Dynamics and rheology of soft phase-change materials
Massachusetts Institute of Technology. Department of Mechanical Engineering.
Gareth H. McKinley.
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Many industrial processes involve multicomponent or composite materials in which one component can undergo a phase transition leading to the appearance of a solid phase dispersed in a liquid-like continuous phase. Examples of soft phase-change materials can be found in a variety of applications from food products (e.g., organogels, casein gels and gelatin), pharmaceutical products (e.g., tissue mimicking phantoms and encapsulating agents), cosmetics (e.g., foundations and lipsticks), and in the oil and gas industry, where formation of paraffin waxes and clathrate hydrates represent major issues for upstream production and flow assurance.Historically, phase-changing materials have been exploited for their unique thermal properties in energy storage applications, however soft solids and complex fluids that undergo phase transformation have broader impact in industrial and biomedical applications because of the dramatic changes in mechanical properties that result from the conditions across the phase transition. Typically, these soft phase-change materials are part of the broader class of elasto-visco-plastic materials, showing both viscoelasticity at small deformations and plasticity at large deformations. However, their material properties are greatly influenced by the specific processing conditions during formation, such as temperature and applied deformation, leading to a thermo-rheological complexity that still poses major challenges for their experimental and theoretical characterization.In this Thesis, we develop novel experimental protocols and theoretical frameworks to characterize and describe the complex rheological behavior of soft phase-changing materials, under both linear and non-linear deformations. We focus mainly on two types of materials that are of major importance in the oil and gas industry: paraffin gels, as model waxy crude oils, and clathrate hydrate suspensions. In the limit of small deformations, we are usually interested in measuring the frequency response of the material as it evolves, or mutates, over time. Current state-of-the-art techniques have major limitations in providing both time- and frequency-resolution primarily due to the type of input signals used. To overcome this, we develop a robust excitation signal that allows us to perform time-resolved mechanical spectroscopy of fast mutating systems. Inspired by the biosonar signals of bats and dolphins, we introduce a joint frequency- and amplitude- modulated chirp signal.Combining experiments and numerical simulations, we show that there exists an optimized range of amplitude modulation that minimizes the estimation error while reducing the total acquisition time by almost two orders of magnitude. With this new technique, which we call the Optimally Windowed Chirp (or OWCh), we then explore the phase transition during gelation of a series of mutating, phase-changing materials, including casein gels, gelatin and paraffin gels. To address large, non-linear deformations, we start from a thorough investigation of the steady state and transient response of paraffin gels under shear. We develop a robust protocol that enables us to systematically extract the main rheological features including the thermokinematic memory (i.e. the effect of thermal and shear history on the rheological behavior of the gel) and thixotropy (i.e. the time-dependent behavior under constant applied deformation).We show that these features can be understood in terms of microstructural rearrangements of the underlying solid particle network, which can be quantified through differential scanning calorimetry, birefringence imaging and rheometry. Based on this understanding, we present a constitutive framework that captures all of the different features while respecting thermodynamic and objectivity constraints. We also investigate mechanical instabilities that may arise during rheological measurements. Combining ultrasonic image velocimetry and rheometry, we show that both shear banding and slip can take place during steady shear below a critical value of the shear rate. However, the thixotropic nature of these materials precludes the banding instability from growing in the sheared region of the gap, ensuring that the measured stress response corresponds to the real bulk behavior. Finally, we study the visco-plastic response of clathrate hydrate suspensions.To do so, we develop a novel method to robustly control their formation, which so far has been a major issue in experimental studies due to uncontrolled nucleation and growth of hydrate crystals. Our method, based on the use of "frozen emulsions", decreases the induction time by orders of magnitude while guaranteeing that all the water droplets initially frozen into ice particles are converted into hydrate particles. Rheological measurements for different water volume fractions and shear rates reveal that the macroscopic rheological response is again governed by rearrangements of the microstructure; however, due to the very strong interparticle forces (which are the result of a continuous sintering process) the microstructure evolves towards a fully connected network that behaves as a porous solid structure.Incorporating this limit into our theoretical model, we show that the framework developed for softer interparticle interaction can also capture the macroscopic plastic response of hydrate suspensions. The results from this Thesis have the potential to impact many industrial processes that involve soft phase-change materials, such as flow assurance and oil extraction, thermal energy storage, gas transport and storage, and other processes where the dynamics of gelation are used to control the rheological properties of the ultimate product.
Thesis: Ph. D., Massachusetts Institute of Technology, Department of Mechanical Engineering, 2019Cataloged from PDF version of thesis.Includes bibliographical references (pages 325-353).
DepartmentMassachusetts Institute of Technology. Department of Mechanical Engineering
Massachusetts Institute of Technology