机械合金化制备W-Ni-Fe纳米-非晶材料

按照80．7W-13．2Ni-6．1Fe的原子分数．采用机械合金化(MA)方法，制备了W-Ni-Fe合金纳米晶和非晶相的混晶结构。结合XRD，利用近似内标法计算了球磨不同时间球磨粉中残留晶体W的体积分数和非晶相中的W含量，并分析了球磨过程中非晶形成的机制。结果表明：随球磨时间的延长，W晶粒不断细化．球磨60h，钨晶粒尺寸可达到10nm-20nm，非晶相的形成过程主要是Ni(Fe)首先溶入W中形成过饱和固溶体，球磨20h后形成W-Ni(Fe)非晶。过饱和固溶体的形成是由于携带较大晶界存储能的小粒子不断溶入W中，计算得到可固溶的临界Ni粒子尺寸约为3nm。由于Fe污染不断溶入W中，在球磨过程中，残留晶体W的体积分数不断减少．而非晶相中的W-Ni(Fe)比例基本保持恒定，为63W-37Ni(Fe)。     

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%。     

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。     

Formation of crystalline and amorphous solid solutions of W–Ni–Fe powder during mechanical alloying

The tungsten heavy alloy with the composition of 76.6W–17.3Ni–6.1Fe in atom percent was mechanically alloyed (MA) from the elemental powders of W, Ni and Fe. Nanocrystalline supersaturated solid solutions and amorphous phase were obtained during MA. Phase evolution, grain size and lattice distortion of these powders were determined and discussed. A thermodynamic model was developed based on semi-experimental theory of Miedema to calculate the driving force for phase evolution. The thermodynamic analysis showed that there is no chemical driving force to form the solid solution and the amorphous phase. The effect of the work of milling on the amorphization during MA was discussed and the model of multilayer amorphization during MA was applied to illustrate the feasibility of amorphization of powder with neither ΔH_mix0 nor D_BD_A. The driving force for amorphization is provided not by the negative heat of mixing or the stored energy in the grain boundaries but by the sharp concentration gradients in this system. Amorphization is mechanically driven and not by the negative heat of mixing. Crystallization is suppressed by sharp concentration gradients.     

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.     

Thermodynamic Characteristic and Phase Evolution in Immiscible Cr–Mo Binary Alloys

This paper systematically reports the thermodynamic characteristic and phase evolution of immiscible Cr–Mo binary alloy during mechanical alloying(MA) process. The Cr–35Mo(in at%) powder mixture was milled at 243 and258 K, respectively, for different time. For comparative study, Cr–15Mo and Cr–62Mo powder mixtures were milled at 243 K for 18 h. Solid solution Cr(Mo) with body-centered cubic(bcc) crystal structure and amorphous Cr(Mo) alloy was obtained during MA process caused by high-energy ball milling. Based on the Miedema's model, the free-energy change for forming either a solid solution or an amorphous in Cr–Mo alloy system is positive but small at a temperature range between 200 and 300 K. The thermodynamical barrier for forming alloy in Cr–Mo system can be overcome when MA occurs at 243 K, and the supersaturated solid solution crystal nuclei with bcc structure form continually, and three supersaturated solid solutions of Cr–62Mo, Cr–35Mo and Cr–15Mo formed. Milling the Cr–35Mo powder mixture at 258 K, the solid solution Cr(Mo) forms firstly, and then the solid solution Cr(Mo) transforms into the amorphous Cr(Mo)alloy with a few of nanocrystallines when milling is prolonged. At higher milling temperature, it is favorable for the formation of the amorphous phase, as indicated by the thermodynamical calculation for immiscible Cr–Mo alloy system.     

