International Journal of Engineering & Technology IJET-IJENS Vol:12 No:06
60
Rapid Quenching of Liquid Lead Base Alloys for
High Performance Storage Battery Applications
Mustafa Kamal , Abu-Bakr El-Bediwi , Mohammed .s. Jomaan*
Metal Physics Lab. Physics Department, Faculty of Science –Mansoura University, Egypt.
*on leave, M.sc student, Ministry of Higher Education, Yemen.
[email protected] , [email protected] , [email protected]
Abstract — The aim of this study was to evaluate the role of
alloying and rapid solidification processing in direct
structural control in lead base batteries. A detailed
investigation on rapid quenching of liquid lead base alloys
for high performance storage battery applications was made
in order to choose suitable lead grid alloys for lead acid
batteries as melt-spun ribbons. S o this paper provides a
comprehensive review of the physical metallurgy and
mechanical properties of the melt-spun ordered alloy based
on Pb, Egyptian grid battery, Germany grid battery, Pb13.1wt.%S b, Pb-13.1wt.%S b-6.9wt.%S n, Pb-13.1wt.%S b5.9wt.%S n-1wt.%Ca, Pb-13.1wt.%S b-4.9wt.%S n-1wt.%Ca1wt.%Al, Pb-1wt.%Ca and Pb-0.5wt.%S n-0.1wt.%Ca for
storage battery applications. The results indicate that the
composition of alloys plays an important role on grid
batteries performed. It is found that Pb-0.5wt.%S n0.1wt.%Ca can be used to make the grids used for ribbon
grid lead-acid batteries.
Index Term—
Rapid quenching , Lead battery grids,
Resistivity, Elastic Moduli, Internal Friction, Thermal
Diffusivit , X-Ray diffraction, Pb-Ca-S n alloys.
I.
INTRODUCTION
Lead base alloys, including PbSb, PbCa binaries and Pb Sb-Sn ternaries have been common use since a very long
time, for two main families of engineering applications.
Firstly, since several centuries in the printing industry,
secondly, since more than one century, in the mechanical
industry, as thin linings for heavy duty bearing.
In 1859, Caston Plantѐ's lead storage battery was the
first battery that could be recharged by passing a reverse
current through it. Plante's first model consisted of two
lead sheets separated by rubber strips, rolled in to a spiral,
and immersed in a solution containing 10 percent sulfuric
acid [1]. In 1881, Camille Alphonse Fauve (French
chemical engineer) invented an improved version that
consisted of a lead grid lattice into which a lead oxide was
pressed, forming a plate [2].
Lead-antimony alloys have been widely used as the
grid metal for lead storage batteries for many years [3]
fig. (1). The role of alloying and thermomechanical
processing in direct microstructural control in lead-base
storage battery alloys was reviewed by Jeff Perkins and
G.R. Edwards in 1975 [4]. Strength, corrosion and
electrochemical correlations are also discussed for
conventional and emerging lead alloy systems.
J. P. Hilger [5] reported the hardening process in lead
–antimony – tin alloys for battery grids. His study was
focused on the type of precipitation, the nature and the
morphology of the precipitated phases, and the intensity
of hardening in Pb-Sb-Sn alloys in relation to the
composition of the alloys and the ternary diagram. R.
David Prengaman [6] and E. Cattaneo et al in
Fig. 1. lead acid battery.
1997 [7] reported different aspects of continuous casting
system of low-antimony alloys. Their experience showed
that, basically, it is not impossible to obtain corrosion
stable microstructure for positive antimonial grids with
the wirtz concast system. The Writz process [8] consists
of feeding the molten lead through the orifices of a
casting shoe into a rotating drum. Frost [9] investigated in
his study the present and proposed changes in materials
and construction for lead acid batteries and discussed th e
implications for recycling. Barkleit et al [10] studied a
novel processing route to produce battery grids by electro
deposition of lead with dispersed particles. David
Prengman in 2001 [11], described the new corrosionresistant grid materials, explained the high corrosion
resistance, assessed problems of processing corrosionresistant grids, and suggested modifications of alloy
compositions to improve performance. Keizo yamada et
al [12] were developed a method to obtain a lowresistance grid design for high power lead-acid batteries.
R. David Prengaman in 2006 [13] described a new lowantimony alloy that contains a substantial amount of tin.
The high tin content reduced the rate of corrosion of lowantimony positive grid alloys, improved conductivity,
increased the bond between the grid and the active
material. The alloy is also used as a corrosion-resistant
cast – on – strap alloy for automotive batteries for high
temperature service, as well as for posts, bushings, and
connectors for all well batteries. Wislei R. Oserio et al
[14-15] were investigated the different mechanisms and
tendencies of corrosion action on cellular microstructures
of a dilute Pb-Sb alloy and on dendritic microstructures
of a more concentrated Pb-Sb alloy. They found that with
increasing temperatures the general corrosion resistance
of Pb-Sb dendritic alloys decreases, and that
independently of the working temperature finer dendritic
spacings exhibit better corrosion resistance than coarser
ones [15]. In (2012) Francisco A. Perez – Gonzalez et al
[16] presented in their work the results of a series of
studies carried out to evaluate the distribution of CaSn 3
precipitates formed in a calcium and tin bearing lead
1215206-7979- IJET-I JENS @ Dece mber 2012 IJENS
IJENS
International Journal of Engineering & Technology IJET-IJENS Vol:12 No:06
61
alloy used for copper electrowinning. It was found that
13.1wt.%Sb-5.9wt.%Sn-1wt.%Ca,
Pb-13.1wt.%Sbthe mechanical properties of the material correlate with
4.9wt.%Sn-1wt.%Ca-1wt.%Al, Pb-1wt.%Ca and Pbthe minimum average distance between precipitates,
0.5wt.%Sn-0.1wt.%Ca melt-spun alloys are shown in fig.
