机械合金化制备Al-Pb纳米相复合结构的热力学分析

参考Miedema半经验公式,建立Al-Pb系机械合金化过程的热力学模型,并对所制备的Al-10%Pb粉末进行热力学计算和对比分析。实验表明利用机械合金化方法可以获得在Al基体上均匀弥散分布着纳米相Pb的复合结构;热力学计算结果表明,Al-Pb系粉末机械合金化过程不具备形成非晶相、固溶体和中间化合物的热力学驱动力。采用X射线衍射仪(XRD)和扫描电子显微镜(SEM)分析Al-10%Pb合金在高能球磨过程中的组织结构,表明,所建立的热力学模型是正确的。     

机械合金化制备Al-10Pb纳米相复合结构的热稳定性

利用X射线衍射仪、扫描电镜和透射电镜,研究机械合金化制备的Al-10%Pb(质量分数)纳米相复合结构的热稳定性。结果表明Al-10%Pb纳米相复合结构中Pb相的长大可以用LSW理论描述。但是Pb相的长大激活能显著低于常规多晶材料中溶质原子(Pb)在溶剂基体(Al)晶格中扩散的激活能,而接近于溶剂基体(Al)的晶界自扩散激活能。这主要是由于纳米相复合结构中Pb相的长大机制与常规两相合金不同所致。在纳米相复合结构中,溶质原子的迁移以沿溶剂基体的晶界扩散为主,纳米相基体高的晶界分数可促进扩散的进行。     

Indentation creep in nanocrystalline Fe-TiN and Ni-TiN alloys prepared by mechanical alloying

Mechanical properties of nanocrystalline Fe-TiN and Ni-TiN alloys with various TiN contents between 17 and 64 vol pct, which are prepared by dynamically consolidating mechanically alloyed powders, have been investigated by means of hardness measurements and indentation creep tests at intermediate temperatures. The hardness increases with decreasing grain size to about 10 nm. The indentation creep curves conform well to an equation derived from a transient creep rate equation. The analysis of creep curves indicates that the deformation occurs by a dislocation mechanism controlled by grain boundary diffusion.     

Nb含量对机械合金化Cu-Nb合金组织与性能的影响

在金属铜粉中分别加入1.5%和6%的Nb粉(质量分数),通过机械合金化和800℃/2 h/30 MPa条件下真空热压,制备Cu-1.5%Nb和Cu-6%Nb合金,采用X射线衍射仪(XRD)、扫描电镜(SEM)、透射电镜(TEM)以及电导率与硬度测试,研究Nb含量对合金微观组织结构与性能的影响。结果表明,通过机械合金化得到的Cu-1.5%Nb和Cu-6%Nb复合粉末,Cu相平均晶粒尺寸分别约为17和13 nm。Nb含量增加有助于抑制Cu晶粒长大,热压Cu-6%Nb合金中Cu相的平均晶粒尺寸保持纳米级(65 nm),而Cu-1.5%Nb合金的Cu晶粒平均尺寸为亚微米级,约为110 nm。热压过程中脱溶析出的Nb颗粒尺寸分布为双模态,既有尺寸大于100 nm的粗大Nb粒子,也有尺寸小于10 nm的纳米Nb粒子。与Cu-1.5%Nb合金相比,Cu-6%Nb合金的显微硬度(HV)提高了112,但电导率降低约7.54×10~6 S/m。细晶强化和弥散强化是Cu-Nb合金的主要强化机制。     

Metastable nanocrystalline nickel-boron alloys obtained by mechanical alloying

Ni-B and Ni-Nb-B alloys are produced by mechanical alloying of mixtures of Ni, Nb, and B powders. X-ray diffraction analysis of the alloys indicates the formation of Ni(B) and Ni(Nb, B) solid solutions with nanocrystalline structure. The phase composition of the alloys is studied at different stages of mechanical alloying, along with the thermal stability and the phase transformations on heating.     