机械合金化W-Ni-Fe纳米复合粉的制备及结构研究

W,Ni,Fe粉末按照91.16W6．56Ni2.26Fe和95W5Ni的成分配比进行了机械合金化(MA)．通过调整球磨转速、球磨时间等工艺参数研究了其对粉末结构的影响,并对机械合金化粉末的物相、合金化特性、晶粒尺寸、点阵畸变及粉末形貌和颗粒度作了测定和分析讨论.机械合金化使晶粒细化并产生孪晶和位错．有利于原子扩散形成过饱和固溶体和非晶；高的球磨能有利于形成非晶相、晶粒细化和点阵畸变，350r／min球磨20h后晶粒尺寸可达25nm；输入的球磨能不同．粉末粒度的变化路径不同，但都会经历长大，变小和稳定三个不同阶段.     

钼硅混合粉末在机械合金化过程中的结构演变

采用X射线衍射仪（XRD）和差热分析仪（DTA）研究了Mo-67at%Si元素混合粉末在中等强度的机械研磨（合金化）过程中的结构变化过程，结果表明，在中等强度的研磨过程中，β－MoSi2是初生相，且在随后的研磨过程中非晶化；在高研磨强度下生成α－MoSi2的量大于β－MoSi2,且α－MoSi2的含量随研磨时间的增加而增加，差热分析表明亚稳相β－MoSi2随温度的升高会向α－MoSi2转变。     

Mechanical alloying of Mo—Si—Fe powders

Mechanical milling behavior of Mo-Si-Fe powders was investigated u sing XRD, SEM and TEM techniques. The mixtures of elemental molybdenum (>99%), s ilicon (>99%) and iron (>98%) powders with a stoichiometry of Mo5-xFe xSi3 (x=0.5, 1, 2) were milled in a planetary mill for up to 195 h. For all three powder mixt ures, high-energy milling of 60h led to formation of the Mo(Fe, Si) supers aturated solid solution (Moss); and to a remarkable expansion of the solub ility of Fe, Si in molybdenum. The transformation of Moss to an amorphous phase was identified after longer time milling. In the milling process, the grain size of Mo (Fe, Si) decreased gradually and the internal stress increased linearly. After 40 h milling, the grain size was reduced to about 11 nm. SEM analysis of milled powders showed that the particle size increased initially with milling time. After 195 h milling, particles exhibited a spherical morphology and the particle size were reduced to about 100 nm.     

高能球磨制备Al-Pb-Si-Sn-Cu纳米晶粉末的特性

通过机械合金化制备了Al-15％Pb-4％Si-1％Sn-1．5％Cu(质量分数)纳米晶粉末。采用X射线衍射(XRD)，扫描电镜(SEM)和透射电镜(TEM)对不同球磨时间的混合粉末的组织结构、晶粒大小、微观形貌以及颗粒中化学成分分布情况进行了研究。结果表明混合粉末经过球磨后形成了纳米晶，其组织非常均匀。球磨对Pb的作用效果明显大于对Al的作用效果，经过40h球磨后Pb粒子达到40nm，而Al在球磨60h后晶粒为65nm；经球磨后，Cu和Si固溶于Al的晶格中，而Sn则固溶于Pb晶格中，并且Al和Pb发生了互溶，形成了Pb(Al）超饱和固溶体；在球磨过程中硬度高的脆性粒子Si难于完全实现合金化。     

W的添加对MoSi2显微组织的影响

以Mo、W、Si粉为原料,采用机械活化结合热压烧结的方法制备了不同W含量的MoSi2合金试样.结果表明,合金元素W加入后,其主要物相为MoSi2、(Mo,W)Si2固溶体及少量Mo4.8Si3C0.6碳化物,引起MoSi2显微应变增大,晶粒尺寸减小,从而细化了晶粒,晶粒尺寸在59.7～78.6 nm之间,具有纳米晶结构,强化了基体;随着W含量的增多,MoSi2合金材料的晶格参数和晶格体积增大,晶格密度减小.     

