See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/244603455

Coating Fine Copper Powder with Polyaniline

Article  in  Journal of Dispersion Science and Technology · January 2008

DOI: 10.1080/01932690701688490

CITATIONS READS

13 175

4 authors, including:

Yanhui Guo Binbo Jiang

Fudan University Zhejiang University
70 PUBLICATIONS   2,344 CITATIONS    110 PUBLICATIONS   1,270 CITATIONS   

SEE PROFILE SEE PROFILE

Some of the authors of this publication are also working on these related projects:

dvanced H2-Storage System Fabricated Through Chemical Layer Deposition in a Well-Designed Porous Carbon Scaffold View project

Gold Catalysts for Acetylene Hydrochlorination Reaction View project

All content following this page was uploaded by Yanhui Guo on 26 November 2018.

The user has requested enhancement of the downloaded file.

 Journal of Dispersion Science and Technology

ISSN: 0193-2691 (Print) 1532-2351 (Online) Journal homepage: http://www.tandfonline.com/loi/ldis20

Coating Fine Copper Powder with Polyaniline

Jizhong Chen , Yanhui Guo , Binbo Jiang & Shijie Zhang

To cite this article: Jizhong Chen , Yanhui Guo , Binbo Jiang & Shijie Zhang (2008) Coating Fine
Copper Powder with Polyaniline, Journal of Dispersion Science and Technology, 29:1, 97-100, DOI:
10.1080/01932690701688490

To link to this article: https://doi.org/10.1080/01932690701688490

Published online: 24 Sep 2008.

Submit your article to this journal

Article views: 79

Citing articles: 9 View citing articles

Full Terms & Conditions of access and use can be found at

http://www.tandfonline.com/action/journalInformation?journalCode=ldis20
Journal of Dispersion Science and Technology, 29:97–100, 2008
Copyright # Taylor & Francis Group, LLC
ISSN: 0193-2691 print/1532-2351 online
DOI: 10.1080/01932690701688490

Coating Fine Copper Powder with Polyaniline

Jizhong Chen, Yanhui Guo, Binbo Jiang, and Shijie Zhang
College of Materials Science & Chemical Engineering, Zhejiang University, Hangzhou, China

To improve the stability of fine copper powder, three methods were tried to coat it with
polyaniline. Pretreated, the powder was put into aniline solution. As ammonium persulfate
solution was added slowly, aniline changed into polyaniline and coated on copper powder. It
is proved that one of the methods is effective and can form good core-shell structure. The
shell of the composite contains reduced undoped polyaniline and a little cuprous oxide. The
composite has four stages of degradation in nitrogen and is more stable than fine copper
powder in air.

