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Coating Fine Copper Powder with Polyaniline

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DOI: 10.1080/01932690701688490

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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

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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,
electromagnetic interference (EMI) shielding, electrostatic dis-
sipation, etc.[1] As a noble metal, it is inert in air, but when its
size reduces, oxidation becomes apparent. To improve copper
powder’s stability, many materials were coated on it such as
surfactant, conducting polymers, Benzotriazole, silver, silicon,
titanium, etc.[2 – 13]
Polyaniline (PANI) is one of the promising conducting
polymers due to its comparative stability in air, easy synthesis,
low price, and high conductivity.[14 – 19] Until now, polyaniline
successfully has been coated on many metals, such as Cu, Ni,
Al, Pt, Fe, Zn,[20 – 27] etc. To get the polyaniline film, two
methods were used: electro-polymerization and chemical
polymerization. Electro-polymerization is mainly used to
coat metal plates or poles with PANI, and chemical polymeriz-
ation method is used when the matrixes are inert enough to
resist the corrosion action of aggressive media.
As fine copper powder is so small and active, it is difficult to
coat it with polyaniline by electro-polymerization or just
chemical polymerization method. In the present work, four
methods were tried to form a pre-protective film first. Then
chemical polymerization method was applied to coat copper
with polyaniline. The morphologies of the composites
obtained were characterized by transmission electron micro-
scope (TEM) and field emission scanning electron microscope
(FESEM). Then infrared spectra (IR) and x-ray diffraction
(XRD) were used to analyze the components of the composite
Received 9 November 2006; Accepted 20 November 2006.
Address correspondence to Binbo Jiang, College of Materials
Science & Chemical Engineering, Zhejiang University, Hangzhou
310027, China. E-mail: soar03@tom.com
97
of good morphology. The thermal stability and degradation
behaviors of the composite were studied by thermogravimetric
analysis (TGA) under nitrogen and air atmosphere.
2 EXPERIMENTAL
2.1 Materials
In this article, A.R grade chemicals were used. Aniline,
ammonium persulfate ((NH4)2S2O8, APS), polyethylene
glycol (PEG), polyvinyl alcohol (PVA), ethanol, and distilled
water were used as received.
Before used, copper powder was dipped in 1 M H2SO4 for
30 minutes to remove oxide layer. Then rinsed by distilled
water and ethanol three times, the powder was dried in
vacuum at 608C for 45 minutes. The number average
diameter of the copper powder is 1.57 mm.
2.2 Coating Copper Powder with Polyaniline
Polyethylene glycol, PVA was dissolved in distilled water
and then some copper powder was added in these solutions,
after 1 hour, the pretreated copper powder was dissociated;
in another pretreatment method, copper powder was oxidized
in air at 1508C for 20 minutes.
The resulting 3.0 g pretreated powder in a beaker, then
40 mL distilled water and 0.4 mL aniline added at 208C.
Next, the suspension was stirred for 15 minutes by a
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
synthesized with copper pretreated by PEG, PVA, and oxi-
dation are labeled as composite-PEG, composite-PVA, and
composite-oxidation, respectively.
98
3 RESULTS AND DISCUSSION
3.1 Morphology and Structure of the Composite
SEM and TEM were used to observe the morphology and
structure of these samples.
The SEM image of copper powder (Figure 1a) shows that
the original copper powder is global and has a wide distri-
bution. Its surface was covered with nano acantha.
The SEM and TEM images of composite-PEG (Figures 1b
and 1c ) show that the surface of the particle changes and some-
thing was coated on the surface. But there is sign of corrosion
in the particles.
The SEM and TEM images of composite-PVA (Figures 1d
and 1e) show the same pattern as was seen in composite-PEG.
The SEM and TEM images of composite-oxidation (Figures
1g and 1h) show clearly that the particle has core-shell struc-
ture, and their surface was coated with a compact film. And
there is no sign of corrosion in the particles.
Through these images we may conclude that all these
methods could form core-shell structure composite. But there
are signs of corrosion in composite-PEG and composite-
PVC. This may justify that PEG and PVC cannot form the
effective films to protect copper from the corrosion of APS
entirely. On the contrary, oxidation pretreatment seems effec-
tive, and its morphologies are good.
