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www.rsc.org/jem | Journal of Environmental Monitoring

Remediating plastic waste into carbon nanotubes

Vilas Ganpat Pol*a and Pappanan Thiyagarajanb

Published on 23 November 2009. Downloaded by Universitas Indonesia on 04/10/2016 03:36:09.

Received 21st July 2009, Accepted 19th October 2009

First published as an Advance Article on the web 23rd November 2009
DOI: 10.1039/b914648b
Polyethylene-based used plastics needs hundreds of years to degrade in atmospheric conditions. Thus,
in addition to conventional recycling facilities for polymer waste (PW), innovative solutions are
required. This paper describes a solvent-free process that converts PW such as low-density (LD) and
high-density polyethylene (HDPE) into multi-walled carbon nanotubes (MWCNTs) via thermal
dissociation in the presence of chemical catalysts in a closed system under autogenic pressure.
Specifically, the optimization of process parameters, e.g. selection and amounts of catalysts, density
effects of PE, autogenic pressure measurements, and a reaction mechanism for the growth of
MWCNTs is explained. The composition, morphology, and atomic structure of the as-obtained
MWCNTs are characterized employing advanced structural, spectroscopic, and imaging techniques.
We have measured the unique magnetic and electrical conductivity behaviours of as-prepared
MWCNTs to assess their potential applications as advanced materials. This reproducible process
presents an opportunity to use PW as a feedstock for the production of MWCNTs, industrially
significant value-added products. Among the known methods for the fabrication of MWCNTs, the
present controlled dissociation of PW is one of the inexpensive and straightforward methods.

1. Introduction
The enormous and escalating volume of waste from the ubiquitous polyethylene-based plastics1 might cause severe negative
environmental impact on life on earth. Since plastics offer
features such as light weight, strength, heat resistance, high
convenience, and low cost, which make them versatile for business and consumer uses, it would be impractical to ban them
entirely. An additional reason for the retention of plastics is that
they are frequently the best all-round environmental option for
many applications. Although a number of communities
encourage the public to recycle these plastics, only a small
percentage of recyclable plastic waste actually reaches recycling
facilities; the rest ends up as waste in burial sites across the globe
or goes for incineration. Incinerating polymer waste (PW) is
comparatively expensive and could harm the environment.
Nowadays, extensive collection, transportation, separation
and recycling facilities are available for processing a wide range
of thermoplastic products. The process includes densification,
grinding, shredding, and blending. Mixing chemically different
a
Intense Pulse Neutron Source, Argonne National Laboratory, Argonne,
IL, 60439, USA. E-mail: pol@anl.gov
b
Office of Basic Energy Sciences, Department of Energy, SC-22.1/
Germantown Building, 1000 Independence Ave. SW, Washington, DC,
20585

polymers might not yield homogenous materials suitable for

making new quality products from the recycled PW. Thus the
problem of mixed plastics is solved by separation technologies
such as flotation, X-ray fluorescence of chlorinated polymers,
followed by recycling of individual polymers. Finally the separated PW recycling yields a variety of versatile end products. A
few companies are using advanced plasma gasification technology to recover energy and useful by-products from PW.
However, additional innovative approaches are required to take
care of PW. To address the environmental issues associated with
PW, we developed a novel process to systematically degrade
HDPE and LDPE wastes, which converts them into technologically important MWCNTs. By virtue of MWCNTs curved
graphitic structure, smaller diameter, and high aspect ratio, they
possess many appealing properties, including semiconducting or
metallic electrical behaviour, high mechanical strength, and
interesting chemical and surface properties. Potential applications include mechanical actuators,2 electronics,3 catalysis,4
sensors,5 high-strength composites,6 and adsorbents.7 Because of
the potential range of applications for MWCNTs, a variety of
synthesis techniques have been developed to produce them,
including plasma-arc,8 laser ablation,9 chemical vapor deposition,10 fluidized bed reactors,11 and flame synthesis.12 Beside the
catalyst particles, these methods generally require a vacuum
environment and special ambient gas to prevent carbon from