Mechanical alloying behavior of Nb–Ti–Si-based alloy made from elemental powders by ball milling process

Nb-Ti-Si-based alloy powders were prepared by mechanical alloying(MA) of elemental particles.The evolutions of morphology,size,phase constituents,crystallite size,lattice strain,composition and internal microstructure,etc.,of the alloy powders were analyzed by X-ray diffraction(XRD),scanning electron microscopy(SEM),energy-dispersive spectroscopy(EDS),laser particle size analyzer and transmission electron microscope(TEM) analyses.The alloy particles are gradually refined and their shapes become globular with the increase in milling time.The diffraction peaks of Nb solid solution(Nbss) phase shift toward lower29 angles during ball milling from 2 to 5 h,and after that Nbss diffraction peaks shift toward higher 29 angles with the increase in milling time from 5 to 70 h,which is mainly attributed to the alteration of the lattice parameter of Nbss powders due to the solution of the alloying element atoms into Nb lattice to form Nbss.During ball milling process,the decrease in crystallite size and increase in lattice strain of Nbss powders lead to continuous broadening of their diffraction peaks.A typical lamellar microstructure is formed inside the powder particles after ball milling for 5 h and becomes more refined and homogenized with the increase in milling time.After 40-h-ball milling,the typical lamellar microstructure disappears and a very homogeneous microstructure is formed instead.This homogeneous microstructure is proved to be composed of only supersaturated Nbss phase.     

Synthesis of Mo-Si-B intermetallic compounds with continuous α-Mo matrix by pulverization of ingot and hydrogen reduction of MoO3 powders

The fabrication of the intermetallic phase T2-Mo₃Si with continuous matrix of α-Mo was attempted with the combination process of high energy ball milling, pulverization of arc-melted ingot, addition of Mo by hydrogen reduction of MoO₃ and spark plasma sintering processes. High energy ball milling or arc melting of Mo-16.7Si-16.7B (at %) powders were performed to obtain to intermetallic phase T2 and Mo₃Si. The Mo phase of 57 vol% distributed intermetallic compound powders were prepared by hydrogen reduction of MoO₃ and further mixing of elemental Mo powders. X-ray diffractometry analysis revealed that the intermetallic phase T2-Mo₃Si can be produced by the pulverization process of arc-melted ingot. Hydrogen reduction of 1 vol% MoO₃ mixed intermetallic powder followed by further addition of Mo powders was a more adequate method enabling the homogeneous distribution of the Mo phase than that of added MoO₃ powders with total amount. The powder mixture was successfully consolidated by spark plasma sintering yielding a sound microstructure comprising the intermetallic phase T2-Mo₃Si uniformly distributed in a continuous matrix of α-Mo.     

机械化学还原法快速制备Mo5Si3-Al2O3纳米复合粉体（英文）

以MoO3粉、Mo粉、Si粉及Al粉为原料,采用机械合金化法合成了纳米Mo5Si3-20%Al2O3(质量分数)复合粉体。采用XRD、SEM、TEM和DTA等对复合粉体在球磨过程中结构变化进行了研究。结果表明:球磨10h后合成的Mo5Si3-20%Al2O3复合粉体,反应以爆炸模式进行。球磨30h后,Mo5Si3和Al2O3的晶粒尺寸分别为36.3nm和21.9nm。随着球磨时间的延长,Mo5Si3和Al2O3的晶粒尺寸变小,衍射峰宽化程度降低。DTA和XRD分析结果表明,复合粉体具有好的热稳定性,球磨30h后再在1000℃退火1h后复合粉体没有发生物相转变。     

Synthesis of α-Mo-Mo5SiB2-Mo3Si nanocomposite powders by two-step mechanical alloying and subsequent heat treatment

A two-step mechanical alloying process followed by heat treatment was developed as a novel approach for fabrication of Mo-12.5 mol%Si-25 mol%B nanocomposite powders. In this regard, a Si-43.62 wt.% B powder mixture was milled for 20 h. Then, Mo was added to the mechanically alloyed Si-B powders in order to achieve Mo-12.5 mol%Si-25 mol%B powder. This powder mixture was further milled for 2,5,10 and 20 h. All of the milled powders were annealed at 1100 °C for 1 h. After first step of milling, a nanocomposite structure composed of boron particles embedded in Si matrix was formed. On the other hand, an α-Mo/MoSi₂ nanocomposite was produced after second step while no ternary phases between Mo, Si and B were formed. At this stage, the subsequent annealing led to formation of α-Mo and Mo₅SiB₂ as major phases. The phase evolutions during heat treatment of powders can be affected by milling conditions. It should be mentioned that the desirable intermetallic phases were not formed during heat treatment of unmilled powders. On the other hand, α-Mo-Mo₅SiB₂-Mo₃Si nanocomposites were formed after annealing of powders milled for 22 h. With increasing milling time (at the second step), the formation of Mo₃Si during subsequent heat treatment was disturbed. Here, an α-Mo-Mo₅SiB₂-MoSi₂ nanocomposite was formed after annealing of 30 and 40 h milled powders.     

