Difference between mechanical alloying and mechanical disordering in the amorphization reaction of Al50Ta50 in a rod mill

Amorphous Al₅₀Ta₆₀ alloy powders have been synthesized by mechanical alloying (MA) from elemental powders of aluminium and tantalum, and mechanical disordering (MD) from crystalline intermetallic compound powders of AlTa respectively using the rod milling technique. The mechanically alloyed and the mechanically disordered alloy powders were characterized by X-ray diffraction, scanning electron microscopy, electron probe microanalysis, transmission electron microscopy, differential thermal analysis, differential scanning calorimetry and chemical analysis. The results have shown that the crystal-to amorphous transformation in the MD process occurs through one stage, while the crystallineto-amorphous formation in the MA process occurs through three stages. At the early and intermediate stages of the MA time, heating the alloy powders to 700 K leads to the formation of an amorphous phase by a solid-state amorphizing reaction. At the final stage of the MA time, the amorphous phase is crystallized through a single sharp exothermic peak. Contrary to this, amorphous alloy powders produced by MD are crystallized through two broad exothermic peaks.     

Mechanical alloying characteristic and thermal stability of Al<Subscript>78</Subscript>Fe<Subscript>20</Subscript>Zr<Subscript>2</Subscript> amorphous powders

The powders of pure Al, Fe, and Zr for preparing Al₇₈Fe₂₀Zr₂ were subject to a high-energy planetary ball milling. The microstructure evolution of the mixtures at the different intervals of milling was characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and differential scanning calorimetry (DSC). It was found that a nearly complete amorphization could be achieved in the mixtures after ball milling for 23 h. Further ball milling led to the crystallization of the amorphous powders. A long time ball milling, e.g., 160 h, led to a complete crystallization of the amorphous powders and the formation of Al₃Zr and Al1₃Fe₄. The crystallization products caused by ball milling are almost the same as that produced by isothermal annealing of the amorphous powders in vacuum at 800 K for 1 h.     

Mechanochemical synthesis of Al2O3-TiB2 nanocomposite powder from Al-TiO2-H3BO3 mixture

Alumina-titanium diboride nanocomposite (Al₂O₃-TiB₂) was produced using mixtures of titanium dioxide, acid boric and pure aluminum as raw materials via mechanochemical process. The phase transformation and structural characterization during mechanochemical process were utilized by X-ray diffractometry (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and thermogravimetric analyses (TG-DTA) techniques. A thermodynamic appraisal showed that the reaction between TiO₂, B₂O₃ and Al is highly exothermic and should be self-sustaining. XRD analyses exhibited that the Al₂O₃-TiB₂ nanocomposite was formed after 1.5 h milling time. The results indicate that increasing milling time up to 40 h had no significant effect other than refining the crystallite size.     

Structural and Mössbauer studies on mechanical milled SmCo5/α-Fe nanocomposite magnetic powders

The SmCo₅/α-Fe nanocomposite powders were prepared by high energy ball milling and the inter-diffusion reaction between the SmCo₅ and α-Fe magnetic phases were investigated by X-ray diffraction (XRD), transmission electron microscopy (TEM), vibrating sample magnetometry (VSM) and ⁵⁷Fe Mössbauer spectroscopy. While structural and magnetic measurements could reveal only the presence of SmCo₅ and α-Fe phases, Mössbauer studies could clearly specify the extent of alloying between Fe and Co atoms in terms of evolution of α-Fe(Co) phase as a function of milling time. It has been found that the fractional volume of α-Fe(Co) solid solution tends to increase at the expense of the initial α-Fe phase upon progressive milling.     

Structural, microstructural and magnetic properties of amorphous/nanocrystalline Ni63Fe13Mo4Nb20 powders prepared by mechanical alloying

This paper focuses on the magnetic, structural and microstructural studies of amorphous/nanocrystalline Ni₆₃Fe₁₃Mo₄Nb₂₀ powders prepared by mechanical alloying. The ball-milling of Ni, Fe, Mo and Nb powders leads to alloying the element powders, the nanocrystalline and an amorphization matrix with Mo element up to 120 h followed by the strain and thermal-induced nucleation of a single nanocrystalline Ni-based phase from the amorphous matrix at 190 h. The results showed that the saturation magnetization decreases as a result of the electronic interactions between magnetic and non-magnetic elements and finally increases by the partial crystallization of the amorphous matrix. The coercive force increases as the milling time increases and finally decreases due to sub-grains formation.     

