Impact of oxygen transport properties on the kinetic modeling of polypropylene thermal oxidation. II. Effect of oxygen diffusivity

The kinetic model, established in a previous article (François‐Heude et al., J. Appl. Polym. Sci., in press) to predict the homogeneous oxidation in iPP films typically thinner than 100 µm, is now extended to simulate the oxidation profiles in thicker plates by coupling the oxygen diffusion and its consumption by the chemical reactions. In this perspective, oxygen transport properties (namely oxygen solubility, diffusivity, and permeability) are measured by permeametry on a reference iPP. These values are compared with an exhaustive compilation of literature data to evaluate their variability among the whole iPP family, which one has been reasonably ascribed to initial differences in polymer morphology, but also to evaluate their consistency, especially their temperature dependence between 20 and 140°C. Failing to simulate oxidation profiles, the kinetic model is then used as an inverse resolution method for estimating more satisfactory values of oxygen transport properties. It is thus evidenced that the crystallinity changes induced by thermal oxidation largely explains the dramatic decrease in oxygen penetration toward the sample core just after the induction period. A strategy aimed for introducing the relationship between the polymer crystalline morphology and oxygen transport properties into the kinetic model is given in the graphical abstract, although the effect of polymer polarity remains to be established prior to this implementation. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41562.     

Preparation and properties of β‐phase graphene oxide/PVDF composite films

We report preparation of graphene oxide (GO) from expanded graphite (EG) via a modified Hummers method. GO/PVDF composites films were obtained using solvent N, N‐Dimethylformamide (DMF) and cosolvent comprising deionized water/DMF combination. X‐ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR) analyses revealed that the main crystal structure of the composite films is β‐phase, and use cosolvent method tends to favor the formation of β‐phase. Scanning electron microscopy (SEM) was used to investigate the microstructure of composite films. Storage modulus and loss modulus were measured by Dynamic mechanical analysis (DMA). Broadband dielectric spectrum tests showed an increase in the dielectric constant of the GO/PVDF composite films with the rising content of GO, and by cosolvent method could improve the dielectric constant while reducing the dielectric loss. Our method that uses GO as an additive and deionized water/DMF as the cosolvent provides a promising and low‐cost pathway to obtain high dielectric materials. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41577.     

Influences of pre‐ordered melt structures on the crystallization behavior and polymorphic composition of β‐nucleated isotactic polypropylene with different stereo‐defect distribution

As part of continuous efforts to understand the surprising synergetic effect between β‐nucleating agent and pre‐ordered structures of isotactic polypropylene (iPP) in significant enhancement of β‐crystallization (Ordered Structure Effect, OSE), two β‐nucleated iPP with different uniformities of stereo‐defect distribution (WPP‐A and WPP‐B) were prepared, their crystallization behaviors with variation of melt structures were studied in detail. The results revealed that β‐phase can hardly form in WPP‐A (whose stereo‐defect distribution is less uniform) because of its strong tendency of α‐nucleation caused by its less uniform stereo‐defect distribution, while WPP‐B is more favorable for β‐crystallization; As fusion temperature decreases, similar variation trends of crystallization temperature and β‐phase proportion can be observed from WPP‐A and WPP‐B, indicating the occurrence of OSE behavior, which provides unsurpassed β‐nucleation efficiency and induces β‐crystallization even in WPP‐A which is less favorable for β‐crystallization; moreover, the upper and lower limiting temperatures of Region II of WPP‐A and WPP‐B are identical, suggesting the uniformity of stereo‐defect distribution has little influence on temperature window for OSE (denoted as Region II). To explore the physical nature of Region II, self‐nucleation behavior and equilibrium melting temperature of PP‐A and PP‐B were studied. The lower limiting temperatures of exclusive self‐nucleation domain of both PP‐A and PP‐B are identical with the lower limiting temperatures of Region II in OSE (168°C); moreover, the T_m⁰ of both PP‐A and PP‐B are close to their upper limiting temperatures of Region II in OSE behavior (189°C). The possible explanation was proposed. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42632.     

