Article

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Nanoscience and Nanotechnology
All rights reserved Vol. 16, 1–5, 2016
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Electrical and Tensile Properties of Carbon

Nanotubes-Reinforced Aluminum Alloy 6101 Wire
Fabrício Augusto dos Santos Rodrigues1 , Waldeci Paraguassu2 , Sónia Simões3 , Manuel F. G. Vieira3 ,
José Antônio da Silva Souza4 , Eduardo de Magalhães Braga4 , and Marcos Allan Leite dos Reis1
4
∗
1
Programa de Pós-Graduação em Engenharia de Processos, Universidade Federal do Pará, 66075-110, Belém, PA, Brazil
2
Programa de Pós-Graduação em Física, Universidade Federal do Pará, 66075-110, Belém, PA, Brazil
3
Faculdade de Engenharia da Universidade do Porto, Universidade do Porto, 4200-465, Porto, Portugal
4
Programa de Pós-graduação em Engenharia de Recursos Naturais da Amazônia, Universidade Federal do Pará,
66075-110, Belém, PA, Brazil

The wires from aluminum alloy 6101 (AA-6101) used in power cables were covered by carbon
nanotubes (CNTs) and graphite powders, and then they were subjected to solubilization heat treat-
ment at a temperature of 550  C and aged at 180  C. The effects of the processing temperature on
the mechanical and electrical properties of the wires based on CNTs@AA-6101 and graphite@AA-
6101 composites were investigated by electron microscopes, thermogravimetric analysis, tensile
tests, conductor tests and Raman spectroscopy. The results show that CNTs were successfully
incorporated on the surface of aluminum wires; the tensile strength of CNTs@AA-6101 increased
by 30% and 34% as compared to graphite@AA-6101 and standard AA-6101 wire without CNTs,
respectively. Moreover, the resistivity had a decrease 13.7% less than conventional wires. The sol-
ubilization process added with the incorporation of CNTs represents a new way for manufacturing
nanostructured power cables to achieve high-performance energy transmission lines.
Keywords: Carbon Nanotubes, Transmission Lines, Solubilization, AA-6101 wire.

1. INTRODUCTION aluminum–zirconium (Al–Zr). It provides nearly 8 times

Nowadays, the aluminum conductor steel reinforced the strength of pure aluminum with 3 times the stiff-
(ACSR) is a conventional wire utilized in power lines; this ness, yet more than twice the transmission capacity of
current technology presents several challenges, e.g., sig- conventional cables of similar size.7 Similarly, MMC
nificant energy losses due to long-distance transmission, incorporating CNTs to form a nanocomposite CNTs-
high weight of cables caused by steel core and high tem- aluminum (CNTs-Al) was proposed by Bourne et al.,
perature of the transmission lines.1
2 An alternative way to where a hot isostatic pressing (HIP) of AA-6063 tube
solve these problems could come from the development of filled with single-wall carbon nanotubes (SWCNTs) and
new conductors based on nanomaterial. In this sense, the silver powder was reported. As a result, they obtained an
CNTs have singular characteristics, such as an electrical electric resistivity comparable to pure Al.8
and thermal conductivity higher than copper and silver at In this work, MMC was obtained on the surface of
one-sixth the weight,3
4 it is twice as strong as steel,5 and AA-6101 wires forming CNTs@AA-6101 through the
exhibits thermoelectricity effect.6 These interesting prop- conventional process of solubilization and followed by
erties could be applied to develop a nanomaterial-based aging the wires; but, in the first step, the multi-wall car-
metal-matrix conductor known as the aluminum conductor bon nanotubes (MWCNTs) were added around the wires
composite reinforced (ACCR) wire. under heat treatment. Moreover, other samples beyond
The 3M Corporation© has developed an ACCR the standard wire were prepared, i.e., graphite@AA-6101,
based on metal matrix composite (MMC) like which consisted of a control sample with a three dimen-
sional allotropic structure of carbon to compare with
∗
Author to whom correspondence should be addressed. sp2 -hibridized nanostructure of CNTs; and a conventional

J. Nanosci. Nanotechnol. 2016, Vol. 16, No. xx 1533-4880/2016/16/001/005 doi:10.1166/jnn.2016.13429 1

Electrical and Tensile Properties of Carbon Nanotubes-Reinforced Aluminum Alloy 6101 Wire Rodrigues et al.

