Phase transformations in nanocrystalline alloys synthesized by mechanical alloying

The effect of nanometer grain size and extensive grain boundary regions in nanocrystalline alloy systems was investigated for the chemical order-disorder, structural, precipitation, and spinodal phase transformations. The kinetic paths for approach to the chemically ordered phase from the disordered phase in FeCo-Mo alloys were observed to be the same at different temperatures due to grain boundaries acting as short-circuited diffusion paths for atom movements. The structure of Fe₃Ge was bcc for small crystallite size and the equilibrium fcc phase developed only after a critical grain size was attained. This was understood as a manifestation of the Gibbs Thomson effect. The precipitation phase transformation in Fe-Mo alloys proceeded by a rapid movement and clustering of the Mo atoms to the grain boundaries that was correlated to the size of the nano grains, and subsequent formation of the Mo rich lambda phase directly in the grain boundary regions. The composition fluctuation domains for spinodal decomposition in nanophase Fe-Cr alloys were observed to be linearly correlated to the growth of grains.     

Properties and in vivo investigation of nanocrystalline hydroxyapatite obtained by mechanical alloying

Mechanical alloying has been used successfully to produce nanocrystalline powders of hydroxyapatite (HA) using three different procedures. The milled HA was studied by X-ray diffraction, Infrared, Raman scattering spectroscopy and Scanning Electron Microscopy (SEM). We obtained HA with different degrees of crystallinity and time of milling. The grain size analysis through SEM and XRD shows particles with dimensions of 36.9, 14.3 and 35.5 nm (for (R1), (R2) and (R3), respectively) forming bigger units with dimensions given by 117.2, 110.8 and 154.4 nm (for (R1), (R2) and (R3), respectively). The Energy-Dispersive Spectroscopy (EDS) analysis showed that an atomic ratio of Ca/P=1.67, 1.83 and 1.50 for reactions (R1), (R2) and (R3), respectively. These results suggest that the R1 nanocrystalline ceramic is closer to the expected value for the ratio Ca/P for hydroxyapatite, which is 5/3≅1.67. The bioactivity analysis shows that all the samples implanted into the rabbits can be considered biocompatible, since they had been considered not toxic, had not caused inflammation and reject on the part of the organisms of the animals, during the period of implantation. The samples implanted in rabbits had presented new osseous tissue formation with the presence of osteoblasts cells.     

Microstructure correlated electrical conductivity of Manganese alloyed nanocrystalline cubic zirconia synthesized by mechanical alloying

Fully stabilized cubic (c) ZrO₂ phase has been synthesized by mechanical alloying (MA) the stoichiometric powder mixture of elemental Mn (5–20 mol%) and monoclinic (m) ZrO₂ at room temperature. XPS study reveals that major part of metallic Mn is ionized to Mn²⁺ oxidation state during MA. Mn-alloyed c-ZrO₂ nanoparticles with ～18 nm particle size have been synthesized within 10 h of MA. Microstructures of the compounds have been precisely evaluated by analyzing the X-ray powder diffraction patterns employing Rietveld refinement and transmission electron microscopy images. A decrease in lattice parameter from 5.11 Å to 5.09 Å is correlated with an increase in oxygen vacancy from 14% to 26% with increasing Mn concentrations. Elemental compositions in the compounds are obtained from electron probe microanalysis. The role of Mn alloying in the polymorphic phase transformation (m → c) has been established with changes in structure and microstructure parameters. Electrical conductivities of all c-ZrO₂ compounds are measured in the temperature range 350–550 °C. Grain and grain boundary contributions to total conductivity are calculated from frequency dependent real and imaginary impedance. Conductivity of Mn alloyed c-ZrO₂ increases with increasing temperature and Mn concentrations. Electrical transport mechanism in the compound is studied by impedance and modulus spectroscopy. The relaxation frequency is found to be temperature, microstructure and composition dependent.     

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.     

