Comparing emulsion polymerization of methacrylate-monomers with different hydrophilicity

A comprehensive experimental study concerning the influence of various types of initiator-emulsifier systems on emulsion polymerization of methacrylate monomers (2-hydroxyethyl methacrylate (HEMA), methyl methacrylate (MMA) and butyl methacrylate (BMA)) reveals interesting relations between initiator and surfactant hydrophilicity on the one hand and the hydrophilicity of the monomers on the other hand. For the water-soluble HEMA stable latexes are only obtained if hydrophobic initiators such as 2,2′-azobisisobutyronitrile or dibenzoyl peroxide in combination with alkyl sulfate surfactants with carbon chain lengths greater than 10 or surface active initiators of the 2,2′-azobis(N-2′-methylpropanoyl-2-amino-alkyl-1)-sulfonate type with alkyl chain lengths greater than 8 are employed. Stable nano size range poly(2-hydroxyethyl methacrylate) (PHEMA) particles have been prepared also by batch emulsion polymerization using ionic surface active initiators (inisurfs). The results clearly show that the formation of stable latex particles requires a proper choice of the initiator-emulsifier system regarding its hydrophilic-hydrophobic balance. The PHEMA particles prepared with surface-active initiators keep their identity and spherical shape even in the dried state whereas in the case of the other initiator-emulsifier systems complete coagulation and coalescence occurs during drying.     

Kinetics of Thermal Dehydroxylation and Carbonation of Magnesium Hydroxide

The kinetics of simultaneous dehydroxylation and carbonation of precipitated Mg(OH)₂ were studied using isothermal and nonisothermal thermogravimetric analyses. Specimens were analyzed using X-ray diffraction, transmission electron microscopy, and through measurements of the volume of carbon dioxide evolved in a subsequent reaction with hydrochloric acid. From 275° to 475°C, the kinetics of isothermal dehydroxylation in helium were best fit to a contracting-sphere model, yielding an activation energy of 146 kJ/mol, which was greater than values reported in the literature for isothermal dehydroxylation under vacuum (53–126 kJ/mol). The carbonation kinetics were complicated by the fact that dehydroxylation occurred simultaneously. The overall kinetics also could be fit to a contracting-sphere model, yielding a net activation energy of 304 kJ/mol. The most rapid carbonation kinetics occurred near 375°C. At this temperature, Mg(OH)₂ underwent rapid dehydroxylation and subsequent phase transformation, whereas thermodynamics favored the formation of carbonate. During carbonation, MgCO₃ precipitated on the surface of disrupted Mg(OH)₂ crystals acting as a kinetic barrier to both the outward diffusion of H₂O and the inward diffusion of CO₂.     

Applying a formal analysis technique to the CCITT X.509 strong two-way authentication protocol

In the quest for open systems, standardization of security mechanisms, framework, and protocols are becoming increasingly important. This puts high demands on the correctness of the standards. In this paper we use a formal logic-based approach to protocol analysis introduced by Burrows et al. [1]. We extend this logic to deal with protocols using public key cryptography, and with the notion of duration to capture some time-related aspects. The extended logic is used to analyse an important CCITT standard, the X.509 Authentication Framework. We conclude that protocol analysis can benefit from the use of the notation and that it highlights important aspects of the protocol analysed. Some aspects of the formalism need further study.This research was sponsored by the Royal Norwegian Council for Scientific and Industrial Research under Grant IT 0333.22222, and was performed while K. Gaarder was at Alcatel STK Research Centre.     

Man vs machine: examining the three themes of service robotics in tourism and hospitality

Electronic Markets - There is a growing need in the tourism and hospitality literature to harmonise service robots and artificial intelligence’s (AI) meaning and foundations, while also...     

