Structural and magnetic studies of Fe2O3/SiO2 granular nanocomposites

Fe₂O₃/SiO₂ nanocomposites were synthesized by mechanical alloying, using Fe and SiO₂ powders as precursors. After 340 h milling, the sample essentially consists of hematite and amorphous silica. TEM images show hematite particles embedded in and surrounded by an amorphous silica matrix. A broad size distribution—5–50 nm—of hematite particles is found, and other group of very small—2–3 nm—unidentified particles are observed. Room temperature Mössbauer spectra show a paramagnetic doublet, which may correspond to a non-crystalline phase in the sample (probably the small unidentified particles), and a sextet corresponding to hematite. Magnetic properties were investigated by measuring hysteresis curves at different temperatures (5–300 K) and by zero-field-cooled (ZFC) and field-cooled (FC) magnetization curves (10 mT). The hysteresis loops were well fitted by a ferromagnetic contribution. No evidence of Morin transition is found down to 5 K.     

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.     

Crystallization of mechanically alloyed amorphous W-Mg alloy under high pressure

Pure metal powder mixtures of W and Mg at the desired composition were milled in conventional high-energy ball mill, and amorphous alloy W₅₀Mg₅₀ was obtained after milling for 20 h. The structure evolution of elemental powder mixtures was studied following milling and subsequent high pressure and high temperature treatment. The amorphous alloy transform into a nanocrystalline material below 1050 °C at 4.0 GPa. On increasing the temperature, it transforms into a mixture of several new crystal phases under high-pressure condition. It also found that both mechanical alloying and high pressure treatment are the two necessary processes to form the nanocrystalline and the new phases.     

Mechanical and thermal properties of a nanopowder talc compound produced by controlled ball milling

A powdered compound constituted by over the 95% of talc Mg₃Si₄O₁₀(OH)₂ with MgCO₃ and CaMg(CO₃)₂ as minor phases was mechanically deformed by compaction and shear to a nanosized particulate (crystallite size ~5 nm) in a specifically built planetary ball mill. The mechanical milling was conducted in a controlled thermodynamic environment (25 °C and 0.13 Pa) by using low mechanical load to minimise amorphisation of the material. Mechanical τ(ε) shear analysis and thermo-structural modifications of the nanostructured talc particulate were investigated after selected milling times (0, 1, 5 and 20 h). At the very early stages of milling (1 h) layer flattening, lamination and texturing of the talc particles occurred. For prolonged milling (up to 20 h), a progressive reduction of the TOT talc stacking layer coherence, from about 20–5 nm, and an increase of (001) microstrain from about 0.6–2.2 × 10⁻² nm, as a non-linear function of the treatment time, were observed. A progressive increase of the specific surface area up to 28 m²/g as a consequence of the particle size reduction took place at intermediate milling times (5 h) and reduced to about 10 m²/g at prolonged milling (20 h). Even the thermo-structural behaviour of the particulate was significantly modified. For 20-h milled talc, a severe decrease of the dehydroxylation temperature from about 900–600 °C was observed with a concomitant anticipation of the recrystallisation of talc into MgSiO₃ (enstatite). The τ(ε) behaviour of the compound was strongly affected by the milling treatment changing from a shear-softening regime (untreated and 1 h) to a shear-hardening one (20 h). The observed changes of talc are of great importance to understand the rheology and the thermal transformation kinetics of talc compounds and can be exploited in those industrial applications that required milling of talc, such as in the production of talc-polymers nanocomposites or in medium–high-temperature ceramic processes.     

Silicon nanoparticles formation in annealed SiO/SiO2 multilayers

We present a study on amorphous SiO/SiO₂ superlattice performed by grazing-incidence small-angle X-ray scattering (GISAXS). Amorphous SiO/SiO₂ superlattices were prepared by high-vacuum evaporation of 3 nm thin films of SiO and SiO₂ (10 layers each) onto Si(1 0 0) substrate. After the deposition, samples were annealed at 1100 °C for 1 h in vacuum, yielding to Si nanocrystals formation. Using a Guinier approximation, the shape and the size of the crystals were obtained. The size of the growing nanoparticles in the direction perpendicular to the film surface is well controlled by the bilayer thickness. However, their size varies more significantly in the direction parallel to the film surface.     

