Materials Letters 57 (2003) 2280 – 2286

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Effect of silicon addition on grain refinement of copper alloys

Keiichiro Oishi *, Isao Sasaki, Junichi Otani
Sambo Copper alloy Co., Ltd. Research and Development, 374, 8-cho, Sanbo-cho, Sakai, Osaka 590-0906, Japan

Received 1 August 2002; accepted 27 September 2002

Abstract

The influence of additional elements on grain refinement of copper alloys was considered. It was found that the addition of
silicon to Cu – Zn alloys increases number of nucleation sites, and the addition of minute amounts of cobalt to Cu – Zn – Si alloys
inhibits grain growth. Exploiting these effects, a Cu – 10Zn – 2.0Si – 0.1Co alloy with fine grains of approximately 1.6 Am was
obtained. The increase in the number of nucleation sites is considered to be due to the decreasing stacking fault energy upon the
addition of silicon. Inhibition of grain growth is considered to be due to the formation of fine precipitates upon the addition of
cobalt.
D 2002 Elsevier Science B.V. All rights reserved.

Keywords: Grain refinement; Fine grain; Nucleation sites; Stacking fault energy; Precipitates; Copper alloys; Mechanical properties; Electronic
materials

1. Introduction tions have been successful in the laboratory experi-

Grain refinement of metals has received consider-
able attention, because the strength of metals is
proportional to grain size (d
1/2) according to the
Hall – Petch relationship [1,2]. It is important to
develop high-strength materials for use in various
fields. The copper alloys investigated in this research
are unexceptional, and there are great demands for the
improvements in their material strength in the field of
connector materials such as phosphor bronze, electri-
cal and electronic components and structural mate-
rials.
Various investigations in grain refinement of met-
als have been carried out [3– 8], and these investiga-
* Corresponding author. Tel.: +81-72-233-9208; fax: +81-72-
223-7233.
E-mail address: oishik@sambo.co.jp (K. Oishi).
ments to the submicron order. However, most of the
previous experimental results have been difficult to
apply in mass production, because special methods,
such as high-strain working [3– 7] and low-temper-
ature working [8], were used to increase the accumu-
lation of strain energy. Hence, the development of
metals with fine grains that can be manufactured by
general manufacturing methods is needed in many
fields of engineering.
The purpose of this investigation is to refine
recrystallized grains of metals from an approach of
material properties, and moreover, to clarify the
mechanism of such grain refinement. Concretely,
we develop metals with low stacking fault energy
by investigating the alloy composition, and obtain
metals with a fine recrystallized structure by facil-
itating the increase in the accumulation of strain
energy.

0167-577X/02/$ - see front matter D 2002 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0167-577X(02)01211-9
 K. Oishi et al. / Materials Letters 57 (2003) 2280–2286 2281

2. Experimental procedure grain growth. Hence, we prepared Cu – 10Zn – Si alloys

The chemical composition and the electron –atom
ratio of specimens are listed in Table 1. Throughout
this paper, the specimen composition is expressed in
mass percent, unless otherwise stated. The following
are important in refining recrystallized grains.
(1) Increase in the number of nucleation sites in
recrystallization.
(2) Inhibition of grain growth.
Increasing the accumulation of strain energy,
which is the driving force of recrystallization, leads
to an increase in the number of nucleation sites.
Decreasing stacking fault energy lessens the cross slip
of dislocations, facilitating an increase in dislocation
density. It is known that stacking fault energy depends
mainly on the electron – atom ratio, and thus, the
addition of a high-valence element decreases the
stacking fault energy of alloys. We prepared Cu –
10Zn alloys to which approximately 1% aluminum,
manganese, nickel, silicon or tin was added, and Cu –
10Zn alloys to which 0.3 –2.0% silicon, the valence of
which is four, was added, which will decrease the
stacking fault energy considerably.
The dispersion of fine precipitates, which retard
grain boundary migration, has an effect on inhibiting
with minute amounts of cobalt, which is expected to
form a precipitate with silicon, which will decrease the
stacking fault energy of alloys. The cobalt concentra-
tion is in the range of 0.029 –0.1%.
Specimens were prepared at atmospheric pressure.
The method of specimen preparation is as follows.
Having been kept at a temperature of 1123 K for 7.2
ks, the ingots whose size were 180  90  25 mm3
were hot-rolled to 6.0 mm thickness. The 6.0-mm-
thick plates were cold-rolled to 1.0 mm thickness.
Then cold-rolled plates were annealed for 3.6 ks in a
temperature range of 523 –973 K.
The experiments carried out on annealed specimens
with a recrystallized structure are as follows: observa-
tion of microstructure, hardness testing, tensile testing
and measurement of electrical resistivity. The micro-
structure of specimens was observed using an optical
microscope and a transmission electron microscope.
Specimens for structure observation with an optical
microscope were mounted in room-temperature-set-
ting polyester resin and their cross sections were
polished by a buff rag and then etched in an aqueous
solution of hydrogen peroxide and ammonia. The
grain size of specimens was determined using the
intercept method with optical micrographs. A Vickers
hardness tester was used for measuring the surface
hardness of specimens. Tensile testing was carried out