AA-6101 wire that was only subjected to solubilization 2.2. Characterization

without CNTs. Therefore, this work shows a development The morphology of MWCNTs was characterized by
of ACCR wires based on CNTs with improved electrical Scanning Electron Microscopy (SEM) from model
and mechanical properties that could be applied in trans- VEGA3 SB–TESCAN at 20 kV; Transmission Electron
mission lines. Microscopy (TEM) from TECNAI G2 20 S-TWIN at
100 kV; and its purity and temperature of solubiliza-
tion were obtained by Thermogravimetric Analysis (TGA)
2. EXPERIMENTAL DETAILS
from Netzsch equipment model 209 F1 Libra using a con-
2.1. Preparation of the Samples
trolled atmosphere, with a heating rate of 5  C/min. The
The standard wire of 3.45 mm of diameter was an alu- micrographs of superficial structure of the CNTs@AA-
minum 6101 alloy that is composed of magnesium (Mg) 6101 wire were obtained by SEM. The Raman spectra
and silicon (Si) elements, with composition in weight of were collected with a triple-grating spectrometer in the
nearly 0.60 wt.% and 0.50 wt.%, respectively. It was cut subtractive mode of a Jobin Yvon, T64000 equipment. The
off in several specimens with a length of 300 mm each. 514.5 nm line of an Argon ion laser was used as an exci-
After that, the process was started, i.e., the chemical attack tation. An Olympus microscopic lens with a focal distance
based on Keller’s reagent was performed for 60 seconds of 20.5 mm and a numeric aperture of 0.35, was used
with the goal of increasing the surface area; next, the to focus the laser into the sample surface. Hence, in this
pieces of AA-6101 were placed in steel vessels filled with study the slits were set for a resolution of about 2 cm−1 .
either CNTs or graphite powders, but a standard AA- The tensile test was performed by Shimadzu Servopulser-
6101 wire without solution phase was placed in a sepa- Multipurpose Test at a constant velocity of 0.03 mm/s.
rate vessel, forming a conventional AA-6101 wire. These with a maximum test force of 3 kN in all test samples;
specimens were subjected to solubilization in the baking lastly, the electric resistivity was measured by Kelvin’s
furnace under a temperature of 550  C for 180 min, and bridge using ohmmeter model MPK-2000. Both the tensile
immediately followed by quenching in water at 23  C. and the electric resistivity measurements were performed
Finally, the samples: CNTs@AA-6101 wire with 1.6 wt.% in all samples with a length of 300 mm.
of CNTs incorporated on its surface; graphite@AA-6101
wire; conventional AA-6101 wire (treated); and standard
AA-6101 wire (untreated) were artificially aged with a 3. RESULTS AND DISCUSSION
temperature of 180  C for 180 min. 3.1. Microstructural and Thermal Analysis
Figure 1 shows a summarized scheme of the process Figures 2(a and b) show the morphology of purified CNTs
applied to obtain the samples, beginning with a chemical used in this work. The SEM shows agglomerated bun-
attack; then, a solubilization; thirdly, a quenching; and at dles of CNTs (Fig. 2(a)) and the TEM image reveals
the end, an aging. MWCNTs with variable diameters from approximately
The MWCNTs were synthesized by chemical vapor 5 nm to 55 nm, where the medium external diameters cor-
deposition using transition metals as catalysts that were respond to 12 nm ± 2 nm, as shown inset in Figure 2(b). In
later removed by chemical purification. These CNTs are this case, the temperature of solubilization of Al–Mg–Si
densely agglomerated, with medium external diameters of alloy could be performed from 500  C to 585  C; since
12 nm±2 nm, a length of several micrometers and a chem- the latter temperature is nearly the peak of the maximum
ical purity of over 92 wt.%. The graphite powder was pro- oxidation of MWCNTs at 578  C, as shown in Figure 3, a
vided by Nacional do Grafite, with particle sizes smaller temperature of 550  C was chosen in our case, because it
than 150 m with electrical resistivity of 5 × 10−6  · m in improves the mechanical properties of 6101 alloy, as also
the parallel direction to the carbon–carbon bond plan. reported in another work.9

Figure 1. Process applied in the AA-6101 to obtain ACCR wires.

2 J. Nanosci. Nanotechnol. 16, 1–5, 2016

Rodrigues et al. Electrical and Tensile Properties of Carbon Nanotubes-Reinforced Aluminum Alloy 6101 Wire

Figure 2. Micrographs of CNTs. (a) SEM of dense agglomerated seen in white arrows, and (b) TEM shows several MWCNTs with variable diameters
(scale bar at 100 nm) with its histogram (inset).

