Volume 36, Issue 3

The rheological behavior of multi-walled carbon nanotube (MWCNT)-filled polypropylene (PP) nanocomposites with different filler loadings was experimentally studied and simulated using constitutive modeling. Rheological behavior was characterized in small amplitude oscillatory shear (SAOS) flow, large amplitude oscillatory shear (LAOS) flow, startup of shear flow, steady shear flow, and stress relaxation after the imposition of a step shear strain. Virgin PP and PP with CNT loadings of 1, 3, and 5 wt% were used. The formation of a rheological percolation network was observed at these loadings. The Leonov and Simhambhatla-Leonov models were used to simulate the rheological behavior. In the linear region, the simulations provided good predictions of the experimental data for both the unfilled and filled PP. In the nonlinear region, the simulations also provided good results for the virgin PP and satisfactory results for the PP/1 wt%CNT nanocomposite under most flow conditions. However, for the other two nanocomposites the model showed mixed results.

Sheet Molding Compounds (SMC) offer a cost efficient way to enhance mechanical properties of a polymer with long discontinuous fibers, while maintaining formability to integrate functions, such as ribs, beads or other structural reinforcements. During SMC manufacturing, fibers remain often in a bundled configuration and the resulting fiber architecture determines part properties. Accurate prediction of this architecture by simulation of flow under consideration of the transient rheology and transient fiber orientations can speed up the development process. In particular, the interaction of bundles is of significance to predict molding pressures correctly in a direct simulation approach, which resolves individual fiber bundles. Thus, this work investigates the tangential short-range lubrication forces between fiber bundles with analytical and numerical techniques. A relation between the effective sheared gap between bundles and the bundle separation distance at the contact point is found and compared to experimental results from literature. The result is implemented in an ABAQUS contact subroutine to incorporate short-range interactions in a direct bundle simulation framework.

Cast film extrusion allows producing technical polymer films for packaging and coating applications. Different kinds of defects may be observed. For packaging applications, the challenge is to obtain very thin films in stable conditions at the highest throughput. For coating applications, the challenge is to master the film width reduction (called neck-in) and the induced non-uniform film thickness (called dog-bone defect). Well instrumented experiments point out the influence of the polymer and of the processing conditions on the occurrence of these defects. Numerical models of increasing complexity allow capturing the main experimental features and this makes possible to propose technological solutions to delay or even to suppress defects occurrence.

The mechanical, electrical, thermal, and rheological properties of micro injection molded nanocomposites comprising 2% and 5% carbon nanotubes (CNTs) incorporated in polycarbonate (PC), and polyamide 66 (PA) were studied. The design of experiments method was used to investigate the composition-process – properties relationship. Results indicated that the process variables significantly affected the flow patterns and resulting morphology during the filling stage of the microinjection molding (lIM) process, using 0.45 mm diameter lIM samples. Two distinct flow regimes have been identified in lIM using the low cross-section samples. The first was a conventional “fountain flow,” which resulted in a skin/core structure and reduced volume resistivity up to 10 X cm in the case of 5% CNTs and up to 100 X cm in 2% CNTs, in both polymers, respectively. In addition, inferior mechanical properties were obtained, attributed to polymer degradation under high shear rate conditions, when practicing high injection speeds, high mold temperatures, and high screw rotation velocities. The second was a “plug flow” due to wall slippage, obtained under low injection speeds, low mold temperatures, and low rotation velocities, leading to a substantial increase in modulus of elasticity (60%) with increased electrical resistivity up to 103 X cm for 5% CNTs and 105 X cm for 2% CNTs, respectively. The rheological percolation threshold was obtained at 2% CNTs while the electrical threshold was attained at 0.4% CNTs, in both polymers. It was concluded that in lIM, the process conditions should be closely monitored. In the case of high viscous heating, degradation of mechanical properties was obtained, while skin- core morphology formation enhanced electrical conductivity.

Blends of a poly(butylene adipate-co-terephthalate) (PBAT) and a low density polyethylene (LDPE) (80 wt%/20 wt%) were prepared through a twin screw extruder while incorporating 3 wt% Cloisite 30B (C30B) nanoclay that possessed a much higher affinity with PBAT. The blends were processed through three melt mixing strategies: ( i) direct mixing of all three components, (ii) mixing C30B and PBAT followed by mixing with LDPE, and (iii) mixing C30B and LDPE followed by mixing with PBAT. The rheological properties of each system were determined in small amplitude oscillatory shear (SAOS) experiments. The migration of C30B nanoparticles from the LDPE minor phase towards the PBAT matrix was then monitored in the blend nanocomposites prepared through strategy (iii) via SAOS time sweep experiments. It was firstly understood that the C30B migration could be detected during time sweep SAOS experiments. The migration time was observed to be frequency dependent due to the smaller length scales probed at larger frequencies. Such migration occurred even faster when the SAOS time sweep experiments were conducted at a higher temperature due to the viscosity reduction.

