Jinyao Chen

New understanding in the influence of melt structure and β-nucleating agents on the polymorphic behavior of isotactic polypropylene

The β-nucleation behavior of isotactic polypropylene (iPP) is a fascinating and important issue in polymer physics; however, little about this phenomenon or its physical nature has been clearly understood. In the present study, by tuning the heating temperature (fusion temperature, Tf), the amount of ordered structures in iPP melt was controlled. In this way, the influence of five types of representative β-nucleating agents (β-NA) on the crystallization behavior of iPP with different melt structures (i.e. the amount of ordered structures) was comparatively studied by differential scanning calorimetry (DSC), polarized optical microscopy (PLOM), scanning electron microscopy (SEM), wide-angle X-ray diffraction (WAXD) and rheological measurement. A surprising synergetic effect was observed between β-NAs with α-/β-dual polymorphic selectivity (dual-selective β-NA) and the ordered structure of iPP, resulting in significant increases of the β-nucleation efficiency and the β-phase proportion of the sample. PLOM observation of the crystallization process confirmed that with the presence of ordered structures in iPP melt, a mass of dark, small crystal embryos derived from self-nuclei uniformly distributed in the melt and exhibited β-nucleation efficiency. This work provides the first evidence that for iPP nucleated with dual-selective β-NA, the ordered structures play a determining role in the β-nucleation of iPP. Under the influence of the dual-selective β-NA, the ordered structures exhibited β-nucleation efficiency and therefore encouraged β-nucleation. A possible mechanism was proposed.

Dynamic crystallization and melting behavior of β-nucleated isotactic polypropylene polymerized with different Ziegler-Natta catalysts

Large amount of work has be published on the dynamic crystallization and melting behavior of β-nucleated polypropylene (β-PP). However, the relationship between molecular structure and dynamic crystallization behavior of β-PP is still not clear. In this study, the dynamic crystallization and melting behavior of two β-nucleated isotactic polypropylene (β-iPP) with nearly same average isotacticity but different stereo-defect distribution, were studied by differential scanning calorimetry (DSC), wide angel X-ray diffraction (WAXD) and temperature modulated DSC (TMDSC). The results indicated that stereo-defect distribution of iPP can significantly influence the dependence of the β-crystal content and thermal stability on the cooling rate. NPP-A with less uniform stereo-defect distribution favors the crystallization at higher temperature region and the formation of β-crystal with high thermal stability in all cooling rates concerned, moreover, the β-crystal content is influenced by cooling rate; for NPP-B with more uniform distribution of stereo-defect, the crystallization temperature and the regular insertion of molecular chains can be reduced in a larger extent. NPP-B is more suitable for the formation of high proportion of β-crystal in both low and high cooling rates, meanwhile, the thermal stability of crystal is sensitive to the cooling rate. This work provides a new insight into the design of β-iPP in dynamic crystallization.

Investigation on the structure and crystallization behavior of controlled-rheology polypropylene with different stereo-defect distribution

Understanding concerning the influence of peroxide degradation on the stereo-defect distribution and related crystallization kinetics of controlled-rheology polypropylene are of great importance. In this study, two iPP samples (PP-A, PP-B) with similar molecular weights and average isotacticities, but different stereo-defect distributions and their degradation productions after the addition of dicumyl peroxide (DCP) were prepared. Their melt flow indexes (MFI), stereo-defect distributions, crystallization behaviors and kinetics were studied using MFI measurement, differential scanning calorimetry, wide-angle X-ray diffraction, non-isothermal crystallization kinetics and successive self-nucleation and annealing fractionation. The results showed that as the content of DCP increased, the MFI, the crystallization temperature and crystallization rate of PP increased gradually, the crystallization peak width became narrower, and the crystallite size decreased. Meanwhile, the addition of DCP greatly restrained the formation of thick lamellae and narrowed its stereo-defect distribution [meso-sequence length (MSL) distribution]. On the other hand, results showed that PP resins with different stereo-defect distribution have similar MFI variations after degradation. PP-A (whose stereo-defect distribution was less uniform than PP-B) and its degradation products still possess higher crystallization rate, stronger crystallizability, smaller crystallite size and higher fractions of long MSL, compared with their counterparts of PP-B.

