A study of nanocrystalline iron and aluminium metals and Fe3Al intermetallic by mechanical alloying

Pure iron and aluminium powders and a mixture of composition Fe₇₅Al₂₅ were treated mechanically in a high-energy mill for up to 40 h. X-ray diffraction and analytical transmission electron microscopy were coupled to elastic energy dissipation and dynamic Young's modulus measurements to study the structural transformation of the specimens induced by the mechanical treatment. A quantitative comparison between the structural behaviour of the pure elements and of the mixture was carried out. The role of the parameters such as the composition, the grain size and the activation energy during the process was examined in relation to the competing mechanisms of plastic deformation and recovery.     

Thermal and structural study of nanocrystalline Fe(Co)NiZrB alloys prepared by mechanical alloying

Three nanocrystalline alloys, Fe_75−x Co _x (Ni₇₀Zr₃₀)₁₅B₁₀ (x = 0, 10, and 20), were synthesized from elemental powders in a planetary high-energy ball mill. Their microstructure, magnetic properties, and thermal stability were characterized by X-ray diffraction, transmission M?ssbauer spectroscopy, transmission electron microscopy, scanning electron microscopy, induction coupled plasma, vibrating sample magnetometry, and differential scanning calorimetry. After 80 h of milling, the nanocrystallites size of alloys is in the range 6–10 ± 1 nm. The lattice parameter decreases when increasing (decreasing) milling time (Fe content). Furthermore, the thermal stability of the nanocrystalline phase increases when increasing Co concentration. The activation energy of the main crystallization process, between 275 ± 8 and 311 ± 10 kJ mol⁻¹, is associated with grain growth. Slight contamination from milling tools and milling atmosphere was detected. Minor differences were detected after M?ssbauer analysis.     

Nanocrystalline Al/Al12(Fe,V)3Si alloy prepared by mechanical alloying: Synthesis and thermodynamic analysis

Al–Al₁₂(Fe,V)₃Si nanocrystalline alloy was fabricated by mechanical alloying (MA) of Al–11.6Fe–1.3V–2.3Si (wt.%) powder mixture followed by a suitable subsequent annealing process. Structural changes of powder particles during the MA were investigated by X-ray diffraction (XRD). Microstructure of powder particles were characterized using scanning electron microscopy (SEM). Differential scanning calorimeter (DSC) was used to study thermal behavior of the as-milled product. A thermodynamic analysis of the process was performed using the extended Miedema model. This analysis showed that in the Al–11.6Fe–1.3V–2.3Si powder mixture, the thermodynamic driving force for solid solution formation is greater than that for amorphous phase formation. XRD results showed that no intermetallic phase is formed by MA alone. Microstructure of the powder after 60 h of MA consisted of a nanostructured Al-based solid solution, with a crystallite size of 19 nm. After annealing of the as-milled powder at 550 °C for 30 min, the Al₁₂(Fe,V)₃Si intermetallic phase precipitated in the Al matrix. The final alloy obtained by MA and subsequent annealing had a crystallite size of 49 nm and showed a high microhardness value of 249 HV which is higher than that reported for similar alloy obtained by melt spinning and subsequent milling.     

Grain growth and recrystallization of nanocrystalline Al3Ti prepared by mechanical alloying

The grain sizes and lattice strains during mechanical alloying of Ti-75 at.% Al powder mixtures were studied using X-ray diffraction methods. Nanocrystalline L1₂-Al₃Ti was obtained after a certain time period of ball milling. Minimum grain sizes of 17 nm for Al and 28 nm for Ti have been determined using XRD. During subsequent thermal annealing processing, an obvious recrystallization resulting in significant reduction of grain size was observed. The recrystallization in nanocrystalline Al₃Ti was affected by both the temperature and the degree of order. The incubation period for recrystallization at 400°C was about 6 hours while those at 510 and 700°C were about 2 hours. The completion time of recrystallization in Al₃Ti at 400 and 700°C was about 15 hours and 8 hours at 510°C. It is clear that the recrystallization at 700°C was retarded as a result of the higher degree of order structure which limited the mobility of the boundaries. Phase transformation occurring within the recrystallization temperature range was observed to have little influence on the recrystallization itself. However, transformation products do have significant effects on it which is originated from the degree of order in the products. The recrystallization in this alloy system provides an excellent means to maintain the nanocrystalline microstructure during the necessary consolidation thermal cycle by decreasing the processing temperature and increasing the hold time considerably.     

