Carbon nanotubes formed in graphite after mechanical grinding and thermal annealing

Multi-walled carbon nanotubes with cylindrical and bamboo-type structures are produced in a graphite sample after mechanical milling at ambient temperature and subsequent thermal annealing up to 1400 °C. The ball milling produces a precursor structure and the thermal annealing activates the nanotube growth. Different nanotubular structures indicate different formation mechanisms: multi-wall cylindrical carbon nanotubes are probably formed upon micropores and the bamboo tubes are produced because of the metal catalysts. A two-dimensional growth governed by surface diffusion is believed to be one important factor for the nanotube growth. A potential industrial production method is demonstrated with advantages of large production quantity and low cost.

Purification of boron nitride nanotubes

A purification process was developed for the first time for boron nitride (BN) nanotubes. BN nanotubes, prepared using a ball milling and annealing method, contain a high yield of nanotubes and a small amount of BN and metal catalyst particles. The metal particles can be dissolved in an HCl solution. Fine BN nanoparticles and thin layers were first converted to water soluble B₂O₃ via a partial oxidation treatment at 800 °C. The oxide particles and layers can then be dissolved in hot water. Thermogravimetric analysis has been used to determine an adequate oxidation temperature at which fine BN particles were oxidized.

11B nuclear magnetic resonance study of boron nitride nanotubes prepared by mechano-thermal method

We reported ¹¹B nuclear magnetic resonance studies of boron nitride (BN) nanotubes prepared by mechano-thermal route. The NMR lineshape obtained at 192.493 MHz (14.7 T) was fitted with two Gaussian functions, and the ¹¹B nuclear magnetization relaxations were satisfied with the stretched–exponential function, exp[-(tlT₁)^(D+1)/6] (D: space dimension) at all temperatures. In addition, the temperature dependence of spin–lattice relaxation rates was well described by T_i^-1 = aT (a: constant, T: temperature) and could be understood in terms of direct phonon process. All the 11BNMR results were explained by considering the inhomogeneous distribution of the paramagnetic metal catalysts, such as α-Fe, Fe–N, and Fe₂ B, that were incorporated during the process of high-energy ball milling of boron powder and be synthesized during subsequent thermal annealing. X-ray powder diffraction as well as electron paramagnetic resonance (EPR) on BN nanotubes were also conducted and the results obtained supported these conclusions.

Transmission electron microscopy investigation of substitution reactions from carbon nanotube template to silicon carbide nanowires

Substitution reactions between multiwalled carbon nanotubes and silicon monoxide vapour have been investigated using transmission electron microscopy. Different reactions occurred inside the multiwalled nanotubes and on the nanotube external surfaces, resulting in the formation of silicon carbide nanowires with a core–shell structure. The substitution reaction process and end products are strongly affected by nanotube structures and a ball milling treatment of the starting materials.

Growth and structure of prismatic boron nitride nanorods

Prismatic boron nitride nanorods have been grown on single crystal silicon substrates by mechanical ball-milling followed by annealing at 1300 °C. Growth takes place by rapid surface diffusion of BN molecules, and follows heterogeneous nucleation at catalytic particles of an Fe/Si alloy. Lattice imaging transmission electron microscopy studies reveal a central axial row of rather small truncated pyramidal nanovoids on each nanorod, surrounded by three basal planar BN domains which, with successive deposition of epitaxial layers adapt to the void geometry by crystallographic faceting. The bulk strain in the nanorods is taken up by the presence of what appear to be simple nanostacking faults in the external, near-surface domains which, like the nanovoids are regularly repetitive along the nanorod length. Growth terminates with a clear cuneiform tip for each nanorod. Lateral nanorod dimensions are essentially determined by the size of the catalytic particle, which remains as a foundation essentially responsible for base growth. Growth, structure, and dominating facets are shown to be consistent with a system which seeks lowest bulk and surface energies according to the well-known thermodynamics of the capillarity of solids.

In situ formation of BN nanotubes during nitriding reactions

High-yield multiwalled boron nitride (BN) nanotubes have been produced using a ball milling-annealing method. The BN nanotubes with a diameter less than 10 nm and a well-crystallized multiwalled structure were formed via an in situ nitriding reaction. The systematic investigation of the formation process at different annealing temperatures and for different times suggested that the formation of the unique multiwalled structure was attributed by a two-dimensional growth of the BN phase and a nonmetal catalytic growth.

A morphology-related study on photodegradation of protein fibres

The wool fibre has a complex morphology, consisting of an outer layer of cuticle scales surrounding an inner cortex. These two components are hard to separate effectively except by using harsh chemical treatments, making it difficult to determine the susceptibility of the different components of the fibre to photoyellowing. An approach to this problem based on mechanical fibre modification is described. To expose the inner cortex of wool to different degrees, clean wool fibres were converted into ‘powders’ of various fineness via mechanical chopping, air-jet milling, ball milling or their combination. Four types of powdered wool (samples A, B, C and D) were produced with reducing particle size distributions and an increasing level of surface damage as observed using SEM. Sample A contained essentially intact short fibre snippets and sample D contained a large amount of exposed cortical materials. Samples B and C contained a mixture of short fibre snippets and cortical materials. Solid wool discs were then compressed from the corresponding powder samples in a polished stainless steel die to enable colour measurement and UV irradiation studies. ATR-FTIR studies on powder discs demonstrated a small shift in the amide I band from 1644 cm−1 for disc A to 1654 cm−1 for disc D due to the different structures of the wool cuticle and cortex, in agreement with previous studies. Similarly an increase in the intensity ratio of the amide I to amide II band (1540 cm−1) was observed for disc D, which contains a higher fraction of cortical material at the surface of the disc.