Amorphization process induced by mechanical alloying in the immiscible Cu-Ta system

The mechanism for the amorphization induced by mechanical alloying (MA) has been studied in the immiscible Cu- Ta system. A mixture of copper and tantalum powders at a composition ratio of Ta: Cu = 7:3 was used. The first 30 h of milling essentially results in the reduction in Ta and Cu grain size down to ∼10 nm without measurable formation of an amorphous phase. The thermally assisted amorphization (TAA) becomes noticeable after 60 h of milling. The higher the ambient temperature, the faster the amorphization proceeds. The TAA effect is also observed by annealing a partially amorphous MA powder. The microstructure after 30 h of milling is such that fine Cu crystallites are embedded in a fine- grained Ta matrix. Here an interfacial energy contribution is large enough to raise the Gibbs energy to that of an amorphous phase. Now high temperature milling or annealing allows an energetically downhill process to occur. This is most likely responsible for the observed TAA effect in the Cu- Ta system characterized by a positive heat of mixing.     

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.     

MoSi_2-WSi_2复合体系的自蔓延燃烧合成

利用自蔓延燃烧合成法制备了 Mo Si2 - WSi2 复合粉体 ,并对合成产物进行了 X射线衍射分析。研究表明 ,通过自蔓延燃烧合成反应既可实现 Mo Si2 与 WSi2 的复合 ,又可通过调整反应物 Mo,W,Si的比例 ,在 Mo Si2 中引入 WSi2的同时还能引入足够量的 Mo5 Si3- W5 Si3相。W量的增加使体系的绝热温度降低 ,对自蔓延燃烧合成反应产生影响。研究还表明 Mo Si2 - WSi2 和 Mo5 Si3- W5 Si3均以固溶体的形式存在。     

MoSi2—WSi2复合体系的自蔓延燃烧合成

自蔓延燃烧合成法制备了ＭｏＳｉ２－ＷＳｉ２ 事粉体,并对合成产物进行了Ｘ射线衍射分析。研究表明,通过自蔓延燃烧合成反应既可实现ＭｏＳｉ２与ＷＳｉ２的复合,又可通过调整尖物Ｍｏ,Ｗ,Ｓｕｉ的比例,在ＭｏＳｉ２中引入ＷＳｉ２的同时还能引入足够量的Ｍｏ５Ｓｉ３－Ｗ５Ｓｉ３相。Ｗ量的境加使体系的绝热温度降低,对自蔓延燃烧合成反应产生影响,研究还表明ＭｏＳｉ２－ＷＳｉ２和Ｍｏ５Ｓｉ３－Ｗ５Ｓｉ３均以固溶体的     

W-Ni-Fe系机械合金化过程中的相变及热力学和动力学研究

W,Ni,Fe粉末按照91.16W6.56Ni2.28Fe的成分配比进行机械合金化(MA)。用XRD确定物相,用TEM(JEM-2000CX型)观察微观形貌和显微结构。并对机械合金化粉末的物相、颗粒尺寸、晶格畸变作了分析讨论。MA可以使W-Ni-Fe系形成纳米晶超饱和固溶体和非晶。参照Miedema半经验理论模型,计算了该合金系的相变驱动力,热力学分析指出该合金系不存在发生非晶化反应的化学驱动力。应用固态反应模型解释了MA过程非晶形成的热力学可能性,在MA过程中,非晶的形成并不绝对要求体系ΔHmix<<0和DB>>DA