J Mater Sci: Mater Electron
DOI 10.1007/s10854-015-3773-x
Preparation of micro-size flake silver powder by planetary
ball mill
Qiuying Li1 • Shouchao Liu1 • Shourui Li1 • Weihong Guo1 • Chifei Wu1
Received: 2 August 2015 / Accepted: 7 September 2015
Ó Springer Science+Business Media New York 2015
Abstract Flake silver powder with controllable particle
size and specific surface area was prepared using planetary
ball mill by varying milling parameters including milling
time, revolution speed, and the weight ratio of balls to
powder (BRP). As-prepared flake silver powder was
characterized by laser particle analyzer, scanning electron
microscope, X-ray diffraction (XRD) and thermal gravity
analysis (TGA). Results showed that the flake silver pow-
der with the mean size of 4.0 lm and the specific area of
0.64 m2 g-1 can be obtained when the revolution speed
was 350 r/min, the BRP was 15:1, the grinding time was
approximately 30 h and a mixture of 1.5 % stearic acid and
0.5 % oleic acid was used as grinding aids. XRD patterns
confirmed that the milled powder was pure silver, indi-
cating there were no silver oxide and the alleged impurities
caused by oxidation reaction and friction and wear with the
increase of BRP value respectively under the present
experimental conditions. TGA showed that the obtained
powder was easy to wash and without absorption, which is
very important and beneficial to the conductivity of the
electrodes.
1 Introduction
For its application as a clean and renewable energy source,
crystalline silicon solar cell has been paid more and more
attention with the energy crisis and environmental
& Qiuying Li
liqiuying75713@163.com
1 energy ball milling, photo-induced method, thermal pro-
School of Material Science and Engineering, East China
University of Science and Technology, 130 Meilong Rd,
Shanghai 200237, People’s Republic of China
problems being more serious [1, 2]. Nowadays, silicon
solar cells have been applied in industrial production
because of mature technology and high conversion effi-
ciency. Generally speaking, silver electrodes are important
components and play an important role in the conversion
efficiency of silicon solar cells, which includes front-side
and back-side silver electrodes. Silver electronic paste is
the key material for fabricating the electrodes. In general,
the silver electronic paste of silicon solar cell consists of
three main components: (1) silver particle as the conduc-
tive phase; (2) glasses as binding phase; (3) organic med-
ium as dispersant and supplying rheological performance
for the paste. The weight percent of silver particles in
electronic paste is more than 80 % [3]. Therefore, silver
particles as the conductive phase is the most important one
that determines the conductivity and compactness of the
electrodes directly.
For back-side silver electrode, its function is to output
photo-generated current that collected by back-side alu-
minum electrode from silicon wafer. Therefore, back-side
silver electrode is needed to have excellent electrical
conductivity and welding performance, large welding ten-
sion with silicon wafer and good plyability with back-side
aluminum electrode [4]. As a result, flake silver powders
are necessary due to the good formation of conductive
channels through the line contacts or surface contacts
between sheet metal instead of dot–dot contact of spherical
particles. In addition to excellent photovoltaic perfor-
mance, the paste and solar cell prepared by flake silver
powders own better adhesion, improved solderability and
paste viscosity and reduced silver content. So far, the
preparation methods for flake silver powders include high
cessed method, heterogeneous crystals nuclear method and
template method and so on, whereas the present industrial
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preparation of flake silver powders is mainly by ball mil-
ling process due to simple craft and high efficiency [5].
In the current marketplace, there are few flake silver
powders specially developed for back-side silver paste and
the product specifications are far from enough to meet
market demand. As such, in this paper we studied the
process of manufacturing flake silver powders by ball
milling. Some predominantly influential factors, such as
the kind of grinding aids, ball milling time, rotation speed
of the planet carrier and the weight ratio of balls to powder,