Table 1
Chemical composition and electron – atom ratio of specimens
Specimen Chemical composition (mass%) Electron –
number Cu Zn Si Al Mn Ni Sn Co ratio atom

1 balance 10.31 – – – – – – 1.10

2 balance 10.19 – 0.89 – – – – 1.14
3 balance 10.35 – – 0.90 – – – 1.09
4 balance 10.26 – – – 1.04 – – 1.09
5 balance 10.14 – – – – 1.00 – 1.12
6 balance 10.06 0.30 – – – – – 1.12
7 balance 10.02 0.49 – – – – – 1.13
8 balance 10.00 0.98 – – – – – 1.16
9 balance 10.30 1.50 – – – – – 1.20
10 balance 9.87 2.07 – – – – – 1.23
11 balance 9.72 0.33 – – – – 0.110 1.12
12 balance 10.00 0.50 – – – – 0.115 1.13
13 balance 9.96 1.02 – – – – 0.110 1.16
14 balance 10.17 1.51 – – – – 0.116 1.20
15 balance 10.11 2.01 – – – – 0.112 1.23
16 balance 10.28 1.51 – – – – 0.029 1.20
17 balance 10.24 1.51 – – – – 0.057 1.20
2282 K. Oishi et al. / Materials Letters 57 (2003) 2280–2286

on an Amsler-type universal testing machine. The
tensile strength, 0.2% proof stress and elongation were
measured. Electrical resistivity was converted from the
electrical conductivity measured using Sigmatest D
2.068 from Forester Instruments.
3. Results and discussion
3.1. Increasing number of nucleation sites
The annealing temperature, the grain size and the
mechanical properties obtained for all specimens
with a recrystallized structure are listed in Table
2. The grain size of alloys with 1% aluminum,
manganese, nickel or tin is from 3.8 to 4.9 Am.
The grain size of these specimens tends to become
smaller with increasing electron –atom ratio. Next,
we describe the results for Cu – 10Zn – Si alloys.
Fig. 1 shows the optical micrograph whereas Fig.
2 shows the transmission electron micrograph of the
Cu –10Zn– 1.0Si alloy. Annealing twins can be seen
in Fig. 2 and elongation is sufficient, which con-
firm that the specimen has a recrystallized structure.
The Cu – 10Zn –1.0Si alloy has a grain size of 2.4
Am, the finest grain size of Cu – 10Zn alloys with
1% aluminum, manganese, nickel, silicon or tin.
The grain size of specimens annealed at recrystalliza-
tion temperature is plotted as a function of silicon
concentration in Fig. 3. The grain size of the Cu –
10Zn– Si alloy becomes smaller with increasing sili-
con concentration. Gradually, the extent of variation
of grain size decreases in high silicon concentration;
the effect of silicon on grain refinement becomes
weak according to an increase in silicon concentra-
tion.
The discussion focuses on the influence of the
addition of silicon to Cu – 10Zn alloys on grain
refinement. According to Howie and Swann [9], the
addition of solute atoms to alloys lowers the stacking
fault energy, and the energy depends mainly on the
electron – atom ratio of alloys. According to Gal-
lagher [10], the lower the stacking fault energy is,
the higher the valence of the added solute. As shown
in Table 1, the electron – atom ratio of Cu –10Zn–
1.0Si is the lowest in the Cu – 10Zn alloys with 1%
aluminum, manganese, nickel, silicon or tin. And
silicon, the valence of which is four, has a high
valence.
We discuss the influence of the addition of
silicon on the decrease in stacking fault energy.
Stacking fault energy of Cu –Zn and Cu –Si alloys
is plotted as a function of the electron –atom ratio
of each alloy in Fig. 4 [9– 11]. The stacking fault