Magnetic and structural studies of mechanically alloyed (Fe50Co50)62Nb8B30 powder mixtures

Amorphous (Fe₅₀Co₅₀)₆₂Nb₈B₃₀ powder mixture was prepared by mechanical alloying from elemental Fe, Co, B and Nb powders in a planetary ball mill under argon atmosphere. Structural, thermal and magnetic properties were performed on the milled powders by means of X-ray diffraction, differential scanning calorimetry and magnetic measurements. The amorphous state is reached after 125 h of milling. The excess enthalpy due to the high density of defects is released at temperature below 300 °C. Crystallisation and growth of crystal domains are the dominating processes at high temperatures. The saturation magnetisation decreases rapidly during the first 25 h of milling to about 15.24 A m²/kg and remains nearly constant on further milling. Coercivity, H_c, value of about 160 Oe is obtained after 125 h of milling.     

Mechanical alloying characteristic and thermal stability of Al_(78)Fe_(20)Zr_2 amorphous powders

The powders of pure Al, Fe, and Zr for preparing Al78Fe20Zr2 were subject to a high-energy planetary ball milling.The microstructure evolution of the mixtures at the different intervals of milling was characterized by X-ray diffraction(XRD), transmission electron microscopy(TEM) and differential scanning calorimetry(DSC).It was found that a nearly complete amorphization could be achieved in the mixtures after ball milling for 23 h.Further ball milling led to the crystallization of the amorphous powders.A long time ball milling, e.g., 160 h, led to a complete crystallization of the amorphous powders and the formation of Al3Zr and Al13Fe4.The crystallization products caused by ball milling are almost the same as that produced by isothermal annealing of the amorphous powders in vacuum at 800 K for 1 h.     

A comparative study of mechanical alloying and mechanical milling of Nd8Fe88B4

A comparative study was made of structure and magnetic properties of Nd₈Fe₈₈B₄ prepared by mechanical alloying (MA) using elemental powders as starting materials and by mechanical milling (MM) of the alloy. X-ray diffraction (XRD) and differential scanning calorimetry (DSC) combined with transmission electron microscopic (TEM) studies revealed that both milling procedures resulted in a mixture of α-Fe and an amorphous phase. The thermal stability of the as-milled powders produced by MA was comparable to that of the as-milled powders produced by MM. Heat treatment of the milled powders above the crystallization temperature resulted in the formation of a nanocrystalline mixture of Nd₂Fe₁₄B and α-Fe, but annealed MA powders demonstrated a somewhat coarser structure in comparison with annealed MM powders. Therefore, higher remanences and coercivities were obtained by MM.     

Structural and magnetic properties of nanostructured Fe50(Co50)-6.5 wt% Si powder prepared by high energy ball milling

This work investigates the effects of 6.5 wt% Si addition and milling times on the structural and magnetic properties of Fe₅₀Co₅₀ powders. For this purpose, at first the elemental Fe and Co powders were milled for 10 h to produce Fe₅₀Co₅₀ alloy and then Si was added and the new product was milled again for different times. The microstructural and magnetic properties were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM) and vibrating sample magnetometer (VSM). The results show that the minimum crystallite size of the as-milled powders (∼12 nm) has been achieved after introducing Si and milled for 8 h (total milling time of 18 h). Also an amount of 188 emu/g has been achieved for M_s. This amount of M_s is higher than most of those which have been already reported for M_s of different Fe-Si systems.     

Microstructural evolution of nanostructured Ti0.9Al0.1N prepared by reactive ball-milling

Nanocrystalline stoichiometric Ti_0.9Al_0.1N powder has been prepared by ball-milling the α-Ti (hcp) and aluminum (fcc) powders under N₂ at room temperature. Initially, α-Ti phase partially transformed to the transient cubic β-Ti phase and Ti_0.9Al_0.1N (fcc) phase is noticed to form after 3 h of milling. Nanocrystalline stoichiometric Ti_0.9Al_0.1N phase is formed after 7 h of milling. After 1 h of milling, all Al atoms are diffused into the α-Ti matrix. The transient β-Ti phase is noticed to form after 1 h of milling and disappears completely after 7 h of milling. Microstructure characterization of unmilled and ball-milled powders by analyzing XRD patterns employing the Rietveld structure refinement reveals the inclusion of Al and nitrogen atoms into the Ti lattice on the way to formation of Ti_0.9Al_0.1N phase. Microstructure of ball-milled samples is also characterized by HRTEM. The particle size of Ti_0.9Al_0.1N phase, as obtained from XRD method, is ∼5 nm which is very close to that obtained from HRTEM.     