Amorphization and nanocrystalline Nb3Al intermetallic formation during mechanical alloying and subsequent annealing

In this paper the formation as well as the stability of Nb₃Al intermetallic compounds from pure Nb and Al metallic powders through mechanical alloying (MA) and subsequent annealing were studied. According to this method, the mixture of powders with the proportion of Nb-25 at% Al were milled under an argon gas atmosphere in a high-energy planetary ball mill, at 7, 14, 27 and 41 h, to fabricate disordered nanocrystalline Nb₃Al. The solid solution phase transitions of MA powders before and after annealing were characterized using X-ray diffractometry (XRD). The microstructural analysis was performed using scanning electron microscopy (SEM) as well as transmission electron microscopy (TEM). The results show that in the early stages of milling, Nb(Al) solid solution was formed with a nanocrystalline structure that is transformed into the amorphous structure by further milling times. Amorphization would appear if the milling time was as long as 27 h. Partially ordered Nb₃Al intermetallic could be synthesized by annealing treatment at 850 °C for 7 h at lower milling times. The size of the crystallites after subsequent annealing was kept around 45 nm.     

Solid-state reaction in nanocrystalline Fe/SiC composites prepared by mechanical alloying

Different solid-state reactions, i.e. Fe + SiC → Fe₃C + Fe(Si), and Fe + SiC → Fe₃Si + Fe₂Si + C, were found in mechanically alloyed nanocrystalline Fe/SiC composites induced by prolonged milling or heat treatment, respectively. The solid-state reaction between nanocrystalline iron and SiC upon heating is greatly enhanced when compared with that between bulk iron and SiC. It is believed that the prolonged milling-induced reaction is related to the changed thermodynamics and kinetics while the heat-treatment-induced reaction, completed during a short time, is attributable to the changed reaction kinetics. This revised version was published online in November 2006 with corrections to the Cover Date.     

Grain growth in nanocrystalline NbAl3 prepared by mechanical alloying

Grain growth and its kinetics were studied on an intermetallic compound, NbAl₃ powder prepared by mechanical alloying of elemental Nb and Al powders for 1.8 Ms in an argon atmosphere at ambient temperature. The initial and grown grain sizes were measured from the X-ray line broadening of as-alloyed and annealed powders. Isochronal annealing of mechanically alloyed powders from 573 to 1373 K indicated that substantial grain growth occurs only in a temperature range of 1048 to 1173 K and ceases at 1273 K regardless of anneal time. Accordingly isothermal annealing of 1.8 to 18 ks was carried out at 1048, 1073 and 1098 K to obtain the grain growth kinetic that is described by In (dD/dt) = In(r_o/3) –2.0 In D where D is the measured grain size and r _o a constant. This r _o depends on temperature according to r _o=r_o exp (– Q/kT) where Q is the activation energy for grain growth, k the Boltzmann constant and T the absolute temperature. Arrhenius plots of r _o against the reciprocal of temperature yield a straight line, from whose slope the activation energy for grain growth is deduced to be 162±2 kJ mol^–1. Of significance is the fact that the ultimate grain size at 1273 K is approximately 70 nm, which will not grow by further annealing even at 1373 K.On leave from Ibaraki University, Japan.     

纳米金属间化合物Cu4Al的制备及其结构表征

采用自悬浮定向流法制备了Cu—Al合金纳米复合微粒，对样品进行TEM和XRD分析表明该纳米复合微粒主要由纳米金属间化合物Cu4Al构成，粒径分布在30—50nm之间，并结合自悬浮定向流技术的基本原理对制备过程和形成机理进行了初步研究。同时，对自悬浮定向流法制备纳米复合微粒的一般规律进行了预测。     

Synthesis and structural characterization of nanocrystalline silicon by high energy mechanical milling using Al2O3 media

High energy mechanical milling was used to fabricate nanoparticulate Si using Al₂O₃ grinding media. Two ratios of grinding media to charge of 5 and 10 were used with milling times, such as 7, 10, 13, 16, and 19 h. Morphology of the milled powders was investigated by scanning and transmission electron microscopy. Crystallinity of the milled powders was found to be preserved for all milling conditions without amorphization. Crystallite size of the milled powders was calculated from x-ray diffractograms by various methods. From morphology and crystallite size it was observed that 13 h of milling is the optimum time to produce well dispersed Si nanoparticulates. Further increase in milling duration clearly indicated agglomeration of the powders and cold welding of the crystallites for samples of both media-to-charge ratios. X-ray diffractograms and Raman spectrographs of the milled samples were used to calculate the strain induced in the materials, which indicated progressive increase in strain with milling duration. The results indicate that Al₂O₃ milling media can be used with optimized process conditions for the production of large quantities of nanoparticulate Si.     

