Cobalt promoted TiO2/GO for the photocatalytic degradation of oxytetracycline and Congo Red

A family of titania derived nanocomposites synthesized via sol-gel and hydrothermal routes exhibit excellent performance for the photocatalytic degradation of two important exemplar water pollutants, oxytetracycline and Congo Red. Low loadings of Co3O4 nanoparticles dispersed over the surfaces of anatase TiO2 confer visible light photoactivity for the aqueous phase decomposition of organics through the resulting heterojunction and reduced band gap. Subsequent modification of these Co3O4/TiO2 composites by trace amounts of graphene oxide nanosheets in the presence of a diamine linker further promotes both oxytetracycline and Congo Red photodegradation under simulated solar and visible irradiation, through a combination of enhanced photoresponse and consequent radical generation. Radical quenching and fluorescence experiments implicate holes and hydroxyl radicals as the respective primary and secondary active species responsible for oxidative photodegradation of pollutants.

Time-resolved Q-factor measurement and its application in performance analysis of 42.6 Gbit/s packets generated by SGDBR lasers

We demonstrate a novel time-resolved Q-factor measurement technique and demonstrate its application in the analysis of optical packet switching systems with high information spectral density. For the first time, we report the time-resolved Q-factor measurement of 42.6 Gbit/s AM-PSK and DQPSK modulated packets, which were generated by a SGDBR laser under wavelength switching. The time dependent degradation of Q-factor performance during the switching transient was analyzed and was found to be correlated with different laser switching characteristics in each case.

Performance characterisation of 42.65 Gbit/s dual-gate asynchronous digital optical regenerator using single MZM

The tolerance of a 42.65 Gbit/s dual-gate asynchronous digital optical regenerator using a single Mach-Zehnder modulator to optical signal-to-noise-ratio degradation and chromatic dispersion is experimentally demonstrated.

Fiber optical parametric amplifier performance in a 1-Tb/s DWDM communication system

We have reduced signal-signal four-wave mixing crosstalk in a fiber optical parametric amplifier (OPA) by using a short nonlinear fiber for the gain medium and a high-power pump. This allowed us to obtain less than 1 dB penalty for amplification of 26 dense wavelength-division multiplexed (WDM) channels modulated at 43.7Gb/s return to zero-differential phase-shift keying, with the OPA placed between transmitter and receiver. We then used the same OPA in several different roles for a long-haul transmission system. We did not insert the OPA within the loop, but investigated this role indirectly by using equivalent results for small numbers of loop recirculations. We found that standard erbium-doped fiber amplifiers currently hold an advantage over this OPA, which becomes negligible for long distances. This paper shows that at this time OPAs can handle amplification of WDM traffic in excess of 1 Tb/s with little degradation. It also indicates that with further improvements, fiber OPAs could be a contender for wideband amplification in future optical communication networks.

Performance modelling and analysis of multiple coexisting IEEE 802.15.4 wireless sensor networks

With the features of low-power and flexible networking capabilities IEEE 802.15.4 has been widely regarded as one strong candidate of communication technologies for wireless sensor networks (WSNs). It is expected that with an increasing number of deployments of 802.15.4 based WSNs, multiple WSNs could coexist with full or partial overlap in residential or enterprise areas. As WSNs are usually deployed without coordination, the communication could meet significant degradation with the 802.15.4 channel access scheme, which has a large impact on system performance. In this thesis we are motivated to investigate the effectiveness of 802.15.4 networks supporting WSN applications with various environments, especially when hidden terminals are presented due to the uncoordinated coexistence problem. Both analytical models and system level simulators are developed to analyse the performance of the random access scheme specified by IEEE 802.15.4 medium access control (MAC) standard for several network scenarios. The first part of the thesis investigates the effectiveness of single 802.15.4 network supporting WSN applications. A Markov chain based analytic model is applied to model the MAC behaviour of IEEE 802.15.4 standard and a discrete event simulator is also developed to analyse the performance and verify the proposed analytical model. It is observed that 802.15.4 networks could sufficiently support most WSN applications with its various functionalities. After the investigation of single network, the uncoordinated coexistence problem of multiple 802.15.4 networks deployed with communication range fully or partially overlapped are investigated in the next part of the thesis. Both nonsleep and sleep modes are investigated with different channel conditions by analytic and simulation methods to obtain the comprehensive performance evaluation. It is found that the uncoordinated coexistence problem can significantly degrade the performance of 802.15.4 networks, which is unlikely to satisfy the QoS requirements for many WSN applications. The proposed analytic model is validated by simulations which could be used to obtain the optimal parameter setting before WSNs deployments to eliminate the interference risks.

