Recovery of electroluminescence by ageing of ball milled powders

The paper studies the influence of ageing on the electroluminescence of ball milled powders of zinc sulphide and it is shown that partial recovery of the electroluminescence (EL) brightness of ball milled samples occurs. The EL brightness of a non-milled sample did not change with ageing. The recovery of EL ball milled samples is explained by the recovery of the EL barriers by diffusion of the copper ions which were dispersed over the crystallites of the EL powders by ball milling.     

Preparation and investigation of magnetic properties of MnNiTi-substituted strontium hexaferrite nanoparticles

A series of M-type strontium hexaferrite powders with substitution of Mn²⁺, Ni²⁺ and Ti⁴⁺ ions for Fe³⁺ ions according to the formula SrFe₉(Mn_0.5−xNi_xTi_0.5)₃O₁₉, where x ranges from 0 to 0.5 with a step of 0.1, has been prepared via the conventional ceramic method. In order to get nanoparticles, the obtained powders were milled in a high energy SPEX mill for 1 h. XRD investigations of the unmilled and milled powders show that the prepared samples are all single phase hexaferrite. Lattice parameters and mean crystallite sizes of the powders were determined from the XRD data and Scherrer’s formula. Transmission electron microscope (TEM) was used to analyze their structures. Room temperature magnetizations and coercivities of the samples in a magnetic field of 15 kOe have been determined from the hysteresis loops. It was found that magnetizations of the milled samples were smaller than the magnetization of the unmilled samples. This decrease, based on core-shell model, has been attributed to the presence of a magnetically dead layer on the particles’ surface of the milled powders. In addition, the magnetizations of the milled samples decrease with the increase in x value. This decrease has been discussed according to site occupation of the substituted cations on the sublattices. The discussion also supports the increase of lattice parameters and the decrease of Curie temperature as x increases.     

The effect of La-substitution on magnetic properties of nanosized Sr1−xLaxTi0.05Zn0.2(Fe)11.75−δ(Fe)δO19 powders

A series of La-substituted M-type Sr hexaferrite powders Sr_1−xLa_xTi_0.05Zn_0.2Fe³⁺_11.75O₁₉, wherein x ranges from 0.1 to 0.5 with a step of 0.1, have been prepared by the conventional ceramic method and were then milled in a high energy mill to prepare nanosized powders. XRD investigation of the calcined and the milled powders shows that single phase hexaferrite structure has been formed after calcining and has not changed after milling. The lattice parameters and the mean crystallite sizes of the samples have been determined from the XRD data and Scherrer's formula. The results show that the lattice parameters (“а” and “c”) decrease with increase in La-substitution and the mean crystallite size of the milled powders is about 17 nm. Coercivities and magnetizations of the samples in a magnetic field of 16 kOe have been determined from the room temperature hysteresis loops. It was found that both parameters increase with La substitutions up to 0.3 and then decrease for higher substitutions. These variations were attributed to the enhancement of hyperfine field and spin-canting magnetic structure when La content increases. In addition, the magnetizations were smaller for the nanosized samples in comparison with those of bulk ones, which were discussed according to the core-shell model. Also the results show that annealing of the nanosized samples up to 500 °C can enhance coercivity and magnetization of the samples, which is discussed based on crystallite size growth.     

Use of the helium medium for preparation of nano-sized powder materials by the example of industrial cement

Based on the phenomenon of the mechanodynamic diffusion of particles of the external medium in solids, a new in principle method has been proposed for the first time for producing nano-sized powder materials using industrial cement milled in a helium medium as an example. The temperature dependences of the extraction rate and the amount of helium in powders upon their heating in a temperature range of 20–1200°C have been obtained using mass spectrometry. It has been shown that milling of the cement powder of the M-400 brand using an MK-1 laboratory mill in helium leads to a considerable shift of its extraction curve towards lower temperatures compared with the air medium. The particle sizes of the powder milled in helium lie in a range of 5–10 nm, which is smaller than the powder size (～500 nm) after milling in the air medium by a factor of 100. The compression strength of cement samples obtained from the powders milled in helium increased by a factor of 2 compared with the strength of the samples from the initial material. The activation energies of helium extraction from the cement powders milled in helium and in air have been analyzed. The obtained results indicate a high efficiency of the method for producing nano-sized powder materials in the helium medium. The method can be used in the industrial scale based on the existing mill equipment with its minimal modernization.     

