Overview Lead: Non-Battery Applications

Lead Alloys for Permanent Anodes in

the Nonferrous Metals Industry
Aaron Felder and R. David Prengaman

This paper reviews the common lead used in electrolytic solutions. During use, To prevent this type of creep failure, the
alloys associated with insoluble anodes the lead surface is oxidized to its highest lead is normally alloyed to increase the
in different metal deposition operations. valence state, coating the anode surface mechanical properties during operation.
Metallographic techniques were used to with a smooth, adherent layer of PbO2. A more rigid anode maintains the uni-
evaluate microstructures as they relate The layer inhibits further oxidation and form corrosion-resistant layer. Table I
to physical and mechanical properties. corrosion and remains highly conduc- shows typical alloys used throughout the
Alloy additions and manufacturing tive, thus passing the electrowinning industry and corresponding mechanical
processes are examined as appropriate current. properties.2
methods to meet the performance needs Oxygen evolved at the anode during
of a lead anode. operation is released at the surface as a
The Pb-Ca anodes gas. The oxygen can oxidize materials
INTRODUCTION
were developed to in the electrolyte, corrode the anode, or
Electrowinning anodes continue to form peroxides at the anode surface. The
employ lead alloys as the major materials reduce corrosion and major consequence of oxygen evolution
suitable for use in electrometallurgical spalling rates of the is the corrosion of the lead anode. The
plant practice. Lead alloys are used as oxygen corrodes the anode directly by
permanent anodes for electrowinning PbO2 corrosion the formation of PbO, PbSO4, complex
and plating of metals such as copper, product compared sulfates, PbO2, and PbO2 on the sur-
zinc, nickel, cobalt, chromium, and face. The PbSO4 compound is especially
manganese. Different alloys are utilized with conventional undesirable because it acts as an insulator
throughout these nonferrous industries. Pb-Sb alloys, thus and passivating the anode surface. The
The desired properties of the anode can morphology of the PbO2 layer is impor-
help achieve less contamination of the reducing the lead tant in inhibiting the spalling effect which
cathode, longer anode life, lower anode contributes to cathode contamination.
potential, and consequently, reduced
contamination of Alloy additions and anode fabrication
oxygen overpotential. the cathode. techniques can promote a more continu-
The primary objective of an electro- ous, adherent layer. Once formed, the
winning or plating practice is to produce a Pure lead, however, is not strong PbO2 layer serves to evolve oxygen as a
high-purity cathode or metal deposit with enough to support its own weight. A pure gas instead of corroding the underlying
good physical appearance at the lowest lead anode will creep during use. As the lead surface.
possible consumption of energy.1 Lead lead elongates and deforms, the adherent
COPPER ELECTROWINNING
anodes are preferred because of their high PbO2 layer cracks and exposes fresh lead
resistance to corrosion in the sulfuric acid surface to oxidation and rapid corrosion. Rolled Pb-Ca-Sn alloys are the pre-
ferred anode materials in copper solvent
Table I. Mechanical Properties of Various Lead Alloy Anode Sheets* extraction-electrowinning (SX-EW)
Alloy UTS 0.2% YS Elongation Hardness facilities. The rolled anodes replaced
(wt.%) (MPa) (MPa) (%) (RR30) cast anodes, which have lower strength.
Pb-3Sb Cast 65.5 55.2 10 85 The Pb-Ca anodes were developed to
Pb-3Sb Rolled 24.6 16.3 40 64 reduce corrosion and spalling rates of
Pb-6Sb Cast 73.8 71.0 8 87 the PbO2 corrosion product compared
Pb-6Sb Rolled 30.6 19.5 35 65 with conventional Pb-Sb alloys, thus
Pb-0.07Ca-1.35Sn Cast 46.4 35.3 29 71
reducing the lead contamination of
Pb-0.07Ca-1.35Sn Rolled 71.0 65.3 14 85
Pb-0.07Ca-1.35Sn-0.05Ag Rolled 80.0 76.8 10 88 the cathode. The calcium strengthens
Pb-0.07Ca-0.35Ag Rolled 37.8 35.5 42 68 the lead via a precipitation-hardening
Pb-0.75Ag Rolled 18.8 9.0 54 26** process. The calcium particles are very
*UTS = ultimate tensile strength, YS = yield strength; **extrapolated value. small and are formed after solidification

28 JOM October 2006


a 200 m
b 200 m
Figure 1. (a) A cast Pb-Ca-Sn alloy
exhibiting large grains, segregation,
and porosity and (b) corrosion product
penetrating into the lead along grain
boundaries of a cast structure.
via a cellular precipitation mechanism.3,4
During service the calcium reacts with
the sulfuric acid to form CaSO4, which
serves to reinforce the PbO2 layer and
produce larger flakes instead of many
small flakes.