were investigated systematically. Finally, the flake silver
powder with controllable particle size and specific surface
area have been fabricated under the optimal processing
parameters. The most important is that the flake silver
powder can be easily cleaned, which is beneficial to its
conductivity and industrialization.
2 Experiment section
2.1 Materials and samples preparation
Silver (Ag 99.95 % purity, mean particle size 0.65 lm,
bulk density 1.16 g cm-3, tap density 2.31 g cm-3) pow-
der was used as raw material. Absolute ethyl alcohol
(C2H6O, AR, Shanghai Titan Scientific Co., Ltd, China),
stearic acid (C18H36O2, AR, Shanghai Lingfeng Chemical
Reagent Co., Ltd, China), oleic acid (C18H34O2, CP,
Shanghai Lingfeng Chemical Reagent Co., Ltd, China)
were used as the dispersion medium, grinding aid agents
respectively. All reagents were used as received without
further purification.
The transformation in particle micro-morphology and size
of Ag was carried out by planetary ball mill (QM1SP2) in a
agate jar using agate balls of 2–6 mm diameter. Figure 1
shows a schematic diagram of the planetary ball mill [6].
During the preparation process of flake silver powders
by planetary ball mill, every time the ball mill adopts
double pots symmetrically. To obtain satisfactory product,
Fig. 1 Schematic diagram of the planetary ball mill and the jar
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J Mater Sci: Mater Electron
a series of experiments were carried out under different
milling parameters. In a typical procedure, a certain
amount of stearic acid and oleic acid were dissolved in
ethyl alcohol, then the mixed solution was added into agate
jar containing well-selected agate balls and silver powders.
The filling coefficient of jar was controlled between 0.25
and 0.3. When the ball milling ended, the silver powder
was separated from slurry and washed with alcohol for
three times, then dried at 60 °C in vacuum oven for 12 h.
2.2 Characterization
The micrographs of the milled powders were determined
by a Hitachi S-4800 scanning electron microscope (SEM)
with an accelerating potential of 15 kV. The preparation
for milled powders on scanning electron microscope is to
disperse the sample in ethanol and apply proper amount to
the aluminum foil which adheres to the electric conductive
adhesive, then put it on the sample platform for observa-
tion. The phase identification and purity of the products
were monitored by X-ray diffraction equipped with Cu Ka
radiation (Rigaku, Japan). Thermal gravity analysis (TGA)
was used to detect whether the surface of milled flake silver
powders adsorb grinding aids. TGA of silver powder was
operated on a NETZSCH STA 449F thermoanalyzer by
heating the sample from room temperature to 500 °C at a
heating rate of 10 K/min under an air atmosphere. The
average particle size and size distribution were measured
with LS230 laser size analyzer (Beckman Coulter). The
specific surface and tap density were tested by a specific
surface area analyzer (ASAP2460) and a particles density
tester (HY-100) respectively.
3 Results and discussion
3.1 Choice of grinding aids
During the ball milling process, particles are repeatedly
flattened, fractured, and welded. Fracture and welding are
the two basic events that produce a permanent exchange of
matter between particles. To avoid welding, the sur-
face property and dispersion effect of silver particles could
be controlled by the addition of various grinding aids.
Their adsorption actions on the surface of particles can
stabilize the silver particles suspension and prevent
agglomeration of small particles.
In our experiment, single stearic acid, single oleic acid and
a mixture of stearic acid and oleic acid were selected as the
grinding aids respectively. The total dosage was controlled in
2 wt% to the weight of starting powders [7, 8]. Figure 2
showed SEM images of raw particles and 18 h ball milled
silver powders when different grinding aids were used,
J Mater Sci: Mater Electron
Fig. 2 SEM images of raw and milled powders applying different
grinding aids. a Raw powders, b stearic acid, c oleic acid, and d a
mixture of 1.5 % stearic acid and 0.5 % oleic acid
which were carried out under the condition of 200 r/min and
BRP of 15:1. As seen from Fig. 2a, the morphology of raw
particles was anomalous and the particle size was badly