Disordering of the Ni3Si intermetallic compound by mechanical milling

The ordered f c c intermetallic compound Ni₃Si was mechanically milled in a high-energy ball mill. The severe plastic deformation produced by milling induced transformations with increasing milling time as follows: ordered f c c disordered f c c nanocrystalline f c c. The structural and microstructural evolution with milling time was followed by X-ray diffraction, TEM, hardness tests, and differential scanning calorimetry (DSC). Complete disordering occurred at milling times of 2 h and kept the saturated H of the DSC peak in the range of estimated enthalpy even after 60 h milling. The structural development during milling of the f c c solid solution for Ni₃Si was presumably dominated by the formation and refinement of a dislocation cell structure into microcrystallites which eventually reached nanometre dimensions.     

机械合金化制备SbSn金属间化合物的研究

用机械合金化法制备SbSn金属间化合物.使用X射线衍射仪、扫描电子显微镜、透射电镜和DSC差热分析方法对Sb、Sn混合粉末经不同工艺条件合成的产物进行了分析.结果表明:机械合金化法可合成Sb-Sn金属间化合物;随着机械合金化持续进行,合金化的粉末和晶粒不断细化,晶粒内部产生很大的晶格畸变,并且球磨产生的密度和缺陷使原子扩散加快.     

NiAl-B composites with nanocrystalline intermetallic matrix produced by mechanical alloying and consolidation

Powder mixtures with equiatomic Ni–Al stoichiometry and with the addition of 5, 10, 20 and 30 vol% of boron were mechanically alloyed in a high-energy SPEX mill. Differential scanning calorimetry (DSC) was used for examination of the thermal behaviour of the milled powders. The mechanically alloyed powders and powders after DSC examinations were investigated by X-ray diffraction (XRD). For all the powder mixtures, a nanocrystalline NiAl intermetallic phase was formed during milling. With the increase of boron concentration in the mixtures, more intense refinement of the NiAl grain size during mechanical alloying was observed. Scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS) examinations showed that the produced powders have composite structure, with boron particles uniformly distributed in the nanocrystalline NiAl intermetallic matrix. The density of the composite powders decreases with the increase of boron content, following the rule of mixture.The produced powders were subjected to consolidation by hot-pressing at 800 °C under the pressure of 7.7 GPa for 180 s. The produced bulk materials were investigated by XRD, SEM and EDS as well as characterised by hardness, density and open porosity measurements. It was found that during applied consolidation process the nanocrystalline structure of the NiAl matrix was maintained. The average hardness of the bulk composite samples is in the range of 10.58–12.6 GPa, depending on boron content, increases with the increase of boron content, and is higher than that of the NiAl intermetallic reference sample (9.53 GPa). The density of the bulk composite samples is the same as that of the corresponding powders after milling, decreases with the increase of boron content and is lower than that of the NiAl reference sample. To the best of our knowledge, the NiAl-B composites with nanocrystalline intermetallic matrix have been produced for the first time.     

Synthesis and characterization of nanocrystalline Mg2CoH5 obtained by mechanical alloying

The stoichiometric mixture of 2MgH₂ + Co was ball milled under a hydrogen atmosphere to synthesize nanocrystalline metal hydride Mg₂CoH₅. Upon milling, the mixture was analyzed by X-ray powder diffraction (XRD) and thermal methods employing the techniques of differential scanning calorimetry (DSC), thermogravimetry (TG) and differential thermal analysis (DTA). Hydrogen absorption and desorption measured by pressure-composition-temperature (P-C-T) curves indicated that the capacity loss was small after 20 consecutive cycling tests. The enthalpies associated with hydride formation and decomposition were measured to be –69.5 and –83.2 kJ mol^–1 H₂, respectively. At the temperatures of this study (553 to 653 K), hysteresis decreases with increasing temperature.     

