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A. Daoud, M.T. Abou El-Khair, A.Y. Shenouda, F. Fairouz, E. Mohamed, M.E. Abdel
Aziz, K. Yanamandra, N. Gupta
PII: S2588-8404(21)00039-1
DOI: https://doi.org/10.1016/j.ijlmm.2021.09.001
Reference: IJLMM 171
Please cite this article as: A. Daoud, M.T. Abou El-Khair, A.Y. Shenouda, F. Fairouz, E. Mohamed,
M.E. Abdel Aziz, K. N. Gupta, Novel Pb Alloys Based Composite Foams Containing Hybrid Pores
Produced by Liquid Metallurgy for Lightweight Batteries, International Journal of Lightweight Materials
and Manufacture, https://doi.org/10.1016/j.ijlmm.2021.09.001.
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© 2021 The Authors. Publishing services by Elsevier B.V. on behalf of KeAi Communications Co. Ltd.
Novel Pb Alloys Based Composite Foams Containing Hybrid Pores Produced
by Liquid Metallurgy for Lightweight Batteries
Abstract
High-quality novel Pb alloys based composite foams reinforced with fly ash cenospheres of
different diameters in a variety of volume fractions were successfully synthesized by stir
casting. Several crucial parameters such as wetting between the cenospheres and molten Pb
alloy, volume fraction and size of the cenospheres, melt temperature, rate of cenosphere
addition, stirring time and speed, foaming agent amount, foaming temperature and foaming
time were optimized to produce high-quality composite foams. The microstructure of the
composite foams revealed uniform cell distribution and size with mostly closed cell structure.
The cells were measured to be of the size range of 290-430 µm. Microscopy and spectroscopy
of the composite foams indicated that limited or no interfacial reaction products are formed
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between fly ash cenospheres and Pb alloys. The specific discharge electrical capacity of the
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composite foams was higher than those of the Pb alloys used in conventional Pb-acid batteries.
Moreover, the weights of the composite foam electrodes were much lower than those of the
conventional lead alloys, providing benefits in transportation applications. The cyclic
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voltammetric and galvanostatic polarization results indicated that the rates of oxidation of Pb
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into PbSO4 in the composite foam were much lower than those in Pb-grids and the oxidation
of the Pb in the positive and negative grids occurred at much lower voltage than that in
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composite foams.
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1 Introduction
Vehicle weight reduction can help in reducing the fuel consumption and emissions [1]. Due to
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the use of heavy batteries made of lead (Pb) or Pb alloys, weight remains a significant challenge
for all transportation applications. Generally, Pb acid battery consists of at least two grids made
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of Pb or Pb alloys (one positive and one negative grid) and an electrolytic solution. The heavy
weight of Pb grids results in low energy-to-weight ratios, and smaller specific surface area of
the Pb grids results in low specific capacity and utilization efficiency of the active material.
Despite these limitations associated with the heavy weight, Pb-acid batteries are still the most
widely used rechargeable batteries [2-6].
Use of metallic foams instead of solid metallic grids can provide an option for weight reduction
of Pb-acid batteries. Metallic foams can be tailored to have mechanical properties such as high
compressive strength and energy absorption as well as attractive physical properties such as
high thermal and electrical conductivity compared to other cellular materials [7, 8]. One of the
possible ways of developing metallic foams with high compressive strength is to use a
combination of open and close cell foams. The closed cell foam structure can be achieved by
incorporating hollow ceramic particles, which can further help with the improvement in the
compressive properties of the composite foam. Hollow particles can provide several advantages
in such metal matrix composite foams (MMC foams) apart from mechanical property
improvement. The presence of ceramic hollow particles in the metallic matrix stabilizes the
foam structure and enhances the strength of the foam cell walls and ligaments [9]. Cenosphere
filled closed-cell metal foams, called syntactic foams, have been widely studied [10]. Syntactic
foams exhibit higher compressive strength, energy absorption and specific strength, but they
have higher densities than those of traditional metallic foams. A combination of open- and
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closed-cell porosity in syntactic composite foams presents vast opportunities for optimizing the
parameters for specific applications, which is explored in this work for Pb-acid battery
applications.
