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Journal of Physics and Chemistry of Solids 69 (2008) 13911394 www.elsevier.com/locate/jpcs

Electrodeposition and mechanical properties of Nicarbon nanotube nanocomposite coatings

Y.S. Jeona, J.Y. Byunb, T.S. Oha,
b

Department of Materials Science and Engineering, Hongik University, Seoul 121-791, Republic of Korea Center for Metals Processing, Korea Institute of Science and Technology, Seoul 158-791, Republic of Korea Received 30 June 2007; received in revised form 3 October 2007; accepted 30 October 2007

Abstract Electrodeposition behavior and mechanical properties of Nicarbon nanotube (NiCNT) nanocomposites were examined with variations of dispersion additive and the content of multiwalled carbon nanotubes (MWCNTs) in the nanocomposites. Incorporation of MWCNTs into Ni matrix was greatly enhanced by using sodium dodecyl sulfatehydroxypropylcellulose mixture as dispersion additive. With increasing the MWCNT content of the NiCNT composite to 14.6 vol%, a fracture stress of the NiCNT/Cu bi-layer lm was improved from 607 to 780 MPa, showing that strengthening can be achieved for the NiCNT nanocomposite by incorporating MWCNTs into Ni matrix. r 2007 Elsevier Ltd. All rights reserved.
Keywords: A. Nanostructures; B. Chemical synthesis; C. Electron microscopy; D. Microstructure

1. Introduction Nanocomposite coatings, where nano-sized ceramic particles are incorporated into metal matrix, have been widely investigated for various applications such as wearresistant and tribological coatings [13]. Among various process technologies for nanocomposites, electrodeposition has advantages such as cost-effectiveness relative to spray and sputtering processes [4]. Conventionally, nanopowders such as alumina, silicon carbide, and diamond were used as reinforcements for Ni-based nanocomposite coatings [1,3]. Recently, carbon nanotube (CNT) has been applied as a new reinforcement material for nanocomposite coatings due to its excellent mechanical properties and high thermal conductivity [47]. As Ni exhibits high wear resistance, good ductility, and ferromagnetism, NiCNT composite coatings have potential applications for wear-resistance coatings and MEMS structures [47]. Property enhancement of a nanocomposite with embedding CNTs depends on the dispersion characteristics as well as the volume fraction of CNTs in a nanocomposite
Corresponding author. Tel.: +82 2 320 1655; fax: +82 2 333 0127.

[6,7]. In this study, NiCNT nanocomposites were processed by electrodeposition and the intercalation behavior of multiwalled carbon nanotubes (MWCNTs) into Ni matrix was investigated with different electrodeposition additives such as sodium dodecyl sulfate (SDS) and hydroxypropylcellulose (HPC). Electrodeposition behavior and fracture stress of the NiCNT nanocomposites were also examined as a function of the MWCNT content in the nanocomposites.

2. Experimental procedure NiCNT nanocomposite coatings were electrodeposited in a sulfate Watts bath of the following composition: 260 g/L nickel sulfate (NiSO4 6H2O), 45 g/L nickel chloride (NiCl2 6H2O), 15 g/L boric acid (H3BO3), and 0.5 g/L saccharine. To improve MWCNT dispersion, SDS and HPC were added into the electrodeposition solutions by varying the amounts of SDS and HPC from 0 to 10 g/L. The total amount of SDS and HPC was always kept as 10 g/L. MWCNTs of 1015 nm diameter, produced by CVD, were used to form the NiCNT electrodeposition solutions. As the length of the as-received MWCNTs, about

E-mail address: ohts@hongik.ac.kr (T.S. Oh). 0022-3697/$ - see front matter r 2007 Elsevier Ltd. All rights reserved. doi:10.1016/j.jpcs.2007.10.049

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20 mm, was too long for coelectrodeposition, MWCNTs were cut to a length less than 5 mm by ball-milling with ZrO2 balls for 24 h at 200 rpm. The weight ratio of MWCNT-toZrO2 was kept as 1:25 in an alumina jar. After producing the NiCNT electrodeposition solutions with MWCNT contents of 0, 1, 2, 5, 10 g/L, NiCNT nanocomposites of 50 mm thickness were electrodeposited on Cu substrates of 2 cm 2 cm size at a current density of 40 mA/cm2. During electrodeposition of a NiCNT nanocomposite, the bath was maintained at 40 1C with mechanical stirring at 500 rpm. To evaluate fracture stress, NiCNT nanocomposites of 50 mm thickness were electrodeposited on 20 mm-thick Cu lms laminated onto 30 mmthick polyimide (PI) lms of 1 cm 3 cm size. After electrodepositing NiCNT nanocomposites, PI lms were peeled off and tensile tests were conducted for the NiCNT/Cu bi-layer specimens.

Morphologies of the NiCNT composites were observed by using eld emission scanning electron microscopy (FESEM). The content of MWCNTs in the NiCNT composites was characterized with a carbon/sulfur analyzer (ELTRA CS800). 3. Results and discussion Fig. 1 illustrates surface morphologies of the NiCNT nanocomposites electrodeposited in solutions with different amounts of SDS and HPC as dispersion additives. The MWCNT concentration of the electrodeposition solutions was maintained as 10 g/L and the total amount of SDS and HPC was also kept as 10 g/L. Comparing Fig. 1(a) with Fig. 1(e) indicates that SDS is more effective for MWCNT dispersion than HPC. As shown in Fig. 1(b) and (c), however, incorporation of MWCNTs into Ni matrix was greatly enhanced by using SDSHPC mixture with the

1 m

1 m

1 m

1 m

1 m
Fig. 1. FESEM micrographs of the NiCNT nanocomposite electrodeposited in a bath containing dispersion additive of (a) 10 g/L SDS, (b) 7.5 g/L SDS and 2.5 g/L HPC, (c) 5 g/L SDS and 5 g/L HPC, (d) 2.5 g/L SDS and 7.5 g/L HPC, and (e) 10 g/L HPC.