Synthesis of nanocrystalline magnetite by mechanical alloying of iron and hematite

The synthesis of magnetite has been studied by mechanical alloying in an inert atmosphere of a stoichiometric mixture of micrometric particle size iron and hematite powders. The final products have been characterised by chemical analysis, SEM, TEM, XRD, Mössbauer spectroscopy as well as specific surface and magnetic measurements. The magnetite obtained in this way exhibits a high magnetic hardness. The formation of a wüstite layer on the magnetite core, because of the reaction between magnetite and iron contamination coming from the bowls and grinding balls, tends to decrease the coercive force of magnetite. The formation of this phase would be avoided by controlling the grinding time.     

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.     

Alloying behaviour in nanocrystalline materials during mechanical alloying

The alloying behaviour in a number of systems such as Cu-Ni, Cu-Zn, Cu-Al, Ni-Al, Nb-Al has been studied to understand the mechanism as well as the kinetics of alloying during mechanical alloying (MA). The results show that nanocrystallization is a prerequisite for alloying in all the systems during MA. The mechanism of alloying appears to be a strong function of the enthalpy of formation of the phase and the energy of ordering in case of intermetallic compounds. Solid solutions (Cu-Ni), intermetallic compounds with low ordering energies (such as Ni₃Al which forms in a disordered state during MA) and compounds with low enthalpy of formation (Cu-Zn, Al₃Nb) form by continuous diffusive mixing. Compounds with high enthalpy of formation and high ordering energies form by a new mechanism christened as discontinuous additive mixing. When the intermetallic gets disordered, its formation mechanism changes from discontinuous additive mixing to continuous diffusive one. A rigorous mathematical model, based on iso-concentration contour migration method, has been developed to predict the kinetics of diffusive intermixing in binary systems during MA. Based on the results of Cu-Ni, Cu-Zn and Cu-Al systems, an effective temperature (T _eff) has been proposed that can simulate the observed alloying kinetics. TheT _eff for the systems studied is found to lie between 0·42–0·52T ₁.     

Discharge properties of Mg2Ni-Ni alloy synthesized by mechanical alloying

The electrochemical characteristics of Mg₂Ni-Ni alloys prepared by mechanical alloying (MA) using a planetary ball mill were investigated. The discharge capacity depends on the molar ratio in Ni andMg₂Ni, and it has a maximum value of about 480 mAh/g at the equimolar ratio of Ni/Mg₂Ni. This discharge capacity (480 mAh/g) is about 74% of the theoretical one. The discharge capacity is reduced to about half within five cycles. Thus, the cycle time would be improved by inhibiting the oxidation of Mg₂Ni.     

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.     

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.     

Synthesis of nanocrystalline NiAl over a wide composition range by mechanical alloying

The paper reports the synthesis of nanocrystalline NiAl by mechanical alloying of pure metal mixture and a mixture of prealloyed powder with Ni/Al. A large number of compositions have been studied to establish the phase field of NiAl in the milled state. The phase field of NiAl in the ball milled condition was found to be much wider (10–68 at.% Ni) than its equilibrium phase field (45–59 at.% Ni). The metastable equilibrium achieved by mechanical alloying was identical for a given composition irrespective of the starting ingredients. The crystallite size of NiAl reached a minimum (5 nm) at the phase boundary of NiAl/Ni₃Al.     

Low temperature synthesis of nanocrystalline Sb2Te3 by mechanical alloying

Sb₄₀Te₆₀ thermoelectric compound was fabricated via mechanical milling of bismuth and tellurium as starting materials. Effects of the milling time and heat treatment were investigated. X-ray diffraction (XRD) was used for the characterization of the ball-milled powders. Thermal behavior of the mechanically alloyed powders was studied by differential thermal analysis (DTA) and the morphological evolutions were monitored by scanning electron microscopy (SEM). Results showed that the reaction between Sb and Te initiated after 5 h of milling and completed after 10 h. The synthesized Sb₂Te₃ had anisotropic property with the mean grain size of 13 nm at the end of milling. Also this compound could not be formed during heating by DTA at low temperatures (<500 °C). Under the sintering conditions the maximum values of electrical conductivity and power factor were found to be 860 (Ω cm)⁻¹ and 45 (μW cm⁻¹ K⁻¹), respectively.     