Figure 4 shows micrographs of the CNTs@AA-6101 485  C as shown in derivative TGA (Fig. 3). Moreover,
surface, where the CNTs were successfully incorporated the G-band position was shifted from 1578 to 1589 cm−1
(Fig. 4(a)). By the way, the fracture region shows evidence because the stress in CNTs can reduce carbon–carbon dis-
of CNTs inside (Fig. 4(b)). This suggests that the tem- tance, i.e., the shift of G-band position is attributed to the
perature used in the solubilization process was sufficient increases of stretching of the carbon bonds,10 on the other
to add the CNTs on the metal matrix, and thus, has been hand, the Raman amplitude was increased more than 10×.
enough to diffuse them into the matrix or displace the This is evidence of a strong interaction between photons
CNTs together with the aluminum crystal planes during from CNTs and density of electrons from oxide alu-
the tensile test. The effect of the temperature on the crys- minum on the metal matrix, resulting in Plasmon reso-
tallinity of CNT was performed by Raman spectroscopy, nance. This similar behavior was reported by Langhammer
as shown in Figure 5, where the ID /IG ratio of 0.6 was et al.11 Finally, the peak centered around 850 cm−1 cor-
obtained from pure MWCNT, while the outer surface of responds to formation of aluminum carbide (Al4 C3 ,12
13
CNTs@AA-6101 wire shows an ID /IG ratio of 0.9, i.e., the which it increases the electrical resistivity of MMC based
solubilization temperature of 550  C damaged the graphitic on CNTs;8 but, in our process, the formation of Al4 C3 was
structures of CNTs. This effect was expected because successfully inhibited (Inset in Fig. 5).
the MWCNT started its decomposition at approximately
3.2. Electrical and Tensile Measurements
1 110
The tensile curves from a tensile test of AA-6101 wire
100
0 (standard sample) processed by temperature treatment (sol-
90 ubilization; quenching; and aging) with and without CNTs
Derivative weight (%/min.)

–1
485 °C
80 are presented in Figure 6. The reinforcement effect of the
–2 70 CNTs is evident in the ultimate tensile strength (UTS) of
Weight (%)

60 CNTs@AA-6101. It was increased by 34%, 30%, and 27%

–3
50 as compared to standard AA-6101, graphite@AA-6101,
–4 40 and conventional AA-6101 wires, respectively. However,
–5 578 °C
30 in this case, the elongation decreases from 193 mm to
20 59 mm. The UTS and elongation of ACCR wire based
–6
10 on graphite does not perform as well as the other sam-
–7 0 ples. These results prove that sp2 -hibridized nanostructure
0 50 100 150 200 250 300 350 400 450 500 550 600 650 700 750 of CNTs is responsible for the reinforcement effect in the
Temperature (°C) same conditions of temperature treatment.
Figure 3. TGA shows the initial burning temperature and peak of oxi- Electrical resistivity results for conventional AA-6101,
dation of the MWCNTs. The dashed line corresponds to differential graphite@AA-6101, and CNTs@AA-6101 wires are
thermo-gravimetric curve. shown in Figure 7. The electric resistivity of ACCR wire

J. Nanosci. Nanotechnol. 16, 1–5, 2016 3

Electrical and Tensile Properties of Carbon Nanotubes-Reinforced Aluminum Alloy 6101 Wire Rodrigues et al.

Figure 4. SEM of CNTs@AA-6101 wire. (a) CNTs (white arrows) were spread on the surface of aluminum matrix (red arrow), and (b) Moderately
ductile fracture for specimen test with MWCNTs inside fractured region (white arrow).

based on CNTs decreases 13.7% and 6.7% less than 300

conventional and graphite wires, respectively. This effect 275
could be attributed to the contribution of quantum transport 250
from CNTs to carrier transport on the aluminum matrix
Tensile strength (MPa)

225
surface and the synergetic electronic interaction between 200
them, i.e., electron transport in the CNTs@AA-6101 is 175
moved from the metal matrix where we can find much 150
more electron scattering at grain boundaries to the metal 125 Wire samples:
surface where the CNTs were added, hence the conductiv- 100 Standard AA-6101
ity increases. 75
CNTs@AA-6101
Conventional AA-6101
The UTS and electrical resistivity results for 50 Graphite@AA-6101
CNTs@AA-6101 wire are summarized in Table I, where 25
they are compared with conventional AA-6101 wire, as 0
well as other ACCR wires data, which were obtained 0 25 50 75 100 125 150 175 200
elsewhere. Elongation (mm)