Long-haul transmission performance evaluation of ultra-long Raman fibre laser based amplification influenced by second order co-pumping

A transmission performance investigation using ultra-long Raman fibre laser based amplification with different co-pump power is presented. We attribute Q2 factor degradation to RIN of co-pump and induced fibre laser as well as increased SBS.

The icephobic performance of alkyl-grafted aluminum surfaces

This work analyzes the anti-icing performance of flat aluminum surfaces coated with widely used alkyl-group based layers of octadecyltrimethoxysilane, fluorinated alkylsilane and stearic acid as they are subjected to repeated icing/deicing cycles. The wetting properties of the samples upon long-term immersion in water are also evaluated. The results demonstrate that smooth aluminum surfaces grafted with alkyl groups are prone to gradual degradation of their hydrophobic and icephobic properties, which is caused by interactions and reactions with both ice and liquid water. This implies that alkyl-group based monolayers on aluminum surfaces are not likely to be durable icephobic coatings unless their durability in contact with ice and/or water is significantly improved.

Synthesis of Cr and La-codoped SrTiO3 nanoparticles for enhanced photocatalytic performance under sunlight irradiation

In this study, we report a facile polymeric citrate strategy for the synthesis of Cr,La-codoped SrTiO3 nanoparticles. The synthesized samples were well characterized by various analytical techniques. The UV-vis DRS studies reveal that the absorption edge shifts towards the visible light region after doping with Cr, which is highly beneficial for absorbing the visible light in the solar spectrum. More attractively, codoping with La exhibits greatly enhanced photocatalytic activity for the degradation of Rhodamine B under sunlight irradiation. The optimum photocatalytic activity at 1 atom% of Cr,La-codoped SrTiO3 nanoparticles is almost 6 times higher than that of pure SrTiO3 nanoparticles and 3 times higher than that of Cr-doped SrTiO3 nanoparticles. The high photocatalytic performance in the present photocatalytic system is due to codoping with La, which acts as a most effective donor for stabilizing Cr3+ in Cr,La-codoped SrTiO3 nanoparticles. More importantly, the synthesized photocatalysts possess high reusability. A proposed mechanism for the enhanced photocatalytic activity of Cr,La-codoped SrTiO3 nanoparticles was also investigated by trapping experiments. Therefore, our results not only demonstrate the highly efficient visible light photocatalytic activity of the Cr,La-codoped SrTiO3 photocatalyst, but also enlighten the codoping strategy in the design and development of advanced photocatalytic materials for energy and environmental applications.

Evaluation of 100G DP-QPSK long-haul transmission performance using second order co-pumped Raman laser based amplification

We present, for the first time, a detailed investigation of the impact of second order co-propagating Raman pumping on long-haul 100G WDM DP-QPSK coherent transmission of up to 7082 km using Raman fibre laser based configurations. Signal power and noise distributions along the fibre for each pumping scheme were characterised both numerically and experimentally. Based on these pumping schemes, the Q factor penalties versus co-pump power ratios were experimentally measured and quantified. A significant Q factor penalty of up to 4.15 dB was observed after 1666 km using symmetric bidirectional pumping, compared with counter-pumping only. Our results show that whilst using co-pumping minimises the intra-cavity signal power variation and amplification noise, the Q factor penalty with co-pumping was too great for any advantage to be seen. The relative intensity noise (RIN) characteristics of the induced fibre laser and the output signal, and the intra-cavity RF spectra of the fibre laser are also presented. We attribute the Q factor degradation to RIN induced penalty due to RIN being transferred from the first order fibre laser and second order co-pump to the signal. More importantly, there were two different fibre lasing regimes contributing to the amplification. It was random distributed feedback lasing when using counter-pumping only and conventional Fabry-Perot cavity lasing when using all bidirectional pumping schemes. This also results in significantly different performances due to different laser cavity lengths for these two classes of laser.

New genre of antioxidants from renewable natural resources:synthesis and characterisation of rosemary plant-derived antioxidants and their performance in polyolefins