Table 2
Grain size and mechanical properties of specimens
Specimen Annealing Hardness Tensile stress 0.2 % Proof Elongation Grain size
number temperature (K) HV5 (N mm
2) stress (N mm
2) (%) (Am)
1 623 85.8 322 198 43.7 4.0
2 623 98.4 352 221 43.0 3.8
3 673 91.2 331 187 43.5 4.6
4 623 89.9 325 203 40.1 4.9
5 623 109 371 282 41.7 3.9
6 623 98.4 347 229 41.1 3.2
7 623 106 366 256 41.4 2.6
8 623 126 416 308 45.0 2.4
9 623 142 481 312 43.8 2.2
10 623 159 528 360 43.1 1.9
11 723 115 383 286 36.4 2.8
12 723 112 381 287 36.8 2.3
13 673 161 498 403 31.6 2.0
14 673 159 509 415 40.0 1.7
15 673 167 558 438 36.8 1.6
16 673 140 483 333 43.7 2.0
17 673 150 497 372 40.5 1.8
 K. Oishi et al. / Materials Letters 57 (2003) 2280–2286 2283

Fig. 1. Optical micrograph of the Cu – 10Zn – 1.0Si alloy annealed at

623 K for 3.6 ks shows grain size of 2.4 Am. Fig. 3. Grain size of specimens annealed at recrystallization
temperature plotted as a function of silicon concentration. Circles
show the data for Cu – 10Zn – Si alloys, triangles show the data for
energy tends to decrease with increasing electron – Cu – 10Zn – Si – 0.1Co alloys.
atom ratio, and the plot for the Cu –Si alloy is
lower than that for the Cu – Zn alloy at the same interpolation between the two binary systems [12].
electron – atom ratio. This implies that stacking fault energy of a ternary
Furthermore, there is a stacking fault parameter a system is lower than that of a binary system having
related to its energy. The values of the stacking fault the same electron – atom ratio.
parameter a, determined from the displacement of the
peaks of diffraction lines in X-ray powder spectra,
increase with decreasing stacking fault energy. In the
ternary system, the stacking fault parameter a shows a
positive deviation from the prediction made by linear

