Materials Letters 65 (2011) 22692273

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Materials Letters
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / m a t l e t

Incorporation of carbon nanotubes into micro-coatings lm formed on aluminum alloy via plasma electrolytic oxidation
Kang Min Lee a, Young Gun Ko b,, Dong Hyuk Shin a,
a b

Department of Metallurgy and Materials Engineering, Hanyang University, Ansan 426-791, Republic of Korea School of Materials Science and Engineering, Yeungnam University, Gyeongsan 712-749, Republic of Korea

a r t i c l e

i n f o

a b s t r a c t
The inuence of the incorporation of carbon nanotubes (CNTs) on the coating structure of aluminum alloy processed by plasma electrolytic oxidation (PEO) has been studied as a function of the current density. A series of PEO coatings was applied in a silicate-electrolyte containing CNTs at three current densities, such as 50, 100, and 150 mA/cm2. As the current density increased, the responding voltage also increased due to a gradual increment in the amount of CNTs incorporated uniformly into the coating lm. In addition, a number of CNTs were observed mainly near micro-pores formed in the coating lm by plasma explosive arcs, resulting in a fairly uniform coating structure with a low density of micro-pores. This phenomenon was discussed based on the electrophoretic activity of CNTs. 2011 Elsevier B.V. All rights reserved.

Article history: Received 31 December 2010 Accepted 1 April 2011 Available online 8 April 2011 Keywords: Plasma electrolytic oxidation Metals and alloys Carbon nanotube Coating Microstructure

1. Introduction In recent years, aluminum and its alloys have been regarded as one of the good candidate materials in various industry elds due to their good specic strength and electro-thermal conductivity [13]. Despite these outstanding properties, the surface treatment was required to improve their mechanical reliability, including surface characteristics and tribology [46]. In relation to this, aqueous anodizing, chemical conversion coating, and plasma electrolytic oxidation (PEO) have been extensively studied [79]. Among these coating methods, the PEO technique was receiving considerable interest presently since it could lead to generate the strong bonding between the metal substrate and a ceramic-like coating lm by extremely high activation voltages imparted by an electrochemical cell. In the case of PEO coating of light aluminum alloys, strong passivation barriers with a micro-length scale were formed. Unfortunately, it was undoubtful that they were accompanied by micro-pores associated with plasma discharge, which deteriorated the mechanical properties of the alloys. The scaffold structure of the coating lm on aluminum alloys formed by the PEO method depended upon coating variables, such as the electrolyte, substrate, and electrochemical parameters [1013]. Recent work has shown that the secondary substances added to the electrolyte were of importance in determining the formation of the coating lm suitable for preventing mechanical failure of aluminum alloys even in severe atmospheres. Matykina et al. reported favorable

inuences of monoclinic zirconia (ZrO2) incorporation on the corrosion resistance of the PEO-coated pure aluminum [14]. Also, Jin et al. found that the use of Fe micrograins in an electrolyte improved the surface hardness and wear resistance of aluminum alloys, since coating lms became denser with a lower population of the micropores [15]. Thus, in the present study, carbon nanotubes (CNTs), which offered an excellent mechanical response and low electrical resistivity, were added as a chemical substance to an electrolyte prior to PEO coating [1618]. The effects of the incorporation of the CNTs in the electrolyte on the structure of the coating lm of aluminum alloy fabricated by the PEO process were investigated. 2. Experimental The chemical composition of a 7075 Al alloy supplied from Alcoa Inc is shown in Table 1. Prior to PEO coating, the initial samples were cut into the rod shape whose diameter and thickness were 20 and 10 mm, respectively. They was polished with #1000 abrasive paper, rinsed with distilled water, and ultrasonically cleaned in ethanol. A schematic illustration of PEO setup is shown in Fig. 1(a). The PEO machine had an electrolyte cell consisting of stainless steel cathode and 7075 Al alloy anode. The distance between cathode and anode was 50 mm in the electrolyte. The chemical composition of the electrolyte is listed in Table 2. The electrolyte also contained the CNTs with an average diameter of ~ 30 nm as shown in Fig. 1(b). PEO coatings were carried out at several applied current densities of 50, 100, and 150 mA/cm2 for 600 s. In general, several research groups have used the current density ranging 50 to 150 mA/cm2 (or 200 mA/ cm2 in some cases) [19,20]. The growth of the coating lm was very slow when the current densities lower than 50 mA/cm2 were applied,

Corresponding author. Tel.: + 82 53 810 2537; fax: + 82 53 810 4628. Corresponding author. Tel.: + 82 31 400 5224; fax: + 82 31 417 3701. E-mail addresses: younggun@ynu.ac.kr (Y.G. Ko), dhshin@hanyang.ac.kr (D.H. Shin). 0167-577X/$ see front matter 2011 Elsevier B.V. All rights reserved. doi:10.1016/j.matlet.2011.04.001

2270 Table 1 Chemical composition of 7075 Al alloy used in this study. Zn 5.8 Mg 2.6 Cu 1.6 Fe 0.3 Si 0.1 Mn 0.08

K.M. Lee et al. / Materials Letters 65 (2011) 22692273 Table 2 Chemical composition of the electrolyte used for the present PEO coating. Cr 0.2 Ti 0.04 Al bal. CNTs (mL/L) 150 Na2SiO3 (mol/L) 0.16 KOH (mol/L) 0.27 KF (mol/L) 0.09