Origin of porosity in oxide-dispersion-strengthened alloys produced by mechanical alloying

Oxide-dispersion-strengthened (ODS) alloys produced by mechanical alloying (MA) are very prone to the occurrence of porosity. The reason for this has not been fully understood so far. In this work, a model ferritic ODS alloy has been examined by optical microscopy and scanning electron microscopy in both the powder form and the consolidated condition. Submicron-sized pores have been found in the as-mechanically alloyed powder and in the consolidated alloy. Moreover, pores can be observed in loose powder particles annealed at 1000 °C and 1100 °C. Based on these results, it has been suggested that the MA process might be largely responsible for the porosity problem in ODS alloys.     

The chemical kinetics of mechanical alloying

The chemical kinetics of a mechanically induced double displacement reaction exhibiting a self-sustaining combustion event have been investigated using differential thermal analysis. In particular, the effect of milling time on the activation energy for the reduction of cupric oxide by iron has been evaluated. It has been shown that the activation energy decreases from 575 kJ/mol at the start of milling to 199 kJ/mol at combustion. This is an indication that the rate-controlling step changes during milling from intrinsic ionic diffusion initially to diffusion down short-circuit pathways prior to combustion. It is suggested that this is dependent on the rate at which strain accumulates in milled powders and is hence a consequence of the mechanical alloying action.     

Microstructures and properties of CuZrAl and CuZrAlTi medium entropy alloys prepared by mechanical alloying and spark plasma sintering

Equiatomic CuZrAl and CuZrAlTi medium entropy alloys were designed and synthesized by mechanical alloying and spark plasma sintering technique.The alloying behavior,phase evolutions,microstructures and properties of samples were investigated by X-ray diffraction,differential scanning calorimetry,field emission scanning electron microscopy,microscopy/Vickers hardness testing and electrochemical polarization measurement.The results indicate that the final products of as-milled alloys consist of amorphous phases.Ti addition improves the glass forming ability of as-milled alloys.The as-sintered CuZrAl alloy contains face-centered cubic(fcc)solid solution,Al_(1.05)Cu_(0.95) Zr and AlZr_2 phases at different sintering temperatures.With Ti addition,the as-sintered sample is only composed of intermetallics at 690°C,while fcc1,fcc2 and CuTi3phases are formed at 1100°C.CuZrAlTi-1100°C alloy exhibits the highest hardness value of 1173HV0.2owing to the high sintering density,solid solution strengthening and homogeneous precipitation of nano-size crystalline phase.CuZrAlTi-690°C alloy presents a similar corrosion resistance with304 Lstainless steel in seawater solution and further possesses the lower corrosion rate.     

机械合金化制备β-FeSi2热电材料的研究

采用MA(Mechanical Alloying)法进行β-FeSi2热电材料的合成研究.以Fe粉(Fe>98%),Si粉(Si>99.9%)为原料,将Fe、Si 元素粉末按原子分数Fe33Si67混合,并将混合料放入高能星型球磨机进行长时间球磨.经不同的工艺进行机械合金化并取样,借助XRD、DSC等手段进行分析.研究结果表明在机械合金化大约20h以上开始形成ε-FeSi相,至机械合金化大约40h有β-FeSi2形成,随时间的延长β-FeSi2相增多.     

机械合金化Mg-LaNi5合金的研究

采用X射线衍射(XRD)、扫描电子显微镜(SEM)、差热分析(DTA)等测试方法研究了新型材料Mg-69％LaNi5(质量分数)的组织形貌及热稳定性能等。结果表明：该合金在转速为280r／min的条件下球磨250h后形成了短程有序或无序的镧、镁、镍等非晶及MgNi2纳米晶(3nm)组织；所得样品的颗粒形状主要为规则的球形或近球形，还有少量多角形等不规则形状。球磨样品在763K温度下保温35d，得到热稳定性较好的具有纳米尺度(2．5nm)的Mg2NiLa，Mg2Ni，MgNi2三相合金。     