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).
J. CHEN ET AL.
3.2 Components of the Composites with Good
Morphology
The x-ray diffraction of the composite-oxidation (Figure 2)
shows that the main crystal materials in composite-oxidation
are copper and Cu2O.
The IR spectrum taken from the composite-oxidation
(Figure 3) shows the major characteristic vibrational bands of
polyaniline 3438, 1631, 1468, 1384, 1291 cm21. The peak at
3438 is due to N-H vibration and deformation.[28] The peak
at 1631 cm21 is assigned to C55N vibration, the appearance
of this peak may indicate that the polyaniline we got is
undoped.[29] The ring stretching of N-B-N (B denoted
benzene ring) forms is observed at 1468 cm21. The C-N
stretching band of amine appears at 1384, 1291 cm21 in
Figure 3a.[31,30] Peaks at 2921 and 2851 cm21 can be
observed in the spectra. These peaks may be assigned to the
asymmetric and symmetric aliphatic C-H stretching vibrations,
respectively.[30,31]
The structure formula of polyaniline is
. The intensity ratio
of the peaks at 1600/1500 cm21 is a quantitative
measure of the oxidation state of the polymer.[32] Compare
the two spectrums, we can see that the ratio is smaller, so the
polyaniline of composite-oxidation is mainly in reduced state.
 COATING FINE COPPER POWDER WITH POLYANILINE
FIG. 2. XRD pattern of the composite-oxidation.
From the measurement above we presume that: in compo-
site-oxidation, its core is copper, and its shell is composed of
undoped reduced polyaniline and a little Cu2O.
3.3 The Functions of Pretreatment of Oxidation
It is very important to have copper powder pretreated. In
other research, we did not have the copper pretreated. The
experiment was then taken with the same process. After
the experiment, the solution was clarified for a moment, and
the clarifying liquid appeared blue. This may indicate that
some copper was converted into Cu2þ. Some blue solution
was then taken out and more APS added in it. A moment
later, atrovirens polyaniline deposition was observed. This
may clarify that if copper is not protected first, APS will
oxidize copper directly and little PANI can be obtained.
There may be two functions of oxidation pretreatment. First,
oxidized at 1508C, some copper converted into CuO. As aniline
can be oxidized by CuO,[33] some polyaniline formed by in situ
polymerization on the surface of fine copper powder before
APS was added, meanwhile CuO was converted into Cu2O
which can be seen in and XRD pattern, and the polymer film
FIG. 3. IR spectra of the composite-oxidation.
99
FIG. 4. TG and DTG curves under nitrogen atmosphere of the composite-
oxidation.
may protect copper from being corroded. Second, the polyani-
line film can absorb aniline, when APS solution was added.
Polyaniline would grow on the surface well.
3.4 Thermal Analysis of the Composites and Discussion
A thermogravimetric analyzer (TGA/SDTA851e Mettler,
Toledo, Switzerland) was used for measurements of the sample
from 50 to 6008C under nitrogen atmosphere at the heating
rate of 108C/minute and under air atmosphere at the heating
rate of 158C/minute.
The TGA result of composite-oxidation under nitrogen
atmosphere (Figure 4) is similar to the previously reported
TG curves and DTG curves.[34,35] The TG and DTG curves
show that the composite mainly undergoes four stages of
degradation: a) loss of adsorbent water; b) removal of small
molecules, such as bound water, NH4þ and oligmers; c) degra-
dation of polymeric chains; d) decomposition of polyaniline
backbone and benzene ring-opening accompanying by other
degradation processes (Figure 5).[26]
The TGA results for pure copper and the particulate compo-
site under air atmosphere (Figure 5) show that: First composite-
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. 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
polyaniline.
The final weight ratio of pure copper and composite-
oxidation are 125.0% and 112.5%. As both the Cu2O and
degradation of polyaniline in composite-oxidation may cause
less weight gain, so the final weight gain of composite-
oxidation is lower than that of pure copper.
4 CONCLUSION
With copper pretreated by PEG, PVA, and oxidation, poly-
aniline was coated on fine particulate copper powder by
chemical polymerization method. It is found that better core-
shell structure composite can only be generated with copper
pretreated by oxidation. The surface of the composite-
oxidation is smooth and compact, and it is composed of
undoped reduced polyaniline and Cu2O. Tested by thermogra-
vimetric analyzer, the composites have four stages of degra-
dation in nitrogen atmosphere and are more stable than fine
copper powder in air.
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