which is related to the average cooling rate from solution
(2). For Pb, is shown in fig. (2a) contains pure lead as
heat treatment.
quenched. For Egyptian battery lead storage as quenched
ribbons fig. (2b) contains pure lead-phase.
For
II.
SCOPE OF T HIS RESEARCH
Germany battery lead storage as quenched ribbons fig.
However, the majority of research on lead acid battery
(2c), It also contains the same phase pure Pb-phase. Fig.
grids has been limited to corrosion-resistant grid alloys in
(2d) reproduces an X-ray diffraction pattern of an
lead acid battery manufacturing and very little work has
quenched ribbons of Pb-13.1wt.%Sb eutectic alloy.
been done in the mechanical and physical properties of
The pattern shows the existence of two kind of phases
rapidly solidified for lead battery grids using meltwith fcc structure of α-Pb solid solution, Sb phases and
spinning technique except for very few melt spun lead
traces of intermetallic compound from PbSb metastable
alloys for storage battery applications [17-18]. In this
phase which indicated at 2θ = 23.540 , and 76.990 . From
paper we report for the first time the synthesis of meltthese results, it has been achieved that the solid solubility
spun lead alloys ribbons for storage battery applications.
of Sb in Pb has been increased from a maximum of 3
So the intent of the present work is to review the physical
wt.% Sb to 9 wt.% representing a threefold solubility
characteristics of rapid quenching of liquid lead alloys for
increase indicating that about 9 wt.% can be retained in
storage battery application. It also is undertaken to
the Pb-rich phase by liquid-quenching [18].
determine the impact of quenching from the melt on the
For Pb-1wt.%Ca melt spun alloy is shown in fig. (2e)
solubility of antimony, calcium or aluminum in lead and
contains face centered cubic structure corresponding to αto investigate the possibility of producing high quality
Pb phase with a = 4.593 A 0 . it is found no metastable
metastable phase in the system.
phase is formed. For Pb-13.1wt.%Sb-6.9wt.%Sn meltspun alloy is shown in fig. (2f). The patterns show lines
III.
M ATERIAL AND M ETHODS
corresponding to α-Pb, β-Sb, and SbSn type phases. The
During four past decades of development, rapid
intensity of Pb lines is indicating a significant
quenching from melt has become a major field of research
concentration of this phase is the fully crystalline meltactivity in material processing. One main feature is to
spun ribbons.
attain high cooling rates during the quenching process.
For Pb-13.1wt.%Sb-5.9wt.%Sn-1wt.%Ca melt spun
The motivation of using high cooling rates lies in the
ribbons, is shown in fig. (2g). The X-ray diffraction
resulting beneficial effects [19]; as the cooling rate in
patterns indicate a face- centered cubic Pb matrix phase,
alloy solidification is increased, the microstructure of the
Sb-phase and SnSb intermetallic compound. There is no
product is more uniform, size-refined, extended solid
any peak characteristic due to Ca phase, which indicated
solution, metallic glasses and non-equilibrium crystalline
that a complete solubility of Ca atoms in Pb matrix phase
phase.
has been obtained. For Pb-13.1wt.%Sb-4.9wt.%SnThe most widely used techniques for alloy production at
1wt.%Ca-1wt.%Al as quenched ribbons is shown in fig.
high cooling rates are Chill methods [20], these
(2h). The patterns show lines corresponding to α-Pb, few
techniques include chill-block melt-spinning technique
lines from Sb-phase, and SnSb intermetallic compound.
which used in this investigation [21]. The experimental
There is no any peak characteristic due to Ca-phase or Altechniques utilized have been described in details in [22]
phase, which indicated that a complete solubility of Ca
and will be repeated here only briefly. Melt-spun ribbons
atoms or Al atoms in Pb-matrix phase has been well
thickness 8 μm to 2 μm, width about 5 mm, cooling rate
obtained.
about 105 K/sec [23-24], were prepared from Pb, Egyptian
Finaly for Pb-0.5wt.%Sn-0.1wt.%Ca melt spun alloys
grid battery, Germany grid battery, Pb-13.1wt.%Sb, Pbas show in fig. (2i) consist of only one phase; a face
13.1wt.%Sb-6.9wt.%Sn,
Pb-13.1wt.%Sb-5.9wt.%Sncentered cubic Pb matrix phase. There is no any peak
1wt.%Ca,
Pb-13.1wt.%Sb-4.9wt.%Sn-1wt.%Cacharacteristic due to Sn phase or Ca phase, which
1wt.%Al, Pb-1wt.%Ca and Pb-0.5wt.%Sn-0.1wt.%Ca
indicated that a complete solubility of Sn atoms or Ca
melt-spun alloys.
