NUCLEATING EFFECT OF MONTMORILLONITE NANOPARTICLES IN POLYPROPYLENE

The nucleation effect of two layered montmorillonite silicates of different origin was studied in polypropylene (PP). Composites were prepared as a function of composition in an internal mixer or by homogenization in a twin-screw compounder. Melting and crystallization characteristics were determined by differential scanning calorimetry. The gallery distance of the silicates and the structure of the composites were studied by WAXS. The results prove that montmorillonite may considerably influence the crystallization of PP. The effect depends very much on the origin and treatment of the filler. Both treatment and composite preparation lead to considerable changes in the separation distance of the silicate layers. Even though the composites contain fillers with more than one population of layer distances, the nucleating effect is related to the completely collapsed galleries of 1 nm distance. Besides gallery distance, organophillization also modifies the surface tension of the filler, but this apparently does not influence its nucleating efficiency. The efficient gallery distance is twice as large as the characteristic matching lattice dimension determined by Lotz et al. Although a few observations could not be explained and the tentative explanation given earlier may need further verification, the results prove that nucleation does not occur at the flat surface of the filler but between its galleries, where polymer molecules may adsorb preferentially.     

Rheological Behaviors of Polypropylene/Poly(1-butene) Blends

The rheological behaviors of polypropylene (PP)/poly(1-butene) (PB) blends with homo-polypropylene (PP₁) or impact polypropylene (PP₂), a poly(propylene-co-ethylene) as the PP component were studied. With increasing of PB resin content for both PP/PB blends, the blends showed higher G'(ω), G''(ω) and η*(ω) at low frequencies but lower values at high frequencies which implied that the processability was improved. A two-phase morphology was observed through the various rheological responses, including G'(ω)-ω terminal region curves, Cole-Cole plots and the weighted relaxation spectra with the PB contents up to 40?wt%. With the same PB content, the rheological parameters of the PP₂/PB blends were quite different from those of the PP₁/PB, which can be attributed to the stronger interaction between PB chains and the ethylene-co-propylene copolymer in PP₂. The impact strength of the PP₂/PB blends was improved dramatically over that of the PP₁/PB. The more significant toughening effect for the PP₂/PB blends can be attributed to the special responses of its rheological behaviors.     

Experimental measurement and modeling study for estimation of wax disappearance temperature

Wax deposition is a frequent problem in oil pipelines and down-stream industries. Correct prediction of wax formation conditions is required to prevent this phenomenon. In this study, wax appearance temperature (WAT) of 12 Iranian oil and condensate samples were measured using viscometry data and differential scanning Calorimetry (DSC) analysis. Also, a new empirical correlation and intelligent artificial neural network (ANN) model were developed to estimate wax disappearance temperature (WDT) of crude oils. Specific gravity, pressure, and molecular weight of oil sample were used as input variables for these models. The ANN model was trained using different hidden neurons and training algorithms. Experimental measurements studies were used for validation of the new correlation. Comparing the results indicated that the ANN model has 0.27% error while most thermodynamic models have an average error of 0.35% to 2.19%. Also, the proposed correlation can predict WDT with good accuracy and minimum input data. Results show that this correlation has a maximum error of 1.16% for 310 published experimental data and 1.19% for 9 Iranian samples.     

Wax deposition rate model for heat and mass coupling of piped waxy crude oil based on non-equilibrium thermodynamics

In this paper, wax deposition in waxy crude oil transportation process was regarded as an irreversible process. Based on the entropy production rate equations, the linear phenomenological equations for the diffusion of wax molecules were derived by using the theory and method of non-equilibrium thermodynamics and heat-mass transfer. Combined with the mass and energy conservation laws, the differential equations of heat and mass transfer in the process of pipeline transportation were established, and the molecular diffusion rate of dissolved wax was solved. On the basis of this, the mathematical model of actual wax deposition rate was established by considering the attachment process and scouring process of the wax molecules. Taking an oil pipeline in Daqing as an example, the change law and influencing factors of the wax molecular diffusion coefficient, the wax deposition rate, and the net wax deposition rate were studied by numerical simulation. The wax deposition rate test results of the laboratory loop test were compared with the theoretical calculation results in order to analyze the accuracy and the adaptability of heat and mass coupling mechanism and to provide a theoretical basis for further study of wax deposition in the process of waxy oil pipeline transportation.     

Preparation and characterization of polypropylene/waste tyre dust blends with addition of DCP and HVA-2 (PP/WTDP-HVA2)

Preparation of polypropylene (PP)/waste tyre dust (WTD) blends with addition of dicumyl peroxide (DCP) and N,N′-m-phenylenebismaleimide (HVA-2) (PP/WTD_P-HVA2) was described. The blends were characterized based on their tensile properties, swelling resistance and morphology, as well as thermal properties. The results reveal that the presence of both chemicals in PP/WTD_P-HVA2 blends brought about noticeable improvements in tensile properties, swelling resistance and interfacial adhesion. The thermal stability was also improved, indicating existence of some chemical interaction between WTD and the PP matrix in the presence of both DCP and HVA-2 during processing. The results imply that both chemicals had great influences on WTD destabilization, leading to the enlargement and intensification of the copolymer formation and, hence, improved the interfacial adhesion between WTD and the PP matrix. A competing reaction mechanism that may contribute to the property enhancement of PP/WTD_P-HVA2 blends was proposed.     