Several ester derivatives of rosmarinic acid (rosmarinates) were synthesised, characterised (1D and 2D NMR, UV and FTIR spectroscopy) and tested for their potential use as antioxidants derived from a renewable natural resource. The intrinsic free radical scavenging activity of the rosmarinates was assessed, initially using a modified DPPH (2, 2-diphenyl-1-picrylhydrazyl radical) method, and found to be higher than that of commercial synthetic hindered phenol antioxidants Irganox 1076 and Irganox 1010. The thermal stabilising performance of the rosmarinates in polyethylene (PE) and polypropylene (PP) was subsequently examined and compared to that of samples prepared similarly but in the presence of Irganox 1076 (in PE) and Irganox 1010 (in PP) which are typically used for polyolefin stabilisation in industrial practice. The melt stability and the long-term thermo-oxidative stability (LTTS) of processed polymers containing the antioxidants were assessed by measuring the melt flow index (MFI), melt viscosity, oxidation induction time (OIT) and long-term (accelerated) thermal ageing performance. The results show that both the melt and the thermo-oxidative stabilisation afforded by the rosmarinates, and in particular the stearyl derivative, in both PE and PP, are superior to those of Irganox 1076 and Irganox 1010, hence their potential as effective sustainable bio-based antioxidants for polymers. The rosmarinic acid used for the synthesis of the rosmarinates esters in this study was obtained from commercial rosemary extracts (AquaROX80). Furthermore, a large number of different strains of UK-grown rosemary plants (Rosmarinum officinalis) were also extracted and analysed in order to examine their antioxidant content. It was found that the carnosic and the rosmarinic acids, and to a much lesser extent the carnosol, constituted the main antioxidant components of the UK-plants, with the two acids being present at a ratio of 3:1, respectively.

Fe-doped and -mediated graphitic carbon nitride nanosheets for enhanced photocatalytic performance under natural sunlight

Herein, we demonstrate the synthesis of highly efficient Fe-doped graphitic carbon nitride (g-C3N4) nanosheets via a facile and cost effective method. The synthesized Fe-doped g-C3N4 nanosheets were well characterized by various analytical techniques. The results revealed that the Fe exists mainly in the +3 oxidation state in the Fe-doped g-C3N4 nanosheets. Fe doping of g-C3N4 nanosheets has a great influence on the electronic and optical properties. The diffuse reflectance spectra of Fe-doped g-C3N4 nanosheets exhibit red shift and increased absorption in the visible light range, which is highly beneficial for absorbing the visible light in the solar spectrum. More significantly, the Fe-doped g-C3N4 nanosheets exhibit greatly enhanced photocatalytic activity for the degradation of Rhodamine B under sunlight irradiation. The photocatalytic activity of 2 mol% Fe-doped g-C3N4 nanosheets is almost 7 times higher than that of bulk g-C3N4 and 4.5 times higher than that of pure g-C3N4 nanosheets. A proposed mechanism for the enhanced photocatalytic activity of Fe-doped g-C3N4 nanosheets was investigated by trapping experiments. The synthesized photocatalysts are highly stable even after five successive experimental runs. The enhanced photocatalytic performance of Fe-doped g-C3N4 nanosheets is due to high visible light response, large surface area, high charge separation and charge transfer. Therefore, the Fe-doped g-C3N4 photocatalyst is a promising candidate for energy conversion and environmental remediation.

g-C3N4/NaTaO3 organic–inorganic hybrid nanocomposite:high-performance and recyclable visible light driven photocatalyst

Novel g-C3N4/NaTaO3 hybrid nanocomposites have been prepared by a facile ultrasonic dispersion method. Our results clearly show the formation of interface between NaTaO3 and g-C3N4 and further loading of g-C3N4 did not affect the crystal structure and morphology of NaTaO3. The g-C3N4/NaTaO3 nanocomposites exhibited enhanced photocatalytic performance for the degradation of Rhodamine B under UV–visible and visible light irradiation compared to pure NaTaO3 and Degussa P25. Interestingly, the visible light photocatalytic activity is generated due to the loading of g-C3N4. A mechanism is proposed to discuss the enhanced photocatalytic activity based on trapping experiments of photoinduced radicals and holes. Under visible light irradiation, electron excited from the valance band (VB) to conduction band (CB) of g-C3N4 could directly inject into the CB of NaTaO3, making g-C3N4/NaTaO3 visible light driven photocatalyst. Since the as-prepared hybrid nanocomposites possess high reusability therefore it can be promising photocatalyst for environmental applications.

