Surface Pressure and Microstructure of Carbon Nanotubes at an Air-Water Interface

This article reports the surface pressure and microstructure of two different types of carbon nanotubes (CNTs) at an air-water interface; namely, as-produced CNTs (nf-CNTs) and CNTs functionalized with carboxyl groups (f-CNTs). Both types of CNTs formed 3D aggregates upon compression using a Langmuir-Pockels trough. However, f-CNTs showed a lower degree of aggregation compared with that of nf-CNTs. This is attributed to the deprotonation of the carboxyl groups within the water subphase, leading to additional electrostatic repulsion between f-CNTs. For the same initial amount of CNTs spread onto the interface, the actual coverage of f-CNTs was higher than that of nf-CNTs at a given trough area. At high compression, f-CNTs formed aligned CNT domains at the interface. These 2D domains resembled 3D liquid-crystalline structures formed by excluded volume interactions. The denser packing and orientational ordering of f-CNTs also contributed to a compressional modulus higher than that of nf-CNTs, as calculated from the surface pressure isotherms. A Volmer equation of state was applied to model the measured surface pressure containing both thermodynamic and mechanical contributions. The Volmer model, however, did not consider the loss of CNTs from the interface due to 3D aggregation and consequently overestimated the surface pressure at high compression. The actual coverage of CNT during compression was back calculated from the model and was in agreement with the value obtained independently from optical micrographs. The findings of this work may have a broader impact on understanding the assembly and collective behavior of rod-like particles with a high aspect ratio at an air-water interface.