Comparison of the Structural Evolution of β Polypropylene during the Sequential and Simultaneous Biaxial Stretching Process

In this work, the lamellar structural evolution and microvoids variations of β polypropylene(β-PP) during the processing of two different stretching methods, sequential biaxial stretching and simultaneous biaxial stretching, were investigated in detail. It was found that different stretching methods led to significantly different lamellae deformation modes, and the microporous membranes obtained from the simultaneous biaxial stretching exhibited better mechanical properties. For the sequential biaxial stretching, abundant coarse fibers originated from the tight accumulation of the lamellae parallel to the longitudinal stretching direction, whereas the lamellae perpendicular to the stretching direction were easily deformed and separated. Those coarse fibers were difficult to be separated to form micropores during the subsequent transverse stretching process, resulting in a poor micropores distribution. However, for the simultaneous biaxial stretching, the β crystal had the same deformation mode, that is, the lamellae distributed in different directions were all destroyed, forming abundant microvoids and little coarse fibers.     

Fracture toughness assessment of polypropylene random copolymer with multiple stress modes using the essential work of fracture theory

In recent years, the essential work of fracture (EWF) method has been extensively employed for assessing a material's toughness by specific essential fracture work, especially for polymers showing ductile failure. However, most research has studied either the in-plane stress mode or the out-of-plane stress mode. To obtain a more in-depth understanding of the EWF theory, the specific essential and non-essential fracture work of polypropylene random copolymer (PP-R) was investigated in both in-plane stress mode and out-of-plane stress mode. The effects of ligament length, amount of pre-cracking and pre-cracking method on the specific essential and non-essential fracture work were explored. The specific essential fracture work obtained in both stress modes is compared and discussed.     

Influence of polymer reprocessing cycles on the microstructure and rheological behavior of polypropylene/mineral oil oleogels

The overall objective of this work was to study the effect of reprocessing cycles of isotactic polypropylene (PP) on the rheological behavior and microstructure of gel-like dispersions in mineral oil. PP was subjected to 10 reprocessing cycles and oleogel samples were further prepared by using the mixing rheometry technique and characterized from a rheological point of view and polarized light optical microscopy (PLOM). Recycled polymer samples were also characterized by means of rheological measurements, differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) to evaluate the property changes induced by reprocessing. The values of different linear viscoelastic functions (elastic modulus and complex viscosity) of recycled PP decrease with the number of reprocessing cycles, which influences oleogel rheological response. An empirical exponential correlation between the storage modulus (G′) of PP samples and the plateau modulus ($G_N^o$) of oleogels has been proposed to predict the rheological behavior of oleogels. Results were explained considering the scission of PP chains induced by the thermomechanical reprocessing treatment applied.     

Fabrication of microporous membranes from melt extruded polypropylene precursor films via stretching: Effect of annealing

In this work, the effects of annealing conditions on the microstructure of polypropylene(PP) precursor films and further on the porous structure and permeability of stretched membranes were investigated. Combinations of WAXD, FTIR, DSC and DMA results clearly showed the crystalline orientation and crystallinity of the precursor film increased with annealing temperature, while the molecular chain entanglements in the amorphous phase decreased. Changes in the deformation behavior suggested more lamellar separation occurred for the films annealed at higher temperatures. Surface morphologies of the membranes examined by SEM revealed more pore number and uniform porous structure as the annealing temperature increased. In accordance with the SEM results, the permeability of the membranes increased with annealing temperature. On the other hand, it was found that 10 min was almost enough for the annealing process to obtain the microporous membranes with an optimal permeability.     

Flame-retardant Wrapped Ramie Fibers towards Suppressing “Candlewick Effect” of Polypropylene/Ramie Fiber Composites

In this work, a flame-retardant polypropylene(PP)/ramie fiber(RF) composite was prepared. The ramie fibers were wrapped chemically by a phosphorus- and nitrogen-containing flame retardant(FR) produced via in situ condensation reaction so as to suppress their candlewick effect. Fourier transform infrared spectroscopy(FTIR), X-ray photoelectron spectroscopy(XPS) and scanning electron microscopy(SEM) demonstrated that the ramie fibers wrapped chemically by FR(FR-RF) were obtained successfully. Thermogravimatric test showed that the PP/FR-RF composite had more residue and better thermal stability at high temperatures than the PP/RF composite. Cone calorimeter(CC) results indicated that the peak of heat release rate(PHRR) and total heat release(THR) correspondingly decreased by 23.4% and 12.5% compared with the values of neat PP/RF. The PP/FR-RF composite created a continuous and compact char layer after the combustion. Combining FTIR analysis of char residue after CC test with heat conduction coefficient results, it could be concluded that the charring of FR on RF greatly weakened the candlewick effect of RF, and more char residue in the RF domain facilitated the formation of more continuous and compact char layer in the whole combustion zone, consequently protected PP composites during combustion, resulting in the better flame retardancy of PP/FR-RF composite than that of PP/RF composite.     

