In-situ generation of silica particles in solution styrene butadiene rubber – A possible material solution to improve the performance of rubber

In the field of tyre technology, silica filled tyres are generally considered as a lower energy consumption product due to their lower rolling resistance characteristics. Additionally, they can offer excellent grip on the wet and snowy conditions which are more essential from the safety perspective. However, the proper dispersion of the silica in rubber compounds is one of the challenging tasks to engineers, physicist and chemist. In this thesis, a very controlled in-situ silica based solution styrene butadiene rubber composites were developed and intensively investigated by the synthesis of sol-gel silica in presence of polymer solution. It means the silica particles were allowed to grow in the presence of rubber in the reaction mixture. It was observed that the sizes of the synthesized silica particles are rather larger than standard precipitated commercial silica particles. In depth morphological investigation revealed that the obtained sol-gel silica particles appear in strong cluster form with primary particle size of 10 - 15 nm and final aggregated size of 200 to 400 nm. Nevertheless, the final mechanical performance and other rubber related properties of in-situ derived silica composites are better in many important aspects for technical applications as compared with commercial silica at a given loading of fillers. Owing to the presence of more active hydroxyl group on the surface of sol-gel silica, the effective coupling between silica and rubber has been established. Furthermore, the permanent trapped rubber chains inside the large aggregates of sol-gel silica particles enable the compounds to offer good mechanical reinforcement, higher resilience, and dynamic mechanical properties. The present work is a humble approach to pave an alternative novel way for silica-rubber composite preparation in order to minimize the problem of silica mixing with the rubbers.Auf dem Gebiet der Reifentechnologie zeichnen sich Kieselsäure-(Silika)-gefüllte Reifen aufgrund ihres charakteristisch geringeren Rollwiderstands allgemein als ein Produkt mit geringerem Energieverbrauch aus. Darüber hinaus bieten sie ein hervorragendes Nasshaftvermögen, welches eine essentielle physikalische Kenngröße für die Fahrsicherheit darstellt. Allerdings stellt eine optimale Dispergierung der Silikafüllstoffs in Kautschukmischungen eine anspruchsvolle Aufgabe für Ingenieure, Physiker und Chemiker dar. Im Rahmen der vorliegenden Arbeit wurden Silika / Styrol-Butadien-Kautschuk-Verbundwerkstoffe mittels eines in-situ Sol-Gel-lösungsmittelbasierten Reaktionsverfahrens entwickelt. Diese Technologie beruht auf der Nukleierung von Kieselsäure-Partikeln in Gegenwart des Elastomers in einer Syntheselösung. Dabei wurde beobachtet, dass die Partikel der so synthetisierten Silika-Teilchen größer sind, als die eines kommerziellen Standard-Silika-Füllstoffs. Eine umfassende morphologische Untersuchung zeigt, dass die in-situ synthetisierten Silikapartikel sphärisch sind und eine Primärteilchengröße von 10 bis 15 nm aufweisen. Diese nanoskaligen Teilchen agglomerieren sich zu größeren sphärischen Clustern mit einer Größe von 200 bis 400 nm und weisen somit eine andere Morphologie auf, als die kommerziell erhältlichen Silika-Füllstoffe. Die statisch- und dynamisch-mechanischen Eigenschaften, sowie weitere elastomerbezogene Eigenschaften der in-situ synthetisierten Silika/Styrol-Butadien-Kautschuk-Verbundwerkstoffe, wie z.B. Rückprallelastizität, mechanisch induzierte Wärmeentwicklung und Spannung-Dehnungshysterese, zeigen verbesserte Werte im Vergleich zu Elastomermaterialien gefüllt mit kommerzieller Kieselsäure. Eine erhöhte Anzahl von Hydroxylgruppen auf der Oberfläche der in-situ synthetisierten Silikapartikel, verbunden mit permanenter Adsorption der Polymerketten des Elastomers auf der Teilchenoberfläche ermöglicht die Ausbildung eines Elastomerverbundes mit verbesserter mechanischer Verstärkung mit oder ohne Einsatz eines haftvermittelnden Silans, wie z.B. TESPT (Bis [3-(triethoxysilyl)propyl]-tetrasulfid). Die Wechselwirkungen zwischen Elastomer und Füllstoff, zwischen den Füllstoffpartikeln, sowie der Verstärkungsmechanismus des in-situ synthetisierten Füllstoffes wurden mittels dynamischmechanischer Analyse (Amplitudentests), Festkörper-NMR und energiedispersiver Röntgenspektroskopie umfassend analysiert. Der vorliegende Ansatz verdeutlicht, dass die in-situ Generierung des Füllstoffes im Elastomer ein vielversprechendes und alternatives Verfahren zur Herstellung von Elastomermaterialien mit verbesserter Silika-Dispergierung, sowie erhöhter Elastomer-Füllstoff-Wechselwirkung bietet

