Neodymium oxide co-catalyzed melt free radical grafting of maleic anhydride onto co-polypropylene by reactive extrusion

Rare earth oxide, neodymium oxide (Nd2O3), CO-catalyzed melt grafting of maleic anhydride (MAH) onto co-polypropylene (co-PP) in the presence of dicumyl peroxide (DCP) was carried out by reactive extrusion. The experimental results reveal that the addition of Nd2O3 as a coagent leads to an enhancement in both MFR and the grafting degree of MAH, along with a simultaneous decrease in the gel content. When the Nd2O3 concentration is 6.0 mmol%, the increment of the grafting degree of MAH maximally is up to about 20% compared with the related system without adding Nd2O3, and the gel content decreases simultaneously to a very low level of about 3%. Attenuated total reflection FTIR (ATR-FTIR) indicates that the gel in the graft copolymers mainly arise from the cross-linking reaction between ethylene units of co-PP. A reasonable reaction mechanism has been put forward on the basis of our experimental results and other mechanisms reported in the literature. We also tentatively explain above results by means of synergistic effect between DCP and Nd2O3, which causes a higher concentration of the macroradical, in particular the tertiary macroradical.

Melt rheological properties of polypropylene-polyarnide6 blends compatibilized with maleic anhydride-grafted polypropylene

The melt rheological properties of binary uncompatibilized polypropylene -polyamide6 (PP-PA6) blends and ternary blends compatibilized with maleic anhydride-grafted PP (PP-PP-g-MAH-PA6) were studied using a capillary rheometer. The experimental shear viscosities of blends were compared with those calculated from Utracki's relation. The deviation value delta between these two series of data was obtained. In binary PP-PA6 blends, when the compatibility between PP and PA6 was poor, the deformation recovery of dispersed PA6 particles played the dominant role during the capillary flow, the experimental values were smaller than those calculated, and delta was negative. The higher the dispersed phase content, the more deformed the droplets were and the lower the apparent shear viscosity. Also, the absolute value of delta increased with the dispersed phase composition. In ternary PP-PP-g-MAH-PA6 systems, when the compatibility between PP and PA6 was enhanced by PP-g-MAH, the elongation and break-up of the dispersed particles played the dominant role, and the experimental values were higher than calculated. It was observed that the higher the dispersion of the PA6 phase, the higher the delta values of the ternary blends and the larger the positive deviation.

Nano-reactors for controlling the selectivity of the free radical grafting of maleic anhydride onto polypropylene in the melt

This paper reports on a successful application of the concept of nanoreactors to effectively controlling the selectivity of the free radical grafting of maleic anhydride (MAH) onto polypropylene (PP) in the melt, an industrially relevant process. More specifically, a free radical initiator of type ROOR was first confined into (or encapsulated by) the galleries of an organically modified montmorillonite (o-MMT) whose interdistance was 2.4 nm. Primary free radicals (RO center dot) formed inside the o-MMT galleries had to diffuse out before they could react with the PP backbone. The controlled release of the primary free radicals significantly increased the grafting degree of MAH onto PP and greatly reduced the level of the chain scission of the latter. Those results were better understood by electron spin resonance studies on model systems and by Monte Carlo simulations.

Neodymium oxide-assisted melt free-radical grafting of maleic anhydride on isotactic-polypropylene by reactive extrusion

Rare earth oxide, neodymium oxide (Nd2O3), -assisted melt free-radical grafting of maleic anhydride (MAH) on isotactic-polypropylene (i-PP) was carried out by reactive extrusion. The experimental results reveal that the addition of Nd2O3 into reactive system leads to an enhancement of the grafting degree of MAH, along with an elevated degradation of i-PP matrix. When Nd2O3 content is 4.5 mmol %, the increment of the grafting degree of MAH (maximally) is up to about 30% compared with that of the related system without adding Nd2O3, while the severest degradation of i-PP matrix simultaneously occurs. On the basis of the reaction mechanism of PP-g-MAH proposed before, the sequence of beta-scission and grafting reaction is discussed in detail. It is found that, for the reactive system studied, most tertiary macroradicals first undergo beta-scission, and then, grafting reaction with MAH takes place at the new radical chain ends. The imported Nd2O3 has no effect on the aforementioned reaction mechanism, whereas it enhances the initiating efficiency of the initiator, dicumyl peroxide (DCP).

Morphology and melt rheology of nylon 11/clay nanocomposites

Nylon 11 (PA11)/clay nanocomposites have been prepared by melt-blending, followed by melt-extrusion through a capillary. Transmission electron n-Licroscopy shows that the exfoliated clay morphology is dominant for low nanofiller content, while the intercalated one is prevailing for high filler loading. Melt rheological properties of PA11 nanocomposites have been studied in both linear and nonlinear viscoelastic response regions. In the linear regime, the nanocomposites exhibit much higher storage modulus (G') and loss modulus (G") values than neat PAIL The values of G' and G" increase steadily with clay loading at low concentrations, while the G' and G" for the sample with 5 wt % clay show an inverse dependence and lie between the modulus values of the samples with 1 and 2 wt % of clay. This is attributed to the alignment/orientation of nanoclay platelets in the intercalated nanocomposite induced by capillary extrusion. In the nonlinear regime, the nanocomposites show increased shear viscosities when compared with the neat resin. The dependence of the shear viscosity on clay loading has analogous trend to that of G' and G".