Environmental impact
The escalating volume of waste polyethylene-based plastics might cause stern negative environmental impacts on life on earth. Thus,
in addition to conventional recycling facilities for polymer waste (PW), environment friendly innovative solutions are required to
deal with PW in the short term. This paper describes a pioneering solvent-free process that transforms low- and high-density
polyethylene PW into MWCNTs, value added products.
This journal is The Royal Society of Chemistry 2010

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high temperature oxidation. Additionally, MWCNTs can also be

produced by diffusion flame synthesis, heat treatment of a polymer, and use of solar energy. In flame synthesis, combustion of
a portion of the hydrocarbon gas provides the elevated temperature required, with the remaining fuel conveniently serving as
the required hydrocarbon reagent. Hence the flame constitutes
an efficient source of both energy and hydrocarbon raw material.
While these techniques are capable of producing MWCNTs, they
are typically limited to relatively small-scale production. All
above mentioned methods for the fabrication of MWCNTs have
their own advantages and disadvantages. Comparatively our
distinct approach uses PW as a feedstock or as a precursor in the
presence of catalyst for the synthesis of multi-walled MWCNTs
in a controlled system.
This paper describes a process for producing MWCNTs from
PW using a solvent-free, one-pot process; and provides characterization data and measurements of adsorption, magnetic, and
electrical conductivity behaviours, to assess MWCNTs potential
applications as advanced materials. The process, which is simple,
reproducible, affordable, involves thermal decomposition of PW
in the presence of catalysts at 700  C in a closed reactor under an
inert or air atmosphere, followed by cooling. When cobalt
acetate (CoAc) is used during degradation of PW, this process
produces MWCNTs. The interesting 1D morphology and
growth of MWCNTs results from the autogenic pressure that
arises during the thermal degradation of PW in a closed system.
We developed an understanding of a reaction mechanism for the
growth of MWCNTs on the basis of the data obtained. The
composition, morphology, and atomic structure of the asobtained MWCNTs are characterized using advanced structural,
spectroscopic, and imaging techniques. This invention presents
an opportunity to use PW as a raw material for the production of
MWCNTs. Furthermore, the as-prepared MWCNTs showed
promise in water purification, adsorbing inorganic particles on
the MWCNT surfaces. In other words, the value added
MWCNTs can be used for water purification using PW, therefore being environmentally friendly.

system, in addition to hydrocarbon feedstock, it is indeed

important to seal the reactor while combustion of PW in the
presence of catalyst is occurring. That allows hydrocarbons to be
in close proximity to the cobalt acetate catalyst, facilitating the
growth of MWCNTs. In the present system, not only the
temperature but also the autogenic pressure plays an important
role in the growth of MWCNTs. The MWCNTs settle nicely at
the bottom of the autoclave for easy collection.
The schematic presentation of the process is shown in the inset
of Fig. 1. The lab-made equipment, which measures autogenic
pressure as a function of temperature during the reaction, is
designed and described elsewhere.13 The partially filled autoclave
with PW catalyst generated 50 psi pressure up to 680  C, which
increased to 1000 psi at 700  C. However, it continued to increase
to a value of 1200 psi due to catalytic cracking in dissociated PW
components during the growth of the MWCNTs (Fig. 1). The
gaseous products responsible for generating autogenic pressure
are measured as a function of temperature using an in situ mass
spectrometer (MS). The MS measurements revealed that the
decomposition of PW starts at about 300  C and the products
have masses correlating to water vapour, CO2, and molecules
with 25 carbon atoms. Analogous mass spectra were obtained
up to 600  C. However, at temperatures above 600  C, small
amounts of hydrogen, water vapour, and larger amounts of
hydrocarbons are recorded. As the temperature reached 700  C,
species with a mass greater than 36 disappeared, leaving only
smaller species with 13 carbon atoms along with hydrogen.
Thus, at 700  C, all the CH and CC bonds seem to break,
forming pure solid carbon along with hydrogen gas and a small
number of hydrocarbons. These results are also consistent with
the pressure measurements, suggesting that the main decomposition of the PW occurs in a temperature range of 600 to 700  C.
To produce large amounts of MWCNTs, the size of the reactor
and the amounts of PW with catalysts must be multiplied proportionately.