atoms in Pb matrix has been also obtained. This effect
A variety of technique was used to characterize the
was interpreted as indication that cooling rate for the
crystallographic, and transformation features of the meltmelt-spun ribbons used in this study as lead base alloys
spun ribbons lead alloys including x-ray diffraction. The
for high performance storage battery was high enough to
mechanical properties were examined in air atmosphere
retain most of the alloying elements in solid solution. To
with a dynamic resonance method. The hardness of
determine the amount of retained antimony, calcium,
ribbons samples were measured on a Vickers microaluminum or tin upon rapid quenching, the cell
hardness tester (Modd FM7-Tech Group Tokoy-Japan).
parameters of α-Pb phase are presented in table I.
In-suite resistivity measurements have been carried out
using the so-called double bridge method. The x-ray
diffraction study was carried out using CuKα radiation at
room temperature [25].
IV.
RESULTS AND DISCUSSIONS
S TRUCTURAL ANALYSIS
The X-ray diffraction patterns for the as -quenched Pb,
Egyptian grid battery, Germany grid battery, Pb13.1wt.%Sb,
Pb-13.1wt.%Sb-6.9wt.%Sn,
PbA.
1215206-7979- IJET-I JENS @ Dece mber 2012 IJENS
IJENS
International Journal of Engineering & Technology IJET-IJENS Vol:12 No:06
62
T ABLE I
cell volume
(A 0) 3
Pb
Egyptian grid
battery
Germany grid
battery
4.9546
121.627
4.9535
121.547
4.9517
121.418
Pb86.9-Sb13.1
4.9523
121.458
Pb99-Ca1
4.9525
121.471
4.9560
121.728
4.9535
121.545
4.94985
121.277
4.9525
121.471
30
40
-pb(400)
-pb(311)
-pb(222)
70
60
70
80
20
90
30
40
8000
-pb(331)
-pb(420)
-pb(400)
-pb(222)
2000
-pb(311)
-pb(220)
-pb(200)
8000
-pb(331)
-pb(420)
pbsb(400)
-sb(122)
-pb(311)
(2 e)
Pb-Ca1
Pb99-Ca1
6000
-pb(220)
Intensity
10000
4000
90
4000
2000
-pb(422)
Egyptian
gridbattery
battery
Egyptian grid
(2 b)
6000
80
-pb(420)
10000
-pb(200)
12000
70
-pb(331)
-pb(111)
14000
60
-pb(111)
2(degree)
16000
50
2(degree)
-pb(400)
50
-pb(222)
40
-sb(214)
1000
-sb(104)
pbsb(003)
2000
-pb(311)
30
90
(2 d)
0
20
80
Pb86.9-Sb13.1
Pb86.9-Sb13.1
3000
-sb(012)
Intensity
-Pb(331)
-Pb(420)
-Pb(400)
-Pb(311)
-Pb(222)
-Pb(220)
Intensity
4000
0
Intensity
60
-pb(222)
6000
(2 a)
6000
2000
50
2(degree)
5000
4000
-pb(220)
-pb(200)
Intensity
20
-pb(200)
Pb
(2 c)
0
-pb(111)
-Pb(111)
8000
5000
7000
-Pb(200)
10000
10000
-pb(220)
Pb-0.5Sn-0.1Ca
Germany
gridbattery
battery
Germany grid
15000
-sb(110)
Pb80-Sb13.1Sn6.9
Pb80-Sb13.1Sn5.9-Ca1
Pb80-Sb13.1Sn4.9-Ca1-Al1
20000
-pb(331)
-pb(420)
a (A 0)
-pb(111)
CELL P ARAMETERS
System in wt%
0
0
-2000
20
30
40
50
60
70
80
90
100
20
30
40
50
2(degree)
60
70
80
90
100
2(degree)
1215206-7979- IJET-I JENS @ Dece mber 2012 IJENS
IJENS
Pb80-Sb13.1-Sn6.9
Pb80-Sb13.1-Sn6.9
(2 i)
Pb-0.5
Pb--0.5 Sn-0.1Ca
Sn-0.1 Ca
1000
-pb(200)
2000
-pb(200)
-pb(200)
3000
-pb(200)
-pb(200)
-pb(200)
-pb(200)
-sb(217)
-pb(422)
Intensity
4000
-pb(331)
-sb(119)
sbsn(208)
-pb(400)
0
-sb(214)
500
sbsn(220)
1000
-pb(311)
-pb(222)
1500
-pb(220)
2000
sbsn(202)
Intensity
2500
5000
(2 f)
-pb(200)
3000
6000
sbsn(404)
3500
-pb(200)
-pb(111)
4000
63
-pb(200)
International Journal of Engineering & Technology IJET-IJENS Vol:12 No:06
0
-500
20
30
40
50
60
70
80
90
20
100
30
40
50
60
70
80
90
100
2(degree)
2(degree)
-pb(111)
Fig. 2. X-ray diffraction patterns of (a,b,c,d,e,f,g,h and i) melt -spun
alloys.