Discs prepared from sample D appeared the lightest in colour before exposure and had the slowest photoyellowing rate, whereas discs made from powders A–C with a higher level of cuticle coverage were more yellow before exposure and experienced a faster rate of photoyellowing. This suggests that the yellow chromophores of wool may be more prevalent in cuticle scales, and that wool photoyellowing occurs to a greater extent in the cuticle than in the cortex. Photo-induced chemiluminescence measurements showed that sample D had a higher chemiluminescence intensity after exposure to UVA radiation and a faster decay rate than samples A and B. Thus one of the roles of the wool cuticle may be to protect the cortex by quenching of free radical oxidation during exposure to the UV wavelengths present in sunlight.

Synthesis of Ti–Sn–Nb alloy by powder metallurgy

The microstructural evolution and characteristics of the Ti–16Sn–4Nb powder particles and bulk alloys sintered from the powders ball-milled for various periods of time were studied. Results indicated that ball milling to 8 h led to the development of a supersaturated hcp α-Ti and partial amorphous phase due to the solid solution of Sn and Nb into Ti lattice. The bulk Ti–16Sn–4Nb alloy made from the powders ball milled for a short time, up to 2 h, exhibited a primary α and a Widmanstätten structure consisting of interlaced secondary α and β. With an increase in ball milling time up to 10 h, the microstructure evolved into a fine β phase dispersed homogeneously within α phase matrix. The microhardness values of the bulk alloy in both α- and β-phases increased with the increasing of the ball milling time and reached a plateau value at 8 h and longer, i.e. 687 and 550 HV for α- and β-phases, respectively. Likewise, the microhardness of the α phases was always higher than that of the β phases in the bulk alloys made from the powders ball milled for the same milling time.

Recent developments in mechanochemical nanoparticle synthesis

The results of recent investigations of the mechanochemical synthesis of CaC0₃, Cr₂0₃ and Nb₂0₅ nanopowders are reported. With all three materials studied, it is shown that the volume fraction of the matrix phase is crucial to the formation of separate, unagglomerated particles. With Cr₂0₃ and Nb₂0₅, amorphous particles were formed by mechanochemical reaction and low temperature heat treatment was required for crystallization. It is shown that, as a 'bottom up' process, mechanochemical processing enables the building up nanoparticles through solid-state chemical reaction in a microscopically uniform environment, leading to the formation of nanoparticles with narrow size distributions.

A novel approach for real mass transformation from V2O5 particles to nanorods

A solid-state, mass-quantity transformation from V2O5 powders to nanorods has been realized via a two-step approach. The nanorods were formed through a controlled nanoscale growth from the nanocrystalline V2O5 phase created by a ball milling treatment. The nanorods grow along the [010] direction and are dominated by {001} surfaces. Surface energy minimization and surface diffusion play important roles in their growth mechanism. Real large quantity production can be achieved when the annealing process is conducted in a fluidized bed which can treat large quantities of the milled materials at once. The crystal orientation of nanorods provides an improved cycling stability for lithium intercalation.

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.

The importance of particle size in porous titanium and nonporous counterparts for surface energy and its impact on apatite formation

The importance of particle size in titanium (Ti) fabricated by powder metallurgy for the surface energy and its impact on the apatite formation was investigated. Four sorts of Ti powders of different mean particle size were realized through 20 min, 2 h, 5 h and 8 h of ball milling, respectively. Each sort of Ti powder was used to fabricate porous Ti and its nonporous counterparts sharing similar surface morphology, grain size and chemical composition, and then alkali-heat treatment was conducted on them. Surface energy was measured on the surfaces of the nonporous Ti counterparts due to the difficulty in measuring the porous surfaces directly. The surface energy increase on the alkali-heat-treated porous and nonporous Ti was observed due to the decrease in the particle size of the Ti powders and the presence of Ti–OH groups brought by the alkali-heat treatment. The apatite-inducing ability of the alkali-heat-treated porous and nonporous Ti with different surface energy values was evaluated in modified simulated body fluid and results indicated that there was a strong correlation between the apatite-inducing ability and the surface energy. The alkali-heat-treated porous and nonporous Ti discs prepared from the powders with an average particle size of 5.89 ± 0.76 μm possessed the highest surface energy and the best apatite-inducing ability when compared to the samples produced from the powders with the average particle size varying from 19.79 ± 0.31 to 10.25 ± 0.39 μm.

Novel metal structures through powder metallurgy for biomedical applications

Biocompatible porous Ti-16Sn-4Nb alloys were synthesised in quest of a novel tissue engineering biomaterial for bone regeneration. The alloys were prepared from elemental powders via mechanical alloying followed by space-holder sintering. The effects of ball milling variables on the characteristics and mechanical properties of bulk and porous Ti-16Sn-4Nb alloy have been investigated.