In Pb-Ca-Sn alloys, the calcium con-
tent produces large grains with minimal
alloy segregation, as seen in Figure 1a.
However, even fine-grain cast structures
have exposed grain boundaries at the
surface of the anode. During casting
the highly reactive calcium oxidizes and
can become entrained throughout the
structure as dross. As seen in Figure 1b,
corrosion product penetrates along the
boundaries to internal dross and holes,
eventually cracking and failing.
The rolling process deforms the cast
grain structure to produce uniform,
fine grains with less segregation while
eliminating cracks, defects, and pores,
as seen in Figure 2a. During re-crystal-
lization, diffusion uniformly distributes
calcium and tin throughout the sheet via
secondary precipitation. The finer grains
and laminar structure in rolled sheet
impedes penetrating corrosion and the
anodes corrode more uniformly, as seen
in Figure 2b.
The tin addition serves to further
2006 October JOM
increase strength and reduce creep rates.
Tin reacts with the calcium alloys to form
Sn3Ca precipitates which strengthen the
lead matrix. The energy impacted by the
rolling process enhances the precipita-
tion of the fine Sn3Ca particles in the
form of rods or needles in preferred
orientations.5 During corrosion, the tin
is not leached but oxidized to SnO2. The
SnO2 rod-like particles, remnants of the
original precipitate, are semiconductors
and are able to carry current through any
insulating PbSO4 layer formed during
current interruptions, thus preventing
passivation.6 A tin-to-calcium ratio of
15:1 and a minimum tin content of 1.25
wt.% is carefully maintained to assure
reduced rates of corrosion by full con-
version of calcium to Sn3Ca precipitate.
The calcium content is kept below 0.08
wt.% to prevent the formation of Pb3Ca
particles, which cause severe non-uni-
form corrosion.7
The wrought Pb-Ca-Sn alloys have
proven to be a superior material for
anodes over cast Pb-Ca or Pb-Sr. The
Pb-Ca-Sn is more rigid and ductile with
a mechanism to inhibit passivation.
Service life is expected to be at least 7
years depending on tankhouse operating
conditions such as current density and
temperature.
ZINC ELECTROWINNING
The standard anode in the zinc industry
is cast Pb-Ag alloy, typically containing
0.25 wt.% to 1.0 wt.% silver. Recently
a trend from cast to rolled Pb-Ag and
eventually Pb-Ag-Ca alloys has devel-
oped to increase mechanical properties
and power efficiency. The Pb-Ag alloy
is used in both cast and rolled form, as
seen in Figure 3. Rolled Pb-Ag alloy
remains weak (see Table I), so a calcium
addition is used to impart strength and
creep resistance.
Due to the high corrosion resistance
of the segregated silver particles, Pb-Ag
anodes, and in particular rolled sheets,
require a relatively long time to form
a stable PbO2/MnO2 corrosion layer
once in service. The formation of the
adherent PbO2/MnO2 typically requires
3060 days. The time to fully condition
the anode increases with silver content.
Four pre-treatment methods are used
to accelerate the formation of an MnO2
corrosion layer. Sandblasting and shot
peening abrade the anode surface and
create more surface area to which the
corrosion layer can attach during forma-
tion. In addition, sandblasting breaks
up the grain structure in the top anode
surface layer, increasing the surface
area even further. An electrochemical
KF pretreatment forms a thick, dense
adherent layer of PbO2 but is labor-,
energy-, and cost-intensive. A potassium
permanganate treatment chemically
deposits a flaky, initial MnO2 corrosion
layer with subsequent spalling generat-
ing elevated sludge volumes in the tank
bottoms. Once in service, the MnO2 layer
formed on top of the PbO2 is frequently
washed off between operation cycles.
Removal is easier from the smoother,
rolled surface.
The silver addition imparts negligible
strength to the lead alloy to reduce creep.
The major effect of the silver is the
formation of very thin layers of PbO2, a
reduction of oxygen over-potential, and
reduced rates of anode corrosion.6 The
mechanism is believed to be the ability
of the small silver eutectic particles to
effectively increase the evolution of
oxygen from the anode.8 An addition of
calcium improves the mechanical and
electrical properties. Typical silver and
calcium contents of the alloy are 0.3
0.4% and 0.030.08 wt.%, respectively.9
a 200 m
b 200 m
Figure 2. (a) The rolled Pb-Ca-Sn micro-
structure with small directional grains and
(b) corrosion product evenly distributed on
the surface of a rolled lead sheet.
