Fluorescence quenching of fluoranthene by maleic anhydride in solution and during nonreactive and reactive twin‐screw extrusion

Fluorescence quenching of fluoranthene by maleic anhydride (MAH) in polypropylene (PP) during twin‐screw extrusion (TSE) was investigated using an online fluorescence measurement system. The fluorescence quenching effect was clearly seen from the decrease of the peak intensity and integrated area of the residence time distribution (RTD) curves when MAH was introduced into PP. Fluorescence quenching effect in TSE was compared with that in chloroform solution and in both cases, it followed the linear Stern‐Volmer equation although it showed lower quenching effect in TSE than in solution. Using this quenching phenomenon, it was possible to measure online the grafting degree of PP with MAH in the TSE. The obtained results showed that MAH grafting degree and total conversion measured by both fluorescence technique and by Fourier transform infrared spectroscopy were in good agreement for MAH weight concentrations up to 0.8 wt%. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Templated Grain Growth in Macroporous Materials

We demonstrate a facile method to produce crystallographically textured, macroporous materials using a combination of modified ice templating and templated grain growth (TGG). The process is demonstrated on alumina and the lead‐free piezoelectric material sodium potassium niobate. The method provides macroporous materials with aligned, lamellar ceramic walls which are made up of crystallographically aligned grains. Each method showed that the ceramic walls present a long‐range order over the entire sample dimensions and have crystallographic texture as a result of the TGG process. We also present a modification of the March–Dollase equation to better characterize the overall texture of materials with textured but slightly misaligned walls. The controlled crystallographic and morphologic orientation at two different length scales demonstrated here can be the basis of multifunctional materials.     

Commonly used UV filter toxicity on biological functions: review of last decade studies

Sunscreens provide broad‐spectrum UV skin protection and contain more often UV filter combinations. Their efficacy reducing skin photo carcinogenesis and photo ageing is widely documented. However, there are many concerns about UV filter safety. Organic UV filters were the first targeted by scientist concerns, as they were showed to trigger skin allergic reactions. Inorganic UV filters were then at the heart of scientist debate especially because of their nanometric size. Over the last years, many studies have been published tending to highlight that organic as well as inorganic UV filters could lead to variable side effects after sunscreen application. However, these studies are still very controversial due to different experimental conditions and models. This review reveals that complementary studies using standardized methods are mandatory before ascertaining that UV filters threaten human health.     

Dielectric properties of copolymers based on cyano monomers and methyl α‐acetoxyacrylate

With the aim of developing dielectric polymers containing CN groups with strong dipole moment, alternating and statistical copolymers of the cyano monomers vinylidene cyanide (VCN), acrylonitrile and methacrylonitrile with methyl α‐acetoxyacrylate (MAA) were synthesized and characterized. The copolymer's composition and microstructure were analysed by NMR spectroscopy, SEC and elemental analysis. The reactivity ratios calculated from the Q–e Alfrey–Price parameters for these copolymers indicated the alternating and statistical structures confirmed by NMR analysis. The copolymers have glass transition temperatures T_g in the range 83–146 °C and are stable up to 230 °C. The thermal stability of the copolymers depends on the nature of the cyano monomers. Their molecular dynamics were investigated by dielectric relaxation spectroscopy. We revealed a weak relaxation β at sub‐T_g temperature for poly(VCN‐co‐MAA) usually originating from molecular motions that are restricted to the scale of a few bond lengths. Strong α‐relaxation processes occurred above T_g for these copolymers. This primary relaxation was associated with cooperative movements of the polar groups (CN) at the time of mobility of the principal chains. The activation energy of the α‐relaxation process was also calculated. The values of the dielectric increment Δε for these copolymers were determined by Cole–Cole plots and indicated that the copolymers exhibit interesting dielectric properties compared with similar cyano materials. The polarity–permittivity relationship was also established. © 2012 Society of Chemical Industry     

