‫‪Tahar Laoui‬‬

‫‪CORROSION PERFORMANCE OF COPPER COATED‬‬

‫‪WITH CARBON NANOTUBES‬‬

‫‪Tahar Laoui‬‬
‫)‪Department of Mechanical Engineering/Center of Research Excellence in Nanotechnology (CENT‬‬
‫‪KFUPM, Dhahran, Saudi Arabia‬‬

‫اﻟﺨﻼﺻـﺔ‪:‬‬
‫ﻃﺒﻘﺔ ﺳﻤﻴﻜﺔ ﻣﻦ اﻷ ﻧﺎﺑﻴﺐ اﻟﻜﺮوﺑﻮﻧﻴﺔ اﻟﻤﺘﻨﺎهﻴﺔ اﻟﺼﻐﺮ اﻟﻤﺘﻌﺪدة اﻟﺠﺪار ﺗﺮﺳﺒﺖ ﺑﻮﺳﺎﻃﺔ اﻟﺠﺎذﺑﻴﺔ ﻋﻠﻰ ﺳﻄﺢ أﻧﺒﻮب ﻣﻦ اﻟﻨﺤﺎس ﻣﻮﺿﻮع ﻓﻰ ﻣﺤﻠﻮل‬
‫ﻣﺎﺋﻰ ﻳﺤﺘﻮى ﻋﻠﻰ اﻷﻧﺎﺑﻴﺐ اﻟﻜﺮوﺑﻮﻧﻴﺔ ﻣﺨﻠﻮط ﻓﻴﻪ ﺑﺸﻜﻞ ﺟﻴﺪ‪.‬‬
‫وﻗﺪ اﺳ ُﺘﺨﺪم ﺟﻬﺎز اﻟﻔﺤﺺ اﻟﻤﺠﻬﺮى اﻹﻟﻜﺘﺮوﻧﻰ ﻟﻔﺤﺺ أﺳﻄﺢ و ﺗﻮزﻳﻊ و ﺳﻤﺎآﺔ اﻷ ﻧﺎﺑﻴﺐ اﻟﻜﺮوﺑﻮﻧﻴﺔ اﻟﻤﺘﺮﺳﺒﺔ ﻋﻠﻰ ﺳﻄﺢ اﻟﻨﺤﺎس ‪ .‬وﺑﺎﻟﻨﻈﺮ اﻟﻰ‬
‫ﺗﻜﺒﻴﺮﺑﺴﻴﻂ ﺗﻈﻬﺮ ﻃﺒﻘﺔ اﻷ ﻧﺎﺑﻴﺐ ﻣﺘﺠﺎﻧﺴﺔ ﺑﻴﻨﻤﺎ ﺑﺘﻜﺒﻴﺮ أﻋﻠﻰ اﺗﻀﺢ أن اﻷ ﻧﺎﺑﻴﺐ اﻟﻜﺮوﺑﻮﻧﻴﺔ ﻣﺘﺮﺳﺒﺔ ﻋﻠﻰ ﺷﻜﻞ ﻣﺠﻤﻮﻋﺔ آﺒﻴﺮة ﻣﻠﺘﺼﻘﺔ ﺑﻌﻀﻬﺎ ﺑﺒﻌﺾ‬
‫وﻣﻮزﻋﺔ ﻋﻠﻰ اﻟﺴﻄﺢ ﺑﺸﻜﻞ ﻏﻴﺮ ﻣﺘﺠﺎﻧﺲ‪.‬‬
