Colloids of electrically charged nanorods can spontaneously develop a fluid yet ordered liquid crystal phase, but this ordering competes with a tendency to form a gel of percolating rods. The threshold for ordering is reduced by increasing the rod aspect ratio, but the percolation threshold is also reduced with this change; hence, prediction of the outcome is nontrivial. Here, we show that by establishing the phase behavior of suspensions of cellulose nanocrystals (CNCs) fractionated according to length, an increased aspect ratio can strongly favor liquid crystallinity without necessarily influencing gelation. Gelation is instead triggered by increasing the counterion concentration until the CNCs lose colloidal stability, triggering linear aggregation, which promotes percolation regardless of the original rod aspect ratio. Our results shine new light on the competition between liquid crystal formation and gelation in nanoparticle suspensions and provide a path for enhanced control of CNC self-organization for applications in photonic crystal paper or advanced composites.
The influence of Al(2)O(3) nanoparticles on the curing of an epoxy thermoset based on diglycidyl ether of bisphenol A was investigated using temperature-modulated differential scanning calorimetry (TMDSC) and rheology. Diethylene triamine was used as a hardener. TMDSC not only allows for a systematic study of the kinetics of cure but simultaneously gives access to the evolution of the specific heat capacities of the thermosets. The technique thus provides insight into the glass transition behaviour of the nanocomposites and hence makes it possible to shed some light on the interaction between the nanoparticles and the polymer matrix. The Al(2)O(3) fillers are shown to accelerate the growth of macromolecules upon isothermal curing. Several mechanisms which possibly could be responsible for the acceleration are described. As a result of the faster network growth chemical vitrification occurs at earlier times in the filled thermosets and the specific reaction heat decreases with increasing nanoparticle concentration. Rheologic measurements of the zero-shear viscosity confirm the faster growth of the macromolecules in the presence of the nanoparticles.
Kinetic processes, which are joined with mass transport, are studied in the vicinity of the sharp LCST-type demixing transition of semi-dilute aqueous poly(N-isopropyl acrylamide) (PNIPAM) solutions. These processes are slow as compared to the highly cooperative collapse of individual polymer chains. Purely elastic properties, that are particularly sensitive to this phase transition, are addressed depending on the temperature, space and time by Brillouin spectroscopy. Above the demixing temperature T c , we discriminate between kinetics related to the phase separation into PNIPAM-rich and PNIPAM-poor domains and kinetics connected to the impact of gravitation on the on-going phase separation. Using shallow temperature jumps of 0.3 C, the growth of compact PNIPAM-rich agglomerates with identical gel-like mechanical consistency is provoked independently of temperature and position within the sample above T c . Astonishingly, the transition temperature does not vary while heating or cooling the solutions across the phase transition, although the elastic properties depend strongly on space and time during the equilibration of PNIPAM concentration gradients following the re-entrance into the lowtemperature phase.
The phase separation of aqueous poly(N-isopropyl acrylamide) (PNIPAM) solutions is known to strongly affect their volume expansion behaviour and the elastic moduli, as the latter are strongly coupled to the macroscopic order parameter. On the molecular scale, considerable changes in H-bonding and hydrophobic interactions, as well as in the structure govern the demixing process. However, the relationship between the molecular and macroscopic order parameters is unclear for such complex phase-separating solutions. We contribute to the clarification of this problem by relating optical to volumetric properties across the demixing transition of dilute to concentrated aqueous PNIPAM solutions. Far from the demixing temperature, the temperature dependence of the refractive index is predominantly determined by thermal expansion. In the course of phase separation, the refractive index is dominated by the anomalous behaviour of the specific refractivity, which reflects the spatio-temporally averaged changes in molecular interactions and the structural reorganization of the demixing solutions. Moreover, the presence of relaxation processes is studied by the complex expansion coefficient using the novel technique of temperature modulated optical refractometry.
Elastic nonlinearities are particularly relevant for soft materials because of their inherently small linear elasticity. Nonlinear elastic properties may even take over the leading role for the transformation at mechanical instabilities accompanying many phase transitions in soft matter. Because of inherent experimental difficulties, only little is known about third order (nonlinear) elastic constants within liquids, gels and polymers. Here we show that a key concept to access third order elasticity in soft materials is the determination of mode Grüneisen parameters. We report the first direct observation of third order elastic constants across mechanical instabilities accompanying the liquid-liquid demixing transition of semi-dilute aqueous poly(N-isopropylacrylamide) (PNIPAM) solutions. Immense elastic nonlinearities, leading to a strong strain-softening in the phase-separating PNIPAM solutions, are observed. Molecular mechanisms, which may be responsible for these immense elastic nonlinearities, are discussed. The importance of third order elastic constants in comparison to second order (linear) elastic constants in the demixing PNIPAM solutions evidences the need to focus more on the general role played by nonlinear elasticity at phase transitions within synthetic and biological liquids and gels. A IntroductionFor so condensed matter, knowledge about its continuum mechanics plays a decisive role in understanding the molecular cohesion and organization.1-21 When so matter is subjected to a sufficiently small static strain, the mechanical response is controlled by linear elastic, but not viscoelastic, properties.21 If liquids, gels or polymers are excited by a dynamical mechanical probe, their viscoelastic properties become relevant. This relevance increases with the complexity of the molecular structure in terms of inter-and intramolecular degrees of freedom. At sufficiently high probe frequencies, oen lying in the upper MHz or GHz regime, the mechanical relaxation processes are dynamically clamped and the mechanical response of the system is purely elastic again. Hence, for so materials the mechanical response may be of linear elastic nature when probed either statically or at sufficiently high probe frequencies. In such case, it can be described by Hooke's law, using the second order elastic constants (SOECs) provided by the linear elastic stiffness tensor of 4 th order.Of course linear elasticity only describes one aspect of the complex mechanical behaviour of so matter. The regime of linear elastic response is oen soon abandoned for so materials as the stress or strain amplitude is increased in stress-strain or dynamic mechanical experiments (e.g. ref. 4-6, 8 and 11-14). In order to quantify this nonlinear elastic response of the material within the frame of continuum mechanics, Hooke's law must be extended. Usually the consideration of third order elastic constants (TOECs), but no higher order elastic constants, is sufficient to describe the nonlinear elastic response. 21,22Because of the usually...
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