-pb(331)
-pb(420)
snsb(422)
-sb(108)
snsb(420)
-pb(311)
-pb(222)
-sb(204)
-sb(014)
2000
SnSb(222)
-sb(102)
4000
-pb(220)
-pb(200)
6000
Intensity
(2 g)
Pb80-Sb13.1-Sn5.9-Ca1
Pb80-Sb13.1-Sn5.9-Ca1
-sn(312)
8000
B. NUMBER OF ATOMS IN A UNIT CELL
To return to the subject of structure determination, the
next step after setting up the shape and size of the unit
cell is to find the number of atoms in that cell. To find the
number, we use the fact that the volume of the unit cell
calculated from the lattice parameters, of α-Pb rich-phase
in each melt-spun ribbons of the system used in this
study, multiplied by the measured density of each meltspun ribbons equals the weight of all the atoms in the cell.
From the following equation
∑
0
We have
20
30
40
50
60
70
80
90
2(degree)
-pb(111)
snsb(422)
-sb(300)
-pb(222)
2000
-pb(311)
-sb(124)
4000
(2 h)
snsb(222)
snsb(200)
6000
-sb(014)
snsb(220)
8000
Intensity
Pb80
-Sb13.1 -Sn4.9 -Ca1 -Al1
Pb80-Sb13.1-Sn4.9-Ca1-Al
-pb(200)
10000
Where ∑ is the sum of the atomic weight of atoms in
the unit cell, is the density (gm/cm3 ), is the volume of
the unit cell (A 0 )3 , and n is the number of atoms per unit
cell.
In these melt-spun ribbons as showed in Table II,
atoms are simply missing from a certain fraction of those
lattice sites which they would be expected to occupy, and
the result is a non integral number of atoms per cell.
However when determined in this way, the number of
atoms per cell is always an integer, within experimental
error, expect for a few substances which have defect
structures.
-pb(331)
-pb(420)
12000
0
20
30
40
50
60
2(degree)
70
80
∑
90
V.
ELECTRICAL PROPERTIES
The electrical resistivity behavior of the Pb, Egyptian grid
battery, Germany grid battery, Pb-13.1wt.%Sb, Pb1wt.%Ca,
Pb-13.1wt.%Sb-6.9wt.%Sn, Pb-0.5wt.%Sn0.1wt.%Ca,
Pb-13.1wt.%Sb-5.9wt.%Sn-1wt.%Ca
and
Pb-13.1wt.%Sb-4.9wt.%Sn-1wt.%Ca-1wt.%Al
rapidly
solidified is well summarized by the curves shown in fig.
(3).
1215206-7979- IJET-I JENS @ Dece mber 2012 IJENS
IJENS
International Journal of Engineering & Technology IJET-IJENS Vol:12 No:06
T ABLE II
1100
Pb
Egyptian grid battery
Germany grid battery
Pb86.9-Sb13.1
Pb99-Ca1
Pb80-Sb13.1-Sn6.9
Pb-0.5Sn-0.1Ca
Pb80-Sb13.1-Sn5.9-Ca1
Pb80-Sb13.1-Sn4.9-Ca1-Al1
1000
900
-8
Resistivityx10 (..m)
64
800
700
600
SHOWN DENSITY , UNIT CELL VOLUME AND N .
Density
cell
volumes
9.5
121.627
Number of
atoms per
unit cell of
lead phase
3.36
7.7
121.547
2.72
6.7
121.418
2.36
8.346
121.458
3.11
9.069
6.939
121.471
121.728
3.23
2.68
4.320
121.545
1.68
4.294
121.277
1.66
9.295
121.471
3.29
System in wt%
500
400
300
200
100
280
300
320
340
360
380
400
420
440
460
480
Temperature(K)
Fig. 3. Electrical resistivity versus temperature for pure lead, Egyptian
grid battery, Germany grid battery, binary, ternary, quaternary,
penternary rapidly solidified as melt -spun ribbons for battery grids.
The electrical resistivity varies with the metal's
temperature in a characteristic manner. This variation is
usually interpreted in terms of the behavior of the
resistivity versus temperature. At T ranging from 300 to
400 K, resistivity has a small approximately constant
value, above that resistivity increas es with temperature,
slowly at first but then it increases linearly with
temperature, except in the case of pure lead rapidly
solidified. The linear behavior continues essentially until
the melting point is reached in all melt-spun ribbons for
battery grids studied in this work. In an ideal metallic
crystal, at zero Kelvin electron-lattice would not occur,
according to the predictions of quantum mechanics [26].
At higher temperatures, the thermal disturbance of the
lattice can be described in term of quantized elastic waves
or phonons. The high resistivity of pure lead and
Germany grid battery melt spun ribbon compared with
that of Egyptian grid battery, Pb-13.1wt.%Sb, Pb1wt.%Ca,
Pb-13.1wt.%Sb-6.9wt.%Sn,
Pb-0.5wt.%Sn0.1wt.%Ca, Pb-13.1wt.%Sb-5.9wt.%Sn-1wt.%Ca and Pb13.1wt.%Sb-4.9wt.%Sn-1wt.%Ca-1wt.%Al
melt-spun
ribbons is related to the increased scattering of the
conduction electrons due to a random atomic
arrangement. Since crystalline defects act as scattering
centers for the conduction electrons in metal, increasing
their number increases the resistivity as shown in fig. (3)
and in table III.