asymmetric. From Fig. 2b–d, we can see that different levels
of flaky deformation have occurred obviously. Furthermore,
few amount raw particles in Fig. 2d can be found and most of
the particles have been flattened into sheets through micro-
forging and formed layered structures compared with
Fig. 2b, c, from which we can clearly observe the coexis-
tence of a great number of small, raw particles and some
flakes. It demonstrated that the mixed use of stearic acid and
oleic acid tended to accelerate the plastic deformation pro-
cess under same conditions. Moreover, relatively little
dosage of oleic acid was used in experiments owing to its
high viscosity and difficult removal.
3.2 Influence of the revolution speed of planetary
ball mill
The energy of ball milling and movement of grinding
medium is relative to the speed of the tank [9–11]. There
are different kinds of motion state for the grinding medium
depending on the revolution speed, it includes (a) state of
adhesion, (b) state of pouring, (c) state of throwing down,
at which materials will be subject to the biggest impact
force and abrasive effect. Figure 3 shows a schematic
diagram of motion states of the grinding medium relying
on the revolution speed. In the actual process, the move-
ment of grinding medium is very complex and may be
known to be a blend of two or three motion states. The
comprehensive effect of these movements will make the
original silver powders into sheets. This experiment based
on the weight ratio of ball to powder at 15:1 and took the
speed of carrier with 200, 270 and 350 r/min. Figure 4
showed the SEM images of silver particles prepared at
different speed when the ball milling time is 30 h. As can
be seen, all milled samples showed a sufficient plastic
deformation. However, a large number of small particles
can be seen from Fig. 4a, b. In contrast, the radius–thick-
ness ratio in Fig. 4c is higher and the uniformity is better.
3.3 Study of the weight ratio of balls to powder
(BRP)
The weight ratio of balls to powder (BRP) is an important
variable in the milling process, which directly influenced
the flaky degree and the quality of silver particles [12, 13].
The low BRP may not be easy to obtain lamellar grains in
that impact energy and shear energy are not sufficient to
flatten particles into flakes. Whereas, a high BRP, because
of an increase in the weight proportion of the balls, the
probability of collision per unit time increases and conse-
quently more energy is transferred to the raw materials, so
morphology formation takes place faster. But if the BRP
exceeds the optimum value, there will be excess of wear
between the balls, balls and inner wall of the jar. As a
result, it will destroy the purity of flake silver powders and
bring about the decrease in electric conductivity. This
paper took the weight ratio of balls to powder with 9:1,
12:1, 15:1 respectively and the revolution speed at 350 r/
min to investigate the influence on the milled powders.
Figure 5 showed the SEM images of milled flake silver
powders for 30 h under different BRP value. It can be seen
from Fig. 5 that all milled samples showed a sufficient
plastic deformation and a huge increase of the size of
microflakes from the nanopowders. It proved that the
impact of collision in the milling process has tremendously
disintegrated the agglomerated particles into fragments and
enabled them form layered structures which are charac-
teristic of ductile–ductile powders after an extended mil-
ling time of 30 h. However, as is clear that the uniformity
and dispersability of flake powders in Fig. 5c is better than
a and b with the increase of BRP value.
Figure 6 illustrated the XRD patterns of flake silvers
obtained under different BRP value, which was used for the
phase identification and to detect whether the obtained
flake silver powders contain the alleged impurities caused
by friction and wear with the increase of BRP value under
the present experimental conditions. As can be seen, all the
peaks are in accordance with standard crystalline silver
card (JCPDS Cards No. 04-0783) [14], indicating the
obtained powder is indeed silver powder with face-cen-
tered cubic structure. At the same time, there do not con-
tain any significant diffraction peaks such as SiO2 and
Ag2O except Ag. This is to say, the as-milled flake powder
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 J Mater Sci: Mater Electron