3. Results and discussion

2. Experimental
To fabricate MWCNTs from PW, we thermally decomposed 1 g
pieces (for uniform distribution) of used HDPE containing 20
wt% C4H6CoO4, cobalt acetate (CoAc) catalyst, by introducing
them into a 5 cc autoclave (made up of Haynes 230 alloy) at room
temperature in an nitrogen atmosphere. We then placed the
closed autoclave, filled with used HDPE, at the centre of
a furnace, heated it at 700  C for an optimised time, and allowed
the material to cool gradually. The chemical reaction that took
place under created autogenic pressure during the thermolysis of
HDPE in the presence of CoAc lead to the growth of MWCNTs.
This process produced MWCNTs from a 1 g mixture of PW
containing 20 wt% CoAc with a 0.4 g yield of a dark black
powder. In the incineration of PW treatment technology which
involves the combustion of organic materials and/or substances,
our present approach can be implemented. However, the design
of the incinerator has to be modified to facilitate the fabrication
of MWCNTs in the presence of Co acetate catalyst. Namely, the
incinerators are not sealed allowing formation of flue gases,
bottom ash, fine particles and heat. As shown in the present
456 | J. Environ. Monit., 2010, 12, 455459

The readily available used/waste HDPE is introduced for the

fabrication of the MWCNTs. The digital image of such feedstock
is shown Fig. 2a. The grocery bags are extruded from a machine

Fig. 1 Temperature vs. autogenic pressure during the decomposition of

waste HDPE bags with CoAc catalyst (insert shows the scheme of the
degradation of PW in the presence of catalyst in a closed system to
produce MWCNTs).

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Fig. 2 (a) Digital image of HDPE (inset the arrangement of PE groups) PW; (b) field emission scanning electron microscope (FE-SEM) image; (c) HRSEM image of as-prepared MWCNTs using a mixture of HDPE and CoAc; (d) digital image of LDPE (inset shows the arrangement of PE groups) PW;
(e) FE-SEM of MWCNTs prepared from LDPE; and (f) energy dispersive spectroscopy (EDS) measurements of as-prepared MWCNTs fabricated from
LDPE with CoAc catalyst (inset shows powder X-ray diffraction [XRD] pattern).

that works in the following manner: for the length of the bag,
polyethylene molecules (inset Fig. 2a) are arranged in the longchain direction, allowing maximum lengthwise stretch and possessing greater strength. Complete conversion of HDPE into
MWCNTs requires a minimum of 20 wt% CoAc catalyst.
Amounts below 20 wt% grew only part of the carbon inside the
reactor as MWCNTs; the rest fabricated into carbon spheres. In
the presence of dissociated carbonaceous species of PW,
MWCNTs continue to grow around the metallic core above
600  C at 1000 psi pressure. As shown in Fig. 2b, the MWCNTs
grow outwards forming bunches of 23 mm size. Each bunch is
comprised of hundreds of MWCNTs growing outwards.
This journal is The Royal Society of Chemistry 2010

Polyethylene is the polyolefin produced by polymerizing the

olefin ethylene. Under the above mentioned experimental
conditions, polyolefins will reduce to carbon, further producing
MWCNTs around the cobalt nanocatalyst obtained from the
dissociation of CoAc.
The diameters of the MWCNTs are 80 nm; a length of more
than a micron (Fig. 2c) is observed within 2 h of the initial
reaction time; thus, the growth of MWCNTs is a function of
reaction time. In comparison with the known methods for the
fabrication of MWCNTs, we believe that this is one of the easiest
and cheapest environmentally friendly ways. In our present
process MWCNTs can be grown randomly and the cobalt
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nanoparticles are trapped inside the tubes. To achieve pure