Literature review reveals that a few attempts have been carried out to fabricate Pb or Pb-alloy
foam electrodes for batteries. The synthesis techniques used suffer from either high costs or a
poor control over the quality of the foamed material or both. In some cases, Pb foams were
prepared by using powder metallurgy technique [11]. Pb powders and foaming agent powders
were mixed, pressed and formed by heating. The synthesized Pb-foams could be used as an
alternative to the conventional Pb grid in batteries. However, besides the high cost of the
powders, the powder metallurgy technique is complicated to be utilized for manufacturing of
Pb foam electrodes. In another study, Pb was electrodeposited on a copper-foam substrate to
fabricate Pb-foam electrodes [12] and the stability of Pb foam as negative active material was
studied. Improvement in cyclic voltammetry performance was reported in this work. Carbon
foam substrate was used in another study, which was coated with Pb-1 wt.% Sn to make Pb–
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acid battery electrodes [13]. Two techniques were proposed by Costanza et al. [14] to synthesize
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Pb-foams. In the first technique, Pb powder and particles of urea or NaCl were mixed, cold
compacted, sintered and finally, washed in hot water to dissolve urea or NaCl. In the second
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technique, particles of Pb and NaCl were mixed, heated above melting point of Pb and then
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pressure was applied by a piston on the mixture. After solidification, the mixture was washed
in hot water to dissolve NaCl. The produced Pb-foam revealed irregular pores and
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inhomogeneous pores distribution with very large porosities and cracks.
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The limitations of the available synthesis methods are clear in providing high quality foam
material. In addition, scale-up is a challenge for these processes and the cost is high. There is a
need to develop low-cost technique for production of Pb-foam electrodes, having fine and
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homogeneously distributed cell size with the possibility of large volume production at low cost,
which is addressed by the present work.
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In this work, Pb composite foam electrodes, containing hybrid pores , are designed to have a
lower weight and higher specific surface area for use as alternative to the conventional Pb grid
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in the Pb-acid batteries. The idea of replacing conventional Pb-alloy grid in lead-acid batteries
by lead based composite foam electrodes, containing hybrid pores of fly ash cenospheres waste
and gas pores, fabricated by simple and inexpensive stirring technique and direct foaming of
the composite melt using as a low cost blowing agent through process optimization, is not found
studied before to the best of our knowledge, and would have a substantial impact on battery
industries requiring lightweight, high performance and long lasting batteries. Addition of
cenospheres into Pb alloys to act as thickening agent, pores and reinforcements adds to the
novelty.
The influence of processing parameters on the structures and densities of the produced Pb based
composite foam was studied in the present work. Moreover, the specific discharge electrical
capacity of the composite foams was investigated.
2 Experimental work
Pb0.08Ca1.6Sn0.008Al and Pb0.07Ca0.5Sn0.008Al were used as the matrix alloys. Ni-
coated fly ash cenospheres, having an average diameter of 80 or 170 µm, an average wall
thicknesses of 7 µm and a density of 0.9 g/m3 were used. The Ni-coated fly ash cenospheres
act as reinforcement, pores, which are wholly contained within the cenospheres, and
thickening agent.
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First, Pb alloys containing homogenously distributed Ni- coated fly ash cenospheres were
prepared according to the following procedure: the Pb alloy was melted in a steel crucible
heated up to a temperature of 350 C. When the melt temperature reached 400C, the alloying
elements (Ca, Sn and Al) were added and then, the melt temperature was raised to a
temperature of 450C. A stainless-steel stirrer connected to a variable speed motor was
introduced and positioned below the surface of the melt. As-received Ni-coated fly ash
cenospheres were preheated at 200 oC for 2 hr. Then, they were incorporated into the vortex
formed by stirring. Stirring of the melt mixture was continued for 1 min after the completion of
the cenospheres incorporation to ensure assimilation of the cenospheres in the melt. After that,
the temperature of the melt was decreased to 400C. Then foaming agent (white lead carbonate)
powder with an average particle size of 60 µm was added into the melt while stirring. The slurry
was vigorously stirred to homogeneously disperse the foaming agent powder and the
cenospheres. The molten metal was held at the foaming temperature for 3 min to allow foaming
agent to release gas bubbles. Then, the composite foam was immediately cooled down using
forced air. Fig.1 presents schematic diagram of the Pb alloy based composite foam preparation.
