Compressive behaviour of nanocrystalline Mg-5Al alloys

Magnesium alloys are attracting increasing research interests due to their low density, high specific strength, good machinability and availability as compared to other structural materials. However, the deformation and failure mechanisms of nanocrystalline (nc) Mg alloys have not been well understood. In this work, the deformation behaviour of nc Mg-5Al alloys was investigated using compression test, with focus on the effects of grain size. The average grain size of the Mg- Al alloy was changed from 13 to 50 nm via mechanical milling. The results showed that grain size had a significant influence on the yield stress and ductility of the Mg alloys, and the materials exhibited increased strain rate sensitivity with a decrease in grain size. The deformation mechanisms were also strongly dependent on the grain sizes.

Mechanically activated synthesis of nanocrystalline powders of ferroelectric bismuth vanadate

Mechanical milling of a stoichiometric mixture of Bi2O3 and V2O5 yielded nanosized powders of bismuth vanadate, Bi2VO5.5 (BN). Structural evolution of the desired BiV phase, through an intermediate product (BiVO4), was monitored by subjecting the powders, ball milled for various durations to X-ray powder diffraction (XRD), differential thermal analysis (DTA), and transmission electron microscopic (TEM) studies. XRD studies indicate that the relative amount of the BiV phase present in the ball-milled mixture increases with increase in milling time and its formation reaches completion within 54 h of milling. Assynthesized powders were found to stabilize in the high-temperature tetragonal (gamma) phase. DTA analyses of the powders milled for various durations suggest that the BN phase-formation temperature decreases with increase in milling time. The nanometric size (30 nm) of the crystallites in the final product was confirmed by TEM and XRD studies. TEM studies clearly demonstrate the growth of BiV on Bi2O3 crystallites. (C) 1999 Academic Press.

Interaction anisotropy and shear instability of aspirin polymorphs established by nanoindentation

Nanoindentation is applied to the two polymorphs of aspirin to examine and differentiate their interaction anisotropy and shear instability. Aspirin provides an excellent test system for the technique because: (i) polymorphs I and II exhibit structural similarity in two dimensions, thereby facilitating clear examination of the differences in mechanical response in relation to well-defined differences between the two crystal structures; (ii) single crystals of the metastable polymorph II have only recently become accessible; (iii) shear instability has been proposed for II. Different elastic moduli and hardness values determined for the two polymorphs are correlated with their crystal structures, and the interpretation is supported by measured thermal expansion coefficients. The stress-induced transformation of the metastable polymorph II to the stable polymorph I can be brought about rapidly by mechanical milling, and proceeds via a slip mechanism. This work establishes that nanoindentation provides ``signature'' responses for the two aspirin polymorphs, despite their very similar crystal structures. It also demonstrates the value of the technique to quantify stability relationships and phase transformations in molecular crystals, enabling a deeper understanding of polymorphism in the context of crystal engineering.

Structural Evolution and Phase Stability of Hume-Rothery Phase in a Mechanically Driven Nanostructured Ag-15 at. pct Sn Alloy

The paper reports phase evolution in mechanically driven Ag-15 at. pct Sn alloy powder starting with elemental powders in order to establish the feasibility of designing nanocomposites of a Ag-Sn solid solution. This alloy lies in the phase field of the hexagonal zeta-phase which is a well-known Hume-Rothery electron compound with an electron-to-atom ratio of about 1.45 and hexagonal crystal structure (a = 0.2966 nm, c = 0.4782 nm). Through a systematic use of X-ray diffraction and transmission electron microscopy, the results establish the formation of the zeta-phase which co-exists with the Ag solid solution during the initial phase of milling. Mechanical milling for long duration (55 hours) destabilizes the zeta-phase. A complete solid solution of Ag with a grain size of similar to 8 nm could be achieved after 60 hours of milling. Additional milling can induce decomposition of the solid solution that results in a reappearance of zeta-phase. We present a detailed thermodynamic calculation which indicates that complete Ag solid solution of the present alloy composition would be possible if the crystallites size can be reduced below a certain critical size. In particular, we show that both Ag and zeta-phase grain sizes need to be taken into account for determining the metastable equilibrium and the phase change that has been experimentally observed. Finally, we argue that recrystallization processes set a limit to the achievable size of the nanoparticles with metastable Ag solid solution.

