Study on the formation of beta-crystal during the crystallization process of polypropylene reactor granule

A notable amount of PP beta-crystal (30%, by X-ray diffraction pattern) has been found in the PP samples as polymerized at normal static isothermal crystallization conditions without using any extra nucleating agents. Existence of catalyst residues in the sample is decisive, which slows down the crystallization rate facilitating the formation of beta-form spherulites. Comparatively, high molecular weight PP favors the formation of beta-form spherulites, deducting from no beta-crystal detected in the degraded samples. Finally, high isotacticity is also required for obtaining qualitative beta-form spherulites, demonstrated by increased beta-crystal content after removal of weak crystalline fraction of the sample.

Thermal stability, crystallization, structure and morphology of syndiotactic 1,2-polybutadiene/organoclay nanocomposite

Syndiotactic 1,2-polybutadiene/organoclay nanocomposites were prepared and characterized by thermogravimetry analysis (TGA), X-ray diffraction (XRD), polarized optical microscopy (POM), and differential scanning calorimetry (DSC), respectively. The XRD shows that exfoliated nanocomposites are formed dominantly at lower clay concentrations (less than 2%), at higher clay contents intercalated nanocomposites dominate. At the same time, the XRD indicates that the crystal structures of sPB formed in the sPB/organoclay nanocomposites do not vary, only the relative intensity of the peaks corresponding to (0 1 0) and (2 0 0)/(1 1 0) crystal planes, respectively, varies. The DSC and POM indicate that organoclay layers can improve cooling crystallization temperature, crystallization rate and reducing the spherulite sizes of sPB. TGA shows that under argon flow the nanocomposites exhibit slight decrease of thermal stability, while under oxygen flow the resistance of oxidation and thermal stability of sPB/organoclay nanocomposites were significantly improved relative to pristine sPB. The primary and secondary crystallization for pristine sPB and sPB/organoclay (2%) nanocomposites were analyzed and compared based on different approaches.

Submicrometre scale single-crystalline gold plates of nanometre thickness: synthesis through a nucleobase process and growth mechanism

Synthesis of submicrometre scale single-crystalline gold plates of nanometre thickness in the presence of nucleobase guanine through chemical reduction of HAuCl4 was investigated. The elemental composition of the as-prepared gold nanoplates was estimated using energy-dispersive x-ray spectroscopy. The as-prepared gold plates were composed of essentially (111) lattice planes, as revealed by both x-ray diffraction (XRD) and transmission electron microscopy (TEM) results. It was found that the molar ratio of HAuCl4 to guanine played a very important role in the formation of gold nanoplates. Gold nanoplates could be produced at a molar ratio of [HAuCl4]/[guanine] = 50: 1 while only smaller gold spherical nanoparticles were obtained at molar ratios of [HAuCl4]/[guanine] <= 20:1. A possible growth mechanism of the as-prepared gold nanoplates is proposed and discussed. The results and conclusion presented in this work may be valuable for our further understanding of the roles of precursor ligands in the control of nanoparticles aggregation states and the preparation of shape-controlled nanoparticles.

The effect of multiwall carbon nanotube on the crystallization, morphology, and rheological properties of nylon1010 nanocomposites

Nanocomposites based on poly(iminosebacoyl imino-decamethylene) (PA1010) and multiwall carbon nanotubes (MWNTs) were successfully prepared by melt blending technique. environmental scanning electron microscope micrographs of the fracture surfaces showed that not only is there an evenly dispersion of MWNTs throughout the PA1010 matrix but also a strongly interfacial adhesion with the matrix. The combined effect of more defects on MWNTs and low temperature buckling fracture is mainly responsible for the broken tubes. Differential scanning calorimeter results showed that the MWNTs acted as a nucleation agent and increased the crystallization rate and decreased crystallite size. In the linear region, rheological measurements showed a distinct change in the frequency dependence of storage modulus, loss modulus, and complex viscosity particularly at low frequencies. We conclude that the rheological percolation threshold might occur when the content of MWNTs is over 2 wt% in the composites.