Synthesis of nanocrystalline alloys and intermetallics by mechanical alloying

Nanocrystalline Al₃Ni, NiAl and Ni₃Al phases in Ni-Al system and theα, β, γ, ɛ and deformation induced martensite in Cu-Zn system have been synthesized by mechanical alloying (MA) of elemental blends in a planetary mill. Al₃Ni and NiAl were always ordered, while Ni₃Al was disordered in the milled condition. MA results in large extension of the NiAl and Ni₃Al phase fields, particularly towards Al-rich compositions. Al₃Ni, a line compound under equilibrium conditions, could be synthesized at nonstoichiometric compositions as well by MA. The phases obtained after prolonged milling (30 h) appear to be insensitive to the starting material for any given composition > 25 at.% Ni. The crystallite size was finest (∼ 6 nm) when NiAl and Ni₃Al phases coexisted after prolonged milling. In contrast, in all Cu-Zn blends containing 15 to 85 at.% Zn, the Zn-rich phases were first to form, and the final crystallite sizes were coarser (15–80 nm). Two different modes of alloying have been identified. In case of NiAl and Al₃Ni, where the ball milled product is ordered, as well as, the heat of formation (ΔH _f) is large (> 120 kJ/mol), a rapid discontinuous mode of alloying accompanied with an additive increase in crystallite size is detected. In all other cases, irrespective of the magnitude of ΔH _f, a gradual diffusive mode of intermixing during milling seems to be the underlying mechanism of alloying.     

The preparation of Al2O3/M (Fe,Co, Ni) nanocomposites by mechanical alloying and the catalytic growth of carbon nanotubes

Mechanical alloying was employed to produce Al₂O₃/M (M=Fe, Co, Ni) nanocomposites. It was found that high-energy mechanical milling could realize not only drastic refinement but also the well dispersion of catalyst precursors in oxide matrixes. After mechanical milling, the solid-state alloying and the accelerated substitutional reactions were observed between the parent oxides. The as-obtained Al₂O₃/M nanocomposites possessed the fine-grained and porous structures and thus high reducibility. Large-scale formation of multiwalled and single-walled carbon nanotubes were achieved by using these mechanical alloying-derived Al₂O₃/M nanocomposites.     

Al-Permalloy (Ni71.25Fe23.75Al5) obtained by mechanical alloying. The influence of the processing parameters on structural,microstructural, thermal,and magnetic characteristics

A new alloy, permalloy alloyed with aluminum, has been obtained by mechanical alloying using elemental powders as raw materials. The new alloy was obtained in powder form by adding an amount of 5 wt% of Al to permalloy (75% Ni and 25% Fe, wt.%) resulting Al-Permalloy with Ni71.25Fe23.75Al5 composition. The alloy was obtained using different ball to powder ratio (BPR): 4:1, 8:1 and 17:1 and keeping the rest of the mechanical alloying/milling parameter constant. The BPR influences the time required for the alloy synthesis and alloy characteristics. The time required for alloy synthesis as FCC single phase varies from 4 h when using a BPR of 17:1 to 8 h when using a BPR of 4:1. A more compact cubic structure is obtained when using a BPR of 8:1. The particles are flattened for all BPRs used, but upon changing the BPRs particles shape is changing and become more or less flattened. Large particles have been obtained when using BPRs of 4:1 and 17:1 and finer particles when using a BPR of 8:1. Curie temperature of the Al-Permalloy is depending on synthesis conditions varying from 478 °C to 501 °C. The higher saturation magnetization has been found when using a BPR of 8:1. The powder characteristics evolution upon increasing the milling time for all three BPRs is discussed in the light of X-ray diffraction, scanning electron microscopy, energy dispersive X-ray spectrometry, differential scanning calorimetry, particles size analyses and magnetic investigation.     

Synthesis of nanocrystalline (Co, Ni)Al2O4 spinel powder by mechanical milling of quasicrystalline materials

In the present study, attempts have been made to synthesize the nano-crystalline (Co, Ni)Al2O4 spinel powders by ball milling and subsequent annealing. An alloy of Al70Co15Ni15, exhibiting the formation of a complex intermetallic compound known as decagonal quasicrystal is selected as the starting material for mechanical milling. It is interesting to note that this alloy is close to the stoichiometry of aluminum and transition metal atoms required to form the aluminate spinel. The milling was carried out in an attritor mill at 400 rpm for 40 hours with ball to powder ratio of 20 : 1 in hexane medium. Subsequent to this annealing was performed in an air ambience for 10, 20, and 40 h at 600 degrees C in side the furnace in order to oxidize the decagonal phase and finally to form the spinel structure. The X-ray diffraction (XRD) and transmission electron microscopy (TEM) confirmed the formation of nano-sized decagonal phase after milling and then (Co, Ni)Al2O4 spinel type phase after annealing. The XRD studies reveal the lattice parameter to be 8.075 angstroms and the lattice strain as 0.6%. The XRD and TEM explorations of spinel phase indicate the average grain size to be approximately 40 nm.