A novel hybrid based on carbon nanotubes and heteropolyanions as effective catalyst for hydrogen evolution

Heteropolyanions of tungstophosphoric acid (PWA) have been successfully hybridized with carbon nanotubes (CNTs) by a severe mechanical milling. The obtained hybrid is electroactive for hydrogen evolution (HE) at potentials as positive as -0.16 V vs. Ag/AgCl in 0.2 M HClO4 aqueous solution and its electrocatalysis is up to the level of Pt/CNTs (20 wt% Pt) for HE, indicating a vigorous alternative to Pt group metals. The HE mechanism of the hybrid was also studied and it was found that the tungsten oxycarbides are the electroactive components for HE.

Crystallization and characterization of substoichiometric compound (W0.5Al0.5)C-0..5 obtained by solid-state reaction

(W0.5Al0.5)C-0.5 substoichiometric compound is synthesized by a combination of mechanical milling and high-pressure reactive sintering. X-ray diffraction is used to monitor the phase changes and crystallization of (W0.5Al0.5) C-0.5 during the whole reaction process. As a result, (W0.5Al0.5) C-0.5 is identified as the hexagonal WC-type belonging to the P-6m2 space group (No. 187), and the lattice parameters of (W0.5Al0.5)C-0.5 are calculated to be a = 2.907 (1) angstrom, c = 2.838 (1) angstrom, which are very similar to those of WC even if there are approximately 50 pct carbon vacancies in the cell of (W0.5Al0.5)C-0.5 as compared with WC. The substoichiometric (W0.5Al0.5)C-0.5 compound has a Vickers microhardness of 2385 +/- 70 kg mm(-2), which is as high as that of WC, while its density is far lower than that of WC.

Nucleation and growth of carbon nanotubes in a mechano-thermal process

Separate nucleation and growth processes of carbon nanotubes were found in a mechano-thermal method in which carbon nanotubes are produced by first mechanical milling of graphite powder at room temperature and subsequent thermal annealing up to 1400 °C. The ball-milled graphite contains nucleation structures (nanosized metal particles and deformed (0 0 2) layers containing pentagons), and disordered carbon as a free carbon atom source. The subsequent annealing activates the growth of two types of multi-walled nanotubes in the absence of carbon vapor. Thin nanotubes (diameter <20 nm) are formed via crystallization of the disordered carbon with the preferred formation of the (0 0 2) basal planes. Thick nanotubes (diameter >20 nm) are formed through a metal catalytic solution–precipitation process (solid–liquid–solid). In both cases, carbon nanotubes grew out from disordered carbon particles with closed tips.

Properties of mechanically milled and spark plasma sintered Al–15 at.% MgB2 composite materials

Air-atomized pure aluminium powder with 15 at.% MgB₂ was mechanically milled (MMed) by using a vibrational ball mill, and MMed powders were consolidated by spark plasma sintering (SPS) to produce composite materials with high specific strength. Solid-state reactions of MMed powders have been examined by X-ray diffraction (XRD), and mechanical properties of the SPSed materials have been evaluated by hardness measurements and compression tests. Orientation images of microstructures were obtained via the electron backscatter diffraction (EBSD) technique.

The solid-state reactions in the Al–15 at.% MgB₂ composite materials occurred between the MMed powders and process control agent (PCA) after heating at 773–873 K for 24 h. The products of the solid-state reaction were a combination of AlB₂, Al₃BC and spinel MgAl₂O₄. Mechanical milling (MM) processing time and heating temperatures affect the characteristics of those intermetallic compounds. As the result of the solid-state reactions in MMed powders, a hardness increase was observed in MMed powders after heating at 573–873 K for 24 h. The full density was attained for the SPSed materials from 4 h or 8 h MMed powders in the Al–15 at.% MgB₂ composite materials under an applied pressure of 49 MPa at 873 K for 1 h. The microstructure of the SPSed materials fabricated from the MMed powders presented the bimodal aluminium matrix grain structure with the randomly distributions. The Al–15 at.% MgB₂SPSed material from powder MMed for 8 h exhibited the highest compressive 0.2% proof strength of 846 MPa at room temperature.

Tailoring the photocatalytic activity of nanoparticulate zinc oxide by transition metal oxide doping

The successful use of nanoparticulate ZnO in applications such as UV-screening agents or photocatalyst for the destruction of chemical waste requires the development of techniques for controlling its photocatalytic activity. In this study, we have investigated transition metal doping as a means of achieving this goal. Powders of ZnO, Mn_xZn_1−xO, and Co_xZn_1−xO were synthesised by a three-stage process consisting of high-energy mechanical milling, heat treatment, and washing. The photocatalytic activity of these powders was evaluated using the spin-trapping technique with electron paramagnetic resonance spectroscopy. It was found that the photocatalytic activity of Co_xZn_1−xO progressively decreased with the doping level. In contrast, the activity of Mn_xZn_1−xO initially increased with doping up to a level of 2 mol% and thereafter declined. These results demonstrate that doping with transition metal oxides can be used to tailor the photocatalytic properties of nanoparticulate ZnO.

