungsten [W(B, C)], C in tungsten boride [W_2 B(C) or WB(C)]formed by the crystallization of amorphous W–B–C. The formation temperature of W_2 B(C) and WB(C) is lower than that of W_2 B and WB reported previously. As the 80 h-milled mixtures were annealed at 1200 °C, W reacted with amorphous W–B–C completely to form WB and W_2B_5 or W_2B_5 instead of the solid solutions of C in tungsten borides, which is determined by the mole ratio of W to B_(13) C_2. The formation mechanisms of the W_2 B(C) and WB(C) solid solutions as well as phase transition rules of the mixtures at annealing temperature and mole ratio were also investigated using first-principle calculation.     

Synthesis of TiAl-Al2O3 composites by high energy milling and hot-press sintering

A sub-microstructure titanium aluminide alloy/Al2O3 （3A） composite was obtained by crystallization of the amorphous powders, which were prepared by mechanical alloying （MA） in a planetary ball milling system using Ti-AI-TiO2 as raw materials. The experimental results show that, when the milling time increases up to 30 h, the hep Ti（Al） supersaturated solid solution disappears, only amorphous phase is left. The compact samples were synthesized by hot-press to 1 200 ℃ with the amorphous as a precursor; the final phases of the matrix and strengthened phase are y-TiAl and Al2O3. The phases come from in situ crystallization and transformation. The samples, fabricated from the amorphous phase by hot press sintering, have high bending strength and fracture toughness.     

Analysis of precipitation in a Cu-Cr-Zr alloy

Precipites in Cu-0.42%Cr-0.21%Zr alloy were analyzed by using scanning electron microscope （SEM）, energy dispersive X-ray spectroscopy （EDXS） and transmission electron microscope （TEM）. After the solid solution was performed at 980℃ for 2 h, water-quenched and aged at 450℃ for 20 h, the precipite had a bimodal distribution of precipitate size. The coarse precipitates are pure Cr and Cu5Zr, the dispersed fine precipitate is CrCu2（Zr, Mg） and pure Cr ranging from 1 to 50 nm. The coarse phases formed during solidification and were left undissolved during solid solution. The fine precipitates are the hardening precipitates that form due to decomposition of the supersaturated solid solution during aging.     

Mechanical behaviors of NiAl-Cr(Mo)-based near eutectic alloy with Ti, Hf, Nb and W additions

Effects of Ti, Hf, Nb and W alloying elements addition on the microstructure and the mechanical behaviors of NiAl-Cr(Mo) intermetallic alloy were investigated by means of XRD, SEM, EDX and compression tests. The results show that Ni-31Al-30Cr-4Mo-2(Ti, Hf, Nb, W) alloy consists of four phases: NiAl, α-Cr solid solution, Cr2Nb and Ni2Al(Ti, Hf). The mechanical properties are improved significantly compared with the base alloy. The compression yield strength at 1 373 K is 467 MPa and the room temperature compression ductility is 17.87% under the strain rate of 5.56×10-3 s-1, due to the existence of Cr2Nb and Ni2Al(Ti, Hf) phases for strengthening and Ti solid solution in NiAl matrix and coarse Cr(Mo, W) solid solution phase at cellular boundaries for ductility. The elevated temperature compression deformation behavior of the alloy can be properly described by power-law equation: ε =0.898 σ8.47exp[-615/(RT)].     

Stability of supersaturated solid solution of quenched Al–X(X 5 Zn,Mg, Cu) binary alloys

In this study, the changing trend of crystal-lattice constant and the influential factors of the stability of supersaturated solid solutions with various alloying additions in the Al–X(Zn, Mg, Cu) binary alloys were investigated. The samples were analyzed using X-ray diffraction(XRD),X-ray absorption fine structure(XAFS), and scanning electron microscope(SEM). It is found that the addition of Cu causes the largest change of crystal-lattice constant of the Al–xCu supersaturated solid solution binary alloy. The most dramatic change occurs in the initial stage of Cu addition.The change is stabilized thereafter. Also, at the same alloying element addition to the Al–X(X = Zn, Mg, Cu)binary alloys, the Al–xCu is the most unstable system.Influential factors of the stability include the lattice constant change and the type of alloying element. The larger the lattice constant changes, the more unstable the supersaturated solid solution is. The alloying element, easy to aggregate, often leads to the solid solution less stable.     

