Title

The measurement of low-frequency linear viscoelastic properties of polyolefins using creeping squeeze flow

Date of Completion

January 2002

Keywords

Engineering, Chemical|Engineering, Materials Science

Degree

Ph.D.

Abstract

The characterization of the low-frequency linear viscoelastic properties of polymers is a classical problem in rheometry, especially for broad molecular weight (MW), fractional melt-flow index (MFI) polyolefins with small time-temperature shift factors. By interconversion of high-temperature, low-shear steady-viscosity data in the terminal flow regime into low-frequency data using the Cox-Merz rule, the experimental window is expanded towards lower frequencies. ^ A squeeze-flow apparatus using Newton interferometry as a drift-free transducer to measure the gap between a spherical lens and a flat glass plate with high spatial resolution was constructed. Trials with a Newtonian silicone oil and a viscoelastic polydimethylsiloxane (PDMS) gum were undertaken to examine the various experimental factors that might contribute to errors in the calculation of the viscosity. After taking into account those factors during the runs with PDMS gum, the squeeze-flow-derived viscosities at the terminal flow regime (at shear rates accessible to a commercial rheometer) were in good agreement with low frequency dynamic data. To achieve much lower shear rates for the runs with polyolefins, an increase in the working gap range was made by switching from Newton interferometry to Fizeau interferometry. A hermetically sealed high vacuum chamber was built to allow high-temperature runs with polyolefins with minimal degradation. ^ Interconversion of the measured viscosities of a broad MW, 1.04 MFI high-density polyethylene (HDPE) with the squeeze flow apparatus resulted in complex viscosity data at ∼10−5 rad/s, expanding the experimental window by 2 decades. The squeeze-flow derived complex viscosity data was used to decide which of the two popular viscosity models was more accurate in predicting the zero-shear rate viscosity based on its fit to dynamic data limited to higher frequencies. ^