Synthesis of magnetically separable and recyclable g‑C3N4−Fe3O4 hybrid nanocomposites with enhanced photocatalytic performance under visible-light irradiation

Herein we demonstrate a facile, reproducible, and template-free strategy to prepare g-C3N4–Fe3O4 nanocomposites by an in situ growth mechanism. The results indicate that monodisperse Fe3O4 nanoparticles with diameters as small as 8 nm are uniformly deposited on g-C3N4 sheets, and as a result, aggregation of the Fe3O4 nanoparticles is effectively prevented. The as-prepared g-C3N4–Fe3O4 nanocomposites exhibit significantly enhanced photocatalytic activity for the degradation of rhodamine B under visible-light irradiation. Interestingly, the g-C3N4–Fe3O4 nanocomposites showed good recyclability without loss of apparent photocatalytic activity even after six cycles, and more importantly, g-C3N4–Fe3O4 could be recovered magnetically. The high performance of the g-C3N4–Fe3O4 photocatalysts is due to a synergistic effect including the large surface-exposure area, high visible-light-absorption efficiency, and enhanced charge-separation properties. In addition, the superparamagnetic behavior of the as-prepared g-C3N4–Fe3O4 nanocomposites also makes them promising candidates for applications in the fields of lithium storage capacity and bionanotechnology.

A methodological framework for modeling pavement maintenance costs for projects with performance-based contracts

Performance-based maintenance contracts differ significantly from material and method-based contracts that have been traditionally used to maintain roads. Road agencies around the world have moved towards a performance-based contract approach because it offers several advantages like cost saving, better budgeting certainty, better customer satisfaction with better road services and conditions. Payments for the maintenance of road are explicitly linked to the contractor successfully meeting certain clearly defined minimum performance indicators in these contracts. Quantitative evaluation of the cost of performance-based contracts has several difficulties due to the complexity of the pavement deterioration process. Based on a probabilistic analysis of failures of achieving multiple performance criteria over the length of the contract period, an effort has been made to develop a model that is capable of estimating the cost of these performance-based contracts. One of the essential functions of such model is to predict performance of the pavement as accurately as possible. Prediction of future degradation of pavement is done using Markov Chain Process, which requires estimating transition probabilities from previous deterioration rate for similar pavements. Transition probabilities were derived using historical pavement condition rating data, both for predicting pavement deterioration when there is no maintenance, and for predicting pavement improvement when maintenance activities are performed. A methodological framework has been developed to estimate the cost of maintaining road based on multiple performance criteria such as crack, rut and, roughness. The application of the developed model has been demonstrated via a real case study of Miami Dade Expressways (MDX) using pavement condition rating data from Florida Department of Transportation (FDOT) for a typical performance-based asphalt pavement maintenance contract. Results indicated that the pavement performance model developed could predict the pavement deterioration quite accurately. Sensitivity analysis performed shows that the model is very responsive to even slight changes in pavement deterioration rate and performance constraints. It is expected that the use of this model will assist the highway agencies and contractors in arriving at a fair contract value for executing long term performance-based pavement maintenance works.

The development of optimized high performance liquid chromatography systems for the analysis of improvised explosives

Existing instrumental techniques must be adaptable to the analysis of novel explosives if science is to keep up with the practices of terrorists and criminals. The focus of this work has been the development of analytical techniques for the analysis of two types of novel explosives: ascorbic acid-based propellants, and improvised mixtures of concentrated hydrogen peroxide/fuel. In recent years, the use of these explosives in improvised explosive devices (IEDs) has increased. It is therefore important to develop methods which permit the identification of the nature of the original explosive from post-blast residues. Ascorbic acid-based propellants are low explosives which employ an ascorbic acid fuel source with a nitrate/perchlorate oxidizer. A method which utilized ion chromatography with indirect photometric detection was optimized for the analysis of intact propellants. Post-burn and post-blast residues if these propellants were analyzed. It was determined that the ascorbic acid fuel and nitrate oxidizer could be detected in intact propellants, as well as in the post-burn and post-blast residues. Degradation products of the nitrate and perchlorate oxidizers were also detected. With a quadrupole time-of-flight mass spectrometer (QToFMS), exact mass measurements are possible. When an HPLC instrument is coupled to a QToFMS, the combination of retention time with accurate mass measurements, mass spectral fragmentation information, and isotopic abundance patterns allows for the unequivocal identification of a target analyte. An optimized HPLC-ESI-QToFMS method was applied to the analysis of ascorbic acid-based propellants. Exact mass measurements were collected for the fuel and oxidizer anions, and their degradation products. Ascorbic acid was detected in the intact samples and half of the propellants subjected to open burning; the intact fuel molecule was not detected in any of the post-blast residue. Two methods were optimized for the analysis of trace levels of hydrogen peroxide: HPLC with fluorescence detection (HPLC-FD), and HPLC with electrochemical detection (HPLC-ED). Both techniques were extremely selective for hydrogen peroxide. Both methods were applied to the analysis of post-blast debris from improvised mixtures of concentrated hydrogen peroxide/fuel; hydrogen peroxide was detected on variety of substrates. Hydrogen peroxide was detected in the post-blast residues of the improvised explosives TATP and HMTD.