Keywords Fine copper powder, polyaniline film, coating

1 INTRODUCTION
Copper is widely used in microelectronics for wiring, of good morphology. The thermal stability and degradation
electromagnetic interference (EMI) shielding, electrostatic dis- behaviors of the composite were studied by thermogravimetric
sipation, etc.[1] As a noble metal, it is inert in air, but when its analysis (TGA) under nitrogen and air atmosphere.
size reduces, oxidation becomes apparent. To improve copper
powder’s stability, many materials were coated on it such as 2 EXPERIMENTAL
surfactant, conducting polymers, Benzotriazole, silver, silicon,
titanium, etc.[2 – 13] 2.1 Materials
Polyaniline (PANI) is one of the promising conducting In this article, A.R grade chemicals were used. Aniline,
polymers due to its comparative stability in air, easy synthesis, ammonium persulfate ((NH4)2S2O8, APS), polyethylene
low price, and high conductivity.[14 – 19] Until now, polyaniline glycol (PEG), polyvinyl alcohol (PVA), ethanol, and distilled
successfully has been coated on many metals, such as Cu, Ni, water were used as received.
Al, Pt, Fe, Zn,[20 – 27] etc. To get the polyaniline film, two Before used, copper powder was dipped in 1 M H2SO4 for
methods were used: electro-polymerization and chemical 30 minutes to remove oxide layer. Then rinsed by distilled
polymerization. Electro-polymerization is mainly used to water and ethanol three times, the powder was dried in
coat metal plates or poles with PANI, and chemical polymeriz- vacuum at 608C for 45 minutes. The number average
ation method is used when the matrixes are inert enough to diameter of the copper powder is 1.57 mm.
resist the corrosion action of aggressive media.
As fine copper powder is so small and active, it is difficult to 2.2 Coating Copper Powder with Polyaniline
coat it with polyaniline by electro-polymerization or just Polyethylene glycol, PVA was dissolved in distilled water
chemical polymerization method. In the present work, four and then some copper powder was added in these solutions,
methods were tried to form a pre-protective film first. Then after 1 hour, the pretreated copper powder was dissociated;
chemical polymerization method was applied to coat copper in another pretreatment method, copper powder was oxidized
with polyaniline. The morphologies of the composites in air at 1508C for 20 minutes.
obtained were characterized by transmission electron micro- The resulting 3.0 g pretreated powder in a beaker, then
scope (TEM) and field emission scanning electron microscope 40 mL distilled water and 0.4 mL aniline added at 208C.
(FESEM). Then infrared spectra (IR) and x-ray diffraction Next, the suspension was stirred for 15 minutes by a
(XRD) were used to analyze the components of the composite magnetic stirrer; 15 mL 5.3% APS solution was added
slowly within 1.5 hours. After another 2 hours, the composite
was filtered and dried in air at 608C for 2 hours. Composites
Received 9 November 2006; Accepted 20 November 2006.
Address correspondence to Binbo Jiang, College of Materials
synthesized with copper pretreated by PEG, PVA, and oxi-
Science & Chemical Engineering, Zhejiang University, Hangzhou dation are labeled as composite-PEG, composite-PVA, and
310027, China. E-mail: [email protected] composite-oxidation, respectively.
97
98 J. CHEN ET AL.

3 RESULTS AND DISCUSSION 3.2 Components of the Composites with Good

Morphology
3.1 Morphology and Structure of the Composite The x-ray diffraction of the composite-oxidation (Figure 2)
SEM and TEM were used to observe the morphology and shows that the main crystal materials in composite-oxidation
structure of these samples. are copper and Cu2O.
The SEM image of copper powder (Figure 1a) shows that The IR spectrum taken from the composite-oxidation
the original copper powder is global and has a wide distri- (Figure 3) shows the major characteristic vibrational bands of
bution. Its surface was covered with nano acantha. polyaniline 3438, 1631, 1468, 1384, 1291 cm21. The peak at
The SEM and TEM images of composite-PEG (Figures 1b 3438 is due to N-H vibration and deformation.[28] The peak
and 1c ) show that the surface of the particle changes and some- at 1631 cm21 is assigned to C55N vibration, the appearance
thing was coated on the surface. But there is sign of corrosion of this peak may indicate that the polyaniline we got is
in the particles. undoped.[29] The ring stretching of N-B-N (B denoted
The SEM and TEM images of composite-PVA (Figures 1d benzene ring) forms is observed at 1468 cm21. The C-N
and 1e) show the same pattern as was seen in composite-PEG. stretching band of amine appears at 1384, 1291 cm21 in
The SEM and TEM images of composite-oxidation (Figures Figure 3a.[31,30] Peaks at 2921 and 2851 cm21 can be
1g and 1h) show clearly that the particle has core-shell struc- observed in the spectra. These peaks may be assigned to the
ture, and their surface was coated with a compact film. And asymmetric and symmetric aliphatic C-H stretching vibrations,
there is no sign of corrosion in the particles. respectively.[30,31]
Through these images we may conclude that all these The structure formula of polyaniline is
methods could form core-shell structure composite. But there
. The intensity ratio
are signs of corrosion in composite-PEG and composite-
PVC. This may justify that PEG and PVC cannot form the of the peaks at 1600/1500 cm21 is a quantitative
effective films to protect copper from the corrosion of APS measure of the oxidation state of the polymer.[32] Compare
entirely. On the contrary, oxidation pretreatment seems effec- the two spectrums, we can see that the ratio is smaller, so the
tive, and its morphologies are good. polyaniline of composite-oxidation is mainly in reduced state.