Understanding in the morphology and tensile behavior of isotactic polypropylene cast films with different stereo-defect distribution

In this study, two iPP resins with similar molecular weight and average isotacticity but different uniformities of stereo-defect distribution were used in the production of cast films. The crystalline morphology and orientation, and tensile behavior during room temperature stretching of the cast films were investigated by scanning electronic microscopy (SEM), 2D-wide angle X-ray diffraction (2D-WAXD) and 2D-small-angle X-ray scattering (2D-SAXS). It was found that under fixed processing condition, iPP with more uniform stereo-defect distribution (PP2) favors the formation of row nucleated lamellar structure during cast film production, and therefore exhibiting hard-elastic deformation behavior during stretching; meanwhile, the sample with less uniform stereo-defect distribution (PP1) shows un-oriented spherulitical morphology in the cast film, and typical plastic deformation behavior during stretching. The crystallization and rheological analysis on the iPP raw materials revealed that, the uniformity of stereo-defect distribution determines the ability of nucleation and crystallization, and further influences the response of the crystalline morphology to the elongation effect of cast film production process, which is of great importance in the structure–property design in the production of iPP membranes.

Investigation on the Self-nucleation Behavior of Controlled-rheology Polypropylene

Self-nucleation (SN) behavior is one of the most fascinating behaviors of semicrystalline polymers; it is of great scientific and practical importance. In this study, the crystallization and melting behavior of a series of controlled-rheology polypropylene (CRPP) with different molecular weights were studied by differential scanning calorimetry (DSC) scanning and successive self-nucleation and annealing (SSA) fractionation, and their self-nucleation behavior was studied according to the conventional SN measurement, in order to provide a new understanding on the relationship between the molecular weight and the SN behavior of polymers. The results of DSC scanning and SSA fractionation showed that the decrease of molecular weight led to higher molecular chains mobility, making the crystallization temperature higher and the crystalliation peak narrower; in addition, it significantly restrained the formation of thick lamellae. The results of SN measurements showed that both the upper and lower temperatures of the samples decreased as the molecular weight decreased, which was suggested to be closely related to the reduction of the formation of thick lamellae. The related mechanism is discussed, and it was found that the key parameter determining the occurrence of SN and annealing of CRPP was the ability to form thick lamellae with high melting point, which might be related to the ability for ordered structures to persist at high temperature.

An alkaline direct oxidation glucose fuel cell using three-dimensional structural Au/Ni-foam as catalytic electrodes

Glucose is an ideal fuel for fuel cells because it is abundant in nature, renewable, non-toxic and easy to produce. Glucose fuel cells using enzymes and microbes as the catalysts are limited by their very poor performance and rather short durability. In this work, a direct oxidation glucose fuel cell using an anion-exchange membrane and three-dimensional structural Au/Ni foam electrodes is developed. The effects of the concentration of glucose and KOH and operation temperature on the fuel cell performance are investigated. The results show that this type of direct oxidation glucose fuel cell with a relatively cheap membrane and non-platinum catalysts can produce a maximum power density of 26.6 mW cm−2 at a current density of 89 mA cm−2 with 0.5 M glucose and 6 M KOH at a temperature of 70 °C, which is favorable for large-scale use. The high performance of the fuel cell is attributed mainly to the increased kinetics of both the glucose oxidation reaction and oxygen reduction reaction, rendered by a better electrocatalytic activity of the Au/Ni foam and higher operating temperature.

Synergistic Effect of Organic Vermiculite on the Flame Retardancy and Thermal Stability of Intumescent Polypropylene Composites

Organic vermiculite (OVMT) prepared from vermiculite (VMT), with high aspect ratio and orderly arranged platelets intercalated by octadecyl trimethyl ammonum bromide (OTAB), was used as a synergistic agent on the flame retardancy of a polypropylene/intumescent flame retardant (PP/IFR) system. The flammability and thermal stability of PP/IFR/OVMT composites were investigated by limiting oxygen index (LOI), UL-94 testing, cone calorimetry tests, and thermogravometric analysis. The results of LOI and UL-94 testing showed that low loading of OVMT improved the flame retardancy and retarded dripping for PP/IFR composites. OVMT, with 1% loading, increased the char residue of PP/IFR composites and could act as an effective additive for improvement in flame retardancy, which was confirmed by the cone data. The char layer morphological structures observed by scanning electron microscopy (SEM) showed that OVMT with 1% loading can promote formation of a continuous and compact intumescent char layer. Raman spectroscopy results indicated that the OVMT or its pyrolytic products led to a decrease in size of the carbonaceous micro-domain during combustion, resulting in formation of more compact charred layers. Thus, OVMT with 1% loading showed a synergistic effect with IFR in the combustion of the PP/IFR composites.