Fig. 3 Motion states of the

grinding medium as a function
of revolution speed. a State of
adhesion, b state of pouring, and
c state of throwing down

Fig. 4 SEM images of flake silvers after ball milling for 30 h at different speed a 200 r/min, b 270 r/min, and c 350 r/min

Fig. 5 SEM images of flake silvers obtained under different BRP value a 9:1, b 12:1, and c 15:1

(111) is very pure, which excluded the occurrence of oxidation

reaction and the alleged impurities caused by friction and
wear with the increase of BRP value.

3.4 Influence of different ball milling time

Intensity(a.u.)

(200) on the morphology and particle size of silver

(220)
(311) powders
(222)
(c)
Milling time is one of the most important parameters for
affecting powder structure and size [15, 16]. Based on above
(b)
experimental results, in this section the BRP value and rev-
(a)
olution speed were set to be 15:1 and 350 r/min, respectively.
The grinding time was varied from 6 to 36 h. Figure 7 dis-
20 30 40 50 60 70 80 90 played the mean particle size versus milling time with the
2 Theta(degree) associated particle size distribution for 30 and 36 h. It can be
seen that in the forepart of the milling process, the mean
Fig. 6 XRD patterns of flake powders obtained under different BRP
value a 9:1, b 12:1, and c 15:1 particle size of powders decreased rapidly from *3.6 to

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J Mater Sci: Mater Electron

4.4

4.2

Mean particle size(µm)

4.0

3.8

3.6

3.4

3.2

3.0

2.8
0 6 12 18 24 30 36
Time(h)

7 7
30h 36h
6 6

5 5
Volume (%)

Volume (%)
4 4

3 3

2 2

1 1

0 0
0.01 0.1 1 10 100 0.01 0.1 1 10 100
Particle Diameter(µm) Particle Diameter(µm)

Fig. 7 Mean particle size of the flake silver powder versus milling time and size distribution for 30 and 36 h

*2.9 lm. This is because the grinding aids penetrated into

gap between silver particles as so to destroy the soft
agglomeration. However, as the milling time was prolonged,
the mean particle size of powders increased owing to the
great mechanical force from frication between mill media, as
a result, the silver powder precursor became flake particles
and the thickness of the flakes decreased gradually. When the
milling time was further prolonged to 30 h, the growth trend
was limited and the mean particle size of powders decreased
slowly. It can be assigned to the work hardening and to the
reduction of plasticity after a long and repeated cold welding,
so the fatigue fragmentation happened easily along the
margin of flakes resulting in the decrease of particle size. As
it exhibited in Fig. 8c, d, when globe mill proceeded from 30
to 36 h, a few of fragments appeared in powders and the
homogeneity of powders deteriorated, which agreed with the
particle size distribution curve in Fig. 7. As it can be seen in
Fig. 8 SEM images of silver flakes after ball milling for: a 12 h,
Fig. 7, the mean particle size decreased from 4.23 to 3.87 lm b 18 h, c 30 h, and d 36 h
when the time was prolonged from 24 to 36 h. Considering
the particle size and homogeneity, the optimal milling time In conclusion, the experimental results based on the
was chosen to be 30 h, which can meet corresponding above discussion showed that when the BRP value, revo-
requirements. lution speed and milling time were set to be 15:1, 350 r/

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120
110
100
Mass /%
90
80
70
60
50
100 200 300 400 500
Temperature /°C
Fig. 9 TGA curve of flake silver powder obtained under the
optimized condition
min, and 30 h respectively, the obtained powders can sat-
isfy corresponding proposed requests. As-prepared flake
powder has a specific area of 0.64 m2 g-1 and tap density
of 3.36 g cm-3. Its dispersability and size uniformity
behave well.
In general, the adsorbed grinding aids on the surface of
silver particles is a great handicap to the conductivity. So
the choice and removal of grinding aids are very important
considering its practical application. Figure 9 showed the
TG analysis of the powders prepared under the optimized
condition. It was made to detect whether existing residual
grinding aids absorbed on the surface of silver powders
[17]. The curve of TGA showed that no featured weight loss
was observed except for a slight loss at 50 °C, which may
be a trace of residual alcohol during the drying process. This
suggested that the chemical absorption of oleic acid, which
has effect on physical properties and conductivity, was
removed completely. A kind of flake silver powders without
absorption and easy cleaning was obtained.
4 Conclusion
In general, flake silver powders in microscale used for solar
cell back-side paste have been successfully prepared via a
high-energy ball milling. The ball milling parameters
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J Mater Sci: Mater Electron
including the kinds of grinding aids, weight ratio of balls to
powder, revolution speed and milling time were systemat-
ically investigated. As a conclusion, optimized milling
parameters was found to be 15:1 of BRP value, 350 r/min of
revolution speed and 30 h of milling time when a mixture of
1.5 % stearic acid and 0.5 % oleic acid was selected as
grinding aids. Under optimized parameters, the as-prepared
flake powder with an excellent dispersability and size uni-
formity has a specific area of 0.64 m2 g-1 and tap density of
3.36 g cm-3 and the mean particle size is 4 lm. The XRD
and TGA results showed the obtained silver powder is pure
and without absorption of grinding aids, which can satisfy
corresponding proposed requirements.
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