Figure 6. Tensile curves of specimens from standard AA-6101 to

7000
CNTs@AA-6101 wire.
6500 Al4C3
Intensity

6000
D G 1589 4.0
5500
3.9 25 ºC
5000
Electrical resistivity (Ω m) × 10–8

4500 3.8 Conventional AA-6101

830 840 850 860 870
4000 3.7
Intensity (a.u)

–1
Raman Shift (cm )
3500
Outer surface 3.6 Graphite@AA-6101
3000
G 1582 3.5
2000
1750 3.4
CNTs@AA-6101
1500 3.3
1250 D 3.2
1000 Fractured region
750 3.1
500 G 1578 3.0
D CNTs
250
0
2.9
1300 1350 1400 1450 1500 1550 1600 1650 1700 1750 1800 1850 2.8
Raman Shift (cm–1) 2.7
Sample Wires
Figure 5. Raman spectra of the outer surface and fractured region of
CNTs@AA-6101 wire compared with as-purified CNTs. Inset: Absence Figure 7. Electrical resistivity measurements of sample wires at room
of the Raman signal of aluminum carbide. temperature (error bar at ±0.12  m).

4 J. Nanosci. Nanotechnol. 16, 1–5, 2016

Rodrigues et al. Electrical and Tensile Properties of Carbon Nanotubes-Reinforced Aluminum Alloy 6101 Wire

Table I. Electrical and mechanical properties for conventional and ELETROBRAS ELETRONORTE. This research is
ACCR wires.
sponsored by Chamada Universal 14/2013–Project
UTS Electrical 475659/2013-9.
Sample Processing (MPa) resistivity ( m)

Ag@SWCNT-Al8 Hot isostatic pressing 120 37 × 10−8 References and Notes
Conventional AA-6101 Solubilization 204 356 × 10−8
1. E. Benedict, T. Collins, D. Gotham, S. Hoffman, D. Karipides,
CNTs@AA-6101 Solubilization 259 313 × 10−8
S. Pekarek, and R. Ramabhadran, ECE Technical Reports (1992).
Al–Zr7
14 Not mentioned 162 287 × 10−8
2. M. Mahamood, O. Shivam, P. Kumar, and G. Krishnan, IJAREEIE
3, 131 (2014).
3. B. Q. Wei, R. Vajtai, and P. M. Ajayan, Appl. Phys. Lett. 79, 1172
4. CONCLUSION (2001).
MWCNTs were successfully incorporated on the AA-6101 4. S. Berber, Y.-K. Kwon, D. Tománek, Phys. Rev. Lett. 84, 4613
wire surface by temperature treatment based on solubiliza- (2000).
tion process. MEV micrographs show CNTs spread on the 5. M. S. Dresselhaus, G. Dresselhaus, and P. Avouris, Springer Verlag
(2000).
aluminum surface and Raman spectrum shows absence of 6. P. R. Bandaru, J. Nanosci. Nanotechnol. 7, 1 (2007).
aluminum carbide; and strong interaction between CNTs 7. 3M, ACCR Technical Notebook (2003).
and metal matrix; that is, a shifted G-band position and 8. O. Bourne, J. Guan, M. B. Jakubinek, S. Lin, R. MacNeil, B. Simard,
Plasmon effect as well. The UTS of 259 MPa was and A. Akhtar, 19th Int. Conf. Comp. Mat. (2013), Vol. 13.
greater than other tested specimens and electrical resis- 9. S. Shivkumar, S. Ricci, C. Keller, and D. Apelian, J. Heat Treat.
8, 63 (1990).
tivity decreases of 13.7% less than conventional wire. 10. L. S. Schadler, Appl. Phys. Lett. 73, 3842 (1998).
These results represent a significant improvement in the 11. C. Langhammer, M. Schwind, B. Kasemo, and I. Zorić, Nano Lett.
field of ACCR wires based on CNTs and encourage the 8, 1461 (2008).
development of nanostructured cables for overhead power- 12. M. Kozlov, M. Hirabayashi, K. Nozaki, M. Tokumoto, and H. Ihara,
transmission lines. Appl. Phys. Lett. 66, 1199 (1995).
13. D. J. Woo, B. A. Bottolfson, L. N. Brewer, J. P. Hooper, and
S. Osswalda, J. Mater. Res. 29, 2644 (2014).
Acknowledgments: Marcos Allan Leite Dos Reis 14. K. Kawakami, M. Okuno, K. Ogawa, M. Miyauchi, and K. Yoshida,
thanks to Brazilian financing agency, CNPq and Furukawa Rev. 9, 81 (1991).

Received: 12 January 2016. Accepted: 17 June 2016.

J. Nanosci. Nanotechnol. 16, 1–5, 2016 5