‫وﻗﺪ ﺗﻢ ﻗﻴﺎس ﻗﻴﻤﺔ ﻓﻴﻜﺮز ﻟﺼﻼﺑﺔ اﻟﻌﻴﻨﺔ ﺑﺎﺳﺘﺨﺪام ‪ 300gf‬ﻟﻠﺤﻤﻞ اﻟﻤﺴﻠﻂ ﻋﻠﻰ اﻟﻨﺤﺎس وﻋﻠﻰ اﻷﻧﺎﺑﻴﺐ اﻟﻜﺮوﺑﻮﻧﻴﺔ اﻟﻤﺘﺮﺳﺒﺔ ﻋﻠﻰ ﺳﻄﺢ اﻟﻨﺤﺎس ﻓﻜﺎﻧﺖ‬
‫ﻋﻨﺪ ‪ 104HV‬و ‪ 111HV‬ﻋﻠﻰ اﻟﺘﻮاﻟﻰ ‪ .‬وهﺬا ﻳﻮﺿﺢ أن اﻷﻧﺎﺑﻴﺐ اﻟﻜﺮوﺑﻮﻧﻴﺔ اﻟﻤﺘﺮﺳﺒﺔ زادت ﻗﻠﻴﻼ ﻣﻦ ﺻﻼﺑﺔ ﺳﻄﺢ اﻟﻨﺤﺎس اﻟﻤﺘﺮﺳﺒﺔ ﻋﻠﻴﻪ‪.‬‬
‫ﻟﻘﺪ ﺗﻢ إﺟﺮاء اﺧﺘﺒﺎراﻟﺘﺂآﻞ ﻟﻠﻌﻴﻨﺔ ﻓﻰ ﻣﻴﺎﻩ ﻣﺎﻟﺤﺔ ذات ﺗﺮآﻴﺰ ‪ 3wt%‬ﻟﺪراﺳﺔ ﺗﺄﺛﻴﺮ اﻷﻧﺎﺑﻴﺐ اﻟﻜﺮوﺑﻮﻧﻴﺔ ﻋﻠﻰ ﺗﺂآﻞ اﻟﻤﻌﺪن ﺛﻢ ﻗﻴﺎس ﻣﻔﺎﻋﻞ اﻟﺘﺂآﻞ )‪(Rp‬‬
‫ﺑﺎﺳﺘﺨﺪام ﻃﺮﻳﻘﺔ اﻻﺳﺘﻘﻄﺎب وأﻋﻄﺖ ‪ 585 Ohms‬ﻟﻠﻨﺤﺎس ﻓﻰ ﺣﻴﻦ أﻋﻄﺖ ‪ 26,460 Ohms‬اﻷﻧﺎﺑﻴﺐ اﻟﻜﺮوﺑﻮﻧﻴﺔ اﻟﻤﺘﺮﺳﺒﺔ ﻋﻠﻰ ﺳﻄﺢ ﻣﻤﺎ وﺿﺢ أن‬
‫اﻷﻧﺎﺑﻴﺐ اﻟﻜﺮوﺑﻮﻧﻴﺔ ﻗﻠﻠﺖ ﺗﺂآﻞ اﻟﻤﻌﺪن ﺑﻨﺴﺒﺔ ‪ 45‬ﺿﻌﻔًﺎ ﻣﻘﺎرﻧﺔ ﺑﺎﻟﻤﻌﺪن ﻟﻮﺣﺪﻩ‪.‬‬
‫وﺑﻤﻌﻨﻰ ﺁﺧﺮ ‪ :‬إن ﻣﻌﺪل ﺗﺂآﻞ اﻟﻨﺤﺎس ﻟﻮﺣﺪﻩ ﻗﻞ ﺑﺸﻜﻞ آﺒﻴﺮ وﻣﻠﺤﻮظ ﻋﻨﺪ ﺗﻐﻄﻴﺘﻪ ﺑﺎﻷﻧﺎﺑﻴﺐ اﻟﻜﺮوﺑﻮﻧﻴﺔ ﻣﻤﺎ ﺳﻴﺰﻳﺪ ﻣﻦ ﻋﻤﺮ اﻟﻤﻌﺪن‪.‬‬