Cysteamine functionalised reduced graphene oxide (rGO) was grafted to polypropylene-graft-maleic anhydride (PP-g-MA) and subsequently melt blended with PP. The covalent bridging of rGO to PP-g-MA via the cysteamine molecule and co-crystallization are routes to promoting interfacial interactions between rGO and the PP matrix. A rheological percolation threshold was achieved for a nanofiller loading between 3 wt% and 5 wt%, but none detected for the composites prepared with un-functionalized rGO. At low loadings (0.1 wt%), functionalized rGO is well dispersed in the PP matrix, an interconnecting filler-filler, polymer-filler and polymer-polymer network is formed, resulting in increased tensile toughness (1 500%) and elongation at break (40%) relative to neat PP. Irrespective of whether the rGO was functionalised or not, it had a significant effect on the crystallization behavior of PP, inducing heterogeneous nucleation, increasing the crystallisation temperature (T m ) of PP by up to 10°C and decreasing the crystalline content (X c ) by ∼30% for the highest (5 wt%) filler loading. The growth of the monoclinic a-phase of PP is preferred on addition of functionalised rGO and b crystal growth suppressed.

This work studies the effects of uniaxial stretching on molecular orientation, crystallinity, crystallography and oxygen permeability of high barrier multilayer films based on EVOH barrier layer. Film samples were prepared using two different blow-up ratios (BUR) of 1 and 3. Uniaxial stretching was applied at 100°C using a tensile machine equipped with an environmental chamber. Fourier transform infrared (FTIR) spectroscopy was used to examine the molecular orientation in the EVOH layer before and after stretching and confirmed a considerable increase in the molecular orientation in the EVOH layer. Dynamic scanning calorimetry (DSC) and wide-angle X-ray diffraction (XRD) results point to the perfection of EVOH crystal structure by applying uniaxial stretching at high temperatures. Oxygen permeability results showed a considerable 25% decrease after stretching of the sample with lower BUR while a significant 80% reduction in oxygen permeability was observed for the sample prepared at higher BUR. The mechanism involved in increasing oxygen permeability due to the uniaxial stretching at high temperature is discussed in detail.

This study focuses on fabrication of aerogel-coated macroporous polyester fabrics for the purposes of filtration of nanometric airborne particles and potential application in facemasks. Syndiotactic polystyrene (sPS) and polyimide (PI) gels that provide respectively majority macropores (diameter > 50 nm) and mesopores (diameter 2 to 50 nm) are coated onto woven polyester fabrics via a dip coating process. The resultant materials are supercritically dried to obtain aerogelcoated fabrics. The results show that sPS is more suitable for the dip coating process. However, evaporation of the solvent during handling of gel-coated fabrics leads to closure of the surface pores that are later recovered via solvent annealing. The resultant aerogel-coated fabrics offer high air permeability (∼10 –10 m 2 ) and high filtration efficiency (> 99.95%) of airborne sodium chloride test particles of size 25 to 150 nm.

In situ generation of polyethylene terephthalate (PET) nanofibrils in polypropylene (PP) microfibers via fiber spinning in a spunbond process was studied in this work. The effects of polymer flow rate and air speed in the drafter on the formation of PET fibrils were investigated using a pilot scale machine. An in-situ visualization technique was applied to examine the fiber evolution events and stretch profile at die exit. A scanning electron microscope was used to analyze and investigate the morphology of the dispersed domain. The PET dispersed phase was fibrillated within the PP matrix such that a nonofibrillated composite containing fibrils with an average size around 100 nm was obtained. It was found that the final fibril size directly depends on the degree of die swell, the air speed and the polymer flow rate. It was also found that the in situ observed size of the micro-scale PP/PET fibers was well correlated to the size of the nano-scale PET fibers formed in the PP matrix. The visualization results revealed that a smaller fibril diameter was obtainable by increasing the stretching on the spin line and/or decreasing the die swell.