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.

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.

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.

One-dimensional nanomaterials synthesized using high-energy ball milling and annealing process

One-dimensional (1D) nanomaterials including nanotubes, nanowires and nanorods have many new properties, functionalities and a large range of promising applications. A major challenge for these future industrial applications is the large-quantity production. We report that the ball milling and annealing process has the potential to achieve the mass production. Several examples including C, BN nanotubes and SiC, Zn nanowires are presented to demonstrate such capability. In addition, both size and structure of 1D nanomaterials can be controlled by varying processing conditions. New growth mechanisms involved in the process have been investigated and the high-energy ball milling has an important role in the formation of these 1D nanomaterials.

Substitution reactions of carbon nanotube template

Substitution reactions between carbon nanotube (CNT) template and SiO with the formation of carbon rich silicon oxide nanowires (SiO–C-NWs) have been investigated using transmission electron microscopy and x-ray energy dispersive spectroscopy. The reaction was carried out by thermal annealing at 1200 °C for 1 h of a mixture of silicon monoxide (SiO) and iron (II) phthalocyanine, FeC32N8H16 (FePc) powders. Multiwalled CNTs were produced first via pyrolysis of FePc at a lower temperature (1000 °C). SiO vapors reacted with the CNTs at higher temperatures to produce amorphous SiO–C-NWs with a uniform diameter and a length in tens of micrometers. The special bamboolike structure of the CNTs allows the reaction to start from the external surface of the tubes and transform each CNT into a solid nanowire section by section.

Scalable production of wrinkled and few-layered graphene sheets and their use for oil and organic solvent absorption

High-quality wrinkled and few-layered graphene sheets have been produced via a mechano-thermal exfoliation process for a simple, effective and low-cost mass production. Graphene sheets were produced by first ball milling of graphite with ammonium chloride followed by thermal annealing at 800 °C in nitrogen gas. The few layered graphene sheets show highly efficient selectivity and capacity for the absorption of petroleum products as well as organic solvents such as ethanol, cyclohexane and chloroform (up to 82, 42 and 98 times of their own weight, respectively). The saturated few-layered graphene sheets can be cleaned for reuse by simply burning in air. The low-cost strategy for mass production and easy recycling routes demonstrate the great potential of few-layered graphene sheets for oil removal.

Compositional effects of large graphene oxide sheets on the spinnability and properties of polyurethane composite fibers

Recent advances in wearable electronics, technical textiles, and wearable strain sensing devices have resulted in extensive research on stretchable electrically conductive fibers. Addressing these areas require the development of efficient fiber processing methodologies that do not compromise the mechanical properties of the polymer (typically an elastomer) when nanomaterials are added as conductive fillers. It is highly desirable that the addition of conductive fillers provides not only electrical conductivity, but that these fillers also enhance the stiffness, strength, stretchability, and toughness of the polymer. Here, the compatibility of polyurethane (PU) and graphene oxide (GO) is utilized for the study of the properties of elastomeric conductive fibers prepared by wet-spinning. The GO-reinforced PU fibers demonstrate outstanding mechanical properties with a 200-fold and a threefold enhancement in Young's modulus and toughness, respectively. Postspinning thermal annealing of the fibers results in electrically conductive fibers with a low percolation threshold (≈0.37 wt% GO). An investigation into optimized fiber's electromechanical behavior reveals linear strain sensing abilities up to 70%. Results presented here provide practical insights on how to simultaneously maintain or improve electrical, mechanical, and electromechanical properties in conductive elastomer fibers.

Thermal behavior of copper processed by ECAP with and without back pressure

Samples of electrolytic tough pitch (ETP) pure copper were subjected to 12 passes of Equal-Channel Angular Pressing (ECAP) at room temperature with and without back pressure. Subsequent annealing was performed to evaluate the influence of back pressure during ECAP on the thermal behavior of ultrafine-grained copper. The microstructural and hardness changes caused by annealing were characterized by orientation imaging microscopy (OIM) and microhardness measurements. The application of back pressure resulted in an earlier drop in hardness upon annealing, which is believed to be associated with a lower critical temperature for the initiation of recrystallization and a rapid coarsening of microstructure. Regardless of whether back pressure was applied or not, structure coarsening during short-time annealing of ECAP-processed copper was governed by discontinuous static recrystallization. This is seen as a result of microstructure heterogeneity. Analysis of recrystallization kinetics was carried out based on observations of the microstructure after annealing in terms of the Avrami equation. The magnitude of the apparent activation energies for recrystallization in the absence of back pressure and in the case of back pressure of 100 MPa was estimated to be ~99 kJ/mol and ~91 kJ/mol, respectively. The reasons for reduced activation energy in the case of processing with back pressure are discussed.

Rapid composite tube manufacture utilizing the quickstep™ process

In this study, a novel method for manufacturing composite tubes utilizing the Quickstep^TM process has been developed. Tubes manufactured from `quick-cure' Toray G83C prepreg have demonstrated highly repeatable axial crush behavior with an average specific energy absorption (SEA) of 86 kJ/kg. The cure cycle is optimized by comparing the results from compression, dynamic mechanical thermal analysis (DMTA), differential scanning calorimetry (DSC), and porosity testing. The tube lay-up is optimized using compression and porosity test results. The effect of changes in fiber-orientation on SEA is also investigated. Process development has resulted in a robust manufacturing method capable of producing fully cured, high performance composite tubes with a cure cycle of 7 min. This corresponds to a 95% reduction in time compared to an equivalent autoclave cycle.

