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Different concentrations of boron nitride (BN) (0.2–0.8 wt %) are added to poly (3‐hydroxybutyrate) (PHB) as a nucleating agent. Polarized Optical Microscopy (POM) coupled to Differential Scanning Calorimetry (DSC) allow to monitor the isothermal and nonisothermal crystallization of neat and nucleated PHBs. It is found that the addition of BN to PHB modifies the mechanisms of crystallization without changing the crystallinity degree. DSC can replace POM whenever POM does not allow to estimate the spherulites growth rate. The Hoffman‐Lauritzen theory is used to explain the role of BN. The nucleating agent allows polymer crystallization at lower supercooling degrees. The regime II of crystallization is observed for nucleated PHBs. A modification of the coupling effect between the amorphous and the crystalline phases is evidenced. It is shown that a concentration of 0.2 wt % BN is sufficient to decrease the glass transition temperature and modify the crystallization mechanisms of PHB. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013

A Saiter, et al.. Segmental mobility and glass transition of poly(ethylene-vinyl acetate) copolymers : Is there a continuum in the dynamic glass transitions from PVAc to PE?. Polymer, Elsevier, 2015, 76, pp.213-219. 10.1016/j.polymer.2015 The segmental dynamics of amorphous poly(ethylene-vinyl acetate) copolymers (from PVAc to EVA50) were studied. In that sample set with similar backbone stiffness and different amount of dipoles, the dynamic glass transition was investigated by Modulated Temperature Differential Scanning Calorimetry and Broadband Dielectric Spectroscopy measurements. A decrease of the cooperativity length scale was obtained with the vinyl acetate (VAc) content decreasing. On the other hand, there was no modification of the temperature dependence of the relaxation time. Thus, the fragility value is quite constant whatever the VAc content. These results show that fragility and cooperativity have two different origins. An extrapolation to nonconstrained polyethylene amorphous phase was proposed and new glass transition temperature and fragility values were determined. Highlights 1.Amorphous phase mobility is studied for poly(ethylene-vinyl acetate) copolymers 2.Fragility is constant from PVAc to EVA50 while cooperativity length decreases 3.New extrapolated T g and fragility values are proposed for PE 4.Fragility and cooperativity are not governed by the same macromolecular properties Keywords Amorphous phase, dynamic glass transition, poly(ethylene-vinyl acetate) . Therefore, structural relaxation temperature dependences can be defined as Super-Arrhenius, due to a possible behavior between two extreme limits: "strong" glass forming liquids for which the viscosity variations (or relaxation time) are very slow and follow an Arrhenius law, and the "fragile" glass forming liquids for which a very abrupt and steep non-Arrhenian variations can be observed.The fragility index (m) quantifies the steepness of the temperature dependence of the relaxation time () close to T g (defined at τ = 100s) and can be calculated as follows:The fragility values for different materials such as polymers, metallic glasses, organic and inorganic ionic glasses, and for small organic molecules were summarized Several approaches have been proposed to explain the correlation between the fragility and the molecular mobility near T g [10,16,17]. According to the theory proposed by Adam and Gibbs [18], it is well accepted that the α relaxation process is cooperative in nature: a structural unit can move only if a certain number of neighboring structural units move also. Besides, the molecular motions are mainly governed by the intermolecular interactions having important effects in the viscous slowing down of molecular dynamics when the glass-forming liquid is cooled-down close to T g . Thus, the notion of Cooperative Rearranging Region (CRR) was introduced, and the CRR size can be estimated according to different models and theories in terms of characteristic length scale or in terms of structural unit number [16,19-22]. Accordi...

Summary: Three different grades of Boron Nitride (BN) powder (BN NX1, BN NX5 and BN HCV) having different mean particle size (0.7 to 11 mm) and specific surface area (16 to 40 m 2 · g À1 ) were used as nucleating agents for poly (3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) at a fixed concentration of 2 wt %. Polarized Optical Microscopy (POM) observations, coupled to Differential Scanning Calorimetric (DSC) measurements, allowed to monitor both the isothermal and non-isothermal crystallization of neat and nucleated PHBVs. It was found that the addition of BN to PHBV modifies the mechanisms of crystallization by starting it at lower supercooling degrees and reducing the half-crystallization time. This work proved that DSC can replace POM whenever POM does not allow to estimate directly the average linear growth rate of the spherulites during crystallization. The Hoffman-Lauritzen theory was used to explain the effects of the addition of different grades of BN on PHBV crystallization. As a result, a transition from growth regime III to the growth regime II could be observed for nucleated PHBVs, no matter the grade of BN added. It was evidenced that the coupling between the amorphous and the crystalline phase is modified by the presence of the BN particles. In particular, for a given concentration of nucleating agent, it is the mean size and the specific surface area of BN particles that affect PHBV crystallization.