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Details of the synthesized composite foams are given in Table 1.
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Table 1 Details of the produced composite foams.
Cenosphere Average cenospheres
Foam Alloy
vol.% diameter (µm)
M Pb0.08Ca1.6Sn0.008Al ------- --------
C1 Pb0.08Ca1.6Sn0.008Al 8 80
C2 Pb0.08Ca1.6Sn0.008Al 5 80
C3 Pb0.07Ca0.5Sn0.008Al 5 80
C4 Pb0.08Ca1.6Sn0.008Al 5 170
Samples were cut from the produced Pb composite foams for macro- and micro-structure
examination. The samples were polished with (3 and 0.25 m) diamond paste. The samples
were examined with optical microscope and scanning electron microscope (SEM), model
(JEOL5650). Element maps were acquired by using Electron Probe Micro-Analyzer (EPMA).
Compositional spot analyses were performed in the cenospheres using an Energy Dispersive
X-ray Analysis (EDXA) detector attached to the SEM. Also, X-ray diffraction (XRD) analysis
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was carried out to detect the phases in the Pb composite foams. The cell size was measured by
the mean intercept method.
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Differential Thermal Analysis (DTA) and Thermal Gravimetric (TG) were carried out to
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investigate the thermal decomposition of basic lead carbonate. The DTA and TG experiments
were conducted by using STA 504 BAHR Thermo Analyze. The weight of the sample was 364
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mg. The sample was heated from room temperature up to 500°C in air atmosphere at heating
rate of 5 Co/min.
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The density of the produced Pb based composite foam was calculated by dividing mass of the
sample by its volume. A digital balance with accuracy of 0.001 g was used.
Specific discharge galvanostatic measurements were carried out for the composite foams and
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Pb alloys used in conventional Pb-acid battery grid as electrodes. The paste was slurred from
70% PbO, 30% free Pb powders (50 g lead oxide powder and 15 g free lead) and mixed with 5
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g distilled water and 10 g (1M) of H2SO4, which were gradually added and mixed thoroughly
in order to form a homogenous paste. The paste was applied to previously weighed electrodes,
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where three grids were pasted and prepared in order to get one positive and two negative
electrodes. The plates were set for curing conditions of 25°C for 72 h. The formation regime
was carried out using 1 M H2SO4 electrolyte and the charging current was gradually increased,
stepping up from 20 to 300 mA/cm2 through 12 h until complete formation was achieved, giving
PbO2 material on the positive electrode and spongy Pb on the negative one. The specific
discharge capacity was measured after charging at 20 mA/cm3 for 2 h and discharging at 15
mA cm-2 until the cut-off voltage (1.75 V), Fig. 2.
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Cyclic voltammograms (CV) for lead alloy grids and lead alloys based composite foams were
conducted at sweep rate of 1 mV/s in 1M H2SO4 at room temperature (298 K). To clean the
investigated electrodes from any grease and oxidized residues before the start of the cyclic
voltammetric experiment, they were reduced at the potential of hydrogen evolution (-2V) for
about 3 min. A platinum wire was employed as the counter electrode and a Hg/ Hg2Cl2/ KCl
(SCE= 0.244 V vs. NHE). was the reference electrode.
Galvanostaic polarization for lead alloy grids and lead alloys based composite foams was
investigated at different current densities of 0.26, 0.52, 1.3, 2.6, 5, 10 and 20 mAcm-2 in 1M
H2SO4 . The electrodes were set at the potential of hydrogen evolution (-2V) for 3 min. The
time of oxidation and reduction was 60 and 45 min, respectively.
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as well as large and complex shapes can be produced by using stir casting at low cost. Use of
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fly ash cenospheres provides the advantages of (a) using a waste material in synthesizing
advanced composite foams, (b) reducing in the requirement of Pb, potentially saving the energy
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and pollution associated with its production and (c) reducing weight of Pb-alloy.
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In the present work, several attempts were conducted using different processing parameters to
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fabricate Pb based composite foams by stir casing. It was found that a number of crucial
parameters such as wetting between the cenospheres and molten Pb-alloy, volume fraction and
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size of the cenospheres, melt temperature, rate of cenosphere addition, stirring time and speed,
foaming agent amount, foaming temperature and foaming time should be taken into
consideration to produce Pb based composite foam.