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SDSHPC weight ratios of 3:1 and 1:1. Such SDSHPC mixture might modify the surface chemistry of MWCNTs more suitable for uniform dispersion in the electrolytic bath, resulting in great increase in the MWCNT content of the NiCNT nanocomposite. SDSHPC mixture additive affected not only the MWCNT dispersion characteristics but also the properties of Ni matrix itself. While the hardness of a Ni coating electrodeposited without MWCNTs in a Watt bath containing SDS of 10 g/L was 430 Hv, the value of one processed in a solution with the SDSHPC mixture of the 3:1 weight ratio increased to 527 Hv. Fig. 2 shows SEM micrographs of the NiCNT nanocomposites processed in the electrodeposition solutions with the MWCNT concentrations of 010 g/L and the 10 g/L SDSHPC mixture of the weight ratio of 3:1. The NiCNT nanocomposites were etched in nitric acid to remove the surface layer for observation of the internal morphology. With increasing the MWCNT concentration in the electrodeposition bath up to 5 g/L, more MWCNTs were incorporated into Ni matrix. However, microstructure of the NiCNT composite became porous with increasing the MWCNT concentration in the bath beyond 2 g/L. Using the weight fractions of the MWCNTs measured for the NiCNT composites electrodeposited with different MWCNT concentrations, volume percentages of MWCNTs in the nanocomposites were evaluated and plotted in Fig. 3, as a function of the MWCNT concentration of the electrodeposition bath. To convert the weight fraction of the MWCNTs in the composite to

volume fraction, the following relation was used with values of 8.91 and 0.05 g/cm3 as the density of Ni and the bulk density of MWCNT, respectively [8]; volume fraction of MWCNTs dCNT wCNT/[dNi wCNT+dCNT

25

20

CNT content (vol%)

15

10

0 0 2 4 6 8 10

CNT concentration (g/l)

Fig. 3. The MWCNT content (vol%) of the NiCNT nanocomposite as a function of the MWCNT concentration (g/L) in the bath.

1 m

1 m

1 m

1 m

Fig. 2. FESEM micrographs of the NiCNT nanocomposite electrodeposited in a bath containing an MWCNT concentration of (a) 1 g/L, (b) 2 g/L, (c) 5 g/L, and (d) 10 g/L.

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Y.S. Jeon et al. / Journal of Physics and Chemistry of Solids 69 (2008) 13911394

800

Fracture stress (MPa)

700

600

transmission electron microscopy is going on to understand well the phenomenon of the drastic fracturestress drop for the specimen with the MWCNT content of 22.5 vol%. While various reports are available for hardness increase in NiCNT nanocomposites [6,7,9], very few works can be found for strength increment of metalmatrix composites reinforced by MWCNTs [10]. Although we measured the fracture stress of the NiCNT/Cu bi-layer specimen instead of the NiCNT itself, our result shown in Fig. 4 would be a useful indication that strength improvement can be achieved for the NiCNT composite by incorporating MWCNTs into Ni matrix. 4. Conclusions

500

400

10 15 CNT content (vol%)

20

25

Fig. 4. Fracture stress of the NiCNT/Cu bi-layer lm as a function of the MWCNT content in the NiCNT nanocomposite.

(1wCNT)], where dCNT and dNi are densities of MWCNT and Ni, respectively, and wCNT is weight fraction of MWCNTs. The MWCNT content in the NiCNT nanocomposite became larger and reached a maximum of 22.5 vol% with increasing the MWCNT concentration in the bath up to 5 g/L. However, the MWCNT content in the composite decreased with further increasing the MWCNT concentration in the bath beyond 5 g/L, which could be due to the agglomeration of MWCNTs in the bath containing MWCNTs above the saturation concentration [4]. As the MWCNT content decreased and the microstructure became substantially porous for the nanocomposite processed in the bath containing MWCNTs of 10 g/L, mechanical characterization was not conducted for this specimen. Fracture stress required to break the NiCNT/Cu bi-layer lm, fabricated by peeling off a PI lm after electrodepositing the NiCNT onto a Cu/PI, is illustrated in Fig. 4. Thicknesses of the NiCNT composite and the Cu were 50 and 20 mm, respectively. With increasing the MWCNT content of the NiCNT composite to 14.6 vol%, the fracture stress was improved from 607 to 780 MPa. However, the fracture stress dropped drastically to 534 MPa for the specimen with the MWCNT content of 22.5 vol% as fabricated in the bath of the MWCNT concentration of 5 g/L. This might be due to the porous microstructure of the nanocomposite with MWCNT content of 22.5 vol%, as shown in Fig. 2(d). Microstructural analysis using

For electrodeposition of the NiCNT nanocomposite, incorporation of MWCNTs into Ni matrix was greatly enhanced by using SDSHPC mixture instead of SDS as dispersion additive. The MWCNT content in the NiCNT nanocomposite increased, reached a maximum of 22.5 vol% with increasing the MWCNT concentration in the bath up to 5 g/L, and then decreased with further increasing the MWCNT concentration in the bath due to the agglomeration of MWCNTs in the bath. With increasing the MWCNT content of the NiCNT composite to 14.6 vol%, fracture stress of the NiCNT/Cu bi-layer was improved from 607 to 780 MPa, showing that strengthening can be achieved for the NiCNT composite by incorporating MWCNTs into Ni matrix. Acknowledgment This work was supported by the Center for Electronic Packaging Materials of Korea Science Engineering Foundation. References
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