A novel method for the synthesis of monodisperse gold-coated silica nanoparticles

Monodisperse silica nanoparticles were synthesised by the well-known Stober protocol, then dispersed in acetonitrile (ACN) and subsequently added to a bisacetonitrile gold(I) coordination complex ([Au(MeCN)2]?) in ACN. The silica hydroxyl groups were deprotonated in the presence of ACN, generating a formal negative charge on the siloxy groups. This allowed the [Au(MeCN)2]? complex to undergo ligand exchange with the silica nanoparticles and form a surface coordination complex with reduction to metallic gold (Au0) proceeding by an inner sphere mechanism. The residual [Au(MeCN)2]? complex was allowed to react with water, disproportionating into Au0 and Au(III), respectively, with the Au0 adding to the reduced gold already bound on the silica surface. The so-formed metallic gold seed surface was found to be suitable for the conventional reduction of Au(III) to Au0 by ascorbic acid (ASC). This process generated a thin and uniform gold coating on the silica nanoparticles. The silica NPs batches synthesised were in a size range from 45 to 460 nm. Of these silica NP batches, the size range from 400 to 480 nm were used for the gold-coating experiments.

Low temperature synthesis of carbon nanotubes on indium tin oxide electrodes for organic solar cells

The electrical performance of indium tin oxide (ITO) coated glass was improved by including a controlled layer of carbon nanotubes directly on top of the ITO film. Multi-wall carbon nanotubes (MWCNTs) were synthesized by chemical vapor deposition, using ultra-thin Fe layers as catalyst. The process parameters (temperature, gas flow and duration) were carefully refined to obtain the appropriate size and density of MWCNTs with a minimum decrease of the light harvesting in the cell. When used as anodes for organic solar cells based on poly(3-hexylthiophene) (P3HT) and phenyl-C61-butyric acid methyl ester (PCBM), the MWCNT-enhanced electrodes are found to improve the charge carrier extraction from the photoactive blend, thanks to the additional percolation paths provided by the CNTs. The work function of as-modified ITO surfaces was measured by the Kelvin probe method to be 4.95 eV, resulting in an improved matching to the highest occupied molecular orbital level of the P3HT. This is in turn expected to increase the hole transport and collection at the anode, contributing to the significant increase of current density and open circuit voltage observed in test cells created with such MWCNT-enhanced electrodes.

Experimental and theoretical investigation of ligand effects on the synthesis of ZnO nanoparticles

ZnO nanoparticles with highly controllable particle sizes(less than 10 nm) were synthesized using organic capping ligands in Zn(Ac)2 ethanolic solution. The molecular structure of the ligands was found to have significant influence on the particle size. The multi-functional molecule tris(hydroxymethyl)-aminomethane (THMA) favoured smaller particle distributions compared with ligands possessing long hydrocarbon chains that are more frequently employed. The adsorption of capping ligands on ZnnOn crystal nuclei (where n = 4 or 18 molecular clusters of(0001) ZnO surfaces) was modelled by ab initio methods at the density functional theory (DFT) level. For the molecules examined, chemisorption proceeded via the formation of Zn...O, Zn...N, or Zn...S chemical bonds between the ligands and active Zn2+ sites on ZnO surfaces. The DFT results indicated that THMA binds more strongly to the ZnO surface than other ligands, suggesting that this molecule is very effective at stabilizing ZnO nanoparticle surfaces. This study, therefore, provides new insight into the correlation between the molecular structure of capping ligands and the morphology of metal oxide nanostructures formed in their presence.

Physically sound vehicle-driver model for realistic microscopic simulation

In microscopic traffic simulators, the interaction between vehicles is considered. The dynamics of the system then becomes an emergent property of the interaction between its components. Such interactions include lane-changing, car-following behaviours and intersection management. Although, in some cases, such simulators produce realistic prediction, they do not allow for an important aspect of the dynamics, that is, the driver-vehicle interaction. This paper introduces a physically sound vehicle-driver model for realistic microscopic simulation. By building a nanoscopic traffic simulation model that uses steering angle and throttle position as parameters, the model aims to overcome unrealistic acceleration and deceleration values, as found in various microscopic simulation tools. A physics engine calculates the driving force of the vehicle, and the preliminary results presented here, show that, through a realistic driver-vehicle-environment simulator, it becomes possible to model realistic driver and vehicle behaviours in a traffic simulation.

The sound of music : sharing song selections between collocated strangers in public urban places

This paper presents Capital Music, a mobile application enabling real-time sharing of song choices with collocated urban dwellers. Due to the real-time, location-based peer-to-peer approach of the application, a user experience study was performed utilising the Wizard of Oz method. The study provides insight into how sharing non-privacy sensitive but personal data in an anonymous way can influence the user experience of people in public urban places. We discuss the findings in relation to how Capital Music influences the process of “cocooning” in public urban places, the practice of designing anonymous interactions between collocated strangers, and how the sharing of song choices can create a sense of commonality between anonymous users in the urban space. The outcomes of this study are relevant for future location-based social networking applications that aim to create interactions between collocated strangers.