In-situ generation of silica particles in solution styrene butadiene rubber – A possible material solution to improve the performance of rubber

In the field of tyre technology, silica filled tyres are generally considered as a lower energy consumption product due to their lower rolling resistance characteristics. Additionally, they can offer excellent grip on the wet and snowy conditions which are more essential from the safety perspective. However, the proper dispersion of the silica in rubber compounds is one of the challenging tasks to engineers, physicist and chemist. In this thesis, a very controlled in-situ silica based solution styrene butadiene rubber composites were developed and intensively investigated by the synthesis of sol-gel silica in presence of polymer solution. It means the silica particles were allowed to grow in the presence of rubber in the reaction mixture. It was observed that the sizes of the synthesized silica particles are rather larger than standard precipitated commercial silica particles. In depth morphological investigation revealed that the obtained sol-gel silica particles appear in strong cluster form with primary particle size of 10 - 15 nm and final aggregated size of 200 to 400 nm. Nevertheless, the final mechanical performance and other rubber related properties of in-situ derived silica composites are better in many important aspects for technical applications as compared with commercial silica at a given loading of fillers. Owing to the presence of more active hydroxyl group on the surface of sol-gel silica, the effective coupling between silica and rubber has been established. Furthermore, the permanent trapped rubber chains inside the large aggregates of sol-gel silica particles enable the compounds to offer good mechanical reinforcement, higher resilience, and dynamic mechanical properties. The present work is a humble approach to pave an alternative novel way for silica-rubber composite preparation in order to minimize the problem of silica mixing with the rubbers.Auf dem Gebiet der Reifentechnologie zeichnen sich Kieselsäure-(Silika)-gefüllte Reifen aufgrund ihres charakteristisch geringeren Rollwiderstands allgemein als ein Produkt mit geringerem Energieverbrauch aus. Darüber hinaus bieten sie ein hervorragendes Nasshaftvermögen, welches eine essentielle physikalische Kenngröße für die Fahrsicherheit darstellt. Allerdings stellt eine optimale Dispergierung der Silikafüllstoffs in Kautschukmischungen eine anspruchsvolle Aufgabe für Ingenieure, Physiker und Chemiker dar. Im Rahmen der vorliegenden Arbeit wurden Silika / Styrol-Butadien-Kautschuk-Verbundwerkstoffe mittels eines in-situ Sol-Gel-lösungsmittelbasierten Reaktionsverfahrens entwickelt. Diese Technologie beruht auf der Nukleierung von Kieselsäure-Partikeln in Gegenwart des Elastomers in einer Syntheselösung. Dabei wurde beobachtet, dass die Partikel der so synthetisierten Silika-Teilchen größer sind, als die eines kommerziellen Standard-Silika-Füllstoffs. Eine umfassende morphologische Untersuchung zeigt, dass die in-situ synthetisierten Silikapartikel sphärisch sind und eine Primärteilchengröße von 10 bis 15 nm aufweisen. Diese nanoskaligen Teilchen agglomerieren sich zu größeren sphärischen Clustern mit einer Größe von 200 bis 400 nm und weisen somit eine andere Morphologie auf, als die kommerziell erhältlichen Silika-Füllstoffe. Die statisch- und dynamisch-mechanischen Eigenschaften, sowie weitere elastomerbezogene Eigenschaften der in-situ synthetisierten Silika/Styrol-Butadien-Kautschuk-Verbundwerkstoffe, wie z.B. Rückprallelastizität, mechanisch induzierte Wärmeentwicklung und Spannung-Dehnungshysterese, zeigen verbesserte Werte im Vergleich zu Elastomermaterialien gefüllt mit kommerzieller Kieselsäure. Eine erhöhte Anzahl von Hydroxylgruppen auf der Oberfläche der in-situ synthetisierten Silikapartikel, verbunden mit permanenter Adsorption der Polymerketten des Elastomers auf der Teilchenoberfläche ermöglicht die Ausbildung eines Elastomerverbundes mit verbesserter mechanischer Verstärkung mit oder ohne Einsatz eines haftvermittelnden Silans, wie z.B. TESPT (Bis [3-(triethoxysilyl)propyl]-tetrasulfid). Die Wechselwirkungen zwischen Elastomer und Füllstoff, zwischen den Füllstoffpartikeln, sowie der Verstärkungsmechanismus des in-situ synthetisierten Füllstoffes wurden mittels dynamischmechanischer Analyse (Amplitudentests), Festkörper-NMR und energiedispersiver Röntgenspektroskopie umfassend analysiert. Der vorliegende Ansatz verdeutlicht, dass die in-situ Generierung des Füllstoffes im Elastomer ein vielversprechendes und alternatives Verfahren zur Herstellung von Elastomermaterialien mit verbesserter Silika-Dispergierung, sowie erhöhter Elastomer-Füllstoff-Wechselwirkung bietet

