scholarly journals In-Depth Analysis of the Effect of Fragmentation on the Crystallization-Driven Self-Assembly Growth Kinetics of 1D Micelles Studied by Seed Trapping

Polymers ◽  
2021 ◽  
Vol 13 (18) ◽  
pp. 3122
Author(s):  
Gerald Guerin ◽  
Paul A. Rupar ◽  
Mitchell A. Winnik

Studying the growth of 1D structures formed by the self-assembly of crystalline-coil block copolymers in solution at elevated temperatures is a challenging task. Like most 1D fibril structures, they fragment and dissolve when the solution is heated, creating a mixture of surviving crystallites and free polymer chains. However, unlike protein fibrils, no new nuclei are formed upon cooling and only the surviving crystallites regrow. Here, we report how trapping these crystallites at elevated temperatures allowed us to study their growth kinetics at different annealing times and for different amounts of unimer added. We developed a model describing the growth kinetics of these crystallites that accounts for fragmentation accompanying the 1D growth process. We show that the growth kinetics follow a stretched exponential law that may be due to polymer fractionation. In addition, by evaluating the micelle growth rate as a function of the concentration of unimer present in solution, we could conclude that the micelle growth occurred in the mononucleation regime.

MRS Advances ◽  
2015 ◽  
Vol 1 (23) ◽  
pp. 1703-1708 ◽  
Author(s):  
M. Yako ◽  
N. J. Kawai ◽  
Y. Mizuno ◽  
K. Wada

ABSTRACTThe kinetics of Ge lateral overgrowth on SiO2 with line-shaped Si seeds is examined. The growth process is described by the difference between the growth rates of Ge on (100) planes (GR100) and <311> facets (GR311). The theoretical calculations well reproduce the growth kinetics. It is shown that narrowing the line-seeds helps Ge coalescence and flat film formation.


1999 ◽  
Vol 564 ◽  
Author(s):  
H. Y. Huang ◽  
L. J. Chen

AbstractThe oxidation of Si catalyzed by 170-nm-thick Cu3Si at elevated temperatures has been investigated by transmission electron microscopy and Auger electron spectroscopy. For wet oxidation at 140–180 °C, the growth rate of the oxide layer was increased with the temperature. On the other hand, as the temperature was increased above 200 °C, the growth rate slowed down. The growth kinetics of oxide was investigated. Controlling mechanisms for the growth of oxide owing to the grain growth of Cu3Si are discussed. The activation energy for the linear growth of oxide was measured to be 0. 19 ± 0.1 eV.


2005 ◽  
Vol 901 ◽  
Author(s):  
Stephen Berkebile ◽  
Georg Koller ◽  
Gregor Hlawacek ◽  
Martin Oehzelt ◽  
Roland Resel ◽  
...  

AbstractThe molecular/crystal orientation and morphology of active molecular structures is a key determinant for the function of nanoscaled organic devices. In π-conjugated systems, both charge transport and optical properties will strongly depend on the molecular orientation due to the highly anisotropic charge carrier mobility in these organic crystals and the anisotropic absorption and luminescence behavior of the molecules. Although the importance of organic on inorganic interface formation and thin film growth is widely acknowledged, little is known regarding the growth kinetics. A better understanding of the processes driving molecular self-assembly is necessary if the self-assembly process is to be controlled. Moreover, it is interesting as the anisotropy of the molecular building blocks presents a fundamental difference from what is known from inorganic growth. Here we show that either sticking or diffusion anisotropy can control the growth depending on preparation conditions. This is illustrated by an investigation into the growth of sexiphenyl (6P) on the anisotropic TiO2(110)-(1×1) surface for temperatures between 80K and 400K using in-situ UHV photoemission, x-ray absorption spectroscopy, synchrotron x-ray diffraction and ex-situ atomic force microscopy. For 6P adsorption even at 80K we found that the molecules orient parallel to the TiO2 oxygen rows and form small crystallites. At 300K this molecular orientation is retained and large micrometer sized 6P(203) oriented needles running perpendicular to oxygen substrate rows are formed. In contrast, for growth at elevated temperatures the 6P molecular axis is near perpendicular to the surface and large islands elongated parallel to the substrate rows are formed. These differences in crystallite orientation and morphology can be explained by the domination of the growth kinetics by either sticking or diffusion anisotropy depending on growth temperature.


