Oriented crystallization process of polypropylene fractions

Melting recrystallization processes of melt-sheared films of polypropylene (S28C) fractions have been investigated in situ by polarized optical microscope equipped with CCD camera and hot-stage. Actually, the morphological developments in the melting recrystallization are partially reappearance of oriented crystallization processes during melt-shearing the fractions, which is due to a memory effect of oriented structure of polymer. For low molecular weight fraction, only incomplete spherulites with some orientation along shear direction are observed in the melting recrystallization processes of the sheared films. For middle molecular weight fractions, extended chain fiber crystals(or bands) are formed first at higher temperatures, and the bands can act as self-nuclei (i. e., row nuclei), resulting in epitaxial growth of chain-folded lamellae(or fibril), i. e., the formation of cylindrites, with further decrease of the crystallization temperature. For high molecular weight fraction, however, it is not possible to shear the melt film because of its high melt viscosity. When the low molecular weight fraction in which no fiber crystals or cylindrites are observed, are mixed with small amount(about 1%-2%) of the high molecular weight fraction, quite large number of cylindrites are formed during the melting recrystallization process of its sheared film, which implies that the component of high molecular weight plays an important role in the formation of cylindrites during the shear process of polypropylene.

Compatibilization of side-chain, thermotropic, liquid-crystalline ionomers to blends of polyamide-1010 and polypropylene

A novel side-chain, liquid-crystalline ionomer (SLCI) with a poly(methyl hydrosiloxane) main chain and side chains containing sulfonic acid groups was used in blends of polyamide-1010 (PA1010) and polypropylene (PP) as a compatibilizer. The morphological structure, thermal behavior, and liquid-crystalline properties of the blends were investigated by Fourier transform infrared, differential scanning calorimetry, thermogravimetric analysis, and scanning electron microscopy. The morphological structure of the interface of the blends containing SLCI was improved with respect to the blend without SLCI. The compatibilization effect of greater than 8 wt % SLCI for the two phases, PA1010 and PP, was better than the effects of other SLCI contents in the blends.

Preparation, characterization, and crystallization of naphthalene-labeled polypropylene

Naphthalene-labeled polypropylene (PP) was prepared by melt reaction of maleic anhydride-grafted-polypropylene (PP-g-MA) with 1-aminonaphthalene in a Barabender mixer chamber. The structure of the product was analyzed with fourier transform infrared (FT-IR), ultraviolet (UV) and fluorescence. The results showed that naphthyl groups grafted onto the PP molecular chains through the imide bonds formed between MA and 1-aminonaphthalene. The content of the chromophores was 1.8 X 10(-4) mol g(-1) measured by elemental analysis. Isothermal crystallization behavior was studied by differential scanning calorimeter (DSC). Labeled PP had a higher crystallization rate than PP-g-MA. Wide-angle X-Ray diffraction (WAXD) analysis revealed that labeled PP had higher crystallinity than PP-g-MA.

Electron self-exchange reaction of viologen and its derivatives in poly(ethylene glycol)

The electron self-exchange rates (k(ex)) of viologen and its derivatives are estimated by using microelectrode voltammetry in poly(ethylene glycol) films. The dependences of supporting electrolyte concentration and sizes of viologen and its derivatives on k(ex) and diffusion coefficients (D) are discussed. Results show that k(ex) increases with the decrease of supporting electrolyte concentration and sizes of reactants. (C) 2000 Elsevier Science S.A. All rights reserved.

Further study on double-melting endotherms of isotactic polypropylene

The origins of the single- and double-melting endotherms of isotactic polypropylene crystallized at different temperatures were studied carefully by differential scanning calorimetry, wide-angle X-ray diffraction, and small-angle X-ray scattering. The experimental data show that spontaneous crystallization occurs when the crystallization temperature is lower than 117 degrees C; thus the lamellae formed are imperfect. At a lower heating rate, the recrystallization or reorganization of these imperfect lamellae leads to double endotherms. On the other hand, when the crystallization temperature is higher than 136 degrees C, two major kinds of lamellae with different thickness are developed during the isothermal process, which also results in the double-melting endotherms. In the intermediate temperature range the lamellae formed are perfect, and there is only a single peak in the distribution of lamellar thickness. This explains the origin of the single-melting endotherm. (C) 2000 John Wiley & Sons, Inc.