Investigating the magnetic properties of soft magnetic composites based on mechanically alloyed nanocrystalline Fe-5 wt% Ni powders

In this work, the soft magnetic composites (SMCs) of the nanocrystalline Fe-5 wt% Ni powders coated with phenolic resin were studied. The nanocrystalline powders with an average diameter of 10 nm were obtained by mechanical alloying up to 96 h milling in a high-energy planetary ball mill. The microstructure and magnetic properties of the milled powders were characterized by X-ray diffraction, energy dispersive X-ray spectroscopy and a vibrating sample magnetometer. The results of X-ray diffraction showed that the bcc Fe(Ni) solid solution is formed after 24 h milling. Magnetic measurements indicated that the 96 h milled powders with a steady-state grain size of 10 nm have the highest saturation magnetization and the lowest coercivity. The SMCs based on nanocrystalline powders showed higher electrical resistivity and magnetic permeability up to 1 MHz, as compared with the pure iron-based composites. Besides, the nanocrystalline-based SMCs exhibited higher relaxation frequency and a significantly lower loss factor up to 1 MHz.     

Mössbauer spectroscopic studies of Fe-20 wt.% Cr ball milled alloy

Interesting differences were noticed in the alloying process during ball milling of Fe-10 wt.% Cr and Fe-20 wt.% Cr alloys by ⁵⁷Fe Mössbauer spectroscopic studies. In both cases, there is almost no diffusion of Fe in Cr or vice versa up to 20 h of milling time. As the powders are milled for another 20 h substantive changes occur in the Mössbauer spectra showing atomic level mixing. But the two compositions behave differently with respect to alloying. Fe-20 wt.% Cr sample does not differ much in the hyperfine field distribution as it is milled from 40 to 100 h. On the other hand, the hyperfine field distribution keeps on changing with milling time for Fe-10 wt.% Cr sample even up to 100 h of milling. The average crystallite size is found to be 7.5 nm for Fe-10 wt.% Cr and 6.5 nm in Fe-20 wt.% Cr after milling.     

等离子壁材料钨基纳米粉末的制备

用机械合金化的方法制备了可为等离子壁材料的W-30%TiC(体积百分数)纳米复合粉末。用BET N2吸附法测量了球磨前后复合粉末的比表面,用激光粒度仪测量复合粉末的粒径分布,用X射线衍射分析了粉末的晶粒尺寸,用SEM观察了球磨前后粉末形貌。研究结果表明,W-TiC粉末的最佳球磨参数为：球磨介质比约2:1,球料比约10:1,球磨转速约200r•min^-1,球磨时间约25h。     

Hysteresis losses of magnetic nanoparticle powders in the single domain size range

Magnetic iron oxide nanoparticle powders were investigated in order to optimise the specific hysteresis losses for biomedical heating applications. Different samples with a mean particle size in the transition range from superparamagnetic to ferromagnetic behaviour (i.e. 10–100 nm) were prepared by two different chemical precipitation routes. Additionally, the influence of milling and annealing on hysteresis losses of the nanoparticles was investigated. Structural investigations of the samples were carried out by X-ray diffraction, measurement of specific surface area, and scanning and transmission electron microscopy. The dependence of hysteresis losses of minor loops on the field amplitude was determined using vibrating sample magnetometry and caloric measurements. For small field amplitudes, a power law was found which changes into saturation at amplitudes well above the coercive field. Maximum hysteresis losses of 6.6 J/kg per cycle were observed for milled powder. For field amplitudes below about 10 kA/m, which are especially interesting for medical and technical applications, hysteresis losses of all investigated powders were at least by one order of magnitude lower than reported for magnetosomes of comparable size.     