Increasing the Hydrophobicity of a PP Film Using a Helium/CF<Subscript>4</Subscript> DBD Treatment at Atmospheric Pressure

Plasma surface modification is widely used to tailor the surface properties of polymeric materials. Most treatments are performed using low pressure plasma systems, but recently, atmospheric dielectric barrier discharges (DBDs) have appeared as interesting alternatives. Therefore, in this paper, an atmospheric He + CF₄ DBD is used to increase the hydrophobicity of a polypropylene (PP) film. The surface characterization of the PP film is performed using contact angle measurements, X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). Results show that the hydrophobic properties of the polymer films are greatly enhanced after plasma treatment as evidenced by an increased contact angle. The incorporation of fluorine on the surface is significant (45 at%), demonstrating the ability of the used DBD set-up to generate fluorine-containing functional groups on the PP surface.     

Antistatic ability of 1-n-tetradecyl-3-methylimidazolium bromide and its effects on the structure and properties of polypropylene

In this study, 1-n-tetradecyl-3-methylimidazolium bromide ([C₁₄mim]Br), one kind of imidazolium ionic liquid (imi-IL), was incorporated into polypropylene (PP) via melt blending. The measurement of surface resistance (R_s) and volume resistance (R_v) of neat PP and PP/[C₁₄mim]Br blends indicated that [C₁₄mim]Br had excellent antistatic properties. The PP/[C₁₄mim]Br blend had the best antistatic ability, when the weight ratio of [C₁₄mim]Br to PP reached 3/100. The surface resistance of PP/[C₁₄mim]Br decreased from the 7.67 × 10¹³ to 1.40 × 10⁷ Ω whereas the volume resistance of PP decreased from 2.67 × 10¹⁴ to 2.60 × 10⁷ Ω. Semicrystalline morphology and crystal structure were investigated by polarized optical microscopy (POM) and X-ray diffraction (XRD). The spherulites of PP became smaller with the addition of [C₁₄mim]Br, implying that [C₁₄mim]Br had a nucleating effect in the PP matrix. The XRD study indicates the crystallization process of PP was affected by [C₁₄mim]Br, and the crystallinity of PP was thus decreased. Scanning electron microscopy (SEM) studies reveal that [C₁₄mim]Br had good dispersion in PP; thermogravimetric analysis (TGA) shows the addition of [C₁₄mim]Br remarkably increased the thermal stability of PP even though it is a small molecule.     

Electrical characteristics of electrostatic precipitator with a wet membrane-based collecting electrode

Electrostatic precipitators (ESPs) with the wet membrane-based collecting electrode play an important role on the flue gas cleaning process. However, the mechanism researches on the excellent collection efficiency of the membrane-based ESPs are insufficient. This paper aims at characterizing the excellent collection efficiency of the ESPs in the aspect of the electrical characteristics. The discharge current density and distribution of the metal and wet membranes collecting electrode were measured using the boundary probe method under different conditions. The differences of the discharge current density and distribution between the wet membranes collecting electrode and the metal one were discussed in detail. In addition, the effects of applied voltage, distance between the electrodes and discharge electrode construction on the difference of the discharge current density between the wet membranes electrode and the metal one were also presented. The results show that the discharge current density is strongly increased by the wet membranes electrode, the increased discharge current density is the main reason for the excellent collection efficiency of the membrane-based WESPs.     

Synergistic toughening effect of β-nucleating agent and long chain branching on polypropylene random copolymer

β-nucleated long chain branched (LCB) polypropylene random copolymers (PPRs) were prepared via reactive extrusion by introducing β nucleating agent (NA), dicumyl peroxide (DCP) and various contents of 1, 6-Hexanediol diacrylate (HDDA) into PPR. Results of Fourier infrared spectroscopy (FTIR) and the rheological properties demonstrate the existence of LCB polypropylene. Mechanical properties including impact strength, tensile strength and elongation at break were studied. The crystal structure, morphology and crystallization behavior were investigated via wide-angle X-ray diffraction (WAXD), polarized light microscopy (PLM) and differential scanning calorimetry (DSC). Non-isothermal crystallization kinetics using the Jeziorny method was also studied. The results show an increased LCB degree with increasing HDDA amount. For the sample with a moderate LCB level, synergistic toughening effect of NA and LCB is achieved without deterioration of yield strength or elongation at break, partially because of its higher β-phase content and much smaller spherulite size. It exhibits the minimum values of T_c and Z_c1, and the maximum values of t_1/2 and n₁ in the primary stage of crystallization, regardless of the cooling rate, indicating a slower crystallization rate and more complicated nucleation and crystal growth model.     

Multi walled carbon nanotubes induced viscoelastic response of polypropylene copolymer nanocomposites: Effect of filler loading on rheological percolation

Polypropylene random copolymer nanocomposites having 0.2–7.0 vol% multi-walled carbon nanotubes (MWCNTs) were prepared via melt processing. Transmission electron microscopy (TEM) was employed to determine the nano scale dispersion of carbon nanotubes. Linear viscoelastic behavior of these nanocomposites was investigated using parallel plate rheometry. Incorporation of carbon nanotubes in the polymer matrix resulted in higher complex viscosity (η*), storage (G′) and loss modulus (G″) as compared to neat polymer, especially in the low-frequency region, suggesting a change from liquid to solid-like behavior in the nanocomposites. By plotting storage modulus vs. carbon nanotube loading and fitting with a power law function, the rheological percolation threshold in these nanocomposites was observed at a loading of ∼0.27 vol% of MWCNTs. However, electrical percolation threshold was reported at ∼0.19 vol% of MWCNTs loading. The difference in the percolation thresholds is understood in terms of nanotube connectivity with nanotubes and polymer chain required for electrical conductivity and rheological percolation.