Kinetics and formation mechanism of amorphous Fe52Nb48 alloy powder fabricated by mechanical alloying

A single phase amorphous Fe₅₂Nb₄₈ alloy has been synthesized through a solid state interdiffusion of pure polycrystalline Fe and Nb powders at room temperature, using a high-energy ball-milling technique. The mechanisms of metallic glass formation and competing crystallization processes in the mechanically deformed composite powders have been investigated by means of X-ray diffraction, Mössbauer spectroscopy, differential thermal analysis, scanning electron microscopy and transmission electron microscopy. The numerous intimate layered composite particles of the diffusion couples that formed during the first and intermediate stages of milling time (0–56 ks), are intermixed to form amorphous phase(s) upon heating to about 625 K by so-called thermally assisted solid state amorphization, TASSA. The amorphization heat of formation for binary system via the TASSA, ΔH_a, was measured directly as a function of the milling time. Comparable with the TASSA, homogeneous amorphous alloys were fabricated directly without heating the composite multilayered particles upon milling these particles for longer milling time (86 ks–144 ks). The amorphization reaction here is attributed to the mechanical driven solid state amorphization. This single amorphous phase transforms into an order phase (μ phase) upon heating at 1088 K (crystallization temperature, T_x) with enthalpy change of crystallization, ΔH_x, of −8.3 kJ mol⁻¹.     

Microwave-assisted combustion synthesis in a mechanically activated Al-TiO2-H3BO3 system

The Al₂O₃-TiB₂ in-situ composite has been fabricated by different techniques. In this work, the mechanical activation process has been used to aid microwave-assisted combustion synthesis (MACS) to produce the Al₂O₃-TiB₂ in-situ composite. For this purpose, the thermite mixture of Al, TiO₂ and boric acid (H₃BO₃) powders was used as the raw materials, and was mechanically activated at different milling speeds. The results of X-ray phase analysis of the mechanically activated samples after combustion synthesis showed that the Al₂O₃-TiB₂ in-situ composite has been successfully fabricated by thermal explosion mode of combustion synthesis in microwave, while no combustion synthesis occurred for the unmilled sample. Also, it was found that by increasing the milling speed from 250 to 400 rpm, the purity of the final products has been increased; while further milling speed up to 550 rpm reduced the purity of the final products. The effects of milling speed were also studied by means of differential scanning calorimetry (DSC) measurements. It was shown that by increasing the energy level of the reactants via milling speed, the ignition temperature and the intensity of exothermic peaks in the DSC curves have been changed. Finally, in order to have a good understanding about the in-situ formation of such ceramic composites, a reaction mechanism was proposed based on the experimental results. The synthesized composite exhibited high microhardness value of about 1950 Hv in dense parts.     

The synthesis of nanocrystalline Ni75Nb12B13 alloys by high energy ball milling of elemental components

Ni₇₅Nb₁₂B₁₃ alloys were synthesized by mechanical alloying (MA) of individual Ni, Nb and B components. X-ray investigation showed the formation of Ni (Nb, B) solid solution and amorphous phase at the intermediate stage of milling. Metastable phases formed by MA turned into Ni (Nb), Ni₂₁Nb₂B₆ and Ni₃Nb stable phases during heating up to 720 °C. The exothermal effects on DSC curves were caused with these processes. The disintegration of Ni (Nb, B) solid solution and crystallization of an amorphous phase resulted in the stable phases formation during the milling prolongation as well as after thermal treatment.     

Influence of partial substitution of Ge on crystallization kinetics, microstructure and magnetic property of Fe44Co44−xZr7B5Gex alloys

Partial substitution of Ge for Co in Fe₄₄Co₄₄Zr₇B₅ amorphous alloy is found to have a large influence on crystallization kinetics and magnetic property of the alloy. Activation energy of nanocrystallization of FeCo phase (primary crystallization) decreases by 90 kJ/mol with 4 at.% Ge substitution, while that of precipitations of Zr-type phase from a residual amorphous phase (secondary crystallization) increases by 106 kJ/mol. The suppression of the secondary crystallizations stabilizes the FeCo nanocrystals embedded in the residual amorphous phase for the Fe₄₄Co_44−xZr₇B₅Ge_x until higher temperatures. It is proposed that the stabilization mechanism is attributed to preferential partitioning of Ge in the residual amorphous phase revealed by scanning transmission electron microscopy analysis. Microstructure and coercivity for the annealed alloys are also presented in combination with the effect of the Ge substitutions.     

Formation and magnetic properties of nanocrystalline Fe60Co40 alloys produced by mechanical alloying

The Fe₆₀Co₄₀ alloys were prepared by mechanical alloying of the Fe and Co powders using a high-energy ball mill. They were studied with respect to phase formation and magnetic properties using x-ray diffraction, scanning electron microscopy, and measurements of coercivity and remanence (B _r). The evaluation of Fe lattice parameters during milling showed that formation of a body-centered cubic solid solution occurred by mechanical alloying after 12 h of milling. Intensive milling of Fe-Co powders results in a nonequilibrium microstructure characterized by grain refinement to a minimum of 10–13 nm and the introduction of internal strain up to 0.5%.     