Characterization of nanocrystalline FeSiCr powders prepared by ball milling

FeSi₁₀Cr₁₀ powder was mechanically alloyed by high energy planetary ball milling, starting from elemental powders. The microstructural and magnetic properties of the milled powders were characterized by scanning electron microscopy, X-ray diffraction, ⁵⁷Fe Mössbauer spectrometry and a vibratory sample magnetometer.After 3 h of milling, the formation of two bcc solid solutions α-Fe₁ (Si, Cr) and α-Fe₂ (Si, Cr) is observed. Their grain sizes decrease with increase in milling time attaining, at 15 h of milling, 23 and 11 nm, respectively. Mössbauer spectra of the milled powder show the presence of two components. One is a ferromagnetic type with a broad sextuplet. Its distribution of hyperfine field is characterized by high and low hyperfine field’s peaks and a mean value of 26.5 T. The other is a single paramagnetic peak. Its low concentration increases to ∼4% at 15 h of milling. These results can be explained by different atomic environments affected by Si or/and Cr elements, as well as the increased disordered grain boundaries.Magnetic measurements of the milled FeSi₁₀Cr₁₀ alloy powder exhibit a soft ferromagnetic character with a decrease of both magnetization at saturation (Ms) and coercive force (Hc) with milling time attaining values of Ms=151 emu/g and Hc=2500 A/m at 30 h of milling time.     

Development of magnetic softness in high-energy ball milling alloyed Fe50B50

Results are reported about the phase distribution and magnetic properties of high-energy ball milled samples prepared from pure Fe and B powders and having nominal equiatomic composition. After milling the precursor powders for times from 40 to 270 h, the milling product consists of a majority amorphous phase and of milling-time-dependent small percentages of α-Fe, Fe₂B and FeB. The coercivities measured in the as-milled samples were of the order of thousands of A/m and decreased to tens of A/m after a short time; low temperature treatments decreased the coercivity. We propose that this softening process is linked to a combination of stress relaxation and of enhancement of the exchange coupling between the minority crystalline phases and amorphous matrix, this last fact leading to the elimination of hindrances to the domain wall motion.     

Radioluminescence of Lu2O3:Eu nanocrystalline powder and vacuum-sintered ceramic

Nanocrystalline powders of Lu₂O₃:Eu with the activator content varying in the range of 0.2–10% were prepared through a combustion technique. The powders were only slightly agglomerated and the size of crystallites were about 30 nm. Some of the powders were co-doped with Mg, Ca, Sr, Ba, La of various concentrations. Such powders were cold-pressed and sintered at 1750°C for 5 h in vacuum. X-ray-excited luminescence spectra of both the powders and the sintered ceramics were recorded and the efficiency was compared to the commercial standard Gd₂O₂S:Pr,Ce,F X-ray phosphor. It was found that the nanocrystalline powders of Lu₂O₃:Eu,Ca emit photons four-times less than the commercial micron-sized Gd₂O₂S:Pr,Ce,F powder. In the case of sintered materials the emission efficiency from our Lu₂O₃:Eu5%, Ca was roughly equal to the efficiency of the commercial-sintered Gd₂O₂S:Pr,Ce,F. The co-doping ions were shown to have various effects on the transparency of the sintered Lu₂O₃:Eu. Mg hindered the sintering process producing completely opaque pellets. Other ions facilitated the sintering course and the best results were obtained by co-doping the samples with 0.5% of Ba. Sr and La also significantly stimulated the sintering and the final pellets were only slightly cloudy.     

Effect of mechanical milling on the magnetic properties of garnets

Rare earth garnets after milling to nanosizes are found to decompose into rare earth orthoferrite and other rare earth and iron oxide phases. The magnetization for the yttrium iron garnet decreases in the nano state due to the formation of antiferromagnetic phases. But for the gadolinium iron garnet when milled up to 25 h, the room temperature magnetization increases despite the formation of antiferromagnetic and non-magnetic phases. This is attributed to the uncompensated moments of the sublattices because of the weakening of the superexchange interaction due to change in bond angles and the breaking of some superexchange bonds on account of the defects and oxygen vacancies introduced on milling. For the 10 h milled gadolinium iron garnet at 5 K, after correcting for the non-magnetic phases present, there is an increase in the magnetic moment of about 10% as compared to the value for the as-prepared garnet. The magnetic hyperfine fields corresponding to the various phases were measured using ⁵⁷Fe Mössbauer spectroscopy at 16 K. The isomer shift values indicate the loss of oxygen for the samples milled for larger duration.     