Robust control applied to metal spraying for rapid tooling

The spray forming process is a novel method of rapidly manufacturing tools and dies for stamping and injection operations. The process sprays molten tool steel from a set of arc spray guns onto a ceramic former to build up a thick steel shell. The volumetric contraction that occurs as the steel cools is offset by a volumetric expansion taking place within the sprayed steel, which allows the dimensional accurate tools to be produced. To ensure that the required phase transformation takes place, the temperature of the steel is regulated during spraying. The sprayed metal acts both as a source of mass and a source of heat and by adjusting the rate at which metal is sprayed; the surface temperature profile over the surface of the steel can be controlled. The temperature profile is measured using a thermal imaging camera and regulated by adjusting the rate at which the guns spray the steel. Because the temperature is regulated by adjusting the feed rate to an actuator that is moving over the surface, this is an example of mobile control, which is a class of distributed parameter control. The dynamic system has been controlled using a PI controller before. The paper describes the application of H∞ tracking type controller as the desire was for the average temperature to follow a desired profile. A study on the controllability of the underlying system was aimed at.

Rapid synthesis of TiC–Fe3C composite by electric discharge assisted mechanical milling of ilmenite (FeTiO3) with graphite

Carbo-thermic reduction of ilmenite (FeTiO₃) to TiO₂ and/or TiC is traditionally carried out by a high temperature annealing treatment at  _~1500 °C. In this work, electric discharge assisted mechanical milling (EDAMM) has been used to synthesise TiC + Fe₃C from FeTiO₃ in 5 min. In this study we report of the reduction of FeTiO₃ with C that does not require an additional high temperature annealing treatment.

Rapid synthesis of Bi and Sb sulfides using electric discharge assisted mechanical milling

Group V–VI binary sulfides are semiconductors, and find application in a number of commercial devices. Synthesis of these metal sulfides is problematic, and traditional synthesis techniques utilizing thermal and chemical means have disadvantages such as a long process time, contamination, and the use of toxic substances. In this work, the novel synthesis technique of electric discharge assisted mechanical milling (EDAMM) has been used to rapidly synthesize Bi₂S₃ and Sb₂S₃ powders from elemental S and Sb/Bi powders. This technique is shown to be both rapid and successful, and produces crystalline metal sulfide powders with a particle size of approximately 2 μm.

Microstructure evolution and softening processes occurring during annealing of hot deformed Ni-30Fe austenite

The current work investigates the microstructure evolution and softening processes that take place during annealing of an austenitic Ni-30Fe model alloy subjected to hot deformation in the dynamic recrystallization (DRX) regime. The substructure of the deformed matrix grains largely comprised organized microband arrays, though that of the DRX grains consisted of more random, complex subgrain/cell arrangements. This substructure disparity was also reflected by the distinct difference in the mechanism of post-deformation softening taking place during annealing of the deformed matrix and DRX grains. In the former, the recrystallization process took place through nucleation and growth of new grains fully replacing the deformed structure, as expected for the classical static recrystallization (SRX). The corresponding texture was essentially random, in contrast to that of the DRX grains dominated by low Taylor factor components. The microbands originally present within the deformed matrix grains displayed some tendency to disintegrate during annealing, nonetheless, they remained largely preserved even at prolonged holding times. During annealing of the fully DRX microstructure, a novel softening mechanism was revealed. The initial post-dynamic softening stage involved rapid growth of the dynamically formed nuclei and migration of the mobile boundaries in correspondence with the well-established metadynamic recrystallization (MDRX) mechanism. However, in contrast to the deformed matrix, SRX was not observed and the sub-boundaries within DRX grains rapidly disintegrated through dislocation climb and dislocation annihilation, which led to the formation of dislocation-free grains already at short holding times. Consequently, the DRX texture initially became slightly weakened and then remained largely preserved throughout the annealing process.

Texture evolution and softening processes in an austenitic Ni-30Fe alloy subjected to hot deformation and subsequent annealing

The current work has investigated the texture development in an austenitic Ni-30Fe model alloy during deformation within the dynamic recrystallization (DRX) regime and after post-deformation annealing. Both the deformed matrix and DRX texture displayed the expected FCC shear components, the latter being dominated by the low Taylor factor grains, which was presumably caused by their lower consumption rate during DRX. The deformed matrix grains were largely characterized by organized, microband structures, while the DRX grains showed more random, complex subgrains/cell arrangements. The latter substructure type proved to be significantly less stable during post-deformation annealing. The recrystallization of the deformed matrix occurred through nucleation and growth of new grains fully replacing the deformed structure, as expected for the classical static recrystallization (SRX). Unlike the DRX grains, the SRX texture was essentially random. By contrast, a novel softening mechanism was revealed during annealing of the fully DRX microstructure. The initial post-dynamic softening stage involved rapid growth of the dynamically formed nuclei and migration of the mobile boundaries in line with the well-established metadynamic recrystallization (MDRX) mechanism, which weakened the starting DRX texture. However, in parallel, the sub-boundaries within the deformed DRX grains progressively disintegrated through dislocation climb and dislocation annihilation, which ultimately led to the formation of dislocation-free grains. Consequently, the weakened DRX texture largely remained preserved throughout the annealing process.

Effect of compositional gradient on thermal behavior of synthetic graphite-phenolic nanocomposites

Synthetic graphite–phenolic nanocomposites were designed and synthesized with a compositional gradient which is shown to influence transient temperature fields during rapid temperature changes. Such nanocomposites were fabricated using a compression moulding technique, and thermal conductivity and heat capacity of nanocomposites were experimentally determined using a modified transient plane source technique over a wide temperature range from 253.15 to 373.15 K. The effects of four compositional gradient configurations on the transient temperature field across the thickness of a nanocomposite plate, at a high imposed temperature, was investigated. The transient time and temperature fields in nanocomposite structures were highly affected by the compositional gradient configurations.