Sudies on non-isothermal melt crystallization kinetics in PET/PEN/DBS blends

Macrokinetic models, namly the modified Avrami, Ozawa and Zibicki models, were applied to study the non-isothermal melt crystallization process of PET/PEN/DBS blends by DSC measurement. The modified Avrami model was found to describe the experimental data fairly well. With the cooling rates in the range from 5 to 20 K/min, Ozawa model could be well used to describe the early stages of crystallization. However, Ozawa model did not fit the polymer blends during the late stages of crystallization, because it ignored the influence of secondary crystallization. The crystallization ability of the blends decreases with increasing the DBS content from analysis by using Ziabicki kinetic model, which is similar to the results based on calculation of the effective energy barrier of the blends.

Microstructures and properties of melt-spun and as-cast Mg-20Gd binary alloy

Mg-20Gd(%, mass fraction) samples were prepared using melt-spinning and copper mold casting techniques. Microstructures and properties of the Mg-20Gd were investigated. Results show that the melt-spun ribbon is mainly composed of supersaturated alpha-Mg solid solution phase and the as-east ingot mainly contains alpha-Mg solid solution and Mg5Gd phase. The differential scanning calorimeter (DSC) curve of the ribbon exhibits a small exothermic peak in the temperature range from 630 to 680 K, which indicates that the ribbon contains a metastable phase (amorphous). Tensile strength at room temperature of the melt-spun ribbon and as-cast specimen are 308 and 254 MPa, respectively. The elongations of the two samples are less than 2%. The fracture surfaces demonstrate that the fracture mode of the as-cast Mg-20Gd is a typical cleavage fracture and that of the melt-spun sample is a combination of brittle fracture and ductile fracture.

Direct formation of form I poly(1-butene) single crystals from melt crystallization in ultrathin films

The morphologies and crystalline structures of melt-crystallized ultrathin isotactic poly(1-butene) films have been studied with transmission electron microscopy and electron diffraction. It is demonstrated that a bypass of form II crystallization can be achieved with an increase in its crystallization temperature. Electron microscopy observations show that melt-grown isotactic poly(1-butene) single crystals have a well-shaped hexagonal form, whereas form I crystals converted from form II display the morphologies of their tetragonal precursors. Electron diffraction results indicate that, instead of the twinned hexagonal pattern of the converted form I crystal, the directly formed form I single crystals exhibit an untwinned hexagonal pattern.

Effect of PMR-POI on the melt behavior and isothermal crystallization of poly(phenylene sulfide)

The crystallization behavior of neat PPS and PPS in blends with PMR-POI prepared by melt mixing were investigated by differential scanning calorimetry (DSC). It was found that POI was an effective nucleation agent of the crystallization for PPS. The enthalpy of crystallization of PPS in the blends increased compared with that of neat PPS. During isothermal crystallization from melt, the dependence of relative degree of crystallinity on time was described by the Avrami equation. It has been shown that the addition of POI causes an increase in the overall crystallization rate of PPS; it also changed the mechanism of nucleation of the PHB crystals from homogeneous nucleation to heterogeneous nucleation. The equilibrium melting temperature of PPS and PPS/POI blends were determined. The analysis of kinetic data according to nucleation theories shows that the increase in crystallization rate of PPS in the composite is due to the decrease in surface energy of the extremity surface.

Isothermal and nonisothermal melt-crystallization kinetics of syndiotactic polystyrene

Analyses of the isothermal and nonisothermal melt kinetics for syndiotactic polystyrene have been performed with differential scanning calorimetry, and several kinetic analyses have been used to describe the crystallization process. The regime II-->III transition, at a crystallization temperature of 239degrees, is found. The values of the nucleation parameter K-g for regimes II and III are estimated. The lateral-surface free energy, sigma = 3.24 erg cm(-2), the fold-surface free energy, sigma(e) = 52.3 +/- 4.2 erg cm(-2), and the average work of chain folding, q = 4.49 +/- 0.38 kcal/mol, are determined with the (040) plane assumed to be the growth plane. The observed crystallization characteristics of syndiotactic polystyrene are compared with those of isotactic polystyrene. The activation energies of isothermal and nonisothermal melt crystallization are determined to be DeltaE = -830.7 kJ/mol and DeltaE = -315.9 kJ/mol, respectively.

