Stabilisation of polypropylene using polymer-bound antioxidants

variety of hindered phenol and hindered piperidine antioxidants containing vinyl or vinylidine functional groups have been synthesised and some of these were successfully bound to Polypropylene backbone during processing operations in presence of a radical generator. Up to 20% concentrates were prepared using this technique. Commercially acceptable concentrates (MASTERBATCHES) can only be prepared with antioxidants that are only weakly chain breaking such as hindered piperidines. One of the antioxidants, AATP was found to polymrise as well as bind to Polypropylene. Bound antioxidants were found to be resistant to such channels of physical loss as solvent extraction. Temperature and concentration of the additive and radical generator were found to be important parameters in the preparation of the concentrates. The stabilising efficiences of the diluted bound antioxidants alone, and in combination (synergistic) with other antioxidants have been evaluated. Results of both thermal and photo-oxidative stabilities of the bound samples in Polypropylene show that the restriction on free mobility of the bound antioxidants in the polymer has virtually no effect on its stabilising efficiency. Bound AATP was found to generate nitroxyl radicals during the course of its stabilising activities, and in combination with a small amount of Irganox 1076, it was shown to be highly synergistic thermally. A mechanism of catalytic phenol regeneration by the resultant piperidine hydroxylamine was proposed. Although the mechanical properties of the masterbatches were affected by the transformation, this was not found to be carried over to the diluted samples. This work has shown that bound concentrates can be effectively prepared in saturated polymers for subsequent dilution to normal concentrates used in commercial stabilisation.

The detection of automated perimetric stimuli in ocular disease

Automated perimetry has made viable a rapid threshold examination of the visual field and has reinforced the role of perimetry in the diagnostic procedure. The aim of this study was twofold: to isolate the influence of certain extraneous factors on the sensitivity gradient, since these might limit the early detection and accurate monitoring of visual field loss and to investigate the efficacy of certain novel combinations of stimulus parameters in the detection of early visual field loss. The work was carried out with particular reference to glaucoma and to ocular hypertension. The effects of media opacities on the visual field were assessed by forward intraocular light scatter (n= 15) and were found to mask diffuse glaucomatous visual field loss and underestimate focal loss. Correction of the visual field indices for the effects of forward intraocular light scatter (n= 26) showed the focal losses to be, in reality, unaffected. Measurements of back scatter underestimated forward intraocular light scatter (n= 60) and the resultant depression of the visual field. Perimetric sensitivity improved with patient learning (n= 25) and exhibited eccentricity- and depth-dependency effects whereby improvements in sensitivity were greatest for peripheral areas of the field and for those areas which initially demonstrated the lowest sensitivity. The effects of practice were retained over several months (n= 16). Perimetric sensitivity decreased during prolonged examination due to fatigue effects (n&61 19); these demonstrated a similar eccentricity-dependency, being greatest for eccentricities beyond 30o. Mean sensitivities over the range of adaptation levels employed obeyed the Weber-Fechner law (n= 10) and, as would be expected, were independent of pupil size. No relationship was found between short-term fluctuation and adaptation level. Detection of diffuse glaucomatous visual field loss was facilitated using a size III stimulus of duration 200msec at an adaptation level of 31.5asb, compared with a size III stimulus of duration 100msec at an adaptation level of 4asb (n= 20). In a pilot study (n= 10), temporal summation was found to be higher in glaucomatous patients compared with age-matched controls, although the difference was not statistically significant.

The study of ultra-low energy deposition of hydrogenated amorphous carbon thin films

This thesis is dedicated to the production and analysis of thin hydrogenated amorphous carbon films. A cascaded arc plasma source was used to produce a high density plasma of hydrocarbon radicals that deposited on a substrate at ultra low energies. The work was intended to create a better understanding of the mechanisms responsible for the film formation, by an extensive analysis on the properties of the films in correlation with the conditions used in the plasma cell. Two different precursors were used: methane and acetylene. They revealed a very different picture for the mechanism of film formation and properties. Methane was less successful, and the films formed were soft, with poor adhesion to the substrate and decomposing with time. Acetylene was the better option, and the films formed in this case were harder, with better adhesion to the substrate and stable over time. The plasma parameters could be varied to change the character of films, from polymer-like to diamond-like carbon. Films deposited from methane were grown at low deposition rates, which increased with the increase in process pressure and source power and decreased with the increase in substrate temperature and in hydrogen fraction in the carrier gas. The films had similar hydrogen content, sp3 fractions, average roughness (Ra) and low hardness. Above a deposition temperature of 350°C graphitization occurred - an increase in the sp2 fraction. A deposition mechanism was proposed, based upon the reaction product of the dissociative recombination of CH4+. There were small differences between the chemistries in the plasma at low and high precursor flow rates and low and high substrate temperatures; all experimental conditions led to formation of films that were either polymer-like, soft amorphous hydrogenated carbon or graphitic-like in structure. Films deposited from acetylene were grown at much higher deposition rates on different substrates (silicon, glass and plastics). The film quality increased noticeably with the increase of relative acetylene to argon flow rate, up to a certain value, where saturation occurred. With the increase in substrate temperature and the lowering of the acetylene injection ring position further improvements in film quality were achieved. The deposition process was scaled up to large area (5 x 5 cm) substrates in the later stages of the project. A deposition mechanism was proposed, based upon the reaction products of the dissociative recombination of C2H2 +. There were large differences between the chemistry in the plasma at low and medium/high precursor flow rates. This corresponded to large differences in film properties from low to medium flow rates, when films changed their character from polymer-like to diamond-like, whereas the differences between films deposited at medium and high precursor flow rates were small. Modelling of the film growth on silicon substrates was initiated and it explained the formation of sp2 and sp3 bonds at these very low energies. However, further improvements to the model are needed.

