Study of nanocrystalline and amorphous powders prepared by mechanical alloying

The process of mechanical alloying consists of intimate mixing and mechanical working of elemental powders in a high-energy ball mill. It has been well established that this process is able to produce nanocrystalline and amorphous material. In this study, the structural effects of mechanical alloying of pure Fe, Fe₅₀W₅₀ and Fe₅₀Mo₅₀ powders were investigated by X-ray diffraction and Mössbauer spectroscopy. For all cases, nanocrystalline and/or amorphous fractions were found after milling. The resulting particle size was determined by X-ray diffraction. Pure Fe does not amorphize even after prolonged milling times. For the nanocrystalline powder, significant changes in the linewidth and the hyperfine field are found. Powder mixtures of Fe₅₀Mo₅₀ and Fe₅₀W₅₀ are completely amorphous after milling times of 10 h, as seen by Mössbauer spectroscopy, but nanocrystalline fractions of the non-iron part are still found in X-ray diffraction. Also in the amorphous state, further changes in the hyperfine parameters are found with increasing milling time.     

Hexaferrite magnetic materials prepared by mechanical alloying

The structure and properties of hexaferrites in the form of MFe₁₂O₁₉ with M = Ba, Sr and Pb prepared by mechanical alloying and heat treatment have been studied. Coercivities of 6–7 kOe were measured for Ba- and Sr-hexaferrite powders. The high values of coercivities have been associated with small particle sizes ( 0.1 μm) resulting from the mechanical alloying and subsequent heat treatment. High-coercivity anisotropic samples have been synthesized using hot-pressing, with remanences of 70–75% of the saturation magnetisation being obtained.     

Optical properties of hydroxyapatite obtained by mechanical alloying

Calcium phosphate based bioceramics, mainly in the form of hydroxyapatite (HA), have been in use in medicine and dentistry for the last 20 years. Applications include coatings of orthopaedic and dental implants, alveolar ridge augmentation, maxillofacial surgery, otolaryngology, and scaffolds for bone growth and as powders in total hip and knee surgery. These materials exhibit several problems of handling and fabrication, which can be overcome by mixing with a suitable binder. In this paper, mechanical alloying has been used successfully to produce nanocrystalline powders of HA using five different experimental procedures. The milled HA were studied by X-ray powder diffraction, infrared and Raman scattering spectroscopy. For four different procedures, HA was obtained after a couple of hours of milling (on an average, 20 h of milling depending on the reaction procedure). The XRD patterns indicate that the grain size is within the range of 29-103 nm. This milling process, used to produce HA, presents the advantage that melting is not necessary and the powder obtained is nanocrystalline with extraordinary mechanical properties. The material can be compacted and transformed in solid ceramic samples. The high efficiency of the process opens a way to produce commercial amount of nanocrystalline HA. Due to the nanocrystalline character of this powder, their mechanical properties have changed and for this reason a pressure of 1 GPa is enough to shape the sample into any geometry.     

Hyperfine interactions, structure and magnetic properties of nanocrystalline Co–Fe–Ni alloys prepared by mechanical alloying

Mechanical alloying method was used to prepare nanocrystalline Co₅₀Fe₄₀Ni₁₀, Co₅₂Fe₂₆Ni₂₂ and Co₆₅Fe₂₃Ni₁₂ alloys. X-ray diffraction proved that during milling Co–Fe-based solid solution with b.c.c. lattice was formed in the case of Co₅₀Fe₄₀Ni₁₀, while for Co₅₂Fe₂₆Ni₂₂ and Co₆₅Fe₂₃Ni₁₂ compositions Co–Ni-based solid solutions with f.c.c. lattice were obtained. Mössbauer spectroscopy revealed similar values of the average hyperfine magnetic fields for all alloys, e.g. 32.17, 32.24 and 31.21 T for Co₅₀Fe₄₀Ni₁₀, Co₅₂Fe₂₆Ni₂₂ and Co₆₅Fe₂₃Ni₁₂ alloys, respectively. Magnetization measurements allowed to determine the effective magnetic moment, Curie temperature, saturation magnetization and coercive field for the obtained alloys.     

Magnetic and magnetotransport properties of nanocrystalline Ag0.85Fe0.15 and Ag0.70Fe0.30 alloys prepared by mechanical alloying

The magnetic and magnetotransport properties of nanocrystalline Ag_0.85Fe_0.15 and Ag_0.70Fe_0.30 alloys have been studied by Mössbauer spectroscopy, magnetization and resistivity measurements. The samples were prepared by mechanical alloying of Fe and Ag powders in a high-energy ball mill. Mössbauer spectroscopy and magnetic measurements of the final milled samples indicate the presence of single-domain ‘Fe’ particles. The magnetoresistance values, at 4.2 K and for a magnetic field of 8 T, are 2.5% and 5.7% for samples Ag_0.85Fe_0.15 and Ag_0.70Fe_0.30, respectively. The magnetoresistance behavior indicates the cluster-glass-like features in both the final milled samples.     