Effect of Temperature and Comonomer Content on Thermal Behavior and Crystallization Property of the Propylene–Ethylene Random Copolymers

The effects of ethylene units content and crystallization temperature on the conformations, and the thermal and crystallization behavior were investigated by a combination of Fourier transform infrared (FTIR) spectroscopy, wide angle X-ray diffraction (WAXD), and differential scanning calorimetry (DSC). The characterization of FTIR spectroscopy proves that the longer helical conformation sequences of the propylene–ethylene random (PER) samples decrease, whereas the shorter helical conformation sequences increase with the increase in ethylene units content. The increase of the shorter helical conformation sequences is favorable for the formation of the γ-phase in the crystals. A group of broad endothermic peaks can be seen clearly in the DSC curves of PER copolymers, which may be associated with the melting of mixtures of the α- and γ-forms in the crystals. The melting point, crystallization temperature, and crystallinity degree of the PER copolymers decrease with the increase in ethylene units contents. Three typical melting peaks of the PER copolymers crystallized isothermally between 80°C and 130°C were observed. The two higher melting peaks result from melting of the α- and γ-phase in the crystals, whereas the materials crystallized on quenching give the lowest peak. The WAXD results confirm that the PER copolymers crystallize from the melt, as mixtures of α and γ forms, in a wide temperature range. The critical number ζlim of the crystallizable units for the α-form increases with the increase in crystallization temperature for PER copolymers, which is favorable for the formation of the γ phases. The amount of γ-form increases with the increase in crystallization temperature at the expense of its α component, then reaches a maximum value at the crystallization temperature of 115°C, and finally decreases with further increase in the crystallization temperature.

Influence of L-lysine on the permeation and antifouling performance of polyamide thin film composite reverse osmosis membranes

Polyamide thin film composite (TFC) reverse osmosis (RO) membranes were prepared in this study. L-Lysine is used as a type of aqueous additive during interfacial polymerization. As a result, the pure water flux (PWF) of the resulting membranes increased by around 18% and their salt rejection improved from 98.17% to 98.40% at an optimum L-lysine dosage of 0.1 wt%. Additionally, the anti-fouling properties of the resulting membranes were enhanced. The chemical structure of the membranes was investigated using attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS). The morphologies of the top surface and cross-section of the membranes were revealed by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and atomic force microscopy (AFM). Furthermore, contact angle (CA) and zeta potential measurements were carried out to determine the surface properties of the membranes. The results showed that the TFC RO membrane became thinner, smoother, smaller in surface area, more hydrophilic and more negatively charged after the introduction of L-lysine. Accordingly, the reason for the enhancement in the PWF and anti-fouling properties of the TFC RO membranes with the introduction of L-lysine was analyzed. The thinner selective layer (increase in concentration gradient across the membrane) with carboxyl groups (hydrogen bond interactions) and loose structure (greater free volume and sub-nanometer pores) resulted in low hydraulic resistance to the permeability of the polyamide selective layer, which led to the enhancement in PWF. Also, the smoother and more hydrophilic top surface and the increase in negative charges in the selective layer contribute to the improvement in anti-fouling property.

Effects of Polypropylene Orientation on Mechanical and Heat Seal Properties of Polymer-Aluminum-Polymer Composite Films for Pouch Lithium-Ion Batteries

In this study, polyamide-aluminum foil-polypropylene (PA-Al-PP) composite films with different orientation status of the PP layer were prepared, and their morphology, tensile, peeling and heat seal behavior were studied. The comparative study of tensile and fracture behaviors of single-layer film of PA, Al and PP, as well as the composite films of PA-Al, PP-Al and PA-Al-PP revealed that in PA-Al-PP composite film, the PA layer with the highest tensile strength can share the tensile stress from the Al layer during stretching, while the PP layer with the lowest tensile strength can prevent further development of the small cracks on boundary of the Al layer during stretching. Moreover, the study of heat seal behavior suggested that both the orientation status and the heat seal conditions were important factors in determining the heat seal strength (HSS) and failure behavior of the sample. Four failure types were observed, and a clear correspondence between HSS and failure types was found. The results also elucidated that for the composite film, only in the cases where the tensile stress was efficiently released by each layer during HSS measurement could the composite film exhibit desired high HSS that was even higher than its tensile strength.