Microstructure characterization of mechanosynthesized nanocrystalline NiFe2O4 by Rietveld's analysis

Nanocrystalline nickel ferrite (NiFe₂O₄) is synthesized at room temperature by high-energy ball milling the stoichiometric mixture of (1:1 mol%) of NiO and α-Fe₂O₃ powders. The structural and microstructural evolution of NiFe₂O₄ caused by milling is investigated by X-ray powder diffraction. The relative phase abundance, particle size, r.m.s. strain, lattice parameter changes of different phases have been estimated employing Rietveld structure refinement analysis of X-ray powder diffraction data. Particle size and content (wt%) of both NiO and α-Fe₂O₃ phases reduce rapidly with increasing milling time and a significant amount of nanocrystalline NiFe₂O₄ is formed within 1 h of ball milling. Particle sizes of all the phases reduce to ∼10 nm within 5 h of milling and remain almost unchanged with increasing milling time up to 20 h. Lattice parameter of cubic NiO decreases linearly with increasing milling time, following the Vegard's law of solid-solution alloy. A continuous decrease in lattice parameter of cubic NiFe₂O₄ phase clearly suggests that smaller Ni atoms have occupied some of the vacant oxygen sites of ferrite lattice. Cation distribution both in octahedral and tetrahedral sites changes continuously with milling time and the normal spinel lattice formed at early stage of milling, transforms to inverse spinel lattice in the course of milling. High-resolution transmission electron microscope (HRTEM) micrographs of 11 h milled sample corroborates the findings of X-ray profile analysis.     

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.     

Mechanochemical Route for the Synthesis of Cobalt Ferrite–Silica and Iron–Cobalt Alloy–Silica Nanocomposites

CoFe₂O₄–SiO₂ and Fe–Co alloy–SiO₂ nanocomposites were prepared by high energy ball milling of Si, -Fe₂O₃, Co₃O₄ and SiO₂ mixtures, followed by thermal treatment under appropriate oxidative/reductive conditions. XRD and TEM measurements carried out after 50 h of milling show highly dispersed unidentified reaction products. Further thermal treatment at 900°C in air leads to spherical CoFe₂O₄ nanocrystals (NCs) with a narrow size distribution centered around 2.5 nm, uniformly dispersed in the amorphous SiO₂ matrix. Reduction of this sample in a H₂ flow at 800°C produces a mixture of dispersed metallic cobalt and iron silicate with traces of Fe–Co alloy NCs. Reduction of the as-milled sample, on the contrary, leads almost completely to Fe–Co alloy NCs uniformly dispersed in the SiO₂ matrix and with an average particles size around 11.2 nm.     

Application of mechanochemical treatment to the synthesis of A- and G-forms of La2Si2O7

The impact of mechanochemical treatment on a mixture of La₂O₃ and silica gel (in molar ratio La₂O₃/SiO₂=1:2) was examined by X-ray powder diffractometry, infrared spectroscopy and thermal analysis. Unlike pure La₂O₃, complete amorphization of the mixture takes place after 3-h milling. A lanthanum orthosilicate is formed in an amorphous state as a precursor of La₂Si₂O₇. Subsequent thermal treatment of the milled samples leads to the crystallization of pure A- or G-La₂Si₂O₇, depending on the temperature.     

Microwave electromagnetic property of SiO2-coated carbonyl iron particles with higher oxidation resistance

Flake carbonyl iron (CI) particles and amorphous silica were used to fabricate SiO₂-coated CI particles through the Stober process. The as-prepared SiO₂-coated CI particles were annealed at 500 °C for 1 h under argon and air atmosphere. The XRD results showed that only a little amount of oxides were formed when the SiO₂-coated CI particles were annealed under the air atmosphere. The magnetic properties of the SiO₂-coated CI particles before and after annealing treatment showed little change, indicating that amorphous silica appears to be very effective in reducing oxidation of the CI particles. The reflection loss exceeding −10 dB can be obtained in the frequency range of 9.9-14.6 GHz and a minimum value can be reached to −21.5 dB at 12.2 GHz for the annealed SiO₂-coated CI particles with the composite thickness being 1.5 mm. The mechanism of annealing treatment influence on the electromagnetic properties and microwave absorption of the SiO₂-coated CI particles was also discussed.     