Influence of amorphous alkaline lignin on the crystallization behavior and thermal properties of bacterial polyester

Bacterial polyester poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV) and alkaline lignin composites were prepared via melt processing method, and the influence of amorphous lignin on the crystallization behavior and thermal properties of PHBV were investigated. It was found that dual melting peaks appeared in DSC curves of PHBV/lignin composites, while only one single peak existed in PHBV. The non‐isothermal crystallization process analyzed by Jeziorny method suggested that lignin changed the nucleation mode of composites and hindered the crystallization rate of PHBV. Data calculated from the results of WAXD demonstrated that lignin did not change the basic crystal structure of PHBV, but decreased the average size of the lamellar stacks. POM results confirmed that the effect of lignin on the crystallization behavior of PHBV carried out in two opposite way, namely the enhanced effect of nucleation and the hindered effect of growth. Besides, the thermal stability of composites was also decreased significantly. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41325.     

一种新型磁流变复合胶及其可控流变特性

以羰基铁粉为磁性颗粒、甲基硅油和明胶/琼脂胶溶胶溶液的复合物为基体及各种添加剂制备了多组类液态磁流变复合胶样品。利用流变仪分别在旋转剪切模式和振荡剪切模式下对样品进行流变特性试验研究。结果表明,基体胶质物的含量对其流变特性影响较大。基体胶质物含量越高,剪切屈服强度越大且最大为92.1k Pa;胶质物含量对磁流变复合胶的线性粘弹性范围几乎没有影响;胶质物含量越高,磁流变复合胶的剪切储能模量越大,且绝对模量最大变化可达2.526MPa;添加纳米Si O2能提高磁流变复合胶的剪切屈服应力且能拓宽磁流变复合胶在磁场下的可调范围。     

Drop printing of pharmaceuticals: Effect of molecular weight on PEG coated‐naproxen/PEG 3350 solid dispersions

Solid dispersions have been used to enhance the bioavailability of poorly water‐soluble active pharmaceutical ingredients (APIs). However, the solid‐state phase, compositional uniformity, and scale‐up problems are issues that need to be addressed. To allow for highly controllable products, the drop printing (DP) technique can provide precise dosages and predictable compositional uniformity of APIs in two‐/three‐dimensional structures. DP was used to prepare naproxen (NAP)/polyethylene glycol 3350 (PEG 3350) solid dispersions with PEG coatings of different molecular weights (MWs). A comparison of moisture‐accelerated crystallization inhibition by different PEG coatings was assessed. Scanning electron microscopy, second harmonic generation microscopy, and differential scanning calorimetry analysis were performed to characterize the morphology and quantify the apparent crystallinity of NAP within the solid dispersions. Thermogravimetric analysis was employed to measure the water content within each sample. The results suggest that the moisture‐accelerated crystallization inhibition capability of the PEG coatings increased with increasing MW of the PEG coating. Besides, to demonstrate the flexibility of DP technology on manufacturing formulation, multilayer tablets with different PEG serving as barrier layers were also constructed, and their dissolution behavior was examined. By applying DP and appropriate materials, it is possible to design various carrier devices used to control the release dynamics of the API. © 2015 American Institute of Chemical Engineers AIChE J, 61: 4502–4508, 2015     

A Prediction Method of the Behavior of Adhesively Bonded Structures under Cyclic Shear Loading Based on a Characterization of the Viscous Aspects of the Adhesive in an Assembly