Effects of milling and crystallization conditions on microstructure of Nd2Fe14B/α-Fe powder

Effects of milling and crystallization conditions on microstructure,such as amorphous phase and nanocrystalline phase, were investigated by X-ray diffractometry(XRD),differential scanning calorimetry(DSC),and transmission electron microscopy (TEM),respectively.The results show that nanocomposite Nd2Fe14B/α-Fe powder can be prepared by mechanical milling in argon atmosphere and a subsequent vacuum annealing treatment.The grain sizes of both Nd2Fe14B andα-Fe phase decrease drastically with increasing milling time.After milling for 5 h,the as-milled material consists ofα-Fe nanocomposite phases with the grain size of 10 nm,and some amorphous phases,which can be turned into Nd2Fe14B/α-Fe nanocomposite phases by the subsequent annealing treatment.Milling energy of mechanical milling after 5 h by theoretical calculation is 6 154.25 kJ/g.     

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.     

Mechanochemical synthesis of nanocrystalline ZnWO4 at room temperature

Single nanocrystalline ZnWO₄ powders were successfully synthesized by ball milling at room temperature. A stoichiometric mixture of ZnO and WO₃ in a 1:1 molar ratio was subjected to intense mechanical treatment in air using a planetary ball mill (Fritsch - Premium line - Pulversette No. 7) for a period varying from 5 to 300 min. The influence of the four different milling conditions was investigated on the formation of ZnWO₄. The products obtained were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), Brunauer-Emmer-Teller (BET) surface area, infrared (IR) spectroscopy and X-ray photoelectron spectroscopy (XPS). The synthesis of ZnWO₄ powder started after 5 min milling time and finished after 30 min milling time at a higher speed (1000 rpm). The mechanical treatment up to 300 min did not lead to phase and structure change of ZnWO₄. The product obtained contained nanoparticles with a size of about 50 nm. The photocatalytic activity of the ZnWO₄ powders obtained was investigated by degradation of a model aqueous solution of Malachite Green (MG) upon UV-light irradiation.     

Microstructural, thermal and magnetic properties of amorphous/nanocrystalline FeCrMnN alloys prepared by mechanical alloying and subsequent heat treatment

Amorphous FeCrMnN alloys were synthesized by mechanical alloying (MA) of the elemental powder mixtures under a nitrogen gas atmosphere. The phase identification and structural properties, morphological evolution, thermal behavior and magnetic properties of the mechanically alloyed powders were evaluated by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), differential scanning calorimetry (DSC) and vibrating sample magnetometer (VSM), respectively. According to the results, at the low milling times the structure consists of the nanocrystalline ferrite and austenite phases. By progression of the MA process, the quantity and homogeneity of the amorphous phase increase. At sufficiently high milling times (>120 h), the XRD pattern becomes halo, indicating complete amorphization. The results also show that the amorphous powders exhibit a wide supercooled liquid region. The crystallization of the amorphous phase occurs during the heating cycle in the DSC equipment and the amorphous phase is transformed into the crystalline compounds containing ferrite, CrN and Cr₂N. The magnetic studies reveal that the magnetic coercivity increases and then decreases. Also, the saturation magnetization decreases with the milling time and after the completion of the amorphization process (>120 h), the material shows a paramagnetic behavior. Although the magnetic behavior does not considerably change by heating the amorphous powders up to the crystallization temperature via DSC equipment, the material depicts a considerable saturation magnetization after the transformation of the amorphous phase to the nanocrystalline compounds.     

Synthesis, structural and magnetic characterization of nanocrystalline nickel ferrite—NiFe2O4 obtained by reactive milling

Nanocrystalline nickel ferrite (NiFe₂O₄) has been synthesized from a stoichiometric mixture of oxides NiO and α-Fe₂O₃ in a high energy planetary mill. An annealing at 350 °C, after milling, was used to improve the solid state reaction. The obtained powders were investigated by X-ray diffraction, magnetic measurements, scanning electron microscopy, X-ray microanalysis and differential scanning calorimetry. The particles size distribution was analyzed using a laser particle size analyser. The nickel ferrite begins to form after 4 h of milling and continuously form up to 16 h of milling. The obtained nickel ferrite has many inhomogeneities and a distorted spinel structure. The mean crystallites size at the final time of milling is 9 ± 2 nm and the lattice parameter increases with increase the milling time. DSC measurements revealed a large exothermic peak associated with cations reordering in the crystalline structure. The magnetization of the obtained powder depends on the milling time and annealing. After the complete reaction between the starting oxides the milling reduces the magnetization of the samples. The magnetization increases after annealing, due to the reorganization of the cations into the spinel structure.