angbin Li

Graphene Oxide Nanosheet Induced Intrachain Conformational Ordering in a Semicrystalline Polymer

The physical origin of graphene oxide nanosheet (GONS)-driven polymer crystallization was studied from the perspective of intrachain conformational ordering. Time-resolved Fourier-transform infrared spectroscopy indicated that both conformational ordering and crystallization of isotactic polypropylene (iPP) were obviously accelerated by the presence of GONSs, indicating their efficient nucleation activity for iPP crystallization. Furthermore, the ordering of long helical segments occurred prior to the crystallization of iPP, as revealed by two-dimensional correlation infrared analysis. Compared to pure bulk system, the presence of GONSs was in favor of the formation of long ordering segments, especially at the early stage, accompanied by considerable enhancement of the crystallization kinetics. GONS-driven iPP crystallization was suggested to be attributed to this GONS-induced intrachain conformational ordering.

Shear-Induced Conformational Ordering, Relaxation, and Crystallization of Isotactic Polypropylene

The shear-induced coil-helix transition of isotactic polypropylene (iPP) has been studied with time-resolved Fourier transform infrared spectroscopy at various temperatures. The effects of temperature, shear rate, and strain on the coil-helix transition were studied systematically. The induced conformational order increases with the shear rate and strain. A threshold of shear strain is required to induce conformational ordering. High temperature reduces the effect of shear on the conformational order, though a simple correlation was not found. Following the shear-induced conformational ordering, relaxation of helices occurs, which follows the first-order exponential decay at temperatures well above the normal melting point of iPP. The relaxation time versus temperature is fitted with an Arrhenius law, which generates an activation energy of 135 kJ/mol for the helix-coil transition of iPP. At temperatures around the normal melting point, two exponential decays are needed to fit well on the relaxation kinetic of helices. This suggests that two different states of helices are induced by shear: (i) isolated single helices far away from each other without interactions, which have a fast relaxation kinetic; (ii) aggregations of helices or helical bundles with strong interactions among each other, which have a much slower relaxation process. The helical bundles are assumed to be the precursors of nuclei for crystallization. The different helix concentrations and distributions are the origin of the three different processes of crystallization after shear. The correlation between the shear-induced conformational order and crystallization is discussed.

Investigation of the Hydrolysis of Perovskite Organometallic Halide CH3NH3PbI3 in Humidity Environment.

Instability of emerging perovskite organometallic halide in humidity environment is the biggest obstacle for its potential applications in solar energy harvest and electroluminescent display. Understanding the detailed decay mechanism of these materials in moisture is a critical step towards the final appropriate solutions. As a model study presented in this work, in situ synchrotron radiation x-ray diffraction was combined with microscopy and gravimetric analysis to study the degradation process of CH3NH3PbI3 in moisture, and the results reveal that: 1) intermediate monohydrated CH3NH3PbI3·H2O is detected in the degradation process of CH3NH3PbI3 and the final decomposition products are PbI2 and aqueous CH3NH3I; 2) the aqueous CH3NH3I could hardly further decompose into volatile CH3NH2, HI or I2; 3) the moisture disintegrate CH3NH3PbI3 and then alter the distribution of the decomposition products, which leads to an incompletely-reversible reaction of CH3NH3PbI3 hydrolysis and degrades the photoelectric properties. These findings further elucidate the picture of hydrolysis process of perovskite organometallic halide in humidity environment.

Molybdenum sulfide/graphene-carbon nanotube nanocomposite material for electrocatalytic applications in hydrogen evolution reactions

We report a three-dimensional hierarchical ternary hybrid composite of molybdenum disulfide (MoS2), reduced graphene oxide (GO), and carbon nanotubes (CNTs) prepared by a two-step process. Firstly, reduced GO–CNT composites with three-dimensional microstructuresare synthesized by hydrothermal treatment of an aqueous dispersion of GO and CNTs to form a composite structure via π–π interactions. Then, MoS2 nanoparticles are hydrothermally grown on the surfaces of the GO–CNT composite. This ternary composite shows superior electrocatalytic activity and stability in the hydrogen evolution reaction, with a low onset potential of only 35 mV, a Tafel slope of ~38 mV·decade−1, and an apparent exchange current density of 74.25 mA·cm−2. The superior hydrogen evolution activity stemmed from the synergistic effect of MoS2 with its electrocatalytically active edge-sites and excellent electrical coupling to the underlying graphene and CNT network.

Phase transition of [Cn-mim][PF6] under high pressure up to 1.0 GPa

Behavior of the phase transition of an ionic liquid, [Cn-mim][PF(6)], has been investigated under pressures up to 1.0 GPa by using a high-pressure differential thermal analysis (DTA) apparatus. The T versus P phase diagrams of [BMIM][PF(6)] and [EMIM][PF(6)] are constructed. The DTA curve of [BMIM][PF(6)] shows one endothermal valley in heating course at each given pressure, which indicates that a simple phase transition from solid to liquid has taken place under high pressure and that the melting point is an increase function of pressure. However, the DTA curve of [EMIM] x [PF(6)] shows two endothermal valleys in the heating course within the tested pressure range, implying that there may exist another phase. After treatment of [EMIM][PF(6)] at different temperatures under high pressure, the structures of the recovered samples are also investigated by wide-angle x-ray scattering. By considering the results above, it indicates that another crystalline phase exists between the solid and liquid of [EMIM][PF(6)].