X-ray diffraction and Mössbauer studies of X20Cr13 steel subjected to ball milling

The powders of X20Cr13 steel were subjected to ball milling process in a planetary ball mill. X-ray diffraction and Mössbauer spectroscopy studies revealed the refinement of the structure of this steel down to a nanocrystalline range practically without any phase transformations. Both techniques allowed to detect the alloyed ferrite as well as residual content of iron containing M₂₃C₆-type carbide, which was dissolved into the ferrite during milling. Hyperfine magnetic fields in ball milled steel samples did not differ significantly from those for the bulk steel disc.     

Defects induced ferromagnetism in Mn doped ZnO

Single phase Mn doped (2 at%) ZnO samples have been synthesized by the solid-state reaction technique. Before the final sintering at 500 °C, the mixed powders have been milled for different milling periods (6, 24, 48 and 96 h). The grain sizes of the samples are very close to each other (～32±4 nm). However, the defective state of the samples is different from each other as manifested from the variation of magnetic properties and electrical resistivity with milling time. All the samples have been found to be ferromagnetic with clear hysteresis loops at room temperature. The maximum value for saturation magnetization (0.11 μ_B/Mn atom) was achieved for 96 h milled sample. Electrical resistivity has been found to increase with increase in milling time. The most resistive sample bears the largest saturation magnetization. Variation of average positron lifetime with milling time bears a close similarity with that of the saturation magnetization. This indicates the key role played by open volume vacancy defects, presumably zinc vacancies near grain surfaces, in inducing ferromagnetic order in Mn doped ZnO. To attain optimum defect configuration favorable for ferromagnetism in this kind of samples proper choice of milling period and annealing conditions is required.     

A structural,magnetic and microwave study on mechanically milled Fe-based alloy powders

Fe₉₀M₁₀ powders with M=Fe, Co, Ni, Si, Al, Gd, Dy and Nd were prepared by mechanical milling. Their structure and magnetic properties were investigated. Microwave measurements were performed on the mechanically milled Fe₉₀M₁₀ powders. The results were compared with those of carbonyl Fe powders and coarse Fe powder. It has been shown that fine nanocrystalline Fe-based alloy powders prepared by mechanical milling are promising for microwave applications.     

High-Energy Ball Milling of NiAl(Fe) System

High-energy ball milling was used to promote the solubilization of iron into NiAl powder for an iron concentration range of 10–30 wt.%. The microstructural evolution induced by the intense mechanical deformations, under different milling conditions, was followed by X-ray diffraction and Mössbauer spectroscopy. The Mössbauer spectra are dominated by a magnetic sextet of about 33 T. Increasing the time and the speed of milling gives rise to a non-resolved doublet, having parameters typical of a NiAl compound with Fe atoms in solution. At the same time a reduction of lattice parameter occurs, which can be correlated to composition variations and partial disordering of the NiAl structure. Subsequent annealing modifies the Mössbauer spectra noticeably. In particular, the non-magnetic component becomes a broad singlet. Both diffraction analysis and Mössbauer spectroscopy indicate that a fcc Ni(Al,Fe) solid solution is forming in samples milled in agate. It is observed that the grain size of the milled products remains in the nanometric range even after thermal treatment, which adds interest to possible applications.     

