Supercooled liquids

In this discussion, we present a theory for the computation of poling processes which is based on a constitutive model taking into account all electro-mechanically coupled ferroelectric and ferroeleastic hysteresis properties. In addition, this theory includes as a unique feature weak electric conductivity. The author presents an example where the developed finite element tool has been used to compute poling processes in piezoceramic devices. In particular, the author demonstrates the effect of subsequent charge transport following the poling process induced by depolarization fields

Templated Self Assemble of Nano-Structures

This project will identify and model mechanisms that template the self-assembly of nanostructures. We focus on a class of systems involving a two-phase monolayer of molecules adsorbed on a solid surface. At a suitably elevated temperature, the molecules diffuse on the surface to reduce the combined free energy of mixing, phase boundary, elastic field, and electrostatic field. With no template, the phases may form a pattern of stripes or disks. The feature size is on the order of 1-100 nm, selected to compromise the phase boundary energy and the long-range elastic or electrostatic interaction. Both experimental observations and our theoretical simulations have shown that the pattern resembles a periodic lattice, but has abundant imperfections. To form a perfect periodic pattern, or a designed aperiodic pattern, one must introduce a template to guide the assembly. For example, a coarse-scale pattern, lithographically defined on the substrate, will guide the assembly of the nanoscale pattern. As another example, if the molecules on the substrate surface carry strong electric dipoles, a charged object, placed in the space above the monolayer, will guide the assembly of the molecular dipoles. In particular, the charged object can be a mask with a designed nanoscale topographic pattern. A serial process (e.g., e-beam lithography) is necessary to make the mask, but the pattern transfer to the molecules on the substrate is a parallel process. The technique is potentially a high throughput, low cost process to pattern a monolayer. The monolayer pattern itself may serve as a template to fabricate a functional structure. This project will model fundamental aspects of these processes, including thermodynamics and kinetics of self-assembly, templated self-assembly, and self-assembly on unconventional substrates. It is envisioned that the theory will not only explain the available experimental observations, but also motivate new experiments

Smoothening creases on surfaces of strain-stiffening materials

When an elastic block (e.g., an elastomer or a soft tissue) is compressed to a critical strain, the smooth surface of the block forms creases, namely, localized regions of self-contact. Here we show how this instability behaves if the solid stiffens steeply. For a solid that stiffens steeply at large strains, as the compression increases, the surface is initially smooth, then forms creases, and finally becomes smooth again. For a solid that stiffens steeply at small strains, creases will never form and the surface remains smooth for all levels of compression. We also obtain the critical conditions for the formation and disappearance of wrinkles. When the surface does become unstable, we find that creases always set in at a lower compression than wrinkles. Our findings may shed light in developing crease-resistant materials.Engineering and Applied Science

A model of ideal elastomeric gels for polyelectrolyte gels

The concept of the ideal elastomeric gel is extended to polyelectrolyte gels and verified using a polyacrylamide-co-acrylic acid hydrogel as a model material system. A comparison between mixing and ion osmosis shows that the mixing osmosis is larger than the ion osmosis for small swelling ratios, while the ion osmosis dominates for large swelling ratios. We show further that the non-Gaussian chain effect becomes important in the elasticity of the polymer network at the very large swelling ratios that may occur under certain conditions of pH and salinity. We demonstrate that the Gent model captures the non-Gaussian chain effect well and that it provides a good description of the free energy associated with the stretching of the network. The model of ideal elastomeric gels fits the experimental data very well.Engineering and Applied Science

Stiff, strong, and tough hydrogels with good chemical stability

Most hydrogels have poor mechanical properties, severely limiting their scope of applications. Here a hybrid hydrogel, consisting of hydrophilic and crystalline polymer networks, achieves an elastic modulus of 5 MPa, a strength of 2.5 MPa, and a fracture energy of 14 000 J m−2, while maintaining physical integrity in concentrated electrolyte solutions.Engineering and Applied Science

Temporal evolution and instability in a viscoelastic dielectric elastomer

Dielectric elastomer transducers are being developed for applications in stretchable electronics, tunable optics, biomedical devices, and soft machines. These transducers exhibit highly nonlinear electromechanical behavior: a dielectric membrane under voltage can form wrinkles, undergo snap-through instability, and suffer electrical breakdown. We investigate temporal evolution and instability by conducting a large set of experiments under various prestretches and loading rates, and by developing a model that allows viscoelastic instability. We use the model to classify types of instability, and map the experimental observations according to prestreches and loading rates. The model describes the entire set of experimental observations. A new type of instability is discovered, which we call wrinkle-to-wrinkle transition. A flat membrane at a critical voltage forms wrinkles and then, at a second critical voltage, snaps into another state of winkles of a shorter wavelength. This study demonstrates that viscoelasticity is essential to the understanding of temporal evolution and instability of dielectric elastomers.Engineering and Applied Science

Variation of stress with charging rate due to strain-rate sensitivity of silicon electrodes of Li-ion batteries

Silicon is a promising anode material for lithium-ion batteries due to its enormous theoretical energy density. Fracture during electrochemical cycling has limited the practical viability of silicon electrodes, but recent studies indicate that fracture can be prevented by taking advantage of lithiation-induced plasticity. In this paper, we provide experimental insight into the nature of plasticity in amorphous LixSi thin films. To do so, we vary the rate of lithiation of amorphous silicon thin films and simultaneously measure stresses. An increase in the rate of lithiation results in a corresponding increase in the flow stress. These observations indicate that rate-sensitive plasticity occurs in a-LixSi electrodes at room temperature and at charging rates typically used in lithium-ion batteries. Using a simple mechanical model, we extract material parameters from our experiments, finding a good fit to a power law relationship between the plastic strain rate and the stress. These observations provide insight into the unusual ability of a-LixSi to flow plastically, but fracture in a brittle manner. Moreover, the results have direct ramifications concerning the rate-capabilities of silicon electrodes: faster charging rates (i.e., strain rates) result in larger stresses and hence larger driving forces for fracture.Engineering and Applied Science

Mechanics of Supercooled Liquids

Pure substances can often be cooled below their melting points and still remain in the liquid state. For some supercooled liquids, a further cooling slows down viscous flow greatly, but does not slow down self-diffusion as much. We formulate a continuum theory that regards viscous flow and self-diffusion as concurrent, but distinct, processes. We generalize Newton’s law of viscosity to relate stress, rate of deformation, and chemical potential. The self-diffusion flux is taken to be proportional to the gradient of chemical potential. The relative rate of viscous flow and self-diffusion defines a length, which, for some supercooled liquids, is much larger than the molecular dimension. A thermodynamic consideration leads to boundary conditions for a surface of liquid under the influence of applied traction and surface energy. We apply the theory to a cavity in a supercooled liquid and identify a transition. A large cavity shrinks by viscous flow, and a small cavity shrinks by self-diffusion.Engineering and Applied Science

Elastic leak of a seal

An elastomeric seal may leak by elastic deformation without any material damage. We describe elastic leak using a theoretical model, and watch a seal deform and leak using a transparent experimental setup. The elastomer seals the fluid by forming contact with surrounding hard materials. As the fluid pressure increases, the contact stress also increases but not as much. When the fluid pressure surpasses the contact stress, the elastomer and t he hard materials lose contact in some region, forming a leaking path. The critical fluid pressure for elastic leak depends on the geometry and constraint of the seal, but is insensitive to the rate at which the fluid is injected. Our study points to the significance of elastic deformation in modes of failure that also involve material damage.Engineering and Applied Science