Density functional study of low-lying isomers of SiO<Subscript>4</Subscript>, GeO<Subscript>4</Subscript> and CO<Subscript>4</Subscript>, and their relation to tetrahedral solid phases

In silica (SiO₂) and in most silicates, atomic associations exist with composition SiO₄ and a structure with four O atoms in tetrahedral coordination around the Si atom. A similar feature is observed in germania (GeO₂) and some solids containing Ge instead of Si, although the number of phases containing GeO₄ tetrahedra is smaller. In contrast, and in spite of the fact that C is in the same column of the periodic table as Si and Ge, CO₂ is a molecular solid, and crystalline and amorphous phases of CO₂ showing CO₄ tetrahedra are only obtained under extremely high pressures. We have investigated the relation between free SiO₄, GeO₄ and CO₄ clusters and the tetrahedral associations found in the solids mentioned above. The lowest energy structure of those three free clusters is planar, but they have near-tetrahedral and distorted-tetrahedral isomers. The promotion energy from the planar structure to the distorted tetrahedral is low in SiO₄, large in CO₄, and intermediate in GeO₄. This correlates with the facility to form tetrahedral associations in the solids.     

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.     

Electrical and optical characterization of SiOxNy and SiO2 dielectric layers and rear surface passivation by using SiO2/SiOxNy stack layers with screen printed local Al-BSF for c-Si solar cells

In c-Si solar cells, surface recombination velocity increases as the wafer thickness decreases due to an increase in surface to volume ratio. For high efficiency, in addition to low surface recombination velocity at the rear side, a high internal reflection from the rear surface is also required. The SiO_xN_y film with low absorbance can act as rear surface reflector. In this study, industrially feasible SiO₂/SiO_xN_y stack for rear surface passivation and screen printed local aluminium back surface field were used in the cell structure. A 3 nm thick oxide layer has resulted in low fixed oxide charge density of 1.58 × 10¹¹ cm⁻² without parasitic shunting. The oxide layer capped with SiO_xN_y layer led to surface recombination velocity of 155 cm/s after firing. Using single layer (SiO₂) rear passivation, an efficiency of 18.13% has been obtained with V_oc of 625 mV, J_sc of 36.4 mA/cm² and fill factor of 78.7%. By using double layer (SiO₂/SiO_xN_y stack) passivation at the rear side, an efficiency of 18.59% has been achieved with V_oc of 632 mV, J_sc of 37.6 mA/cm², and fill factor of 78.3%. An improved cell performance was obtained with SiO₂/SiO_xN_y rear stack passivation and local BSF.     

Preparation and properties of ferromagnetic Z-type hexaferrite from wet milled mixtures of intermediates

Almost pure Z-type phases of hexaferrites were synthesized by firing preliminarily milled M- and Y-type phases intermediates at 1250 °C. These phases were obtained by calcining the stoichiometric powder mixture precursors at 1080 °C, followed by wet milling in a planetary mill for 1 h and subsequent heating at 1250 °C that increased the fractional crystallization of the Z-phase up to 96%. Addition of 0.2 wt% SiO₂ to the intermediates reduced the milling time necessary for the sintered density required for practical permeability measurement. Z-phase hexaferrite sintered at 1250 °C for 2 h exhibited fairly good high-frequency properties, i.e. an initial real permeability of up to 19.3 below 100 MHz and 8–10 at around 1 GHz.     