Microstructure and strength of nanocrystalline copper alloy prepared by mechanical alloying

Polycrystalline materials having an ultrafine grain size may be prepared by mechanical alloying. Such a material has been prepared here with a copper matrix and a uniform dispersion of particles which stabilises the fine microstructure. It is shown that the grain size of the copper matrix may be explained in terms of the conventional models of boundary pinning by particles, even for grain sizes below 40 nm. For grain sizes larger than about 100 nm, material strength may be explained by dislocation-particle interactions as illustrated by TEM observations. For grain sizes below this limit, however, strengthening is not as great as dislocation theory would predict based on the distribution of particles in the material; in addition TEM observations show no indication of the presence of dislocations. A different deformation mechanism seems to control strengthening for these materials of nano-scale grain size.     

机械合金化制备TiC弥散强化440 C不锈钢复合材料

在440C高铬不锈钢粉末中分别添加25%、35%、45%(体积分数)TiC粉末,利用机械合金化球磨制备复合粉,再经过成形、真空烧结、热等静压等工艺,得到了TiC弥散强化440C不锈钢.通过对试片进行XRD、SEM和激光粒度分析以及视孔隙率、硬度和抗弯强度的测试,研究机械合金化工艺对制备弥散强化复合材料的影响.结果显示,在球磨转速为600 r/min、BPR80、温度30℃、球磨时间16 h的条件下,得到TiC粒径从90 μm降至3 μn、均匀分布在440C基体中的最佳复合粉.提高真空烧结温度,或再经热等静压处理,都可得到视孔隙率低的合金,合金的硬度与强度提高,其中添加35%TiC,1 300～1 400℃真空烧结以及热等静压处理的合金有较高的硬度与强度.     

机械合金化制备Co80Zr20非晶合金粉末

采用行星式高能球磨机，通过室温下球磨纯元素混合粉末制备出原子数分数比为Co80Zr20的非晶合金粉末。应用X射线衍射（XRD）、差示扫描量热分析仪（DSC）、扫描电镜及透射电镜对不同球磨时间的混合粉末进行了研究。结果发现，球磨时间对混合粉末的结构及颗粒形貌存在显著影响。原始混合粉末由密排六方的β-Co和α—Zr组成，经过0．5h球磨，β—Co转变为同素异构的面心立方的α—Co，随着球磨时间的增加，Co、Zr颗粒都发生严重塑性变形，并且通过冷焊团聚起来，形成具有层状结构的复合颗粒。球磨导致基体元素Co品格中的晶体缺陷密度大大增加，使得合金元素Zr原子向Co品格中扩散迁移，扩散迁移到Co晶格中的Zr原子数量随球磨时间的增加而增加，导致Co元素的品格常数单调增大。当球磨时间达到8h时，形成Co80Zr20固溶体，继续球磨至10～20h，固溶体转变为非晶。球磨20h得到的非晶粉末的玻璃化转变温度为759K，它可以在840K通过单一放热过程或者继续球磨至40h而发生晶化反应，这两种不同晶化工艺所得到的晶化产物完全相同，均为面心立方的Co23Zr6。     

机械合金化制备Ag-Cu_(28)合金过程的研究

采用机械合金化法制备Ag-Cu28二元共晶合金,通过正交试验研究球磨机转速、球料比及过程控制剂对合金化过程的影响,利用XRD、SEM、TG-DSC等方法对球磨粉料的物相组成、微观形貌、熔化特性等进行表征.结果表明:Ag、Cu经过30h球磨,生成了Ag(Cu)过饱和固溶体,其熔化温度为783.8℃,该合金属于亚稳态结构,退火处理后以富银、富铜相形式存在.合金化过程中,硬脂酸作为过程控制剂的加入可以有效地减小颗粒尺寸,但对合金化不利.     