A nonequilibrium model for particle networking/jamming and time-dependent dynamic rheology of filled polymers

We describe an approach for modeling the filler network formation kinetics of particle-reinforced rubbery polymers—commonly called filler flocculation—that was developed by employing parallels between deformation effects in jammed particle systems and the influence of temperature on glass-forming materials. Experimental dynamic viscosity results were obtained concerning the strain-induced particle network breakdown and subsequent time-dependent reformation behavior for uncross-linked elastomers reinforced with carbon black and silica nanoparticles. Using a relaxation time function that depends on both actual dynamic strain amplitude and fictive (structural) strain, the model effectively represented the experimental data for three different levels of dynamic strain down-jump with a single set of parameters. This fictive strain model for filler networking is analogous to the established Tool–Narayanaswamy–Moynihan model for structural relaxation (physical aging) of nonequilibrium glasses. Compared to carbon black, precipitated silica particles without silane surface modification exhibited a greater overall extent of filler networking and showed more self-limiting behavior in terms of network formation kinetics in filled ethylene-propylene-diene rubber (EPDM). The EPDM compounds with silica or carbon black filler were stable during the dynamic shearing and recovery experiments at 160 °C, whereas irreversible dynamic modulus increases were noted when the polymer matrix was styrene-butadiene rubber (SBR), presumably due to branching/cross-linking of SBR in the rheometer. Care must be taken when measuring and interpreting the time-dependent filler networking in unsaturated elastomers at high temperatures

Designing an Optimum Fiscal Policy for Tobacco to Maximise the Tax Revenue, Social Savings and the Net Monetary Benefits in Sri Lanka

Background: Fiscal policy targeting tobacco control is identified as the most effective strategy for rapid control of tobacco use. An optimum fiscal policy to estimate the percentage taxation that will maximise the government tax revenue, social savings and the net monetary benefit has not been empirically designed before in Sri Lanka.Methods: A model was developed using Microsoft Excel 2016, utilizing up-to-date published evidence on the cigarette sales, current fiscal policy, social cost of tobacco use, consumer response and the price elasticity of cigarettes. Univariate estimates on the expected revenue from tobacco tax, average annual social savings and the net monetary benefit were predicted for different levels of tobacco taxation. A deterministic sensitivity analysis was performed covering all possibilities. The percentage taxation maximizing the government tax revenue and the net monetary benefit were identified.Results: It was estimated that a further 30% tax increase from the 2019 baseline will generate approximately LKR 3544 million per year of additional tax revenue for the government while saving LKR 28 069 million per annum as social savings. A fiscal elevation of 50% will produce identical annual tax revenue to that of 2018, while securing a social saving of more than LKR 47 600 million per annum. The maximum net monetary benefit is achievable at an overnight tax increase of 90% from the baseline, however with a short-term compromise in tax revenue.Conclusion: The well-defined thresholds take tobacco taxation advocacy in Sri Lanka a step forward and will assist the government in taking an informed decision on its fiscal policy for cigarettes