Influence of the memory effect of a mesomorphic isotactic polypropylene melt on crystallization behavior

In this study, the memory effect of a polymer is investigated with a mesomorphic isotactic polypropylene (iPP) melt as the initial state. It is found that the nucleation density and crystallization rate at low temperatures are strongly dependent on the initial melting temperature and melting time, indicating a strong memory effect. High melting temperatures decrease the nucleation density, while a short melting time causes a faster crystallization rate than in the melt with its thermal history removed. At 180 °C, it takes about 1 hour for the crystallization rate to be restored to the normal value found in the melt with erasure of its thermal history at 220 °C. Further experiments indicate that the increase in spherulite growth rate is mainly responsible for acceleration of the overall crystallization kinetics. Through comparison between meso crystallization and self-seeding crystallization, it is suggested that some ordered structures with higher thermal stability exist in the mesomorphic iPP melt. The high thermal stability of the ordered structure may be due to the random arrangement of helices of different tacticity. We propose that the ordered structure accelerates spherulite growth, however, long melting times at 180 °C can break down the ordered structure, leading to the formation of an ideal melt and restoration of the spherulite growth rate. This study indicates that a thermodynamically unstable ordered structure can survive in a supercooled melt for a long time and is involved in the crystallization process.

Morphology of a highly asymmetric double crystallizable poly(ε-caprolactone-b-ethylene oxide) block copolymer

The morphology of a highly asymmetric double crystallizable poly(epsilon-caprolactone-b-ethylene oxide) (PCL-b-PEO) block copolymer has been studied with in situ simultaneously small and wide-angle x-ray scattering as well as atomic force microscopy. The molecular masses Mn of the PCL and PEO blocks are 24 000 and 5800, respectively. X-ray scattering and rheological measurements indicate that no microphase separation occurs in the melt. Decreasing the temperature simultaneously triggers off a crystallization of PCL and microphase separation between the PCL and PEO blocks. Coupling and competition between microphase separation and crystallization results in a morphology of PEO spheres surrounded by PCL partially crystallized in lamella. Further decreasing temperature induces the crystallization of PEO spheres, which have a preferred orientation due to the confinements from hard PCL crystalline lamella and from soft amorphous PCL segments in different sides. The final morphology of this highly asymmetric block copolymer is similar to the granular morphology reported for syndiotactic polypropylene and other (co-) polymers. This implies a similar underlying mechanism of coupling and competition of various phase transitions, which is worth further exploration

Steady–shear‐induced Isothermal Crystallization of Poly(L‐lactide) (PLLA)

The isothermal crystallization of poly(L‐lactide) (PLLA) under steady‐shear flow was investigated in situ using an optical polarizing microscope with a hot shear stage. The steady–shear‐induced crystalline morphology of PLLA, to a great degree, depends on the crystallization temperature. There is a critical temperature, 120°C, below which shear‐induced row nuclei enhance nucleation ability, leading to the improvement of crystallinity, and above which cylindrite structure is generated. Their numbers increase and size reduces with temperature owing to the better movement and relaxation behavior of chains in the presence of shear flow. The results of 2D wide‐angle x‐ray diffraction (WAXD), showing the oriented structure at high T c , and differential scanning calorimetry (DSC), detecting the rising of T m with increasing T c , well confirm the effect of T c on the crystallization of PLLA under shear flow.

Heat stress induced apoptosis is triggered by transcription-independent p53, Ca 2+ dyshomeostasis and the subsequent Bax mitochondrial translocation

In this study, We demonstrated that Bax mitochondrial translocation plays a vital role in the initiation of the mitochondrial signaling pathway upon activation by heat stress. In addition, both p53 mitochondrial translocation and Ca2+ signal mediated MPTP opening activate Bax mitochondrial translocation. Employing pifithrin-α (a p53 mitochondrial translocation inhibitor) and CsA (a permeability transition pore (MPTP) inhibitor), we found that heat stress induced Bax mitochondrial translocation was significantly inhibited in cells pretreated with both PFT and CsA. Furthermore, we demonstrated that generation of reactive oxygen species (ROS) is a critical mediator in heat stress induced apoptosis and that the antioxidant MnTBAP significantly decreased heat stress induced p53 mitochondrial translocation and Ca2+ signal mediated MPTP opening, as well as the subsequent Bax mitochondrial translocation and activation of the caspase cascade. Taken together, our results indicate that heat stress induces apoptosis through the mitochondrial pathway with ROS dependent mitochondrial p53 translocation and Ca2+ dyshomeostasis, and the ensuing intro Bax mitochondrial translocation as the upstream events involved in triggering the apoptotic process observed upon cellular exposure to heat stress.

Ordered nanostructure of single-crystalline GaN nanowires in a honeycomb structure of anodic alumina

Ordered nanostructure of single-crystalline GaN nanowires in a honeycomb structure of anodic alumina was synthesized through a gas reaction of Ga2O vapor with a constant ammonia atmosphere at 1273 K in the presence of nano-sized metallic indium catalysis. Atomic force microscopy, x-ray diffraction, Raman backscattering spectroscopy, scanning electron microscopy, and transmission electron microscopy indicate that the ordered nanostructure consists of single-crystalline hexagonal wurtzite GaN nanowires in the uniform pores of anodic alumina about 20 nm in diameter and 40-50 mu m in length. The growth mechanism of the ordered nanostructure is discussed. The photoluminescence spectrum of this nanostructure is also reported.