which might limit the practical applications. On the other hand, the current densities as high as 200 mA/cm2 led to a number of large micro-pore within the coating lms. The use of high current density deteriorated the quality of the coating lms. Thus, the specic current densities of 50, 100, and 150 mA/cm2 were selected in this study. The working temperature of the electrolyte was maintained within 293 K during PEO coating. After the PEO process, there were no signicant surface and weight changes in the stainless steel used as cathode, implying that no carbon came from the stainless steel during coating. The surface morphology and chemical composition of each sample were observed utilizing a eld-emission scanning electron microscope (FE-SEM) equipped with an energy dispersive X-ray spectrometer (EDS). The acceleration voltage and the working distance used during FE-SEM imaging were 15 kV and 10 mm, respectively. Carbon tape was not used. The zeta potentials were measured using a zeta potential analyzer. 3. Results and discussion Fig. 2 shows the responding voltage vs. time curves of the present sample processed in the electrolyte containing CNTs at three different current densities. In general, the value of the responding voltage increased abruptly in the initial stage of PEO coating, and the rate of increase was lowered as the coating time increased. At the breakdown points where the slopes of the curves changed, micro-arcs and related visible sparking started to take place, and the responding voltage thereby increased slowly due to the relatively steady growth rate of

the coating lm. The breakdown voltages of the PEO-coated samples at three different current densities were measured to be 226, 234, and 249 V, respectively, and the nal voltages in the samples were found to be 339, 358, and 372 V, respectively. It is clear that the responding voltage increased with increasing current density. This fact indicated that the effect of the current density on the responding voltage was signicant. According to an earlier work reported by Srinivasan et al. [21], the responding voltage of aluminum alloy was directly proportional to the increment in the current density during PEO coating since the current density worked as an energy input. Thus, the present results were consistent with the conventional electrical behavior. In order to explore the relationship between the coating morphology and the incorporation of CNTs with respect to the current density, observations were made utilizing the FE-SEM technique. Fig. 3 displays the surface morphologies of the coating lm on an aluminum alloy sample after PEO coating with CNTs at three different current densities and without CNTs at 150 mA/cm2 for 600 s. It is apparent that, after PEO coating, the coating surface exhibited a number of the micro-pores which resulted from the occurrence of plasma sparks. In an ordinary PEO process, the fraction of the micro-pores increased with increasing current density [22]. As the current density increased, high energy was dissipated into the coating lm in order to form plasma sparks, and consequently the size of the micro-pores increased. Contrary to the widely accepted mechanism, the number and fraction of the micro-pores were observed to decrease in this study even when the current density increased. This was mainly attributed to the micro-pores being lled with metal oxides such as Al2O3 and/or SiO2. To monitor the pore structure in detail, the high magnication images of the coating lm on aluminum alloy were taken, and they are shown in Fig. 4. With increasing current density, the number of CNTs deposited in the vicinity of the micro-pores increased. Moreover, some metallic oxides grew well on CNTs. This nding suggested that the incorporation of CNTs played an important role in blocking the pores that already existed in the coating lm when the current density would be sufcient. These micro-pores might be detrimental to the mechanical stability and the corrosion resistance. Thus, among the current densities we studied, a current density of 150 mA/cm2 would be desirable for suppressing the formation of micro-pores with the aid of the facile incorporation of CNTs into the coating lm.

Fig. 1. (a) Schematic illustration of the PEO experimental setup and (b) initial CNTs used in this study.

Fig. 2. Timevoltage responses for PEO processing of aluminum alloy at three different current densities.

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Fig. 3. SEM images of the surface morphologies of the coating lm of aluminum alloy formed by PEO coating at different current densities of (a) 50, (b) 100, and (c) 150 mA/cm2 with CNTs and (d) 150 mA/cm2 without CNTs. Inset indicates the direction to observe the structure.

Fig. 4. High magnication SEM images of the surface morphologies of the coating lm of aluminum alloy formed by PEO coating at different current densities of (a) 50, (b) 100, and (c) 150 mA/cm2 with CNTs and (d) 150 mA/cm2 without CNTs. Inset indicates the direction to observe the structure.

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Fig. 5. EDS result of the coating lm of aluminum alloy formed by PEO coating at different current densities of (a) 50, (b) 100, and (c) 150 mA/cm2 with CNTs and (d) 150 mA/cm2 without CNTs.

In order to inspect the chemical elements found in the coating lm, the EDS prole was obtained, and is shown in Fig. 5. During PEO coating, the occurrence of the coating lm was a result of both the outward migration of Al3+ from the substrate and the inward migration of O2 and Si4+ from the silicate electrolyte [23]. In addition, C element was detected. Since neither the present electrolyte nor the substrate contained any C4+, it is obvious that most C atoms were thought to be originated from the CNTs consisting of C atoms. From the qualitative EDS data, the amounts of C and Si relatively increased while Al and O comparably decreased as the current density increased. This fact indicated that the content of C atoms uniformly distributed in the coating lm increased with increasing current density. On the basis of the zeta potential result of 60 mV, the surface charge showed that the CNTs became negative due to the decreased amounts of protons and polar molecules reacting with the surface of the CNTs dispersed in the silicate electrolyte (pH: ~ 14) [24,25]. Thus, the CNTs tended to move toward the anode surface. Once the dielectric sparks appeared, a number of CNTs moved into the coating lm due to electrophoresis. This tendency of CNTs movement could be triggered by high current density, which was in agreement with the previous SEM observations. 4. Summary This study investigated the inuence of the CNTs added to the electrolyte on the surface structure of the coating lm on aluminum alloy coated by the PEO process as a function of the current density.

As the current density increased, the responding voltage in the cell and the amount of CNTs in the coating lm increased. CNTs having a zeta potential of 60 mV in the electrolyte used in this study were incorporated due to the electrophoresis. The CNTs that were deposited around pores played an important role in the surface structure, yielding a reduction in the size of the micro-pores. In this study, a current density of 150 mA/cm2 was found to be desirable for fabricating a coating lm incorporating CNTs. Acknowledgment This work was supported by the National Research Foundation of Korea (No. 2010-0000812). References
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