The impact of the introduction and use of an informational website on offline customer buying behavior

Do customers increase or decrease their spending in response to the introduction of an informational website? To answer this question, this study considers the effects of the introduction and use of an informational website by a large national retailer on offline customer buying behavior. More specifically, we study a website's effects on the number of shopping trips and the amount spent per category per shopping trip. The model is calibrated through the estimation of a Poisson model (shopping trips) and a type-II tobit model (the amount spent per category per shopping trip), with effect parameters that vary across customers. For the focal retailer, an informational website creates more bad than good news; most website visitors engage in fewer shopping trips and spend less in all product categories. The authors also compare the characteristics of shoppers who exhibit negative website effects with those few shoppers who show positive effects and thus derive key implications for research and practice.

Characteristics of motor resonance predict the pattern of flash-lag effects for biological motion

Background - When a moving stimulus and a briefly flashed static stimulus are physically aligned in space the static stimulus is perceived as lagging behind the moving stimulus. This vastly replicated phenomenon is known as the Flash-Lag Effect (FLE). For the first time we employed biological motion as the moving stimulus, which is important for two reasons. Firstly, biological motion is processed by visual as well as somatosensory brain areas, which makes it a prime candidate for elucidating the interplay between the two systems with respect to the FLE. Secondly, discussions about the mechanisms of the FLE tend to recur to evolutionary arguments, while most studies employ highly artificial stimuli with constant velocities. Methodology/Principal Finding - Since biological motion is ecologically valid it follows complex patterns with changing velocity. We therefore compared biological to symbolic motion with the same acceleration profile. Our results with 16 observers revealed a qualitatively different pattern for biological compared to symbolic motion and this pattern was predicted by the characteristics of motor resonance: The amount of anticipatory processing of perceived actions based on the induced perspective and agency modulated the FLE. Conclusions/Significance - Our study provides first evidence for an FLE with non-linear motion in general and with biological motion in particular. Our results suggest that predictive coding within the sensorimotor system alone cannot explain the FLE. Our findings are compatible with visual prediction (Nijhawan, 2008) which assumes that extrapolated motion representations within the visual system generate the FLE. These representations are modulated by sudden visual input (e.g. offset signals) or by input from other systems (e.g. sensorimotor) that can boost or attenuate overshooting representations in accordance with biased neural competition (Desimone & Duncan, 1995).

Increase of the photosensitivity of undoped poly(methylmethacrylate) under UV radiation at 325 nm

In this paper we report, for the first time to our knowledge, an increase of the photosensitivity of a microstructured polymer optical fibre (mPOF) made of undoped PMMA due to applied strain during the fabrication of the gratings. In the work, fibre Bragg gratings (FBGs) have been fabricated in undoped PMMA mPOFs with a hexagonal structure of three rings in the inner cladding. Two sets of FBGs were inscribed at two different resonant wavelengths (827 nm and 1562 nm) at different strains using an UV He-Cd laser at 325 nm focused by a lens and scanned over the fibre. We observed an increase of the reflection of the fibre Bragg gratings when the fabrication strain is higher. The photosensitivity mechanism is discussed in the paper along with the chemical reactions that could underlie the mechanism. Furthermore, the resolution limit of the material was investigated. © 2014 Copyright SPIE.

Vulnerability of exporting nations to the development of a carbon label in the United Kingdom

Carbon labels inform consumers about the amount of greenhouse gases (GHGs) released during the production and consumption of goods, including food. In the future consumer and legislative responses to carbon labels may favour goods with lower emissions, and thereby change established supply chains. This may have unintended consequences. We present the carbon footprint of three horticultural goods of different origins supplied to the United Kingdom market: lettuce, broccoli and green beans. Analysis of these footprints enables the characterisation of three different classes of vulnerability which are related to: transport, national economy and supply chain specifics. There is no simple relationship between the characteristics of an exporting country and its vulnerability to the introduction of a carbon label. Geographically distant developing countries with a high level of substitutable exports to the UK are most vulnerable. However, many developing countries have low vulnerability as their main exports are tropical crops which would be hard to substitute with local produce. In the short term it is unlikely that consumers will respond to carbon labels in such a way that will have major impacts in the horticultural sector. Labels which require contractual reductions in GHG emissions may have greater impacts in the short term.