Structure and magnetic properties of nanocrystalline Fe75Si25 powders prepared by mechanical alloying

Nanocrystalline Fe₇₅Si₂₅ powders were prepared by mechanical alloying in a planetary ball mill. The evolution of the microstructure and magnetic properties during the milling process were studied by X-ray diffraction, scanning electron microscope and vibrating sample magnetometer measurements. The evolution of non-equilibrium solid solution Fe (Si) during milling was accompanied by refinement of crystallite size down to 10 nm and the introduction of high density of dislocations of the order of 10¹⁷ m⁻². During the milling process, Fe sites get substituted by Si. This structural change and the resulting disorder are reflected in the lattice parameters and average magnetic moment of the powders milled for various time periods. A progressive increase of coercivity was also observed with increasing milling time. The increase of coercivity could be attributed to the introduction of dislocations and reduction of powder particle size as a function of milling time.     

Atomic structure and magnetic properties of Cu80Co20 nanocrystalline compound produced by mechanical alloying

Direct observation of the atomic structure of the mechanically alloyed Cu₈₀Co₂₀ compounds has been made using the field ion microscope (FIM). Phase composition, defect structure and morphology of material on the atomic scale have been determined. It has been established that the studied material is chemically inhomogeneous, presenting a mixture of two main phases: heterogeneous solid solution of cobalt in copper, and pure cobalt. Phase volume ratios, particle and cluster sizes have been estimated. An evaluation of Co content in Cu---Co solid solution has been made. The width of interfaces in this mechanically alloyed material was revealed to be at least twice the width of phase boundaries in metals and alloys. Superparamagnetism of the compound studied at elevated temperatures and saturation magnetization deficit at low temperatures are discussed on the basis of the above-mentioned structural data.     

Evolution of structure, microstructure and hyperfine properties of nanocrystalline Fe50Co50 powders prepared by mechanical alloying

Nanostructured Fe₅₀Co₅₀ powders were prepared by mechanical alloying of Fe and Co elements in a vario-planetary high-energy ball mill. The structural properties, morphology changes and local iron environment variations were investigated as a function of milling time (in the 0-200 h range) by means of X-ray diffraction, scanning electron microscopy (SEM), energy dispersive X-ray analysis and ⁵⁷Fe Mössbauer spectroscopy. The complete formation of bcc Fe₅₀Co₅₀ solid solution is observed after 100 h milling. As the milling time increases from 0 to 200 h, the lattice parameter decreases from 0.28655 nm for pure Fe to 0.28523 nm, the grain size decreases from 150 to 14 nm, while the meal level of strain increases from 0.0069% to 1.36%. The powder particle morphology at different stages of formation was observed by SEM. The parameters derived from the Mössbauer spectra confirm the beginning of the formation of Fe₅₀Co₅₀ phase at 43 h of milling. After 200 h of milling the average hyperfine magnetic field of 35 T suggests that a disordered bcc Fe-Co solid solution is formed.     

Vibrational properties of nanograins and interfaces in nanocrystalline materials

The vibrational dynamics of nanocrystalline Fe(90)Zr(7)B(3) was studied at various phases of crystallization. The density of phonon states (DOS) of the nanograins was separated from that of the interfaces for a wide range of grain sizes and interface thicknesses. The DOS of the nanograins does not vary with their size and down to 2 nm grains still closely resembles that of the bulk. The anomalous enhancement of the phonon states at low and high energies originates from the DOS of the interfaces and scales linearly to their atomic fraction.     

The effects of the finest grains on the mechanical behaviours of nanocrystalline materials

This article proposes a new constitutive model to account for effects of the finest grains, with sizes ranging from 2 to 4 nm, on the mechanical behaviours of nanocrystalline (NC) materials. In this model, the normal nanograins (ranging from 20 to 100 nm) were treated as though they were composed of a grain interior (GI) and a grain boundary (GB) affected zone (GBAZ). The finest grains were considered to be part of the GBAZ, denoted as super triple junctions (STJs). For the initial plastic deformation stage of the NC materials, a phenomenological constitutive equation was suggested to predict the deformation behaviours of the GBAZ. The formation of GB dislocation (GBD) pileups provides dramatic strain hardening in deformed NC materials and thereby enhances their ductility. Then, the constitutive equations to describe the plastic deformation of the GI and the GBAZ lattice region were established. In this stage, the GBAZ are already saturated with GBD pileups, and GI deformation is the dominant mechanism. Finally, the mechanical model for the NC materials with the finest grains was built using the self-consistent method, and an overall moderate “work hardening,” sustained over a long range of plastic strain, was predicted. The effects of TJs/STJs on the deformation mechanism were quantitatively analysed. The analysis demonstrated that the existence of the finest grains will simultaneously lead to good strength and good ductility.     

