Ph.D. Thesis Northwestern University, Department of Materials Science and Engineering, September, 2017
Author: Chyi-Huey Joshua Ye
Abstract: The quartz crystal microbalance (QCM) is a versatile characterization tool capable of tracking changes in areal mass and high frequency MHz rheology of micron thick films. The QCM primarily consists of a single quartz disc with electrodes deposited on both sides of the disc. Due to the piezoelectric nature of quartz, introduction of an oscillating voltage near the resonance condition of the quartz disc produces a traveling shear wave that can be measured with electrical admittance analysis. This technique behaves like an acoustic reflectometer, where an induced mechanical shear wave propagates and reflects at the interfaces between material layers with differing acoustic impedances. Based on how the shear wave interacts with the interfaces, information on the material properties can be quantitatively modeled. In this dissertation, a quantitative approach of determining the magnitude and sources of error is presented, so that interpretation of viscoelastic information and areal mass changes can be performed with confidence. Specifically, the role of anharmonic coupling with harmonic modes are explored and simulated with COMSOL Multiphysics.
Several case studies motivating and highlighting the utility of the QCM is presented. The fracture and thermal aging behavior of several nanofilled silicone elastomers are examined using traditional mechanical tests, such as pure shear geometry and dynamic mechanical analysis (DMA). Results can be qualitatively explained by the concept of dynamic mechanical heterogeneity, where a high mechanical contrast is desired for high fracture toughness. However, DMA results can be difficult to interpret (especially at shifted high frequencies) due to thermal rheological complexity, a characteristic commonly found in many polymer composites. This motivates the application of the QCM, where MHz viscoelastic behavior can be directly probed, providing insight on the dissipative behavior at local length scales.
Investigation of polysilicate nanofillers on the high frequency viscoelastic behavior of polydimethylsiloxane (PDMS) melt is discussed. The amount of filler varied from pure PDMS to pure filler, highlighting the advantage of using an acoustic rheometer to measure properties of films exhibiting viscous to highly brittle behavior. An empirical mixing law is proposed in describing the changes in visceolasticity as a function of filler content, so that the critical filler content at the liquid to solid transition can be estimated. The liquid to solid transition is qualitatively explained by percolation rigidity of the polysilicate nanofillers.
The QCM is also extended as a photorheometer, capable of measuring in situ rheology of fast radical photopolymerizations. A model acrylate system is examined as a means to demonstrate the value of the QCM and to provide context for the examination of a more interesting thiol-ene photopolymer system. Due to insensitivity of thiol-ene chemical kinetics towards oxygen inhibition during curing, the impact of oxygen incorporation on the crosslinked viscoelastic network is investigated. In addition to studying thiol-ene reactions, photoinitiated copper catalyzed alkyne azide cycloaddition is also explored. The effects of plasticization on the curing kinetics and mechanical properties are presented.
Altogether, this dissertation serves to contribute to the fundamental development of the QCM as a quantitative MHz rheometer. By thoroughly presenting a quantitative approach towards error analysis and providing successful QCM case studies, the barrier of entrance for using the QCM is substantially lowered. Future researchers will be able to efficiently conduct QCM experiments and analysis at a higher level of operation. Several ideas are also briefly proposed in which the QCM can provide valuable insights and contributions.