AMORPHIZATION TRANSFORMATION BY MECHANICAL ALLOYING IN THE Mo-Si SYSTEM

1.IntroductionInrecelltyears,MoSiZhasattractedconsiderableattentionasapotentialhigh-temperaturestructuralmaterial.Thecombinationofhighmeltingpoint(2030"C),moderatedensity(6.24gcm--'),excellentoxidationresistance,andhighmodulusatelevatedtemperaturemakesMoSiZoneofthemostpromisingmatrixphasetobeusedattemperaturesupto1600oC[l].Anothermolybdenumsilicide,Mo5Si3,hasbeenproposedasapotentialreinforcementforMoSt,[1,2].AmongawidevarietyofprocessingtechniquesutilizedtosynthesizeMoSt2,mechanicalalloy…     

Cu-Cr-Zr复合粉末机械合金化研究

以Cu、Cr和Zr粉末为原料,采用机械合金化制备了Cu-90%Cr2Zr复合粉末。利用X射线衍射仪(XRD)和扫描电镜(SEM)研究了机械合金化过程中粉末的物相和微观形貌。结果表明:Cu-Cr-Zr粉末可通过机械合金化获得过饱和固溶体;在一定的球磨时间内,随球磨的进行,Cu-Cr-Zr粉末晶粒细化至纳米尺寸,晶格常数增加,晶格畸变降低,粉末形貌呈片状;但进一步球磨会导致铬的晶格常数降低,导致畸变增加,使得粉末变得不规则及颗粒大小不均。     

Phase analysis of the mechanically alloyed Fe−Si powder by differential dissolution technique

The binary Fe?Si elemental powders mixture (1∶2 in atomic proportion) has been milled for different milling times in an attrition mill. The phase characterization of mechanically alloyed powder was investigated using the chemical method of differential dissolution (DD) and the X-ray diffraction (XRD) method. In powder specimens milled for more than 15 hr, ∈-FeSi and unreacted Si were observed. The formation of a supersaturated solid solution of Si in ∈-FeSi induced by mechanical alloying (MA) was also verified. The lattice parameter of the ∈-FeSi of as-milled powders changed from 4.4876 Å to 4.4668 Å according to the increase of MA time. Based on the results of the DD analysis, unreacted Si could be classified as (1) crystalline Si, (2) Si supersaturated in ∈-FeSi, or (3) amorphous Si. Therefore formation of the β-FeSi₂ after annealing could be explained by the reaction between the ∈-FeSi and the Si classified into types (1) and (2). It seemed that the amorphous Si induced by MA did not react with the ∈-FeSi during annealing at 700°C.     

钼-钴-硅混合粉末的机械合金化研究

采用X射线衍射、扫描电镜及透射电镜研究了配比为Mo5-xCoxSi3(x=0．5，l，2)的混合粉末的机械球磨行为。结果表明：随球磨时间延长，混合粉末中首先形成Co，Si在Mo中的过饱和固溶体Mo(Co，Si)，高能球磨大大扩展了硅和钴在钼中的固溶度。进一步延长球磨时间，过饱和固溶体转变成为非晶。在球磨过程中，Mo(Co，Si)的晶粒不断细化，球磨至40h，晶粒尺寸约为8nm。球磨初期，内应力急剧增加。随球磨时间延长，混合粉末的颗粒尺寸增大，40h后，逐渐减小，且形状球化，100h后成为尺寸不超过100nm的球形粉末。     

Microstructural evolution of mechanically alloyed Mo–Si–B–Zr–Y powders

Elemental powder mixtures with compositions of Mo–13.8Si, Mo–20B and Mo–12Si–10B–3Zr–0.3Y (at.%) were respectively milled in a high energy planetary ball mill at a speed of 500 rpm. Microstructural evolution of powder particles during milling processes was evaluated. The results show that B can hardly be dissolved into Mo under present milling conditions and the additions of B and Si both accelerate the refining rate of Mo crystallites. For Mo–12Si–10B–3Zr–0.3Y system, the morphology and internal structure of powder particles change significantly with milling time. After 40 h of milling, an almost strain-free super-saturated molybdenum solid solution with a grain size of about 6.5 nm forms. The grain refinement mechanism and dissolution kinetics of solute atoms are highlighted. Both thermodynamic calculation and experimental results reveal that for the present alloy composition it is more favorable to form solid solution than amorphous phase.     

粉末冶金Nb-35Ti-6Al-5Cr-8V合金组织演变及其力学行为

采用粉末冶金法对不同球磨时间的Nb-35Ti-6Al-5Cr-8V合金机械合金化粉末塑变行为,热压烧结材料的微观组织结构和力学行为进行了研究。研究结果表明：塑性良好的Nb-35Ti-6Al-5Cr-8V粉末随着球磨时间增加首先变形为大尺寸的片状、后经持续的加工硬化破碎成絮状;热压烧结能够制备微观组织可控晶粒细化的Nb-35Ti-6Al-5Cr-8V合金,合金由单一的Nbss相构成,Ti、Al、Cr、V元素固溶引起Nb晶格尺寸减小0.0685 ?;随着球磨时间增加合金晶粒明显细化进而显著提高了合金的维氏硬度和室温压缩强度,其变化符合材料硬度和强度的Hall-Petch规律。粉末冶金制备Nb-35Ti-6Al-5Cr-8V合金的各项力学性能明显优于熔铸法制备合金。     