Fig. 2. TEM micrograph of Cu – 10Zn – 1.0Si alloy annealed at 623 Fig. 4. Variation of stacking fault energy plotted as a function of
K for 3.6 ks, showing recrystallized fine grains and annealing twins. electron – atom ratio in copper-base alloys [9 – 11].
2284 K. Oishi et al. / Materials Letters 57 (2003) 2280–2286
Therefore, we consider that the stacking fault
energy of a Cu –10Zn– Si alloy decreases consider-
ably for two reasons. One is that the alloying elements
of this system are zinc, the valence of which is two,
and silicon, the valence of which is four. The other is
that this alloy is a ternary system. Hence, we consider
that the large decrease in the stacking fault energy of
alloys easily leads to the accumulation of large strain
energy, and this results in an increase in the number of
nucleation sites.
3.2. Inhibition of grain growth
We discuss the influence of the addition of cobalt
on the inhibition of grain growth. Fig. 5 shows the
relationship between grain size and annealing temper-
ature. Conspicuous grain growth of the Cu – 10Zn –
1.5Si alloy takes place as annealing temperature
increases, while that of the Cu –10Zn– 1.5Si – 0.1Co
alloy is inhibited compared with the former. Further-
more, cobalt addition affects the grain size of Cu –
10Zn –Si alloys annealed at recrystallization temper-
ature. It is confirmed in Fig. 3 that the grain size of
Cu –10Zn– Si– 0.1Co alloys is smaller than that of
Fig. 5. Grain size of annealed specimens plotted as a function of
annealing temperature. Circles show the data for the Cu – 10Zn –
1.5Si alloy, triangles show the data for Cu – 10Zn – 1.5Si – 0.1Co
alloys.
Fig. 6. TEM micrograph of the Cu – 10Zn – 1.5Si – 0.1Co alloy
annealed at 773 K for 3.6 ks, showing fine precipitates as particles.
Cu – 10Zn – Si alloys over the entire concentration
range of the experiment.
This inhibition of grain growth upon adding cobalt
is considered to be due to the formation of fine
precipitates. Fig. 6 shows the transmission electron
micrograph of the Cu – 10Zn – 1.5Si – 0.1Co alloy
annealed at 773 K. Particles can be observed in the
grain boundary and grain. On the other hand, no
particles could be confirmed in the microstructure of
Cu – 10Zn –Si alloys. Observation of the microstruc-
ture of the Cu – 10Zn – 1.5Si – 0.1Co alloys using a
transmission electron microscope revealed the pres-
ence of fine precipitates.
In addition, we can also confirm the formation of
fine precipitates by the following phenomenon. Fig. 7
shows the variation of electrical resistivity of the Cu –
10Zn– 1.0Si and Cu –10Zn– 1.0Si –0.1Co alloy upon
cold-rolling and annealing; the reference electrical
resistivity is that of each hot-rolled specimen. The
electrical resistivity of the Cu – 10Zn – 1.0Si –0.1Co
alloy annealed in the temperature range of 623– 973
K is lower than that of the hot-rolled specimen, while
that of the annealed Cu – 10Zn –1.0Si alloy is almost
equivalent to that of the hot-rolled specimen. It is
considered to be a result of the formation of precip-
itates consisting of cobalt and silicon-solid solution
state after they are hot-rolled that the electrical resis-
tivity of the annealed Cu – 10Zn –1.0Si – 0.1Co alloy is
lower than that of hot-rolled specimen.
The grain size of Cu – 10Zn – 1.5Si – Co alloys
annealed at recrystallization temperature is plotted in
Fig. 8 as a function of the cobalt concentration to
 K. Oishi et al. / Materials Letters 57 (2003) 2280–2286
Fig. 7. Variation of electrical resistivity of specimens plotted as a
function of annealing temperature. Circles show the data for the
Cu – 10Zn – 1.0Si alloy, triangles show the data for the Cu – 10Zn –
1.0Si – 0.1Co alloy.
determine the optimal amount of cobalt for the inhib-
ition of grain growth. The grain size becomes smaller
as the cobalt concentration rises up to 0.05%, above
which the extent of variation of the grain size grad-
Fig. 8. Grain size of Cu – 10Zn – 1.5Si – Co alloys annealed at
recrystallization temperature plotted as a function of cobalt
concentration.
2285
Fig. 9. Relationship between 0.2% proof stress and grain size for
various silicon concentrations.
ually become small. The effect of the inhibition of
grain growth increases with increasing cobalt concen-
tration, because the amount of precipitates formed
upon annealing increases. However, the curve ap-
proaches saturation in high cobalt concentration.
Fig. 10. Value of k in the Hall – Petch equation plotted as a function
of silicon concentration.
2286 K. Oishi et al. / Materials Letters 57 (2003) 2280–2286
3.3. Hall – Petch relationship
According to the Hall – Petch relationship [1,2],
0.2% proof stress r0.2 is related to the grain size d by
r0:2 ¼ r0 þ kd
1=2 ;
where r0 and k represent constant values for each
material property. Experimental results are shown in
Fig. 9. Data obtained in this investigation are consis-
tent with the Hall – Petch relationship.
The data points were subjected to least-squares
fitting to obtain the k value. Fig. 10 shows the k value
obtained in this investigation against silicon concen-
tration. According to Koster and Screidel [13], the k
value increases with decreasing stacking fault energy.
The k value obtained increases with an increase in
silicon concentration. This result is consistent with the
phenomenon that stacking fault energy decreases with
increasing silicon concentration. The k value for the
Cu –Zn – Si alloy system with high silicon concentra-
tion is large; thus this alloy system has an advantage
in the degree of strengthening.
4. Conclusions
The following conclusions were derived from
results and discussion on the experiment of grain
refinement, performed using a method applicable to
mass production, for Cu – 10Zn – Si and Cu – 10Zn –
Si– Co alloys.
(1) We have developed a new alloy with fine
recrystallized grains from the approach of
material properties. The mechanical properties
of the Cu – 10Zn – 2.0Si – 0.1Co alloy having a
grain size of 1.6 Am are as follows: tensile
strength 558 N mm
2; 0.2% proof stress 438 N
mm
2; elongation 36.8%. This alloy has an
excellent balance between strength and ductility,
and is tough.
(2) Grain size of Cu – 10Zn – Si alloys becomes
smaller with increasing silicon concentration.
This phenomenon is considered to result as
follows. The addition of silicon decreases the
stacking fault energy considerably, leading to the
accumulation of large strain energy. Therefore,
the number of nucleation sites is increased.
(3) The addition of cobalt to Cu –10Zn– Si alloys
leads to the formation of fine precipitates, which
inhibit grain growth.
(4) The stacking fault energy of the Cu –10Zn– Si
alloy system is estimated to be very low, because
the k value in the Hall –Petch equation increases
with increasing silicon concentration.
(5) The results obtained in this investigation are
related to the Hall–Petch relationship. In the Cu –
Zn – Si alloy system with low stacking fault
energy, the k value is large with a high silicon
concentration, thus this alloy system is an
advantageous in the development of high-
strength metals, moreover, can surpasses phos-
phor bronze in the degree of toughness.
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