A new kinetic model for predicting polyamide 6-6 hydrolysis and its mechanical embrittlement

PA 6-6 hydrolysis at 60, 70, 80 and 90 °C in distilled water has been studied by Fourier transform infrared spectroscopy, viscometry in molten state, differential scanning calorimetry and uniaxial tensile testing. The molar mass decreases sharply from the early periods of exposure to reach an equilibrium value of about MnE ≈ 10−11 kg mol−1 almost temperature independent. Hydrolytic chain scissions destroy the entanglement network in the amorphous phase and liberate small macromolecular segments which rearrange locally and initiate a chemicrystallisation. As expected, the embrittlement occurs at a very low conversion of the hydrolysis, in particular when the number average molar mass becomes lower than a critical value of about MnF ≈ 17 kg mol−1, i.e. very close to its initial value. A new kinetic model has been derived from the classical mechanistic scheme of reversible hydrolysis. This model describes satisfyingly all the kinetic characteristics of the reversible hydrolysis of PA 6-6 not controlled by water diffusion: decrease in molar mass, increase in crystallinity ratio and decrease in ultimate elongation, but also of other types of polyamides previously studied, such as PA 11. Moreover, when it is used as an inverse method, this model gives access to the rate constants of hydrolysis and condensation reactions. It is thus an interesting tool for elucidating structure/rate constant relationships in common families of hydrolysable polymers

X-Secure:protecting users from big bad wolves

In 2014 over 70% of people in Great Britain accessed the Internet every day. This resource is an optimal vector for malicious attackers to penetrate home computers and as such compromised pages have been increasing in both number and complexity. This paper presents X-Secure, a novel browser plug-in designed to present and raise the awareness of inexperienced users by analysing web-pages before malicious scripts are executed by the host computer. X-Secure was able to detect over 90% of the tested attacks and provides a danger level based on cumulative analysis of the source code, the URL, and the remote server, by using a set of heuristics, hence increasing the situational awareness of users browsing the internet

Nonempirical Kinetic Modeling of Non-fickian Water Absorption Induced by a Chemical Reaction in Epoxy-Amine Networks

In the last two decades, several studies made in our laboratory have shown that hydrolytic reactions may occur during water absorption and may be responsible for behavioral deviations from the classical Fick’s law in epoxy-amine networks. On one hand, water is chemically consumed by specific groups initially present in the repetitive structural unit (e.g., unreacted epoxies and amides) or formed by oxidation under operating conditions. On the other hand, water establishes strong molecular interactions (hydrogen bonds) with new highly polar groups resulting from hydrolysis (alcohols and acids). Due to both contributions, the kinetic curves of water absorption no longer tend towards an equilibrium value, i.e., a final saturation plateau, but display a slow and continuous increase over time in the water mass uptake. On this basis, a diffusion/reaction model has been developed for predicting such a peculiar water sorption behavior. In addition, the classical Henry’s law has been modified for describing the changes in boundary conditions during the course of the hydrolytic reaction. This chapter provides an overview of the recent theoretical advances made in this field and demonstrates, through two case studies, the good predictive value of the kinetic modeling approach set up in our laboratory

Oxidation induced changes in viscoelastic properties of a thermostable epoxy matrix

The thermal ageing of a neat epoxy matrix has been studied at 200°C in air by three complementary analytical techniques: optical microscopy, mechanical spectrometry and nano-indentation. Thermal oxidation is restricted in a superficial layer of about 195 µm of maximal thickness. It consists in a predominant chain scission process involving, in particular, chemical groups whose β motions have the highest degree of cooperativity and thus, are responsible for the high temperature side of β dissipation band. As a result, chain scissions decrease catastrophically the glass transition temperature, but also increase significantly the storage modulus at glassy plateau between Tβ and Tα. This phenomenon is called “internal antiplasticization”. Starting from these observations, the Di Marzio and Gilbert’s theories have been used in order to establish relationships between the glass transition temperature and number of chain scissions, and between the storage modulus and β transition activity respectively. The challenge is now to establish a relationship between the transition activity and the concentration of the corresponding chemical group

Mayall:a framework for desktop JavaScript auditing and post-exploitation analysis