Four water insoluble room-temperature protic ionic liquids (PILs) based on the N-alkylimidazolium cation with the alkyl chain length from 1 to 4 and bis(trifluoromethylsulfonyl)imide anion were synthesized and their chemical structure was confirmed by the 1H NMR and 19F NMR analysis. PILs were revealed to be thermally stable up to 360 and 400 °C. At the same time, the proton conductivity of PILs was found to be dependent mostly on the temperature and, to a less extent, on the type of the cation, i.e., the increase of the conductivity from ~3 × 10−4 S/cm at 25 °C to 2 × 10−2 S/cm at 150 °C was observed. The water vapour sorption capacity of PILs was evaluated as a function of relative humidity and the influence of the alkyl chain length on the phase behaviour in the PIL-water system was discussed. The composite polyimide/PILs membranes were prepared by the PIL immobilization in the porous polymer (Matrimid® 5218) film. The composite membranes showed a high level of proton conductivity (~10−3 S/cm) at elevated temperatures (up to 160 °C). The obtained results reveal that the elaborated composite polyimide/PIL membranes are promising candidates for the application as proton exchange membrane at middle and high temperatures.

A three-layered membrane based on poly(ethylene-co-vinyl acetate) (EVA) and hydrolyzed EVA-poly(ethylene-co-vinyl alcohol) (EVOH), was elaborated by the surface hydrolysis of a dense EVA membrane. Because of the chemical modifications, the three-layered EVOH/EVA/EVOH membrane was characterized by the particular microstructure (amorphous EVA and semicrystalline EVOH) and the tunable hydrophilic/hydrophobic balance. Also, these modifications led to the membrane with the selective barrier properties compared with the pure EVA and completely hydrolyzed EVOH membranes. The water barrier behavior was related to the strong hydrogen-bond interactions of water and vinyl alcohol groups, whereas the weak chemical interactions were revealed for gases (N and O). Furthermore, the influence of the polymer rubbery or glassy state on the permeation kinetics was established. In the case of the three-layered membrane, the considerably high selectivity values were obtained for HO/O (∼11 900) and HO/N (∼48 000) at 25 °C. In addition to these highly selective properties, the three-layered structure does not present delamination features due to its elaboration procedure. Thus, these new layered membranes are very promising as selective materials for the water and gas separation and can be potentially used in food packaging or for the gas dehydration.

Very long aging times, up to 15,100 h (629 days) at 110°C, were achieved on flame‐retardant printed circuit board laminates commonly used in automotive design. This composite was fabricated from glass fibers embedded in an epoxy resin. Aging was performed in an oven under an air atmosphere at a temperature lower than the glass‐transition temperature. Temperature‐modulated differential scanning calorimetric analysis was used to investigate the influence of such aging on the glass‐transition phenomena. A new amorphous phase appeared during aging. By extending the analysis to samples collected at different thicknesses, we demonstrated the existence of a time‐dependent gradient of the properties. A skin–core structure was evidenced, and this slowed down oxidation and allowed physical aging to occur in the bulk sample. An exponential law described the variations of the glass‐transition of the new external compound. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 786‐792, 2013

This work clarifies the notion of correlated and cooperative motions appearing during the α-relaxation process through the role of the molecular weight of the constitutive units and of the interchain dipolar interactions. By studying amorphous copolymers of poly(ethylene-co-vinyl acetate) with different vinyl acetate contents, we show that the correlated motions are not sensitive to the interchain dipolar interactions, in contrast to the cooperative motions, which increase with a strengthening of the intermolecular interactions for this sample family. Concerning the influence of the molecular weight m 0 , the notion of "correlated motions" seems to be equivalent to the notion of "cooperative motions" only for low m 0 systems.