Mechanically induced crystalline–glassy phase transformations of mechanically alloyed Ta55Zr10Al10Ni10Cu15 multicomponent alloy powders

New multicomponent Ta-based glassy alloy powder was synthesized by mechanical alloying (MA) the elemental powders of Ta₅₅Zr₁₀Ni₁₀Al₁₀Cu₁₅ at room temperature, using a low-energy ball milling technique. During the early stage of milling the agglomerated crystalline powders are mechanically crushed and fresh surfaces are rapidly created. Kneading of such ground powders enhances the atomic diffusion and leads to local alloying. As the MA time increases, the number of vacancies in the Ta lattice (base material) increases so that the atoms of the alloying elements for Zr, Al, Ni and Cu tend to migrate to the open defected lattice of metallic Ta. The number of atoms of the alloying elements that migrate to the bcc lattice of the base material are increasing with increasing MA time and this leads to a monotonic expansion of the Ta lattice. Further milling time (86–130 ks) plays an important role in increasing the rate of diffusion and this leads to an increase in the number of migrated atoms of the alloying elements that pass into the Ta lattice. The a₀ of the yielded solid solution at this stage does not change anymore with increasing MA time and a homogeneous supersaturated bcc-solid solution is obtained after 130 ks of MA time. This solid solution, which is subjected to continuous imperfections, is gradually transformed into a glassy phase upon increasing the MA time. The glassy powders of the final-product (1080 ks) in which its glass transition temperature (T_g) lies at a high temperature (834 K), crystallize through a single sharp exothermic peak at 1004 K (T_x). The total enthalpy change of crystallization (ΔH_x) is −10.32 kJ/mol. The width of the supercooled liquid region before crystallization (ΔT_x) of the synthesized glassy powder shows the largest value (170 K) of any reported metallic glassy system.     

The correlation of microstructural development and thermal stability of mechanically alloyed multicomponent Fe-Co-Ni-Zr-B alloys

The microstructural evolution of multicomponent Fe_70-x-yCo_xNi_yZr₁₀B₂₀ (x = 0, 7, 21; y = 7, 14, 21, 28) alloys during mechanical alloying (MA) has been studied using XRD, SEM and TEM. Mixtures of elemental and pre-alloyed powders have been transformed initially into the single supersaturated bcc α-Fe solid solution phase for the alloys investigated. Subsequently, an amorphous phase has been obtained in Co-free alloys and Co-containing alloys with high Ni/Co ratios of 1 and 3. However, no amorphous phase was detected in another Co-containing alloy with a lower Ni/Co ratio (e.g. 0.33). The thermal stability of the as-milled powders has been investigated by a combination of DSC and the Pendulum magnetometer experiments. The DSC studies provide information on the thermodynamics and kinetics of crystallization of amorphous structure as a function of alloying contents. The Pendulum magnetometer studies reveal the phase transformation from nanocrystalline bcc α-Fe solid solution to amorphous structure during MA and the thermomagnetization behavior of the as-milled powder.     

机械合金化Nb-Cr粉末的热力学分析

在球、料质量比为13∶1的条件下对Nb-Cr二元粉末进行了高能球磨,研究了摩尔比为1∶2的Nb、Cr混合粉末的机械合金化（MA）过程,用X射线衍射（XRD）分析了球磨粉末的物相组成.结果表明,球磨20 h后粉末变化为先形成Nb（Cr）的过饱和固溶体,45 h后逐步形成非晶,进一步球磨,159 h后发生非晶的晶化.参考Miedema半经验模型理论,建立了Nb-Cr系MA过程的热力学模型.该模型的计算结果表明,Nb-Cr二元系具有形成非晶、固溶体和化合物的热力学驱动力.对摩尔比为1∶2的Nb、Cr混合粉末不同时间XRD结果进行了分析,发现与热力学计算结果吻合.     

机械合金化制备Ni-W(B)非晶-纳米晶的粉末特性

利用机械合金化(MA)制备了Ni-20.7W和Ni-17.9W-27B(at%)非晶-纳米晶粉末,分别采用扫描电镜(SEM)和X射线衍射(XRD)仪分析了不同球磨时间粉末的微观形貌和结构参数,探讨了B的添加对非晶化过程的影响。研究结果表明:MA过程中,Ni-20.7W样品没有明显发生非晶化,而Ni-17.9W-27B样品在40 h时发生了非晶化,说明B提高了Ni-W合金体系的非晶化形成能力;非晶化过程为W/B首先固溶于Ni中生成Ni(W,B)过饱和固溶体,然后转变为非晶;Ni-20.7W样品球磨30 h后Ni的晶粒尺寸为32.9 nm,晶格畸变为0.48%,而Ni-17.9W-27B样品球磨10 h后的晶粒尺寸为9 nm,晶格畸变为0.62%。