The role of cooling rate in crystallization-driven block copolymer self-assembly

Self-assembly of crystalline-coil block copolymers (BCPs) in selective solvents is often carried out by heating the mixture until the sample appears to dissolve and then allowing the solution to cool back to room temperature. In self-seeding experiments, some crystallites persist during sample annealing and nucleate the growth of core-crystalline micelles upon cooling. There is evidence in the literature that the nature of the self-assembled structures formed is independent of the annealing time at a particular temperature. There are, however, no systematic studies of how the rate of cooling affects self-assembly. We examine three systems based upon poly(ferrocenyldimethylsilane) BCPs that generated uniform micelles under typical conditions where cooling took pace on the 1–2 h time scale. For example, several of the systems generated elongated 1D micelles of uniform length under these slow cooling conditions. When subjected to rapid cooling (on the time scale of a few minutes or faster), branched structures were obtained. Variation of the cooling rate led to a variation in the size and degree of branching of some of the structures examined. These changes can be explained in terms of the high degree of supersaturation that occurs when unimer solutions at high temperature are suddenly cooled. Enhanced nucleation, seed aggregation, and selective growth of the species of lowest solubility contribute to branching. Cooling rate becomes another tool for manipulating crystallization-driven self-assembly and controlling micelle morphologies.

In the self-assembly of crystalline-coil block copolymers in solution, heating followed by different cooling rates can lead to different structures.     

Wetting, Bonding and Interfacial Energy of Nanocrystalline Metal Particles on Crystalline DCH Polymer and Amorphous Carbon Substrates

Experimental results concerning the interaction between a variety of nanocrystalline metals (gold, silver, nickel and chromium) and both crystalline polymer [poly-DCH (1,6-di (N-carbazolyl)-2,4-hexadiene)] and amorphous carbon substrates, are presented and analyzed. Attention is focused on aspects of the interaction that concern interfacial bonding, its correlation with the cohesive energies of the various metals and the energy of the interfaces. Experimental contributions include qualitative estimates of the magnitude of interfacial energies for the crystalline polymer/metal and amorphous carbon/metal interfaces and a direct measurement of the interfacial energies for gold and silver nanocrystals deposited on the amorphous carbon substrate. The sequence of interfacial energy values for the polymer/metal and amorphous carbon/metal systems is also determined. The interfacial energies for both the poly-DCH and amorphous carbon substrates decreases in the order silver, gold, nickel, and chromium, as expected from cohesive energy, melting point and surface energy data for these elements. The crystalline polymer/metal interfaces were examined for the presence of orientation relationships using selected area diffraction and optical diffractometry of high-resolution TEM images. No orientation relationships were found for any of the polymer/metal combinations spanning a large range of metal reactivities. Lack of atomic matching or some as yet unknown surface condition on the polymer may be responsible for this effect.     

The displacement-thickness theory of trailing edge noise

The problem of estimating the sound generated by turbulent boundary layer flow over the edge of a rigid half-plane is re-examined. A theory is proposed which is strictly valid at low Strouhal numbers based on boundary layer width, wherein the flow inhomogeneities are specified in terms of the fluctuations in the boundary layer displacement thickness. This enables account to be taken of changes in the properties of the turbulence as it translates past the edge, which are shown to result in the appearance of an acoustic dipole whose axis is aligned with the mean flow, and which supplements the radiation field predicted by conventional methods [1,2]. Detailed comparison is made with acoustic and surface pressures which are calculated according to the evanescent wave theory of edge noise [3–5].     

The structure of aqueous solutions

A series of neutron diffraction experiments has been carried out on solutions of NiCl₂, NaCl and BaCl₂ in heavy water. Both the concentration of the solute and the degree of isotopic enrichment were varied in order to investigate whether the multiple-pattern method, which has been used previously to determine the partial structure factors for simple liquids, can be applied to aqueous solutions. It is concluded that the multiple-pattern method is feasible. Some general comments on the structural information contained in the single-pattern data are made.     

On the unsteady,wake induced lift on a slotted airfoil

A theoretical model is examined to determine the influence of a slot in a thin airfoil on the unsteady lift caused by vortices shed into the wake. It is shown that at sufficiently low reduced frequencies based on the width of the slot, vorticity production at the edges of the slot can prevent penetration by the unsteady flow so that the airfoil behaves as if the slot were absent. There exists a range of frequencies, however, in which the magnitudes of both the lift and the accompanying radiated sound can be significantly reduced relative to their respective levels for the unslotted airfoil.     

Measurement of the total active 8B solar neutrino flux at the Sudbury Neutrino Observatory with enhanced neutral current sensitivity

The Sudbury Neutrino Observatory has precisely determined the total active (nu(x)) 8B solar neutrino flux without assumptions about the energy dependence of the nu(e) survival probability. The measurements were made with dissolved NaCl in heavy water to enhance the sensitivity and signature for neutral-current interactions. The flux is found to be 5.21 +/- 0.27(stat)+/-0.38(syst) x 10(6) cm(-2) s(-1), in agreement with previous measurements and standard solar models. A global analysis of these and other solar and reactor neutrino results yields Deltam(2)=7.1(+1.2)(-0.6) x 10(-5) eV(2) and theta=32.5(+2.4)(-2.3) degrees. Maximal mixing is rejected at the equivalent of 5.4 standard deviations.     

Multiwavelength pulse generator using time-lens compression

We demonstrate a novel method of generating a multiwavelength pulse train by use of time-lens compression. In addition to pulse compression, this time lens simultaneously displaces the pulses according to their center wavelengths, resulting in a temporally evenly spaced multiwavelength pulse train. We further demonstrate a new aberration-correction technique based on the temporal analog of a spatial correction lens to improve the quality of the compressed pulses. Through the use of cw distributed-feedback lasers and electro-optic phase modulators, the all-fiber system allows complete tunability of temporal spacing, spectral profile, and repetition rate.     

Nucleation of single-walled carbon nanotubes

The nucleation pathway for single-wall carbon nanotubes on a metal surface is demonstrated by a series of total energy calculations using density functional theory. Incorporation of pentagons at an early stage of nucleation is energetically favorable as they reduce the number of dangling bonds and facilitate curvature of the structure and bonding to the metal. In the presence of the metal surface, nucleation of a closed cap or a capped single-wall carbon nanotube is overwhelmingly favored compared to any structure with dangling bonds or to a fullerene.     

Plane quartics with Jacobians isomorphic to a hyperelliptic Jacobian

We show how for every integer one can explicitly construct distinct plane quartics and one hyperelliptic curve over all of whose Jacobians are isomorphic to one another as abelian varieties without polarization. When we say that the curves can be constructed ``explicitly', we mean that the coefficients of the defining equations of the curves are simple rational expressions in algebraic numbers in whose minimal polynomials over can be given exactly and whose decimal approximations can be given to as many places as is necessary to distinguish them from their conjugates. We also prove a simply-stated theorem that allows one to decide whether or not two plane quartics over , each with a pair of commuting involutions, are isomorphic to one another.