Joseph R. Royer

High-pressure rheology of polystyrene melts plasticized with CO2: Experimental measurement and predictive scaling relationships

A high-pressure extrusion slit die rheometer was constructed to measure the viscosity of polymer melts plasticized by liquid and supercritical CO2. A novel gas injection system was devised to accurately meter the follow of CO2 into the extruder barrel. Measurements of pressure drop, within the die, confirm the presence of a one-phase mixture and a fully developed flow during viscosity measurements. Experimental measurements of viscosity as a function of shear rate, pressure, temperature, and CO2 concentration were conducted for three commercial polystyrene melts. The CO2 was shown to be an effective plasticizer for polystyrene, lowering the viscosity of the polymer melt by as much as 80%, depending of the process conditions and CO2 concentration. Existing theories for viscoelastic scaling of polymer melts and the prediction of Tg depression by a diluent were used to develop a free volume model for predicting the effects of CO2 concentration and pressure on polymer melt rheology. The free volume model, dependent only on material parameters of the polymer melt and pure CO2, was shown to accurately collapse the experimental data onto a single master curve independent of pressure and CO2 concentration for each of the three polystyrene samples. This model constitutes a simple predictive set of equations to quantify the effects of gas-induced plasticization on molten polymer systems.

Generation of microcellular foams of PVDF and its blends using supercritical carbon dioxide in a continuous process

Abstract Use of supercritical carbon dioxide (scCO 2 ) as a blowing agent to generate microcellular polymer foams (MPFs) has recently received considerable attention due to environmental concerns associated with conventional organic blowing agents. While such foams derived from amorphous thermoplastics have been previously realized, semicrystalline MPFs have not yet been produced in a continuous scCO 2 process. This work describes the foaming of highly crystalline poly(vinylidene fluoride) (PVDF) and its blends with amorphous polymers during extrusion. Foams composed of neat PVDF and immiscible blends of PVDF with polystyrene exhibit poor cell characteristics, whereas miscible blends of PVDF with poly(methyl methacrylate) (PMMA) yield foams possessing vastly improved morphologies. The results reported herein illustrate the effects of blend composition and scCO 2 solubility on PVDF/PMMA melt viscosity, which decreases markedly with increasing PMMA content and scCO 2 concentration. Morphological characterization of microcellular PVDF/PMMA foams reveals that the cell density increases as the PMMA fraction is increased and the foaming temperature is decreased. This study confirms that novel MPFs derived continuously from semicrystalline polymers in the presence of scCO 2 can be achieved through judicious polymer blending.

Tailored rheology of a metallocene polyolefin through silane grafting and subsequent silane crosslinking

Polymer modification through silane grafting and its subsequent crosslinking allows the rheological properties of a polymer to be tuned from those of a viscous melt to those of a crosslinked elastic network. In this study, a metallocene polyolefin resin is grafted with vinyl trimethoxy silane (VTMS) using dicumyl peroxide (DCP) as the initiator and is subsequently crosslinked in an oxidative environment. Dynamic rheological experiments are conducted to elucidate the effects of DCP and VTMS concentrations on the grafting and ensuing crosslinking processes. We find that the addition of VTMS alone to the polymer produces no grafting. In contrast, the presence of DCP by itself leads to direct crosslinking between polymer chains as suggested by an increase in elastic modulus and complex viscosity. Samples containing both DCP and VTMS undergo silane grafting, with the extent of grafting increasing with increasing DCP concentration. This conclusion is borne out by both rheological and Fourier transform infrared measurements. The grafted samples undergo silane crosslinking only in an oxidative environment and at temperatures equal to or greater than 190 °C. During crosslinking, the samples undergo a transition from a viscous melt with frequency-dependent moduli to a gel exhibiting frequency-independent moduli with the elastic modulus exceeding the viscous modulus. However, the kinetics of crosslinking and the extent of the modulus increase are a function of the DCP concentration, with both exhibiting a maximum at a specific DCP and VTMS combination.

Compressive stress relaxation of metallocene‐based polyolefin foams: Effect of gamma‐ray‐induced crosslinking

Metallocene-based polyolefin (MPO) foams possess a closed-cell structure which is in contrast to the open-celled structure of polyurethane (PU) foams. In this study, we investigate the effects of gamma-irradiation on the mechanical behavior of MPO foams using PU foam behavior as a basis. Compressive step-strain experiments reveal a two-step relaxation process in MPO foams, dominated by polymer chain relaxation at short times and gas diffusion from the closed cells at longer times. On the other hand, the relaxation in PU foams is similar to fully crosslinked polymers with the relaxation modulus reaching an equilibrium value after an initial decay. The closed-celled structure of MPO foams lends to rapid stress relaxation and low structural recoverability upon application of compressive loads. Exposure to gamma radiation induces crosslinking in MPO foams and improves their resilience and recoverability. Stress relaxation tests reveal that nonradiated MPO foams show complete relaxation and structural loss at high temperatures. In contrast, radiated MPO foams show a significant retardation in relaxation kinetics and structural stability attributed to radiation-induced crosslinking. Dynamic rheology and solvent-extraction studies also support the results obtained from stress-relaxation experiments.

Microcellular Polymeric Foams (MPFs) Generated Continuously in Supercritical Carbon Dioxide

Microcellular polymeric foams (MPF s ) hold tremendous promise for engineering applications as substitutes to their solid analogs in light of reduced manufacturing/materials costs and improved properties. We present a two-part study addressing the generation of such materials in the presence of supercritical carbon dioxide ( sc CO2). The first part describes the production of polystyrene MPF s in a continuous extrusion process, as well as the effect of operating conditions such as temperature and CO 2 concentration on foam morphology. The second part discusses microcellular foaming of poly (vinylidene fluoride) (PVDF), a semicrystalline polymer, via blending with the amorphous polymer poly (methyl methacrylate) PMMA. Foams of pure PVDF possess ill-defined morphologies, whereas those of PVDF-PMMA blends show an improvement with cell sizes on the order of 10 mm or less and cell densities in excess of 10 9 cells/cm 3 .