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incorporation of cenospheres in the molten Pb alloy. To overcome this problem, Nickel (Ni) –
coated fly ash cenospheres were used, where the surface energy of the cenospheres has
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increased by coating and the contact surfaces are changed to be metal/metal instead of
metal/ceramic. It was found that the Ni layer present on the cenospheres leads to improvement
in the cenospheres dispersion in the molten Pb-alloy by preventing the formation of cenosphere
clusters. Coating of fly ash cenospheres by Ni also inhibits the infiltration of molten Pb alloy
into the cenospheres by closing the pores and covering the cracks on the surface of the
cenospheres. The infiltration of molten Pb alloy into the cenospheres is unfavorable because it
will lead to increase in the density of the composite foams. The presence of Ni layer on the
cenosphere surface also enhances conductivity of the cenospheres.
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3.1.3 Incorporation of the cenospheres
To obtain a uniform distribution of the cenospheres in the Pb-alloy melt, the stirrer material
type, dimensions, and position in the melt as well as the stirring speed and rate of cenospheres
addition were considered. The type and dimensions of the stirrer depend on the ratio of diameter
of the crucible to the melt pool height. In the present work, the ratio of the diameter of the
crucible to the melt pool height was about 2. Therefore, stainless steel with three-blade stirrer
was successfully utilized. To induce a high shear and generate a sufficient vortex for
incorporation of the cenospheres into the Pb alloy melt, the stirrer was designed to rotate close
to the wall of the crucible and it was situated below the surface of the molten Pb-alloy to divert
flow pattern in the melt and assist in trapping of the cenospheres under the surface of the melt.
Low stirring speeds (200-400 rpm) were not enough to incorporate the cenospheres as the
vortex created was shallow. However, a stirring speed of 700 rpm was adequate to generate the
vortex, which provided shearing and wiping action in the melt.
During the addition of the cenospheres into the molten Pb-alloy, it was noted that high rates of
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cenospheres addition led to agglomeration and rejection of the cenospheres from the melt.
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However, slow rates of additions extended the total duration for introducing the cenospheres.
The optimum rate of cenospheres addition is found to be 15 g/min.
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3.1.4 Foaming agent type, amount, temperature and holding time
Different hydrides such as Mg-, Ti-, Zr- and carbonates such as Cu-, Mg, Zn-, Pb- [11] can be
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used as foaming agents for Pb alloys. Several important parameters must be considered in
selecting the foaming agent type such as the temperature range in which the blowing agent
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releases gas, and the chemical composition of the foaming agent and its density. It should be
noted that the temperature range of the foaming agent for releasing the gas should match the
melting range of the Pb-alloy. Also, the foaming agent should be selected with appropriate
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chemical composition to avoid introduction of unwanted elements into the Pb alloy, which can
dramatically affect the properties of the Pb-alloy. Based on the above-mentioned factors, white
lead carbonate was selected for fabrication of the present Pb based composite foam. Figs. 3 and
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4 show XRD pattern and TG-DTA curves of basic lead carbonate, respectively. In the DTA,
four clear endothermic decomposition peaks can be observed (marked as I, II, III and IV). The
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first peak in Fig. 4 is due to the evolution of the H2O, and three subsequent peaks are due to
evolution of CO2 gas, indicating that the temperature range for the decomposition of white lead
carbonate for releasing the CO2 gas matches with the melting range of the Pb alloy. During the
foaming process, it has been observed that increasing the temperature of the molten Pb alloy
above 350 °C or increasing holding time significantly affect the expansion of the foam or the
foam quality, including cells size and distribution of the cells. Thus, it is expected that white
lead carbonate may entirely decompose at temperature of 350 °C when it is incorporated into
the molten Pb-alloy. This implies that the surrounding substance affects the thermal
decomposition behavior of white lead carbonate. Finally, white lead carbonate decomposes
within the molten Pb alloy and releases H2O, the gaseous phase CO2 and the solid phase PbO,
which do not contain unwanted elements. It was found that the optimum temperature of the
foaming process used in the present work is 350 °C to produce fine cells and homogeneous cell
distribution. It was found that heating the white lead carbonate particles to 100 oC for one hour
before adding them into the molten Pb enhanced the wetting between the particles and molten
Pb-alloy and thus improved the distribution of the white lead carbonate particles in the molten
Pb, leading to production of high quality Pb foam.