An Unusual Complication of Suprapubic Catheter Insertion

A patient who had a small bowel mesentery perforation following insertion of a suprapubic catheter (SPC) is described. He had no bowel complaints immediately following the procedure, but presented 10 weeks later with insidious onset bowel obstruction due to the kink caused by the catheter. This complication occurred despite cystoscopy control and adequate bladder distension prior to the procedure. This isolated case illustrates the fact that regardless of the ease and frequency of SPC insertion, complications do occur

Impact of a general practitioner-led integrated model of care on the cost of potentially preventable diabetes-related hospitalisations

Aim To estimate potential savings for Australia's health care system through the implementation of an innovative Beacon model of care for patients with complex diabetes. Methods A prospective controlled trial was conducted comparing a multidisciplinary, community-based, integrated primary-secondary care diabetes service with usual care at a hospital diabetes outpatient clinic. We extracted patient hospitalisation data from the Queensland Hospital Admitted Patient Data Collection and used Australian Refined Diagnosis Related Groups to assign costs to potentially preventable hospitalisations for diabetes. Results 327 patients with complex diabetes referred by their general practitioner for specialist outpatient care were included in the analysis. The integrated model of care had potential for national cost savings of $132.5 million per year. Conclusions The differences in hospitalisations attributable to better integrated primary/secondary care can yield large cost savings. Models such as the Beacon are highly relevant to current national health care reform initiatives to improve the continuity and efficiency of care for those with complex chronic disease in primary care

Numerical Estimation of Surface Parameters by Level Set Methods

A modular level set algorithm is developed to study the interface and its movement for free moving boundary problems. The algorithm is divided into three basic modules : initialization, propagation and contouring. Initialization is the process of finding the signed distance function from closed objects. We discuss here, a methodology to find an accurate signed distance function from a closed, simply connected surface discretized by triangulation. We compute the signed distance function using the direct method and it is stored efficiently in the neighborhood of the interface by a narrow band level set method. A novel approach is employed to determine the correct sign of the distance function at convex-concave junctions of the surface. The accuracy and convergence of the method with respect to the surface resolution is studied. It is shown that the efficient organization of surface and narrow band data structures enables the solution of large industrial problems. We also compare the accuracy of the signed distance function by direct approach with Fast Marching Method (FMM). It is found that the direct approach is more accurate than FMM. Contouring is performed through a variant of the marching cube algorithm used for the isosurface construction from volumetric data sets. The algorithm is designed to keep foreground and background information consistent, contrary to the neutrality principle followed for surface rendering in computer graphics. The algorithm ensures that the isosurface triangulation is closed, non-degenerate and non-ambiguous. The constructed triangulation has desirable properties required for the generation of good volume meshes. These volume meshes are used in the boundary element method for the study of linear electrostatics. For estimating surface properties like interface position, normal and curvature accurately from a discrete level set function, a method based on higher order weighted least squares is developed. It is found that least squares approach is more accurate than finite difference approximation. Furthermore, the method of least squares requires a more compact stencil than those of finite difference schemes. The accuracy and convergence of the method depends on the surface resolution and the discrete mesh width. This approach is used in propagation for the study of mean curvature flow and bubble dynamics. The advantage of this approach is that the curvature is not discretized explicitly on the grid and is estimated on the interface. The method of constant velocity extension is employed for the propagation of the interface. With least squares approach, the mean curvature flow has considerable reduction in mass loss compared to finite difference techniques. In the bubble dynamics, the modules are used for the study of a bubble under the influence of surface tension forces to validate Young-Laplace law. It is found that the order of curvature estimation plays a crucial role for calculating accurate pressure difference between inside and outside of the bubble. Further, we study the coalescence of two bubbles under surface tension force. The application of these modules to various industrial problems is discussed.Numerische Abschätzungen von Oberflächenparametern durch die Level-Set-Method