The concentration of these imperfections depends on
temperature, composition, and the degree of cold working
of metal alloys. It is found experimentally that the total
resistivity of a metal is the sum of the contributions from
thermal vibration, impurities and plastic deformation, that
is the scattering mechanisms act independently of one
another. This is known as Matthiessen's rule, it is named
after A' Matthiessen's who in 1864 discovered
experimentally a more restrictive from this relationship.
This may be represented in mathematical form as follows:
Where
is the resistivity of the pure host material
at that temperature. This relationship implies that the
temperature-independent resistivity contributed by
impurities
is effectively in series with the temperaturedependent part ρ (T), contributed by the phonons. The
equivalent circuit is shown in fig. (4).
Pb
Egyptian grid
battery
Germany grid
battery
Pb86.9-Sb13.1
Pb99-Ca1
Pb80-Sb13.1-Sn6.9
Pb80-Sb13.1-Sn5.9Ca1
Pb80-Sb13.1-Sn4.9Ca1-Al1
Pb-0.5Sn-0.1Ca
0
Fig. 4. T he circuit equivalent to Matthiessen's rule.
Its theoretical basis is straightforward. Suppose that the
scattering electrons by the impurity can be described by a
relaxation time . At low temperatures, the value of the
electrical conductivity according to quantum theory is
therefore
Where n is the number of electrons per unit volume and
m and e are their mass and charge. If at high temperature
T the relaxation time in the pure metal due to phonon
scattering is
, then for pure metal
It is now consider the alloy at temperature T when both
impurity scattering and phonon scattering operate
together. The relaxation time
for both processes is
therefore
This holds if the two scattering mechanisms operate
independently, since the probability of scattering is
inversely proportional to the corresponding the
(relaxation time). The resistivity of the alloy
at
temperature T is related to by the expression
The value of for any particular metal alloy may be
calculated directly from equation (6) provided the
conductivity is known. It is governed by the collision
processes in which the electrons take part. If we combine
equations 3, 4, 5, and 6 we have:
Which is Matthiessen's rule.
Matthiessen's rule [27-28], is often used as a means of
1215206-7979- IJET-I JENS @ Dece mber 2012 IJENS
IJENS
International Journal of Engineering & Technology IJET-IJENS Vol:12 No:06
65
deriving from measurements on necessarily impure what
stressed material not due to external process. Internal
the resistivity of the pure material would be. In
friction arises from a material deviation from Hooke's law
multiphase alloys the resistivity tends to change proporsuch as anelastic behavior. The presence of defects within
tionally with composition between the resistivity of the
phase. Factors, such as thermal agitation, impurities and
a melt-spun ribbon often causes internal friction to occur
T ABLE III
P B, EGYP TIAN GRID BATTERY , GERMANY GRID BATTERY , P B-13.1 WT.%SB, P B-1 WT.%CA , P B-13.1 WT.%SB-6.9 WT.%SN , P B0.5 WT.%SN -0.1 WT.%CA , P B-13.1 WT.%SB-5.9 WT.%SN -1 WT.%CA AND P B-13.1 WT.%SB-4.9 WT.%SN -1 WT.%CA -1 WT.%AL RAP IDLY
SOLIDIFIED USING MELT- SP INNING TECHNIQUE .
System in wt%
Pb
Egyptian grid
battery
Germany grid
battery
Pb86.9-Sb13.1
Pb99-Ca1
Pb80-Sb13.1-Sn6.9
Pb-0.5Sn-0.1Ca
Pb80-Sb13.1-Sn5.9Ca1
Pb80-Sb13.1-Sn4.9Ca1-Al1
631.1 x10-8
Temperature
coefficient
resistivity
k-1
3160
231.2
864.9
0.5627
0.4132
0.4849
0.48
294.3
1698.9
0.4791
0.3813
0.4129
0.44
175.2
175.9
140.8
165.2
399.4
397.8
213.0
423.72
0.6768
0.6751
0.7833
0.7042
0.4532
0.4526
0.4875
0.4622
0.5833
0.5818
0.6750
0.6069
0.53
0.53
0.57
0.53
121.70
328.6
0.8632
0.5118
0.7439
0.55
96.34
311.3
1.009
0.5532
0.8693
0.64
Resistivity
(Ohm.m)
Concentration of
conduction
electrons
Fermi
Energy
eV
Fermi
Velocity
m.s -1
Electron
mobility
(m2. v-1.s-1)
0.2881x1028
0.2957
0.2483x106
0.44x10-3
crystal imperfections such as dislocations and grain
boundaries all reduce conductivity of metal alloy, because
these imperfections mean that there are irregularities
reduce the mean free paths of the electron, the mobility of
an electron and finally the electrical conductivity.