Several experiments were carried out using different white lead carbonate percentages and it
was found that the best quality of foaming, including fine cells and homogenously distributed
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cells, was obtained by adding 1 wt.% of white lead carbonate. Lower quality foams were
obtained at lower and higher than 1 wt.% of white lead carbonate. During foaming process,
holding time of 5 min after addition of the white lead carbonate was found enough to complete
the foaming process leading to fine and homogenously distributed cells. Increasing the holding
time has a marginal effect on the foam quality. However, too long holding time may cause
release of CO2 gas from the foam and draining of the foam leading to directionality in the cell
shape and gradient in the cell size and volume fraction. The heating rate of the furnace also has
a vital effect on the foaming process. The furnace with lower heating rate extends the time
required to reach the suitable foaming temperature and consequently, CO2 gas may leak from
the molten Pb-alloy without generating pores.
Photos of Pb-cenosphere composite foams are shown in Fig.5. It can be noted that the
distribution of the cells is uniform without foaming defects such as deep and long cracks.
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Fig. 4 TG-DTA curves of basic lead carbonate
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Fig. 5. Photos of Pb alloy based composite foams produced with the addition of 1 wt.% of
foaming agent, at stirring speed of 700 rpm and cenospheres addition rate of 15 g/min
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discharged current densities and electrochemical utilization efficiency of the composite foam
electrode [15].
The relatively smaller cell size of M foam in comparison to C1 and C2 composite foams,
observed in Fig 6, can be attributed to the higher flowability of the molten Pb-alloy, which
results in easy drainage of the melt. But the presence of cenospheres in Pb-alloy melt increases
the viscosity and impedes the flow of molten Pb-alloy in all direction, leading to the formation
of a relatively larger cell size.
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Fig. 6. Macrostructures of Pb alloy based composite foams produced with the addition of
1 wt.% of foaming agent, at stirring speed of 700 rpm and cenospheres addition rate of 15
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g/min, (a)-(e) figures are labeled according to the nomenclature presented in Table 1
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430
330
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300 310
Cell size, µm
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M C1 C2 C3 C4
Foams
Fig. 7. Cell size of the foams.
It can be observed in Figs. 6b, 6c and 7 that as the volume of the cenospheres increases from 5
(C2 composite foam) to 8 vol.% (C1 composite foam), the cell size and cell wall thickness
increase. Increasing the volume fraction of cenospheres leads to an increase in the viscosity of
the molten Pb-alloy, leading to stabilization of the melt. Due to the stability of the melt, the
cells grow to larger sizes without collapsing or rupturing. Moreover, higher volume fraction of
cenospheres aids in retaining the molten Pb-alloy for longer periods in the cell wall region.
Consequently, more melt is accommodated at the cell wall, resulting in increasing the cell wall
thickness.
From Figs. 5 and 6c, 6e, it can be noted that the cell thickness of C2 composite foam containing
smaller (80 µm) cenospheres is thinner than that of the C4 composite foam containing larger
(170 µm) cenospheres. It has been reported that [9] the cell walls of the composite foam with
larger particle size are thicker than those of the composite foams with smaller particle size. The
large size particles are more effective to hamper the flow of molten metal from the cell wall
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towards the plateau border. The drainage of the cell wall is retarded, which results in the
formation of thicker cell walls.
3.2.2 Microstructure
SEM micrographs of the composite foam microstructures, EPMA, EDXA and XRD results are
shown in Figs. 8 and 9. The microstructures of the composite foams show homogeneously
distributed cenospheres in the cell walls (marked “W”) and plateau region ( marked “P”) of
the Pb-matrix alloys Fig. 8(a). Large size cenospheres have a greater tendency to brake and get
filled with the Pb-alloys, Fig. 8. The presence of infiltrated cenospheres with Pb-alloys is
undesirable because the density of the foam will be increased. Two types of pores can be
observed in the microstructures of the composite foams. The first one is wholly contained
within the cenospheres (marked “M”). The second form of the pores has a typical multi-faceted
shape, which is caused by decomposition of lead carbonate releasing CO2 gas at elevated
temperatures.
