NEW CARBON MATERIALS
Volume 29, Issue 3, June 2014
Online English edition of the Chinese language journal
Cite this article as: New Carbon Materials, 2014, 29(3): 193–202.
Received date: 20 February 2014; Revised date: 07 June 2014
*Corresponding author. E-mail: marcia@if.ufrgs.br; marciagallas@gmail.com
Copyright©2014, Institute of Coal Chemistry, Chinese Academy of Sciences. Published by Elsevier Limited. All rights reserved.
DOI: 10.1016/S1872-5805(14)60134-7
RESEARCH PAPER
Preparation of carbon nanotube monoliths by
high-pressure compaction
Pamela Andréa Mantey dos Santos
1,3
, Ivana Zanella
1
, Tania Maria Haas Costa
2
, Patrícia
Rodrigues da Silva
3
, Marcia Russman Gallas
3
1
Área de Ciências Tecnológicas, Centro Universitário Franciscano, UNIFRA, Santa Maria 97010-032, RS, Brasil;
2
Instituto de Química, Universidade Federal do Rio Grande do Sul, UFRGS, Porto Alegre, 91501-970, RS, Brasil;
3
Instituto de Física, Universidade Federal do Rio Grande do Sul, UFRGS, Porto Alegre, 91501-970, RS, Brasil
Abstract: High-pressure compaction was used to produce monolithic multiwall carbon nanotubes (MWCNTs) from different sources: (1)
high-purity commercial Baytubes®, (2) chemical-vapor deposited MWCNTs without purification at the Laboratory of Production of
CNT/UNIFRA, and (3) the same MWCNTs as (2) purified with HCl. Pressures of 4.0 GPa and 7.7 GPa were applied at room temperature using
two different pressure-transmitting media, lead and graphite. Cylindrical monolithic MWCNTs with diameters of about 6 mm were obtained. The
samples were characterized by Raman spectroscopy, X-ray diffraction, elemental analysis, N2 adsorption and transmission electron microscopy.
Results showed that the best sample was obtained with MWCNTs without purification, containing residues of MgO catalyst, and using lead as the
pressure-transmitting medium at 7.7 GPa. High-pressure may cause compressive stress and shear stress for the MWCNTs. The lead container, as a
quasi-hydrostatic pressure-transmitting medium, provided more compressive stress than shear stress while the impurities acted as binding
materials. Both helped to obtain better densification of the MWCNTs.
Key Words: Multiwall carbon nanotubes; High-pressure; Bulk MWCNTs samples; Raman spectroscopy; TEM
1 Introduction
The discovery of carbon nanotubes (CNTs) has opened a
new frontier in the chemistry and physics of carbon, attracting
the attention of world-wide research since the early 1990s
[1-3]
.
These cylindrical structures are formed by hexagonal arrays of
carbon atoms, having a diameter between few angstroms to
tens of nanometers and the length can be of the order of
centimeters
[1]
. CNTs are unique structures with remarkable
electronic and mechanical properties and have been
extensively studied, aiming at the applications in several fields
such as medical sciences
[4-6]
, electronics
[7]
, and composite
materials
[8-13]
. During the last decade, ceramic matrice
composites reinforced by CNTs have been studied, seeking to
improve the intrinsic brittleness of these materials. One of the
techniques used to produce ceramic compacts with CNTs as
reinforcement is the high-pressure. Andrade et al. obtained
dense compacts of silica/CNT with great tenacity (greater than
60% compared to silica without reinforcement) by this
technique
[12]
. High-pressure (up to 8.0 GPa) has been used as
an important tool for compaction and densification of
nanometric powders, producing new materials. This process
promotes the improvement of mechanical properties, allowing
the production of hard and dense materials, optically
transparent, and crack free
[12,14-17]
. In these works it was only
possible to obtain such impressive properties using lead (Pb)
containers as quasi-hydrostatic pressure-transmitting medium
assembled in toroidal-type high-pressure chambers and
making the processing at room temperature.
Recently, the preparation of macroscopic CNTs has been
investigated, here including sheets, fibers, pellets and films,
targeting at exploring the important properties, such as
mechanical and electrical, of the individual nanotubes. If these
properties were preserved in macroscopic samples, they could
present numerous applications in various systems such as
solar cells, capacitors, electrodes, chemical sensors and
others
[18]
. However, the actual performance of CNTs
macroscopic samples is still far from the expectations,
requiring a great deal of research yet. There are few studies in
literature dealing with the preparation of self-supported CNTs
bulk samples, i.e. a matrix formed only by CNTs, or with a
very high content of CNTs. Some studies showed the
preparation of pellets obtained from solutions of CNTs
functionalized with HCl
[19,20]
. Cha et al.
[18]
produced other kind
of samples prepared with CNTs interconnected via functional
groups acquired during chemical treatment and plasma
sintering. Xu et al.
[21]
prepared pellets by CVD method
obtained from nanosized MgO powders, containing CNTs and