Slow regions percolate near glass transition

A nano-second scale in situ probe reveals that a bulk linear polymer undergoes a sharp phase transition as a function of the degree of conversion, as it nears the glass transition. The scaling behaviour is in the same universality class as percolation. The exponents \gamma and \beta are found to be 1.7 \pm .1 and 0.41\pm 0.01 in agreement with the best percolation results in three dimensions.Comment: 7 pages, 3 figure

Glyceraldehyde as an efficient chemical crosslinker agent for the formation of chitosan hydrogels

The rheological changes that occur during the chemical gelation of semidilute solutions of chitosan in the presence of the low‐toxicity agent glyceraldehyde (GCA) are presented and discussed in detail. The entanglement concentration for chitosan solutions was found to be approximately 0.2 wt.% and the rheological experiments were carried out on 1 wt.% chitosan solutions with various amounts of GCA at different temperatures (25 \ub0C and 40 \ub0C) and pH values (4.8 and 5.8). High crosslinker concentration, as well as elevated temperature and pH close to the pKa value (pH ≈ 6.3–7) of chitosan are three parameters that all accelerate the gelation process. These conditions also promote a faster solid‐like response of the gel‐network in the post‐gel region after long curing times. The mesh size of the gel‐network after a very long (18 h) curing time was found to contract with increasing level of crosslinker addition and elevated temperature. The gelation of chitosan in the presence of other chemical crosslinker agents (glutaraldehyde and genipin) is discussed and a comparison with GCA is made. Small angle neutron scattering (SANS) results reveal structural changes between chitosan solutions, incipient gels, and mature gels

Isometric immersions, energy minimization and self-similar buckling in non-Euclidean elastic sheets

The edges of torn plastic sheets and growing leaves often display hierarchical buckling patterns. We show that this complex morphology (i) emerges even in zero strain configurations, and (ii) is driven by a competition between the two principal curvatures, rather than between bending and stretching. We identify the key role of branch-point (or "monkey-saddle") singularities in generating complex wrinkling patterns in isometric immersions, and show how they arise naturally from minimizing the elastic energy.Comment: 6 pages, 6 figures. This article supersedes arXiv:1504.0073

Investigating Structural Proteins by Light Scattering

This thesis evaluates the organization of the structural proteins, Human Gamma D crystallin and Collagen type II, into higher-order structures using light scattering. Specifically, it evaluates the natures of incipient aggregation in Human Gamma D crystallin and the nature of its interactions with CAPEGn, an electrostatic blocker. Additionally, this thesis evaluates whether Collagen type II growth kinetics follows Classical nucleation theory

Guar gum/borax hydrogel: Rheological, low field NMR and release characterizations

Guar gum (GG) and Guar gum/borax (GGb) hydrogels are studied by means of rheology, Low Field Nuclear Magnetic Resonance (LF NMR) and model drug release tests. These three approaches are used to estimate the mesh size (ζ) of the polymeric network. A comparison with similar Scleroglucan systems is carried out. In the case of GGb, the rheological and Low Field NMR estimations of ζ lead to comparable results, while the drug release approach seems to underestimate ζ. Such discrepancy is attributed to the viscous effect of some polymeric chains that, although bound to the network to one end, can freely fluctuate among meshes. The viscous drag exerted by these chains slows down drug diffusion through the polymeric network. A proof for this hypothesis is given by the case of Scleroglucan gel, where the viscous contribution is not so significant and a good agreement between the rheological and release test approaches was found

Cellulosic materials as biopolymers and supercritical CO2as a green process: chemistry and applications

In this review, we describe the use of supercritical CO2 (scCO2) in several cellulose applications. The focus is on different technologies that either exist or are expected to emerge in the near future. The applications are wide from the extraction of hazardous wastes to the cleaning and reuse of paper or production of glucose. To put this topic in context, cellulose chemistry and its interactions with scCO2 are described. The aim of this study was to discuss the new emerging technologies and trends concerning cellulosic materials processed in scCO2 such as cellulose drying to obtain aerogels, foams and other microporous materials, impregnation of cellulose, extraction of highly valuable compounds from plants and metallic residues from treated wood. Especially, in the bio-fuel production field, we address the pre-treatment of cellulose in scCO2 to improve fermentation to ethanol by cellulase enzymes. Other reactions of cellulosic materials such as organic inorganic composites fabrication and de-polymerisation have been considered. Cellulose treatment by scCO2 has been discussed as well. Finally, other applications like deacidification of paper and cellulosic membranes fabrication in scCO2 have been reviewed. Examples of the discussed technologies are included as well

Creasing Instability of Hydrogels and Elastomers

CREASING INSTABILITY OF HYDROGELS AND ELASTOMERS MAY 2014 DAYONG CHEN, B.S., TIANJIN UNIVERISTY M.S., TIANJIN UNIVERSITY M.S., UNIVERSITY OF MASSACHUSETTS AMHERST Ph.D., UNIVERSITY OF MASSACHUSETTS AMHERST Directed by: Professor Ryan C. Hayward Soft polymers placed under compressive stress can undergo an elastic creasing instability in which sharp folds spontaneously form on the free surfaces. This process may play an important role in contexts as diverse as brain morphogenesis, failure of tires, and electrical breakdown of soft polymer actuators. While the creasing instability has been used for collotype printing since as early as the 1850s, the scientific appreciation of this instability has become popular only recently and our understanding of this instability is still quite limited. In chapter 2, we describe a simple experimental system to study creasing of thin elastomer films under uniaxial compression. The equilibrium depths, spacings and shapes of creases are characterized and found to show excellent agreements with numerical results. Further, we use this system to explore the important roles played by surface energy. Creases have been found to form in a nucleation and growth fashion, with surface energy providing a barrier in both processes. While this process may play an important role in a variety of materials failures, it can also be harnessed to fabricate dynamic chemical patterns and as a new method for lithography. To understand the role of creasing in materials failures or to engineer it for applications, the study of hysteresis in creasing is of vital importance. In Chapter 3, we review that different degrees of hysteresis have been observed in different systems. By changing the interface energy, we for the first time show that it is the self-adhesion at the folding region rather than plastic deformation that gives rise to hysteresis. We design a soft elastic bilayer that can snap between the flat and creased states repeatedly, with hysteresis. The strains at which the creases form and disappear are highly reproducible, and are tunable over a large range, through variations in the level of pre-compression applied to the substrate and the relative thickness of the film. The introduction of bistable flat and creased states and hysteretic switching is an important step to enable applications of this type of instability. In chapter 4, we design experiments to show that creases can also form on the interface of two soft hydrogels. In comparison with surface creases, which form self-contact, interfacial creases take on a singular non-self-contacting V shape. Interfacial creases form at higher strain than surface creases, but always form prior to interface wrinkles. In chapter 5, we show how the morphology and onset of creases depend on materials properties, geometry, loading history, as well as stress states. While several results are promising, we also propose better experimental setups to facilitate future studies and better control crease morphology. In chapter 6, we introduce an application of the creasing instability, where we utilize creased hydrogels as a dynamic platform to apply tensile strain on cells. We have demonstrated that using temperature as a stimulus, cultured muscle cells can be mechanically deformed with different strain states and amplitudes. This experiment also, for the first time, achieves local actuation of creasing instability with pneumatic/hydraulic pressure. Creases actuated by microfluidics offer potential for realization of high-throughput cell stretching devices on single cell level, through which different strain states, amplitudes, as well as loading rate and frequency could be modulated to mimic the mechanical environment cells experience in vivo