新型纳米晶FexC系软磁合金粉末的制备及磁性研究

用机械球磨方法(MA)制备纳米晶FexC系软磁合金粉末(其中x=1、3、4、8),球磨时间分别为60、120、180、255、300h.用X-ray衍射谱分析样品的物相及其晶格结构,用振动样品磁强计测量粉末样品的磁性.对不同球磨时间而言,发现当球磨时间在小于120h范围内,随着球磨时间的增加,样品的软磁特能不断提高,当球磨时间达120h时,材料有最佳的软磁特能,对不同球磨成分而言,随着C含量减少(Fe含量的增加),其磁性能进一步提高,当x=8时,材料的饱和磁化强度σs达178.24emu/g,矫顽力降为1.76kA/m.其优良的软磁特性可与传统的FeNi、FeCo合金粉末相比.当球磨时间大于120h,样品的软磁性能开始变差.从X-ray衍射谱的分析可看出,这是由于样品发生了相变,从单相体心立方结构的α-Fe(C)固溶体向FeC金属间化合物转变.x=1的样品,经255h球磨后,样品成为单相Fe5C2金属间化物,它具有单斜晶体结构.这说明随着球磨时间的增加,材料由软磁性向硬磁性转化.同时发现样品随C含量增加时材料的抗氧化能力也提高了.并对上述实验结果进行了讨论.     

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.     

Overview of processing of nanocrystalline hydrogen storage intermetallics by mechanical alloying/milling

The objective of this article is to overview processes of mechanical alloying/milling (MA/MM), and their modifications applied to produce nanostructured single- and multi-phase intermetallics, and their composites, for hydrogen storage. In the most typical processing, MA is used as a preliminary step in synthesizing a nanostructured intermetallic powder starting from elemental metal powders. In a subsequent step, the intermetallic powder is hydrogenised under high pressure of hydrogen to produce nanostructured intermetallic hydride. A modified processing variant combines the synthesis of nanostructured intermetallic and its subsequent hydrogenising in one step by MA of elemental metal powders directly under hydrogen atmosphere to form nanostructured intermetallic hydrides (so-called Reactive Mechanical Alloying—RMA). The MM can be applied to produce nanostructured intermetallic powders from pre-alloyed intermetallic cast ingots or to manufacture nanocomposites, by mixing with dissimilar material before milling, which could be hydrogenised in a separate process. In addition, pre-alloyed bulk intermetallics can be mechanically milled directly under hydrogen atmosphere (Reactive Mechanical Milling—RMM) in order to obtain nanostructured intermetallic hydrides as a final product. All the above processes are critically discussed in the present article. The effect of nanostructurization on the hydrogen sorption/desorption characteristics of intermetallics and/or their hydrides is also discussed.     

Parametric optimization of NiFe2O4 nanoparticles synthesized by mechanical alloying

In this study, the Taguchi robust design method is used for optimizing ball milling parameters including milling time, rotation speed and ball to powder weight ratio in the planetary ball milling of nanostructured nickel ferrite powder. In fact, the current work deals with NiFe₂O₄ nanoparticles mechanochemically synthesized from NiO and Fe₂O₃ powders. The Taguchi robust design technique of system optimization with the L9 orthogonal array is performed to verify the best experimental levels and contribution percentages (% ρ) of each parameter. Particle size measurement using SEM gives the average particle size value in the range of 59–67 nm. X-ray diffraction using Cu Kα radiation is also carried out to identify the formation of NiFe₂O₄ single phase. The XRD results suggest that NiFe₂O₄ with a crystallite size of about 12 nm is present in 30 h activated specimens. Furthermore, based on the results of the Taguchi approach the greatest effect on particle size (42.10 %) is found to be due to rotation speed followed by milling time (37.08 %) while ball to powder weight ratio exhibits the least influence.     

纳米晶W-Cu合金粉体的冷压成形研究

研究了纳米晶Ｗ－Ｃｕ微粉在模压及冷等静压工艺下成形特性的对比,试验证明６００ＭＰａ压力下,冷等静压工艺较模压工艺获得的坏体致密度高于１５％,但冷等静压工艺中的包套除气对坯体致密及性能有较大的影响。