Investigating the structure of biomass-derived non-graphitizing mesoporous carbons by electron energy loss spectroscopy in the transmission electron microscope and X-ray photoelectron spectroscopy

We have investigated the microstructure and bonding of two biomass-based porous carbon chromatographic stationary phase materials (alginic acid-derived Starbon® and calcium alginate-derived mesoporous carbon spheres (AMCS) and a commercial porous graphitic carbon (PGC), using high resolution transmission electron microscopy, electron energy loss spectroscopy (EELS), N2 porosimetry and X-ray photoelectron spectroscopy (XPS). The planar carbon sp -content of all three material types is similar to that of traditional nongraphitizing carbon although, both biomass-based carbon types contain a greater percentage of fullerene character (i.e. curved graphene sheets) than a non-graphitizing carbon pyrolyzed at the same temperature. This is thought to arise during the pyrolytic breakdown of hexauronic acid residues into C5 intermediates. Energy dispersive X-ray and XPS analysis reveals a homogeneous distribution of calcium in the AMCS and a calcium catalysis mechanism is discussed. That both Starbon® and AMCS, with high-fullerene character, show chromatographic properties similar to those of a commercial PGC material with extended graphitic stacks, suggests that, for separations at the molecular level, curved fullerene- like and planar graphitic sheets are equivalent in PGC chromatography. In addition, variation in the number of graphitic layers suggests that stack depth has minimal effect on the retention mechanism in PGC chromatography. © 2013 Elsevier Ltd. All rights reserved.

A study of fatigue failure in vulcanized rubber

Some aspects of fatigue failure in rubbers have been examined. Scanning electron micrographs of the surface exposed by the failure confirm the incremental, crack-propagation nature, of the fatigue process. Many other features of the failure surface have been identified and related to this process. The complicating effect of a reinforcing filler has also been investigated. The fatigue resistance of rubber test-pieces deformed in simple tension was measured as a function of frequency and temperature. This showed that an increase in frequency was equivalent to a decrease in temperature; for an amorphous unfilled rubber the time and temperature effects of crystallisation and fillers on the validity of this transformation is considered. This transformation indicates that hysteresis plays an important part in the fatigue process. Torsional pendulum measurements were used to demonstrate the dependence of the fatigue life on the mechanical damping. An apparatus was developed to measure the hysteresial energy loss directly at deformations, rates of deformation and temperatures consistent with a typical fatigue test. Measurements made with this apparatus are compared with fatigue values and a quantitative relationship is suggested describing fatigue, in terms of the energy lost per unit energy input in a cycle of a fatigue test.

A study of field emission from cadmium sulphide

It was decided to investigate field emission from cadmium sulphide because many workers have found that the agreement between theory and experiment for this material, and other semiconductors, is poor. An electron energy analyser, similar to those used in most of the previously reported experiments, was, therefore, built. The performance of the analyser was thoroughly investigated both theoretically and practically and the results of these investigations were used in conjunction with a tungsten emitter. Excellent agreement was obtained between the usually accepted total energy distribution for tungsten and the corresponding .distribution measured with the present analyser. A method of obtaining reliable cadmium sulphide emitter was developed. These emitters were then used in the analyser and it was found that the agreement between theory and experiment was poor. Previous explanations of the lack of agreement are considered and are found to be doubtful. The theory of field emission from semiconductors is reviewed and possible reasons for the discrepancy between theory and experiment are proposed. Finally, further experiments are described which should prove or disprove the conclusions arrived at in this work.

