Unraveling the Mystery of Soft Materials: Bridging the Gap Between Microscopic and Macroscopic Behavior

Significance 

The collapse of soft materials refers to the failure or deformation of materials that possess a low resistance to external forces or stresses. Soft materials are typically characterized by their ability to undergo large deformations without fracturing or breaking. Examples of soft materials include gels, foams, emulsions, colloidal suspensions, and polymers.

When soft materials experience an applied stress or deformation, they may undergo a structural rearrangement or collapse due to the disruption of their internal microstructure. This collapse can manifest as a loss of mechanical integrity, a change in shape, or a transition from a solid-like state to a fluid-like state. Understanding and predicting the collapse behavior of soft materials is crucial for various engineering applications.

The collapse of soft materials can occur through different mechanisms depending on the specific material and the applied stress. In some cases, the collapse may be triggered by the rearrangement or breaking of interparticle or intermolecular bonds, leading to a loss of structural integrity. This can result in a change in material properties, such as stiffness, viscosity, or flow behavior. The collapse of soft materials can have significant implications in a wide range of fields. For instance, in the field of materials engineering, understanding the collapse behavior is essential for designing and formulating materials with desired properties. In industries such as food processing and personal care products, the collapse of soft materials plays a role in texture and product stability. In the field of biomedicine, the collapse behavior of soft materials is important for the development of biomedical implants and drug delivery systems. Additionally, in geotechnical engineering, the collapse of soft soils can lead to landslides and avalanches, posing risks to infrastructure and human safety.

Researchers have long been puzzled by the complexities of soft materials collapse, as it involves intricate interactions at the microscale that ultimately affect the macroscopic behavior. Recent advancements, such as the development of novel measurement techniques like rheo-X-ray photon correlation spectroscopy, have provided insights into the microstructural dynamics during yielding and the correlation between microstructural changes and macroscopic behavior. These findings contribute to unraveling the mechanisms behind the collapse of soft materials and pave the way for advancements in materials engineering and various applications.

The collapse of soft materials has long been a challenge for engineers and researchers, as understanding the underlying mechanics at both the macroscopic and microscopic levels has proven elusive. However, a recent study conducted by chemical engineers from the University of Illinois Urbana-Champaign, in collaboration with teams from Argonne National Laboratory, Johns Hopkins University, and the University of Ottawa, has made significant progress in unraveling this mystery. The research work is now published in the journal Proceedings of the National Academy of Sciences.

The researchers introduced a new metric called the “correlation ratio” that establishes a connection between microscopic-level processes and the macroscopic behavior of soft materials. This breakthrough metric has the potential to revolutionize materials engineering across various applications, including 3D printing inks, flexible electronics, sensors, biomedical implants, landslides and avalanches control, and even improving the textures of processed foods and personal care products. To investigate the relationship between microscale and macroscale behavior, Gavin Donley, Suresh Narayanan, Matthew  Wade, and Simon Rogers utilized a powerful microscopy technique called rheo-X-ray photon correlation spectroscopy (rheo-XPCS). This technique allows for real-time analysis of soft materials as they undergo deformation by combining X-ray analysis with rheometers, devices that measure stress and strain.

By employing rheo-XPCS, the researchers gained unprecedented insights into the microstructural behavior of soft materials under stress. They focused their study on a material called soft colloidal glass, a system of nanoparticles made of silica that exhibits squishy characteristics due to interparticle interactions. This material was chosen because it provided a strong X-ray signal that could be recorded while performing simultaneous macroscopic measurements.

Through their experiments, the researchers were able to observe the direct connection between microscopic displacements and macroscopic behavior. They were also able to define the behavior using mathematical terms, enabling a better understanding of how soft materials yield to stress.

The team conducted creep/recovery tests on the colloidal system while collecting coherent scattering data via XPCS. This approach allowed for time-resolved observations of the microstructural dynamics during yielding, which were then linked back to the applied rheological deformation to establish structure-property relationships.

The results of the study revealed several important findings. First, they demonstrated that the scattering response of the material recorrelates with its predeformed state under small applied creep stresses, indicating nearly complete microstructural recovery. On the other hand, larger creep stresses increased the speed of the microstructural dynamics during both creep and recovery phases.