MWCNTs, acidic treatment will be required to dissolve the
cobalt particles.
A higher percentage of LDPE is used for making soft, transparent grocery sacks (Fig. 2d), shrink/stretch films, pond liners,
construction materials, and agriculture film. In LDPE, the molecules of polyethylene are randomly arranged (inset Fig. 2d). The asformed MWCNTs obtained from the thermolysis of waste LDPE
in the presence of CoAc catalyst in a closed system are shown in
Fig. 2e. The MWCNTs were randomly grown during 2 h of reaction time, not analogous to HDPE. The dissociation of LDPE with
CoAc catalyst also created 1000 psi pressure. In both cases, the
grown MWCNTs were tipped with nanosized metallic Co particles.
HD and LDPE were not the only materials capable of growing
MWCNTs in the presence of catalyst; we found that polystyrene
can also be used as a source of carbon, although the acetates of Ni,
Fe, or bare metallic particles (Co, Ni) were not as effective as CoAc
in the present process environment for fabricating MWCNTs.
Further research work is under way to determine the effect of
catalyst on the growth of MWCNTs from other varieties of PW.
Although the scanning electron micrographs taken using
secondary electrons demonstrate the 1D fiber-like entities, the
transmission electron micrographs further confirmed the hollow
tubular structures of MWCNTs. The energy dispersive spectroscopy (EDS) (Fig. 2f) and X-ray diffraction (XRD) pattern (inset
Fig. 2f) of MWCNTs prepared from the mixture of LDPE and
CoAc confirms that the MWCNTs are comprised of graphitic
carbon and trapped cobalt. The XRD of MWCNTs-Co can be
indexed to fcc (space group: Fm3m) Co, and matches well with
PDF No. 89-4307. No other elemental impurities are observed in
EDS or the XRD measurements.
The schematic presentation given in Fig. 3a shows the mechanistic elucidation for the formation of MWCNTs. The autogenic pressure and mass spectrometry measurements confirmed
that HDPE or LDPE completely dissociate at 700  C, forming
a mixture of carbon, CO2, and hydrocarbons in a closed system.
The thermolysis of individual Co acetate catalysts in analogous
reaction conditions leads to the fabrication of metallic cores with
carbon shells.14 We have considered the yarmulke mechanism,15
originally reported by Smalley et al., for the growth of carbon
around the catalyst. With the formation in the early stage of
a graphene cap (the so-called yarmulke) with its edges strongly
chemisorbed onto the metal (in the present case Co), the newly
arrived carbon from the dissociation of PE would continue to
assemble on the surface of the catalyst. Since the basal plane of
graphite has an extremely low surface energy, the total surface
energy diminishes. Newly arrived carbon will continue to
assemble on the surface of the catalyst. There are three places to
which the additional carbon can go. First, the original surface
shell can continue to grow around the particle,16 which ultimately
results in the over-coating and deactivation of the catalyst.
Second, a second cap can form underneath the first, spaced
roughly by the interspacing of graphite. As additional caps form,
older caps are forced to rise by forming a cylindrical tube whose
open end remains chemisorbed onto the catalytic particle. Third,
carbon can add to the cylindrical section of a growing layer. It
seems that in the present reaction conditions (i.e. formation of
a metallic core with a carbon shell, the supply of additional
carbon, 1000 psi pressure in a closed system, and continuous
458 | J. Environ. Monit., 2010, 12, 455459