‫______________‬
‫‪*Corresponding Author:‬‬
‫‪E-mail: tlaoui@kfupm.edu.sa‬‬
‫________________________________________________________________________________________________________‬
‫‪Paper Received March 20, 2010; Paper Revised April 16, 2010; Paper Accepted June 5, 2010‬‬

‫‪June 2010‬‬ ‫‪The Arabian Journal for Science and Engineering, Volume 35, Number 1C‬‬ ‫‪57‬‬
 Tahar Laoui

ABSTRACT
A thick layer of multi-wall carbon nanotubes (CNTs) was deposited on a copper surface by gravity from a
solution containing dispersed CNTs in water. Scanning electron microscopy (SEM) was utilized to characterize the
morphology, uniformity, and thickness of the CNT coating. A low magnification examination shows a uniform
coating. However, a closer look at the SEM images reveals that the coating consists of clumps of CNTs deposited
rather irregularly on the surface. The Vickers microhardness values measured using a 300 gf load for copper (Cu)
and CNT coated Cu samples were 104 and 111 HV, respectively. This indicates that the CNT coating provided a
slightly harder surface than Cu substrate. A corrosion test was carried out in salted water (3wt% concentration) to
investigate the effect of CNT coating on the corrosion performance of copper. The corrosion resistance (Rp)
calculated from the linear polarization resistance results yielded 585 Ohms for Cu and 26,460 Ohms for the CNT
coated Cu, indicating a drastic increase in the corrosion resistance of about 45 times. In other words, the corrosion
rate of Cu has been greatly reduced by the deposited CNT coating, thus allowing a potentially longer lifetime.
Key words: carbon nanotubes, copper, CNT coating, corrosion performance, corrosion resistance

58 The Arabian Journal for Science and Engineering, Volume 35, Number 1C June 2010
 Tahar Laoui

CORROSION PERFORMANCE OF COPPER COATED WITH CARBON NANOTUBES

1. INTRODUCTION
Research on new materials and associated technologies has attracted the attention of many scientists worldwide
for several decades. Developments are helping to improve the properties of materials and find alternative precursors
that can bestow desirable properties onto the developed materials. Great interest has recently been devoted to the
area of nanostructured carbon materials. Carbon nanostructures are becoming of considerable commercial
importance with interest growing rapidly over the last decade or so since the discovery of buckminsterfullerene,
carbon nanotubes, and carbon nanofibers. Iijima was the first to discover CNTs using the arc discharge method [1,2].
Following this discovery, a number of scientific research studies have been initiated in this field and different
methods have been explored and reported to synthesize CNTs such as laser vaporization [3] and catalytic chemical
vapor deposition of hydrocarbons [4,5]. Carbon nanotubes (CNTs) exhibit unique mechanical, electric, electronic,
thermal, and magnetic properties, which have made them the subject of many investigations [6–8]. CNTs are
probably the strongest substance that will ever exist, with a tensile strength greater than that of steel but with only
one sixth the weight of steel [9].
These exceptional features made CNTs ideal reinforcement for a variety of materials, including polymers,
metals/alloys, and ceramics. In this regard, CNT-reinforced copper nanocomposites were developed by Chai et al.
[10] using the electrochemical co-deposition method yielding a mechanical strength approximately three times
greater than pure copper. The increased strength was attributed to the good distribution of CNTs and good
CNT/copper interfacial bonding. Composite coatings made of single-walled carbon nanotube-reinforced copper were
developed by Yang et al. [11] using electrochemical deposition under an ultrasonic field. The authors reported good
electrical conductivity comparable to pure copper, along with a significant enhancement in mechanical properties.
Ge et al. [12] reported the growth of vertically aligned carbon nanotube (CNT) arrays on copper substrate by thermal
chemical vapor deposition. The copper substrate was first coated with different materials such as titanium, nickel,
and nickel-chromium intermediate layers to eliminate cracking of the copper surface and achieve vertical alignment
of CNTs. Using the same synthesis method, Lahiri et al. [13] prepared an efficient CNT-based field emitter by
growing multi-wall CNTs on copper substrates that were sputtered with thin layers of titanium and nickel. The
authors claim that the developed emitter exhibited superior field emission characteristics attributed to a lower contact
barrier and higher conductivity of the substrate.
The present paper reports the initial results obtained by depositing a relatively thick layer of CNTs on a copper
surface (specifically on a copper tube) and the subsequent characterization of the coating in terms of microstructure,
microhardness, and corrosion performance.
2. EXPERIMENTAL PROCEDURE
A thick layer of multi-wall carbon nanotubes (CNTs, > 95% purity, diameter 10–20nm, length 0.5-50µm, ash
≤0.2%, amorphous carbon <3%, Shenzhen Nanotech Port Co., Ltd, China) was deposited onto a copper surface (Cu,
used in water pipes) from a solution containing dispersed CNTs in distilled water with a CNT concentration of 3wt%
(30 gram/liter). To obtain a homogeneous distribution of the CNTs in water, sodium luryl sulfate was added as a
dispersant agent and the solution was subjected to ultrasonic vibration for 30 minutes. The sonication waves allowed
the agglomerated CNTs to disperse well in the entire volume of the utilized water by breaking down the vander wall
interactions existing between the CNTs’ external surfaces. The homogenized solution was then put in a water bath
and heated to 40oC. After the temperature of the solution reached a steady state (requiring at least 15 min), it was
then pumped into a copper tube of ½ inch diameter at a flow rate of 1 L/min for a period of 2 hours in a closed
system, as shown schematically in Figure 1. This method induced the deposition of a relatively thick coating of
CNTs onto the surface of the copper tube.
The microstructural features of the surface of both Cu and coating were examined using a field emission
scanning electron microscope (FE-SEM, JEOL JSM 6460LV). The Vickers microhardness values were measured
using a 300 gf load (applied for 10 seconds). The corrosion tests were performed using a potentiostat EG&G
Princeton/Applied Research (Potentiostat/Galvano Model 263A) in a glass cell using linear polarization resistance
(lpr) method with a scan rate of 0.1 mV/sec. An amount of 30g salt (NaCl) was dissolved in the distilled water
(concentration = 30g/liter) to simulate a sea water medium.

