Equilibrium Liquid Crystal Phase Diagrams and Detection of Kinetic Arrest in Cellulose Nanocrystal Suspensions

in Frontiers in Materials (2016), 3

The cholesteric liquid crystal self-assembly of water-suspended cellulose nanocrystal (CNC) into a helical arrangement was observed already more than 20 years ago, and the phenomenon was used to produce ... [more ▼]

The cholesteric liquid crystal self-assembly of water-suspended cellulose nanocrystal (CNC) into a helical arrangement was observed already more than 20 years ago, and the phenomenon was used to produce iridescent solid films by evaporating the solvent or via sol–gel processing. Yet, it remains challenging to produce optically uniform films and to control the pitch reproducibly, reflecting the complexity of the three-stage drying process that is followed in preparing the films. An equilibrium liquid crystal phase formation stage is followed by a non-equilibrium kinetic arrest, which in turn is followed by structural collapse as the remaining solvent is evaporated. Here, we focus on the first of these stages, combining a set of systematic rheology and polarizing optics experiments with computer simulations to establish a detailed phase diagram of aqueous CNC suspensions with two different values of the surface charge, up to the concentration where kinetic arrest sets in. We also study the effect of varying ionic strength of the solvent. Within the cholesteric phase regime, we measure the equilibrium helical pitch as a function of the same parameters. We report a hitherto unnoticed change in character of the isotropic–cholesteric transition at increasing ionic strength, with a continuous weakening of the first-order character up to the point where phase coexistence is difficult to detect macroscopically due to substantial critical fluctuations. [less ▲]

Brownian stress relaxation in sheared nanocomposites: Non-monotonic concentration dependency of relaxation frequencies

Presentation (2015, April)

Slow dynamics in sheared DGEBA/SiO2 suspensions

Presentation (2015, March)

Anomalous glass transition behavior of SBR–Al2O3 nanocomposites at small filler concentrations

in Nanotechnology (2014), 25(42), 425704

Elastomers filled with hard nanoparticles are of great technical importance for the rubber industry. In general, fillers improve mechanical properties of polymer materials, e.g. elastic moduli, tensile ... [more ▼]

Elastomers filled with hard nanoparticles are of great technical importance for the rubber industry. In general, fillers improve mechanical properties of polymer materials, e.g. elastic moduli, tensile strength etc. The smaller the size of the particles the larger is the interface where interactions between polymer molecules and fillers can generate new properties. Using temperature-modulated differential scanning calorimetry and dynamic mechanical analysis, we investigated the properties of pure styrene-butadiene rubber (SBR) and SBR/alumina nanoparticles. Beside a reinforcement effect seen in the complex elastic moduli, small amounts of nanoparticles of about 2 wt% interestingly lead to an acceleration of the relaxation modes responsible for the thermal glass transition. This leads to a minimum in the glass transition temperature as a function of nanoparticle content in the vicinity of this critical concentration. The frequency dependent elastic moduli are used to discuss the possible reduction of the entanglement of rubber molecules as one cause for this unexpected behavior. [less ▲]

Strain-induced low-frequency relaxation in colloidal DGEBA/SiO2 suspensions

in Rheologica Acta (2014), 53(9), 715-723

Diglycidyl ether of bisphenol A (DGEBA) is widely exploited as an epoxy resin in adhesives and coatings. In this paper, it is used as an oligomer matrix for silica-filled nanocomposites. Rheological ... [more ▼]

Diglycidyl ether of bisphenol A (DGEBA) is widely exploited as an epoxy resin in adhesives and coatings. In this paper, it is used as an oligomer matrix for silica-filled nanocomposites. Rheological measurements show that the pure matrix obeys power-law relaxation dynamics in the vicinity of the dynamic glass transition of this low-molecular-weight glass former. In the filled systems, a low-frequency relaxation appears additionally to the structural alpha-process of the matrix. Considering the nanocomposites as Newtonian hard-sphere suspensions at low angular frequencies (or high temperatures), the modified terminal regime behavior of the matrix can be linked to strain-induced perturbations of the isotropic filler distributions. While in the low-frequency regime hydrodynamic stresses relax instantaneously, the Brownian stress relaxation is viscoelastic and can be evidenced by dynamic rheological measurements. At higher angular frequencies, the alpha-process of the matrix superimposes on the Brownian stress relaxation. In particular, we were able to depict the low-frequency anomaly for concentrated, semi-dilute, and even for dilute suspensions. [less ▲]