A novel epitaxy of isotactic polypropylene (alpha phase) on PTFE and organic substrates

Isotactic polypropylene in its a modification (alpha iPP) crystallises epitaxially on polytetrafluoroethylene (PTFE) and several hemiacids or salts of substituted benzoic acids via a novel contact plane, namely (110): so far, the only known contact plane involved in alpha iPP homo- and hetero-epitaxies was (010). In spite of its complicated architecture (alternation of antichiral helices with different azimuthal settings), the (110)(alpha iPP) contact plane displays well defined, if not prominent, rows of methyl side chains parallel to the crystallographic (112) direction (at 57 degrees to the c-axis) and approximate to 5.5 Angstrom apart. The matching contact planes of the substrates display linear gratings made of rows of e.g. chlorine atoms or PTFE chains with similar approximate to 5.5 Angstrom inter-row or interchain distances. Various morphologies are observed in iPP thin films crystallised at different cooling rates in the presence of PTFE; they can be analysed in terms of a succession and interplay of successive epitaxies: initial alpha iPP/PTFE heteroepitaxy, followed by alpha iPP/alpha iPP and gamma iPP/alpha iPP homoepitaxies. (C) 1999 Published by Elsevier Science Ltd. All rights reserved.

Isochiral form II of syndiotactic polypropylene produced by epitaxial crystallization

Epitaxial crystallization of syndiotactic polypropylene (sPP) on 2-quinoxalinol (2-Quin) yields, in the lower part of the crystallization range, the less common and metastable form II based on the packing of isochiral helices, rather than the stable antichiral form I. The contact plane is (110)(II). Form II exits only as a thin layer (< 50 nm) near the substrate surface. During further growth away from the surface, a transition takes place to the disordered form I, observed in "conventional" thin film growth. The epitaxial relationship rests only partly on dimensional matching with the chain axis repeat distance (which would be valid for both forms I and II) and on interchain distances. Whereas a better dimensional match would be achieved with form I, selection of the isochiral form II results from better correspondence of the surface topographies of the deposit (110)(II) sPP and substrate 2-Quin (001) contact faces.

Functionalization of isotactic polypropylene with maleic anhydride by reactive extrusion: mechanism of melt grafting

In this work, chemical structures and molecular parameters of grafted materials of PP-g-MAH prepared by melt reactive extrusion were studied by using electrospray ionization-mass spectrometer and gel permeation chromatography. It was found that the initial radicals, due to homolitic scission of dicumyl peroxide could be combined with maleic anhydride (MAH) monomers as well as polypropylene (PP) molecular chains. The homopolymerization of MAH cannot occur and the MAH radicals undergo a dismutational reaction under the processing condition (180-190 degreesC). A modified mechanism of melt grafting MAH onto PP has been proposed tentatively on the basis of our experimental results and other experimental findings published in the literature. (C) 2001 Elsevier Science Ltd. All rights reserved.

Mechanical and thermal induced chain conformational transformations in syndiotactic polypropylene (sPP)

Stretching a stacked sPP lamellar morphology at room temperature leads to a mechanical induced transformation from the (t(2)g(2))(2) (helical) into the (tttt) (zigzag) chain conformation of the polymer. The so prepared samples exhibit after annealing above 80 degreesC a thermal induced retransformation into the cell I and cell III crystal structure of the helical chain conformation. The mechanical induced chain conformational transformation as well as the thermal induced retransformation was studied by means of transmission electron microscopy and electron diffraction. (C) 2001 Kluwer Academic Publishers.

The effect of KSCN on the partition of proteins in polyethylene glycol/(NH4)(2)SO4 aqueous two-phase system

The effect of potassium thiocyanate on the partitioning of lysozyme and BSA in polyethylene glycol 2000/ammonium sulfate aqueous two-phase system has been investigated. As a result of the addition of potassium thiocyanate to the PEG/ammonium sulfate system, the PEG/mixed salts aqueous two-phase system was formed. It was found that the potassium thiocyanate could alter the pH difference between the two phases, and, thus, influence the partition coefficients of the differently charged proteins. The relationship between partition coefficient of the proteins and pH difference between two phases has been discussed. It was proposed that the pH difference between two phases could be employed as the measurement of electrostatic driving force for the partitioning of charged proteins in polyethylene glycol 2000/ammonium sulfate aqueous two-phase system.