Numerical Estimation of Surface Parameters by Level Set Methods

A modular level set algorithm is developed to study the interface and its movement for free moving boundary problems. The algorithm is divided into three basic modules : initialization, propagation and contouring. Initialization is the process of finding the signed distance function from closed objects. We discuss here, a methodology to find an accurate signed distance function from a closed, simply connected surface discretized by triangulation. We compute the signed distance function using the direct method and it is stored efficiently in the neighborhood of the interface by a narrow band level set method. A novel approach is employed to determine the correct sign of the distance function at convex-concave junctions of the surface. The accuracy and convergence of the method with respect to the surface resolution is studied. It is shown that the efficient organization of surface and narrow band data structures enables the solution of large industrial problems. We also compare the accuracy of the signed distance function by direct approach with Fast Marching Method (FMM). It is found that the direct approach is more accurate than FMM. Contouring is performed through a variant of the marching cube algorithm used for the isosurface construction from volumetric data sets. The algorithm is designed to keep foreground and background information consistent, contrary to the neutrality principle followed for surface rendering in computer graphics. The algorithm ensures that the isosurface triangulation is closed, non-degenerate and non-ambiguous. The constructed triangulation has desirable properties required for the generation of good volume meshes. These volume meshes are used in the boundary element method for the study of linear electrostatics. For estimating surface properties like interface position, normal and curvature accurately from a discrete level set function, a method based on higher order weighted least squares is developed. It is found that least squares approach is more accurate than finite difference approximation. Furthermore, the method of least squares requires a more compact stencil than those of finite difference schemes. The accuracy and convergence of the method depends on the surface resolution and the discrete mesh width. This approach is used in propagation for the study of mean curvature flow and bubble dynamics. The advantage of this approach is that the curvature is not discretized explicitly on the grid and is estimated on the interface. The method of constant velocity extension is employed for the propagation of the interface. With least squares approach, the mean curvature flow has considerable reduction in mass loss compared to finite difference techniques. In the bubble dynamics, the modules are used for the study of a bubble under the influence of surface tension forces to validate Young-Laplace law. It is found that the order of curvature estimation plays a crucial role for calculating accurate pressure difference between inside and outside of the bubble. Further, we study the coalescence of two bubbles under surface tension force. The application of these modules to various industrial problems is discussed.Numerische Abschätzungen von Oberflächenparametern durch die Level-Set-Method

Ads in mobile applications

The usage of mobile applications has increased phenomenally with the growth of smart phones. According to Apple, as of Feb 2012, close to 800,000 third party applications were available on the App Store. They have been downloaded more than 15 billion times. The android platform is close behind with 450,000 apps in Google Play that have been downloaded more than 10 billion times. When we look at Advertising revenues from mobile phones (app and browser included), in-app mobile Ads account for only a fraction of the total. IDC estimates 70% of Mobile Ad budgets are spent on search based advertising. The rest is a combination of placements in applications and content on the web. Compared to the application usage statistics for popular platforms, the revenue generated through Ads using these apps as the medium has just not kept pace. The numbers point to a lot of scope for growth. Moreover, with more and more apps becoming free to download, these Ads are here to stay. What makes in-app mobile Ads even more interesting is their potential to deliver highly targeted Ads. In this paper, we study Ads in mobile applications. We limit the scope of our study to in-app mobile Ads, that appear anywhere within a mobile application when it is being used. This could be in the form of text, rich media or banner. Our purpose is to understand how Ads in mobile apps work and how they can be used by advertisers to engage audiences with targeted Ads. To this end, we run Ad campaign experiments in select countries in Asia and North America. Through these experiments; we aim to study the factors affecting the performance of Ad campaigns and inferences that can be made from data obtained through the campaigning processM.S.Includes bibliographical referencesby Aparna Vaikunta