First-principles study on the conducting mechanism of the heavy-fermion system CaCu3Ru4O12

We investigated the electronic structure of the d-electron heavy-fermion system CaCu3Ru4O12 by use of the full-potential linearized augmented plane wave method. Our results indicate that the compound is a paramagnetic metal, in agreement with the experimental observation. The conductivity of the compound is governed by two main factors. One is the Ru-O dp pi coupling around the Fermi energy level, which makes Ru-O-Ru networks conductive. The other is the hybridization between the itinerant Ru 4d electrons and the localized Cu 3d (dz(2) and part of dx(2)-y(2) and dxy) electrons through O 2p orbitals in the energy region from -2.0 to -1.0 eV. The Ru-O-Cu interaction makes the localized Cu electrons start to be itinerant through the coupling with Ru 4d electrons. This results in Ru-O-Cu networks being conductive. Therefore, in the title compound, both Ru-O-Ru and Ru-O-Cu networks contribute to the conducting behavior.

Crystallization behavior of poly(epsilon-caprolactone) in poly(epsilon-caprolactone) and poly(vinyl methyl ether) mixtures

The morphological development and crystallization behavior of poly(epsilon-caprolactone) (PCL) in miscible mixtures of PCL and poly(vinyl methyl ether) (PVME) were investigated by optical microscopy as a function of the mixture composition and crystallization temperature. The results indicated that the degree of crystallinity of PCL was independent of the mixture composition upon melt crystallization because the glass-transition temperatures of the mixtures were much lower than the crystallization temperature of PCL. The radii of the PCL spherulites increased linearly with time at crystallization temperatures ranging from 42 to 49 degrees C. The isothermal growth rates of PCL spherulites decreased with the amount of the amorphous PVME components in the mixtures. Accounting for the miscibility of PCL/PVME mixtures, the radial growth rates of PCL spherulites were well described by a kinetic equation involving the Flory-Huggins interaction parameter and the free energy for the nuclei formation in such a way that the theoretical calculations were in good agreement with the experimental data. From the analysis of the equilibrium melting point depression, the interaction energy density of the PVME/PCL system was calculated to be -3.95 J/cm(3).

Study on crystallization of poly(epsilon-caprolactone) in poly(epsilon-caprolactone)/poly(vinyl methyl ether) blends

The crystallization behaviors of poly( E-caprolactone) (PCL) in poly(epsilon-caprolactone) (PCL) and poly(vinyl methyl ether) (PVME) blends were investigated by POM, DSC, WAXD, SAXS. POM results indicated that spherical crystal morphology was present during isothermal process, and the spheric growth rates were reduced with increasing the contents of PVME in PCL/PVME blends. It was found that the crystallinity of PCL in the blends remained almost constant regardless of the blend composition, but it was dependent on preparation technique. Solution-crystallization was found to be a technique capable of increasing crystallinity levels for some compositions. The melting behavior of the blends is a rather complex process. Both solution-crystallized samples and isothermal-crystallized samples exhibited a single endotherm. Oppositely, melting-crystallized samples exhibited dual-melting endotherms whose mangnitudes vary with blend compositions. On the basis of WAXD and SAXS experiments, it is found that the crystal structure is unchanged, but the long period increases with increasing the content of PVME because of the thickening of the amorphous layers.

Crystallization and orientation of syndiotactic polystyrene in nanorods

Syndiotactic polystyrene (sPS) nanorods of 200 and 80 nm diameters were prepared by infiltrating porous anodic alumina oxide templates with polymer melt, and the crystallinity and orientation of various forms of sPS crystals in the nanorods were studied by FTIR spectroscopy and electron diffraction. For sPS crystallized from amorphous state at lower temperatures, a-form crystals were found in the nanorods with random orientation and the same degree of crystallinity as that in the bulk. However, for sPS crystallized from molten state at 260 degrees C, while no preferred orientation was found for the chains in the melt, the beta-crystals formed in the nanorods oriented preferentially with the c-axis aligning perpendicular to the axial direction of the nanorod, and the degree of crystallinity was significantly lower than that in the bulk. The crystallinity decrease was more profound for nanorods of smaller diameter. These results were also supported by electron diffraction data and can be attributed to competition between nucleation and crystal growth in the nanotemplates.