June 2010 The Arabian Journal for Science and Engineering, Volume 35, Number 1C 59
 Tahar Laoui

Figure 1: Schematic diagram of the closed system used to deposit a coating of CNTs onto the surface of the copper tube
3. RESULTS AND DISCUSSION
The investigation performed in this study to evaluate the influence of CNT coating deposited onto Cu substrate
includes the microstructural characterization of the deposited coating, measurement of the surface Vickers
microhardness, and evaluation of the corrosion performance.
3.1. Microstructural Analysis
The as-received commercial multi-wall carbon nanotubes (CNTs) produced by the chemical vapor deposition
(CVD) technique used in this study were analyzed and found to be of high quality. The batch of CNTs used in the
experimental work was observed by FE-SEM. The diameter of these CNTs varied from 20–30 nm with an average
diameter of 24 nm, while the length of the CNTs was up to several microns. Figure 2(a) shows a low magnification
FE-SEM image of CNTs grouped in the form of clumps, whereas Figure 2(b), taken at high magnification, reveals
clearly the individual CNTs and some of their characteristic features (diameter, shape, purity). From these
observations, the as-received commercial CNTs can be described as a product of high quality (high purity), as no
other materials (particularly amorphous carbon) were observed. The impurities obtained during the production of
CNTs by the CVD process, under non-optimized processing conditions, are carbonaceous products (amorphous
carbon or soot, and carbon nanofibers). A clear illustration of this aspect has been reported elsewhere by Muataz et
al. [15] in their study related to the effect of reaction temperature on the production of carbon nanotubes. The bright
dots shown in Figure 2(b) and approximately 20–30nm in size are iron catalysts used in the CVD technique for
producing the CNTs.

a b

Figure 2: SEM images of CNTs at (a) low resolution and (b) high resolution [14]
SEM was also utilized to characterize the morphology, uniformity, and thickness of the CNT coating. A low
magnification examination shows a uniform coating, as shown in Figure 3(a). However, a close look at the SEM
images displayed in Figure 3(b) reveals that the coating consists of clumps of CNTs deposited rather irregularly on
the surface. The coating seems to be relatively thick, with an approximate average thickness of about 15 µm as
measured by SEM on a cross-sectional area of the specimen.

