A homogeneous aqueous dispersion of cellulose nanocrystals (CNs) that is left to evaporate in a Petri dish self-organizes into smectic liquid crystals that are actually liquid multilamellar structures. As evaporation proceeds, the liquid multilamellar structures solidify to become a solid multilamellar film. Each solid lamella is in the submicrometer range, and its iridescence is easily explained by classical light interference. A careful inspection of each solid lamella revealed long, oriented arrays of colloids. Interestingly, the array orientation is generally the same for each superposed layer. This is exceptional because the stratification appears first in the liquid, and the solid colloids are formed in each stratum at the very end of the process. Our findings are supported by optical, atomic force, and electron microscope observations and by laser diffraction observations. The multilamellar solid film model is easier to engineer than the helical model currently used to explain the iridescence and optical activities of CN solid films. This new understanding should promote the industrial production of colorful CN coatings and inks as a green alternative for decades to come.
Thermodynamic properties of the Lennard-Jones (LJ) fluid are investigated by studying a system of particles interacting with a potential of hard-core plus attractive Yukawa tail (HCY). Due to the similarity of the LJ and the HCY potentials in their overall form, it is worthwhile seeking to approximate the LJ potential in much the same way that the hard-sphere reference potential has been used. The study consists in describing the thermodynamics of the LJ fluid in terms of the equivalent HCY system, whose properties are known accurately, by means of mapping the thermodynamic quantities for the HCY potential parameters. The method is feasible owing to a convenient analytical expression for the Helmholtz free energy in the mean-spherical approximation expanded in powers of the inverse temperature. Two different procedures are used to determine the parameters of the HCY potential as a function of the thermodynamic states: one is based on the simultaneous fits of pressure and internal energy of the LJ system, and the other uses the concept of collision frequency. The reasonable homogeneity of the results in both procedures of mapping makes the HCY potential a very good reference system whose theoretical expressions can be used confidently to predict the thermodynamic properties of systems with more realistic potentials.PACS numbers: 61.20. Gy, 65.90.+i, UDC 536.632, 538.953
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