29
Cast Pb-Ag-Ca anodes contain a higher
calcium content but less than 0.10%
above that at which calcium segregates
to the dendrites as Pb3Ca. The silver is
segregated primarily to the interdendritic
region. Casting defects and holes con-
tribute to penetrating corrosion and
premature failure in the cast anodes.
Rolled Pb-Ca-Ag anodes, processed
at elevated temperature, generate a
recrystallized, uniform microstructure
with increased surface grain boundaries
to which a corrosion layer rapidly forms.
The silver remains segregated equally
throughout the sheet. Figure 4 is a micro-
graph of the typical rolled Pb-Ca-Ag
sheet microstructure. The calcium elec-
trochemically activates the anode and
imparts much more strength for form
stability. The rolled anodes offer a con-
trolled structure with lower calcium
resulting in less corrosion and realistic
service life over 5 years.
NICKEL AND COBALT
Lead-antimony alloys have been the
primary anode material for both nickel
and cobalt winning. The Pb-Sb alloys
exhibit good temperature stability where
the Pb-Ca-Sn alloys begin recrystalliza-
tion at and above 65C. Cobalt winning
a 200 m
b 200 m
Figure 3. (a) The cast microstructure of
a Pb-Ag alloy with dendritic grains and
silver segregated between grains and (b)
a rolled Pb-Ag alloy with dispersed, black
silver constituent.
30
practices operate from 65C to 75C,
and nickel electrolyte temperatures are
around 60C. Despite these operating
temperatures, a trend can be observed
in the nickel winning toward Pb-Ca-Sn
alloys as the more and more employed
anode material. Cobalt winning anodes
have seen an addition of silver to the
usual Pb-Sb alloy predominantly to
increase anode corrosion resistance.
The antimony alloy also benefits the
100 m
corrosion layer formation in the weak
Figure 4. The rolled Pb-Ca-Ag micrograph
sulfuric acid solutions seen in nickel and showing dispersed, dark silver constitu-
cobalt winning. Due to the low acid ents and recrystallized grains.
concentration in the electrolyte, the
oxidation of PbO and Pb(OH)2 to PbO2
is suppressed. The high amount of anti-
mony most likely catalyzes the formation
of PbO2, significantly reducing the rate
of corrosion. The morphology of the
PbO2 corrosion layer on the Pb-Sb alloy
is a stable, hard, dense, black PbO2. In
sulfuric acid solutions, this material does
not react to form PbSO4 as readily as
PbO2 or normal PbO2. Operations 200 m
with frequent power interruptions use Figure 5. A typical microstructure of cast
the Pb-Sb to hinder passivation. Pb-6Sb (wt.%) alloy.
Typical anodes are all cast lead alloyed
with 610% antimony. The hypoeutectic
alloys are extremely strong in the as-cast
CHROMIUM PLATING
condition and are highly resistant to creep
and warping. The strength is imparted Hard chromium plating uses a Pb-
by the needle-like eutectic antimony 7Sn (wt.%) tin anode in a chromic
particles which serve as reinforcing rods acid electrolyte. Lead is used because
to hold the lead rigid.6 Figure 5 shows a the reoxidation of trivalent chromium
typical Pb-Sb microstructure with the occurs more readily on lead than on
eutectic antimony segregated between other available metals.10 The high tin
grains. These needle-like particles are content reduces the rate of corrosion and
broken up and destroyed during rolling improves conductivity. The same PbO2
of Pb-Sb alloys, which makes the alloys corrosion layer is formed on the anode
much weaker in the as-rolled form surface during operation and fosters
(shown in Table I). the reoxidation reaction. For complex
Small amounts of sulfur or copper shapes, anodes can be used in wire form
may be added to refine the crystal struc- to conform to the shape of the cathode.
ture and prevent cracking of the large The tin content may vary from 6 wt.%
dendrites formed upon solidification. to 10 wt.%.