The capabilities of structural bonding are more and more used. Estimating the abilities of an adhesive to endure repetitive loadings and to keep stable its mechanical properties along service life is an essential point to analyze in order to conduct fatigue assessments. The aim of this study is to develop a predictive tool for describing the fatigue behavior of an adhesive in an assembly under cyclic loadings. The approach developed analyzes the influence of viscosity on the mechanical behavior of an adhesive in an assembly based on monotonic and creep test results. Thanks to the evaluation of viscous phenomena, it is possible to predict the cyclic response of the adhesive. The experimental approach uses a unique bonded joint designed to limit the stress concentrations and with a maximum stress state in the center of the adhesive. In this paper, following the strategy developed under monotonic loading, experimental results under cyclic loading are presented for different types of loading using several load ratios and amplitudes. These results underline that the evolution of viscous deformations depends on the loading type. Under shear loading and for a ductile structural adhesive, the experimental results are well described using a viscoelastic–viscoplastic constitutive model with nonlinear viscous parameters. This model makes it possible to analyze the influence of different parameters on the mechanical response of bonded joints under cyclic shear loadings.     

Polypropylene random copolymer/MWCNT nanocomposites: Isothermal crystallization kinetics,structural, and morphological interpretations

This article describes the crystallization process of polypropylene random copolymer (PPCP) under isothermal conditions in presence of varying amounts of multiwalled carbon nanotubes (MWCNT) ranging from 0.5 to 4.0% w/w. Increase in the crystallization temperature under dynamic conditions confirmed the nucleating behavior of MWCNTs, which was also corroborated by crystallization studies under isothermal conditions. The crystallization kinetics was analyzed using Avrami equation and the parameters such as Avrami exponent, the equilibrium melting temperature and fold surface energy for the crystallization of PPCP chains in nanocomposites were obtained from the calorimetric data in order to determine the effect of MWCNTs on these parameters. Spherulitic growth of PPCP crystals was also investigated as a function of time and MWCNT content using hot stage polarizing microscope. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41734.     

Dynamic rheological behavior of reactively compatibilized polypropylene/polyamide 6 blending melts

The dynamic rheological behavior is measured by small amplitude oscillatory shear on rotational rheometer for polypropylene/polyamide 6 (PP/PA6) blends compatibilized by a polypropylene grafted maleic anhydride (PP‐g‐MAH). Scanning electron microscope (SEM) results show that the PP/PP‐g‐MAH/PA6 (=100/6/40wt) is sea‐island structure, the PP/PP‐g‐MAH/PA6 (=100/6/60wt) blend is semi‐cocontinuous. Coarse PA6 zones can be observed when the weight ratio is 100/6/80. At low frequency the complex viscosity, dynamic modulus of the PP/PP‐g‐MAH/PA6 (PP/PP‐g‐MAH = 100/6wt) blends first increase then drop with the increase of PA6 weight content in the range of 0–100, the maximum value arrives at the weight content of 60. The Cole–Cole plots as well as the weighted relaxation spectra of the blends have a main arc and a tail when the weight ratio of PP/PP‐g‐MAH/PA6 is in the range of 100/6/20–100/6/60, but have different shapes when the weight ratio increases to 100/6/80 and 100/6/100. The possible reason is the weight ratio of 100/6/80 and 100/6/100 is close to the phase inversion point. In fitting the storage modulus data at low frequency, Palierne's model with two parameters interfacial tension and interfacial shear modulus is better than Bousmina's model. Palierne's model with only one parameter of interfacial tension can not fit the data well. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42091.     

Microstructure and properties of carbon fiber sized with pickering emulsion based on graphene oxide sheets and its composite with epoxy resin

The Graphene oxide (GO) sheets were used for preparing the epoxy resin Pickering emulsion. The particle size and the zeta potential of the Pickering emulsion were measured to evaluate its stability. The stable emulsion could be served as the film former of sizing agent for carbon fiber (CF). The effect of the Pickering emulsion stabilized by GO sheets on the properties of CF and the interfacial adhesion property of CF reinforced composite were investigated. Scanning electron microscopy (SEM) images showed that there existed a layer of sizing agent film with GO sheets evenly on the CF surface. Abrasion resistance and stiffness values of CF were tested and the results indicated that the sized CF conformed to the requirement of CF handleability. The interlaminar shear strength (ILSS) test indicated that the interfacial adhesion of the composite could be greatly improved. The fracture surfaces of CF composites were examined by SEM after ILSS tests. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42285.