Structural and magnetic properties of nanocrystalline bismuth manganite obtained by mechanochemical synthesis

We have studied the formation of BiMnO3 (BMO) nanocrystalline perovskite powder produced by high-energy milling of the constituent oxides. The crystal structure and the amount of crystalline and amorphous phases in the powder as a function of the milling time were determined with XRPD using Rietveld refinement. BMO perovskite formed directly from highly activated nano-sized constituent oxides after 240 min of milling and subsequently grew during prolonged milling. The morphology, structure, and chemical composition of the powder were investigated by SEM and TEM. A clear ferromagnetic transition was observed at T _C ~66 K for a sample milled for 240 min and increased with milling time. The magnetic hysteresis behavior is similar to that of a soft ferromagnet. The magnetic properties of the obtained BMO powders were found to change as a function of milling time in a manner consistent with variations in the nanocomposite microstructure.     

Magnetic and magnetotransport properties of nanocrystalline (Fe2B)0.20X0.80 (X=Ag or Cu) alloys prepared by mechanical alloying

The magnetic and magnetotransport properties of nanocrystalline (Fe₂B)_0.20X_0.80 (X=Ag or Cu) alloys have been studied by Mössbauer, magnetization and magnetoresistance (MR) techniques. The samples were prepared by mechanical alloying the nanostructured Fe₂B alloy and Ag or Cu chemical elemental powders in a high-impact mill machine. The Mössbauer spectroscopy and magnetic measurements of as-milled (Fe₂B)_0.20Ag_0.80 and annealed (Fe₂B)_0.20Cu_0.80 alloys indicate the presence of small Fe and Fe₂B magnetic particles. The magnetoresistance curves of (Fe₂B)_0.20X_0.80 (X=Ag or Cu) alloys show a non-saturated behavior, an indication of a spin-glass-like state generated by the magnetic coupling between these magnetic particles. The non-saturated effect is more pronounced in the alloy with Ag, where the MR values decrease linearly with the external magnetic field, even at 7 T. The magnetoresistance values, at 4.2 K and for a magnetic field of 7 T, are 4.0% and 4.5%, for (Fe₂B)_0.20Ag_0.80 and (Fe₂B)_0.20Cu_0.80 samples, respectively.     

Measuring mechanical properties of ferromagnetic materials by internal induction

The voltage which is generated during the reversal of the magnetization inside the ferromagnetic specimen itself is measured. This internally produced voltage is sensitive to external forces and internal stresses. The method is compared with the application of strain gages.     

Physical-mechanical properties of nanocrystalline materials based on ultrafine-dispersed diamonds

The physical-mechanical properties of polycrystals produced on the basis of ultrafine-dispersed diamonds (UDDs) at high static pressures with the use of thermal treatment in vacuum are investigated. The properties of the polycrystals are shown to depend on the sintering conditions and sintering technique, as well as on the modification of the starting powders. With the addition of metals (Co, Ti) to UDD powders, the mechanical strength of compacts increases, their structure improves, and their parameters can be optimized at lower thermobaric treatment temperatures. By studying the products of thermal treatment of UDDs in vacuum, it is established that the compacts and individual particles that form during thermal treatment differ significantly in microhardness.     

Fe-doped TiO2 prepared by mechanical alloying

The effect of different milling conditions on the formation of Fe-doped TiO₂ powders by mechanical alloying was investigated by Mössbauer spectrometry. The milling conditions investigated were ball to powder weight ratio, milling time, rotation velocity of supporting disc, and the type of starting reactive iron and its concentration. X-ray diffraction shows that high energy mechanical milling of undoped anatase TiO₂ induce the anatase to rutile phase transformation via high pressure srilankite. Mössbauer spectra for the majority of the doped samples were decomposed into one sextet and one or two doublets. The sextets was attributed to the presence of α-Fe or hematite impurities. The doublets were assigned to Fe^3?+? incorporated in the TiO₂ structure, and to the Fe^2?+? located either at the surface or the interstitial sites of TiO₂. A greater incorporation of Fe in the TiO₂ structure was observed when samples were prepared from hematite instead of α-Fe.     