High pressure induced phase transformation of SiO2 and GeO2: difference and similarity

We report high pressure polymorphism of SiO₂ and GeO₂ at room and high temperatures. It was found that kinetics has a large effect on pressure induced phase transitions of SiO₂ and GeO₂. The high pressure behavior of SiO₂ and GeO₂ polymorphs depends on the starting material and pressure–temperature history. Our studies show that SiO₂ and GeO₂ have a common sequence of high pressure, high temperature structural transformations when the same type of starting material (amorphous or α-quartz) was used: (amorphous or α-quartz)⇒d-NiAs⇒rutile⇒CaCl₂⇒α-PbO₂⇒pyrite (Pa-3) types. In the case of cristobalite as starting material, the α-PbO₂-type phase can be synthesized directly from the high pressure room temperature phase omitting rutile- or CaCl₂-type structure. The crystallization of the d-NiAs phase in a narrow temperature interval 1000–1300 K can be used as an indicator of presence of a cation disordered network in both SiO₂ and GeO₂ materials at high pressure before heating.     

Optical and electrical properties of Ge-implanted SiO2 layers on n-Si and p-Si

Ge ions of 100 keV were implanted into a 120 nm-thick SiO₂ layer on n-Si at room temperature while those of 80 keV were into the same SiO₂ layer on p-Si. Samples were, subsequently, annealed at 500°C for 2 h to effectively induce radiative defects in the SiO₂. Maximum intensities of sharp violet photoluminescence (PL) from the SiO₂/n-Si and the SiO₂/p-Si samples were observed when the samples have been implanted with doses of 1×10¹⁶ and 5×10¹⁵ cm⁻², respectively. According to current–voltage (I–V) characteristics, the defect-related samples exhibit large leakage currents with electroluminescence (EL) at only reverse bias region regardless of the type of substrate. Nanocrystal-related samples obtained by an annealing at 1100°C for 4 h show the leakage at both the reverse and the forward region.     

Microstructure and optical characterizations of mechanosynthesized nanocrystalline semiconducting ZrTiO4 compound

A ZrO₂–TiO₂ solid solution is obtained by high energy ball milling of equimolar mixture of monoclinic (m) ZrO₂ and anatase (a) TiO₂. Nanocrystalline orthorhombic ZrTiO₄ compound is initiated from the nucleation of TiO₂–ZrO₂ solid solution with isostructural s-TiO₂ (srilankite) base after 30 min of milling. After 12 h of milling, 95 mol% non-stoichiometric ZrTiO₄ phase is formed. Post-annealing of 12 h ball-milled powder mixture at 1073 K for 1 h in open air results in complete formation of stoichiometric ZrTiO₄ compound. Microstructures of all powder mixtures milled for different durations have been characterized by Rietveld's structure and microstructure refinement method using X-ray powder diffraction data. HRTEM images of 12 h milled and annealed samples provide direct evidence of the results obtained from the Rietveld analysis. Optical bandgaps of ball milled and annealed ZrTiO₄ compounds lie within the semiconducting region (~2.0 eV) and increases with increase in milling time.     

High lithium ion conductivity glass-ceramics in Li2O–Al2O3–TiO2–P2O5 from nanoscaled glassy powders by mechanical milling

Mechanical milling (MM) has been used to prepare the nanosized Li_1.4Al_0.4Ti_1.6(PO₄)₃ (denoted LATP) glassy powders, which was converted into glass-ceramics through thermal treating at 700–1000 °C. The XRD, TEM, FESEM and ac impedance techniques were used to characterize the products. The results showed that completely amorphous products were prepared by MM for 40 h, and single-phase LiTi₂(PO₄)₃-type structured glass-ceramics were obtained by further heat treatment. The lithium ion conductivity of the glass-ceramics increased with the growth of the crystalline phase and decrease of the grain size. The highest bulk conductivity (σ_b) of 1.09 × 10^− 3 S cm^− 1 with an energy of activation as low as 0.28 eV was obtained at room temperature for the specimen treated at 900 °C for 6 h. The high conductivity, easy fabrication and low cost make the LATP glass-ceramics promising to be used as inorganic solid electrolyte for all-solid-state Li-ion rechargeable batteries.     