Structural and Mössbauer studies of nanocrystalline Mn<Superscript>4+</Superscript>-doped Li<Subscript>0.5</Subscript>Fe<Subscript>2.5</Subscript>O<Subscript>4</Subscript> particles prepared by mechanical milling

The structure and magnetic properties of spinel-related Mn⁴⁺-doped Li_0.5Fe_2.5O₄ nanocrystalline particles of the composition Li_0.5Fe_2.25Mn_0.1875O₄, prepared by milling a pristine sample for different times, were investigated. The average crystallite and particle size, respectively, decreased form ～40 nm to ～10 nm and ～2.5 μm to ～10 nm with increasing milling time from 0 h to 70 h. Rietveld refinement of the XRD data of the non-milled sample show the Mn⁴⁺ dopant ions to substitute for Fe³⁺ at the octahedral B-sites of the spinel-related structure. The Mössbauer spectra of the milled ferrites indicate that more particles turn superparamagnetic with increasing milling time. The Mössbauer data collected at 78 K suggest that while in the non-milled sample the Mn⁴⁺ ions substitute for Fe³⁺ at the octahedral B-sites, this is reversed as milling proceeds with doped Mn⁴⁺ ions, balancing Fe³⁺ vacancies and possibly Li⁺ ions progressively migrate to the tetrahedral A-sites. This is supported by the slight increase observed in the magnetization of the milled samples relative to that of the non-milled one. The magnetic data suggest that in addition to the increasing superparamagentic component of the milled particles, thermal spin reversal and/or spin canting effects are possible at the surface layers of the nanoparticles.     

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.     

Ball milling of Fe40Ni40P20-xSix (x = 6, 10 and 14): production and characterization

Progress in the ball milling amorphization of elemental powders with the overall composition Fe₄₀Ni₄₀P_{20 ? x}Si_x (X = 6, 10 and 14) and thermally induced crystallization of obtained alloys were characterized by differential scanning calorimetry, X-ray diffraction and transmission Mössbauer spectroscopy (TMS). Diffusion of Si into Fe and Ni alloys promotes the formation of the amorphous phase, via previous formation of (Fe, Ni) phosphides. After milling for 32–64 h, most of the powders are amorphous but bcc Fe(Si) crystallites remain (about 5% in volume). TMS results indicate that homogenization of the amorphous phase occurs by interdiffusion of Ni and Fe in Fe(Si,P)-rich and Ni(Si,P)-rich zones respectively. Annealing induces structural relaxation of stresses induced by milling, growth of bcc Fe(Si) crystallites, precipitation of bcc Fe(Si) and fcc Ni–Fe, and minor phases of Ni-rich silicides and (Fe, Ni) phosphides. The main ferromagnetic phase is bcc Fe(Si) for Fe₄₀Ni₄₀P₁₀Si₁₀ powders obtained after milling for 32 h. However, it is fcc Fe–Ni for the same alloy after milling for 64 h. In the later powders, as well as for alloys with x = 6 and 14 milled for 32 h, the fcc Fe–Ni shows the Invar magnetic collapse.     

Enhancement of electromagnetic and microwave absorbing properties of gas atomized Fe-50 wt%Ni alloy by shape modification

In order to increase the electromagnetic parameters and improve the microwave absorbing properties in the range of 1–4 GHz, gas atomized Fe-50 wt%Ni alloys with spherical form were processed in a planetary mill. The morphology, phase composition and saturation magnetization of the FeNi alloy particles were investigated by means of scanning electron microscopy, X-ray diffraction and vibrating sample magnetometer. The complex permittivity, complex permeability and reflection loss of the microwave absorbing material made from Ethylene–Propylene–Diene Monomer rubber, and the Fe-50 wt%Ni alloys were also studied using vector network analyzer and transmission line theory. The results show that the shape of the atomized Fe-50 wt%Ni powders can be modified by mechanical milling. The flaky Fe-50 wt% Ni particles were prepared, and the aspect ratio increases with increasing the milling time from 10 to 30 h. Mechanical milling does not change the phase compositions of the FeNi alloys but decreases the peak intensity and broadens the peak width. The saturation magnetization decreases and the coercivity increases as the milling time increases. The electromagnetic parameters and microwave absorbing properties are enhanced with the increase of the aspect ratio. The rubber absorbers filled with flaky Fe-50 wt%Ni powders milled for 30 h exhibit the low reflection loss in the 1–4 GHz frequency range.