The reactions between cenospheres and Pb matrix alloys can significantly affect the properties
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and aging response of the composite foams. The interfacial reactions can result in depletion or
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reduction of the alloying elements needed for the precipitation hardening process during aging.
Therefore, attention has been paid to study the interfacial reactions between cenospheres and
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Pb-alloys. Fig. 8 (b-d) shows element maps acquired by EPMA, EDXA and XRD of C2
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composite foam. These figures reveal maps of Pb, Sn, and Ni. The cenospheres are surrounded
by tiny layer of Ni, which is the coating of cenospheres. It can be noted that the concentration
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of Pb or Sn is nearly comparable to that in the Pb matrix alloys, indicating that limited or no
interfacial reactions between fly ash cenospheres and Pb alloys have been formed.
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W
(a) (b) Ni
(c) Pb (d) Sn
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(e)
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(f)
Fig. 8 SEM microstructure of C2 composite foam (a), element maps acquired by EPMA of C2
composite (b-d), EDXA of C2 composite foam (e) and XRD of C2 composite foam.
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M Cell BM
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Fig. 9 SEM microstructures of C4 composite.
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3.2.3 Pore content and relative density -p
The relative density (Dr) of a foam is defined as the ratio of the measured density of a foam
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(Dm) to the density of cell wall material (Ds). The pores percent (Pm) in the foam was calculated
as:
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Table 2 presents the density, relative density and pores percent of Pb-cenosphere composite
foams. The density of solid Pb alloy is 11.3 g/cm3, which dramatically reduces to 3.2 g/cm3 for
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the Pb alloy foam (M foam). With the addition of 8 vol.% (C1 composite foam) or 5 vol. % (C1
composite foam) of cenospheres into Pb-alloy foam, the density further reduces to 2.7 and 2.3
g/cm3, respectively. Although the same volume fraction of cenospheres was added into Pb-
alloy to produce C2 and C4 composite foams, the density of C4 is slightly higher than that of
C2 composite foam likely because C4 contains lager size cenospheres than those in C2
composite foam. Larger size cenospheres have a greater tendency to break and their exposed
cavity is filled with Pb-alloy, which result in increasing the density, Fig. 9.
Table 2 Density and pores percent of Pb-fly ash cenosphere composite foams
Foam Dm (g/cm3) DR Pm % Pth% Pw %
M 3.2 0.28 72 0 72
C1 2.7 0.24 76 6.1 69.9
C2 2.3 0.2 80 3.8 77.2
C3 2.6 0.23 77 3.8 74.2
C4 2.8 0.25 75 4.4 71.1
From the above results, it can be observed that C2 and C3 composite foams exhibit
homogeneously distributed cenospheres and uniform cell size with mostly closed cell structure.
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Therefore, C2 and C3 composite foams were selected for further investigations, including
specific discharge electrical capacity, cyclic voltammetric and Galvanostatic polarization.
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conventional Pb-grid with a size of 12 x 10 x 0.3 cm is about 146 gm and weight of the
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composite foam electrode having the same size is about 94 gm. If the conventional Pb- grid is
replaced by composite foam electrode, the weight saved will be about 35%.
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Table 3. Specific discharge electrical capacities of acid cells using conventional lead alloys
and composite foams.
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Alloy /composite foam Dm Is
(g.cm-1) (Ah.kg-1)
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Fig. 10 CV of Pb grids and C2 and C3 composite foams at scan rate of 1 mVs-1
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of oxidation step of Pb to PbSO4 for the positive grid is at -500 mV vs. SCE. The oxidation and
reduction behaviors have 7 steps of potentials as shown in Fig. 11.
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The polarization curves of positive Pb- grid alloy at higher different current densities up to 2.6
mAcm-2 as shown in Fig. 12 have similar characteristics, but the duration of steps 1, 2 and 3
decreases as the current density increases.
The start of the oxidation step 1 for the positive foam electrode (C2) is at -470 mV at current
density of 2.6 mAcm-2 as shown in Fig. 11. The duration of this step for the positive foam is
250s, while it is only 50 s for positive grid as can be seen in Fig. 13. In case of negative grid,
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as shown in Fig. 14, the start of oxidation step at 0 mV for current density 2.6 mAcm-2, while
negative foam electrode (C3), as depicted in Fig.15 at -355 mV at the same Id =2.6 mAcm-2.