heating of the autoclave for up to 2 h) favors the second case

described above. Thus, initially formed metal catalyst particles,
in which the second graphene cap forms underneath the first,
force older caps to rise by forming a cylindrical tubular structure,
which traps the cobalt nanoparticles.
Our process for the remediation of used polymer waste is
proven by considering various probable applications of obtained
MWCNTs. The MWCNTs (from HDPE) are compacted in a die
that applies 5 tons of pressure to form a circular, 1 -mm thick
pellet. We quantified the electrical conductivity of a circular pellet
comprised of MWCNTs using four-point probe electric conductivity measurements at room temperature as well as at 60  C. The
pellet was mounted on a glass slide sandwiched in between silver
paint. Two probes each were connected at both the bottom and
top of the MWCNT pellets, the linear currentvoltage relationship was measured, and the slope (R 1.8 U) was calculated from
the IV curve. The reproducibility of the currentvoltage curve
measurement was observed with minute error. The conductance
was r RS/L, where S is the surface area (pr2) of the pellet and L
is the thickness of the pellet. The calculated room temperature
conductivity (s 1/r) of the MWCNT pellets was 43 S m1. An
analogous four-probe method was used by Ju et al. for the
quantitative electrical conductivity measurement of Al wire.17 As
expected, an increase in conductivity (72 S m1) was recorded at
60  C for the same pellet of MWCNTs.
A representative example is shown, where MWCNTs prepared
from HDPE were used for water purification. The digital images
of gold nanoparticles solution (I), with added MWCNTs (II),
and after removal of MWCNTs (III) are shown in Fig. 3c. It is
notable that inorganic gold nanoparticles are adsorbed on the
MWCNTs surfaces and removed from the water solution (III).
This simple, straightforward laboratory test also supports the
hypothesis that such MWCNTs can be helpful for water purification or filtration technology due to adsorption properties.
Co is a well-known ferromagnetic14 material, while carbon is
known to be paramagnetic18 due to unpaired electrons in its outer
shell. The electron spin resonance (ESR) of the CoC nanocomposites are compared for the MWCNTs obtained from LD
and HDPE. The room-temperature ESR spectra were recorded at
an X-band (y 9.77 GHz) with a 100 kHz magnetic field modulation and are shown in Fig. 3d. The MWCNTs showed a strong
paramagnetic signal, peak-to-peak separation (DHpp) of 50 G and
g values of 2.0017 (HDPE) and 2.019 (LDPE), close to the g factor
for the unbound electron.19 Additional small signals in both EPR
spectra were observed due to interactions with trapped magnetic
cobalt particles. Cambre et al. also reported on the Co(II)OEP
(octaethylporphyrin)-functionalized MWCNTs.20 Their EPR of
cobalt(II)OEP, adsorbed on the nanotube walls by pp stacking,
demonstrated that the MWCNTs acted as electron acceptors
showing additional signals. Additionally, Dai et al. realized that
FeCo/graphitic-shell21 nanocrystals could act as advanced
magnetic resonance imaging and near-infrared agents.

Conclusions
We have demonstrated a solvent-free, reproducible process for
generating MWCNTs through thermal degradation of waste
high- and low-density polyethylene. Systematic morphological
and structural characterizations have been carried out, showing
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the conducting, magnetic, and sorption properties of the resulting materials. The masses formed through thermolysis of PW,
which creates autogenic pressure, were measured in situ, and the
reaction mechanism for the growth of MWCNTs was postulated
on the basis of the data obtained.

Acknowledgements
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This work benefited from the use of the facilities at the Intense
Pulsed Neutron Source, Center for Nanoscale Materials, and
Electron Microscopy Center at Argonne National Laboratory,
supported by the U.S. Department of Energy, Office of Science,
Office of Basic Energy Sciences, under Contract No. DE-AC0206CH11357 by UChicago Argonne, LLC. We acknowledge
Nada Dimitrijevic of the Chemistry division at Argonne
National Laboratory for the EPR measurement of the
MWCNTs.

Notes and references

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Fig. 3 (a) The schematic presentation with mechanistic elucidation of

MWCNT formation, (b) typical currentvoltage relationship curve for

This journal is The Royal Society of Chemistry 2010

the representative MWCNTs obtained from HDPE, (c) removal of gold

nanoparticles from aqueous solution (water purification), and (d) baseline corrected normalized electron paramagnetic resonance (EPR)
measurement of MWCNTs-Co prepared using HDPE (X) and
MWCNTs-Co prepared using LDPE (Y).

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