Upcycling by grafting onto semi-crystalline polymers using supercritical CO2

The creation of graft copolymers by selectively grafting a second polymer to the amorphous fraction of a semi-crystalline polymer in supercritical CO₂ is demonstrated herein. The graft copolymer is synthesized by free radical polymerization of a vinyl monomer within the semi-crystalline polymer below its melt temperature. Such conditions afford selective grafting on the amorphous regions (block “B”) while leaving the crystalline domains (block “A”) unmodified. Accordingly, unique A-B, A-B-A, A-B-A-B-A, and so forth. block structures are formed. In this work, styrene is polymerized within polyamide 6, polyethylene terephthalate, and isotactic polypropylene. Purification of these material is performed to remove the un-grafted homopolymer, allowing for determination of the graft yield, the portion of polymer which covalently bonds to the semi-crystalline matrix. Grafting yields achieved in polyamide 6, polyethylene terephthalate, and isotactic polypropylene were 98%, 59%, and 15%, respectively. Property enhancements were observed upon further characterization of polystyrene-polyamide 6 copolymers, including high glass transition temperatures, the ability to be remelted, and tunable grafting molecular weight. Additionally, hydrophobicity is controlled by varying polystyrene composition. The remarkable range of accessed properties demonstrates this as a potential route to upcycling plastics.     

Upcycling of polypropylene with various concentrations of peroxydicarbonate and dilauroyl peroxide and two processing steps

The influence of two peroxides (peroxydicarbonate/dilauroyl peroxide) with various concentrations (10–200 mmol/kg PP) and their effective opportunity to introduce long chain branched (LCB) were investigated. The dependence of a single and double extrusion step and the changes of the properties were studied. Experiments were carried out in a single screw extruder at 180°C for the first extrusion step (modification) and at 240°C for the second extrusion step (processing simulation). Melt flow rate and dynamic rheological properties were studied at a measuring temperature of 230°C. For the definitive determination of long chain branched polypropylene (LCB-PP) served the extensional rheology measurements. The mechanical properties were examined via tensile test and impact tensile test. Summarized, LCB (melt strength) could be observed via extensional rheology for all modified specimens and the mechanical properties were maintained or even improved for the modified samples. Particularly, samples containing dilauroyl peroxide display excellent mechanical properties in this study.     

Segmentation of the fascia lata and reproducible quantification of intermuscular adipose tissue (IMAT) of the thigh

Magnetic Resonance Materials in Physics, Biology and Medicine - To develop a precise semi-automated segmentation of the fascia lata (FL) of the thigh to quantify IMAT volume in T1w MR images and...     

An efficient method for solving the Signorini problem in the simulation of free-form surfaces produced by belt grinding

Industrial robots are recently introduced to the belt grinding of free-form surfaces to obtain high productive efficiency and constant surface quality. The simulation of belt grinding process can facilitate planning grinding paths and writing robotic programs before manufacturing. In simulation, it is crucial to get the force distribution in the contact area between the workpiece and the elastic contact wheel because the uneven distributed local forces are the main reason to the unequal local removals on the grated surface. The traditional way is to simplify this contact problem as a Signorini contact problem and use the finite element method (FEM) to calculate the force distribution. However, the FEM model is too computationally expensive to meet the real-time requirement. A new model based on support vector regression (SVR) technique is developed in this paper to calculate the force distribution instead of the FEM model. The new model approximates the FEM model with an error smaller than 5%, but executes much faster (1 s vs 15 min by FEM). With this new model, the real-time simulation and even the on-line robot control of grinding processes can be further conducted.     

Ongoing verification of a multiphysics community code: FLASH

When developing a complex, multi‐authored code, daily testing on multiple platforms and under a variety of conditions is essential. It is therefore necessary to have a regression test suite that is easily administered and configured, as well as a way to easily view and interpret the test suite results. We describe the methodology for verification of FLASH, a highly capable multiphysics scientific application code with a wide user base. The methodology uses a combination of unit and regression tests and an in‐house testing software that is optimized for operation under limited resources. Although our practical implementations do not always comply with theoretical regression‐testing research, our methodology provides a comprehensive verification of a large scientific code under resource constraints.Copyright © 2013 John Wiley & Sons, Ltd.     

Simulating protection rackets: a case study of the Sicilian Mafia

Protection racketeering groups are powerful, deeply entrenched in multiple societies across the globe, and they harm the societies and economies in which they operate in multiple ways. These reasons make their dynamics important to understand and an objective of both scientific and application-oriented interest. Legal and social norm-based approaches arguably play significant roles in influencing protection racket dynamics. We propose an agent-based simulation model, the Palermo Scenario, to enrich our understanding of these influences and to test the effect of different policies on protection racket dynamics. Our model integrates the legal and the social norm-based approaches and uses a complex normative agent architecture that enables the analysis of both agents’ behaviours and mental normative representations driving behaviour. We demonstrate the usefulness of the model and the benefits of using this complex normative architecture through a case study of the Sicilian Mafia.