Cationic polymerization of 2,4,6,8-tetramethylcyclotetrasiloxane processed by tuning the pH of the miniemulsion

The preparation of 2,4,6,8-tetramethylcyclotetrasiloxane () miniemulsions stabilized by commercial surfactants, i.e. sodium dodecylbenzenesulfonate (NaDBSA) and sodium laurate/lauric acid mixture, was studied and is first reported. Then, the pH was tuned in order to process polymerization through interfacial protonic initiation. With lauric acid, no polymerization was observed, even at high temperature or large acid contents. Such effect is ascribed to the poor dissociation and reactivity of high pKa's carboxylic acids. With NaDBSA, acidification by HCl was enough to initiate the polymerization, but the pH of the continuous phase was shown to have a strong effect on the polymerization process. Optimal conditions (at pH 5) gave chains with average number molar masses around 16,000 g mol⁻¹ and polydispersity index close to 1.6, for a total conversion in polymer of about 60% after 2 h reaction. Lower pH (4.2) quickly led to a cross-linked network whereas at higher pH (6.1), conversions were too slow (around 10% after 350 min).     

Methane calibration burner and C‐factor determination with cone calorimeter – validation of the standardized calibration protocol

The cone calorimeter is one of the major fire tests. In its reference standard ISO 5660‐1, the apparatus (and especially a characteristic of its orifice plate mass flow meter, called C‐Factor) is calibrated using a methane burner set at 5 kW. However, measurements performed in end‐use are in the range 1–10 kW. In addition, standard proposes to check linearity at 1 and 3 kW, which means in the lowest part of the range. This communication establishes the validation of the linearity on the whole range and determines the optimal condition for C‐factor determination. It justifies the technical choices of the standard. Copyright © 2014 John Wiley & Sons, Ltd.     

Effects of the nature of the doping salt and of the thermal pre-treatment and sintering temperature on Spark Plasma Sintering of transparent alumina

A slurry of α-Al₂O₃ was doped with Mg, Zr and La nitrates or chlorides, in various amounts in the range 150-500 wt ppm and then freeze-dried to produce nanosized doped powder (∼150 nm). The powder was sintered by SPS to yield transparent polycrystalline alpha alumina. The influence of the nature of the doping element and the starting salt, the thermal treatment before sintering and the sintering temperature on the transparency of the ceramics were investigated. The transparency of the ceramics of nanosized Al₂O₃ was shown to depend mainly on the way the powder was prepared, the nature of the doping salt also had an effect. Finally, a high real inline transmittance, reaching 48.1% was achieved after optimization.     

Correlation between mechanical properties and orientation of the crystalline and mesomorphic phases in isotactic polypropylene fibers

The microstructure and mechanical properties of melt-spun isotactic polypropylene (iPP) fibers were studied for different take-up velocities and throughputs with a combination of small- and wide-angle X-ray scattering, calorimetry and tensile tests. With the increase of take-up velocity the mesomorphic fraction of the fibers steadily decreases while the crystalline fraction increases. The addition of an alpha-nucleating agent led to an increase of crystallinity and a slight decrease of the orientation factor. By contrast, a beta-nucleator resulted in a complete suppression of the fiber crystallinity. The orientation factor of the mesophase and/or crystalline phase is found to have a one-to-one correlation with the fiber tenacity and deformation at break. At the same time, the absolute values of crystallinity and/or mesomorphicity are fully uncorrelated with these mechanical characteristics. The observed correlations can be used for example to design and control the fiber mechanical properties by tuning the processing conditions such as take-up velocity, throughput and addition of nucleating agents.     

Polymeric materials as anion-exchange membranes for alkaline fuel cells

After summarizing the different fuel cells systems, including advantages and drawbacks, this review focuses on the preparation of copolymers and polymeric materials as starting materials for solid alkaline fuel cells membranes. The requirements for such membranes are also summarized. Then, different strategies are given to synthesize anion-exchange polymeric materials containing cationic (especially ammonium) groups. The first pathway focuses on heterogeneous membranes that consist in: (i) polymer blends and composites based on poly(alkene oxide)s and hydroxide salts or polybenzimidazole doped with potassium hydroxide, (ii) organic–inorganic hybrid membranes especially those synthesized via a sol–gel process, and (iii) (semi)interpenetrated networks based on poly(epichlorhydrine), poly(acrylonitrile) and polyvinyl alcohol for example, that have led to new polymeric materials for anion-exchange membranes. The second and main part concerns the homogeneous membranes divided into three categories. The first one consists in materials synthesized from (co)polymers obtained via direct (co)polymerization, for example membranes based on poly(diallyldimethylammonium chloride). The second pathway concerns the modification of polymeric materials via radiografting or chemical reactions. These polymeric materials can be hydrogenated or halogenated. The radiografting of membranes means the irradiation via various sources – electron beam, X and γ rays, ⁶⁰Co and ¹³⁷Cs that lead to trapped radicals or macromolecular peroxides or hydroperoxides, followed by the radical graft polymerization of specific monomers such as chloromethyl styrene. The third route deals with the chemical modifications of commercially available hydrogenated aliphatic and aromatic (co)polymers, and the syntheses of fluorinated (co)polymers such as carboxylic and sulfonic perfluoropolymers. In addition, several approaches for the crosslinking of above-mentioned polymeric materials are also reported as this process enhances the properties of the resulting membranes. Moreover, electrochemical and thermal properties of various above ionomers are given and discussed.     