1998 ◽  
Vol 76 (6) ◽  
pp. 843-850
Author(s):  
Angela P Lyon ◽  
Nicola J Banton ◽  
Donal H Macartney

The kinetics and mechanism of the formation and dissociation of a series of [2]pseudorotaxanes, comprised of α -cyclodextrin (α -CD) as the cyclic component and the ([Me3N(CH2)nNMe3]2+ (n = 8-12), [Me2EtN(CH2)10NEtMe2]2+, and [Me3P(CH2)10PMe3]2+) dications as the threads, were determined by means of 1H and 31P NMR in aqueous solution. The length of the polymethylene chain (n) of the thread, which has a minor effect on the rate constant for pseudorotaxane formation, is important in the kinetics of the dissociation reactions, with the longer, more hydrophobic chains resulting in slower pseudorotaxane dissociation. The replacement of one methyl substitutent by an ethyl group in each of the end groups on the [Me3N(CH2)10NMe3]2+ thread results in a 30-fold decrease in the formation rate constant. Replacements, by ethyls, of two or all of the methyl substitutents prevent the formation of the pseudorotaxane, even after prolonged heating. The pseudorotaxane containing the {Me3P(CH2)10PMe3.; α-CD}2+ thread forms only at elevated temperatures by a slippage mechanism, and the rate constant for its self-assembly at 75°C (8 x 10-5 M-1 s-1) is more than 106 smaller than the rate constant at 75°C (200 M-1 s-1) extrapolated for the corresponding {Me3N(CH2)10NMe3 . α -CD}2+complex. The enthalpies and entropies of activation for the formation and dissociation of the [2]pseudorotaxanes decrease with an increase in the size and hydrophobicity of the end groups, suggesting a reduced role of desolvation of the quaternized atoms in the threading or dethreading processes.Key words: pseudorotaxane, α -cyclodextrin, kinetics, self-assembly, slippage, supramolecular.


Author(s):  
Shiro Fujishiro ◽  
Harold L. Gegel

Ordered-alpha titanium alloys having a DO19 type structure have good potential for high temperature (600°C) applications, due to the thermal stability of the ordered phase and the inherent resistance to recrystallization of these alloys. Five different Ti-Al-Ga alloys consisting of equal atomic percents of aluminum and gallium solute additions up to the stoichiometric composition, Ti3(Al, Ga), were used to study the growth kinetics of the ordered phase and the nature of its interface.The alloys were homogenized in the beta region in a vacuum of about 5×10-7 torr, furnace cooled; reheated in air to 50°C below the alpha transus for hot working. The alloys were subsequently acid cleaned, annealed in vacuo, and cold rolled to about. 050 inch prior to additional homogenization


1998 ◽  
Vol 536 ◽  
Author(s):  
E. M. Wong ◽  
J. E. Bonevich ◽  
P. C. Searson

AbstractColloidal chemistry techniques were used to synthesize ZnO particles in the nanometer size regime. The particle aging kinetics were determined by monitoring the optical band edge absorption and using the effective mass model to approximate the particle size as a function of time. We show that the growth kinetics of the ZnO particles follow the Lifshitz, Slyozov, Wagner theory for Ostwald ripening. In this model, the higher curvature and hence chemical potential of smaller particles provides a driving force for dissolution. The larger particles continue to grow by diffusion limited transport of species dissolved in solution. Thin films were fabricated by constant current electrophoretic deposition (EPD) of the ZnO quantum particles from these colloidal suspensions. All the films exhibited a blue shift relative to the characteristic green emission associated with bulk ZnO. The optical characteristics of the particles in the colloidal suspensions were found to translate to the films.


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