Writing desktop applications in JavaScript offers developers the opportunity to write cross-platform applications with cutting edge capabilities. However in doing so, they are potentially submitting their code to a number of unsanctioned modifications from malicious actors. Electron is one such JavaScript application framework which facilitates this multi-platform out-the-box paradigm and is based upon the Node.js JavaScript runtime --- an increasingly popular server-side technology. In bringing this technology to the client-side environment, previously unrealized risks are exposed to users due to the powerful system programming interface that Node.js exposes. In a concerted effort to highlight previously unexposed risks in these rapidly expanding frameworks, this paper presents the Mayall Framework, an extensible toolkit aimed at JavaScript security auditing and post-exploitation analysis. The paper also exposes fifteen highly popular Electron applications and demonstrates that two thirds of applications were found to be using known vulnerable elements with high CVSS scores. Moreover, this paper discloses a wide-reaching and overlooked vulnerability within the Electron Framework which is a direct byproduct of shipping the runtime unaltered with each application, allowing malicious actors to modify source code and inject covert malware inside verified and signed applications without restriction. Finally, a number of injection vectors are explored and appropriate remediations are proposed

A general kinetic model for the photothermal oxidation of polypropylene

A general kinetic model for the photothermal oxidation of polypropylene has been derived from the basic auto-oxidation mechanistic scheme in which the main sources of radicals are the thermolysis and photolysis of the most unstable species, i.e hydroperoxides. Thermolysis is a uni- or bi-molecular reaction whose rate constant obeys an Arrhenius law. In contrast, photolysis is exclusively a unimolecular reaction and its rate constant is independent of temperature. According to the quantum theory, this latter is proportional to the energy absorbed by photosensitive species and thus, accounts for the impact of UV-light intensity and wavelength on the global oxidation kinetics. The validity of this model has been checked on iPP films homogeneously oxidized in air over a wide range of temperatures and UV-light sources. It gives access to the concentration changes of: (i) primary (hydroperoxides) and secondary (carbonyls) oxidation products, (ii) double bonds, (iii) chain scissions and crosslinking nodes, but also to the subsequent changes in molecular masses. These calculations are in full agreement with the photolysis results reported by Carlsson and Wiles in the 70s [1–3]. However, the model seems to be only valid for UV-light energies equivalent to about 10 suns as upper boundary, presumably because of multiphotonic excitations or chromophores photosensitization (i.e. termolecular photo-physical reactions), both enhanced at high irradiances

Influence of temperature, UV-light wavelength and intensity on polypropylene photothermal oxidation

A criterion based on the energy absorbed by photosensitive species was proposed to describe the contribution of UV-light to the initiation of the polypropylene photothermal oxidation whatever the light source. The calculation of this energy was performed using the widely accepted quantum theory. The criterion was then introduced in two different types of analytical models commonly used to describe the combined effects of UV light and temperature on induction time, namely: the reciprocity law and kinetic model. The limitations of both types of analytical models were then investigated: the latter, derived from a realistic mechanistic scheme, was found to be much more relevant than the former, which is presumably valid in a restricted range of light intensities, essentially due to its empirical origin

Thermal oxidation kinetics of additive free polyamide 6-6

Thermal aging of an additive free PA 6-6 has been elucidated at 90, 100, 120, 140, 150 and 160 C in airventiled ovens by Fourier transform infrared spectrophotometry, viscosimetry in molten state and uniaxial tensile testing. Oxidation of methylene groups starts after a considerably shorter induction period but reaches a lower maximal rate than in additive free PE. Cleavage of CeN bonds constitutes the main source of chain scissions. It leads to the formation of aldehyde chain-ends and a catastrophic decrease in molar mass. Embrittlement occurs at a very low conversion ratio of the oxidation process, in particular when the concentration of aldehyde chain-ends reaches a critical value of [PH¼O]F z 5.6 10 3 mol l 1, corresponding to a critical value of the number average molar mass ofMnFz17 kg mol 1. At this stage, the entanglement network in the amorphous phase is deeply damaged. A non-empirical kinetic model has been derived from the oxidation mechanistic scheme previously established for PE, but improved by adding elementary reactions specific to polyamides such as the rapid decomposition of unstable hydroxylated amide groups. This model describes satisfyingly the main features of the thermal oxidation kinetics of PA 6-6, but also of other types of aliphatic polyamides studied previously in the literature such as: PA 6, PA 12 and PA 4-6, as long as it is not controlled by oxygen diffusion. At the same time, it confirms the existence of an universal character for the thermal oxidation kinetics of aliphatic polyamides whatever their origin, i.e. their initial molar mass, crystallinity ratio, concentration of impurities, structural irregularities, etc

Kana Vinaka Contemporary Island Cuisine

A product of generations of Pacific heritage and travel, Colin’s destiny has been fashioned by the unique blending of cultures in Hawaii, a passion for the food, produce and flavours of the Pacific, and island hospitality. Recipes, techniques, knowledge and experiences about local produce, how it can be used in unique and tasty contemporary ways, utilising and producing culturally-based dishes for locals and visitors to enjoy