Vibrational methods applied to NDT testing and fluid density measurement

A system for the NDI' testing of the integrity of conposite materials and of adhesive bonds has been developed to meet industrial requirements. The vibration techniques used were found to be applicable to the development of fluid measuring transducers. The vibrational spectra of thin rectangular bars were used for the NDT work. A machined cut in a bar had a significant effect on the spectrum but a genuine crack gave an unambiguous response at high amplitudes. This was the generation of fretting crack noise at frequencies far above that of the drive. A specially designed vibrational decrement meter which, in effect, measures mechanical energy loss enabled a numerical classification of material adhesion to be obtained. This was used to study bars which had been flame or plasma sprayed with a variety of materials. It has become a useful tool in optimising coating methods. A direct industrial application was to classify piston rings of high performance I.C. engines. Each consists of a cast iron ring with a channel into which molybdenum, a good bearing surface, is sprayed. The NDT classification agreed quite well with the destructive test normally used. The techniques and equipment used for the NOT work were applied to the development of the tuning fork transducers investigated by Hassan into commercial density and viscosity devices. Using narrowly spaced, large area tines a thin lamina of fluid is trapped between them. It stores a large fraction of the vibrational energy which, acting as an inertia load reduces the frequency. Magnetostrictive and piezoelectric effects together or in combination enable the fork to be operated through a flange. This allows it to be used in pipeline or 'dipstick' applications. Using a different tine geometry the viscosity loading can be predoninant. This as well as the signal decrement of the density transducer makes a practical viscometer.

Mechanisms for triggering high-voltage breakdown in vacuum

The electrical and optical characteristics of a cylindrical alumina insulator (94% Al203) have been measured under ultra-high vacuum (P < 10-8 mBar) conditions. A high-resolution CCD camera was used to make real-time optical recordings of DC prebreakdown luminescence from the ceramic, under conditions where DC current magnitudes were limited to less than 50μA. Two concentric metallized rings formed a pair of co-axial electrodes, on the end-face of the alumina tube; a third 'transparent' electrode was employed to study the effect of an orthogonal electric field upon the radial conduction processes within the metallized alumina specimen. The wavelength-spectra of the emitted light was quantified using a high-speed scanning monochromator and photo-multiplier tube detector. Concurrent electrical measurements were made alongside the recording of optical-emission images. An observed time-dependence of the photon-emission is correlated with a time-variation observed in the DC current-voltage characteristics of the alumina. Optical images were also recorded of pulsed-field surface-flashover events on the alumina ceramic. An intensified high-speed video technique provided 1ms frames of surface-flashover events, whilst 100ns frames were achieved using an ultra high-speed fast-framing camera. By coupling this fast-frame camera to a digital storage oscilloscope, it was possible to establish a temporal correlation between the application of a voltage-pulse to the ceramic and the evolution of photonic emissions from the subsequent surface-flashover event. The electro-optical DC prebreakdown characteristics of the alumina are discussed in terms of solid-state photon-emission processes, that are believed to arise from radiative electron-recombination at vacancy-defects and substitutional impurity centres within the surface-layers of the ceramic. The physical nature of vacancy-defects within an alumina dielectric is extensively explored, with a particular focus placed upon the trapped electron energy-levels that may be present at these defect centres. Finally, consideration is given to the practical application of alumina in the trigger-ceramic of a sealed triggered vacuum gap (TVG) switch. For this purpose, a physical model describing the initiation of electrical breakdown within the TVG regime is proposed, and is based upon the explosive destabilisation of trapped charge within the alumina ceramic, triggering the onset of surface-flashover along the insulator. In the main-gap prebreakdown phase, it is suggested that the electrical-breakdown of the TVG is initiated by the low-field 'stripping' of prebreakdown electrons from vacancy-defects in the ceramic under the influence of an orthogonal main-gap electric field.

Finite element analysis of particle impact problems

Particle impacts are of fundamental importance in many areas and there has been a renewed interest in research on particle impact problems. A comprehensive investigation of the particle impact problems, using finite element (FE) methods, is presented in this thesis. The capability of FE procedures for modelling particle impacts is demonstrated by excellent agreements between FE analysis results and previous theoretical, experimental and numerical results. For normal impacts of elastic particles, it is found that the energy loss due to stress wave propagation is negligible if it can reflect more than three times during the impact, for which Hertz theory provides a good prediction of impact behaviour provided that the contact deformation is sufficiently small. For normal impact of plastic particles, the energy loss due to stress wave propagation is also generally negligible so that the energy loss is mainly due to plastic deformation. Finite-deformation plastic impact is addressed in this thesis so that plastic impacts can be categorised into elastic-plastic impact and finite-deformation plastic impact. Criteria for the onset of finite-deformation plastic impacts are proposed in terms of impact velocity and material properties. It is found that the coefficient of restitution depends mainly upon the ratio of impact velocity to yield Vni/Vy0 for elastic-plastic impacts, but it is proportional to [(Vni/Vy0)*(Y/E*)]-1/2, where Y /E* is the representative yield strain for finite-deformation plastic impacts. A theoretical model for elastic-plastic impacts is also developed and compares favourably with FEA and previous experimental results. The effect of work hardening is also investigated.