The role of transient rheology in polymeric sintering

The initial theory of Frenkel and Eshelby for the coalescence of drops in air (or sintering) of Newtonian fluids, which equated the work of surface tension to the work done by viscous stresses while assuming biaxial extensional flow kinematics, was extended to the case of time-dependent material functions using the Upper Convected Maxwell (UCM) model. A numerical scheme was developed to solve the ordinary differential equations (ODE) for the stresses, which are embedded in the ODE based on the mechanical energy balance. Initial conditions required to solve the set of non-linear ODEs were obtained from visualization experiments of the coalescing drops as the theory for elastic contact gave unrealistically high values of the initial neck radius. The transient model predicted that coalescence was accelerated by increasing the relaxation time, the opposite relationship of what was predicted by the steady-state UCM formulation, and was capable of quantitatively predicting the experimental coalescence rates at times when viscoelasticity was important.     

Local fracture resistance based on microstructural efficiency concept and simulation of injection molding

Local fracture resistance (FR) of short (SGF) and discontinuous long glass fibre (LGF) reinforced polypropylene (PP) was predicted using the ‘microstructural efficiency concept’ together with a simulation program for fibre orientation in injection molding. The ‘microstructural efficiency concept’ describes the relation between microstructural parameters such as the fibre content, the fibre aspect ratio and the processing (injection molding) induced layer structure taking also into account the local fibre orientation. The local fibre orientation in injection molding was predicted with the MOLDFLOW^®-software. The predicted local FR was compared with the measured one, which was determined by using compact tension samples and linear elastic fracture mechanics (LEFM). The comparison showed, that for SGF-PP good consistence between the predicted and measured FR existed, for LGF-PP the discrepancy was higher. Yet for both materials, the ‘microstructural efficiency concept’ together with the results obtained from the simulation of the fibre orientation can be used for FR prediction of an injection molded workpiece.     

The effect of slip in the flow of a branched PP melt: experiments and simulations

In this paper visualisation and direct velocity profile measurement experiments for a branched polypropylene melt in a 10:1 axisymmetric contraction demonstrate the onset of wall slip. Video processing of the flow shows the formation of vortices and their diminution with increasing flow rate. Numerical simulations using a multimode K-BKZ viscoelastic and a purely viscous (Cross) model—both of them incorporating a nonlinear slip law—were used to predict the flow kinematics and dynamics as well as to deduce the slip velocity function by performing fitting to the velocity profiles. It was found that the numerical predictions agree well with the experimental results for the velocity profiles, and vortex formation, growth and reduction. It is suggested that such experiments (visualisation of entrance flow and direct velocity profile measurement) can be useful in evaluating the validity of constitutive equations and slip laws in the flow of polymer melts through processing equipment.     

Influence of thermal and UV treatment on the polypropylene/graphite composite

Electrically conductive polypropylene/graphite (PP/graphite) composites were prepared via blending granulated PP with maleic anhydride grafted PP and natural graphite. Electrical conductivity of prepared samples containing either 65, 70, or 75 wt% of graphite was measured and the most conductive sample containing 75 wt% of graphite was exposed to UV irradiation for 1 and 24 h or thermally treated at 170 °C for 1 h. The influence of thermal and UV exposure on the structural and electrical changes in such treated samples was studied. Local current measurements on the surface were made using scanning spreading resistance microscopy and morphology of the surface was studied by atomic force microscopy. X-ray diffraction analysis, infrared and Raman spectroscopy were also used for the structural characterization. Properties of treated and untreated samples are compared and differences are discussed.     

INFLUENCE OF THERMAL TREATMENTS ON THE POLYMORPHISM IN STEREOIRREGULAR ISOTACTIC POLYPROPYLENE: EFFECT OF STEREO-DEFECT DISTRIBUTION

The influence of cooling rate from the melt on the polymorphism and crystallinity is investigated as a function of isotacticity and stereo-defect distribution in polypropylenes. Detailed analysis of wide angle x-ray diffraction patterns shows that crystallinity in the materials used is nearly independent of the experimental cooling rates (0.5–40°C/min). At high cooling rates, the materials exist mainly in the α-phase, whereas the amount of the γ-phase increases at the lower cooling rates. With an increasing amount of stereo-defects, this cooling-rate dependence of the polymorphism is enhanced. The effect of different stereo-defect distributions, as observed in metallocene-(random) and Ziegler–Natta (blocklike) derived isotactic polypropylenes, was investigated. The formation of the γ-phase is more prevalent in materials with a random defect distribution compared to the materials in which the stereo-defects have a blocklike distribution. The crystallinity decreases more rapidly as a function of the tacticity in the random defect-distributed materials.