60 The Arabian Journal for Science and Engineering, Volume 35, Number 1C June 2010
 Tahar Laoui

(a) (b)
Figure 3: Surface topography of CNT coating deposited on Cu substrate, (a) low magnification showing a rather uniform texture,
(b) higher magnification revealing clumps of CNTs
3.2. Microhardness Testing
The Vickers microhardness values measured using a 300 gf load (applied for 10 seconds) for Cu and CNT coated
Cu are (103.7±2.3) HV and (111.±1.0) HV, respectively. This indicates that the CNT coating yielded a relatively
harder surface than Cu substrate, although the increase in hardness is only minor. This can be explained with the
help of the microstructural analysis mentioned above; that is, the deposited CNTs are not forming a dense layer all
throughout the surface of Cu, but rather an agglomerate of CNT clumps 2–8 µm in size, as shown in Figure 3(b),
which contain voids in between them. It should be expected that by altering the parameters of the deposition process
to yield a dense CNT coating with a high degree of uniformity and distribution will result in a relatively much harder
coating.
3.3. Corrosion Performance
A corrosion test was carried out to investigate the effect of CNT coating on the corrosion performance of copper.
The linear polarization resistance (lpr) tests were performed in the range -6 mV to +6 mV vs open circuit potential at
a scan rate of 0.1 mV/sec in order to determine accurately the corrosion/polarization resistance. Figures 4(a) and 4(b)
show the lpr results obtained for Cu and CNT-coated Cu, respectively.

Linear polarization resistance of Cu sample Linear polarization resistance of CNT coated Cu sample

-1.82E-01 -6.5E-02

-1.84E-01 -6.7E-02

-6.9E-02
-1.86E-01

-7.1E-02
-1.88E-01
Potential - E (V)

Potential - E (V)

-7.3E-02
-1.90E-01
-7.5E-02
-1.92E-01
-7.7E-02

-1.94E-01
-7.9E-02

-1.96E-01
-8.1E-02

-1.98E-01 -8.3E-02

-2.00E-01 -8.5E-02
-1.5E-05 -1.0E-05 -5.0E-06 0.0E+00 5.0E-06 1.0E-05 1.5E-05 2.0E-05 -4.0E-07 -3.0E-07 -2.0E-07 -1.0E-07 0.0E+00 1.0E-07 2.0E-07 3.0E-07 4.0E-07
Current - I (A) Current - I (A)

(a) (b)
Figure 4: Linear polarization resistance of (a) Cu and (b) CNT coated Cu
The corrosion resistance (Rp) calculated from the slope of both curves is 585 Ohms for the Cu sample and
26,460 Ohms for the CNT-coated Cu, yielding an increase in the corrosion resistance of about 45 times due to the
CNT coating. To appreciate the comparison in the results obtained from both samples, Figures 4(a) and 4(b) have
been plotted on the same graph, as displayed in Figure 5.

June 2010 The Arabian Journal for Science and Engineering, Volume 35, Number 1C 61
 Tahar Laoui

Linear polarization resistance of Cu (A) and CNT coated Cu (B) samples

0.00

-0.05
Potential - E (V)

-0.10

-0.15

-0.20

-0.25
-1.5E-05 -1.0E-05 -5.0E-06 0.0E+00 5.0E-06 1.0E-05 1.5E-05 2.0E-05

Current - I (A)