Conversion process of the dominant electroluminescence mechanism in a molecularly doped organic light-emitting device with only electron trapping

In this work, the detailed conversion process of the dominant electroluminescence (EL) mechanism in a device with Eu(TTA)(3)phen (TTA=thenoyltrifluoroacetone, phen=1,10-phenanthroline) doped CBP (4,4(')-N,N-'-dicarbazole-biphenyl) film as the emitting layer was investigated by analyzing the evolution of carrier distribution on dye and host molecules with increasing voltage. Firstly, it was confirmed that only electrons can be trapped in Eu(TTA)(3)phen doped CBP. As a result, holes and electrons would be situated on CBP and Eu(TTA)(3)phen molecules, respectively, and thus creates an unbalanced carrier distribution on both dye and host molecules. With the help of EL and photoluminescence spectra, the distribution of holes and electrons on both Eu(TTA)(3)phen and CBP molecules was demonstrated to change gradually with increasing voltage. Therefore, the dominant EL mechanism in this device changes gradually from carrier trapping at relatively low voltage to Forster energy transfer at relatively high voltage.

Change of the dominant luminescent mechanism with increasing current density in molecularly doped organic light-emitting devices

We have fabricated and measured a series of electroluminescent devices with the structure of ITO/TPD/Eu(TTA)(3)phen (x):CBP/BCP/ ALQ/LiF/Al, where x is the weight percentage of Eu(TTA)3phen (from 0% to 6%). At very low current density, carrier trapping is the dominant luminescent mechanism and the 4% doped device shows the highest electroluminescence (EL) efficiency among all these devices. With increasing current density, Forster energy transfer participates in EL process. At the current density of 10.0 and 80.0mA/ cm(2), 2% and 3% doped devices show the highest EL efficiency, respectively. From analysis of the EL spectra and the EL efficiency-current density characteristics, we found that the EL efficiency is manipulated by Forster energy transfer efficiency at high current density. So we suggest that the dominant luminescent mechanism changes gradually from carrier trapping to Forster energy transfer with increasing current density. Moreover, the conversion of dominant EL mechanism was suspected to be partly responsible for the EL efficiency roll-off because of the lower EL quantum efficiency of Forster energy transfer compared with carrier trapping.

Morphology of head-to-tail poly(3-hexylthiophene) single crystals from solution crystallization

Single crystals of head-to-tail poly(3-hexylthiophene)s have been grown through the method of isothermal solution crystallization. Electron diffraction in combination with powder X-ray diffraction revealed the crystal structure, a = 1.52 nm, b = 3.36 nm, c = 1.56 nm and alpha = beta = gamma = 90 degrees.

Investigation of "Rearrangement Step" in classical Beckmann rearrangement mechanism over solid acid by means of O-18 isotopic

The reaction mechanism of the Beckmann rearrangement over B2O3/gamma-Al2O3 and TS-1 in the gas phase has been investigated by isotope labeling approach. The isotopic labeled products were measured by mass spectrometry method. By exchanging oxygen with H, 180 in the rearrangement step, it was found that the exchange reaction between cyclohexanone oxime and (H2O)-O-18 over B2O3/-gamma-Al2O3 and TS-1 could only be carried out in some extent. It suggested that the dissociation of nitrilium, over solid acids be not completely free as the classical mechanism. A concept of the dissociation degree (alpha) that is defined as the ratio of the dissociated intermediate nitrilium to the total intermediate nitrilium has been proposed. By fitting the experimental values with the calculation equation of isotopic labeled products, it is obtained that a values for B2O3/-gamma-Al2O3 and TS-1 are 0.199 and 0.806 at the reaction conditions, respectively.

Exploring the mechanism of flexible biomolecular recognition with single molecule dynamics

Combining a single-molecule study of protein binding with a coarse grained molecular dynamics model including solvent (water molecules) effects, we find that biomolecular recognition is determined by flexibilities in addition to structures. Our single-molecule study shows that binding of CBD (a fragment of Wiskott-Aldrich syndrome protein) to Cdc42 involves bound and loosely bound states, which can be quantitatively explained in our model as a result of binding with large conformational changes. Our model identified certain key residues for binding consistent with mutational experiments. Our study reveals the role of flexibility and a new scenario of dimeric binding between the monomers: first bind and then fold.