Table III gives a list of the electrical resistivities and
other transport parameters for Pb, Egyptian grid battery,
Germany grid battery, Pb-13.1wt.%Sb, Pb-1wt.%Ca, Pb13.1wt.%Sb-6.9wt.%Sn, Pb-0.5wt.%Sn-0.1wt.%Ca, Pb13.1wt.%Sb-5.9wt.%Sn-1wt.%Ca and Pb-13.1wt.%Sb4.9wt.%Sn-1wt.%Ca-1wt.%Al as obtained by the melt
spinning technique for battery grids.
VI.
M ECHANICAL PROPERTIES
Measured values are listed in table IV for Young's
modulus E, shear modulus G, bulk modulus B and
hardness Hv . The data indicate that the elastic stiffness of
the rapidly solidified Germany grid battery, Egyptian grid
battery, Pb-13.1wt.%Sb-6.9wt.%Sn, Pb-1wt.%Ca and
Pb-0.5wt.%Sn-0.1wt.%Ca are nearly the same. But in the
other cases for Pb-13.1wt.%Sb-5.9wt.%Sn-1wt.%Ca and
Pb-13.1wt.%Sb-4.9wt.%Sn-1wt.%Ca-1wt.%Al are also
nearly the same.
For Pb-13.1wt.%Sb and pure lead rapidly solidified are
nearly the same. Thus, the elastic stiffness are relatively
sensitive to the composition in our study in some cases
and other cases are relatively insens itive to composition.
It is interested to note that Ledbetter's theoretical values
of (G/E) [29], are in good agreement with the
experimental data, if we take into account the well-known
relationship between Young's modulus, the shear modulus
and the bulk modulus as follows:
It is found that young's modulus , Egyptian grid battery,
lead rapidly solidified and Pb-13.1wt.%Sb melt-spun
ribbons are quite large as summarized in table IV.
because of realignment of the defect. Internal friction
measurements as indicated in table (V) on Pb, Egyptian
grid battery, Germany grid battery, Pb-13.1wt.%Sb, Pb1wt.%Ca,
Pb-13.1wt.%Sb-6.9wt.%Sn, Pb-0.5wt.%Sn0.1wt.%Ca,
Pb-13.1wt.%Sb-5.9wt.%Sn-1wt.%Ca
and
Pb-13.1wt.%Sb-4.9wt.%Sn-1wt.%Ca-1wt.%Al
indicate
that the internal friction is a useful tool for the study of
the structural aspects of rapidly solidified battery grid
alloys. The results indicate that the internal friction
measurement is sensitive to the lack a mobile dislocation
and the increased interfacial boundary area in the meltspun lead base alloys. A low level of Q-1 for the melt
spun ribbons of lead alloys, whatever the chemical
content of the melt-spun alloys is, implies a rigid
structure which may be due to absence or to the locking
of crystal defects.
B. THERMAL DIFFUSIVITY
From the resonance frequency f0 , at which the peak
damping occurs using the dynamic resonance method [24,
30], the thermal diffusivity formula:
Where d is the thickness of the melt-spun ribbon.
Previous investigations have shown that there is a definite
relationship between the electrical and thermal
conductivity of alloys, although the wiedmann-franz ratio
does not hold [31]. If the thermal conductivity is plotted
against the product of the electrical conductivity and the
absolute temperature of any composition of alloy, a
straight-line relationship results by means of which
thermal conductivities can be calculated. The relationship
for thermal conductivity is that
Where σ is the electrical conductivity see table VI, and T
is absolute temperature.
A. INTERNAL FRICTION
Internal friction is an energy loss or dissipation in a
1215206-7979- IJET-I JENS @ Dece mber 2012 IJENS
IJENS
International Journal of Engineering & Technology IJET-IJENS Vol:12 No:06
66
T ABLE IV
YOUNG 'S MODULUS, BULK MODULUS, SHEAR MODULUS, P OISSON 'SRATIO AND HARDNESS RAP IDLY SOLIDIFIED USING MELT- SP INNING
TECHNIQUE .
Bulk
modulus
B (GPa)
17.6
14.3
10.1
36.5
10.1
9.66
10.1
6.18
Shear
modulus
G (GPa)
6.26
5.08
3.59
5.76
3.58
3.44
3.53
2.20
4.18
4.38
1.56
So by knowing the thermal conductivity and the thermal
diffusivity, it is useful to determine the specific heat
capacity C, from the following equation is that
Where is the density of the melt-spun ribbons used in
this work. The value of thermal diffusivity of a material
controls the time rate of temperature change as heat
passes through a material as shown in the table VI. The
thermal diffusivity of the Egyptian grid battery is higher
than the Germany battery, so in this case the thermal
diffusivity is a function of the way of the manufacture on
the chemical composition used. Since thermal diffusivity
of all types of the melt-spun ribbons of lead alloys for
internal combustion engines is different, so we assume
that this fact is caused by rapid solidification process from
melt.
VII.
CONCLUSION
The present experimental analysis permits the following
conclusion to be drawn:
 It is apparent from our experience there is a great
benefit to be used melt-spinning technique, which
have proved to be a powerful techniques in numerous
commercial melt-spun ribbon alloy systems.
 It was also found that Pb-0.5wt.%Sn-0.1wt.%Ca meltspun alloy can be used to make ribbon alloys battery
grids used for lead storage batteries as indicated in the
following table VII.