Figure 5: Linear polarization resistance results of Cu (lower curve) and CNT coated Cu (top tiny curve)
plotted on the same graph for easy comparison
There is a clear indication that the CNT coating has drastically increased the corrosion resistance of Cu material
in the simulated sea water. These results are quite attractive in applications where the copper tubes/pipes are
subjected to sea water continuously throughout the year (for instance in constructions located near the coast or
offshore). Under these circumstances, the application of CNT coating onto the Cu pipes will allow a higher
corrosion resistance and, thus, a longer lifetime.
4. CONCLUSIONS
The present work reports on the corrosion performance of copper coated with CNTs yielding an enhancement in
the corrosion resistance of copper by a factor of about 45 times in salinated water (3wt% concentration). These
results are quite attractive in applications where copper material (such as tubes/pipes) is subjected to sea water
continuously throughout the year (for instance in constructions located near the coast or offshore). Under these
circumstances, the application of CNT coating onto the Cu pipes will allow a higher corrosion resistance and, thus, a
longer lifetime.
Further studies are underway to characterize and determine the corrosion rate of the CNT-coated Cu as well as
other relevant properties, such as the bonding strength/adhesion characteristics of deposited CNT coating and the
interfacial structure between CNTs and copper substrate. Similar corrosion performance tests will be performed on
traditional coatings such as paints for a useful comparison.
ACKNOWLEDGMENTS
The author acknowledges fruitful discussions with Dr. M.A. Atieh and Dr. R. Ben-Mansour on CNTs, Dr. R.
Rayhan for help with corrosion testing, and Mr. S. Abbas for help with SEM.
REFERENCES
[1] T. W. Ebbesen and P. M. Ajayan, “Large-Scale Synthesis of Carbon Nanotubes”, Nature, 358(6383)(1992),
pp. 220–222.
[2] S. Iijima, “Helical Microtubules of Graphite Carbon”, Nature, 354(1991), pp. 56–58.
[3] A. Thess, R. P. Lee, H. J. Nikolaev, P. Dai, J. Petit, C. H. Robert, Y. H. Xu, S. G. Lee, A. G. Kim, D. T. Rinzler, G.
E. Colbert, D. Scuseria, J. E. Tomanek, and R. E. Smalley, “Crystalline Ropes of Metallic Carbon Nanotubes”,
Science, 273(52)(1996), pp. 483–487.
[4] E. Flahaut, C. Laurent, and A. Peigney, “Catalytic CVD Synthesis of Double and Triple-Walled Carbon Nanotubes
by the Control of the Catalyst Preparation”, Carbon, 43(2005), pp. 375–383.
[5] Y. Kobayashia, H. Nakashimaa, D. Takagib, and Y. Hommaa, “CVD Growth of Single-Walled Carbon Nanotubes
Using Size-Controlled Nanoparticle Catalyst”, Thin Solid Films, 464–465(2004), pp. 286–289.

62 The Arabian Journal for Science and Engineering, Volume 35, Number 1C June 2010
 Tahar Laoui

[6] P. M. Ajayany and T. W. Ebbesenz, “Nanometre-Size Tubes of Carbon”, Rep. Prog. Phys., 60(1997), pp. 1025–
1062.
[7] K. Ching-Hwa, G. William, B. Robert, and S. Donald, “Carbon Nanotubes With Single-Layer Walls”, Carbon,
33(7)(1995), pp. 903–914.
[8] M. Dresselhaus, G. Dresselhaus, and S. Riichiro, Physical Properties of Carbon Nanotubes. London: Imperial
College Press, 1998.
[9] M. Dresselhaus, G. Dresselhaus, and P. Avouris, Carbon Nanotubes: Synthesis, Structure, Properties, and
Applications, Germany: Springer-Verlag Berlin HeidleberG, 2001.
[10] G. Chai, Y. Sun, J. Sun, and Q. Chen, “Mechanical Properties of Carbon Nanotube–Copper Nanocomposites”,
J. Micromech. Microeng., 18(2008) pp. 1–4.
[11] Y. L. Yang, Y. D. Wang, Y. Ren, C. S. He, J. N. Deng, J. Nan, J. G. Chen, and L. Zuo, “Single-Walled Carbon
Nanotube-Reinforced Copper Composite Coatings Prepared by Electrodeposition Under Ultrasonic Field”,
Materials Letters, 62(1)(2008), pp. 47–50.
[12] G. Li, S. Chakrabarti, M. Schulz, and V. Shanov, “Growth of Aligned Multiwalled Carbon Nanotubes on Bulk
Copper Substrates by Chemical Vapor Deposition”, Journal of Materials Research, 24(9)(2009), pp. 2813–2820.
[13] I. Lahiri, R. Seelaboyina, J. Y. Hwang, R. Banerjee, and W. Choi, “Enhanced Field Emission from Multi-Walled
Carbon Nanotubes Grown on Pure Copper Substrate”, Carbon, 48(5)(2010), pp. 1531–1538.
[14] M. A. Atieh, Chemical Engineering Department, KFUPM, 2009.
[15] A. A. Muataz, F. Ahmadun, C. Guan, E. Mahdi, and A. Rinaldi. “Effect of Reaction Temperature on the Production
of Carbon Nanotubes”, Journal of NANO: Brief Reports and Reviews, 1(3)(2006), pp. 251–257.

June 2010 The Arabian Journal for Science and Engineering, Volume 35, Number 1C 63