The data also highlighted a strong connection between the microstructural dynamics and the acquisition of unrecoverable strain. The researchers compared this relationship to predictions based on homogeneous, affine shearing and found that the yielding transition in concentrated colloidal systems is highly heterogeneous on the microstructural level.

The study emphasized the significance of glassy dynamics in a wide range of soft materials, including colloidal suspensions, emulsions, foams, and microgels. These materials undergo a macroscopic yield transition, shifting from solid-like to fluid-like behavior when subjected to a critical threshold of stress or deformation. Understanding and controlling this transition is crucial for applications such as spreadable foods, personal care products, and additive manufacturing materials.

Traditionally, the yielding transition has been considered an instantaneous transition to a flowing state at a fixed stress threshold. However, recent studies have revealed the importance of elasticity and the gradual nature of the transition. Additionally, the processes of yielding and unyielding have been linked to the loss and formation of material memory in glassy systems.

While various techniques have been proposed to study the yielding transition, many assume an instantaneous yield transition and are unable to resolve the evolution of yielding or distinguish between elastic deformation and plastic or viscous flow in real-time. One exception is recovery tests, which separate the applied strain into recoverable and unrecoverable components. These tests have shed light on the onset of yielding and the transition to unrecoverable flow.

To investigate the microstructural dynamics of yielding, it is necessary to perform time-resolved measurements of the changes occurring within the microstructure. Light scattering and microscopy have provided valuable insights into the dynamics of both hard and soft glassy materials. In the case of colloidal soft glasses, X-ray scattering has been particularly useful in accessing structure and dynamics on the nanoparticle scale.

The combination of rheometry and scattering techniques, known as rheo-XPCS, has been instrumental in developing flow-dependent structure-property relations for these systems. By employing rheo-XPCS in their study, the researchers were able to investigate the microstructural evolution of concentrated colloidal suspensions during creep/recovery protocols. They identified the rheological conditions for yielding and established an intimate connection between the accumulation of unrecoverable strain and the microstructural changes that occur during yielding.

The correlation ratio, a key metric introduced in the study, offers valuable insights into the nature of the microscopic processes responsible for the accumulation of unrecoverable strain. The correlation ratio’s behavior as a function of unrecoverable strain provides evidence of localized hardening and the onset of heterogeneous, irreversible flow during the yielding transition.

While the research primarily focused on creep and recovery experiments, similar investigations on more complex flow profiles, such as oscillatory shear, have the potential to further enhance our understanding of the coupling between structural memory, dynamics, and applied deformation.

In conclusion, the recent study conducted by the University of Illinois Urbana-Champaign and its collaborators has unveiled a new metric, the correlation ratio, that bridges the gap between microscopic and macroscopic behavior in soft materials. This breakthrough has the potential to advance materials engineering across numerous applications, leading to improvements in 3D printing, flexible electronics, biomedical implants, and more. The research sheds light on the microstructural dynamics during yielding and provides valuable insights into the intricate processes occurring within soft materials under stress. With further exploration and application of these findings, engineers and scientists can unlock new possibilities for designing and manipulating soft materials to meet diverse technological and industrial demands.

Unraveling the Mystery of Soft Materials: Bridging the Gap Between Microscopic and Macroscopic Behavior - Advances in Engineering

About the author

Simon A. Rogers
Associate Professor, Gunsalus Scholar

Simon A. Rogers is an Assistant Professor in the Department of Chemical and Biomolecular Engineering. Dr. Rogers uses experimental and computational tools to understand and model advanced colloidal, polymeric, and self-assembled materials. He joined the department in 2015. He received his BSc in 2001, BSc (Hons) in 2002; and his PhD from Victoria University of Wellington in New Zealand in 2011. He completed his postdoctoral research at the Foundation for Research and Technology in Crete, the Jülich Research Center in Germany, and the Center for Neutron Research at the University of Delaware.

Research interest: Investigates the fundamental physics behind time-dependent phenomena exhibited by soft matter under deformation for biomedical, energy, and environment applications.

Reference

Gavin J. Donley, Suresh Narayanan, Matthew A. Wade, Jun Dong Park, Robert L. Leheny, James L. Harden, Simon A. Rogers. Investigation of the yielding transition in concentrated colloidal systems via rheo-XPCS. Proceedings of the National Academy of Sciences, 2023; 120 (18) DOI: 10.1073/pnas.2215517120

Go To Proceedings of the National Academy of Sciences

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