Stishovite and post-stishovite polymorphs of silica in the shergotty meteorite: their nature,petrographic settings versus theoretical predictions and relevance to Earth's mantle

The Shergotty meteorite contains three dense silica polymorphs in distinct petrographic settings: (1) two post-stishovite SiO₂ polymorphs in individual multiphase grains coexisting with glass with nearly labradorite composition, and (2) large individual stishovite grains in shock-melt pockets which also contain the new CAS phase (Calcium-aluminosilicate; CaAl₄Si₂O₁₁; [Phys Earth Planet Interiors 97 (1996) 97; Geophys Abstract 5(2003)] and hollandite structured plagioclase composition. Prismatic and wedge-shaped grains of the original accessory tridymite (or cristobalite) in the Shergotty meteorite were densified during a major impact event on the Shergottite–Nakhlite–Chaissingite (SNC) parent body and inverted either to (1) multiphase assemblages of several post-stishovite polymorphs depicting prominent tweed pattern or to (2) Large homogeneous stishovite grains in melt pockets. In the first setting we identified an orthorhombic and a monoclinic post-stishovite silica polymorph, respectively. TEM investigations of a grain containing the orthorhombic polymorph revealed an α-PbO₂ like phase that could be assigned to either Pnc2 (with the cell parameters: a=4.55±0.01 Å, b=4.16±0.03 Å, c=5.11±0,04 Å), or Pbcn space group and dense SiO₂ glass. The X-ray diffraction pattern from a second grain revealed a polymorph with a monoclinic lattice with the space group P21/c, that is related to the baddeleyite (ZrO₂) structure with the cell parameters: a=4.375(1) Å, b=4.584(1) Å, c=4.708(1) Å, β=99.97(3), ρ=4.30(2) g/cm³. TEM-SAED pattern of this grain revealed the presence of the α-PbO₂-like SiO₂ polymorph, stishovite, secondary cristobalite, and dense silica glass. The coexistence of several high-density polymorphs and dense silica glass in the same grain suggests that several post-stishovite phases were formed during the shock event in Shergotty. Some of these polymorphs were highly unstable and vitrified, presumably in the decompression stage. Based on diamond anvil experiments on cristobalite a peak shock pressure in excess of 40 GPa could be deduced. The petrographic setting and texture of the single stishovite grains in the melt pockets is different. The mono-phase individual grains occur exclusively as large (>10 μm) rounded objects inside melt pockets together with hollandite structured plagioclase composition and the new CAS phase [1]. Stishovite in melt pockets is barren of any sign of a tweed pattern and contains no silica glass. This suggests that the mechanisms of phase transitions were different in the two lithologies. Stishovite in the melt pockets probably did not form by a retrograde transformation from a post-stishovite polymorph.     

Effect of ball milling time on the substitution of carbon in glucose doped MgB2 superconductors: Dispersion behavior of glucose

The effect of the ball milling time (BMT) on the substitution of the carbon in the glucose doped MgB₂ samples is investigated here. Using in situ solid state reaction, four different doped samples of Mg(B_.98C_.02)₂ were prepared by mixing powders of Mg, boron and glucose for 2 h, 4 h, 8 h and 12 h using planetary ball milling. A reference sample of un-doped MgB₂ was also prepared under same conditions. The particle size distribution of the un-reacted samples show a decrease in the particle size as the BMT is increased. Both the average particle size as well as the standard deviation show a substantial decrease with the increase in the milling time up to 8 h. After 8 h, the size reduction is rather insignificant. From the XRD data, the crystallite size of the doped MgB₂ computed using the Scherrer formula was found to decrease with the increasing BMT, showing a saturation level after 8 h of the milling time. TEM images also confirm the crystallite size obtained from the XRD data. The substitution of the C in the MgB₂ lattice, measured from the change in the c/a ratio, increases with increasing BMT. The maximum carbon substitution is achieved at approximately 8 h of BMT. Moreover, a systematic enhancement of the residual resistivity and a decrease in T_C with an increasing BMT further confirms a progressive substitution of the carbon in the MgB₂. These results suggest that a minimum ball milling time is necessary to disperse the glucose uniformly for a maximum substitution of nano C in the B plane of MgB₂ lattice. The optimum BMT is found to be 8 h. Thus, the decrease in the particle size due to the ball milling enhances the dispersion of the constituent materials thereby favoring a greater substitution of the dopant in the MgB₂ during the solid-state reaction.