The duration of this step is 3s and about 1000s for negative grid and foam, respectively,
indicating that the composite foams takes longer time for the oxidation of Pb into PbSO4.
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Finally, the composite foams produced in the present work exhibit higher specific discharge
electrical capacity, outstanding cyclic voltammetric and galvanostatic polarization behavior
because the structure of the composite foam comprises Ni layer on the cenosphere surface,
which enhances the conductivity of the foam, and fine cells (pores), having a large surface
area. This large surface area significantly increases the contact surface area between the
composite foam electrode and the active material, leading to diminishing both the polarization
resistance and the ohmic resistance of the electrode surface and the resistance of the
electrochemical reaction. Moreover, the huge surface area of the composite foam leads to a
reduction in the charge-discharge current density passing through the composite foam electrode.
On the contrary, it has been reported that the thickness of conventional Pb grids increases during
discharge and then decreases during recharge, leading to deformation of the grids. Additionally,
the stress generated on the grid due to the formation of the corrosion layer deform the grid and
weaken its electrical contact with the active material [1]. These features of the composite foam
enhance the reaction rate and, thus, the conversion capability of the active material. These
findings make composite foams produced in the present work a strong candidate to replace Pb
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-grids used in Lead Acid Battery.
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4 Conclusions
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High quality novel Pb-alloys based composite foams containing hybrid fly ash cenospheres
waste and gas pores were successfully fabricated by stir casting Its usage as an electrode in
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lead acid batteries was studied in order to produce light weight batteries. several crucial
processing parameters such as wetting between the cenospheres and molten Pb alloy, volume
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fraction and size of the cenospheres, melt temperature, rate of cenosphere addition, stirring
time and speed, foaming agent amount, foaming temperature and foaming time were taken into
consideration to produce these high quality Pb-alloys based composite foams. Through which
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2- SEM microstructures, EPMA and EDXA of the composite foams reveal that limited or
no interfacial reactions between fly ash cenospheres and Pb alloys have been formed.
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3- The specific electrical discharge capacity of the composite foams after number of cycles
was higher than those of the lead alloys used in conventional lead-acid batteries.
4- The weights of the composite foam electrodes are much lower than those of the
conventional lead alloys.
5- Cyclic voltammetric and galvanostatic polarization results indicate that the rates of
oxidation of Pb into PbSO4 in the composite foam are much lower than those in Pb-
grids and the oxidation of the Pb in the positive and negative grid occurs at much lower
voltage than that in composite foam.
5 Acknowledgements
This paper is based upon work supported by Science, Technology & Innovation Funding
Authority (STDF) under grant (EG-US: 42692).
This article is also supported by USAID and NAS through Subaward 2000010558.
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Highlights
- High-quality novel Pb alloys based composite foams reinforced with fly ash cenospheres were
successfully synthesized by stir casting.
- The microstructure of the composite foams revealed uniform cell distribution and size with mostly
closed cell structure.
- The specific discharge electrical capacity of the composite foams was higher than those of the Pb alloys
used in conventional Pb-acid batteries.
-The weights of the composite foam electrodes were much lower than those of the conventional lead alloys,
providing benefits in transportation applications.
-The cyclic voltammetric and galvanostatic polarization results indicated that the rates of oxidation of Pb
into PbSO4 in the composite foam were much lower than those in Pb-grids.
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Novel Pb Alloys Based Composite Foams Containing Hybrid Pores Produced by
Liquid Metallurgy for Lightweight Batteries
1
Composite Materials Laboratory, Central Metallurgical Research and Development Institute
(CMRDI), P.O. Box 87, Helwan, Cairo, Egypt
2
Composite Materials and Mechanics Laboratory, Mechanical and Aerospace Engineering
Department, New York University, Tandon School of Engineering, Brooklyn, NY, 11201, USA
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∗ Corresponding author
Prof. Dr. Eng. A. Daoud
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E-mail address: adaoud_eg@yahoo.com
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Declaration of interests
☒ The authors declare that they have no known competing financial interests or personal relationships
that could have appeared to influence the work reported in this paper.
☐The authors declare the following financial interests/personal relationships which may be considered
as potential competing interests:
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