FIG. 1. SEM image of original copper powder (a), SEM and TEM images of the composite-PEG (b) (c), composite-PVA (d) (e), composite-oxidation (f) (g).
 COATING FINE COPPER POWDER WITH POLYANILINE 99

FIG. 4. TG and DTG curves under nitrogen atmosphere of the composite-

oxidation.
FIG. 2. XRD pattern of the composite-oxidation.
may protect copper from being corroded. Second, the polyani-
From the measurement above we presume that: in compo- line film can absorb aniline, when APS solution was added.
site-oxidation, its core is copper, and its shell is composed of Polyaniline would grow on the surface well.
undoped reduced polyaniline and a little Cu2O.

3.4 Thermal Analysis of the Composites and Discussion

3.3 The Functions of Pretreatment of Oxidation
A thermogravimetric analyzer (TGA/SDTA851e Mettler,
It is very important to have copper powder pretreated. In Toledo, Switzerland) was used for measurements of the sample
other research, we did not have the copper pretreated. The from 50 to 6008C under nitrogen atmosphere at the heating
experiment was then taken with the same process. After rate of 108C/minute and under air atmosphere at the heating
the experiment, the solution was clarified for a moment, and rate of 158C/minute.
the clarifying liquid appeared blue. This may indicate that The TGA result of composite-oxidation under nitrogen
some copper was converted into Cu2þ. Some blue solution atmosphere (Figure 4) is similar to the previously reported
was then taken out and more APS added in it. A moment TG curves and DTG curves.[34,35] The TG and DTG curves
later, atrovirens polyaniline deposition was observed. This show that the composite mainly undergoes four stages of
may clarify that if copper is not protected first, APS will degradation: a) loss of adsorbent water; b) removal of small
oxidize copper directly and little PANI can be obtained. molecules, such as bound water, NH4þ and oligmers; c) degra-
There may be two functions of oxidation pretreatment. First, dation of polymeric chains; d) decomposition of polyaniline
oxidized at 1508C, some copper converted into CuO. As aniline backbone and benzene ring-opening accompanying by other
can be oxidized by CuO,[33] some polyaniline formed by in situ degradation processes (Figure 5).[26]
polymerization on the surface of fine copper powder before The TGA results for pure copper and the particulate compo-
APS was added, meanwhile CuO was converted into Cu2O site under air atmosphere (Figure 5) show that: First composite-
which can be seen in and XRD pattern, and the polymer film oxidation is more stable than pure copper; second there are
both weigh loss and weight gain stages in these curves and
weigh gain proceeded just after some weigh loss. These

FIG. 3. IR spectra of the composite-oxidation. FIG. 5. TG and DTG curves under air atmosphere of copper powder.
100 J. CHEN ET AL.