During service the antimony in its bound-
MANGANESE
ary network can be rapidly oxidized. The
antimony is leached from the lead matrix A cast Pb-Ag anode is utilized in the
as antimony sulfate.6 Pieces of lead sur- sulfuric manganese winning cells. The
rounded by the leached antimony often silver in the anode increases corrosion
spall off and generate a great deal of resistance. Additions of arsenic may also
sludge in the bottom of the electrowin- be used in these cast anodes as a grain
ning tanks. The fine lead-bearing par- refiner. The equiaxed grains show
ticles are agitated by the oxygen evolu- improved corrosion resistance over long,
tion and end up contaminating the dendritic grains with segregation. Arse-
cathode. Lead antimony alloys have lost nic significantly increases mechanical
favor when very low lead levels are properties and stabilizes the anode form.
required in the cathodic deposit. An addition of arsenic to the alloy instead
JOM October 2006
of the electrolyte may be beneficial in
reducing the MnO2 formation on the
anode. A narrower, smaller anode is used
to foster higher current densities. The
anode collects an MnO2 layer during
operation. During cleaning the soft Pb-
Ag material allows flexing in order to
loosen off the MnO2. The anodes are
re-flattened prior to service.
CONCLUSION
The ideal anode alloy should be resis-
tant to corrosion, highly conductive, and
opposed to the formation of passivating
films. Also, it should be ductile, form
stable, and not become embrittled in
service. New alloy additions and
improvements on lead alloys continue
to create the ideal anode. The rolled Pb-
Ca-Ag alloy is being utilized to increase
life and conditioning time. A new Pb-
Ca-Sn-Ag alloy promises increased life,
reduced corrosion, and improved elec-
trochemical properties.11 An alloy with
the addition of cobalt, Pb-Ca-Sn-Co,
may reduce or eliminate the use of cobalt
in the copper electrolyte to improve
oxygen evolution at the anode. Electro-
winning tankhouses continue to trial
these and atypical lead alloys to meet
performance needs of a permanent lead
anode.
ACKNOWLEDGEMENTS
The authors would like to acknowledge
the help, advice, and practical sugges-
tions from Dr. Andreas Siegmund.
References
1. J.G. Jenkins and M.A. Eamon, Plant Practices and
Innovations at Magma Copper Companys San Miguel
SX-EW Plant, Electrometallurgical Plant Practices,
ed. Claessens and Harris (New York: Pergamon Press,
1990), pp. 4445.
2. J.A. Gonzalez, J. Rodrigues, and A. Siegmund,
Advances and Application of Lead Alloy Anodes for
Zinc Electrowinning, Lead & Zinc 05, Vol. 2, ed. T.
Fujisawa (Tokyo: Mining and Materials Processing
Institute of Japan, 2005), p. 1046.
3. R.D. Prengaman, Structural Control of Non-
Antimonial Lead Alloys via Alloy Additions, Heat
Treatment, and Cold Work (Paper #Pb-80 presented
at the 7th International Lead Conference, Madrid, May
1980).
4. H. Borchers and H. Assmann, Effects of Tin
Additives on the Precipitation Behavior of Lead-
Calcium Alloys, Z. Metallkunde, 69 (1978), p. 43.
5. R.D. Prengaman, New Insoluble Anodes for Copper
Electrowinning, The Electrorefining and Winning of
Copper, ed. J.E. Hoffmann et al. (Warrendale, PA: The
Metallurgical Society, 1987), pp. 457467.
6. R.D. Prengaman, The Metallurgy of Lead Alloys for
Electrowinning Anodes, Anodes for Electrowinning,
ed. D.L. Robinson and S.E. James (Warrendale, PA:
TMS, 1984).
7. R.D. Prengaman, The Metallurgy and Performance
of Cast and Rolled Lead Alloys for Battery Grids,
Journal of Power Sources, 67 (1997), p. 267.
8. O. Hyvarinin, The Effect of Silver and Cobalt on the
Oxygen Evolution of Lead Anodes (Thesis for Doctor
Technology Degree, Helsinki University of Technology,
Helsinki, Finland, 1972).
9. A. Siegmund and R.D. Prengaman, New Wrought
Pb-Ag-Ca Anodes for Zinc Electrowinning to Produce
a Protective Oxide Coating Rapidly, Lead-Zinc 2000,
ed. J.E. Dutrizac et al. (Warrendale, PA: TMS, 2000),
pp. 589597.
10. W. Blum and G. Hogaboom, Principles of
Electroplating and Electroforming (New York: McGraw-
Hill Book Company, 1958), pp. 343344.
11. M. Stelter, H. Bombach, and P. Saltykov, Use of
Lead Alloy Anodes in Electrowinning of Metals,
Proceedings of European Metallurgical Conference,
2003, pp. 561571.
Aaron Felder is a research engineer with and R.
David Prengaman is president of RSR Technolo-
gies, Inc. in Dallas, Texas.
For more information, contact R. David Prengaman,
RSR Technologies, Inc., 2777 Stemmons Freeway,
Suite 1800, Dallas, TX 75207; (214) 242-0357;
fax (214) 631-6092; e-mail rdprengaman@
rsrtechnologies.com.

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