Potential of ionic liquids for VOC absorption and biodegradation in multiphase systems

This work aims to evaluate the feasibility of using imidazolium ionic liquids (ILs) in the design of multiphase bioreactors for the removal of volatile organic compounds (VOCs). The IL affinity for three model VOCs (dimethyl sulfide, dimethyl disulfide and toluene) was evaluated by means of the dimensionless partition coefficient (K). It was observed that ILs showed K values comparable to typical liquid solvents used in multiphase bioreactors for VOC biodegradation (K values ranged from 0.009 to 0.011, 0.0012 to 0.0013 and 0.00061 to 0.00096 for dimethyl sulfide, dimethyl disulfide and toluene, respectively). Toxicity tests showed that both ILs at concentrations of 5% and 10% (v/v) inhibited the glucose uptake of an activated sludge during approximately 24 h. After such lag period, the microorganisms were able to recover its metabolic activity. However, VOC biodegradation experiments showed that ILs at 5% (v/v) were toxic for the activated sludge and a toxic synergistic effect of the IL–VOC combination likely occurred. After acclimation to the target VOCs, only the toluene biodegradation capacity was significantly increased in the presence of ILs. These toxic effects represent a key drawback for the potential of IL-based multiphase systems devoted to VOC biodegradation. Therefore, this study suggests that microbial acclimation only to the VOCs is not enough to get an efficient biodegradation in multiphase systems including ILs as non-aqueous phases.     

Synthesis and structural characterization of a liquid polyisoprene bearing amidoxime end groups

Azo-bis(isobutyroamidoxime) was synthesized and used as functionalized initiator to prepare a liquid isoprene bearing amidoxime end groups via radical polymerization. The polymer was characterized by FT-IR, Gel Permeation Chromatography and NMR. In particular, the structure of the polymer was investigated using 1D and 2D NMR techniques. The distribution of the different isoprene units (1,4-trans, 1,4-cis, 1,2 and 3,4), as well as the structure of the amidoxime end-groups was determined. It was found that the structure of the end groups was governed by the steric hindrance of the initiator. Only 1,4 and 4,1 functionalized end units were evidenced, with a majority of 4,1 end units.     

Behavior of Paramagnetic Iron during the Thermal Transformations of Kaolinite

Kaolinites with various degrees of structural order and iron content were heated and subsequently analyzed via electron paramagnetic resonance. Iron was present in two different states in the heated materials, either as dilute structural Fe³⁺ ions or in concentrated Fe³⁺ phases. During metakaolinization, the environment of dilute Fe³⁺ ions changed, following modifications of the Al³⁺ coordination, and the Fe³⁺ concentration increased. With the breakdown of metakaolinite, the diffusion of Fe³⁺ ions induced their exsolution in superparamagnetic iron-rich domains (Fe³⁺ clusters in γ-Al₂O₃ and/or Fe³⁺ oxide nanophases), which produced a decrease in the dilute Fe³⁺ concentration. The subsequent breakdown of γ-Al₂O₃ and the formation of mullite made the dilute Fe³⁺ concentration increase again, because of the incorporation of Fe³⁺ ions in the mullite structure.     

Processing of CaLa2S4 infrared transparent ceramics: A comparative study of HP and FAST/SPS techniques

The densification of CaLa₂S₄ (CLS) powders prepared by combustion method was investigated by the use of Field-Assisted Sintering Technique (FAST) and Hot Pressing (HP). CLS powders were sintered using FAST at 1000°C at different pressures and heating rates and sintered by HP under 120 MPa from 800°C to 1100°C for 6 hours with a heating rate of 10°C/min. Comparison of both techniques was further realized by use of the same conditions of pressure, dwell time, and heating rate. Complementary techniques (XRD, SEM-EDS, density measurements, FTIR spectroscopy) were employed to correlate the sintering processes/parameters to the microstructural/compositional developments and optical transmission of the ceramics. Both sintering techniques produce ceramics with submicrometer grain size and relative density of about 99%. Nevertheless, HP is more suitable to densify CLS ceramics without fragmentation and also reach higher transmission than FAST. Transmission of 40%–45% was measured out of a possible maximum of 69% based on the Fresnel losses in the 8-14 μm window when HP is applied at 1000°C for 6 hours under 120 MPa. In both techniques, ceramics undergo reduction issues that originate from graphitic sintering atmosphere.     

Synthesis and Anticancer Properties of Oxazepines Related to Azaisoerianin and IsoCoQuines

In this article, we report the synthesis and biological properties of a series of novel oxazepines related to isoCA-4 having significant antitumor properties. Among them, three oxazepin-9-ol derivatives display a nanomolar or a sub-nanomolar cytotoxicity level against five human cancer cell lines (HCT116, U87, A549, MCF7, and K562). It was demonstrated that the lead compound in this series inhibits tubulin assembly with an IC₅₀ value of 1 μM and totally arrests the cellular cycle in the G2/M phase at the low concentration of 5 nM in HCT116 and K562 cells. Molecular modeling studies perfectly corroborates these promising results.