Effect of particle size on the photocatalytic activity of nanoparticulate zinc oxide

In this study, a three-stage process consisting of mechanical milling, heat treatment, and washing has been used to manufacture nanoparticulate ZnO powders with a controlled particle size and minimal agglomeration. By varying the temperature of the post-milling heat treatment, it was possible to control the average particle size over the range of 28–57 nm. The photocatalytic activity of these powders was characterized by measuring the hydroxyl radical concentration as a function of irradiation time using the spin-trapping technique with electron paramagnetic resonance spectroscopy. It was found that there exists an optimum particle size of approximately 33 nm for which the photocatalytic activity is maximized. The existence of this optimal particle size is attributable to an increase in the charge carrier recombination rate, which counteracts the increased activity arising from the higher specific surface area for a sufficiently small particle size.

Anomalous evaporation behavior of ZnO powder milled mechanically under high-energy conditions

ZnO powder showed anomalous evaporation behavior after its mechanical milling treatment under high-energy conditions. The amount of generated vapor is about 10 times higher in the first 15 min of annealing at 1300 °C than that of unmilled ZnO powders. The strong ball impacts are responsible for the greatly enhanced evaporation ability. Low-energy ball milling involving shearing actions and rare weak impacts leads only to a small evaporation rate enhancement. The possible explanation of the high evaporation rate of the heavily milled material is the existence of large fraction of weakly bonded atoms in grain boundaries, surface defects and strained areas.

Process for the production of ultrafine powders

A process for the production of ultrafine powders consisting of individual particles with sizes in the range of 1 nm to 200 nm, which is based on the mechanical milling of two or more non-reacting powders. The process includes subjecting a suitable precursor metal compound and a non-reactant diluent phased to mechanical milling which through the process of mechanical activation reduces the microstructure of the mixture of the form of nano-sized grains of the metal compound uniformly dispersed in the diluent phase. Heat treating the milled powder converts the nano-sized grains of the precursor metal compound into a desired metal oxide phase. Alternatively, the precursor metal compound may itself be an oxide phase which has the requisite milling properties to form nanograins when milled with a diluent. An ultrafine powder is produced by removing the diluent phase such that nano-sized grains of the desired metal oxide phase are left behind. The process facilitates a significant degree of control over the particle size and size distribution of the particles in the ultrafine powder by controlling the parameters of mechanical activation and heat treatment.

Synthesis of Al3BC from mechanically milled and spark plasma sintered Al-MgB2 composite materials

The aluminium-rich ternary aluminium borocarbide, Al₃BC was synthesised for the first time by solid-state reactions occurring during heat treatments after mechanical milling (MM) of pure aluminium with 15 or 50 at% MgB₂ powder mixtures in the presence of the process control agent (PCA).

The solid-state reactions in the Al–15 and 50 at% MgB₂ composite materials occurred between the MMed powders and process control agent (PCA) after heating at 773–873 K for 24 h. The products of the solid-state reaction induced Al₃BC, AlB₂, γ-Al₂O₃ and spinel MgAl₂O₄. MM processing time and heating temperatures in the Al–15 and 50 at% MgB₂ composite materials affected the selection of those intermetallic compounds. When MM processing time was increased for a given composition, the formation of the Al₃BC compound started at lower heat treatment temperatures. However, when the amount of MgB₂ was increased in the 4 h MM processing regime, the formation of the Al₃BC compound during heating was suppressed. As a result of the solid-state reactions in MMed powders the hardness was observed to increase after heating at 573–873 K for 24 h.

The fully dense bulk nano-composite materials have been successfully obtained through the combination of the MM and spark plasma sintering (SPS) processes for the 4 h or 8 h MMed powders of the Al–15 at% MgB₂ composite materials sintered under an applied pressure of 49 MPa at 873 K for 1 h.

Recent innovations in silk biomaterials

Silk contains a fibre forming protein, fibroin, which is biocompatible, particularly after removing the potentially immunogenic non-fibroin proteins. Silk can be engineered into a wide range of materials with diverse morphologies. Moreover, it is possible to regenerate fibroin with a desired amount of crystallinity, so that the biodegradation of silk materials can be controlled. These advantages have sparked new interest in the use of silk fibroin for biomedical applications, including tissue engineering scaffolds and carriers for sustained release of biologically active molecules. This article summarizes the current research related to the formation of silk materials with different morphologies, their biocompatibility, and examples of their biomedical applications. Recent work on the preparation of silk particles by mechanical milling and their applications in silk composite scaffolds is also discussed.