Microstructure and mechanical properties of nano-Y2O3 dispersed ferritic steel synthesized by mechanical alloying and consolidated by pulse plasma sintering

Ferritic steel with compositions 83.0Fe–13.5Cr–2.0Al–0.5Ti (alloy A), 79.0Fe–17.5Cr–2.0Al–0.5Ti (alloy B), 75.0Fe–21.5Cr–2.0Al–0.5Ti (alloy C) and 71.0Fe–25.5Cr–2.0Al–0.5Ti (alloy D) (all in wt%) each with a 1.0?wt% nano-Y₂O₃ dispersion were synthesized by mechanical alloying and consolidated by pulse plasma sintering at 600, 800 and 1000°C using a 75-MPa uniaxial pressure applied for 5?min and a 70-kA pulse current at 3?Hz pulse frequency. X-ray diffraction, scanning and transmission electron microscopy and energy disperse spectroscopy techniques have been used to characterize the microstructural and phase evolution of all the alloys at different stages of mechano-chemical synthesis and consolidation. Mechanical properties in terms of hardness, compressive strength, yield strength and Young's modulus were determined using a micro/nano-indenter and universal testing machine. All ferritic alloys recorded very high levels of compressive strength (850–2850?MPa), yield strength (500–1556?MPa), Young's modulus (175–250?GPa) and nanoindentation hardness (9.5–15.5?GPa), with up to 1–1.5 times greater strength than other oxide dispersion-strengthened ferritic steels (<1200?MPa). These extraordinary levels of mechanical properties can be attributed to the typical microstructure of uniform dispersion of 10–20-nm Y₂Ti₂O₇ or Y₂O₃ particles in a high-alloy ferritic matrix.     

Effect of isothermal treatments on the magnetic behavior of nanocrystalline Cu–Ni–Fe alloy prepared by mechanical alloying

The present study concerns magnetic behavior of nanocrystalline Cu–Ni, Cu–Fe and Cu–Ni–Fe alloys prepared by mechanical alloying. It has been found that the magnetic properties e.g. H_c, M_r and M_s of the nanocrystalline alloys were significantly influenced by the changes in microstructural constituents, grain size and evolution of phases. Microstructural changes in the alloys have been effected by carrying out isothermal treatments on the mechanically alloyed products in the temperature range of 450–650 °C. Phase evolution in the samples after the isothermal treatments were identified and characterized by X-ray diffraction (XRD) and differential scanning calorimetric (DSC) techniques and the results were correlated with the magnetic properties of the alloys.     

Formation of Ni3Fe by mechanical alloying

Ni and Fe powders in a 7525 atomic proportion were mechanically alloyed using a high-energy ball mill.⁵⁷Fe Mössbauer measurements were made to determine the reaction mechanism for alloy formation by means of analysis of the evolution of the Fe hyperfine fields during milling. After a latent period of 2 hours, the spectral area of an Fe-like component decreased monotonically with milling time, disappearing after 8 hours. It was replaced by a well-resolved Zeeman pattern with hyperfine fieldH=29.1 T and outer lines of width 0.75 mm/s which is attributed to Fe in disordered Ni₃Fe. The evolution of hyperfine fields rules out alloy formation by dissolution of Ni in the Fe matrix or of Fe in the Ni matrix, so that formation must occur by reaction of Ni and Fe at the interfaces between their grains.     

Structural and magnetic properties of Co2CrAl Heusler alloys prepared by mechanical alloying

Mechanical alloying has been used to produce nanocrystalline samples of Co₂CrAl Heusler alloys. The samples were characterized by using different methods. The results indicate that, it is possible to produce L2₁-Co₂CrAl powders after 15 h of ball-milling. The grain size of 15 h ball milled L2₁-Co₂CrAl Heusler phase, calculated by analyzing the XRD peak broadening using Williamson and Hall approach was 14 nm. The estimated magnetic moment per formula unit is ∼2 μ_B. The obtained magnetic moment is significantly smaller than the theoretical value of 2.96 μ_B for L2₁ structure. It seems that an atomic disorder from the crystalline L2₁-type ordered state and two-phase separation depresses the ferromagnetic ordering in alloy. Also, the effect of annealing on the structural and magnetic properties of ball milled powders was investigated. Two structures were identified for annealed sample, namely L2₁ and B2. The obtained value for magnetic moment of annealed sample is smaller than the as-milled sample due to the presence of disordered B2 phase and improvement of phase separation.