Diameter-Selective Dispersion of Carbon Nanotubes via Polymers: A Competition between Adsorption and Bundling

The mechanism of the selective dispersion of single-walled carbon nanotubes (CNTs) by polyfluorene polymers is studied in this paper. Using extensive molecular dynamics simulations, it is demonstrated that diameter selectivity is the result of a competition between bundling of CNTs and adsorption of polymers on CNT surfaces. The preference for certain diameters corresponds to local minima of the binding energy difference between these two processes. Such minima in the diameter dependence occur due to abrupt changes in the CNT's coverage with polymers and their calculated positions are in quantitative agreement with preferred diameters, reported experimentally. The presented approach defines a theoretical framework for the further understanding and improvement of dispersion/extraction processes.Comment: 22 pages, 5 figures, ACS Nano (2015

Multireference configuration interaction treatment of excited-state electron correlation in periodic systems: the band structure of trans-polyacetylene

A systematic method to account for electron correlation in periodic systems which can predict quantitatively correct band structures of non-conducting solids from first principles is presented. Using localized Hartree-Fock orbitals (both occupied and virtual ones), an effective Hamiltonian is built up whose matrix elements can easily be transferred from finite to infinite systems. To describe the correlation effects wave-function-based multireference configuration interaction (MRCI) calculations with singly and doubly excited configurations are performed. This way it is possible to generate, both, valence and conduction bands with all correlation effects taken into account. Trans-polyacetylene is chosen as a test system.Comment: 9 pages, 2 figures, submitted to Chem. Phys. Let

In-situ quasi-instantaneous e-beam driven catalyst-free formation of crystalline aluminum borate nanowires

The catalyst-assisted nucleation and growth mechanisms for many kinds of nanowires and nanotubes are pretty well understood. At times, though, 1D nanostructures form without a catalyst and the argued growth modes have inconsistencies. One such example is the catalyst-free growth of aluminium borate nanowires. Here we develop an in-situ catalyst-free room temperature growth route for aluminium nanowires using the electron beam in a transmission electron microscope. We provide strong experimental evidence that supports a formation process that can be viewed as a phase transition in which the generation of free-volume induced by the electron beam irradiation enhances the atomic mobility within the precursor material. The enhanced atomic mobility and specific features of the crystal structure of Al5BO9 drive the atomic rearrangement that results in the large scale formation of highly crystalline aluminium borate nanowires. The whole formation process can be completed within fractions of a second. Our developed growth mechanism might also be extended to describe the catalyst-free formation of other nanowires

Boron doping of SWCNTs as a way to enhance the thermoelectric properties of melt‐mixed polypropylene/SWCNT composites

Composites based on the matrix polymer polypropylene (PP) filled with single‐walled carbon nanotubes (SWCNTs) and boron‐doped SWCNTs (B‐SWCNTs) were prepared by melt‐mixing to analyze the influence of boron doping of SWCNTs on the thermoelectric properties of these nanocomposites. It was found that besides a significantly higher Seebeck coefficient of B‐SWCNT films and powder packages, the values for B‐SWCNT incorporated in PP were higher than those for SWCNTs. Due to the higher electrical conductivity and the higher Seebeck coefficients of B‐SWCNTs, the power factor (PF) and the figure of merit (ZT) were also higher for the PP/B‐SWCNT composites. The highest value achieved in this study was a Seebeck coefficient of 59.7 μV/K for PP with 0.5 wt% B‐SWCNT compared to 47.9 μV/K for SWCNTs at the same filling level. The highest PF was 0.78 μW/(m∙K2) for PP with 7.5 wt% B‐SWCNT. SWCNT macro‐ and microdispersions were found to be similar in both composite types, as was the very low electrical percolation threshold between 0.075 and 0.1 wt% SWCNT. At loadings between 0.5 and 2.0 wt%, B‐SWCNT‐based composites have one order of magnitude higher electrical conductivity than those based on SWCNT. The crystallization behavior of PP is more strongly influenced by B‐SWCNTs since their composites have higher crystallization temperatures than composites with SWCNTs at a comparable degree of crystallinity. Boron doping of SWCNTs is therefore a suitable way to improve the electrical and thermoelectric properties of composites. © 2020 by the authors

Boron Doping of SWCNTs as a Way to Enhance the Thermoelectric Properties of Melt-Mixed Polypropylene/SWCNT Composites

Composites based on the matrix polymer polypropylene (PP) filled with single-walled carbon nanotubes (SWCNTs) and boron-doped SWCNTs (B-SWCNTs) were prepared by melt-mixing to analyze the influence of boron doping of SWCNTs on the thermoelectric properties of these nanocomposites. It was found that besides a significantly higher Seebeck coefficient of B-SWCNT films and powder packages, the values for B-SWCNT incorporated in PP were higher than those for SWCNTs. Due to the higher electrical conductivity and the higher Seebeck coefficients of B-SWCNTs, the power factor (PF) and the figure of merit (ZT) were also higher for the PP/B-SWCNT composites. The highest value achieved in this study was a Seebeck coefficient of 59.7 µV/K for PP with 0.5 wt% B-SWCNT compared to 47.9 µV/K for SWCNTs at the same filling level. The highest PF was 0.78 µW/(m·K2) for PP with 7.5 wt% B-SWCNT. SWCNT macro- and microdispersions were found to be similar in both composite types, as was the very low electrical percolation threshold between 0.075 and 0.1 wt% SWCNT. At loadings between 0.5 and 2.0 wt%, B-SWCNT-based composites have one order of magnitude higher electrical conductivity than those based on SWCNT. The crystallization behavior of PP is more strongly influenced by B-SWCNTs since their composites have higher crystallization temperatures than composites with SWCNTs at a comparable degree of crystallinity. Boron doping of SWCNTs is therefore a suitable way to improve the electrical and thermoelectric properties of composites

Diameter-Selective Dispersion of Carbon Nanotubes <i>via</i> Polymers: A Competition between Adsorption and Bundling

The mechanism of the selective dispersion of single-walled carbon nanotubes (CNTs) by polyfluorene polymers is studied in this paper. Using extensive molecular dynamics simulations, it is demonstrated that diameter selectivity is the result of a competition between bundling of CNTs and adsorption of polymers on CNT surfaces. The preference for certain diameters corresponds to local minima of the binding energy difference between these two processes. Such minima in the diameter dependence occur due to abrupt changes in the CNT’s coverage with polymers, and their calculated positions are in quantitative agreement with preferred diameters reported experimentally. The presented approach defines a theoretical framework for the further understanding and improvement of dispersion/extraction processes