Reactive processing of polymers:melt grafting of glycidyl methacrylate on ethylene propylene copolymer in the presence of a coagent

Glycidyl methacrylate (GMA) was grafted on ethylene-propylene copolymer during melt processing with peroxide initiation in the presence and absence of a more reactive comonomer (coagent), trimethylolpropane triacrylate (Tris). The characteristics of the grafting systems in terms of the grafting reaction yield and the nature and extent of the competing side reactions were examined. The homopolymers of GMA (Poly-GMA) and Tris (Poly-Tris) and the GMA-Tris copolymer (GMA-co-Tris) were synthesized and characterized. In the absence of the coagent, high levels of poly-GMA, which constituted the major competing reaction, was formed, giving rise to low GMA grafting levels. Further, this grafting system resulted in a high extent of gel formation and polymer crosslinking due to the high levels of peroxide needed to achieve optimum GMA grafting and a consequent large drop in the melt index (increased viscosity) of the polymer. In the presence of the coagent, however, the grafting system required much lower peroxide concentration, by almost an order of magnitude, to achieve the optimum grafting yield. The coagent-containing GMA-grafting system has also resulted in a drastic reduction in the extent of all competing reactions, and in particular, the GMA homopolymerization, leading to improved GMA grafting efficiency with no detectable gel or crosslinking. The mechanisms of the grafting reactions, in the presence and absence of Tris, are proposed.

Analysis of the Distributions of Color Characteristics in Art Painting Images

In this paper we study some of the characteristics of the art painting image color semantics. We analyze the color features of differ- ent artists and art movements. The analysis includes exploration of hue, saturation and luminance. We also use quartile’s analysis to obtain the dis- tribution of the dispersion of defined groups of paintings and measure the degree of purity for these groups. A special software system “Art Paint- ing Image Color Semantics” (APICSS) for image analysis and retrieval was created. The obtained result can be used for automatic classification of art paintings in image retrieval systems, where the indexing is based on color characteristics.

A technique for mitigating the effect of the writing-beam profile on fibre Bragg grating fabrication

We propose and demonstrate a pre-compensation mechanism to account for the writing-beam profile which when applied to the design of advanced fibre Bragg gratings helps to achieve a desired design spectral response. We use the example of a complex multi-channel grating as an example to demonstrate the improvement achievable using the pre- compensation and find good agreement between experimental results and numerical calculations.

Maximization of a Linear Utility Function over the Set of the Housing Market Short-Term Equilibria

AMS subject classification: 90C05, 90A14.

Smartphone-based digital government model:the case of the beyaz masa (white table) app in Turkey

M-Government services are now at the forefront of both user expectations and technology capabilities. Within the current setting, there is growing evidence that interoperability is becoming a key issue towards service sustainability. Thus, the objective of this chapter is to highlight the case of "Beyas Masa" - a Turkish application for infrastructure repair services. This application requires different stakeholders from different cultural background and geographically dispersed regions to work together. The major aim of this chapter to showcase experiences in as far as implementation and adoption of m-Government is concerned in the case of Turkey. The study utilizes the co-creation literature to investigate the factors influencing successful implementation of the Beyas Masa. This study reveals that initiatives are fragmented due to differences in the characteristics of the targeted audience, the marketing strategy, technology supply, distribution, and media utilized to promote its awareness. The chapter posits that in order to have affluent m-Government implementation in Turkey, it is important that many of the standalone applications are integrated to encourage interoperability and that socio-cultural behaviours should be re-shaped to encourage active engagement and interactive government service provisions that unlock the power of ICT.

Investigating the origin of PM2.5 in Baltimore using highly time-resolved organic molecular markers measured during the Baltimore PM-supersite

