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Thermodynamically stable, size selective solubilization of carbon nanotubes in aqueous solutions of amphiphilic block copolymers
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10.1063/1.3216569
/content/aip/journal/jcp/131/10/10.1063/1.3216569
http://aip.metastore.ingenta.com/content/aip/journal/jcp/131/10/10.1063/1.3216569

Figures

Image of FIG. 1.
FIG. 1.

Schematic representation of the different molecular modes of block copolymer-CNT interactions. The first two modes describe simple adsorption of either singly dispersed block copolymer molecules or spherical block copolymer micelles on the nanotube. The third mode describes the self-assembly of block copolymer molecules around the nanotube, solubilizing the nanotube.

Image of FIG. 2.
FIG. 2.

Representation of equilibrium aggregate shapes for a number of PEO-PPO-PEO symmetric triblock copolymers, in nanotube-free aqueous solutions. For each block copolymer, the entries include the trade name, block composition (the number of ethylene oxide units and propylene oxide units ), molecular weight and the equilibrium aggregate shape in dilute aqueous solution.

Image of FIG. 3.
FIG. 3.

Representation of equilibrium aggregate shapes for a number of PEO-PPO diblock copolymers, in nanotube-free aqueous solutions. For each block copolymer, the entries include a molecular designation (which is the trade name of the triblock of the same molecular weight and composition preceded by the prefix Di), block composition (the number of ethylene oxide units and propylene oxide units ), molecular weight and the equilibrium aggregate shape in dilute aqueous solution.

Image of FIG. 4.
FIG. 4.

The difference between the standard state free energy change on forming a cylindrical aggregate with solubilized nanotube and the standard state free energy change on forming a nanotube-free aggregate as a function of the diameter of the nanotube or nanotube cluster for the parameter . In nanotube-free solutions, these molecules have preferred natural curvatures of sphere (P84), cylinder (P103 and P123) or lamella (L62, L122, and L63). Negative values correspond to preference for nanotube solubilized aggregates over nanotube-free aggregates.

Image of FIG. 5.
FIG. 5.

The difference between the standard state free energy change on forming a cylindrical aggregate with solubilized nanotube and the standard state free energy change on forming a nanotube-free aggregate as a function of the diameter of the nanotube or nanotube cluster for the parameter . In nanotube-free solutions, these molecules have preferred natural curvatures of sphere (P64), cylinder (P103 and P123) or lamella (L63). Negative values correspond to preference for nanotube solubilized aggregates.

Image of FIG. 6.
FIG. 6.

The difference between the standard state free energy change on forming a cylindrical aggregate with solubilized nanotube and the standard state free energy change on forming a nanotube-free aggregate as a function of the diameter of the nanotube or nanotube cluster for the parameter . In nanotube-free solutions, these molecules have preferred natural curvatures of cylinder (P103 and P123) or lamella (L63). Negative values correspond to preference for nanotube solubilized aggregates.

Image of FIG. 7.
FIG. 7.

The influence of the nanotube-domain interfacial tension parameter on the solubilization of nanotubes. For four different values of , the triblock copolymers capable of solubilizing the nanotubes are indicated on the upper part of the figure and the diblock copolymers capable of solubilizing the nanotubes are shown on the lower part of the figure. For the triblocks, P103 and P123 are cylinder formers while the molecules to the left are lamella formers and those on the right are sphere formers. Similarly for diblocks, L63 is the cylinder former and those to its left are lamella formers and those on the right are sphere formers.

Image of FIG. 8.
FIG. 8.

The contributions to the standard state free energy change on forming a cylindrical aggregate with solubilized nanotube, for the P103 block copolymer as a function of the diameter of the nanotube or nanotube cluster, for the parameter .

Image of FIG. 9.
FIG. 9.

Dimensions of the hydrophobic domain R and the hydrophilic domain D for nanotube solubilized cylindrical aggregates for the parameter . In nanotube-free solutions, L64 forms spheres, P103 forms cylinders, and L63 forms lamella.

Image of FIG. 10.
FIG. 10.

Aggregation number g per nm length for the nanotube solubilized cylindrical aggregates corresponding to . In nanotube-free solutions, L64 forms spheres, P103 forms cylinders, and L63 forms lamella.

Image of FIG. 11.
FIG. 11.

The interfacial area of the aggregate per block copolymer molecule at the hydrophobic domain A-hydrophilic domain interface, for the nanotube solubilized cylindrical aggregates, corresponding to . In nanotube-free solutions, L64 forms spheres, P103 forms cylinders, and L63 forms lamella.

Tables

Generic image for table
Table I.

Geometrical properties of aggregates. (The variables , , and are defined per unit length for cylinders and per unit area for lamella. is the radius of the nanotube, either a single tube or a cluster of tubes.)

Generic image for table
Table II.

Predicted structural properties of nanotube-free aggregates ( is the size of the hydrophobic domain, is the size of the hydrophilic domain, is the area per molecule of the domain A-domain interface, is the aggregation number defined as the total number of molecules in a micelle in the case of sphere, the number of molecules per nm length in the case of cylinder and the number of molecules per area in the case of lamella.)

Generic image for table
Table III.

Influence of various free energy contributions on the solubilization of CNT. (The calculated results are for a single wall CNT with a diameter of 1.1 nm.)

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/content/aip/journal/jcp/131/10/10.1063/1.3216569
2009-09-14
2014-04-20
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Thermodynamically stable, size selective solubilization of carbon nanotubes in aqueous solutions of amphiphilic block copolymers
http://aip.metastore.ingenta.com/content/aip/journal/jcp/131/10/10.1063/1.3216569
10.1063/1.3216569
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