Conformation transformation of syndiotactic polypropylene induced by stretching and annealing

Conformation transformation of syndiotactic polypropylene(sPP) induced by stretching and annealing processes has been investigated by WAXD, IR and DSC, The results indicate that not only the quenched samples but also the isothermally crystallized samples can form the crystals with all-trans conformation by means of uniaxially stretching at room temperature. The all-trans conformation crystals are of metastability, which can transform to stable crystals with (TTGG)(2) helical conformation at higher annealing temperatures.

In-situ microscopic FTIR spectroelectrochemistry of ascorbic acid in poly(ethylene glycol)/LiClO4 electrolyte paste and in the presence of dispersed cobalt hexacyanoferrate microcrystalline powder

In-situ microscopic FTIR spectroelectrochemical technique(MFTIRs) was applied to studying the electrochemical oxidation of ascorbic acid(AA) in poly(ethylene glycol)(PEG) paste at a 100 mu m diameter Pt disk electrode. Using this technique, the catalytic ability of cobalt hexacyanoferrate(CoHCF) microcrystalline toward AA oxidation was also studied, it was found that the dispersed CoHCF powder in the PEG paste can generate well-shaped thin-layer cyclic voltammetric waves with the peak height proportional to the scan rate, corresponding to the Fe centered redox reactions. This oxidation step catalyzed the AA oxidation. Also, this pasted CoHCF powder generated well-resolved in-situ MFTIRs spectra, by which a chemical interaction between C = C bond of AA ring and CoHCF lattice was revealed. A corresponding surface docking mechanism for the catalytic reaction has been proposed.

Studies on the interfacial adhesion between functionalized polypropylene and polyamide 1010

The interface behavior of polyamide 1010 (PA1010) and polypropylene (PP) was studied. In order to improve their interfacial adhesion, functional PP was prepared by means of grafting glycidyl methacrylate (GMA) on PP main chains and used instead of plain PP. Several technological characterizations were performed here on their interfaces. ESCA was used to confirm that some kind of reaction occurred between end groups of PA1010 and epoxy species of PP-g-GMA. The peel test was adopted to measure interfacial adhesion. It was found that the fracture energy of interfaces between PA1010 and PP-g-GMA was dramatically increased with the content of GMA. Their interfaces were observed as being blurred by using SEM and TEM and a crack that could be seen in the case of the interfaces of the PA1010 and the plain PP disappeared.

Characterization and ionic conductivity of an amorphous comblike polymer - II: Based on ethylene maleic anhydride copolymer backbone with monoethyl ether of poly(ethylene glycol) of M-W=550 as side chain

Using a graft modification method, a comblike polymer host (CBPE550) was synthesized by reacting monomethyl ether of poly(ethylene glycol) (PEGMA) with ethylene-maleic anhydride copolymer (EMAC) and endcapping the residual carboxylic acid with methanol. The product was characterized by IR and elementary analysis. Result showed that the product was amorphous and semi-ester product is accord with reaction equation. There were two peaks in the plot of the ionic conductivity against Li salt concentration. The plot of log a against 1/(T - T-0) shows a dual VTF behavior when using the glass transition temperature of PEO of side chain as T beta. The comblike polymer is a white rubbery solid. It can be well-dissolved in acetone. (C) 1999 Elsevier Science Ltd. All rights reserved.

A study of dimethylferrocene diffusion and electrode kinetics using microelectrode voltammetry in poly(ethylene glycol) solvent

The heterogeneous electron transfer rate constant (k(s)) of dimethylferrocene (DMFc) was estimated using cyclic voltammetric peak potential separations taken typically in a mixed diffusion geometry regime in a polyelectrolyte, and the diffusion coefficient (D) of DMFc was obtained using a steady-state voltammogram. The heterogeneous electron transfer rate constant and diffusion coefficient are both smaller by about 100-fold in the polymeric solvent than in the monomeric solvent. The results are in agreement with the difference of longitudinal dielectric relaxation time (tau(L)) in the two kinds of solvents, poly(ethylene glycol) (PEG) and CH3CN, indicating that k(s) varies inversely with tau(L); k(s), is proportional to D of DMFc. Both D and k(s) of DMFc in PEG containing different supporting electrolytes and at different temperatures have been estimated. These results show that D and k(s) of DMFc increase with increasing temperature in the polyelectrolyte, whereas they vary only slightly with changing the supporting electrolyte.