The detailed organic composition of atmospheric fine particles with an aerodynamic diameter smaller than or equal to 2.5 micrometers (PM2.5) is an integral part of the knowledge needed in order to fully characterize its sources and transformation in the environment. For the study presented here, samples were collected at 3-hour intervals. This high time resolution allows gaining unique insights on the influence of short- and long-range transport phenomena, and dynamic atmospheric processes. A specially designed sequential sampler was deployed at the 2002-2003 Baltimore PM-Supersite to collect PM2.5 samples at a 3-hourly resolution for extended periods of consecutive days, during both summer and winter seasons. Established solvent-extraction and GC-MS techniques were used to extract and analyze the organic compounds in 119 samples from each season. Over 100 individual compounds were quantified in each sample. For primary organics, averaging the diurnal ambient concentrations over the sampled periods revealed ambient patterns that relate to diurnal emission patterns of major source classes. Several short-term releases of pollutants from local sources were detected, and local meteorological data was used to pinpoint possible source regions. Biogenic secondary organic compounds were detected as well, and possible mechanisms of formation were evaluated. The relationships between the observed continuous variations of the concentrations of selected organic markers and both the on-site meteorological measurements conducted parallel to the PM2.5 sampling, and the synoptic patterns of weather and wind conditions were also examined. Several one-to-two days episodes were identified from the sequential variation of the concentration observed for specific marker compounds and markers ratios. The influence of the meteorological events on the concentrations of the organic compounds during selected episodes was discussed. It was observed that during the summer, under conditions of pervasive influence of air masses originated from the west/northwest, some organic species displayed characteristics consistent with the measured PM2.5 being strongly influenced by the aged nature of these long-traveling background parcels. During the winter, intrusions from more regional air masses originating from the south and the southwest were more important.

What does board capital really bring to the table? Exploring the effect of directors' human and social capital on effective governance during international expansion

What constitutes effective corporate governance? Which director characteristics render boards effective at positively influencing firm-level performance outcomes? This dissertation examines these questions by taking a multilevel, multidisciplinary approach to corporate governance. I explore the individual-, team-, and firm- level factors that enable directors to serve effectively as strategic resources during international expansion. I argue that directors' international experience improves their ability to serve as effective strategic consultants and resource providers to firms during the complex internationalization process. However, unlike prior research, which tends to assume that directors with the potential to provide important resources uniformly do so, I acknowledge contextual factors (i.e. board cohesiveness, strategic relevance of directors' experience) that affect their propensity to actually influence outcomes. I explore these issues in three essays: one review essay and two empirical essays.^ In the first empirical essay, I integrate resource dependence theory with insights from social-psychological research to explore the influence of board capital on firms' cross-border M&A performance. Using a sample of cross-border M&As completed by S&P 500 firms from 2004-2009, I find evidence that directors' depth of international experience is associated with superior pre-deal outcomes. This suggests that boards' deep, market-specific knowledge is valuable during the target selection phase. I further find that directors' breadth of international experience is associated with superior post-deal performance, suggesting that these directors' global mindset helps firms in the post-M&A integration phase. I also find that these relationships are positively moderated by board cohesiveness, measured by boards' internal social ties.^ In the second empirical essay, I explore the boundary conditions of international board capital by examining how the characteristics of firms' internationalization strategy moderate the relationship between board capital and firm performance. Using a panel of 377 S&P 500 firms observed from 2004-2011, I find that boards' depth of international experience and social capital are more important during early stages of internationalization, when firms tend to lack market knowledge and legitimacy in the host markets. On the other hand, I find that breadth of international experience has a stronger relationship with performance when firms' have higher scope of internationalization, when information-processing demands are higher.^

Investigating the origin of PM2.5 in Baltimore using highly time-resolved organic molecular markers measured during the Baltimore PM-supersite

The detailed organic composition of atmospheric fine particles with an aerodynamic diameter smaller than or equal to 2.5 micrometers (PM 2.5) is an integral part of the knowledge needed in order to fully characterize its sources and transformation in the environment. For the study presented here, samples were collected at 3-hour intervals. This high time resolution allows gaining unique insights on the influence of short- and long-range transport phenomena, and dynamic atmospheric processes. A specially designed sequential sampler was deployed at the 2002-2003 Baltimore PM Supersite to collect PM2.5 samples at a 3-hourly resolution for extended periods of consecutive days, during both summer and winter seasons. Established solvent-extraction and GC-MS techniques were used to extract and analyze the organic compounds in 119 samples from each season. Over 100 individual compounds were quantified in each sample. For primary organics, averaging the diurnal ambient concentrations over the sampled periods revealed ambient patterns that relate to diurnal emission patterns of major source classes. Several short-term releases of pollutants from local sources were detected, and local meteorological data was used to pinpoint possible source regions. Biogenic secondary organic compounds were detected as well, and possible mechanisms of formation were evaluated. The relationships between the observed continuous variations of the concentrations of selected organic markers and both the on-site meteorological measurements conducted parallel to the PM2.5 sampling, and the synoptic patterns of weather and wind conditions were also examined. Several one-to-two days episodes were identified from the sequential variation of the concentration observed for specific marker compounds and markers ratios. The influence of the meteorological events on the concentrations of the organic compounds during selected episodes was discussed. It was observed that during the summer, under conditions of pervasive influence of air masses originated from the west/northwest, some organic species displayed characteristics consistent with the measured PM2.5 being strongly influenced by the aged nature of these long-traveling background parcels. During the winter, intrusions from more regional air masses originating from the south and the southwest were more important.