Nanostructure and mechanical measurement of highly oriented lamellae of melt-drawn HDPE by scanning probe microscopy

Scanning probe microscopy was used to simultaneously determine the molecular chain structure and intrinsic mechanical properties, including anisotropic elastic modulus and friction, for lamellae of highly oriented high-density polyethylene (HDPE) obtained by the melt-drawn method. The molecular-scale image of the highly oriented lamellae by friction force microscopy (FFM) clearly shows that the molecular chains are aligned parallel to the drawing direction, and the periodicities along and perpendicular to the drawing direction are 0.26 and 0.50 nm, respectively. The results indicate that the exposed planes of the lamellae resulting from the melt-drawn method are (200), which is consistent with results of transmission electron microscopy and electron diffraction. Because of the high degree of anisotropy in the sample, coming from alignment of the molecular chains along the drawing direction, the measured friction force, F, determined by FFM is strongly dependent on the angle, theta, between the scanning direction and the chain axis. The force increases as theta is increased from 0 degrees (i.e., parallel to the chain axis) to 90 degrees (i.e., perpendicular to the chain axis). The structural anisotropy was also found to strongly influence the measurements of the transverse chain modulus of the polymer by the nanoindentation technique. The measured value of 13.8 GPa with transverse modulus was larger than the value 4.3 GPa determined by wide-angle X-ray diffraction, which we attributed to anisotropic deformation of the lamellae during nanoindentation measurements that was not accounted for by the elastic treatment we adopted from Oliver and Pharr. The present approach using scanning probe microscopy has the advantage that direct correlations between the nanostructure, nanotribology, and nanomechanical properties of oriented samples can be determined simultaneously and simply.

Lateral habits of single crystals of metallocene-catalyzed low molecular weight short chain branched polyethylene from the melt

The lateral habits of low molecular weight short chain branched polyethylene single crystals from the melt were studied. Three crystallization temperatures (102, 104 and 106 degrees C) were selected for single crystal growth. It was found that the lateral habits of single crystals were asymmetric at all the crystallization temperatures selected. The electron diffraction patterns and tilting series experiments evidenced that there existed chain tilting in all the lamellae. It was the chain tilting that lead to the asymmetry of the growth rate and of lateral habits of the single crystals about the b-axis. The lateral habits substantially changed from the growth at 102 degrees C where the truncated lozenge single crystals formed with straight (110) faces to the growth at 104 degrees C where the lenticular single crystals appeared. This change occurred at 20 degrees C lower than that in a low molecular weight linear polyethylene with the same molecular weight. Furthermore, kinetics theory analysis evidenced that the change of lateral habits from truncated lozenge to lenticular shape resulted from the transition of growth regime. The results were the same as that of high molecular weight linear polyethylene but different to that of low molecular weight linear polyethylene. It may be attributed by the existence of short branched chains. (C) 2000 Elsevier Science Ltd. All rights reserved.

Isothermal melt and cold crystallization kinetics of poly(aryl ether ketone ether ketone ketone)

The isothermal melt and cold crystallization kinetics of poly(aryl ether ketone ether ketone ketone) are investigated by differential scanning calorimetry over two temperature regions. The Avrami equation describes the primary stage of isothermal crystallization kinetics with the exponent n approximate to 2 for both melt and cold crystallization. With the Hoffman-Weeks method, the equilibrium melting point is estimated to be 406 degrees C. From the spherulitic growth equation proposed by Hoffman and Lauritzen, the nucleation parameter (K-g) of the isothermal melt and cold crystallization is estimated. In addition, the K-g value of the isothermal melt crystallization is compared to those of the other poly(aryl ether ketone)s. (C) 2000 John Wiley & Sons, Inc.

Nonisothermal melt and cold crystallization kinetics of poly(aryl ether ketone ether ketone ketone)

Nonisothermal melt and cold crystallization kinetics of poly(aryl ether ketone ether ketone ketone) (PEKEKK) were investigated by differential scanning calorimetry (DSC). The Avrami equation modified by Jeziorny could only describe the primary stage of nonisothermal crystallization kinetics of PEKEKK. Also, the Ozawa equation could not describe its nonisothermal crystallization behavior. A convenient and reasonable kinetic approach was used to describe the nonisothermal crystallization behavior. The crystallization activation energy were estimated to be -264 and 370 KJ/mol for nonisothermal melt and cold crystallization by the Kissinger method. (C) 2000 John Wiley & Sons, Inc.

Melt crystallization of poly(ether ether ketone ketone) under strong electric field

In this paper, melt crystallization of poly(ether ether ketone ketone) (PEEKK) under strong electric field was investigated. In the crystal structure of PEEKK, the length of c axis was found to he 1.075 nm, increasing by 7% compared to that of PEEKK crystallized without strong electric field. The molecule chains might take a more extended conformation through the opening of the bridge bond angles by increasing from 124 degrees to 144 degrees under strong electric field in the crystal structure.