phenomena may due to the protective action and degradation of [12] Bateni, M.R., Szpunar, J.A., and Drew, R.A.L. (2002) Wear,
polyaniline. 253: 626– 639.
The final weight ratio of pure copper and composite- [13] Zhang, Y., Chen, F., Su, Y., Pan, J., and Xu, Z. (2001) The China
oxidation are 125.0% and 112.5%. As both the Cu2O and Joural of Nonferrous Coatings Technology, 11: 281–284.
degradation of polyaniline in composite-oxidation may cause [14] Zhang, L. and Wan, M. (2003) J. Phys. Chem. B, 107:
6748– 6753.
less weight gain, so the final weight gain of composite-
[15] Zhang, Q., Jin, H., and Jing, X. (1998) Journal of China Textile
oxidation is lower than that of pure copper.
University, 24: 114– 117.
[16] Li, Y. (2002) Prog. Chemistry, 14: 207– 211.
4 CONCLUSION
[17] Schauer, T., Joos, A., Dulog, L., and Eisenbach, C.D. (1998)
With copper pretreated by PEG, PVA, and oxidation, poly- Prog. Org. Coat., 33: 20 – 27.
aniline was coated on fine particulate copper powder by [18] Viva, F.A., Andrade, E.M., Molina, F.V., and Florit, M.I. (1999)
chemical polymerization method. It is found that better core- J. Electroanal. Chem., 471: 180– 189.
shell structure composite can only be generated with copper [19] Hatchett, D., Josowicz, M., and Janta, J. (1999) J. Electrochem.
pretreated by oxidation. The surface of the composite- Soc., 146: 4535– 4538.
oxidation is smooth and compact, and it is composed of [20] Vandana Shinde, S.R., Sainkar, B., and Patil, P.P. (2005) Corros.
undoped reduced polyaniline and Cu2O. Tested by thermogra- Sci., 47: 1352– 1369.
vimetric analyzer, the composites have four stages of degra- [21] ÖzyVlmaz, A.T. (2006) Surf. Coat. Technol., 200: 3918– 3925.
dation in nitrogen atmosphere and are more stable than fine [22] Özyılmaz, A.T., Erbil, M., and Yazıcı, B. (2005) Appl. Surf. Sci.,
copper powder in air. 252: 2092– 2100.
[23] Kinyanjui, J.M., Wijeratne, N.R., Hanks, J., and Hatchett, D.W.
5 REFERENCES (2006) Electrochim Acta, 51: 2825– 2835.
[24] Wang, T. and Tan, Y.-J. (2006) Corros. Sci., accepted.
[1] Patil, S., Sainkar, S.R., and Patil, P.P. (2004) Appl. Surf. Sci.,
[25] Martyak, N.M. (2004) Mater. Sci. Eng. A, 371: 57 – 64.
225: 204– 216.
[2] Jennings, G.K. and Laibinis, P.E. (1996) Colloids Surf. A, 116: [26] Fenelon, A.M. and Breslin, C.B. (2004) Synth. Met., 144:
105–114. 125– 131.
[3] Yan, J., Cui, H., Du, S., and He, Y. (2003) China Elastomeric., [27] Williams, G., Holness, R.J., Worsley, D.A., and McMurray, H.N.
13: 18 –21. (2004) Electrochem. Commun., 6: 549– 555.
[4] Li, S., Li, X., and Wang, X. (2004) Paint & Coatings Industry, [28] Gong, J., Yu, J., Chen, Y., and Qu, L. (2002) Mater. Lett., 57:
34: 16 –18. 765– 770.
[5] Li, S., Wu, N., and Li, Z. (1999) Acta Materiae Compositae [29] Ping, Z., Nauer, G.E., Neugebauer, H., and Theiner, J. (1997) J
Sinica, 16: 44– 49. Electroanal. Chem., 420: 301– 306.
[6] Bhattacharya, A. and De, A. (1996) Prog. Solid State Chem., 24: [30] Tang, J., Jing, X., Wang, B., and Wang, F. (1988) Synth. Met.,
141–181. 24: 231– 238.
[7] Malinauskas, A. (2001) Polymer, 42: 3957– 3972. [31] Sharma, S., Nirkhe, C., Pethkar, S., and Athawale, A.A. (2050)
[8] Tommesani, L., Brunoro, G., Frignani, A., Monticelli, C., and Dal Sens. Actuators, B, 85: 131– 136.
Colle, M. (1997) Corros. Sci., 39: 1221–1237. [32] Asturias, E. and Macdiarmid, A.G. (1989) Synth. Met., 29:
[9] Fenelon, A.M. and Breslin, C.B. (2001) J. Appl. Electrochem., 157– 162.
31: 509–516. [33] Sunderland, K., Brunetti, P., Spinu, L., Fang, J., Wang, Z., and
[10] Gao, B., Jiang, H., and Zhang, Z. (2000) J. Inorg. Chem., 16: Lu, W. (2004) Mater. Lett., 58: 3136– 3140.
669–674. [34] Wang, S., Tan, Z., Li, Y., Sun, L., and Zhang, T. (2006) Thermo-
[11] Gan, Z., Mao, Z., Shen, F., Li, J., and Ye, B. (1996) Mater. Sci. chim. Acta, 441: 191– 194.
Eng., 14: 38 – 42. [35] Yang, C. and Chen, C. (2005) Synth. Met., 153: 133– 136.

View publication stats