Volume 40, Issue 9 - Special issue: Polymer engineering rheology; Issue editors: Peter van Puyvelde and Nino Grizzuti

We discuss the origin of the plateau modulus enhancement ( χ ) in semi-crystalline segmented block copolymers by increasing the concentration in hard segments within the chains ( X HS ). The message we deliver is that the plateau modulus of these thermoplastic elastomers is greatly dominated by the volume fraction (Φ) and the width ( W ) of crystallites according to χ –1 ~ Φ W in agreement with a recent topological model we have developed. We start by a quick review of literature with the aim to extract χ (Φ) for different chemical structures. As we suspected, we find that most of the data falls onto a mastercurve, in line with our predictions, confirming that the reinforcement in such materials is mainly dominated by the crystallite’s content. This important result is then supported by the investigation of copolymer mixtures in which Φ is fixed, providing a similar reinforcement, while the chains compositions is significantly different. Finally, we show that the reinforcement can be enhanced at constant Φ by increasing W for a given class of block copolymers. This can be done by changing the process route and is again in good agreement with our expectations.

In this study, thermoplastic polyurethanes (TPUs) containing trisilanol isooctyl polyhedral oligomeric silsesquioxane (POSS), a reactive nanofiller, were synthesized and characterized rheologically and morphologically, and the effects of POSS content on the melt thermal stability of the TPUs are investigated. Samples containing 0, 0.23, 0.57, 1.14, and 2.23% (w/w) POSS were synthesized by reactive extrusion and characterized by Fourier transform infrared spectroscopy (FTIR), oscillatory and extensional rheometry, atomic force microscopy (AFM), and small- and wide-angle X-ray scattering (SAXS and WAXS, respectively). The rheological properties of molten TPU are time-dependent and the melt thermal stability of the TPU is maximal at 1.14% of POSS. The addition of 0.23 and 0.57% POSS promotes strain-hardening at low extensional strain rates (0.01 and 0.10 s −1 ), not affecting the extensional characteristics at higher strain rates. The addition of increasing amounts of POSS leads to the formation of POSS-rich clusters well dispersed in the TPU matrix. SAXS and WAXS results show that the POSS domains are amorphous and that POSS does not modify the crystalline structure of TPU. Therefore, this work indicates that synthesizing TPU in the presence of trisilanol isooctyl POSS can increase the melt thermal stability of the polymer, facilitating its processing.

Knowing the flow parameters of a polymer melt under steady state condition is required to assess the performance of the material in die and mold design. Often, however, this is not sufficient for a full understanding of the polymer processing behavior, and information on the linear and non-linear viscoelastic behavior is needed. In this paper, the non-linear viscoelastic behavior of a polymer under shear flow has been investigated by measuring the stress response when a cyclic oscillating shear rate in a capillary rheometer is applied. The time-dependent wall shear stress has been decomposed into in-phase viscous and elastic components. A model to interpret the experimental results is presented and applied to a well-characterized polystyrene and two polyethylenes with similar rheology but different molecular structure (HDPE and LLDPE). The relevant characteristics resulting from the model, such as the generalized elastic and viscous modulus under shear, are compared and discussed.

Processing isotactic polypropylene (iPP) from cast film into biaxially oriented polypropylene (BOPP) involves plastic drawing of a semi-crystalline morphology in the melting range of iPP, where the crystal phase is reduced and the polymer has high mobility. The literature claims that plastic drawing in general and at elevated temperatures in particular depends predominantly on the structure of the amorphous entanglement network. We investigated this aspect using laboratory-scale biaxial drawing experiments. Three iPP homopolymer types differing in chain isotacticity and molecular weight distribution were extruded into 200-μm-thick primary sheets using 10 different extrusion settings. The sheets were biaxially drawn on a laboratory stretcher at 157°C and 160°C, recording the respective stress-strain curves. These curves were evaluated according to a rubber elasticity model to obtain the network modulus, G N , of the entanglement network. The effects of iPP type, the extrusion parameters, the resulting cast film properties, and the draw temperature on G N are discussed.

The digital photoelastic technique is used to characterise the necking behaviour of isotactic polypropylene (iPP) fibres. The effect of stretching rate on necking initiation is studied. The birth of necking is observed using photoelastic patterns of the stretched fibres to understand how the localised difference between the principle stresses grows to form a necking region. Finally, the formation of multiple necking regions is characterised photoelastically. These multiple necks are initiated using the same formation mechanism and conditions as if there is only a single necking region. It was evident that, fast stretching causes faster arrangement of molecular chains and hence decreases the time required for necking initiation. Recommendations are suggested for optimum mechanical processing conditions of iPP fibres to avoid failure by necking. Photoelastic patterns are given for illustration.

Surface roughness and sharkskin of extruded polymers, including blends are affected by the morphology and processing conditions. In this study, different effects on the roughness of the polymer blend extrudates were investigated. Co-continuous poly(ethylene) oxide/ethylene-vinyl acetate (PEO/EVA) blends with three different molecular weight (Mw) PEOs were compounded successfully. It was found that the better co-continuity of the structure and smoother surface were achieved for lower Mw PEO/EVA blend because of more effective stress transfer in the PEO phase. The effect of processing temperature was also studied with decreasing processing temperature reducing the surface roughness of the high Mw PEO/EVA blend, which was also achieved as a result of improved co-continuous morphology by adjusting the viscosity and elasticity ratio with shifting temperatures.

Recycling of thermoplastic polymers is an important element of sustainable circular economy practices. The quality of mechanically recycled polymers is a concern. A method is presented to predict the structure and processability of recycled blends of polymers based on processability knowledge of their virgin precursor components. Blending rules at molecular weight distribution level are well established and form the foundation of the new method. Two essential fundamental building blocks are combined with this foundation. First, component and blend structure are related to viscosity via tube theories. Second, viscosity is related to melt flow index via a continuum mechanics approach. Emulator equations are built based on virtual experimental designs for fast forward and reverse calculations directly relating structure to viscosity and processability. The new combined method is compared with empirical blend rules, and shows important similarities and also clear quantitative differences. Finally, the new method is applied to practical recycling quality challenges.

One of the most significant issues, when thin parts have to be obtained by injection molding (i.e. in micro-injection molding), is the determination of the conditions of pressure, mold temperature, and injection temperature to adopt to completely fill the cavity. Obviously, modern computational methods allow the simulation of the injection molding process for any material and any cavity geometry. However, this simulation requires a complete characterization of the material for what concerns the rheological and thermal parameters, and also a suitable criterion for solidification. These parameters are not always easily reachable. A simple test aimed at obtaining the required parameters is then highly advantageous. The so-called spiral flow test, consisting of measuring the length reached by a polymer in a long cavity under different molding conditions, is a method of this kind. In this work, with reference to an isotactic polypropylene, some spiral flow tests obtained with different mold temperatures and injection pressures are analyzed with a twofold goal: on one side, to obtain from a few simple tests the basic rheological parameters of the material; on the other side, to suggest a method for a quick prediction of the final flow length.