Graphene layers produced from carbon nanotubes by frication

Graphene layers have been produced from multi-walled carbon nanotube (MWCNT) bulk materials by friction when polished on ground-glass, offering a novel and effective method to produce graphene layers, which, more importantly, could be transferred to other substrates by rubbing. Field emission scanning electron microscopy, Raman spectroscopy, atomic force microscopy, transmission electron microscopy and selected area electron diffraction confirmed the formation of graphene layers. They were thought to be peeled away from the MWCNT walls due to friction. The reflection spectra showed that absorption of as-produced graphene layers decreased with wavelength in the range of 250–400 nm, compared to the MWCNT bulk material having strong absorption at 350 nm. Nanoscratch test was used to determine the mechanical properties of graphene films, suggesting the tolerance of as-produced graphene film to flaws introduced by scratch.

A catalytic reactor for the trapping of free radicals from gas phase oxidation reactions

A catalytic reactor for the trapping of free radicals originating from gas phase catalytic reactions is described and discussed. Radical trapping and identification were initially carried out using a known radical generator such as dicumyl peroxide. The trapping of radicals was further demonstrated by investigating genuine radical oxidation processes, e.g., benzaldehyde oxidation over manganese and cobalt salts. The efficiency of the reactor was finally proven by the partial oxidation of cyclohexane over MoO3, Cr2O3, and WO3, which allowed the identification of all the radical intermediates responsible for the formation of the products cyclohexanol and cyclohexanone. Assignment of the trapped radicals was carried out using spin trapping technique and X -band electron paramagnetic resonance spectroscopy. © 2010 American Institute of Physics.

Concentration polarization model of spiral-wound membrane modules with application to batch-mode RO desalination of brackish water

Batch-mode reverse osmosis (batch-RO) operation is considered a promising desalination method due to its low energy requirement compared to other RO system arrangements. To improve and predict batch-RO performance, studies on concentration polarization (CP) are carried out. The Kimura-Sourirajan mass-transfer model is applied and validated by experimentation with two different spiral-wound RO elements. Explicit analytical Sherwood correlations are derived based on experimental results. For batch-RO operation, a new genetic algorithm method is developed to estimate the Sherwood correlation parameters, taking into account the effects of variation in operating parameters. Analytical procedures are presented, then the mass transfer coefficient models are developed for different operation processes, i.e., batch-RO and continuous RO. The CP related energy loss in batch-RO operation is quantified based on the resulting relationship between feed flow rates and mass transfer coefficients. It is found that CP increases energy consumption in batch-RO by about 25% compared to the ideal case in which CP is absent. For continuous RO process, the derived Sherwood correlation predicted CP accurately. In addition, we determined the optimum feed flow rate of our batch-RO system.

Carbon nanowalls grown by microwave plasma enhanced chemical vapor deposition during the carbonization of polyacrylonitrile fibers

We used microwave plasma enhanced chemical vapor deposition (MPECVD) to carbonize an electrospun polyacrylonitrile (PAN) precursor to form carbon fibers. Scanning electron microscopy, Raman spectroscopy, and Fourier transform infrared spectroscopy were used to characterize the fibers at different evolution stages. It was found that MPECVD-carbonized PAN fibers do not exhibit any significant change in the fiber diameter, whilst conventionally carbonized PAN fibers show a 33% reduction in the fiber diameter. An additional coating of carbon nanowalls (CNWs) was formed on the surface of the carbonized PAN fibers during the MPECVD process without the assistance of any metallic catalysts. The result presented here may have a potential to develop a novel, economical, and straightforward approach towards the mass production of carbon fibrous materials containing CNWs. © 2013 American Institute of Physics.