0.373
0.373
0.373
0.351
0.373
0.373
0.372
0.373
0.373
Pb
grid of Egyptian
battery
grid of Germany
battery
Pb86.9-Sb13.1
Pb99-Ca1
Pb80-Sb13.1Sn6.9
Pb-0.5Sn-0.1Ca
Pb80-Sb13.1Sn5.9-Ca1
Pb80-Sb13.1Sn4.9-Ca1-Al1
1.462
4.273
0.1584
1.169
13.166
3.192
0.4325
2.188
2.272
2.508
0.3398
2.569
6.910
3.30
7.969
4.195
1.189
1.823
7.060
5.242
0.5706
0.5684
0.7103
1.304
4.468
0.6053
1.748
1.678
6.064
0.8217
1.426
1.961
7.660
1.038
1.220
T ABLE VII
PROP ERTIES OF PB-0.5SN -0.1CA
System in wt%
Pb-0.5Sn-0.1Ca
0.6053x106
cell volume (A 0) 3
121.471
Number of atoms/unit cell
3.29
Ef (ev)
0.462
E (GPa)
9.49
Poisson's Ratio
Q-1
0.344
-1 -1
K Watt m k
1215206-7979- IJET-I JENS @ Dece mber 2012 IJENS
-1
Dth(m .s )
1.572
MELT-SP UN ALLOY
 (Ohm-1.m-1)
2
Specific
-1)
( -1 mheat
Capacity(c)
(J/kg.k)
() x10 6
T ABLE VI
T HERMAL DIFFUSIVITY , THERMAL CONDUCTIVITY , ELECTRICAL
CONDUCTIVITY , SP ECIFIC HEAT CAP ACITY RAP IDLY SOLIDIFIED
USING MELT- SP INNING TECHNIQUE .
Conductivity
Internal frication
0.032
0.035
0.033
0.044
0.032
0.046
0.041
0.078
0.038
0.339
G/E
Electrical
System in wt%
Pb
grid of Egyptian battery
grid of Germany battery
Pb86.9-Sb13.1
Pb99-Ca1
Pb80-Sb13.1-Sn6.9
Pb-0.5Sn-0.1Ca
Pb80-Sb13.1-Sn5.9-Ca1
Pb80-Sb13.1-Sn4.9-Ca1-Al1
0.44
0.338
0.339
0.423
0.342
0.340
0.344
0.340
Hardness
at Load (10g)
Hv (GPa)
0.116687
0.180424
0.125022
0.075013
0.050499
0.145123
0.047067
0.185817
0.100017
Thermal
Conductivity
(k)
(Watt m-1k-1)
T ABLE V
INTERNAL FRICTION RAP IDLY SOLIDIFIED USING MELTSP INNING TECHNIQUE .
Poisson's
Ratio
Thermal
Diffusivity
Dth 10 -8
(m2/sec)
Pb
grid of Egyptian battery
grid of Germany battery
Pb86.9-Sb13.1
Pb99-Ca1
Pb80-Sb13.1-Sn 6.9
Pb-0.5Sn-0.1Ca
Pb80-Sb13.1-Sn 5.9-Ca1
Pb80-Sb13.1-Sn 4.9-Ca1Al1
Young's
modulus
E (GPa)
16.8
13.6
9.62
16.4
9.61
9.22
9.49
5.90
System in
wt%
System in wt%
0.041
4.46
1.304 x10-8
IJENS
International Journal of Engineering & Technology IJET-IJENS Vol:12 No:06
67
Chill-Block Melt Spin T echnique : T heories and
VIII.
FUT URE WORK
Applications" Bentham Science Publishers, e ISBN : 978-1During the past 20 years, there has been a major
60805-151-9, (2012).
change in the composition of the lead alloys used for
[22] Mustafa Kamal and El-said Gouda "Effect of zinc additions
grids in automotive batteries. A modification to the
on structure and properties of Sn-Ag eutectic lead-free
solder alloy", J. Mater. Sci: Mater Electron (2008) 19: 81manufacturing processes has accelerated this charge.
84.
So it is intended that the future work should present
[23] Mustafa Kamal, Abu-Bakr El-bediwi, Shalabia Badr and
new insights in the production of melt-spun ribbons
Sabah T aha, " Experimental Study on Sn-Bi-In Melt-spun
in a suitable dimensions for automotive batteries can
Ribbons for Intermediate-step Soldering" , International
Journal of Engineering &Technology, IJET -IJENS vol:12
fit in to compact engine compartments, and have
No:03, 6-11.
mechanical properties, which can resist the stresses
[24] Mustafa Kamal, Abu-Bakr El-Bediwi, T amer Dawod and
of the charge / discharge reactions.
Adel. S. Waqlan, "Radiation Interactions with Cerrobend
IX.
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]
[10]
[11]
[12]
[13]
[14]
[15]
[16]
[17]
[18]
[19]
[20]
[21]
REFERENCES
http : // WWW. Corrosion – doctors. Org / Biographies/
plante / Bio. htm
Battery history. Euro pulse. Com. Retrieved 2008-02-22.