Synthesis and characterisation of layered double hydroxides and their application for water purification

Layered doubly hydroxides (LDHs) also known as hydrotalcites or anionic clays are a group of clay minerals that have shown promise for the removal of toxic anions from water through both anion exchange and a process known as the reformation effect. This project has involved the preparation and characterisation of LDH materials as well as the investigation of their ability to remove selected anions from aqueous solutions by the reformation effect. The LDH materials were successfully prepared from magnesium, aluminium, zinc and chromium chloride salts using the co-precipitation method. Samples were characterised using powder X-ray diffraction (XRD) and thermogravimetry (TG) to confirm the presence of LDHs. Powder XRD revealed a characteristic LDH structure for all LDH samples. Thermal Analysis showed decomposition usual occurred through a three or four step process as expected for LDHs. Preliminary investigations of the removal of sulfate, nitrate and fluoride by an Mg/Al LDH were carried out, and the products were characterised using XRD and TG which showed that an LDH material similar to the original hydrotalcite was formed after reformation. A Zn/Al LDH was investigated as a potential sorbent material for the removal of iodine and iodide from water. It was found that the LDH was a suitable adsorbent which is able to remove almost all of the iodine present in the test solutions. Again, the products were characterised by XRD, TG and evolved gas mass spectrometry (EGMS) in an attempt to better understand the iodine removal process. Powder XRD showed successful reformation of the LDH structure and TG/EGMS showed that only a small amount of iodine species were lost during thermal decomposition. Finally, the mineral stichtite a Mg/Cr LDH was successfully synthesised and investigated using XRD, TG and EGMS. Unfortunately, due to lack of time it was not possible to identify any new uses for the mineral stichtite in the current project.

Computationally sound automated proofs of cryptographic schemes

Proving security of cryptographic schemes, which normally are short algorithms, has been known to be time-consuming and easy to get wrong. Using computers to analyse their security can help to solve the problem. This thesis focuses on methods of using computers to verify security of such schemes in cryptographic models. The contributions of this thesis to automated security proofs of cryptographic schemes can be divided into two groups: indirect and direct techniques. Regarding indirect ones, we propose a technique to verify the security of public-key-based key exchange protocols. Security of such protocols has been able to be proved automatically using an existing tool, but in a noncryptographic model. We show that under some conditions, security in that non-cryptographic model implies security in a common cryptographic one, the Bellare-Rogaway model [11]. The implication enables one to use that existing tool, which was designed to work with a different type of model, in order to achieve security proofs of public-key-based key exchange protocols in a cryptographic model. For direct techniques, we have two contributions. The first is a tool to verify Diffie-Hellmanbased key exchange protocols. In that work, we design a simple programming language for specifying Diffie-Hellman-based key exchange algorithms. The language has a semantics based on a cryptographic model, the Bellare-Rogaway model [11]. From the semantics, we build a Hoare-style logic which allows us to reason about the security of a key exchange algorithm, specified as a pair of initiator and responder programs. The other contribution to the direct technique line is on automated proofs for computational indistinguishability. Unlike the two other contributions, this one does not treat a fixed class of protocols. We construct a generic formalism which allows one to model the security problem of a variety of classes of cryptographic schemes as the indistinguishability between two pieces of information. We also design and implement an algorithm for solving indistinguishability problems. Compared to the two other works, this one covers significantly more types of schemes, but consequently, it can verify only weaker forms of security.

Process based synthesis to evaluate design flexibility in airport terminal layout

Flexible design concept is a relatively new trend in airport terminal design which is believed to facilitate the ever changing needs of a terminal. Current architectural design processes become more complex every day because of the introduction of new building technologies where the concept of flexible airport terminal would apparently make the design process even more complex. Previous studies have demonstrated that ever growing aviation industry requires airport terminals to be planned, designed and constructed in such a way that should allow flexibility in design process. In order to adopt the philosophy of ‘design for flexibility’ architects need to address a wide range of differing needs. An appropriate integration of the process models, prior to the airport terminal design process, is expected to uncover the relationships that exist between spatial layout and their corresponding functions. The current paper seeks to develop a way of sharing space adjacency related information obtained from the Business Process Models (BPM) to assist in defining flexible airport terminal layouts. Critical design parameters are briefly investigated at this stage of research whilst reviewing the available design alternatives and an evaluation framework is proposed in the current paper. Information obtained from various design layouts should assist in identifying and defining flexible design matrices allowing architects to interpret and to apply those throughout the lifecycle of the terminal building.