Structural Changes in Tribo-Stressed Zinc Polyphosphates

The influences of pressure, shear stress and temperature on the structure of zinc orthophosphate and zinc metaphosphate was investigated. Tribological tests were performed to study the combined effect of pressure and shear stress at two temperatures. Friction tests were carried out in the boundary lubrication regime from dispersions of zinc polyphosphates in base oil. The effects of pressure alone were investigated using a diamond anvil cell in order to separate it from those of shearing. Raman spectroscopy was used to follow in situ or ex situ the structural changes of the zinc polyphosphate powders and the tribo-stressed areas. Tribofilms obtained with both polyphosphates display a partial and full depolymerization of the zinc metaphosphate at ambient and high (120 °C) temperature, respectively. The large stress and strain conditions of the tribological tests are necessary to induce a tribochemical reaction between zinc metaphosphate and iron oxide leading to a depolymerization of the phosphate in the tribofilm. The tribochemical reaction and antiwear tribofilm formation are significantly enhanced by the modest temperature increase from ambient to 120 °C. Pressure alone induces only disordering in the structure of zinc polyphosphates, with only minor changes of the chain length in phosphates and does not contribute significantly to the observed structural changes in tribofilms.     

Measurement based modeling and control of bimodal particle size distribution in batch emulsion polymerization

In this article, a novel modeling approach is proposed for bimodal Particle Size Distribution (PSD) control in batch emulsion polymerization. The modeling approach is based on a behavioral model structure that captures the dynamics of PSD. The parameters of the resulting model can be easily identified using a limited number of experiments. The resulting model can then be incorporated in a simple learning scheme to produce a desired bimodal PSD while compensating for model mismatch and/or physical parameters variations using very simple updating rules. © 2010 American Institute of Chemical Engineers AIChE J, 2010     

Development and characterization of composite chitosan/active carbon hydrogels for a medical application

Composite chitosan/active carbon (AC) hydrogels were elaborated by a novel route, consisting in exposing the chitosan solution to ammonia vapors. This vapor‐induced gelation method was compared with the conventional elaboration process, a direct immersion of the chitosan solution in liquid ammonia. The hydrogels were characterized to evaluate their potential application as wound‐dressings, mostly regarding their morphology, mechanical properties, swelling behavior, and sorption capacities for malodorous compounds emitted from wounds as diethylamine (DEA). The influence of elaboration route, chitosan concentration, and AC incorporation was studied. The results show that freeze‐dried hydrogels have a porous asymmetric structure dependent on the chitosan concentration and which promotes exudates drainage. The nanostructure of the parent hydrogel is semi‐crystalline and slightly dependent on the gelation conditions. It confers on hydrogel an acceptable mechanical behavior (compressive modulus up to 1.08·10⁵ Pa). Hydrogels including AC display enhanced sorption kinetics for DEA, with sorption capacities up to 49 mg g^?1. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

High‐Solid‐Content Emulsions of PVC: Scale‐Down of an Industrial Process for Enhanced Understanding of Particle Formation Part 1: Introduction and Scale‐Down

A scale‐down study of an industrial reactor for the production of polyvinyl chloride (PVC) via an emulsion polymerization process was carried out in order to understand the source of batch‐to‐batch variations in product quality. In Part 1, an analysis of the plant is presented and the industrial recipe scaled down to a pilot‐scale reactor. In the following Parts 2 and 3 a systematic analysis of the main process parameters revealed that particle generation and stabilization actually occurred in a manner slightly different from what was thought at the production site.     

Weibull statistics in electrical aging of polyesterimide under AC voltage

This article is aimed at the investigation of electrical aging of polyesterimide under AC voltage using Weibull statistical analysis. It's shown that the time to breakdown characteristic (V–t) of polyesterimide includes two zones (segments of straight line). The first zone characterizes a statistical dispersion of the intrinsic defects of material. The second zone expresses the real aging of polymer. The variation of the slope of lifetime curve is attributed to the change in the degradation mechanism. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010