机械合金化在Fe-Si合金制备中的应用

机械合金化是一种新的材料制备方法, 近年来在功能材料的制备中得到了广泛的应用. 该文简要回顾了机械合金化的发展历史, 阐述了机械合金化的原理及反应机制, 介绍了机械合金化技术在过饱和固溶体、非晶、纳米晶及金属间化合物等领域的应用状况. 指出机械合金化过程的热力学和动力学研究及合金相结构、性能与球磨工艺条件之间的规律是今后研究的重点, 后续处理工艺的改进是产品实现从实验室向工业应用转变的重要保证.     

Effect of alloying addition on structure and thermal stability of Ti40Al60 prepared by mechanical alloying

Ternary (Ti₄₀Al₆₀)₁₀₀−XM_X (X = 5–15 at., M = Mo, Nb) alloys have been prepared by Mechanical Alloying, and the process was monitored by X-ray diffraction technique. The effects of a third additional element have been examined concerning the alloying process, structure and phase thermal stability. As already observed in Ti₄₀Al₆₀ matrix prepared with the same conditions, an amorphous alloy was obtained at the end of the process. A different solubility of Mo (very limited) or Nb (total dissolved) into the matrix was detected. Upon thermal treatment the third element addition caused, in both cases, an increased crystallization temperature with respect to the matrix. The more detailed investigation on niobium addition (5–10 at.%) evidenced the following path for powder crystallization: amorphous-disordered Al-ordered L1₀ phase. The evolution of the long-range order parameter revealed that the disorder → order transition is favoured due to the presence of Nb, but independent of its concentration.     

Fe-Cu二元互不溶体系中纳米晶过饱和固溶体的机械合金化制备研究进展

Fe-Cu二元互不溶体系合金在机械合金化过程中形成纳米晶过饱和固溶体,并显示出与其微米尺度结构合金所不同的独特性能。综述了近年来Fe-Cu二元互不溶体系中纳米晶过饱和固溶体的机械合金化研究进展,着重介绍了Fe-Cu纳米晶过饱和固溶体的形成机理及其力学和物理性能等。     

Synthesis of Invar 36 type alloys from elemental and prealloyed powders by mechanical alloying

Invar 36 (Fe₆₄Ni₃₆) nanocrystalline powders were successfully obtained by the mechanical alloying process. The mechanically alloyed Invar 36 powders were obtained from both, Fe–Ni elemental and Fe–Ni₃Fe prealloyed powders. XRD, DSC and magnetic measurements were used to characterise the Invar 36 powders. The lattice parameter evolution versus temperature of Invar 36 powders was investigated by in-situ high-temperature X-ray diffraction (HT-XRD). For both, Invar 36 (Fe, Ni) and Invar 36 (Fe, Ni₃Fe) powders, the lattice parameter values are constant up to about 350°C. The magnetic measurement also indicated that the Invar 36-type alloys are formed after 16?h of milling.     

Effects of process-control agents on mechanical alloying of nanostructured aluminum alloys

The effects of the process-control agents (PCAs) stearic acid and methanol on the mechanical alloying (MA) of a nanostructured aluminum alloy (Al₉₃Fe₃Ti₂Cr₂) have been investigated. The dependency of the powder-particle sizes, grain sizes, atomic-level strains, lattice parameters, formation of solid solutions, and microstructural evolution of the aluminum alloy on the types of PCAs and their concentrations have been studied using a variety of analytical instruments including X-ray diffraction scanning electron microscopy, and transmission electron microscopy. The results clearly indicate that prevention of excessive cold welding of Al particles can be achieved by the addition of a PCA at the expense of reductions in the grain size, formation rate of solid solutions, and rate of microstructural refinement, all of which are desired in MA of the Al alloy. Furthermore, a PCA that is more effective in preventing excessive cold welding will also impose more hindrance to the MA process. These phenomena have been discussed in the light of the adsorption of the PCA on the metal surface and the lubricating function of the PCA.