W. Hofmann, "lead and lead alloys", Springer-Verlage, New
York and
Berlin, (1970) pp. 341 -357.
Jeff Perkins, G. R. Edwards, "Review: Micro-structural
control in lead alloys for storage battery application" ,
Journal of materials science 10 (1975), 136-158.
J. P. Helger, " Hardening process in ternary lead-antimonytin alloys for battery grids", Journal of power sources 53
(1995) 45-51.
R. David Prengaman, "Wrought lead-calcium-tin alloys for
tubular lead/acid battery grids", Journal of power sources 53
(1995) 207-214.
E. Cattaneo, H. stumpf, H. G. T illmann and G.
Sassmannshausen, " Continues casting of lead-antimony
alloys", Journal of power sources 67 (1997) 283 -289.
J. Wirtz, New developments in continuous cast grids, proc.
7th Int. lead conf., Madrid, Spain, 1980; D. Lambert,
Batteries Int., (Oct.) (1992) P. 36 ; J. Wirtz. Batteries Int.,
(Jan.) (1996), P. 56.
P. C. Frost, "Developments in lead-acid batteries : a lead
producer's Perspective ", Journal of power sources 78
(1999) 256-266.
G. Barkliet, A. Grahl, M. Maccgni, M. Olper, P. Scharf, R.
Wagner, H. Warlimont "Electrodeposited, dispersion hardened, light weight grids for lead-acid batteries", journal
of power sources 78 (1999) 73-78.
R. David prengaman, " challenges from corrosion-resistant
grid alloys in lead acid battery manufacturing ", Journal of
power sources 95 (2001) 224-233.
Keizo Yamada, Ken-ichi Maeda, Kazuya Sasaki, Tokiyoshi
Hirasawa, "computer-aided optimization of grid design for
high-power lead acid batteries ", Journal of power sources
144 (2005) 352-357.
R. David Prengaman, " New low-antimony alloy for straps
and cycling service in lead-acid batteries", Journal of power
sources 158 (2006) 1110-1116.
Wislei R. Osorio, Daniel M. Rosa, Amauri Garcia, " T he
roles of cellular and dendritic microstructural morphologies
on the corrosion resistance of Pb-Sb alloys for lead acid
battery grids", Journal of power sources 175, (2008) 595 603.
Wislei R. Osorio, Claudia S. C. Aoki, Amauri Garcia, " Hot
corrosion resistance of Pb-Sb alloy for lead acid battery
grids", Journal of power sources 185 (2008) 1471-1477.
Francisco A. Perez- Gonzalez, Carlos G. Camurri, Claudia
A. Carrasco, Rafael Colas, " precipitation in a lead calcium
tin anode", Materials characterization 64 (2012) 62 -68.
M. Kamal, J. C. Pieri, R. Jouty " Preparation et ѐtude de l'
ѐvolution structural des alliages metalliques amorphes PbSb", Memories et Etudes Scientifiques Revue de
Metallurigie-Mars (1983) 143-148.
Mustafa Kamal and Rizk Mostafa Shalaby " Rapidly
solidification Effects in Pb-Sb Eutectic alloys " Journal of
Materials Sciences and T echnology, Vol. 11. 2003 , No 4,
59-70.
G. Rosen, J. Avissar, Y Gefen and J.Baram " Centrifuge
melt spinning" , J. phys . E: Sci. Instrum. 20 (1987) 571 574.
H. H. Liebermann, " the Dependence of the Geometry of
glassy Alloy ribbons on the chill Block Melt -spinning
process Parameters", Materials science and Engineering, 43
(1980) 203-210.
Mustafa Kamal, and Usama S. Mohammad, " A Review:
[25]
[26]
[27]
[28]
[29]
[30]
[31]
Metal Rapidly Solidified From Melt" International Journal
of Engineering &Technology, IJET-IJENS, Vol:12 No:05,
34-42.
Mustafa Kamal, " Mechanical Properties of Rapidly
Solidified of Cu-Sn shape Memory Alloys", Radiation
Effects & Defects in Solids, Vol. 161, No.3, March 2006,
189-191.
Mustafa Kamal, Abu-Baker El-Bediwi and M. B. Karman, "
structure, mechanical properties and electrical resistivity of
rapidly solidified Pb-Sn-Cd and Pb-Bi-Sn-Cd alloys",
Journal of materials science : Materials in Electronics 9
(1998) 425-428.
J. S. Dugdale, " T he Electrical properties of metals and
alloys", Edward Arnold Publishers limited, London (1977)
Page 221-273.
Ali Omar, Elementary Solid State Physics: principles and
Applications: Addison – Wesley Publishing company
Amesterdam, London, Manila, Singapore, (1975) Ch. 4 :
page 138-174.
H. M. Ledbetter, Mater. Sci. Eng; 27 (1977) 133.
J. J. Gilman, Mechanical behavior of metallic glasses,
Journal of Applied physics, vol. 46, No.4, April 1976,
1625-1633.
Doan, G. E. (1952). T he Principles of physical metallurgy,
3 rd ed. M, Graw Hill Book Company. New York. P.215 217.
1215206-7979- IJET-I JENS @ Dece mber 2012 IJENS
IJENS